CA2147830A1 - Water-borne compositions comprising half esters of anhydride polymers crosslinked by epoxies - Google Patents
Water-borne compositions comprising half esters of anhydride polymers crosslinked by epoxiesInfo
- Publication number
- CA2147830A1 CA2147830A1 CA 2147830 CA2147830A CA2147830A1 CA 2147830 A1 CA2147830 A1 CA 2147830A1 CA 2147830 CA2147830 CA 2147830 CA 2147830 A CA2147830 A CA 2147830A CA 2147830 A1 CA2147830 A1 CA 2147830A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- composition
- anhydride
- binder
- polymer
- 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.)
- Abandoned
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- 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
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2451/00—Type of carrier, type of coating (Multilayers)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Abstract
An aqueous coating composition useful for maintenance coatings for architectural structures or for a finish or refinish for automobiles and trucks. The film-forming binder comprises a neutralized half-ester product of an acrylic polymer having at least two reactive anhydride groups and an epoxy-containing, optionally silane-containing crosslinker. The composition may be used as a multi-package system. The composition is characterized by improved environmental resistance and excellent clarity and ap-pearance, particularly for clearcoats.
Description
WO 94~11122 2 1 ~ 7 8 3 0 PCr/US93/10791 TITLE
WATER-BORNE COMPOSITIONS
COMPRISING HALF E~STERS OF ANHYDRIDE
POLYMERS CROSSLINKED BY EPOXIES
FIELD OF THE INVENTION
This invention is related to a multi-component water-borne coating composition co~ -ising a half-ester of an an_ydride polymer and an epoxy crocclinkin~ agent.
BACKGROUND
There are a wide variety of multi-component coating compositions available for finiching automobiles and trucks. Various co~ting compositions comprising anhydride or epoxy con~ining compositions are knowvn. For example, U.S. Patent 4,906,677 discloses a composition colll~lisillg an acrylic anhydride polymer, a glycidyl component, and a phosphonillm catalyst. U.S. Patent 3,136,736 and British patent 994,881 disclose coating compositions COlll~liSillg polyepoxides and maleic anhydride copolymers. U.S. Patent 4,732,791 concerns a coating 2 0 composition comprising a polyepoxide, a monomeric anhydride curing agent, and a hyd~o~yl cont~ining polyfunctional polymer.
U.S. patent no. 4,906,677, in column 4, lines 40-47, licclQses that anhydride polymers, in epoxy-anhydride compositions, may be COllvt;l ~ed to a half-ester by alcohol solvents.
2 5 European Patent Application, publication no. 0 353 734 A2, published 07.02.90 and European Patent Application, publication no. 0 450 963 A1, published 09.10.91 both ~ ose the combination of a polymer having a half-esterified acid anhydride group and a compound having an epoxy group and a hydroxy group, or a separate epoxy and hydro~y 3 o compound. These patents teach that, in such compositions, high temperature curing is required in order that the half-esteriffed acid anhydride groups are ring-closed to produce acid anhydride groups which then react with hydl o~yl groups, which in turn release carboxyl groups which then react with the epoxy groups. These patents indicate that a 3 5 certain hydroxy equivalent number or hydroxy value is necessary for adequate water resistance of the coating composition.
W O 94J11122 ~ 1 47 ~3 ~ PC~r/US93/10791 .
The afore-men~io~e-l EP 0 353 734 A2 states that water can be used as a "diluent" if the carboxyl groups are neutralized with an amine.
In contrast, the present invention is directed to compositions in which r water is employed as the primary carrier, organic solvents being possible diluents. The afore-mentioned EP 0 450 963 A1 states that the half esterified polymer may be neutralized with amines to make a hydrophilic polymer which can form an aqueous composition. The examples, however, all tlicclose compositions which employ organic solvents.
A problem with present co~tinE compositions for lo automobiles and trucks, or parts thereof, is that durability is not as good as desired. An important aspect of durability is environmental resict~nçe. The present invention offers a high quality finish exhibiting superior e,lvho~".,en~l resistance at lower cost. This is particularly notewolLlly given the fact that the present composition is a waterborne finish.
The present composition is a multi-package system, having use in automotive finishes for new automobiles and for r~finish, for use in maintenance, and for use in both high temperature and low temperature cured systems. Such a coating composition exhibits excellent clarity, appearance and environmental r~ict~n~e Importantly, such compositions z o offer a low voC (volatile organic content) since the binder is waterborne employing an aqueous (primarily water) carrier.
SUMMARY OF THE INVENTION
The present invention is directed to a co~ting composition 2 5 co~ g 20-80% by weight of binder components and 80-20~o by weight of an aqueous carrier which is primarily water. The binder contains (a) a half-ester of an anhydride polymer having at least two anhydride groups and having a weight average molecular weight of about 2,000-100,000;
3 o (b) an epoxy component having at least two reactive glycidyl glOU~S; and (c) a basic compound to neutralize the half ester.
Optionally, these compositions may also include epoxy-silane polymers, silane polymers, acid polymers, lower molecular weight polyester 35 or polyester urethanes, melamine resins, hydroxyl polymers, acrylic latices, waterborne urethane emulsions or dispersions, and combinations thereof.
WO 94/11122 21~ 7 ~ 3 0 PCr/USs3/10791 In one embodiment, the water content of the aqueous carrier is greater than 60 percent by weight of the aqueous carrier.
- The present invention is also directed to a process in which applicant's composition is applied to a substrate as an automotive topcoatl.
DETAILED DESCRIPIION OF THE INVENT~ON
The composition of the present invention forms a durable ellviro~ ental resi~t~nt coating. The composition is especially useful for m~intenence coating of architect~lral structures and for finishing the exterior of ~lltomobiles and trucks.
The composition can also be pigmented to form a colored finish, although the composition is particularly useful as a clearcoat.
Preferably, the co~ting composition has a high solids content and contains about 20-80~o by weight binder and 20-80% by weight aqueous carrier. The binder of the composition contains about 25-90~o, preferably 35 to 65% (by weight of binder) of the half-ester of an anhydride polymer cont~ining at least two anhydride groups; 5-50%, ~refe,ably 15 to 30~o (by weight of binder) of a glycidyl or epoAy cont~ining component.
Optionally, the composition may comprise 5-50~o, preferably 2 0 10 to 25% by weight of binder of an acrylic or a polyester or polyester urethane which may contain hydroAyl and/or acid functionality. If hydluAy functional, the hydl oAy number is 20 to 120. If acid functional, the acid number is 20 to 120.
In the present composition, when used in a baking system, if 2 5 an optional acrylic or polyester or polyester urethane polymer is acidfunctional, then the cure occurs between the acid groups and the epoAy groups and the half ester groups,following ring-closure during baking, and the epoAy group. Some cure may also occur between the acid of the half ester and the epoAy. The main cure, however, is based on the ring closure 3 o during baking.
The anhydride polymer employed in preparing the present composition has a weight average molecular weight of about 2000-100,000, determined by gel permeation chromatography using polymethyl methacrylate as a standard. Preferably the anhydride polymer has a weight 3 5 average molecular weight of 3,000-50,000.
WO94/11122 2~ ~ 830 PCr/USs3/10791 The anhydride polymer may be prepared by conventional techniques in which the monomers, solvent, and conventional catalysts such as t-butyl perbenzoate are charged into a polymerization vessel and heated to about 75-200C for about 0.5-6 hours to form the polymer.
The anhydride acrylic polymer is preferably an acrylic copolymer formed by polymerizing a mixture of monomers comprisiong alkyl methacrylates and/or alkyl acrylates, where the alkyl groups have 1-12 (preferably 1-8) carbon atoms, and ethylenically ~ms~ rated anhydrides (or ethylenically unsaturated dicarboxylic acids which are con~el led to the acid anhydride during the polymerization). Optionally, the anhydride acrylic polymer can cont~in other components such as styrene, methyl styrene, acrylonitrile, and/or methacrylonitrile in amounts of about 0.1-50% by weight.
Typical alkyl acrylates and methacrylates that can be used to form the anhydride acrylic polymer are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, and the like, or 2 0 any others ment;oned below. Other components that can be used to form the anhydride acrylic polymer are acrylamide, methacryl~mide and acrylo alkoxy silanes such as g~mm~- methacryloxyl propyl trimethoxy silane.
Also, the anhydride acrylic polymer can contain about 0.1-5% by weight of an ethylenically lm~ lrated acid such as acrylic acid, methacrylic acid, 2 5 itaconic acid, maleic acid, and the like.
Typically useful ethylenically lm~ rated anhydrides are itaconic anhydride, maleic anhydride, isobutenyl s~lc~inic anhydride, and the like. As stated above, it is also possible to impart the anhydride functionality to the anhydride acrylic polymer by using an ethylenically 3 0 lln~ rated dicarboxylic acid which conver.s to the acid anhydride during the reaction. Suitable ethylenically lm~ lrated dicarboxylic acids that can be used are itaconic acid, maleic acid, isobutenyl succinic acid, and the like.
A preferred anhydride acrylic polymer comprises styrene, butyl methacrylate, butyl acrylate, and itaconic anhydride. Another 3 5 preferred polymer co~ lises methyl methacrylate, butyl acrylate, and WO 94/11122 2 1 ~ 7 ~ ~ ~ PCI/US93/10791 itaconic anhydride. Another preferred polymer comprises styrene, isobornyl methacrylate, butyl acrylate, and maleic anhydride.
The anhydride polymer is half-esterified with an alcohol.
Suitable alcohols inrlllde methanol, ethanol, propanol, butanol;
ethyleneglycol monoalkyl ether, dialkylaminoethanol, in which particularly c~mmon alkyl groups are methyl and ethyl; acetol, allyl alcohol, propargyl alcohol, tetrahydrofurfuryl alcohol; and the like. The reaction to produce the half-ester is generally at ambient or elevated temperatures, suitably in the range of 20 to 150C. Such a reaction may be conducted in the o presence of a catalyst, for example, tertiary amines such as triethyl~mine, quaternary ~mmonillm salts such as benzyltrimethyl ammonium chloride, and the like.
For utility in the aqueous carrier, the anhydride polymer, after it is converted to the half-ester, is neutralized with a base. Suitable bases inchl~le amines which are volatile under the conditions of cure.
Typical amines are triethyl amine, trimethyl amine, ~mmor~ and dimethyl eth~nol~mine. Other bases inrl~lde sodium hydroxide, pot~csillm hydroxide and the like. The base is suitably used in the amount of 0.1 to 10 percent by weight of binder to solublilize or disperse the half ester in the aqueous 2 o carrier.
The epoxy component preferably C~lt~ at least two glycidyl groups and can be an oligomer or a polymer. Typical glycidyl co",l~onents are sorbitol polyglycidyl ether, m~nnitol polyglycidyl ether, pentaelylhlilol polyglycidol ether, glycerol polyglycidyl ether, low 2 5 molecular weight epoxy resins such as epoxy resins of epichlorohydrin and bisphenol A, di- and polyglycidyl esters of acids, polyglycidyl ethers of iso-;y~nulates, such as Denecol EX301'19 from Nagase. Sorbitol polyglycidyl ethers, such as DCE-358~ from Dixie Chem. Co., and di- and polyglycidyl esters of acids, such as Araldite CY-184'l9 from Ciba-Geigy or XUS-71950~9 3 o from Dow Chemical form high quality finiches. Cycloaliphatic epoxies such as CY-179~ from Ciba-Geigy may also be used. For ambient cure refinish applications, generally the choice of epoxy is chosen for room temperature reactivity and the extent of cure with the half ester. (Ambient curing means that the composition cures at 10 to 90C, preferably 15 to 60C
3 5 within a couple of weeks, preferably one week.) W094/t~ 0 PCr/us93/l079l Glycidyl methacrylate or acrylate cont~ining acrylic polymers can be used, such as random and block polymers of glycidyl methacrylate/butyl methacrylate. The block polymers can be prepared by anionic polymerization or by group transfer polymerization. Optionally, the composition may further comprise a copolymer having both epoxy and alkoxy silane groups, prepared as the re~ction product of epoxy monomers such as glycidyl methacrylate and silane monomers as described below.
Optionally the present composition may co~ lise a silane polymer as a separate additional ingredient or component. Such silane polymers may suitably have a weight average molecular weight of about 100~30,000, a number average molecular weight of about 500 10,000. (All molecular weights disclosed herein are determined by gel permeation chromatography using a polystyrene standard.) As indicated above, the binder of the present composition may comprises from about 5 to 50%, preferably 10 to 25%, based on the weight of the binder, of an acrylic or polyester or polyester urethane or copolymer thereof having a ll~dlo~ number of about 20 to 120, preferably 70 to 100, or an acid number of about 20 to 120, preferably 75 to 95. This polymer has a weight average molecular weight of about 2,000 to 20,000, plcfelably 4,000-10,000. Unless otherwise indicated, all molecular weights mentioned herein are measured using gel permeation chrom~tography using polymethyl methacrylate as a standard.
Polyester urethanes are a reaction product of a llydro~yl le. "~ te~ polyester component and a polyisocyanate component, preferably, an aliphatic or cycloaliphatic diisocyanate. The polyester, which may be used alone or as a component of the polyester urethane, may be suitably prepared from linear or branched chain diols, in~ lin~ ether glycols, or ll~ixlures thereof or ~ ufes of diols and triols, cont~ining up to and in~lntling 8 carbon atorns, or mixtures of such diols, triols, and 3 o polycaprolactone~polyols, in combination with a dicarboxylic acid, or anhydride thereof, or a ll~i~lllre of dicarboxylic acids or anhydrides, which acids or anhydrides cont~in up to and inch-~ling 12 carbon atoms, wherein at least 7S~ by weight, based on the weight of dicarboxylic acid, is an aliphatic dicarboxylic acid.
3 5 Representative saturated and -n~t--rated polyols that can be reacted to form a polyester include alkylene glycols such as neopentyl glycol, ethylene glycol, propylene glycol, butane diol, pentane diol, 1,6-hexane diol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 1,4-cyclohexane dimethanol, 2,2-dimethyl 1,3-propanediol, 2,2-bis(hydroxymethyl)propionic acid, and 3-mercapto-1,2-propane diol. Preferred are 1,6-h.oY~n~-liol and butylene glycol.
Polyhydric alcohols, having at least three hydroxyl groups, may also be inclllcled to introduce br~n~hing in the polyester. Typical polyhydric alcohols are trimethylol propane, trimethylol ethane, pentaelyLh~ilol~ glycerin and the like. Trimethylol propane is preferred, in forming a branched polyester.
Polycaprolacone polyols may be also be used in m~king the polyester. A preferred polycaprolactone, a triol, is Tone~9 FCP 310 (available from Union Carbide).
The carboxylic acids used in m~king the polyester component of the polyester urethane include the saturated and nn~tllrated polycarboxylic acids and the derivatives thereof. Aliphatic dicarboxylic acids that can be used to form the polyester are as follows: adipic acid, sebacic acid, snccinic acid, azelaic acid, dodecanedioic acid, 1,3 or 1,4-cyrloh~Y~ne dicarboxylic acid and the like. A preferred acid is adipic acid.
2 o Aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, and the like. Anhydrides may also be used, for example, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like.
Typical polyisocyanates that may be used to form the polyester ulelha-le are as follows: isophorone diisocyanate which is 2s 3-isocyanatemethyl-3,5,5-trimethyl- cyclohexyl-isocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, butylene-1,3-diisocyanate, hexamethylene diisocyanate, methyl-2,6-diisocyanate, methyl-2,6-diisocyanate caproate, octamethlyene diisocyanate, 2,4,4-trimethylheY~methylene diisocyanate, nonamethylene 3 o diisocyante, 2,2,4-trimethylh~oY~methylene diisocyanate, decamethylene diisocyanate, 2,11-diisocyano-dodecane and the like, meta-phenylene diisocyanate, para-phenylene diisoxyanate, toluene-2, 4-diisocyanate, toluene-2,6-diisocyanate, xylene-2, 4-diisocyanate, xylene-2,6-diisocyanate, dialkyl benzene diisocyanates, such as methyl~ro~ylbenzene diisocyanate, 3s methylethylbenzene diisocyanate, and the like: 2,2'-biphenylene diisocyanate, 3,3'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, W O 94~11122 2 1 4 7 8 3 0 PC~r/US93/10791 ~
~ .
..
3,3'-dimethyl~,4'-biphenylene diisocyanate, and the like;
methylene-bis(4-phenyl isocyanate), ethylene-bis(4-phenyl isocyanate), isopropylidene-bis(4-phenyl isocyanate), butylene-bis(4-phenylisocyanate), and the like; 2,2'-oxydiphenyl diisocyanate, 3,3'-oxydiphenyl diisocyanate, 4,4'-oxydiphenyl diisocyanate, 2,2'-ketodiphenyl diisocyanate, 3,3'-ketodiphenyl diisocyanate, 4,4'-ketodiphenyl diisocyanate, 2,2'-thiodiphenyl diisocyanate, 3,3'-thiodiphenyl diisocyanate, 4,4'-thiodiphenyl diisocyanate, and the like; 2,2'-sulfonediphenyl diisocyanate, 3,3'-sulfonediphenyl diisocyanate, 4,4'-sulfonediphenyl lo diisocyanate, and the like; 2,2,-methylene-bis(cyclohexyl isocyanate), 3,3'-methylene-bis(cyclohexyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), 4,4'-ethylene-bis(cyclohexyl isocyanate), 4,4'-propylene-bis-(cyclohexyl isocyanate), bis(paraisocyano-cyclohexyl)sulfide, bis(para-isocyano-cyclohe~yl)sulfone, bis(para-isocyano-cyclohexyl)ether, bis(para-isocyano-cyclohexyl)diethyl silane, bis(para-isocyano-cyclohexyl)diphenyl silane, bis(para-isocyano-cyclohexyl)ethyl phosphine oxide, bis(para-isocyano-cyclohexyl)phenyl phosphine oxide, bis(para-isocyano-cyclohexyl)N-phenyl amine, 2 0 bis(para-isocyano-cyclohexyl)N-methyl amine, 3,3 '-dimethyl-4,4 '-diisocyano biphenyl, 3,3'-dimethoxy-biphenylene diisocyanate, 2,4-bis(b-isocyano-t-butyl)toluene, bis(para-b-isocyano-t-butyl-phenyl)ether, para-bis(2-methyl4-isocyanophenyl)benzene, 3,3-diisocyano ~m~ns~ne, 3,3-diisocyano bi~ m~nt~ne, 3,3-diisocyanoethyl-1'-bi~ m~nt~ne, 1,2-bis(3-isocyano-propoxy)ethane, 2,2-dimethyl propylene diisocyanate, 3-methoxy-he~methylene diisocyanate 2,5-dimethyl heptamethylene diisocyanate, 5-methyl-nonamethylene diisocyanate, 1,4-diisocyano-cyclohtoY~ne, 1,2-diisocyano-octadecane, 2,5-diisocyano-1,3,4-l~Y~ 7Qle, OCN(CH2)30(CH2)20(CH2)3NCO, OCN(CH2)3NCO or the following:
OCN(CH2)3 IN(CH2)3NC
WO 94/11122 2 1 ~ 7 8 3 0 PCI/US93/10791 Aliphatic diisocyanates are preferred, forming urethanes that have excellent weatherability. One aliphatic diisocyanate that is particularly preferred is trimethyl hexamethylene diisocyanate.
A preferred polyester urethane is the re~ction product of trimethylhexamethylene diisocyanate and a hydroxy termin~te~l polyester of 1,3-butylene glycol, 1,6-hexanediol, adipic acid, trimethylolpropalle, and Tone'19 FCP 310.
It is noted that a hydro~y functional polyester urethane can be collvel led to the corresponding acid functional polyester urethane by 0 reaction with methylhexahydropthalic anhydride or other mono-anhydride such as succinic anhydride. Converting the hydroxy to the acid may result in longer pot life in the clearcoat.
A polyester may be prepared by conventional techniques in which the component polyols and carboxylic acids and solvent are esterified at about 110C-250C for about 1-10 hours to form a polyester. To form a polyester urethane, a diisocyanate may then be added and reacted at about 100C for about 15 mimltes to 2 hours.
In preparing the polyester urethane, a catalyst is typically used. Collvelllional catalysts inrl~lcle benzyl trimethyl ammonium 2 o hydro~ide, tetramethyl ~mmQnillm chloride, organic tin compounds, such as dibutyl tin diaurate, dibutyl tin oxide stannous octoate and the like, i.",. complexes and litharge. About 0.1-5% by weight of catalyst, based on the total weight of the re~ct~ntc, is typically used.
The stoichiometry of the polyester preparation is controlled 2 5 by the final hydroxyl number and by the need to obtain a product of low acid number; an acid number below 10 is preferable. The acid number is defined as the number of milligrams of pot~ccinm hydroxide needed to neutralize a one gram sample of the polyester. Additional inform~tion on the preparation of polyester urethanes is disclosed in commonly ~ccigned 3 o U.S. Patent No. 4,810,759, hereby incorporated by reference.
Another optional component are acrylic latices such as Neocryl~ available from ICI. Other latices are available from ICI and Rohm & Haas. Another optional component are urethane dispersions or emulsions such as Neorez~ 9699 and the like from ICI or Spensol L,52 from Reichold. Other suppliers are Witco, American Cy~n~mitl, and wO 94/11122 2 ~ 47 83 ~ pcr/uss3t1o79l Sanncor. Such dispersions include polyethers, polyesters, polycarbonates, or combinations thereof.
An acid resin is optionally added to the coating composition The acid functional material can be formed by polymerizing monomers of alkyl methacrylates, or alkyl acrylates or mixtures thereof, where the alkyl groups have 1-12 carbon atoms and ethylenically lln~hlrated acids.
Optionally, the acid functional polymer can also contain other components such as styrene, methyl styrene, and/or acrylonitrile, methacrylonitrile in arnounts of about 0.1-50% by weight.
Typical alkyl acrylates, methacrylates, and other components that can be used to form the acid functional polymer are the same as those listed above with respect to the anhydride polymer Typically useful ethylenically lln~t~lrated acids are acrylic acid, methacrylic acid, itaconic acid, maleic acid, and the like.
This acid resin may also contain hydro~yl functionali~r by using monomers such as hydro~yethylacrylate, hydroxyethyl methacrylate and llydrol~yl~lo~l acIylate~ The hydroxy functionality may be introduced by a post reaction of the acid with epoxy co~ g co~ mds such as Cardura EZ9 from Shell Chemical Company (a glycidyl ester of versatic 2 o acid) and propylene oxide.
Another optional component of the present composition is the half ester of an anhydride compound, as distin~ hed from a polymer, for example the reaction product of an acid anhydride such as hexahydlop~halic anhydride or a sllcrinic anhydride, which may be substihlte~l, for example with a Cl-Cg alkyl group, with a monofimction~l or polyfunctional alcoholic solvent such as methanol or ethylene glycol. A
prefel~ed half ester is the reaction product of methylhexahydrophthalic anhydride and an alcohol such as ethylene glycol. Other alcoholic solvents are ~,lopallol, isobutanol, isopropanol, tertiary butanol, n-butanol, 3 o propylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like. The half ester is suitably present in the amount of 2 to 25 percent by weight of binder, preferably 4-12 percent.
About 0.1-8~o ~preferably 0.5 to 5~o) by weight, based on the weight of the binder of the coating composition, of a catalyst is added to 3 5 enhance curing of the composition. For refinish (ambient cure systems), typical catalysts are as follows: tertiary amines such as triethylene rli~mine~
WO 94/11122 21 ~ 783~ PCr/US93/10791 .
quinuclirline, dialkyl alkanol amines such as dimethyl ethanol~mine diethyl ethanol amine, dibutyl ethanol amine, diethyl hexanol amine, triethylamine bisdimethylaminoethyl ether (available from Union Carbide), diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, and the like, lithinm tertiary butoxide, tri(dimethylaminometnyl)phenol, bis(dimethylamino)propan-2-ol, N,N,N ,N -tetramethylethylene~ mine, N-methyldiethanol~mine N,N-dimethyl-1,3-propane~ mineand 1-dimethylamino-2-propanol. Tertiary amines and bicyclic tertiary amines are preferred catalysts. For baking systems, typical catalysts are as follows:
0 triethylene ~ mine, quinuclidine, dialkyl alkanol amines such as dimethyl ethanol~mine, diethyl ethanol amine, dibutyl ethanol amine, diethyl hexanol amine and the like, lithium tertiary butoxide, tri(dimethyl-~minomethyl)phenol, bis(dimethylamino)propan-2-ol, N,N,Nl,Nl-tetramethylethylene~ mine, N-methyldiethanol~mine, 15 N,N-dimethyl-1,3-prop~nedi~mine and 1-dimethylamino-2-propanol or quaternary ~mmonillm salts such as tert-butyl ammonium bromide, benzyl trimethyl ~mmonillm formate and the like. Preferred catalyst, howt;ver, are phosphonium compounds such as are disclosed in U.S. Patent No.
4,906,677, hereby incorporated by reference in its entirety.
2 o Typical solvents used to prepare the anhydride acrylic polymer or used as a diluent for the coating composition inclll~le toluene, xylene, butyl ~cet~te~ butyl proprionate, ethyl benzene, higher boiling aromatic hydrocarbons, amyl acetate, ethyl acetate, propyl acetate, ethylene or propylene glycol mono alkyl ether acetates.
2 5 The solvent for the final composition, as sold or applied, comprises primarily water. Suitably at least 60 percent of the liquid carrier, preferably 70 percent is water. Preferably deionized water is employed.
Optional diluents for the water inclnde butyl acetate, butyl proprionate, mono- and di- ethers of proplyene glycol, and butyl cellosolve.
3 o Generally, the present composition is applied as a co~ting to a substrate by conve~llional techniques such as spraying. The composition may be applied as a multi-package system. Multi-package means that at least some of the components are kept separate until shortly before their application. For instance, the glycidyl component must be kept seperate 3 5 from the half ester and optional acid components. For refinish systems, the reslllting coating can be dried and cured at elevated temperatures of 5 to WO 94/11122 . PCI/US93/10791 21~7~3~
90C, preferably 15 to 60C. Coatings are applied to form a finish typically about 0.5-5 mlls thick, and preferably 1-2 mils thick. For OEM (orgiginal equipement m~nllf~ctllre) automotive applications, the co~ting can be dried and cured at elevated temperatures of 100 to 200C.
To i~ rove weatherability of the clear finish of the coating composition, about 0.1-5%, by weight, based on the weight of the binder, of an ultraviolet light stabilizer or a comhin~tion of ultraviolet light stabilizers can be added. These stabilizers inclllcle ultraviolet light absorbers, screeners, quenchers and speci~lc hindered amine light stabilizers. Also, 0 about 0.1-5~o by weight, based on the weight of the binder, of an antioxi~l~nt can be added.
Typical ultraviolet light stabilizers that are useful are listed in U.S. patent no. 4,906,677, previously incorporated by reference.
Particularly useful ultraviolet light stabilizers that can be used are hindered aII~ines of piperidyl derivatives such as those .licl~los~d in Murayama et al., U.S. Patent 4,061,616, issued December 6, 1977, colurnn 2, line 65, through colum~ 4, line 2, and nickel compounds such as [l-phenyl-3-methyl4-decanoylpyr~Ql~te(S)]-Ni, bis[phenyldithiocarbamato]-Ni(II), and others listed in the above patent, 2 o col~lmn 8, line 44 through line 55.
An applicable blend of ultraviolet light stabilizers comprises 2-[2'-hydroxy-3',5'-1(1-1-dimethyl-propyl)phenyl]benzotrizole and bis-[4-(1,2,2,6,6-pen~mell,ylpil)eridyl)] 2-butyl-2-[(3,5-~-butyl-4-hydroxy-phenyl)methyl] propanedioate. Although the stabilizers can be employed in any ratio, a 1:1 ratio of benzotriazole to propanedioate is preferred.
The composition can be applied over a pigmented or colored basecoat finish. For refinish compositions, if over a waterborne basecoat, the basecoat is typically first allowed to dry. For original automotive production, the coating composition is applied over a waterborne basecoat 3 o and baked at conventional curing temperatures in the art, typically 265F.
Before applying the topcoat, however, the waterborne basecoat is typically dried using a warm-air flash or bake, without substantially curing the basecoat, in order to remove a substantial amount of the water. l~uring baking, the half-esterified acid anhydride groups are believed to convert 3 5 back to the original acid anhydride ring groups. These groups then react wO 94~11122 2 1 4 7 ~ 3 0 ~ Pcr/US93/10791 with the epoxy groups. A composition with a relatively faster acting epoxy cro~linker may be employ Basecoats suitably comprise collvenLional pigments, optionally metallic flake or the like, which can be made using convelllional techniques in which a mill base cont~ining pigment, dispersant and solvent or carrier is first formed.
The coating composition for refinish applicatons can be applied over both solvent- and water borne basecoats.
The present composition can be pigmented to form a colored lo finish such as a primer, basecoat, monocoat, or maintenence paint. About0.1-200 percent by weight, based on the weight of the binder, of co~lve~l ior~l pigments can be added using conventional techniques in which a mill base con~ining pigment, dispersant and carrier is first formed.
The mill base is then mixed with the composition to form a colored composition.
The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise indicated. The weight average molecular weight of polymers was determined by GPC (gel permeation chromatography) using polyethyl methacrylate as a st~n~i~rd~
unless stated otherwise.
This example illustrates the preparation of a half ester of a maleic anhydride polymer, specifically the half ester of a styrene/isobornyl 2 5 methacrylate/ butyl acrylate/maleic anhydride copolymer. The anhydride polymer was first prepared, as follows. To a reactor, heated to reflux, equipped with a condensor, stirrer, nitrogen purge, feed system, he~ting mantle, were added, as Part I, 1384.86 parts of bulylplopionate. The following Part II was premixed and then fed to the reactor over four hours.
3 o The next following Part III was added to thc reactor over 30 min~ltes~ held for 30 mimltes.
Parts by Part II We;~ht Styrene monomer 1081.92 Isobornyl methacrylate 735.71 Butyl acrylate 1773.05 W O 94~11122 214 7 8 3 0 PC~r/US93/10791 Maleic anhydride 735.71 Butyl propionate 2077.29 Tertiary butyl peroxyacetate 259.66 Parts by Part III Wei~ht Tertiary butyl peroxyacetate 19.04 Butyl proprionate 138.Q0 TOTAL 8205.24 After the 30 minute holding period, a total of 1090 parts by weight of solvent is stripped off, resulting in a yield of 7115.24 parts by weight.
The product polymer had a Gardner-Holdt viscosity of V and a measured solids of 62.84%. ~he actual molecular weight was measured by gel permeation chromatography to be Mn = 23s5 and M W = 6135.
This maleic anhydride polymer was then coverted to a a methyl half ester by mixing the following components;
2 0 Components Parts Maleic anhydride polymer solution (prepared as described above) 600 Methanol 24 2 5 The first component was heated to 50C and the methanol componentadded over a 2~30 minute period. The mixlllre was then heated to 75-85C for five hours or until the anhydride band in the infrared analysis has disappeared (90-95~o gone).
This example illustrates an epoxy silane polymer, more particularly an epoxy functional acrylo~ ne polymer which was prepared by cha~h~g the following constit~lent~ into a polymerization vessel equipped with a heating m~ntle reflux condenser, thermometer, nitrogen inlet, and stirrer:
WO 94/11122 2 1.4 7 8 3 0PCI/US93/10791 Portion 1 Parts by Weight Xylol (135-145C) 363.2 Aromatic 100 363.2 Portion 2 Styrene 530.9 Gamma-Methacrylo~y~ro~yl trimethoxy silane 1380.3 Methyl methacrylate 318.5 Butyl methacrylate 79.6 0 2-Ethylhexyl acrylate 79.6 Glycidyl methacrylate 265.4 Aromatic 100 40.9 Xylol 40.9 Portion 3 t-Butyl peroxyacetate 132.7 Aromatic 100 99.6 Xylol 99.7 TOTAL 3794.5 Portion 1 was charged into the polymerization vessel and heated under nitrogen to 149C. Portion 2 was then added over 360 mimltes and Portion 3 was added over 420 min~ltes to the vessel. The reslll~in~ polymer solution had the following characteristics:
2 5 Gallon wt.(lbs/gal) 8.56 % wt. solids 72.2 ~o volume solids 68.6 Mv~ of polymer 5000 Mn Of polymer 1650 The polymer composition was, by weight, 20 percent styrene, 52 percent g~"""~-methacrylo~lplo~yl trimethoxy silane (A-174 from Union Carbide), 12 percent methyl methacrylate, 3 percent butyl methacrylate, 3 percent 2-ethylhexyl acrylae, and 10 percent glycidyl 3 5 methacrylate, which may be represented as follows: S~Y/A-174/MMA/BMA/2-EHA/GMA in the ratio of 20 / 52 / 12 / 3 / 3 / 10.
W O 94/11122 2 ~ 4 7 g 3 ~ PC~r/US93/10791 This example illustrates, as an optional component for a composition according to the present invention, a polyester urethane solution which may be prepared by charging the following con~tih1ents in order into a reaction vessel equipped with a stirrer, a he~tin~ source and a reflux condenser:
Parts by Portion 1 Wei~ht o 1,3-butylene glycol 173.4 1,6-hexanediol 163.1 Trimethylol propane 78.8 Adipic acid 403.7 Toluene 20.0 Portion 2 Propylene glycol monomethyl ether acetate294.4 Port;on ~
Tone'19 FCP 310 (caprolactone polyol 934.9 from Union Carbide) 2 o Propylene glycol monomethyl ether acetate185.3 Hydrocarbon solvent 706.1 Portion 4 trimethylh~-Y~methylene diisocyanate 290.3 dibutyl tin dilaurate 0.5 2 5 Portion 5 Hydrocarbon solvent 69.8 Total 3320.3 Portion 1 is charged in order into the reation vessel, and the 3 0 co~ ents of Portion 1 are heated to distill water at 140-230C. The distillation is contin~le-l until the acid number is 6.5 to 8.5. The product is thinned and cooled to 98 to 102C by charging Portion 2 into the vessel.
While the constituents in the vessel are m~int~ined at the above temperature, Portion 3 was charged to the reactor in order. Portion 4 is added to the composition at a unirollll rate over a 30 minute period while WO 94/11122 2 1 4 7 8 3 0 PCr/US93/10791 the batch temperature is m~int~ined at 98-102C. A sample is removed and tested for unreacted isocyanate NCO by infrared analysis. The composition is held at the above temperature until there is no unreacted isocyanate in the composition. Portion 5 then is added as a rinse and the resulting composition was allowed to cool to ambient temperatures.
Following this procedure, the resulting composition had a polymer weight solids content of about 61.0%. The polyester urethane had a Gardner-Holdt viscosity of L The Mn (number average molecular weight) was 3734.0 and the Mw (weight average molecular weight) was o 7818.0 (by gel permeation chromatography using polystyrene as the st~nrl~rd). The acid content was determined to be 4.9 Meq/g. The lydlo~y number was 92.
This example illustrates, as another optional component for use in the present composition, an acid polymer, more specifically a methacrylic acid resin,which may be prepared by charging the following col~Liluents into a reactor equipped with a thermometer, stirrer, dr~ g funnel, and con~le-n~or:
2 o Parts by Portion 1 We;~ht Propylene glycol monomethyl ether acetate155.3 (hereafter PM acetate) Xylene 103.5 2 5 Portion 2 Butyl methacrylate 174.8 Methacrylic acid 97.1 Butyl acrylate 140.8 Styrene 72.8 3 o Portion 3 Tertiary butyl peroxy acetate 35.0 PM acetate 41.7 Xylene 27.8 Total 849.0 WO 94~lll22 ~ 8 3 ~ Pcr/us93/lo7 Portion 1 was charged into the reactor and heated to reflux (a~ploxi",~tely 140C). Portion 2 was premixed and added to the reactor dropwise over a 240 minute period. Portion 3 was pren~ixed and added to t_e reactor over a 270 minute period concurrent with Portion 3. After the addition was complete, the reactor was held at reflux and filled out.
The resnltin~ acid polymer composition had a composition of 15% styrene, 36% butyl methacrylate, 29% n-butyl acrylate, and 20%
methacrylic acid. The solids conten~ was 60% and the polymer had a Gardner-Holdt viscosity of Z1. The polymer had a weight average molecular weight of 5000.
This example illustrates a waterborne refinish clearcoat composition accordillg to the present invention, using a methyl half ester of maleic anhydride and an epoxy cros~linker. The following components were thoroughly blended:
Parts by Part 1 Wei~ht 2 o Methyl half ester of maleic anhydride acrylic polymer (as prepared above) 35.39 Deioni7ed water 48.91 Triethyl amine 4.19 DCE 358 (Sorbitol epoxy from Dixie Co.) 8.9 DABCO (25% triethylene ~ mine in butanol) 2.61 When the composition was thinned with water and cast as a film on glass, the film cures at ambient temperature. The coating was virtually tack free in al,proxi",~tely S hours. After 24 hours. the solvent 3 o resi~t~nce (to MEK) was measured to 17 double rubs. After 5 days the solvent resict~nce (to MEK) was measured to 100+ double rubs.
This composition can be fortified with TINUVIN 1130 and TINUVIN 292 (or TINUVIN 123) light stabilizers to give durable films, the level of the former at 2-3% on binder and the level of the latter at 1-2% on binder.
WO 94/11122 2 ~ 47 ~ 3 0 Pcr/US93/10791 This example illustrates a waterborne clearcoat composition based on latex and a maleic anhydride half ester copolymer. The following components were thoroughly blended:
Parts by Part 1 Wei,~ht Methyl half ester of maleic anhydride acrylic polymer (as prepared above but88.0 34% solids in water/butyl proprionate, neutralized with triethylamine) Deionized water , 77.0 Diethylene glycol monobutyl ether 4.4 Propylene glycol monomethyl ether 4.4 IINUVIN 1130 UV stabilizer 2.1 (benzotriazole adduct from Ciba-Geigy) TINUVIN 292 free radical stabilizer 1.4 (hindered amine from Ciba-Geigy) DEHYDRAN 1620 defoamer (from Henkel) 0.1 ~lTON GR-7M wetting agent 0.2 (from Union Carbide) NEOCRYL A6015 acrylic emulsion latex (45% solids in water from ICI) 66.6 triethylene ~ mine catalyst (25% in water) 4 3 DCE-358 aliphatic epoxy cros~linker (sorbitol polyglycidol ether from Dixie Chem. Co.) 10.0 3 o TOTAL 258.5 The reslllting coating composition had a solids content of 29% and its c~lc~ ed VOC is 2.3 lb/gal. The above clear coating composition was drawn over glass plates and allowed to cure for seven days 3 5 at ambient temperature. The reslllting clearcoat had good clarity and gloss, WO94~1l122 21~783~ pcr/us93/1o79l and exhibite a Persoz hardness of 193 and an MEK solvent resistance of 59 double rubs.
This example illustrates four different compositions (A
through D) based on an anhydride half ester and an epoxy, with and without an ~ rly polyurethane. With respect to each of the composi~ioll~ A through D, respectively, the following components were thoroughly blended:
A B C D
(Parts by (Parts by (Parts by (Parts by ~NGREDIENT we;pht) weight) wei~ht) we;~ht) Maleate half ester 68.73 66.61 18.67 17.45 Deionized H20 94.97 92.04 25.79 24.11 Triethylarnine 8.13 7.88 2.21 2.06 Urethane dispersion 1 2 o (NEOREZ~ XR9679) 0.00 0.00 138.09 0.00 Urethane dispersion 2 (NEOREZ'19 XR9699) 0.00 0.00 0.00 129.06 Butyl carbitol 0.00 0.00 0.00 14.20 TINUVIN~ 1130 1.97 2.15 2.22 2.13 TINUVIN~292 1.31 1.44 1.48 1.42 DEHYDRAN surfactant 0.10 0.10 0.10 0.10 DOWANOL PM surfactant 2.22 0.02 2.96 3.60 TRlTON'i9 surfactant 0.20 0.20 0.20 0.20 Diethlyene triamine catalyst 3 o (25~o) in H20 5.08 4.93 1.38 1.29 Epoxy (XUGY 358) 17.28 14.78 4.14 4.39 Epoxy (ARALDlTE CY184) 0.00 9.85 2.76 0.00 3 5 TOTAL 200.00 200.00 200.00 2.00 WO 94/11122 2 1 ~1 7 ~ 3 0 PCI/US93/10791 Part 1 was premixed in order slowly and Part 2 was added with mixin~. The final compositions A through D exhibited the following properties.
TheoreticalSolids 32.75 35.89 36.98 35/52 TheoreticalVOC 2.90 2.60 :2.40 2.40 Viscosity Zahn #2 71(3) 65(4) 65(4) Very High Viscosity ICI Cone and Plate¢250 CPS175 CPS 155 CPS 225 CPS
Persoz Hardness 1 Day Glass 120 60 Chroma Base* 76 57 Persoz Hardness 3 Day Glass 125 59 107 134 Chroma Base 76 54 53 64 Persoz Hardness 7 Day Glass 265 198 232 202 Chroma Base 114 91 103 118 MEK Re.ci~t~nce (Double Rubs) Glass 100+ 100 100+ 100+
Chroma Base 50 37 100+ 30 Tukon Hardness 33 Days 6.30 2.98 2.71 1.60 Hardness Viscosity Overnight Gelled Gelled Gelled Fluid *Chroma Base is a registered trademark for a solventborne basecoat commercially available from Du Pont Co.
Based on the above results, it is evident that the addition of an ~nxili~ry polyurethane provides greater strength and hardness. However, 3 5 with polyesterurethane, using the less reactive epoxy (ether epoxy) in Wo 94J11122 2 1 4 7 ~ 3 0 pcr/us93/1o79l composition C resulted in better properties than using the more reactive epoxy in composition D.
This example illustrates a clearcoat composition according to the present invention, using a methyl half ester of maleic anhydride and an epoxy cro.c.clinker. The following components were thoroughly blended:
Parts by Part 1 Weight lo Methyl half ester of maleic anhydride acrylic polymer (as prepared above) 27.0 Deionized water 59.8 Triethyl amine 2.7 XU-71950 (Diglycidyl ester from Dow) 6.4 TINUVIN 1130 (UV screener3 O.S
Catalyst solution 2.2 TINUVIN-123 (25%) in butyl cellosolve 1.4 In the above list, the catalyst solution refers to a solution of benzyl triphenyl phosphonium chloride (10%) in isopropanol. The TINUVIN-123 is a hindered amine; both TINUVINs are commercially available from Ciba-Geigy.
The coating composition was sprayed onto primed metal panels coated with a waterborne basecoat and cured at 265F. The coating exhibited excellent hllmitlity resistance, chemical resistance, durability and other film properties.
This example illustrates another clearcoat composition accoldhlg to the present invention, using a methyl half ester of maleic anhydride and an epoxy crosslinker, but also with a silane component. The following components were thoroughly blended:
Parts by Part 1 Wei~ht Methyl half ester of maleic anhydride WO 94/11122 21:4 7 8 3 0 pcr/us93/lo791 acrylic polymer (as prepared above) 17.79 Deionized water 68.02 Triethyl amine 1.94 XU-71950 (Diglycidyl ester from Dow) 4.22 Epoxy silane polymer (as prepared above)3.95 TINUVIN 1130 (UV screener) 0.4 TINUVIN 123 (25% in butyl cellosolve) 1.05 Catalyst solution 1.71 Butyl cellosolve 0.92 In the above list, the catalyst solution refers to a solution of benzyl triphenyl phosphonium chloride (10%) in isopropanol. The TINUVIN 123 is a hindered amine commercially available from Ciba-Geigy.
This clear is adjusted to spray at 32 sec in a #2 Zahn cup with deionized water. The pH equals 9.2. The clear is sprayed over a waterborne basecoat and cured at 265-285F for 30 minntes The reslllting films were hard, glossy, and recict~nt to solvent and hnmi(lity. These films 2 o are durable and enviromnentally resict~nt Various modifications, alterations, additions, or substitutions of the components of the composition of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this 2 5 invention. This invention is not limited to the illustrative embodiments set forth herein, but rather the invention is defined by the following claims.
WATER-BORNE COMPOSITIONS
COMPRISING HALF E~STERS OF ANHYDRIDE
POLYMERS CROSSLINKED BY EPOXIES
FIELD OF THE INVENTION
This invention is related to a multi-component water-borne coating composition co~ -ising a half-ester of an an_ydride polymer and an epoxy crocclinkin~ agent.
BACKGROUND
There are a wide variety of multi-component coating compositions available for finiching automobiles and trucks. Various co~ting compositions comprising anhydride or epoxy con~ining compositions are knowvn. For example, U.S. Patent 4,906,677 discloses a composition colll~lisillg an acrylic anhydride polymer, a glycidyl component, and a phosphonillm catalyst. U.S. Patent 3,136,736 and British patent 994,881 disclose coating compositions COlll~liSillg polyepoxides and maleic anhydride copolymers. U.S. Patent 4,732,791 concerns a coating 2 0 composition comprising a polyepoxide, a monomeric anhydride curing agent, and a hyd~o~yl cont~ining polyfunctional polymer.
U.S. patent no. 4,906,677, in column 4, lines 40-47, licclQses that anhydride polymers, in epoxy-anhydride compositions, may be COllvt;l ~ed to a half-ester by alcohol solvents.
2 5 European Patent Application, publication no. 0 353 734 A2, published 07.02.90 and European Patent Application, publication no. 0 450 963 A1, published 09.10.91 both ~ ose the combination of a polymer having a half-esterified acid anhydride group and a compound having an epoxy group and a hydroxy group, or a separate epoxy and hydro~y 3 o compound. These patents teach that, in such compositions, high temperature curing is required in order that the half-esteriffed acid anhydride groups are ring-closed to produce acid anhydride groups which then react with hydl o~yl groups, which in turn release carboxyl groups which then react with the epoxy groups. These patents indicate that a 3 5 certain hydroxy equivalent number or hydroxy value is necessary for adequate water resistance of the coating composition.
W O 94J11122 ~ 1 47 ~3 ~ PC~r/US93/10791 .
The afore-men~io~e-l EP 0 353 734 A2 states that water can be used as a "diluent" if the carboxyl groups are neutralized with an amine.
In contrast, the present invention is directed to compositions in which r water is employed as the primary carrier, organic solvents being possible diluents. The afore-mentioned EP 0 450 963 A1 states that the half esterified polymer may be neutralized with amines to make a hydrophilic polymer which can form an aqueous composition. The examples, however, all tlicclose compositions which employ organic solvents.
A problem with present co~tinE compositions for lo automobiles and trucks, or parts thereof, is that durability is not as good as desired. An important aspect of durability is environmental resict~nçe. The present invention offers a high quality finish exhibiting superior e,lvho~".,en~l resistance at lower cost. This is particularly notewolLlly given the fact that the present composition is a waterborne finish.
The present composition is a multi-package system, having use in automotive finishes for new automobiles and for r~finish, for use in maintenance, and for use in both high temperature and low temperature cured systems. Such a coating composition exhibits excellent clarity, appearance and environmental r~ict~n~e Importantly, such compositions z o offer a low voC (volatile organic content) since the binder is waterborne employing an aqueous (primarily water) carrier.
SUMMARY OF THE INVENTION
The present invention is directed to a co~ting composition 2 5 co~ g 20-80% by weight of binder components and 80-20~o by weight of an aqueous carrier which is primarily water. The binder contains (a) a half-ester of an anhydride polymer having at least two anhydride groups and having a weight average molecular weight of about 2,000-100,000;
3 o (b) an epoxy component having at least two reactive glycidyl glOU~S; and (c) a basic compound to neutralize the half ester.
Optionally, these compositions may also include epoxy-silane polymers, silane polymers, acid polymers, lower molecular weight polyester 35 or polyester urethanes, melamine resins, hydroxyl polymers, acrylic latices, waterborne urethane emulsions or dispersions, and combinations thereof.
WO 94/11122 21~ 7 ~ 3 0 PCr/USs3/10791 In one embodiment, the water content of the aqueous carrier is greater than 60 percent by weight of the aqueous carrier.
- The present invention is also directed to a process in which applicant's composition is applied to a substrate as an automotive topcoatl.
DETAILED DESCRIPIION OF THE INVENT~ON
The composition of the present invention forms a durable ellviro~ ental resi~t~nt coating. The composition is especially useful for m~intenence coating of architect~lral structures and for finishing the exterior of ~lltomobiles and trucks.
The composition can also be pigmented to form a colored finish, although the composition is particularly useful as a clearcoat.
Preferably, the co~ting composition has a high solids content and contains about 20-80~o by weight binder and 20-80% by weight aqueous carrier. The binder of the composition contains about 25-90~o, preferably 35 to 65% (by weight of binder) of the half-ester of an anhydride polymer cont~ining at least two anhydride groups; 5-50%, ~refe,ably 15 to 30~o (by weight of binder) of a glycidyl or epoAy cont~ining component.
Optionally, the composition may comprise 5-50~o, preferably 2 0 10 to 25% by weight of binder of an acrylic or a polyester or polyester urethane which may contain hydroAyl and/or acid functionality. If hydluAy functional, the hydl oAy number is 20 to 120. If acid functional, the acid number is 20 to 120.
In the present composition, when used in a baking system, if 2 5 an optional acrylic or polyester or polyester urethane polymer is acidfunctional, then the cure occurs between the acid groups and the epoAy groups and the half ester groups,following ring-closure during baking, and the epoAy group. Some cure may also occur between the acid of the half ester and the epoAy. The main cure, however, is based on the ring closure 3 o during baking.
The anhydride polymer employed in preparing the present composition has a weight average molecular weight of about 2000-100,000, determined by gel permeation chromatography using polymethyl methacrylate as a standard. Preferably the anhydride polymer has a weight 3 5 average molecular weight of 3,000-50,000.
WO94/11122 2~ ~ 830 PCr/USs3/10791 The anhydride polymer may be prepared by conventional techniques in which the monomers, solvent, and conventional catalysts such as t-butyl perbenzoate are charged into a polymerization vessel and heated to about 75-200C for about 0.5-6 hours to form the polymer.
The anhydride acrylic polymer is preferably an acrylic copolymer formed by polymerizing a mixture of monomers comprisiong alkyl methacrylates and/or alkyl acrylates, where the alkyl groups have 1-12 (preferably 1-8) carbon atoms, and ethylenically ~ms~ rated anhydrides (or ethylenically unsaturated dicarboxylic acids which are con~el led to the acid anhydride during the polymerization). Optionally, the anhydride acrylic polymer can cont~in other components such as styrene, methyl styrene, acrylonitrile, and/or methacrylonitrile in amounts of about 0.1-50% by weight.
Typical alkyl acrylates and methacrylates that can be used to form the anhydride acrylic polymer are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, and the like, or 2 0 any others ment;oned below. Other components that can be used to form the anhydride acrylic polymer are acrylamide, methacryl~mide and acrylo alkoxy silanes such as g~mm~- methacryloxyl propyl trimethoxy silane.
Also, the anhydride acrylic polymer can contain about 0.1-5% by weight of an ethylenically lm~ lrated acid such as acrylic acid, methacrylic acid, 2 5 itaconic acid, maleic acid, and the like.
Typically useful ethylenically lm~ rated anhydrides are itaconic anhydride, maleic anhydride, isobutenyl s~lc~inic anhydride, and the like. As stated above, it is also possible to impart the anhydride functionality to the anhydride acrylic polymer by using an ethylenically 3 0 lln~ rated dicarboxylic acid which conver.s to the acid anhydride during the reaction. Suitable ethylenically lm~ lrated dicarboxylic acids that can be used are itaconic acid, maleic acid, isobutenyl succinic acid, and the like.
A preferred anhydride acrylic polymer comprises styrene, butyl methacrylate, butyl acrylate, and itaconic anhydride. Another 3 5 preferred polymer co~ lises methyl methacrylate, butyl acrylate, and WO 94/11122 2 1 ~ 7 ~ ~ ~ PCI/US93/10791 itaconic anhydride. Another preferred polymer comprises styrene, isobornyl methacrylate, butyl acrylate, and maleic anhydride.
The anhydride polymer is half-esterified with an alcohol.
Suitable alcohols inrlllde methanol, ethanol, propanol, butanol;
ethyleneglycol monoalkyl ether, dialkylaminoethanol, in which particularly c~mmon alkyl groups are methyl and ethyl; acetol, allyl alcohol, propargyl alcohol, tetrahydrofurfuryl alcohol; and the like. The reaction to produce the half-ester is generally at ambient or elevated temperatures, suitably in the range of 20 to 150C. Such a reaction may be conducted in the o presence of a catalyst, for example, tertiary amines such as triethyl~mine, quaternary ~mmonillm salts such as benzyltrimethyl ammonium chloride, and the like.
For utility in the aqueous carrier, the anhydride polymer, after it is converted to the half-ester, is neutralized with a base. Suitable bases inchl~le amines which are volatile under the conditions of cure.
Typical amines are triethyl amine, trimethyl amine, ~mmor~ and dimethyl eth~nol~mine. Other bases inrl~lde sodium hydroxide, pot~csillm hydroxide and the like. The base is suitably used in the amount of 0.1 to 10 percent by weight of binder to solublilize or disperse the half ester in the aqueous 2 o carrier.
The epoxy component preferably C~lt~ at least two glycidyl groups and can be an oligomer or a polymer. Typical glycidyl co",l~onents are sorbitol polyglycidyl ether, m~nnitol polyglycidyl ether, pentaelylhlilol polyglycidol ether, glycerol polyglycidyl ether, low 2 5 molecular weight epoxy resins such as epoxy resins of epichlorohydrin and bisphenol A, di- and polyglycidyl esters of acids, polyglycidyl ethers of iso-;y~nulates, such as Denecol EX301'19 from Nagase. Sorbitol polyglycidyl ethers, such as DCE-358~ from Dixie Chem. Co., and di- and polyglycidyl esters of acids, such as Araldite CY-184'l9 from Ciba-Geigy or XUS-71950~9 3 o from Dow Chemical form high quality finiches. Cycloaliphatic epoxies such as CY-179~ from Ciba-Geigy may also be used. For ambient cure refinish applications, generally the choice of epoxy is chosen for room temperature reactivity and the extent of cure with the half ester. (Ambient curing means that the composition cures at 10 to 90C, preferably 15 to 60C
3 5 within a couple of weeks, preferably one week.) W094/t~ 0 PCr/us93/l079l Glycidyl methacrylate or acrylate cont~ining acrylic polymers can be used, such as random and block polymers of glycidyl methacrylate/butyl methacrylate. The block polymers can be prepared by anionic polymerization or by group transfer polymerization. Optionally, the composition may further comprise a copolymer having both epoxy and alkoxy silane groups, prepared as the re~ction product of epoxy monomers such as glycidyl methacrylate and silane monomers as described below.
Optionally the present composition may co~ lise a silane polymer as a separate additional ingredient or component. Such silane polymers may suitably have a weight average molecular weight of about 100~30,000, a number average molecular weight of about 500 10,000. (All molecular weights disclosed herein are determined by gel permeation chromatography using a polystyrene standard.) As indicated above, the binder of the present composition may comprises from about 5 to 50%, preferably 10 to 25%, based on the weight of the binder, of an acrylic or polyester or polyester urethane or copolymer thereof having a ll~dlo~ number of about 20 to 120, preferably 70 to 100, or an acid number of about 20 to 120, preferably 75 to 95. This polymer has a weight average molecular weight of about 2,000 to 20,000, plcfelably 4,000-10,000. Unless otherwise indicated, all molecular weights mentioned herein are measured using gel permeation chrom~tography using polymethyl methacrylate as a standard.
Polyester urethanes are a reaction product of a llydro~yl le. "~ te~ polyester component and a polyisocyanate component, preferably, an aliphatic or cycloaliphatic diisocyanate. The polyester, which may be used alone or as a component of the polyester urethane, may be suitably prepared from linear or branched chain diols, in~ lin~ ether glycols, or ll~ixlures thereof or ~ ufes of diols and triols, cont~ining up to and in~lntling 8 carbon atorns, or mixtures of such diols, triols, and 3 o polycaprolactone~polyols, in combination with a dicarboxylic acid, or anhydride thereof, or a ll~i~lllre of dicarboxylic acids or anhydrides, which acids or anhydrides cont~in up to and inch-~ling 12 carbon atoms, wherein at least 7S~ by weight, based on the weight of dicarboxylic acid, is an aliphatic dicarboxylic acid.
3 5 Representative saturated and -n~t--rated polyols that can be reacted to form a polyester include alkylene glycols such as neopentyl glycol, ethylene glycol, propylene glycol, butane diol, pentane diol, 1,6-hexane diol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 1,4-cyclohexane dimethanol, 2,2-dimethyl 1,3-propanediol, 2,2-bis(hydroxymethyl)propionic acid, and 3-mercapto-1,2-propane diol. Preferred are 1,6-h.oY~n~-liol and butylene glycol.
Polyhydric alcohols, having at least three hydroxyl groups, may also be inclllcled to introduce br~n~hing in the polyester. Typical polyhydric alcohols are trimethylol propane, trimethylol ethane, pentaelyLh~ilol~ glycerin and the like. Trimethylol propane is preferred, in forming a branched polyester.
Polycaprolacone polyols may be also be used in m~king the polyester. A preferred polycaprolactone, a triol, is Tone~9 FCP 310 (available from Union Carbide).
The carboxylic acids used in m~king the polyester component of the polyester urethane include the saturated and nn~tllrated polycarboxylic acids and the derivatives thereof. Aliphatic dicarboxylic acids that can be used to form the polyester are as follows: adipic acid, sebacic acid, snccinic acid, azelaic acid, dodecanedioic acid, 1,3 or 1,4-cyrloh~Y~ne dicarboxylic acid and the like. A preferred acid is adipic acid.
2 o Aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, and the like. Anhydrides may also be used, for example, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like.
Typical polyisocyanates that may be used to form the polyester ulelha-le are as follows: isophorone diisocyanate which is 2s 3-isocyanatemethyl-3,5,5-trimethyl- cyclohexyl-isocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, butylene-1,3-diisocyanate, hexamethylene diisocyanate, methyl-2,6-diisocyanate, methyl-2,6-diisocyanate caproate, octamethlyene diisocyanate, 2,4,4-trimethylheY~methylene diisocyanate, nonamethylene 3 o diisocyante, 2,2,4-trimethylh~oY~methylene diisocyanate, decamethylene diisocyanate, 2,11-diisocyano-dodecane and the like, meta-phenylene diisocyanate, para-phenylene diisoxyanate, toluene-2, 4-diisocyanate, toluene-2,6-diisocyanate, xylene-2, 4-diisocyanate, xylene-2,6-diisocyanate, dialkyl benzene diisocyanates, such as methyl~ro~ylbenzene diisocyanate, 3s methylethylbenzene diisocyanate, and the like: 2,2'-biphenylene diisocyanate, 3,3'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, W O 94~11122 2 1 4 7 8 3 0 PC~r/US93/10791 ~
~ .
..
3,3'-dimethyl~,4'-biphenylene diisocyanate, and the like;
methylene-bis(4-phenyl isocyanate), ethylene-bis(4-phenyl isocyanate), isopropylidene-bis(4-phenyl isocyanate), butylene-bis(4-phenylisocyanate), and the like; 2,2'-oxydiphenyl diisocyanate, 3,3'-oxydiphenyl diisocyanate, 4,4'-oxydiphenyl diisocyanate, 2,2'-ketodiphenyl diisocyanate, 3,3'-ketodiphenyl diisocyanate, 4,4'-ketodiphenyl diisocyanate, 2,2'-thiodiphenyl diisocyanate, 3,3'-thiodiphenyl diisocyanate, 4,4'-thiodiphenyl diisocyanate, and the like; 2,2'-sulfonediphenyl diisocyanate, 3,3'-sulfonediphenyl diisocyanate, 4,4'-sulfonediphenyl lo diisocyanate, and the like; 2,2,-methylene-bis(cyclohexyl isocyanate), 3,3'-methylene-bis(cyclohexyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), 4,4'-ethylene-bis(cyclohexyl isocyanate), 4,4'-propylene-bis-(cyclohexyl isocyanate), bis(paraisocyano-cyclohexyl)sulfide, bis(para-isocyano-cyclohe~yl)sulfone, bis(para-isocyano-cyclohexyl)ether, bis(para-isocyano-cyclohexyl)diethyl silane, bis(para-isocyano-cyclohexyl)diphenyl silane, bis(para-isocyano-cyclohexyl)ethyl phosphine oxide, bis(para-isocyano-cyclohexyl)phenyl phosphine oxide, bis(para-isocyano-cyclohexyl)N-phenyl amine, 2 0 bis(para-isocyano-cyclohexyl)N-methyl amine, 3,3 '-dimethyl-4,4 '-diisocyano biphenyl, 3,3'-dimethoxy-biphenylene diisocyanate, 2,4-bis(b-isocyano-t-butyl)toluene, bis(para-b-isocyano-t-butyl-phenyl)ether, para-bis(2-methyl4-isocyanophenyl)benzene, 3,3-diisocyano ~m~ns~ne, 3,3-diisocyano bi~ m~nt~ne, 3,3-diisocyanoethyl-1'-bi~ m~nt~ne, 1,2-bis(3-isocyano-propoxy)ethane, 2,2-dimethyl propylene diisocyanate, 3-methoxy-he~methylene diisocyanate 2,5-dimethyl heptamethylene diisocyanate, 5-methyl-nonamethylene diisocyanate, 1,4-diisocyano-cyclohtoY~ne, 1,2-diisocyano-octadecane, 2,5-diisocyano-1,3,4-l~Y~ 7Qle, OCN(CH2)30(CH2)20(CH2)3NCO, OCN(CH2)3NCO or the following:
OCN(CH2)3 IN(CH2)3NC
WO 94/11122 2 1 ~ 7 8 3 0 PCI/US93/10791 Aliphatic diisocyanates are preferred, forming urethanes that have excellent weatherability. One aliphatic diisocyanate that is particularly preferred is trimethyl hexamethylene diisocyanate.
A preferred polyester urethane is the re~ction product of trimethylhexamethylene diisocyanate and a hydroxy termin~te~l polyester of 1,3-butylene glycol, 1,6-hexanediol, adipic acid, trimethylolpropalle, and Tone'19 FCP 310.
It is noted that a hydro~y functional polyester urethane can be collvel led to the corresponding acid functional polyester urethane by 0 reaction with methylhexahydropthalic anhydride or other mono-anhydride such as succinic anhydride. Converting the hydroxy to the acid may result in longer pot life in the clearcoat.
A polyester may be prepared by conventional techniques in which the component polyols and carboxylic acids and solvent are esterified at about 110C-250C for about 1-10 hours to form a polyester. To form a polyester urethane, a diisocyanate may then be added and reacted at about 100C for about 15 mimltes to 2 hours.
In preparing the polyester urethane, a catalyst is typically used. Collvelllional catalysts inrl~lcle benzyl trimethyl ammonium 2 o hydro~ide, tetramethyl ~mmQnillm chloride, organic tin compounds, such as dibutyl tin diaurate, dibutyl tin oxide stannous octoate and the like, i.",. complexes and litharge. About 0.1-5% by weight of catalyst, based on the total weight of the re~ct~ntc, is typically used.
The stoichiometry of the polyester preparation is controlled 2 5 by the final hydroxyl number and by the need to obtain a product of low acid number; an acid number below 10 is preferable. The acid number is defined as the number of milligrams of pot~ccinm hydroxide needed to neutralize a one gram sample of the polyester. Additional inform~tion on the preparation of polyester urethanes is disclosed in commonly ~ccigned 3 o U.S. Patent No. 4,810,759, hereby incorporated by reference.
Another optional component are acrylic latices such as Neocryl~ available from ICI. Other latices are available from ICI and Rohm & Haas. Another optional component are urethane dispersions or emulsions such as Neorez~ 9699 and the like from ICI or Spensol L,52 from Reichold. Other suppliers are Witco, American Cy~n~mitl, and wO 94/11122 2 ~ 47 83 ~ pcr/uss3t1o79l Sanncor. Such dispersions include polyethers, polyesters, polycarbonates, or combinations thereof.
An acid resin is optionally added to the coating composition The acid functional material can be formed by polymerizing monomers of alkyl methacrylates, or alkyl acrylates or mixtures thereof, where the alkyl groups have 1-12 carbon atoms and ethylenically lln~hlrated acids.
Optionally, the acid functional polymer can also contain other components such as styrene, methyl styrene, and/or acrylonitrile, methacrylonitrile in arnounts of about 0.1-50% by weight.
Typical alkyl acrylates, methacrylates, and other components that can be used to form the acid functional polymer are the same as those listed above with respect to the anhydride polymer Typically useful ethylenically lln~t~lrated acids are acrylic acid, methacrylic acid, itaconic acid, maleic acid, and the like.
This acid resin may also contain hydro~yl functionali~r by using monomers such as hydro~yethylacrylate, hydroxyethyl methacrylate and llydrol~yl~lo~l acIylate~ The hydroxy functionality may be introduced by a post reaction of the acid with epoxy co~ g co~ mds such as Cardura EZ9 from Shell Chemical Company (a glycidyl ester of versatic 2 o acid) and propylene oxide.
Another optional component of the present composition is the half ester of an anhydride compound, as distin~ hed from a polymer, for example the reaction product of an acid anhydride such as hexahydlop~halic anhydride or a sllcrinic anhydride, which may be substihlte~l, for example with a Cl-Cg alkyl group, with a monofimction~l or polyfunctional alcoholic solvent such as methanol or ethylene glycol. A
prefel~ed half ester is the reaction product of methylhexahydrophthalic anhydride and an alcohol such as ethylene glycol. Other alcoholic solvents are ~,lopallol, isobutanol, isopropanol, tertiary butanol, n-butanol, 3 o propylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like. The half ester is suitably present in the amount of 2 to 25 percent by weight of binder, preferably 4-12 percent.
About 0.1-8~o ~preferably 0.5 to 5~o) by weight, based on the weight of the binder of the coating composition, of a catalyst is added to 3 5 enhance curing of the composition. For refinish (ambient cure systems), typical catalysts are as follows: tertiary amines such as triethylene rli~mine~
WO 94/11122 21 ~ 783~ PCr/US93/10791 .
quinuclirline, dialkyl alkanol amines such as dimethyl ethanol~mine diethyl ethanol amine, dibutyl ethanol amine, diethyl hexanol amine, triethylamine bisdimethylaminoethyl ether (available from Union Carbide), diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, and the like, lithinm tertiary butoxide, tri(dimethylaminometnyl)phenol, bis(dimethylamino)propan-2-ol, N,N,N ,N -tetramethylethylene~ mine, N-methyldiethanol~mine N,N-dimethyl-1,3-propane~ mineand 1-dimethylamino-2-propanol. Tertiary amines and bicyclic tertiary amines are preferred catalysts. For baking systems, typical catalysts are as follows:
0 triethylene ~ mine, quinuclidine, dialkyl alkanol amines such as dimethyl ethanol~mine, diethyl ethanol amine, dibutyl ethanol amine, diethyl hexanol amine and the like, lithium tertiary butoxide, tri(dimethyl-~minomethyl)phenol, bis(dimethylamino)propan-2-ol, N,N,Nl,Nl-tetramethylethylene~ mine, N-methyldiethanol~mine, 15 N,N-dimethyl-1,3-prop~nedi~mine and 1-dimethylamino-2-propanol or quaternary ~mmonillm salts such as tert-butyl ammonium bromide, benzyl trimethyl ~mmonillm formate and the like. Preferred catalyst, howt;ver, are phosphonium compounds such as are disclosed in U.S. Patent No.
4,906,677, hereby incorporated by reference in its entirety.
2 o Typical solvents used to prepare the anhydride acrylic polymer or used as a diluent for the coating composition inclll~le toluene, xylene, butyl ~cet~te~ butyl proprionate, ethyl benzene, higher boiling aromatic hydrocarbons, amyl acetate, ethyl acetate, propyl acetate, ethylene or propylene glycol mono alkyl ether acetates.
2 5 The solvent for the final composition, as sold or applied, comprises primarily water. Suitably at least 60 percent of the liquid carrier, preferably 70 percent is water. Preferably deionized water is employed.
Optional diluents for the water inclnde butyl acetate, butyl proprionate, mono- and di- ethers of proplyene glycol, and butyl cellosolve.
3 o Generally, the present composition is applied as a co~ting to a substrate by conve~llional techniques such as spraying. The composition may be applied as a multi-package system. Multi-package means that at least some of the components are kept separate until shortly before their application. For instance, the glycidyl component must be kept seperate 3 5 from the half ester and optional acid components. For refinish systems, the reslllting coating can be dried and cured at elevated temperatures of 5 to WO 94/11122 . PCI/US93/10791 21~7~3~
90C, preferably 15 to 60C. Coatings are applied to form a finish typically about 0.5-5 mlls thick, and preferably 1-2 mils thick. For OEM (orgiginal equipement m~nllf~ctllre) automotive applications, the co~ting can be dried and cured at elevated temperatures of 100 to 200C.
To i~ rove weatherability of the clear finish of the coating composition, about 0.1-5%, by weight, based on the weight of the binder, of an ultraviolet light stabilizer or a comhin~tion of ultraviolet light stabilizers can be added. These stabilizers inclllcle ultraviolet light absorbers, screeners, quenchers and speci~lc hindered amine light stabilizers. Also, 0 about 0.1-5~o by weight, based on the weight of the binder, of an antioxi~l~nt can be added.
Typical ultraviolet light stabilizers that are useful are listed in U.S. patent no. 4,906,677, previously incorporated by reference.
Particularly useful ultraviolet light stabilizers that can be used are hindered aII~ines of piperidyl derivatives such as those .licl~los~d in Murayama et al., U.S. Patent 4,061,616, issued December 6, 1977, colurnn 2, line 65, through colum~ 4, line 2, and nickel compounds such as [l-phenyl-3-methyl4-decanoylpyr~Ql~te(S)]-Ni, bis[phenyldithiocarbamato]-Ni(II), and others listed in the above patent, 2 o col~lmn 8, line 44 through line 55.
An applicable blend of ultraviolet light stabilizers comprises 2-[2'-hydroxy-3',5'-1(1-1-dimethyl-propyl)phenyl]benzotrizole and bis-[4-(1,2,2,6,6-pen~mell,ylpil)eridyl)] 2-butyl-2-[(3,5-~-butyl-4-hydroxy-phenyl)methyl] propanedioate. Although the stabilizers can be employed in any ratio, a 1:1 ratio of benzotriazole to propanedioate is preferred.
The composition can be applied over a pigmented or colored basecoat finish. For refinish compositions, if over a waterborne basecoat, the basecoat is typically first allowed to dry. For original automotive production, the coating composition is applied over a waterborne basecoat 3 o and baked at conventional curing temperatures in the art, typically 265F.
Before applying the topcoat, however, the waterborne basecoat is typically dried using a warm-air flash or bake, without substantially curing the basecoat, in order to remove a substantial amount of the water. l~uring baking, the half-esterified acid anhydride groups are believed to convert 3 5 back to the original acid anhydride ring groups. These groups then react wO 94~11122 2 1 4 7 ~ 3 0 ~ Pcr/US93/10791 with the epoxy groups. A composition with a relatively faster acting epoxy cro~linker may be employ Basecoats suitably comprise collvenLional pigments, optionally metallic flake or the like, which can be made using convelllional techniques in which a mill base cont~ining pigment, dispersant and solvent or carrier is first formed.
The coating composition for refinish applicatons can be applied over both solvent- and water borne basecoats.
The present composition can be pigmented to form a colored lo finish such as a primer, basecoat, monocoat, or maintenence paint. About0.1-200 percent by weight, based on the weight of the binder, of co~lve~l ior~l pigments can be added using conventional techniques in which a mill base con~ining pigment, dispersant and carrier is first formed.
The mill base is then mixed with the composition to form a colored composition.
The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise indicated. The weight average molecular weight of polymers was determined by GPC (gel permeation chromatography) using polyethyl methacrylate as a st~n~i~rd~
unless stated otherwise.
This example illustrates the preparation of a half ester of a maleic anhydride polymer, specifically the half ester of a styrene/isobornyl 2 5 methacrylate/ butyl acrylate/maleic anhydride copolymer. The anhydride polymer was first prepared, as follows. To a reactor, heated to reflux, equipped with a condensor, stirrer, nitrogen purge, feed system, he~ting mantle, were added, as Part I, 1384.86 parts of bulylplopionate. The following Part II was premixed and then fed to the reactor over four hours.
3 o The next following Part III was added to thc reactor over 30 min~ltes~ held for 30 mimltes.
Parts by Part II We;~ht Styrene monomer 1081.92 Isobornyl methacrylate 735.71 Butyl acrylate 1773.05 W O 94~11122 214 7 8 3 0 PC~r/US93/10791 Maleic anhydride 735.71 Butyl propionate 2077.29 Tertiary butyl peroxyacetate 259.66 Parts by Part III Wei~ht Tertiary butyl peroxyacetate 19.04 Butyl proprionate 138.Q0 TOTAL 8205.24 After the 30 minute holding period, a total of 1090 parts by weight of solvent is stripped off, resulting in a yield of 7115.24 parts by weight.
The product polymer had a Gardner-Holdt viscosity of V and a measured solids of 62.84%. ~he actual molecular weight was measured by gel permeation chromatography to be Mn = 23s5 and M W = 6135.
This maleic anhydride polymer was then coverted to a a methyl half ester by mixing the following components;
2 0 Components Parts Maleic anhydride polymer solution (prepared as described above) 600 Methanol 24 2 5 The first component was heated to 50C and the methanol componentadded over a 2~30 minute period. The mixlllre was then heated to 75-85C for five hours or until the anhydride band in the infrared analysis has disappeared (90-95~o gone).
This example illustrates an epoxy silane polymer, more particularly an epoxy functional acrylo~ ne polymer which was prepared by cha~h~g the following constit~lent~ into a polymerization vessel equipped with a heating m~ntle reflux condenser, thermometer, nitrogen inlet, and stirrer:
WO 94/11122 2 1.4 7 8 3 0PCI/US93/10791 Portion 1 Parts by Weight Xylol (135-145C) 363.2 Aromatic 100 363.2 Portion 2 Styrene 530.9 Gamma-Methacrylo~y~ro~yl trimethoxy silane 1380.3 Methyl methacrylate 318.5 Butyl methacrylate 79.6 0 2-Ethylhexyl acrylate 79.6 Glycidyl methacrylate 265.4 Aromatic 100 40.9 Xylol 40.9 Portion 3 t-Butyl peroxyacetate 132.7 Aromatic 100 99.6 Xylol 99.7 TOTAL 3794.5 Portion 1 was charged into the polymerization vessel and heated under nitrogen to 149C. Portion 2 was then added over 360 mimltes and Portion 3 was added over 420 min~ltes to the vessel. The reslll~in~ polymer solution had the following characteristics:
2 5 Gallon wt.(lbs/gal) 8.56 % wt. solids 72.2 ~o volume solids 68.6 Mv~ of polymer 5000 Mn Of polymer 1650 The polymer composition was, by weight, 20 percent styrene, 52 percent g~"""~-methacrylo~lplo~yl trimethoxy silane (A-174 from Union Carbide), 12 percent methyl methacrylate, 3 percent butyl methacrylate, 3 percent 2-ethylhexyl acrylae, and 10 percent glycidyl 3 5 methacrylate, which may be represented as follows: S~Y/A-174/MMA/BMA/2-EHA/GMA in the ratio of 20 / 52 / 12 / 3 / 3 / 10.
W O 94/11122 2 ~ 4 7 g 3 ~ PC~r/US93/10791 This example illustrates, as an optional component for a composition according to the present invention, a polyester urethane solution which may be prepared by charging the following con~tih1ents in order into a reaction vessel equipped with a stirrer, a he~tin~ source and a reflux condenser:
Parts by Portion 1 Wei~ht o 1,3-butylene glycol 173.4 1,6-hexanediol 163.1 Trimethylol propane 78.8 Adipic acid 403.7 Toluene 20.0 Portion 2 Propylene glycol monomethyl ether acetate294.4 Port;on ~
Tone'19 FCP 310 (caprolactone polyol 934.9 from Union Carbide) 2 o Propylene glycol monomethyl ether acetate185.3 Hydrocarbon solvent 706.1 Portion 4 trimethylh~-Y~methylene diisocyanate 290.3 dibutyl tin dilaurate 0.5 2 5 Portion 5 Hydrocarbon solvent 69.8 Total 3320.3 Portion 1 is charged in order into the reation vessel, and the 3 0 co~ ents of Portion 1 are heated to distill water at 140-230C. The distillation is contin~le-l until the acid number is 6.5 to 8.5. The product is thinned and cooled to 98 to 102C by charging Portion 2 into the vessel.
While the constituents in the vessel are m~int~ined at the above temperature, Portion 3 was charged to the reactor in order. Portion 4 is added to the composition at a unirollll rate over a 30 minute period while WO 94/11122 2 1 4 7 8 3 0 PCr/US93/10791 the batch temperature is m~int~ined at 98-102C. A sample is removed and tested for unreacted isocyanate NCO by infrared analysis. The composition is held at the above temperature until there is no unreacted isocyanate in the composition. Portion 5 then is added as a rinse and the resulting composition was allowed to cool to ambient temperatures.
Following this procedure, the resulting composition had a polymer weight solids content of about 61.0%. The polyester urethane had a Gardner-Holdt viscosity of L The Mn (number average molecular weight) was 3734.0 and the Mw (weight average molecular weight) was o 7818.0 (by gel permeation chromatography using polystyrene as the st~nrl~rd). The acid content was determined to be 4.9 Meq/g. The lydlo~y number was 92.
This example illustrates, as another optional component for use in the present composition, an acid polymer, more specifically a methacrylic acid resin,which may be prepared by charging the following col~Liluents into a reactor equipped with a thermometer, stirrer, dr~ g funnel, and con~le-n~or:
2 o Parts by Portion 1 We;~ht Propylene glycol monomethyl ether acetate155.3 (hereafter PM acetate) Xylene 103.5 2 5 Portion 2 Butyl methacrylate 174.8 Methacrylic acid 97.1 Butyl acrylate 140.8 Styrene 72.8 3 o Portion 3 Tertiary butyl peroxy acetate 35.0 PM acetate 41.7 Xylene 27.8 Total 849.0 WO 94~lll22 ~ 8 3 ~ Pcr/us93/lo7 Portion 1 was charged into the reactor and heated to reflux (a~ploxi",~tely 140C). Portion 2 was premixed and added to the reactor dropwise over a 240 minute period. Portion 3 was pren~ixed and added to t_e reactor over a 270 minute period concurrent with Portion 3. After the addition was complete, the reactor was held at reflux and filled out.
The resnltin~ acid polymer composition had a composition of 15% styrene, 36% butyl methacrylate, 29% n-butyl acrylate, and 20%
methacrylic acid. The solids conten~ was 60% and the polymer had a Gardner-Holdt viscosity of Z1. The polymer had a weight average molecular weight of 5000.
This example illustrates a waterborne refinish clearcoat composition accordillg to the present invention, using a methyl half ester of maleic anhydride and an epoxy cros~linker. The following components were thoroughly blended:
Parts by Part 1 Wei~ht 2 o Methyl half ester of maleic anhydride acrylic polymer (as prepared above) 35.39 Deioni7ed water 48.91 Triethyl amine 4.19 DCE 358 (Sorbitol epoxy from Dixie Co.) 8.9 DABCO (25% triethylene ~ mine in butanol) 2.61 When the composition was thinned with water and cast as a film on glass, the film cures at ambient temperature. The coating was virtually tack free in al,proxi",~tely S hours. After 24 hours. the solvent 3 o resi~t~nce (to MEK) was measured to 17 double rubs. After 5 days the solvent resict~nce (to MEK) was measured to 100+ double rubs.
This composition can be fortified with TINUVIN 1130 and TINUVIN 292 (or TINUVIN 123) light stabilizers to give durable films, the level of the former at 2-3% on binder and the level of the latter at 1-2% on binder.
WO 94/11122 2 ~ 47 ~ 3 0 Pcr/US93/10791 This example illustrates a waterborne clearcoat composition based on latex and a maleic anhydride half ester copolymer. The following components were thoroughly blended:
Parts by Part 1 Wei,~ht Methyl half ester of maleic anhydride acrylic polymer (as prepared above but88.0 34% solids in water/butyl proprionate, neutralized with triethylamine) Deionized water , 77.0 Diethylene glycol monobutyl ether 4.4 Propylene glycol monomethyl ether 4.4 IINUVIN 1130 UV stabilizer 2.1 (benzotriazole adduct from Ciba-Geigy) TINUVIN 292 free radical stabilizer 1.4 (hindered amine from Ciba-Geigy) DEHYDRAN 1620 defoamer (from Henkel) 0.1 ~lTON GR-7M wetting agent 0.2 (from Union Carbide) NEOCRYL A6015 acrylic emulsion latex (45% solids in water from ICI) 66.6 triethylene ~ mine catalyst (25% in water) 4 3 DCE-358 aliphatic epoxy cros~linker (sorbitol polyglycidol ether from Dixie Chem. Co.) 10.0 3 o TOTAL 258.5 The reslllting coating composition had a solids content of 29% and its c~lc~ ed VOC is 2.3 lb/gal. The above clear coating composition was drawn over glass plates and allowed to cure for seven days 3 5 at ambient temperature. The reslllting clearcoat had good clarity and gloss, WO94~1l122 21~783~ pcr/us93/1o79l and exhibite a Persoz hardness of 193 and an MEK solvent resistance of 59 double rubs.
This example illustrates four different compositions (A
through D) based on an anhydride half ester and an epoxy, with and without an ~ rly polyurethane. With respect to each of the composi~ioll~ A through D, respectively, the following components were thoroughly blended:
A B C D
(Parts by (Parts by (Parts by (Parts by ~NGREDIENT we;pht) weight) wei~ht) we;~ht) Maleate half ester 68.73 66.61 18.67 17.45 Deionized H20 94.97 92.04 25.79 24.11 Triethylarnine 8.13 7.88 2.21 2.06 Urethane dispersion 1 2 o (NEOREZ~ XR9679) 0.00 0.00 138.09 0.00 Urethane dispersion 2 (NEOREZ'19 XR9699) 0.00 0.00 0.00 129.06 Butyl carbitol 0.00 0.00 0.00 14.20 TINUVIN~ 1130 1.97 2.15 2.22 2.13 TINUVIN~292 1.31 1.44 1.48 1.42 DEHYDRAN surfactant 0.10 0.10 0.10 0.10 DOWANOL PM surfactant 2.22 0.02 2.96 3.60 TRlTON'i9 surfactant 0.20 0.20 0.20 0.20 Diethlyene triamine catalyst 3 o (25~o) in H20 5.08 4.93 1.38 1.29 Epoxy (XUGY 358) 17.28 14.78 4.14 4.39 Epoxy (ARALDlTE CY184) 0.00 9.85 2.76 0.00 3 5 TOTAL 200.00 200.00 200.00 2.00 WO 94/11122 2 1 ~1 7 ~ 3 0 PCI/US93/10791 Part 1 was premixed in order slowly and Part 2 was added with mixin~. The final compositions A through D exhibited the following properties.
TheoreticalSolids 32.75 35.89 36.98 35/52 TheoreticalVOC 2.90 2.60 :2.40 2.40 Viscosity Zahn #2 71(3) 65(4) 65(4) Very High Viscosity ICI Cone and Plate¢250 CPS175 CPS 155 CPS 225 CPS
Persoz Hardness 1 Day Glass 120 60 Chroma Base* 76 57 Persoz Hardness 3 Day Glass 125 59 107 134 Chroma Base 76 54 53 64 Persoz Hardness 7 Day Glass 265 198 232 202 Chroma Base 114 91 103 118 MEK Re.ci~t~nce (Double Rubs) Glass 100+ 100 100+ 100+
Chroma Base 50 37 100+ 30 Tukon Hardness 33 Days 6.30 2.98 2.71 1.60 Hardness Viscosity Overnight Gelled Gelled Gelled Fluid *Chroma Base is a registered trademark for a solventborne basecoat commercially available from Du Pont Co.
Based on the above results, it is evident that the addition of an ~nxili~ry polyurethane provides greater strength and hardness. However, 3 5 with polyesterurethane, using the less reactive epoxy (ether epoxy) in Wo 94J11122 2 1 4 7 ~ 3 0 pcr/us93/1o79l composition C resulted in better properties than using the more reactive epoxy in composition D.
This example illustrates a clearcoat composition according to the present invention, using a methyl half ester of maleic anhydride and an epoxy cro.c.clinker. The following components were thoroughly blended:
Parts by Part 1 Weight lo Methyl half ester of maleic anhydride acrylic polymer (as prepared above) 27.0 Deionized water 59.8 Triethyl amine 2.7 XU-71950 (Diglycidyl ester from Dow) 6.4 TINUVIN 1130 (UV screener3 O.S
Catalyst solution 2.2 TINUVIN-123 (25%) in butyl cellosolve 1.4 In the above list, the catalyst solution refers to a solution of benzyl triphenyl phosphonium chloride (10%) in isopropanol. The TINUVIN-123 is a hindered amine; both TINUVINs are commercially available from Ciba-Geigy.
The coating composition was sprayed onto primed metal panels coated with a waterborne basecoat and cured at 265F. The coating exhibited excellent hllmitlity resistance, chemical resistance, durability and other film properties.
This example illustrates another clearcoat composition accoldhlg to the present invention, using a methyl half ester of maleic anhydride and an epoxy crosslinker, but also with a silane component. The following components were thoroughly blended:
Parts by Part 1 Wei~ht Methyl half ester of maleic anhydride WO 94/11122 21:4 7 8 3 0 pcr/us93/lo791 acrylic polymer (as prepared above) 17.79 Deionized water 68.02 Triethyl amine 1.94 XU-71950 (Diglycidyl ester from Dow) 4.22 Epoxy silane polymer (as prepared above)3.95 TINUVIN 1130 (UV screener) 0.4 TINUVIN 123 (25% in butyl cellosolve) 1.05 Catalyst solution 1.71 Butyl cellosolve 0.92 In the above list, the catalyst solution refers to a solution of benzyl triphenyl phosphonium chloride (10%) in isopropanol. The TINUVIN 123 is a hindered amine commercially available from Ciba-Geigy.
This clear is adjusted to spray at 32 sec in a #2 Zahn cup with deionized water. The pH equals 9.2. The clear is sprayed over a waterborne basecoat and cured at 265-285F for 30 minntes The reslllting films were hard, glossy, and recict~nt to solvent and hnmi(lity. These films 2 o are durable and enviromnentally resict~nt Various modifications, alterations, additions, or substitutions of the components of the composition of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this 2 5 invention. This invention is not limited to the illustrative embodiments set forth herein, but rather the invention is defined by the following claims.
Claims (10)
1. A coating composition, in the form of a multipackage system, for producing a clearcoat, said coating composition comprising 20-80% by weight of reactive binder components and 80-20% by weight of an aqueous liquid carrier which is primarily water; wherein the binder comprises:
(a) 25-90% by weight, based on the weight of the binder, of a half-ester product of an acrylic copolymer having at least two reactive anhydride groups and comprising polymerized monomers of an ethylenically unsaturated anhydride or an ethylenically unsaturated dicarboxylic acid, which has been converted to an anhydride, and polymerized monomers selected from the group consisting of alkyl methacrylate, allyl acrylate and any mixtures therof, wherein the alkyl groups have 1-8 carbon atoms and the polymer has a weight average molecular weight of 2,000-100,000, wherein equal to or greater than 90% of the anhydride groups on said acrylic copolymer have been half-esterified by reaction with an alcohol;
(b) 5-50% by weight, based on the weight of the binder, of a glycidyl ether or ester or cycloaliphatic epoxy compound containing at least two reactive glycidyl groups;
(c) an effective amount of an base to neutralize the half-ester acylic copolymer (a) above; and (d) 0.1-8% by weight, based on the weight of the binder, of a catalyst, wherein the multipackage system comprises keeping components (a) and (b) separate until shortly before their application.
(a) 25-90% by weight, based on the weight of the binder, of a half-ester product of an acrylic copolymer having at least two reactive anhydride groups and comprising polymerized monomers of an ethylenically unsaturated anhydride or an ethylenically unsaturated dicarboxylic acid, which has been converted to an anhydride, and polymerized monomers selected from the group consisting of alkyl methacrylate, allyl acrylate and any mixtures therof, wherein the alkyl groups have 1-8 carbon atoms and the polymer has a weight average molecular weight of 2,000-100,000, wherein equal to or greater than 90% of the anhydride groups on said acrylic copolymer have been half-esterified by reaction with an alcohol;
(b) 5-50% by weight, based on the weight of the binder, of a glycidyl ether or ester or cycloaliphatic epoxy compound containing at least two reactive glycidyl groups;
(c) an effective amount of an base to neutralize the half-ester acylic copolymer (a) above; and (d) 0.1-8% by weight, based on the weight of the binder, of a catalyst, wherein the multipackage system comprises keeping components (a) and (b) separate until shortly before their application.
2. The composition of claim 1, wherein the components are selected such that the composition can be cured at 10 to 90°C.
3. The composition of claim 1,wherein the components are selected such that the composition can be baked during original automotive production.
4. The composition of claim 1, further comprising a silane polymer.
5. The coating composition of claim 1, wherein the base is a volatile amine in an amount to solubilize or disperse the half ester product into the aqueous liquid carrier.
6. The coating composition of claim 1, further comprising a polyester urethane, an acrylic latex, a waterborne urethane dispersion or emulsion, or mixtures thereof.
7. The coating composition of claim 1, in which the half ester product is an acrylic polymer comprising polymerized monomers of styrene, alkyl methacrylates and/or alkyl acrylates having 2-4 carbon atoms in the alkyl group, and the half ester of an ethylenically unsaturated anhydride or ethylenically unsaturated dicarboxylic acid which has been converted to an anhydride.
8. The coating composition of claim 1, further comprising an acid functional polymer formed by polymerizing monomers of alkyl methacrylates or alkyl acrylates or hydroxy alkyl acrylates or hydroxy alkyl methacrylates or mixtures thereof, where the alkyl groups have 1-12 carbon atoms and ethylenically unsaturated acids.
9. A substrate coated with a cured layer of the composition of claim I.
10. A method of coating a substrate comprising the steps of first coating a substrate with a pigmented waterborne basecoat composition to form a basecoat and subsequently coating said basecoat with a clearcoat composition which is a multipackage system compising 20-80% by weight of reactive binder components and 80-20% by weight of an aqueous liquid carrier having at least 60%by weight water; wherein the reactive binder comprises:
(a) 25-90% by weight, based on the weight of the binder, of a half-ester product of an acrylic copolymer having at least two reactive anhydride groups and comprising polymerized monomers of an ethylenically unsaturated anhydride or an ethylenically unsaturated dicarboxylic acid, which has been converted to an anhydride, and polymerized monomers selected from the group consisting of alkyl methacrylate, alkyl acrylate and any mixtures thereof, wherein the alkyl groups have 1-8 carbon atoms and the polymer has a weight average molecular weight of about 2,000-100,000 wherein equal or greater than 90 percent of the anhydride groups on said acrylic copolymer has been half-esterified by reaction with an alcohol;
(b) 5-50% by weight, based on the weight of the binder, of a glycidyl ether or ester or cycloaliphatic epoxy compound containing at least two reactive glycidyl groups;
(c) an effective amount of a base for neutralizing the half ester product of (a) above; and (d) 0.1-5% by weight, based on the weight of the binder, of a curing catalyst.
wherein the multipackage system comprises keeping components (a) and (b) separate until shortly before their application.
(a) 25-90% by weight, based on the weight of the binder, of a half-ester product of an acrylic copolymer having at least two reactive anhydride groups and comprising polymerized monomers of an ethylenically unsaturated anhydride or an ethylenically unsaturated dicarboxylic acid, which has been converted to an anhydride, and polymerized monomers selected from the group consisting of alkyl methacrylate, alkyl acrylate and any mixtures thereof, wherein the alkyl groups have 1-8 carbon atoms and the polymer has a weight average molecular weight of about 2,000-100,000 wherein equal or greater than 90 percent of the anhydride groups on said acrylic copolymer has been half-esterified by reaction with an alcohol;
(b) 5-50% by weight, based on the weight of the binder, of a glycidyl ether or ester or cycloaliphatic epoxy compound containing at least two reactive glycidyl groups;
(c) an effective amount of a base for neutralizing the half ester product of (a) above; and (d) 0.1-5% by weight, based on the weight of the binder, of a curing catalyst.
wherein the multipackage system comprises keeping components (a) and (b) separate until shortly before their application.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/977,863 | 1992-11-17 | ||
| US07/977,864 | 1992-11-17 | ||
| US07/977,864 US5367004A (en) | 1992-11-17 | 1992-11-17 | Ambient curing water-borne compositions comprising half esters of anhydride polymers crosslinked by epoxies |
| US07/977,863 US5376704A (en) | 1992-11-17 | 1992-11-17 | Water-borne coating compositions comprising half esters of anhydride polymers crosslinked by epoxies |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2147830A1 true CA2147830A1 (en) | 1994-05-26 |
Family
ID=27130594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2147830 Abandoned CA2147830A1 (en) | 1992-11-17 | 1993-11-16 | Water-borne compositions comprising half esters of anhydride polymers crosslinked by epoxies |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0670756A4 (en) |
| CA (1) | CA2147830A1 (en) |
| WO (1) | WO1994011122A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09168763A (en) * | 1995-12-19 | 1997-06-30 | Nof Corp | Method for forming paint film and coated article |
| CA2518363C (en) | 2003-04-02 | 2013-01-08 | Valspar Sourcing, Inc. | Aqueous dispersions and coatings |
| US9416294B2 (en) * | 2012-04-30 | 2016-08-16 | H.B. Fuller Company | Curable epoxide containing formaldehyde-free compositions, articles including the same, and methods of using the same |
| EP3160697A1 (en) * | 2014-06-30 | 2017-05-03 | Dow Global Technologies LLC | Treated porous material |
| CN106470810A (en) * | 2014-06-30 | 2017-03-01 | 陶氏环球技术有限责任公司 | Treated porous material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238170A (en) * | 1962-10-08 | 1966-03-01 | Staley Mfg Co A E | Aqueous coating composition comprising a polyepoxide and an alkali soluble copolymer |
| US4247439A (en) * | 1973-11-06 | 1981-01-27 | E. I. Du Pont De Nemours And Company | Water-borne coating composition made from epoxy resin, polymeric acid and tertiary amine |
| US4600737A (en) * | 1983-12-21 | 1986-07-15 | Inmont Corporation | Water dilutable acrylated epoxy-phenolic coating compositions |
| US4614777A (en) * | 1985-08-05 | 1986-09-30 | Ppg Industries, Inc. | Addition interpolymers from isobornyl (meth)acrylate which contain alkoxysilane and/or acyloxysilane groups |
| US4871806A (en) * | 1987-11-16 | 1989-10-03 | The Sherwin-Williams Company | Reactive coatings comprising an acid-functional compound, an anhydride-functional compound, an epoxy-functional compound and a hydroxy-functional compound |
| US4906677A (en) * | 1988-06-27 | 1990-03-06 | E. I. Du Pont De Nemours & Company | Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a phosphonium catalyst |
| JPH0245577A (en) * | 1988-08-04 | 1990-02-15 | Nippon Paint Co Ltd | Thermosetting composition |
| JPH0819315B2 (en) * | 1990-04-05 | 1996-02-28 | 日本ペイント株式会社 | Thermosetting resin composition |
| US5244696A (en) * | 1990-12-17 | 1993-09-14 | E. I. Du Pont De Nemours And Company | Automotive coating composition comprising an organosilane polymer |
-
1993
- 1993-11-16 EP EP94901343A patent/EP0670756A4/en not_active Withdrawn
- 1993-11-16 WO PCT/US1993/010791 patent/WO1994011122A1/en not_active Application Discontinuation
- 1993-11-16 CA CA 2147830 patent/CA2147830A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1994011122A1 (en) | 1994-05-26 |
| EP0670756A1 (en) | 1995-09-13 |
| EP0670756A4 (en) | 1996-08-21 |
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