CA1129131A - Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems - Google Patents
Air drying thermosetting aqueous epoxy-acrylic copolymer coating systemsInfo
- Publication number
- CA1129131A CA1129131A CA317,715A CA317715A CA1129131A CA 1129131 A CA1129131 A CA 1129131A CA 317715 A CA317715 A CA 317715A CA 1129131 A CA1129131 A CA 1129131A
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- monoethylenic
- water
- organic solvent
- monomer
- copolymer
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Abstract
ABSTRACT OF THE DISCLOSURE
Thermosetting aqueous epoxy-acrylic copolymer coating systems adapted to cure on air drying are provided using a first package constituted by acid-neutralized organic solvent soluble tertiary amine copolymer comprising at least about 40% of nonreactive monoethylenic monomer, from 5-35% of monoethylenic hydroxy-functional monomer, and from 5-35% of monoethylenic tertiary amine monomer, said copolymer being in solution in a water-miscible organic solvent, and a second component comprising a resinous poly-epoxide in solution in at least partially water-miscible organic solvent.
Thermosetting aqueous epoxy-acrylic copolymer coating systems adapted to cure on air drying are provided using a first package constituted by acid-neutralized organic solvent soluble tertiary amine copolymer comprising at least about 40% of nonreactive monoethylenic monomer, from 5-35% of monoethylenic hydroxy-functional monomer, and from 5-35% of monoethylenic tertiary amine monomer, said copolymer being in solution in a water-miscible organic solvent, and a second component comprising a resinous poly-epoxide in solution in at least partially water-miscible organic solvent.
Description
llZ9~31 The present invention relates to thermosetting aqueous epoxy-acrylic copolymer coating systems ~hich are adapted to cure on air drying. Such coating systems are two package systems which cure upon admixture with one another and are particularly adapted for the painting of proches and floors, including cementitious substrates.
Aqueous coating compositions of the general type under consideration are in commerce, being produced under the disclosure of United States Patent 3,719,629 issued March 6, 1973. These kno~ compositions are not only expen-sive, but they exhibit poor chalking resistance, and poor tint retention. They are also marginal from the standpoints of (l) applicability to porches; (2) film hardness; and (3) cracking resistance.
In the aqueous coating compositions of said patent 3,719,629, the epoxy resin component is combined in an aqueous medium with an aminoethylated vinyl polymer having pendant aminoethyl groups, these groups having the formula:
0 ~H
-C - 0 - CH2 - CH2 ~ ~ H
and the cure is between the oxirane (epoxy) group in the epoxy resin and the amino hydrogen atoms in the amonoethyl group pictured. In the present invention, the amino hydrogen atoms which are essential in the prior art are not present. More-over, the production of the pendant aminoethyo groups in the prior art required the use of expensive and hazardous ethyl-ene imine, and this is avoided in this invention.
From the broader standpoint, and in addition to the aqueous epoxy system noted previously, other resin systems have been employed to provide air drying porch and floor
Aqueous coating compositions of the general type under consideration are in commerce, being produced under the disclosure of United States Patent 3,719,629 issued March 6, 1973. These kno~ compositions are not only expen-sive, but they exhibit poor chalking resistance, and poor tint retention. They are also marginal from the standpoints of (l) applicability to porches; (2) film hardness; and (3) cracking resistance.
In the aqueous coating compositions of said patent 3,719,629, the epoxy resin component is combined in an aqueous medium with an aminoethylated vinyl polymer having pendant aminoethyl groups, these groups having the formula:
0 ~H
-C - 0 - CH2 - CH2 ~ ~ H
and the cure is between the oxirane (epoxy) group in the epoxy resin and the amino hydrogen atoms in the amonoethyl group pictured. In the present invention, the amino hydrogen atoms which are essential in the prior art are not present. More-over, the production of the pendant aminoethyo groups in the prior art required the use of expensive and hazardous ethyl-ene imine, and this is avoided in this invention.
From the broader standpoint, and in addition to the aqueous epoxy system noted previously, other resin systems have been employed to provide air drying porch and floor
-2-llZ~3131 paints. Thus, the systems of this invention are intended to replace two existing aqueous systems, one based on an alkyd resin and another based on an aqueous copolymer latex, and also to replace an organic solvent-based epoxy system.
The invention exhibits significant superiority to all three as will be documented hereinafter.
A two package system is employed in the present invention. In one component is placed an acid-neutralized tertiary amine copolymer in solution in a water-miscible alcoholic solvent. The other component contains the epoxy resin, desirably together with a catalyst for the epoxy-tertiary amine reaction, in solution in organic solvent which is at least partially water-miscible, and which is preferably alcoholic. Before applying the coating, the two separately stable solution components are mixed together to form an aqueous mixture of limited pot life, and this aqueous mixture is coated upon the surface to be painted. The water which is present in the aqueous mixture is normally added to the first component prior to admixture of the two components, but all or a portion of the water can be added after the mixture is formed. The first com-ponent also desirably includes a surfactant for maintaining the epoxy resin in relatively stable emulsion in the aqueous mixture which is provided.
Typical coatings produced by the present inven-tion have a pot life of at least about 8 hours, usually about 12-14 hours, and can be applied by roller, brush, or air spray. The applied aqueous coatings dry to the touch in air at room temperature in about 6-7 hours and become water and solvent resistant in about 8-12 days. Recoat 1~29131 properties are comparable to that of conventional porch and floor paints. Importantly, polymer solubility is obtained using acids like lactic or acetic acid which are less toxic than anionic systems solubilized with amines, and generally less than 10% of nonobjectionable alcoholic solvents are needed which is advantageous from several well known standpoints, such as cost, hazard, pollution, and the like.
Referring more particularly to the tertiary amine copolymers, these are organic solvent-soluble copolymers comprising three copolymerized monoethylenically unsatu-rated components, namely: (1) nonreactive monomer; (2) hydroxy-functional monomer; and (3) tertiary amine monomer.
While small amounts of other monomers may be present, such as monoethylenic carboxylic acids, monoethylenic amides or M-methylol derivatives thereof, or polyethylenic hydroxy-functional materials such as polyesters, these are not necessary.
The nonreactive monoethylenically unsaturated (monoethylenic) monomer should constitute at least about 40% of the copolymer in order to provide desirably physical characteristics. Styrene is the preferred nonreactive monoethylenic monomer, but vinyl toluene is also useful.
Methyl methacrylate, acrylonitrile, and vinyl acetate will further illustrate the nonreactive monomers which are use-ful. A portion of a flexibilizing nonreactive monomer is also desirably present, such as ethyl acrylate or meth-acrylate or butyl acrylate or methacrylate. These flexi-bilizing monomers can be more generally defines as C2 -C8 alkanol esters of monoethylenic carboxylic acids.
llZ~3131 In preferred practice, the nonreactive monomercomponent will constitute from about 50V/o to about 80% of the weight of the tertiary amine copolymer, typically about 65,~o.
The monoethylenic hydroxy-functional monomer is used in an amount of from 5-35% of the weight of the tertiary amine copolymer, preferably from 10-25%, and it is important for various reasons. First, the hydroxy functionality assists in achieving water solubility with the aid of a solubilizing acid. Second, the presence of the hydroxy group is important to the ultimate cure, and this factor may be only partially satisfied by the presence of the alcoholic solvent since the bulk of the thermosetting cure ~akes place in the solid film after the water and volatile solvent have been removed.
Appropriate monomers are illustrated by hydroxy ethyl acry-late or methacrylate, and simple variations thereof, such as hydroxy propyl acrylate. Polyhydric monomers such as trimethylol propane monoacrylate are also useful, and so are unsaturated alcohols like allyl alcohol and oleyl alcohol, especially when the rest of the monomers are not acrylic, as when large amounts of styrene and/or vinyl acetate are used.
lhe term "hydroxy" refers to the alcoholic groups, and does not embrace related functionalities in which a terminal OI~ is present, such as the phenolic O~ group, the SiOH group, or the N-methylol group.
A limited proportion of polyethylenic polyester having hydroxyl functionality may be present as disclosed in United States Patent 3,506,601 dated April 14, 1970, so 3n long as it does not interfere with water solubility. This l~Z9131 material, if used, will constitute a portion of the hydroxy monomer component.
The crucial component of the tertiary amine copolymer is the monoethylenic tertiary amine monomer.
Typical tertiary amine monomers are dimethyl aminoethyl acrylate or methacrylate, dimethyl aminopropyl acrylate or methacrylate, diethyl aminomethyl acrylate or methacrylate, and diethyl aminoethyl or aminopropyl acrylate or meth-acrylate. The corresponding crotonates and tertiary amino esters of other monoethylenic carboxylic acids are also useful. ~dditionally, the corresponding amides are useful such as dimethyl aminoethyl methacrylamide.
The proportion of the tertiary amine monomer can vary in the same way as the hydroxy monomer, namely, from 5-35% by weight of the copolymer, preferably from 10-25%
by weight.
Water miscible organic solvents which are useful in this invention are preferably alcoholic and are illus-trated by ethanol, propanol, isopropanol, n-butanol, iso-butanol, 2-ethoxy ethanol and 2-butoxy ethanol.
The specific nature of the solubilizing acid used to disperse the amine copolymer in water is of secondary significance. Inorganic acids, such as hydrochloric acid or sulfuric acid, are useful, though not preferred. It is presently preferred to employ phosphoric acid, glycolic acid (hydroxy acetic acid), or acetic acid, but other acids can be used, such as formic acid or carbonic acid. Pro-pionic acid is also useful.
The solubilizing acid is used in an amount to provide a colloidal dispersion having a preferred pH in l~Z9131 the range of pH 610 - 7.0, though a pH in the range of pH3 - 8 is broadly useful.
The epoxy resins which are used in this invention can be broadly referred to as resinous polyepoxides, and those which possess a l,2-epoxy equivalency in the range of about 1.4 to about 2.0 are preferred. Polyepoxides which are diglycidyl ethers of bisphenols are particularly preferred, especially those having an average molecular weight in the range of about 350 to 4000. A diglycidyl ether of bisphenol A having an average molecular weight of about 390 will be used to illustrate the invention.
The polyepoxide component is itself conventional, as discussed in patent 3,719,62 referred to previously.
The polyepoxide is desirably used in an amount providing approximate stoichiometry between epoxy groups in the polyepoxide and tertiary nitrogen atoms in the amine copolymer, + 50V/o~ more preferably + 20%.
The organic solvent component of the package containing the polyepoxide is intended to provide desirably liquidity, particularly since the polyepoxide is normally a viscous liquid or a solid at room temperature. Since it is desired that the polyepoxide be stably dispersed in the aqueous mixture which is ultimately produced, the organic solvent should be at least partially water miscible, but the partial miscibility which is intended need merely be that which is consistent with the ultimate stable disper-sion which is contemplated, and it is most accurate to refer to the form of the dispersion as an emulsion since the presence of the polyepoxide component in the aqueous mixture which is formed is such as to induce considerably ~29~31 opacity to the liquid mixture.
A surfactant is normally included in the poly-epoxide solution in order to stabilize the aqueous emulsions which are formed. Appropriate surfactants may be nonionic or anionic and the selection of surfactants appropriate for the emulsification of epoxy resins in water is well known and is not a feature of this invention.
Surfactants are not needed, however, since the cationic copolymer itself functions to help to maintain the epoxy resin in relatively stable emulsion.
It is also permissible to include catalysts for the tertLary amine-epoxy curing reaction. This reaction is itself well known, and thus the selection of catalysts for the reac~ion is not of primary concern. Appropriate catalysts are Lewis acids, such as dibutyl tin dilaurate.
Indeed, no catalyst is needed, and none is used in the pre-ferred form of the invention.
The systems of this invention can be applied clear or pigmented, but pigmented systems containing titan-ium dioxide rutile at a pigment to binder ratio of 0.3:1.0are preferred.
The invention is illustrated in the following examples.
EXAMPLE I
Preparation of solvent soluble tertiary amine copolymer in solution in water miscible organic solvent.
1360 parts of 2-ethoxy ethanol are heated to 120C. in a reactor equipped with an agitator, a reflux condenser, a thermometer, and a nitrogen inlet tube for - il29131 sparging the reaction mixture.
Monomers and catalysts are premixed in an addition tank. 710 parts of styrene, 360 parts of hydroxy ethyl acrylate, 630 parts of butyl acrylate, 350 parts of dimethyl aminoethyl methacrylate, 24 parts of azobisisobuty-ronitrile and 24 parts of tertiary butyl perbenzoate are thus premixed and slowly added to the reactor over a eriod of 3 hours. The temperature in the reactor is main-tained at 120C. during the period of addition and for one hour thereafter.
To complete monomer conversion, 10 parts of tertiary butyl perbenzoate are added and the reaction con-tinued for one hour at 120C. and then 10 more parts of tertiary butyl perbenzoate are added and the reaction con-tinued for 2 additional hours at the same temperature.
The product is then cooled to about 70C. and 50 parts of 2-ethoxy ethanol are added and the final copolymer solution is filtered to provide a solution having a Gardner viscosity of X-Y, a Gardner-Holdt color of 8-9 and a nonvolatile solids content of 57.7%.
EA~PLE II
Preparation of pigmented acidified copolymer aaueous so ution Parts Component 223.6 solution of Example I
The invention exhibits significant superiority to all three as will be documented hereinafter.
A two package system is employed in the present invention. In one component is placed an acid-neutralized tertiary amine copolymer in solution in a water-miscible alcoholic solvent. The other component contains the epoxy resin, desirably together with a catalyst for the epoxy-tertiary amine reaction, in solution in organic solvent which is at least partially water-miscible, and which is preferably alcoholic. Before applying the coating, the two separately stable solution components are mixed together to form an aqueous mixture of limited pot life, and this aqueous mixture is coated upon the surface to be painted. The water which is present in the aqueous mixture is normally added to the first component prior to admixture of the two components, but all or a portion of the water can be added after the mixture is formed. The first com-ponent also desirably includes a surfactant for maintaining the epoxy resin in relatively stable emulsion in the aqueous mixture which is provided.
Typical coatings produced by the present inven-tion have a pot life of at least about 8 hours, usually about 12-14 hours, and can be applied by roller, brush, or air spray. The applied aqueous coatings dry to the touch in air at room temperature in about 6-7 hours and become water and solvent resistant in about 8-12 days. Recoat 1~29131 properties are comparable to that of conventional porch and floor paints. Importantly, polymer solubility is obtained using acids like lactic or acetic acid which are less toxic than anionic systems solubilized with amines, and generally less than 10% of nonobjectionable alcoholic solvents are needed which is advantageous from several well known standpoints, such as cost, hazard, pollution, and the like.
Referring more particularly to the tertiary amine copolymers, these are organic solvent-soluble copolymers comprising three copolymerized monoethylenically unsatu-rated components, namely: (1) nonreactive monomer; (2) hydroxy-functional monomer; and (3) tertiary amine monomer.
While small amounts of other monomers may be present, such as monoethylenic carboxylic acids, monoethylenic amides or M-methylol derivatives thereof, or polyethylenic hydroxy-functional materials such as polyesters, these are not necessary.
The nonreactive monoethylenically unsaturated (monoethylenic) monomer should constitute at least about 40% of the copolymer in order to provide desirably physical characteristics. Styrene is the preferred nonreactive monoethylenic monomer, but vinyl toluene is also useful.
Methyl methacrylate, acrylonitrile, and vinyl acetate will further illustrate the nonreactive monomers which are use-ful. A portion of a flexibilizing nonreactive monomer is also desirably present, such as ethyl acrylate or meth-acrylate or butyl acrylate or methacrylate. These flexi-bilizing monomers can be more generally defines as C2 -C8 alkanol esters of monoethylenic carboxylic acids.
llZ~3131 In preferred practice, the nonreactive monomercomponent will constitute from about 50V/o to about 80% of the weight of the tertiary amine copolymer, typically about 65,~o.
The monoethylenic hydroxy-functional monomer is used in an amount of from 5-35% of the weight of the tertiary amine copolymer, preferably from 10-25%, and it is important for various reasons. First, the hydroxy functionality assists in achieving water solubility with the aid of a solubilizing acid. Second, the presence of the hydroxy group is important to the ultimate cure, and this factor may be only partially satisfied by the presence of the alcoholic solvent since the bulk of the thermosetting cure ~akes place in the solid film after the water and volatile solvent have been removed.
Appropriate monomers are illustrated by hydroxy ethyl acry-late or methacrylate, and simple variations thereof, such as hydroxy propyl acrylate. Polyhydric monomers such as trimethylol propane monoacrylate are also useful, and so are unsaturated alcohols like allyl alcohol and oleyl alcohol, especially when the rest of the monomers are not acrylic, as when large amounts of styrene and/or vinyl acetate are used.
lhe term "hydroxy" refers to the alcoholic groups, and does not embrace related functionalities in which a terminal OI~ is present, such as the phenolic O~ group, the SiOH group, or the N-methylol group.
A limited proportion of polyethylenic polyester having hydroxyl functionality may be present as disclosed in United States Patent 3,506,601 dated April 14, 1970, so 3n long as it does not interfere with water solubility. This l~Z9131 material, if used, will constitute a portion of the hydroxy monomer component.
The crucial component of the tertiary amine copolymer is the monoethylenic tertiary amine monomer.
Typical tertiary amine monomers are dimethyl aminoethyl acrylate or methacrylate, dimethyl aminopropyl acrylate or methacrylate, diethyl aminomethyl acrylate or methacrylate, and diethyl aminoethyl or aminopropyl acrylate or meth-acrylate. The corresponding crotonates and tertiary amino esters of other monoethylenic carboxylic acids are also useful. ~dditionally, the corresponding amides are useful such as dimethyl aminoethyl methacrylamide.
The proportion of the tertiary amine monomer can vary in the same way as the hydroxy monomer, namely, from 5-35% by weight of the copolymer, preferably from 10-25%
by weight.
Water miscible organic solvents which are useful in this invention are preferably alcoholic and are illus-trated by ethanol, propanol, isopropanol, n-butanol, iso-butanol, 2-ethoxy ethanol and 2-butoxy ethanol.
The specific nature of the solubilizing acid used to disperse the amine copolymer in water is of secondary significance. Inorganic acids, such as hydrochloric acid or sulfuric acid, are useful, though not preferred. It is presently preferred to employ phosphoric acid, glycolic acid (hydroxy acetic acid), or acetic acid, but other acids can be used, such as formic acid or carbonic acid. Pro-pionic acid is also useful.
The solubilizing acid is used in an amount to provide a colloidal dispersion having a preferred pH in l~Z9131 the range of pH 610 - 7.0, though a pH in the range of pH3 - 8 is broadly useful.
The epoxy resins which are used in this invention can be broadly referred to as resinous polyepoxides, and those which possess a l,2-epoxy equivalency in the range of about 1.4 to about 2.0 are preferred. Polyepoxides which are diglycidyl ethers of bisphenols are particularly preferred, especially those having an average molecular weight in the range of about 350 to 4000. A diglycidyl ether of bisphenol A having an average molecular weight of about 390 will be used to illustrate the invention.
The polyepoxide component is itself conventional, as discussed in patent 3,719,62 referred to previously.
The polyepoxide is desirably used in an amount providing approximate stoichiometry between epoxy groups in the polyepoxide and tertiary nitrogen atoms in the amine copolymer, + 50V/o~ more preferably + 20%.
The organic solvent component of the package containing the polyepoxide is intended to provide desirably liquidity, particularly since the polyepoxide is normally a viscous liquid or a solid at room temperature. Since it is desired that the polyepoxide be stably dispersed in the aqueous mixture which is ultimately produced, the organic solvent should be at least partially water miscible, but the partial miscibility which is intended need merely be that which is consistent with the ultimate stable disper-sion which is contemplated, and it is most accurate to refer to the form of the dispersion as an emulsion since the presence of the polyepoxide component in the aqueous mixture which is formed is such as to induce considerably ~29~31 opacity to the liquid mixture.
A surfactant is normally included in the poly-epoxide solution in order to stabilize the aqueous emulsions which are formed. Appropriate surfactants may be nonionic or anionic and the selection of surfactants appropriate for the emulsification of epoxy resins in water is well known and is not a feature of this invention.
Surfactants are not needed, however, since the cationic copolymer itself functions to help to maintain the epoxy resin in relatively stable emulsion.
It is also permissible to include catalysts for the tertLary amine-epoxy curing reaction. This reaction is itself well known, and thus the selection of catalysts for the reac~ion is not of primary concern. Appropriate catalysts are Lewis acids, such as dibutyl tin dilaurate.
Indeed, no catalyst is needed, and none is used in the pre-ferred form of the invention.
The systems of this invention can be applied clear or pigmented, but pigmented systems containing titan-ium dioxide rutile at a pigment to binder ratio of 0.3:1.0are preferred.
The invention is illustrated in the following examples.
EXAMPLE I
Preparation of solvent soluble tertiary amine copolymer in solution in water miscible organic solvent.
1360 parts of 2-ethoxy ethanol are heated to 120C. in a reactor equipped with an agitator, a reflux condenser, a thermometer, and a nitrogen inlet tube for - il29131 sparging the reaction mixture.
Monomers and catalysts are premixed in an addition tank. 710 parts of styrene, 360 parts of hydroxy ethyl acrylate, 630 parts of butyl acrylate, 350 parts of dimethyl aminoethyl methacrylate, 24 parts of azobisisobuty-ronitrile and 24 parts of tertiary butyl perbenzoate are thus premixed and slowly added to the reactor over a eriod of 3 hours. The temperature in the reactor is main-tained at 120C. during the period of addition and for one hour thereafter.
To complete monomer conversion, 10 parts of tertiary butyl perbenzoate are added and the reaction con-tinued for one hour at 120C. and then 10 more parts of tertiary butyl perbenzoate are added and the reaction con-tinued for 2 additional hours at the same temperature.
The product is then cooled to about 70C. and 50 parts of 2-ethoxy ethanol are added and the final copolymer solution is filtered to provide a solution having a Gardner viscosity of X-Y, a Gardner-Holdt color of 8-9 and a nonvolatile solids content of 57.7%.
EA~PLE II
Preparation of pigmented acidified copolymer aaueous so ution Parts Component 223.6 solution of Example I
3 surfactant (note 1) 150 titanium dioxide rutile amorphous silica
4 Attapulgus clay ~ Note 1 - The surfactant utilized is BYK P104-S sold by Mallinckrodt Corporation.
,,~ ff~de~r)a~k _g_ ~129131 The above is ground at high speed and then slowly add, with slow agitation, 12 parts of acetic acid.
After continuing the agitation for 3 minutes, add 558.11 parts of water containing 1 part of 37V/o aqueous formalde-hyde and 1.5 parts of a biocide. The formaldehyde and the B biocide prevent the growth of mold and are optional. 1.0 part of defoamer (Drew Chemical Company L-475) may also be used, but is not necessary.
EXAMPLE III
Preparation of polyepoxide curing solution.
Parts Component D i jlyclJy~
3.04 Cigl-jcid-;l ether of bis-phenol A having an average molecular weight of 390.
10.1 2-butoxy ethanol.
EXAMPLE IV
Upon admixture of the solutions of Examples II
and III, one obtains an aqueous emulsion which has a pot life of about 8 hours. Coating this emulsion by brushing on a concrete surface followed by air drying at room temperature for 8 hours provided a painted surface which was hard enough to be walked upon without being marred.
The advantages of the invention will be apparent from the tabulated data presented below in which X indicates a positive feature, 0 indicates a negative feature, and 1 indicates neither.
~r~G/e r~u~
~lZ913~
TABLE
_ Competitive Materials in Commerce U.S. Patent Example Two-Component3,719,629 Property IV Latex Alkyd Epoxy _(Dow) Water Based X X X
Solvent Based O O
Price X X X O O
One Package X X
Two Package O O O
Ease of Clean Up X X O 0 X
Use on Pre-vious Paints X X X O X
Flammable X X 0 0 X
Use on Interior X X O O X
Hazardous 1 O
Use on Porches X X X O ?
One Coat Hide X O O X X
Alkali Resist- X X O X X
Abrasion Resistance X 1 1 X X
Chemical Resistance X 1 O X X
Hardness X O O 1 Good Adhesion X X X X X
Tire Track Adhesion X O 1 X X
Tint Retentior 1 X 1 O O
Chalking Resistance 1 X 1 O O
Cracking Resistance 1 1 1
,,~ ff~de~r)a~k _g_ ~129131 The above is ground at high speed and then slowly add, with slow agitation, 12 parts of acetic acid.
After continuing the agitation for 3 minutes, add 558.11 parts of water containing 1 part of 37V/o aqueous formalde-hyde and 1.5 parts of a biocide. The formaldehyde and the B biocide prevent the growth of mold and are optional. 1.0 part of defoamer (Drew Chemical Company L-475) may also be used, but is not necessary.
EXAMPLE III
Preparation of polyepoxide curing solution.
Parts Component D i jlyclJy~
3.04 Cigl-jcid-;l ether of bis-phenol A having an average molecular weight of 390.
10.1 2-butoxy ethanol.
EXAMPLE IV
Upon admixture of the solutions of Examples II
and III, one obtains an aqueous emulsion which has a pot life of about 8 hours. Coating this emulsion by brushing on a concrete surface followed by air drying at room temperature for 8 hours provided a painted surface which was hard enough to be walked upon without being marred.
The advantages of the invention will be apparent from the tabulated data presented below in which X indicates a positive feature, 0 indicates a negative feature, and 1 indicates neither.
~r~G/e r~u~
~lZ913~
TABLE
_ Competitive Materials in Commerce U.S. Patent Example Two-Component3,719,629 Property IV Latex Alkyd Epoxy _(Dow) Water Based X X X
Solvent Based O O
Price X X X O O
One Package X X
Two Package O O O
Ease of Clean Up X X O 0 X
Use on Pre-vious Paints X X X O X
Flammable X X 0 0 X
Use on Interior X X O O X
Hazardous 1 O
Use on Porches X X X O ?
One Coat Hide X O O X X
Alkali Resist- X X O X X
Abrasion Resistance X 1 1 X X
Chemical Resistance X 1 O X X
Hardness X O O 1 Good Adhesion X X X X X
Tire Track Adhesion X O 1 X X
Tint Retentior 1 X 1 O O
Chalking Resistance 1 X 1 O O
Cracking Resistance 1 1 1
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of providing a thermosetting aqueous epoxy resin-acrylic copolymer coating system adapted to cure on air drying comprising providing a mixture in water consisting essentially of a first component constituted by acid-neutralized organic solvent soluble tertiary amine copolymer of copolymer-ized monomers comprising at least about 40% of nonreactive monoethylenic monomer, from 5-35% of monoethylenic hydroxy-functional monomer, and from 5-35% of monoethylenic tertiary amine monomer selected from the group consisting of esters and amides of monoethylenic carboxylic acids, said copolymer being in solution in a water-miscible inert organic solvent, and a second component constituted by a resinous polyepoxide in solution in at least partially water-miscible organic solvent.
2. A thermosetting aqueous coating method as recited in claim 1 in which the polyepoxide is present in an amount providing a molar ratio of epoxy groups to tertiary amine groups of from 1.5:1 to 1:1.5.
3. A thermosetting aqueous coating method as recited in claim 1 in which said water miscible organic solvent is alcoholic.
4. A thermosetting aqueous coating method as recited in claim 1 in which said amine copolymer consists essentially of from about 50% to about 80% of said nonreactive monomer, from 10-25% of said hydroxy functional monomer, and from 10-25% of said tertiary amine monomer.
5. A thermosetting aqueous coating method as recited in claim 4 in which said hydroxy-functional monomer is an hydroxy alkyl acrylate or methacrylate.
6. A thermosetting aqueous coating method as recited in claim 4 in which said tertiary amine monomer is a dimethyl or diethyl amino alkyl acrylate, methacrylate, acrylamide or methacrylamide.
7. A thermosetting aqueous coating method as recited in claim 1 in which said component containing said polyepoxide includes a surfactant for emulsifying said polyepoxide in water.
8. A thermosetting aqueous epoxy resin-acrylic copolymer coating composition consisting essentially of a mixture of water and water-miscible inert organic solvent having dissolved therein an acid-neutralized organic solvent soluble tertiary amine copolymer of copolymerized monomers comprising at least about 40% of nonreactive monoethylenic monomer, and from 5-35%
of monoethylenic hydroxy-functional monomer, and from 5-35% of monoethylenic tertiary amine monomer selected from the group consisting of esters and amides of monoethylenic carboxylic acids, said water further having emulsified therein with the aid of a surfactant a resinous polyepoxide in solution in at least partially water-miscible inert organic solvent.
of monoethylenic hydroxy-functional monomer, and from 5-35% of monoethylenic tertiary amine monomer selected from the group consisting of esters and amides of monoethylenic carboxylic acids, said water further having emulsified therein with the aid of a surfactant a resinous polyepoxide in solution in at least partially water-miscible inert organic solvent.
9. A thermosetting aqueous composition as recited in claim 8 in which said resinous polyepoxide is a diglycidyl ether of a bisphenol having an average molecular weight in the range of 350-4000.
10. A two component pack for preparing a thermosetting aqueous epoxy resin-acrylic copolymer coating system adapted to cure on air drying, which pack comprises a first component constituted by acid-neutralized organic solvent soluble tertiary amine copolymer of copolymerized monomers comprising at least about 40% of nonreactive monoethylenic monomer, from 5 to 35% of monoethylenic hydroxy-functional monomer and from 5 to 35% of monoethylenic tertiary amine monomer selected from the group consisting of esters and amides of monoethylenic carboxylic acids, said copolymer being in solution in a water-miscible inert organic solvent, and a second component constituted by a resinous polyepoxide in solution in an at least partially water-miscible organic solvent, the two components being present in the pack in such relative proportions that on mixing of the two components and the addition of water there is obtained a thermosetting aqueous epoxy resin-acrylic copolymer coating system.
11. A two component pack according to claim 10 wherein the relative proportions of the two components are such that there is approximate stoichiometry between epoxy groups in the polyepoxide and tertiary nitrogen atoms in the amine copolymer + 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA317,715A CA1129131A (en) | 1978-12-11 | 1978-12-11 | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA317,715A CA1129131A (en) | 1978-12-11 | 1978-12-11 | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1129131A true CA1129131A (en) | 1982-08-03 |
Family
ID=4113116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA317,715A Expired CA1129131A (en) | 1978-12-11 | 1978-12-11 | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1129131A (en) |
-
1978
- 1978-12-11 CA CA317,715A patent/CA1129131A/en not_active Expired
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