CA1262980A - Aqueous epoxy resin dispersions for can coating use - Google Patents
Aqueous epoxy resin dispersions for can coating useInfo
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- CA1262980A CA1262980A CA000509821A CA509821A CA1262980A CA 1262980 A CA1262980 A CA 1262980A CA 000509821 A CA000509821 A CA 000509821A CA 509821 A CA509821 A CA 509821A CA 1262980 A CA1262980 A CA 1262980A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
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Abstract
ABSTRACT OF THE DISCLOSURE
Aqueous dispersions useful as can coating compositions are made from the ammonia or amine salt of a carboxyl functional acrylic copolymer blended with phenolplast resins, polyepoxide resins partially reacted with a monofunctional acid and, optionally, an epoxidized hydrocarbon or vegetable oil.
Aqueous dispersions useful as can coating compositions are made from the ammonia or amine salt of a carboxyl functional acrylic copolymer blended with phenolplast resins, polyepoxide resins partially reacted with a monofunctional acid and, optionally, an epoxidized hydrocarbon or vegetable oil.
Description
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~Q~ WS EP02~ R~SIN DISPERSI~S ~OR Q ~ o~A~I~G ~S~
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BAC~GRO~ND OF ~HE INVENTION
, The ~ield of art o~ this invention is aqueous modified ¦ epoxy resin dispersions which are particularly usQ~ul for can coating compositions In particular, this invention pertains to aqueous dispersions made ~rom a carboxyl-functional acrylic copslymer, phenolic resins, an epoxy resin partially esterified with a mono~unctional acid, and, optionally, an epoxidized hydrocarbon or unsaturated vegetable oil.
In the manufacture of metal containers, a thin, protective synthetic coating is applied to the interior of the container. The synthetic resins employed for coating the interior of the metal container are heat-curable polymeric compo~itions which are applied in the form o~ a solution or dispersion in a volatile organic solvent or water. When oxganic solvents are used, there is the problem of contendlng with the hazards of solvent vaporization and recovery during the drying and baking cycles of a coating operation.
The ~an manufacturing industry utilizes cans w~ich are fabricated ~rom aluminum or steel which may or ~ay not be coated with tin. The interior o~ the cans are coated with a thin thermoset film to prevent contact of the interior metal surface i of a can with its contents. Such coatings ideally should have good adhesion to the interior metal surface, low extractables to , prevent contamination of the container contents and a rapid cure rate for econom~ of container manufacture. Typical synthetic resin coating compositions include vinyl~, polybutadiene, epoxies, alkyd/aminopla~ and oleoresinous materials.
6,'~
There is a continuing effort to utilize coating compositions dispersed or dissolved in a~ueous media in order to j reduce or eliminate the emission o~ organic solvents to the atmosphere.
¦ U.S. Patent No. 3,118,848 describes coating ¦ compositions which are prepared by mixing together a water-soluble salt of a vinyl polymer and a water-soluble epoxy or polyhydroxy compound. One or more water-soluble phenolaldehyde or amino resins, notably water-soluble urea-aldehyde or melamine-aldehyde resins may optionally be included as curiny agents whare low baking temperatures are contemplated.
In U.S. Patenk No. 3,492,252, an epoxy resin is dispersed in an emulsion of a carboxyl-containing vinyl or acrylic copolymer. Additional film-~orming materials, e.g., phenol/formaldehyde resins, can be added to improve coating properties.
, U.S. Patent ~o. 3,969,300 describes coating compositlons made by copol~merizing epoxy resins partially esterified with acrylic acid with other monomers including ' acrylic acid. These copolymers are solubilized or dispersed in water with amines and are then blended with amino resins.
U.S. Patent No. 4,247,439 describes water-borne reactio~ products of carboxyl-functional polymers, polyepoxides i¦ and tertiary a~ines which are useful a~ film-forming components ¦ of coatinq compositions. Such coating compositions can be sprayed, ~lowed, dipped, rollercoated or elec~rocoated. The coating composikions are useful as such or can be crosslinked : with crosslinking agents such as nitrogen resins a~d phenolic resins.
6'~98C~
U.S. Patent No. 4,283,428 discloses metal containers having ~n internal ~ur~ace coated with a cured layer of a water based coating composition made from an agueous ~edium having dissolved or di~persed therein a n~utrali~ed reaction product of a polyepoxide and an aromati~ amino acid con aining at least one amine group and at least one carboxyl group. The reaction product has unreacted carboxyl groups which ar~ neutralized with a base. Such compositions are crosslinked with aminoplast r~sins and phenolic resins.
U.S. Patent No. 4,289,811 describes agueous dispersions of mixed resins which are prepared by polymerizing in the presence of an aminoplast resin a mixture of polymerizable carboxylic acid monomers and other monomers followed by the addition of an epoxy resin, ammonia or amine to salt the acid groups, and then dispersing the resin mixture in water.
U.S. Patent No. 4,423,165 describes water-borne reaction products of carboxyl-~unctional polymers, polyepoxides and tertiary amines which are blended ~ith carboxy-functional polymers having an acid number dissimilar to tha~ of the ~irst carboxy-functional polymer. The resulting products are useful as film-~orming components of coating compositions, especially useful for coating the insides of two piece tinplated steel cans of beverage and food. The coating compositions are useful as such or can be crosslinked with nitrogen resins or phenolic resins.
In U.S. Patent No. 4,454,265, a~u20us thermoset coating compositions are described which are made from amine adducts of epoxy resins cured with heat hardeniny phenol-formaldehyde resins.
U.S~ Patent No. 4,212,781 describes graft polymers made by reacting epoxy resins with copolymeriz~ble mono~ers in llthe presence o~ at least 3% benzoyl peroxide. These graft ;,copolymers, when dispersed in water, form useful coating l'~compositions ~or ~ans~
¦I European Pate~t Applications 6334 and 6336 describe resinous compositions made from epo~y esters copolymerized with l~acrylic acid and other monomer~. The epoxy esters are the reaction products of polyepoxide resins and acrylic acid.
Before reaction with the acrylic acid, the polyepoxide resins ;can be partially defunctionalized with phenols or saturated monocarboxylic acids. The resulting resinous composi$ions are salted with a base and are di~solved or disparsed in water to form coating compositions. Aminoplast or phenolplast resins can be added to enhance the cure o~ the coatings on baking.
SUMM~RY OF THE INVE~TION
; The coating compositions of this invention are made from aqueous dispersions o~ resinous blends salted ~ith ammonia or an amine. The resinous blends are made from (a) about 15 ~o about 30 weight percent of a carboxyl-functional acrylic copolymer, (b) about 10 to about 25 weight percent of ~ ph~nolplast resins, (c~ about 40 to about 75 weight percent of a j partially defunctionalized polyepoxide resin, and (d) O to about ~15 weight percent of an epoxidized hydrocarbon or vegetable oil.
The carboxyl-functional acrylic copolymer has ~n average molecular weight o~ bout 3,000 to about 30,000 and an acid value o~ about 100 to about 300. The partially defunctionali~ed polyep~xide resin before defunctionalization has an epoxide equivalent welght o~ about 7~0 ~o about 3,000 and is a diglycidyl ~ther of a dihydric phenol~ The polyepoxide resin jl i5 de~unctionalized by having about 2 to about 20 equivalent ,Ipercent of its epoxide functionality reacted with a non-polymerizable ~onofunctional organic acid having a pXa in water of about 2 to ab~ut 5.
¦ Th~ coating compositions o t~is invention when applied to metal substrates and baked at a temperature of about i 360F. to about 410F~ for a time su~ficient to cure the composition exhibit excellent adhesion. The compositions are particu}arly useful when applied to tinplated steel and tin-free steel, and especially to tinplated steel surfaces as low as .05 pound tin per base box~ The compositions o~ this invention not .only have improved adhesion when used to coat the interior of cans, but also have improved water resistance, resulting in improved processing and packed food resistance. For impxov~d sulfur resistance, "C" enam~ls can be made from the compssitions of this invention ~y the addition to the disper~ion of zinc oxide and/or zinc carbonate pastes as well as pastes which contain zinc carboxylates, e.y., zinc stearate, zinc caprate, zinc oleate, zinc linoleate, zinc caprylate and the like.
DESCRIPTION OF THE INVENTION
The carboxyl-functional acrylic copol~mers useful in ~thi~ invention are prepared by conventional free radical polymerization processes from at least one polymerizable ethylenically unsaturated carbvxylic acid monomer and at lPast one polymerizable ethylenically unsaturated monomer free of acid groups. Such polymerizable carboxylic acid monomers include acrylic acid, me~acrylic acid, crotonic acid, itaconic asid, maleic acid or anhydride, fumaric acid, the monoes~ers o~ the 8(~
.;
dicarboxylio acid monomers, ~uch as methyl hydrogen maleate or ethyl hydrogen f~l~arate and the like.
Suitable polymerizable ethylanically unsaturated monomers free o~ acid groups are vinyl aromatic compounds and alkyl esters of p~lymerizable ethylenically unsaturated ¦Icarboxylic acids. Examples of such monomers include styr~ne, ',halostyrene, vinyl toluene, vinyl napthalene~ the methyl, ethyl, !~, propyl, butyl, hexyl, ethylhexyl and lauryl acrylates, methacrylat~s and crotonakes, dimethylmaleate, dibutylfumarate and the like. Mixtures of these monomers can also be used.
Other suitable polymerizable ethylenically unsaturated monomers include ~inyl chloride, acrylonitrile, methacrylonitrile, vinyl acetate, ~inyl propionate, vinyl stearate and the like.
The preferred monomers are styrene, methylacrylate, ethyl acrylate, butyl acrylate, acrylic ~cid and methacrylic acid. The most preferred monomers are styrene, ethyl acrylate and acrylic acid.
The carboxyl-~unctional-acrylic copolymers useful in this invention have a polymerizable acid content o~ about 10 to about 50 weight percent and an acid value of about 100 to about .;300. The average molesular weight o~ the copolymers is about 3,000 to about 30,000.
The phenolplast resins useful in this invention are made from phenols and formaldehyde. Such resins are made by reacting the phenol with formaldehyde under basic conditions.
The resins have the phenol moieties linked together through methylene bridges and contain unreacted methylol groups. Useful phenolplast resins are derived from unsubstituted phenol, creaol and other alkyl phenols wherein the alkyl group contains from 2 to about 12 carbon atoms as well as dihydric phenols such as ~ J
~Q~ WS EP02~ R~SIN DISPERSI~S ~OR Q ~ o~A~I~G ~S~
.~ :
BAC~GRO~ND OF ~HE INVENTION
, The ~ield of art o~ this invention is aqueous modified ¦ epoxy resin dispersions which are particularly usQ~ul for can coating compositions In particular, this invention pertains to aqueous dispersions made ~rom a carboxyl-functional acrylic copslymer, phenolic resins, an epoxy resin partially esterified with a mono~unctional acid, and, optionally, an epoxidized hydrocarbon or unsaturated vegetable oil.
In the manufacture of metal containers, a thin, protective synthetic coating is applied to the interior of the container. The synthetic resins employed for coating the interior of the metal container are heat-curable polymeric compo~itions which are applied in the form o~ a solution or dispersion in a volatile organic solvent or water. When oxganic solvents are used, there is the problem of contendlng with the hazards of solvent vaporization and recovery during the drying and baking cycles of a coating operation.
The ~an manufacturing industry utilizes cans w~ich are fabricated ~rom aluminum or steel which may or ~ay not be coated with tin. The interior o~ the cans are coated with a thin thermoset film to prevent contact of the interior metal surface i of a can with its contents. Such coatings ideally should have good adhesion to the interior metal surface, low extractables to , prevent contamination of the container contents and a rapid cure rate for econom~ of container manufacture. Typical synthetic resin coating compositions include vinyl~, polybutadiene, epoxies, alkyd/aminopla~ and oleoresinous materials.
6,'~
There is a continuing effort to utilize coating compositions dispersed or dissolved in a~ueous media in order to j reduce or eliminate the emission o~ organic solvents to the atmosphere.
¦ U.S. Patent No. 3,118,848 describes coating ¦ compositions which are prepared by mixing together a water-soluble salt of a vinyl polymer and a water-soluble epoxy or polyhydroxy compound. One or more water-soluble phenolaldehyde or amino resins, notably water-soluble urea-aldehyde or melamine-aldehyde resins may optionally be included as curiny agents whare low baking temperatures are contemplated.
In U.S. Patenk No. 3,492,252, an epoxy resin is dispersed in an emulsion of a carboxyl-containing vinyl or acrylic copolymer. Additional film-~orming materials, e.g., phenol/formaldehyde resins, can be added to improve coating properties.
, U.S. Patent ~o. 3,969,300 describes coating compositlons made by copol~merizing epoxy resins partially esterified with acrylic acid with other monomers including ' acrylic acid. These copolymers are solubilized or dispersed in water with amines and are then blended with amino resins.
U.S. Patent No. 4,247,439 describes water-borne reactio~ products of carboxyl-functional polymers, polyepoxides i¦ and tertiary a~ines which are useful a~ film-forming components ¦ of coatinq compositions. Such coating compositions can be sprayed, ~lowed, dipped, rollercoated or elec~rocoated. The coating composikions are useful as such or can be crosslinked : with crosslinking agents such as nitrogen resins a~d phenolic resins.
6'~98C~
U.S. Patent No. 4,283,428 discloses metal containers having ~n internal ~ur~ace coated with a cured layer of a water based coating composition made from an agueous ~edium having dissolved or di~persed therein a n~utrali~ed reaction product of a polyepoxide and an aromati~ amino acid con aining at least one amine group and at least one carboxyl group. The reaction product has unreacted carboxyl groups which ar~ neutralized with a base. Such compositions are crosslinked with aminoplast r~sins and phenolic resins.
U.S. Patent No. 4,289,811 describes agueous dispersions of mixed resins which are prepared by polymerizing in the presence of an aminoplast resin a mixture of polymerizable carboxylic acid monomers and other monomers followed by the addition of an epoxy resin, ammonia or amine to salt the acid groups, and then dispersing the resin mixture in water.
U.S. Patent No. 4,423,165 describes water-borne reaction products of carboxyl-~unctional polymers, polyepoxides and tertiary amines which are blended ~ith carboxy-functional polymers having an acid number dissimilar to tha~ of the ~irst carboxy-functional polymer. The resulting products are useful as film-~orming components of coating compositions, especially useful for coating the insides of two piece tinplated steel cans of beverage and food. The coating compositions are useful as such or can be crosslinked with nitrogen resins or phenolic resins.
In U.S. Patent No. 4,454,265, a~u20us thermoset coating compositions are described which are made from amine adducts of epoxy resins cured with heat hardeniny phenol-formaldehyde resins.
U.S~ Patent No. 4,212,781 describes graft polymers made by reacting epoxy resins with copolymeriz~ble mono~ers in llthe presence o~ at least 3% benzoyl peroxide. These graft ;,copolymers, when dispersed in water, form useful coating l'~compositions ~or ~ans~
¦I European Pate~t Applications 6334 and 6336 describe resinous compositions made from epo~y esters copolymerized with l~acrylic acid and other monomer~. The epoxy esters are the reaction products of polyepoxide resins and acrylic acid.
Before reaction with the acrylic acid, the polyepoxide resins ;can be partially defunctionalized with phenols or saturated monocarboxylic acids. The resulting resinous composi$ions are salted with a base and are di~solved or disparsed in water to form coating compositions. Aminoplast or phenolplast resins can be added to enhance the cure o~ the coatings on baking.
SUMM~RY OF THE INVE~TION
; The coating compositions of this invention are made from aqueous dispersions o~ resinous blends salted ~ith ammonia or an amine. The resinous blends are made from (a) about 15 ~o about 30 weight percent of a carboxyl-functional acrylic copolymer, (b) about 10 to about 25 weight percent of ~ ph~nolplast resins, (c~ about 40 to about 75 weight percent of a j partially defunctionalized polyepoxide resin, and (d) O to about ~15 weight percent of an epoxidized hydrocarbon or vegetable oil.
The carboxyl-functional acrylic copolymer has ~n average molecular weight o~ bout 3,000 to about 30,000 and an acid value o~ about 100 to about 300. The partially defunctionali~ed polyep~xide resin before defunctionalization has an epoxide equivalent welght o~ about 7~0 ~o about 3,000 and is a diglycidyl ~ther of a dihydric phenol~ The polyepoxide resin jl i5 de~unctionalized by having about 2 to about 20 equivalent ,Ipercent of its epoxide functionality reacted with a non-polymerizable ~onofunctional organic acid having a pXa in water of about 2 to ab~ut 5.
¦ Th~ coating compositions o t~is invention when applied to metal substrates and baked at a temperature of about i 360F. to about 410F~ for a time su~ficient to cure the composition exhibit excellent adhesion. The compositions are particu}arly useful when applied to tinplated steel and tin-free steel, and especially to tinplated steel surfaces as low as .05 pound tin per base box~ The compositions o~ this invention not .only have improved adhesion when used to coat the interior of cans, but also have improved water resistance, resulting in improved processing and packed food resistance. For impxov~d sulfur resistance, "C" enam~ls can be made from the compssitions of this invention ~y the addition to the disper~ion of zinc oxide and/or zinc carbonate pastes as well as pastes which contain zinc carboxylates, e.y., zinc stearate, zinc caprate, zinc oleate, zinc linoleate, zinc caprylate and the like.
DESCRIPTION OF THE INVENTION
The carboxyl-functional acrylic copol~mers useful in ~thi~ invention are prepared by conventional free radical polymerization processes from at least one polymerizable ethylenically unsaturated carbvxylic acid monomer and at lPast one polymerizable ethylenically unsaturated monomer free of acid groups. Such polymerizable carboxylic acid monomers include acrylic acid, me~acrylic acid, crotonic acid, itaconic asid, maleic acid or anhydride, fumaric acid, the monoes~ers o~ the 8(~
.;
dicarboxylio acid monomers, ~uch as methyl hydrogen maleate or ethyl hydrogen f~l~arate and the like.
Suitable polymerizable ethylanically unsaturated monomers free o~ acid groups are vinyl aromatic compounds and alkyl esters of p~lymerizable ethylenically unsaturated ¦Icarboxylic acids. Examples of such monomers include styr~ne, ',halostyrene, vinyl toluene, vinyl napthalene~ the methyl, ethyl, !~, propyl, butyl, hexyl, ethylhexyl and lauryl acrylates, methacrylat~s and crotonakes, dimethylmaleate, dibutylfumarate and the like. Mixtures of these monomers can also be used.
Other suitable polymerizable ethylenically unsaturated monomers include ~inyl chloride, acrylonitrile, methacrylonitrile, vinyl acetate, ~inyl propionate, vinyl stearate and the like.
The preferred monomers are styrene, methylacrylate, ethyl acrylate, butyl acrylate, acrylic ~cid and methacrylic acid. The most preferred monomers are styrene, ethyl acrylate and acrylic acid.
The carboxyl-~unctional-acrylic copolymers useful in this invention have a polymerizable acid content o~ about 10 to about 50 weight percent and an acid value of about 100 to about .;300. The average molesular weight o~ the copolymers is about 3,000 to about 30,000.
The phenolplast resins useful in this invention are made from phenols and formaldehyde. Such resins are made by reacting the phenol with formaldehyde under basic conditions.
The resins have the phenol moieties linked together through methylene bridges and contain unreacted methylol groups. Useful phenolplast resins are derived from unsubstituted phenol, creaol and other alkyl phenols wherein the alkyl group contains from 2 to about 12 carbon atoms as well as dihydric phenols such as ~ J
2,2'(4 hydroxyphenyl) propane (Bisphenol A). Mixtures of phenols can be used to vary and control the prop~rties o~ the phenolplast resinsq Phenolplast re6ins useful in this invention have ~olecular weights within the range of about 300 to about 2500 and melting poin~s of about 65 to about 100C. -~ot plate ¦ cure speed at 150C. will vary from about 70 to about 180 seconds. In ~ormula~ing the compositions of this invention, Imixture~ of phenolplast resins, as well as unmixed resins, can be used.
The polyepoxide resins useful in this invention are glyc~dyl polyethers o~ dihydric phenols and contain more than one 1,2-epoxide group per molecule. Such epoxy resins are derived from an epihalohydrin and a polyhydric phenol and have epoxide equivalent w~ights of about 750 to about 3,000.
Examples of epihalohydrins are epichlorohydrin, epibromohydrin, epiiodohydrin with epichlorohydrin being preferred. Dihydric phenols are exemplified by resorrinol, hydroquinone, 2,2'(4-hydroxyphenyl) propane ~or Bisphenol A as it is commonly called), p,p' dihydroxy- diphenyl, p,pl-dihydroxydiph~nyl methane, p,p'-dihydroxydiphenyl ethane, bis-2-hydroxy naphthyl methane, 1,5-dihydroxy naphthalene and the like. Bisphenol A is the preferred dihydric phenol.
Th~ polyepoxide resins as used in this invention are partially defunctionalized by having about 2 to about 20 equiva-lent percent of their epoxide functionality reacted with a non-polymerizable ~onofunctional organic acid having a pKa value of about 2 to about 5. Examples of such monofunctional acids are acetic acid, benzoic acid, dodecyl benzene sulfonic acid, butyric acid, caproic acid, benzyla~Qtic acid, naph~halene sulfonic acid, caprylic acid, stearic acid and the like. The ., ; 7 ~preferred acid i~ dodecyl benzene ~ul~onic acid, the use of llwhich enhances the wet~ability and flexibility of the coating jlcomposit~on. If less than 0.02 eguivalent of the monofunctional acid is used, proc~ssing is dlf~icult and gel-fre2 products l~cannot always be ~btained. If mor~ than 0.2 equivalent of the ¦~monofunctional acid i5 used, the can coating compositions have lower ionic barrier resistance as evidenced by decreased salt, .acid and chemical resistance.
: The epoxidized hydrocarbon or vegetable oil which can be used in the compositions of this invention are epoxidi~ed polybutadiene, epoxidized soybean oil, drying oils which contain oleic, linoleic and linolenic acid, and the like.
Basic reagents used in this invention to neutralize the carboxyl groups of th~ acrylic copol~mer include ammonia, ,primary, secondary and textiary amines, such as ethylamine, butylamine, dimethylamine, trlethylamine, isopropylamine, dimethylethylamine, cyclohexylamine, allylamine, benzylamine, morpholin~, N-methyl morpholine, ethanolamine, diethanolamine and triethanolamine. The preferred amines are tertiary amines, such as dimethylethanolamine, triethylamine and n-methyl morpholine. The amount of basic reagent which is used to :neutralize the carboxylic acid will vary from about 45%
equivalent to about 95% equivalents based on the carboxylic acid ~unctionality.
~¦ The resinous components used in this invention can be ¦dissolved in an organic solvent in order to facilitata their dispersion in water~ The organic solvent is pre~erably one ,which is substantially water-miscible, either in the form of a single polar compound or a mixture of compounds which can include non-polar constituents. The boiling point of the ~Z~
, organic ~olvents will vary between about 150 to about 500F.
I' Suitable solvents, either alone or in a mixture, include n-butanol, monomethyl 2ther of ~thylene glycol, ,monoethyl ether of ethy}Pne glycol, monobutyl ether of ethylene ¦llglycol, monomethyl ~ther of propylene glycol, monopropyl ether of ethylene glycol, monoethyl ~ther of propylene glycol, monobutyl ether of propylene glycol, monomethyl ether o~
;diethylene glycol, monoethyl ~ther of diethylene glycol, monobutyl ether o~ diethylene glycol and the like. Non-polar solvents which can be included as minor constituents of the organic solvent component include aliphatic and aromatic hydrocarbons, such as naphtha, heptane, h~xane, mineral spirits, toluene, xylene and the like. I
In preparing the compositions of this invention, the organic solvents are used in the amount o~ about 5 to about 25 weight percent based upon the tot~l weight of the dispPrsion.
In preparing the compositions o~ this invention, ~he epoxy resln in an organic solvent is partially de~unctionalized by reaction with a monofunctional acid t about 1~0 to about 220F. for 15 to 30 minutes. The carboxyl functional acrylic copolymer is then add~d ~ollowed by ~ddition of the phenolplast resin. When solution is obtained, the mixture is then partially neutralized with an amine and is then dispersed in water. The ;resulting dispersion will hav~ a solids ont~nt of about 30 ~o jabout 50 weight percent, preferably, about 33 to about 43 weight .percent. The order o~ r~actions and additions before the aminP
addition can be varied with compara~le result~.
The co~ting com~ositions of this invention are useful a~ coating compositions ~or the interior of metal cans, i.e,.
~6~
cans made from aluminum, tin ~ree steel, tinplated steel and ! especially tinplated ~teel having a low tin content. The , coatings are generally applied by roller coating or by beiny drawn do~n by Meyer bar at about 2 to abou~ g milligrams per '.~quare inch, andJ preferably, about 4 to about 6 milligrams per !~ square inch. In order to cure the ~oatings, they are baked for about 8 to about 10 minutes at a temp~rature of about 350 to ! about 410~F. By reduction with proper sol~en~s, e.g., butanol and water mixtures, the product can be applied by spraying.
The following examples are presented to more clearly de~ine th~ invention. Parts and percentages, unless otherwise designated, are parts and percentages by weight.
. .
To a sui-table reactor e~uipped with a stirrer, temperakure recording device, re~lux condenser and dropping funnel were added 641 parts of water, 4,108 parts o~ n-butanol and 2,502 parts o~ ethylene glycol monobutyl ether. To ths dropping funnel were added 4,065 parts of styrene, 1,909 parts o~ ethyl acrylat~, 3,058 parts of acrylic acid and 641 parts of benzoyl peroxide. The reactor was heated to reflux (210F.) under agitation. The monomer-catalyst mixture in the dropping funnel was added to the reactor over 150 minutas while holding the temperature at 205 to 210F. A~ter all the ,monomer-catalyst mixture had been added, the dropping funnel was rinsed with 198 parts of ethylene glycol monobutyl ether and the rinse solution was ~dded ~o the reactor~ The reactants were then cooled to 200~F. and held for one hour ~t this temperature.
go parts o~ benzoyl peroxide were then added and the temperature ~6;~
-of the xeactants was held at 2009F. for an additional one hour.
,The reactor contents were then cooled to 130 F. and an ,ladditional 160 part~ of ethylene glycol monobutyl ether were ¦ladded. The resulting carboxyl ~unctional acrylic copolymer Ijsolution at a solids content o~ 54 to 56% and a Gardner -Holdt i viscosity at 25C. f Zl to Z3~
To a ~uitable reactor equipped as described in Example 1, were added 171 parts of a glycidyl polyether o~ Bisphenol A
having an epoxide equivalent weight of 2100 to 2400, 10 parts of diethylene glycol monobutyl ether, 44 parts o~ n-butanol and 4 parts of ethylene glycol monobutyl ether. The reactor contents were heated to 200F. to dissolve the epoxy resin. A solution o~ 3 parts of dodecyl benzene sulfonic acid and 6 parts of ethylene glycol monobutyl ether were added to the reactor over a 5 minute period. After heating for 5 minutes at 200F., 105 parts of the carboxyl ~unctional acrylic copolymer solution of Example 1 were added over a one hour period while keeping the temperature at ~00F. After holding the temperature at 200F.
for an additional 15 minutes, ~2 parts of a solution of a ,Bisphenol A phenolplast resin having an average molecular weight i of about 900 to about 1000 dissolved at 46% solids in n-butanol ;120/Pthylene glycol monobutyl ether 40/xylene 40 were added over ~a 20 min-lte period while holding the temperature at 200F.
After an additional 15 minutes at 200F., 28 parts of a cresol phenolplast resin having an average molecular weight of a~out 2000 and a melting point of 72~ to 78C. were added over a 10 :, ~2~ 10 minute period while holding the temperature a.t 200F. The temperature was then held for 1 hour at 200 F. followed by the addition of 13 parks dimethylethanolamine over a 15 minute period. After holding at 200F. ~or 30 minutes, 355 parts o~
~dsionized water were added o~er an 80 minute period and the jltemperature was allowed to drop to about 140F~ and was held for .30 minutes at 130 to 140F. The reactor contents were cooled ~o 100F. and 6 parts of an emulsion of carnauba wax at 25 solids in water were added. After mixing for 30 minutes, additional deionized water was added to adjust the viscosity.
The resulting product had an 83 sPcond #4 Ford Cup viscosity, a solids content of 34 . 59~ and 2 . 5 VOC (volatile organic content~ . i Using the same procedure as described in Example 2, 137 parts o~ ~ glycidyl polyether of Bisphenol A having an epoxide equivalent weight o~ 2100 to 2400 were dissolved in 17 parts of diethylene glycol monobutyl ether and lJ parts of n-butanol wa~ reacted with 2.2 parts of dodecyl benzene sulfonic acid dissolved in 5 parts of ethylene glycol monobutyl ether.
~he resulting partially defunctionalized epoxy resin was then r~a~ted with 83 parts o~ the carboxyl functional acrylic copolymer solution of Example 1, 23 parts o~ a Bisphenol A
ph~nolplast resin having an average molecular weight of about 600 and a melting point of 65 to 75C., 23 parts of a cresol phenolplast resin having an average molecular weight o~ 2000 and a melting point of 72 to 78C., 11.5 parts of dimethylethanol-amine, 343 parts of deionized water and 4.6 parts of a 25~
d ~
emulsion of carnauba wax in watern The resulting product had a 74 second #4 Ford Cup viscosity at 34.8% solids and 1.8 VOC.
,! .
~, Using the same procedure described in 2xample 2, 73 parts of the epoxy resln described in Example 2 were dissolved in 9 parts of diethylene glycol monobutyl ether and 9 parts of butanol. The epoxy resin wa~ then partiall~ defunctionalized by reaction with 2.4 parts o~ dodecyl benzene sulfonic acid dissolved in 3 parts of ~thylene glycol monobutyl ether. The resulting partially defunctionalized epoxy resin was then reacted with 44 parts of the carboxyl ~unctional acrylic copolymer ~olution of Example 1, 12 parts of the Bisphenol A
phPnolplast resin described in Example 3, 12 parts of the cresol phenolplast described in Example 3, and 6 parts of dimethylethanolamine. The resulting product was disper ed in 133 parts of deionized water. The resulting dispersion had a 29 second #4 Ford Cup viscosi~y and a solids contënt of 40.4%.
Using the same procedure described in Example 2, 137 parts of~he glycidyl polyeth~r described in Example 2 dissolved in 17 parts o~ diethylene glycol monobutyl ether and 17 parts o~
n-butanol was partially defunctionalized by reaction with 2.2 ,parts dodecyl benzene sulfonic acid dissolved in 5 parts of ethylene glycol monobutyl ether. Th~ partially defunctionalized epoxy resi~ was then reacted with 83 parts o~ the carbvxyl functional acrylic copolymer solution described in Example 1, 23 ~Z~f~f3 ;, .
parts o~ the Bisphenol A phenolplast xesin described in Example
The polyepoxide resins useful in this invention are glyc~dyl polyethers o~ dihydric phenols and contain more than one 1,2-epoxide group per molecule. Such epoxy resins are derived from an epihalohydrin and a polyhydric phenol and have epoxide equivalent w~ights of about 750 to about 3,000.
Examples of epihalohydrins are epichlorohydrin, epibromohydrin, epiiodohydrin with epichlorohydrin being preferred. Dihydric phenols are exemplified by resorrinol, hydroquinone, 2,2'(4-hydroxyphenyl) propane ~or Bisphenol A as it is commonly called), p,p' dihydroxy- diphenyl, p,pl-dihydroxydiph~nyl methane, p,p'-dihydroxydiphenyl ethane, bis-2-hydroxy naphthyl methane, 1,5-dihydroxy naphthalene and the like. Bisphenol A is the preferred dihydric phenol.
Th~ polyepoxide resins as used in this invention are partially defunctionalized by having about 2 to about 20 equiva-lent percent of their epoxide functionality reacted with a non-polymerizable ~onofunctional organic acid having a pKa value of about 2 to about 5. Examples of such monofunctional acids are acetic acid, benzoic acid, dodecyl benzene sulfonic acid, butyric acid, caproic acid, benzyla~Qtic acid, naph~halene sulfonic acid, caprylic acid, stearic acid and the like. The ., ; 7 ~preferred acid i~ dodecyl benzene ~ul~onic acid, the use of llwhich enhances the wet~ability and flexibility of the coating jlcomposit~on. If less than 0.02 eguivalent of the monofunctional acid is used, proc~ssing is dlf~icult and gel-fre2 products l~cannot always be ~btained. If mor~ than 0.2 equivalent of the ¦~monofunctional acid i5 used, the can coating compositions have lower ionic barrier resistance as evidenced by decreased salt, .acid and chemical resistance.
: The epoxidized hydrocarbon or vegetable oil which can be used in the compositions of this invention are epoxidi~ed polybutadiene, epoxidized soybean oil, drying oils which contain oleic, linoleic and linolenic acid, and the like.
Basic reagents used in this invention to neutralize the carboxyl groups of th~ acrylic copol~mer include ammonia, ,primary, secondary and textiary amines, such as ethylamine, butylamine, dimethylamine, trlethylamine, isopropylamine, dimethylethylamine, cyclohexylamine, allylamine, benzylamine, morpholin~, N-methyl morpholine, ethanolamine, diethanolamine and triethanolamine. The preferred amines are tertiary amines, such as dimethylethanolamine, triethylamine and n-methyl morpholine. The amount of basic reagent which is used to :neutralize the carboxylic acid will vary from about 45%
equivalent to about 95% equivalents based on the carboxylic acid ~unctionality.
~¦ The resinous components used in this invention can be ¦dissolved in an organic solvent in order to facilitata their dispersion in water~ The organic solvent is pre~erably one ,which is substantially water-miscible, either in the form of a single polar compound or a mixture of compounds which can include non-polar constituents. The boiling point of the ~Z~
, organic ~olvents will vary between about 150 to about 500F.
I' Suitable solvents, either alone or in a mixture, include n-butanol, monomethyl 2ther of ~thylene glycol, ,monoethyl ether of ethy}Pne glycol, monobutyl ether of ethylene ¦llglycol, monomethyl ~ther of propylene glycol, monopropyl ether of ethylene glycol, monoethyl ~ther of propylene glycol, monobutyl ether of propylene glycol, monomethyl ether o~
;diethylene glycol, monoethyl ~ther of diethylene glycol, monobutyl ether o~ diethylene glycol and the like. Non-polar solvents which can be included as minor constituents of the organic solvent component include aliphatic and aromatic hydrocarbons, such as naphtha, heptane, h~xane, mineral spirits, toluene, xylene and the like. I
In preparing the compositions of this invention, the organic solvents are used in the amount o~ about 5 to about 25 weight percent based upon the tot~l weight of the dispPrsion.
In preparing the compositions o~ this invention, ~he epoxy resln in an organic solvent is partially de~unctionalized by reaction with a monofunctional acid t about 1~0 to about 220F. for 15 to 30 minutes. The carboxyl functional acrylic copolymer is then add~d ~ollowed by ~ddition of the phenolplast resin. When solution is obtained, the mixture is then partially neutralized with an amine and is then dispersed in water. The ;resulting dispersion will hav~ a solids ont~nt of about 30 ~o jabout 50 weight percent, preferably, about 33 to about 43 weight .percent. The order o~ r~actions and additions before the aminP
addition can be varied with compara~le result~.
The co~ting com~ositions of this invention are useful a~ coating compositions ~or the interior of metal cans, i.e,.
~6~
cans made from aluminum, tin ~ree steel, tinplated steel and ! especially tinplated ~teel having a low tin content. The , coatings are generally applied by roller coating or by beiny drawn do~n by Meyer bar at about 2 to abou~ g milligrams per '.~quare inch, andJ preferably, about 4 to about 6 milligrams per !~ square inch. In order to cure the ~oatings, they are baked for about 8 to about 10 minutes at a temp~rature of about 350 to ! about 410~F. By reduction with proper sol~en~s, e.g., butanol and water mixtures, the product can be applied by spraying.
The following examples are presented to more clearly de~ine th~ invention. Parts and percentages, unless otherwise designated, are parts and percentages by weight.
. .
To a sui-table reactor e~uipped with a stirrer, temperakure recording device, re~lux condenser and dropping funnel were added 641 parts of water, 4,108 parts o~ n-butanol and 2,502 parts o~ ethylene glycol monobutyl ether. To ths dropping funnel were added 4,065 parts of styrene, 1,909 parts o~ ethyl acrylat~, 3,058 parts of acrylic acid and 641 parts of benzoyl peroxide. The reactor was heated to reflux (210F.) under agitation. The monomer-catalyst mixture in the dropping funnel was added to the reactor over 150 minutas while holding the temperature at 205 to 210F. A~ter all the ,monomer-catalyst mixture had been added, the dropping funnel was rinsed with 198 parts of ethylene glycol monobutyl ether and the rinse solution was ~dded ~o the reactor~ The reactants were then cooled to 200~F. and held for one hour ~t this temperature.
go parts o~ benzoyl peroxide were then added and the temperature ~6;~
-of the xeactants was held at 2009F. for an additional one hour.
,The reactor contents were then cooled to 130 F. and an ,ladditional 160 part~ of ethylene glycol monobutyl ether were ¦ladded. The resulting carboxyl ~unctional acrylic copolymer Ijsolution at a solids content o~ 54 to 56% and a Gardner -Holdt i viscosity at 25C. f Zl to Z3~
To a ~uitable reactor equipped as described in Example 1, were added 171 parts of a glycidyl polyether o~ Bisphenol A
having an epoxide equivalent weight of 2100 to 2400, 10 parts of diethylene glycol monobutyl ether, 44 parts o~ n-butanol and 4 parts of ethylene glycol monobutyl ether. The reactor contents were heated to 200F. to dissolve the epoxy resin. A solution o~ 3 parts of dodecyl benzene sulfonic acid and 6 parts of ethylene glycol monobutyl ether were added to the reactor over a 5 minute period. After heating for 5 minutes at 200F., 105 parts of the carboxyl ~unctional acrylic copolymer solution of Example 1 were added over a one hour period while keeping the temperature at ~00F. After holding the temperature at 200F.
for an additional 15 minutes, ~2 parts of a solution of a ,Bisphenol A phenolplast resin having an average molecular weight i of about 900 to about 1000 dissolved at 46% solids in n-butanol ;120/Pthylene glycol monobutyl ether 40/xylene 40 were added over ~a 20 min-lte period while holding the temperature at 200F.
After an additional 15 minutes at 200F., 28 parts of a cresol phenolplast resin having an average molecular weight of a~out 2000 and a melting point of 72~ to 78C. were added over a 10 :, ~2~ 10 minute period while holding the temperature a.t 200F. The temperature was then held for 1 hour at 200 F. followed by the addition of 13 parks dimethylethanolamine over a 15 minute period. After holding at 200F. ~or 30 minutes, 355 parts o~
~dsionized water were added o~er an 80 minute period and the jltemperature was allowed to drop to about 140F~ and was held for .30 minutes at 130 to 140F. The reactor contents were cooled ~o 100F. and 6 parts of an emulsion of carnauba wax at 25 solids in water were added. After mixing for 30 minutes, additional deionized water was added to adjust the viscosity.
The resulting product had an 83 sPcond #4 Ford Cup viscosity, a solids content of 34 . 59~ and 2 . 5 VOC (volatile organic content~ . i Using the same procedure as described in Example 2, 137 parts o~ ~ glycidyl polyether of Bisphenol A having an epoxide equivalent weight o~ 2100 to 2400 were dissolved in 17 parts of diethylene glycol monobutyl ether and lJ parts of n-butanol wa~ reacted with 2.2 parts of dodecyl benzene sulfonic acid dissolved in 5 parts of ethylene glycol monobutyl ether.
~he resulting partially defunctionalized epoxy resin was then r~a~ted with 83 parts o~ the carboxyl functional acrylic copolymer solution of Example 1, 23 parts o~ a Bisphenol A
ph~nolplast resin having an average molecular weight of about 600 and a melting point of 65 to 75C., 23 parts of a cresol phenolplast resin having an average molecular weight o~ 2000 and a melting point of 72 to 78C., 11.5 parts of dimethylethanol-amine, 343 parts of deionized water and 4.6 parts of a 25~
d ~
emulsion of carnauba wax in watern The resulting product had a 74 second #4 Ford Cup viscosity at 34.8% solids and 1.8 VOC.
,! .
~, Using the same procedure described in 2xample 2, 73 parts of the epoxy resln described in Example 2 were dissolved in 9 parts of diethylene glycol monobutyl ether and 9 parts of butanol. The epoxy resin wa~ then partiall~ defunctionalized by reaction with 2.4 parts o~ dodecyl benzene sulfonic acid dissolved in 3 parts of ~thylene glycol monobutyl ether. The resulting partially defunctionalized epoxy resin was then reacted with 44 parts of the carboxyl ~unctional acrylic copolymer ~olution of Example 1, 12 parts of the Bisphenol A
phPnolplast resin described in Example 3, 12 parts of the cresol phenolplast described in Example 3, and 6 parts of dimethylethanolamine. The resulting product was disper ed in 133 parts of deionized water. The resulting dispersion had a 29 second #4 Ford Cup viscosi~y and a solids contënt of 40.4%.
Using the same procedure described in Example 2, 137 parts of~he glycidyl polyeth~r described in Example 2 dissolved in 17 parts o~ diethylene glycol monobutyl ether and 17 parts o~
n-butanol was partially defunctionalized by reaction with 2.2 ,parts dodecyl benzene sulfonic acid dissolved in 5 parts of ethylene glycol monobutyl ether. Th~ partially defunctionalized epoxy resi~ was then reacted with 83 parts o~ the carbvxyl functional acrylic copolymer solution described in Example 1, 23 ~Z~f~f3 ;, .
parts o~ the Bisphenol A phenolplast xesin described in Example
3, ~3 parts of the cresol phenolplast resin described in Example 3, 4.2 parts o~ a 5~ aqueous solution of lanolin, 12 parts of epoxidized soybean oil and 11. 5 parts of di~ethylethanolamine.
I¦The resulting product, after being dispersed in 290 parts of I deionized ~ater, had a Ford Cup #4 viscosity o~ 65 seconds at 37% solids.
;I EXAMPLE 6 . . I
Each of th~ dispersions in Examples 2 through 5 were roll coated using a ~agner roll coat~r or drawndown by Meyer bar at 2Q-24 milligrams per 4 sq.in. ~ilm weight on tin free steel, ~0.25 pound electrolytic tinplate and .05 pound electrolytic tinplat~. The coatings were baked for 10 minutes at 360 to 400F. When coated panels were subjected to severe processing conditions, either in water or in food products such as lima beans, cream o~ chicken soup or tomato paste, the adhesion of all the coatings was excellent.
In order to improve the sulfur resistance o~ the !. ' !
coatings, the dispersions were blended with zinc oxide paste in the amount o~ 5 to 25 weight percent zinc oxide based on the solids content of the coating.
,, The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing ~pecifica~ion. The invention which ~s intended ~o be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded ,, ~6'~8~
as illustrative rather than restrictive. Variations and changes may be made by thos~ skilled in the art without departing :from thc ~plrit Oe the lmrention.
, I
I¦The resulting product, after being dispersed in 290 parts of I deionized ~ater, had a Ford Cup #4 viscosity o~ 65 seconds at 37% solids.
;I EXAMPLE 6 . . I
Each of th~ dispersions in Examples 2 through 5 were roll coated using a ~agner roll coat~r or drawndown by Meyer bar at 2Q-24 milligrams per 4 sq.in. ~ilm weight on tin free steel, ~0.25 pound electrolytic tinplate and .05 pound electrolytic tinplat~. The coatings were baked for 10 minutes at 360 to 400F. When coated panels were subjected to severe processing conditions, either in water or in food products such as lima beans, cream o~ chicken soup or tomato paste, the adhesion of all the coatings was excellent.
In order to improve the sulfur resistance o~ the !. ' !
coatings, the dispersions were blended with zinc oxide paste in the amount o~ 5 to 25 weight percent zinc oxide based on the solids content of the coating.
,, The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing ~pecifica~ion. The invention which ~s intended ~o be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded ,, ~6'~8~
as illustrative rather than restrictive. Variations and changes may be made by thos~ skilled in the art without departing :from thc ~plrit Oe the lmrention.
, I
Claims (13)
1. A coating composition which comprises an aqueous dispersion of a resinous blend salted with ammonia or an amine wherein the resinous blend is comprised of a) about 15 to about 30 weight percent of a carboxyl functional acrylic copolymer;
b) about 10 to about 25 weight percent of a phenol-plast resin;
c) about 40 to about 75 weight percent of a partially defunctionalized polyepoxide resin; and d) about 0 to about 5 weight percent of an epoxidized hydrocarbon or vegetable oil, wherein (a) has an average molecular weight of about 3,000 to about 30,000 and an acid value of about 100 to about 300, and wherein (c) is a diglycidyl ether of a dihydric phenol having an epoxide equivalent weight of about 750 to about 3,000 before defunctionalization having been reacted with about 0.02 to about 0.2 of equivalents per epoxide equivalent of a non-polymerizable monofunctional organic acid having a pKa of about 2.0 to about 5.
b) about 10 to about 25 weight percent of a phenol-plast resin;
c) about 40 to about 75 weight percent of a partially defunctionalized polyepoxide resin; and d) about 0 to about 5 weight percent of an epoxidized hydrocarbon or vegetable oil, wherein (a) has an average molecular weight of about 3,000 to about 30,000 and an acid value of about 100 to about 300, and wherein (c) is a diglycidyl ether of a dihydric phenol having an epoxide equivalent weight of about 750 to about 3,000 before defunctionalization having been reacted with about 0.02 to about 0.2 of equivalents per epoxide equivalent of a non-polymerizable monofunctional organic acid having a pKa of about 2.0 to about 5.
2. The composition of claim 1 wherein the carboxyl functional acrylic copolymer is a copolymer of at least one polymerizable ethylenically unsaturated carboxylic acid monomer and at least one polymerizable ethylenically unsaturated monomer free of acid groups.
3. The composition of claim 2 wherein the polymerizable ethylenically unsaturated carboxylic acid monomer is acrylic acid.
4. The composition of claim 2 wherein the polymerizable ethylenically unsaturated monomer free of acid groups is styrene and ethyl acrylate.
5. The composition of claim 2 wherein the phenolplast resin has an average molecular weight of about 300 to about 2500 and a melting point of about 65°C. to about 100°C.
6. The composition of claim 5 wherein the phenolplast resin is a resin derived from phenols selected from the group consisting of phenol, cresol and 2,2 '(4-hydroxyphenyl) propane.
7. The composition of claim 2 wherein the diglycidyl ether of the dihydric phenol is a diglycidyl ether of 2,2'(4--hydroxyphenyl) propane.
8. The composition of claim 2 wherein the non--polymerizable monofunctional organic acid having a pKa of about 2 to about 5 is dodecyl benzene sulfonic acid.
9. The composition of claim 1 wherein the epoxidized hydrocarbon is epoxidized polybutadiene.
10. The composition of claim 1 wherein the epoxidized vegetable oil is epoxidized soybean oil.
11. The composition of claim 1 which contains about 5 to about 25 weight percent, based on total solid content, of a zinc salt paste.
12. The composition of claim 11 wherein the zinc salt is zinc oxide.
13. The composition of claim 11 wherein part of the zinc salt is a zinc carboxylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US740,351 | 1985-06-03 | ||
| US06/740,351 US4623680A (en) | 1985-06-03 | 1985-06-03 | Aqueous epoxy resin dispersions for can coating use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1262980A true CA1262980A (en) | 1989-11-14 |
Family
ID=24976128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000509821A Expired CA1262980A (en) | 1985-06-03 | 1986-05-23 | Aqueous epoxy resin dispersions for can coating use |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4623680A (en) |
| EP (1) | EP0204511B1 (en) |
| JP (1) | JPH0696689B2 (en) |
| CA (1) | CA1262980A (en) |
| DE (1) | DE3680241D1 (en) |
| ES (1) | ES8706785A1 (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199487B1 (en) * | 1985-04-19 | 1991-03-06 | Nippon Steel Corporation | Cans and a method for making cans |
| US4752398A (en) * | 1985-08-05 | 1988-06-21 | Holbein Bruce E | Method for removing mercury and other related metals from a liquid medium |
| US4804581A (en) * | 1987-05-14 | 1989-02-14 | Ppg Industries, Inc. | Chip resistant coatings |
| US5302315A (en) * | 1988-09-20 | 1994-04-12 | Schill & Seilacher (Gmbh & Co.) | Vulcanization activator method |
| US5162399A (en) * | 1991-01-09 | 1992-11-10 | Eastman Kodak Company | Ink millbase and method for preparation thereof |
| US5218032A (en) * | 1991-01-09 | 1993-06-08 | Eastman Kodak Company | Process for preparing blends of polyesters and acrylic polymers |
| US5171797A (en) * | 1991-12-03 | 1992-12-15 | The P.D. George Company | Water borne hermetic coating |
| CA2130458A1 (en) * | 1992-12-22 | 1994-07-07 | Mitsui Petrochemical Industries, Ltd. | Resin composition for water-based coating and water-based coating composition |
| US5391636A (en) * | 1993-02-10 | 1995-02-21 | Westvaco Corporation | Polyamine condensates of styrene-maleic anhydride copolymers as corrosion inhibitors |
| US5527840B1 (en) * | 1994-10-04 | 1999-08-10 | Valspar Corp | Aqueous coating composition |
| US5516826A (en) * | 1995-03-13 | 1996-05-14 | Westvaco Corporation | Polyamine condensates of styrene-acrylic acid copolymers as corrosion inhibitors |
| WO1998040443A1 (en) * | 1997-03-12 | 1998-09-17 | Shell Internationale Research Maatschappij B.V. | Aqueous epoxy/phenolic codispersions usable for interior food can coating lacquers |
| EP1333076A4 (en) * | 2000-10-20 | 2004-12-15 | Kansai Paint Co Ltd | Water-based coating composition for can inner surfaces |
| WO2004090020A1 (en) | 2003-04-02 | 2004-10-21 | Valspar Sourcing, Inc. | Aqueous dispersions and coatings |
| JP4697415B2 (en) * | 2004-09-09 | 2011-06-08 | 信越化学工業株式会社 | Polyphenylene ether oligomer sulfonate and process for producing the same |
| US20060078739A1 (en) * | 2004-10-07 | 2006-04-13 | Essary William A | Methods for improving barrier of a coated substrate |
| US20060078740A1 (en) * | 2004-10-07 | 2006-04-13 | Zern John R | Barrier coatings |
| ATE513025T1 (en) | 2004-10-20 | 2011-07-15 | Valspar Sourcing Inc | COATING COMPOSITIONS FOR CANS AND COATING PROCESSES |
| JP4697416B2 (en) * | 2004-10-26 | 2011-06-08 | 信越化学工業株式会社 | Flame retardant polycarbonate resin composition and molded product thereof |
| JP4697417B2 (en) * | 2004-10-26 | 2011-06-08 | 信越化学工業株式会社 | Flame retardant resin composition and molded product thereof |
| PL2416962T3 (en) | 2009-04-09 | 2017-07-31 | Valspar Sourcing, Inc. | Polymer having unsaturated cycloaliphatic functionality and coating compositions formed therefrom |
| US8747979B2 (en) | 2009-07-17 | 2014-06-10 | Valspar Sourcing, Inc. | Coating compositions and articles coated therewith |
| US9011999B2 (en) | 2009-09-18 | 2015-04-21 | Valspar Sourcing, Inc. | Coating composition including an unsaturated polymer |
| JP2011246608A (en) * | 2010-05-27 | 2011-12-08 | Daicel Finechem Ltd | Epoxidized polybutadiene water dispersion-type resin composition |
| US9752044B2 (en) * | 2013-08-16 | 2017-09-05 | Ppg Industries Ohio, Inc. | Aqueous-based coating composition containing an oleoresinous component |
| US20130052380A1 (en) * | 2011-08-29 | 2013-02-28 | Ppg Industries Ohio, Inc. | Coating compositions for food and beverage containers |
| US10442953B2 (en) | 2011-08-29 | 2019-10-15 | Ppg Industries Ohio, Inc. | Aqueous-based coating composition containing hydroxy-terminated polybutadiene |
| US20140072717A1 (en) * | 2012-09-13 | 2014-03-13 | Ppg Industries Ohio, Inc. | Polyepoxide-polyacid coating compositions, related coating processes and coated substrates |
| EP3060617B1 (en) * | 2013-10-25 | 2019-04-03 | PPG Industries Ohio, Inc. | Aqueous-based coating composition containing hydroxy-terminated polybutadiene |
| JP6527402B2 (en) * | 2014-07-10 | 2019-06-05 | ユニチカ株式会社 | Polyolefin resin aqueous dispersion and packaging material |
| US10125276B2 (en) * | 2015-11-06 | 2018-11-13 | Ppg Industries Ohio, Inc. | Container coating compositions with resistance to sulfur staining |
| US10703920B2 (en) | 2016-09-28 | 2020-07-07 | Ppg Industries Ohio, Inc. | Corrosion-resistant epoxidized vegetable oil can interior coating |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5545565B2 (en) * | 1971-11-24 | 1980-11-18 | ||
| CA1186846A (en) * | 1978-06-12 | 1985-05-07 | George L. Brown | Aqueous emulsion coatings composition comprising self-emulsifiable epoxy ester copolymer mixture |
| US4501831A (en) * | 1983-12-27 | 1985-02-26 | Chu Shaw C | Aqueous coating compositions and process for their preparation from epoxy acidic acrylic polymer and polyfunctional amine |
| JPS60215016A (en) * | 1984-04-10 | 1985-10-28 | Toyo Ink Mfg Co Ltd | Aqueous resin dispersion |
-
1985
- 1985-06-03 US US06/740,351 patent/US4623680A/en not_active Expired - Lifetime
-
1986
- 1986-05-23 CA CA000509821A patent/CA1262980A/en not_active Expired
- 1986-05-29 DE DE8686304072T patent/DE3680241D1/en not_active Expired - Lifetime
- 1986-05-29 EP EP86304072A patent/EP0204511B1/en not_active Expired
- 1986-06-02 ES ES555589A patent/ES8706785A1/en not_active Expired
- 1986-06-03 JP JP61129029A patent/JPH0696689B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61293266A (en) | 1986-12-24 |
| EP0204511A2 (en) | 1986-12-10 |
| EP0204511A3 (en) | 1988-05-04 |
| ES555589A0 (en) | 1987-07-01 |
| ES8706785A1 (en) | 1987-07-01 |
| JPH0696689B2 (en) | 1994-11-30 |
| DE3680241D1 (en) | 1991-08-22 |
| EP0204511B1 (en) | 1991-07-17 |
| US4623680A (en) | 1986-11-18 |
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