CA1129132A - Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems - Google Patents
Air drying thermosetting aqueous epoxy-acrylic copolymer coating systemsInfo
- Publication number
- CA1129132A CA1129132A CA343,118A CA343118A CA1129132A CA 1129132 A CA1129132 A CA 1129132A CA 343118 A CA343118 A CA 343118A CA 1129132 A CA1129132 A CA 1129132A
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- organic solvent
- monoethylenic
- monomer
- tertiary amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
-
- 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
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D157/04—Copolymers in which only the monomer in minority is defined
Abstract
ABSTRACT OF THE DISCLOSURE
Thermosetting aqueous epoxy-ethylenically unsaturated amine co-polymer coating systems adapted to cure on air drying are provided using a first package constituted by acid-neutralized organic solvent soluble ter-tiary amine copolymer comprising at least about 60% of nonreactive mono-ethylenic monomer, and from 15-40% of monoethylenic tertiary amine monomer, said copolymer being in solution in a water miscible organic solvent, and a second component comprising a resinous polyepoxide in solution in at least partially water miscible organic solvent.
Thermosetting aqueous epoxy-ethylenically unsaturated amine co-polymer coating systems adapted to cure on air drying are provided using a first package constituted by acid-neutralized organic solvent soluble ter-tiary amine copolymer comprising at least about 60% of nonreactive mono-ethylenic monomer, and from 15-40% of monoethylenic tertiary amine monomer, said copolymer being in solution in a water miscible organic solvent, and a second component comprising a resinous polyepoxide in solution in at least partially water miscible organic solvent.
Description
1~29132 ~ he present invention relates to thermosetting aqueous epoxy-ethylenically unsaturated amine copolymer coating systems which are adapted to cure on air dryine. Such coating systems are two package systems which cure upon admixture with one another and are particularly adapted for the painting of porches and floors, including cementitious substrates.
Aqueous coating compositions of the general type under considera-tion are in commerce, being produced under the disclosure of United States Patent 3,719,629 issued March 6, 1973. These known compositions are not only expensive, but they exhibit poor chalking resistance, and poor tint reten-tion. They are also marginal from the standpoints of (1) applicability toporches; (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 for-mula:
-C - 0 - cH2- CH2- N~H
and the cure is between the oxirane (epoxy) group in the epoxy resin and the amino hydrogen atoms in the aminoethyl group pictured. In the present inven-tion, the amino hydrogen atoms which are essential in the prior art are not present Moreover, the production of the pendant aminoethyl groups in the prior art required the use of expensive and hazardous ethylene imine, and thi~ is avoided in this invention.
From the broader standpoint, and in addition to the aqueous epoxy ~ystem noted previously, other resin systems have been employed to provide air drying porch and floor paints. Thus, the systems of this invention are intended to replace two existing aqueous systems, one based on an alkyd resin " ~
~12913Z
and another based on an aqueous copolymer latex, and also to replace an or-ganic solvent-based epoxy system. The invention exhibits significant supe-riority to all three as will be documented hereinafter.
In one aspect, the present invention provides a method of providing a thermosetting aqueous epoxy resin-ethylenically unsaturated amine 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 copolymerized monomers substantially free of hydroxy functionality and comprising at least about 60% of nonreactive monoethylenic monomer, and from 15-~0% of mono-ethylenic tertiary amine monomer selected from the group consisting of ter~
tiary amino esters and tertiary amino 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 so-lution in at least partially watermiscible organic solvent.
In another aspect, the invention provides a thermosetting aqueous epoxy resin-acrylic copolymer coating composition consisting essentially of water having dissolved therein an acid-neutralized organic solvent soluble tertiary amine copolymer of copolymerized monomers substantially free of hydroxy functionality and comprising at least about ~0% of nonreactive mono-ethylenic monomer, and from 15-40% of monoethylenic tertiary amine monomer selected from the group consisting of esters and amides of monoethylenic car-boxylic acias, said water further having emulsified therein with the aid of a surfactant a resinous polyepoxide.
In yet another aspect, the invention provides a two component pack for preparing a thermosetting aqueous epoxy resin-ethylenically unsaturated amine copolymer coating system which pack comprises a first component con-stituted by acid-neutralized organic solvent soluble tertiary amine copolyer ~129132 of copolymerized monomer substantially free of hydroxy functionality and com-prising at least about 60% of non-reactive monoethylenic monomer; and from 15 - 40% of monoethylenic tertiary amine monomer selected from the group con-sisting of tertiary amino esters and tertiary ~mino amides of monoethylenic acids, said copolymer being in solution in a watermiscible inert organic sol-vent, and a second component constituted by a resinous polyepoxide in solu-tion in an at least partially watermiscible 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 aque-ous epoxy resin-ethylenically unsaturated amine copolymer coating system.
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 watermiscible alcoholic solvent. The other component contains the epoxy resin, desirably together with a catalyst for the epoxy-tertiary amine reac-tion, 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. ~he water which is present in the aqueous mixture is normally added to the first compocent prior to admixture of the two com-ponents, but all or a portion of the water can be added after the mixture is formed. The first component also desirably includes a surfactant for main-taining the epoxy resin in relatively stable emulsion in the aqueous mixture which is provided.
Typical coatings produced by the present invention have a pot life of at least about ô 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 , - 3 -, :, l~Z9132 resistant in about 8-12 days. Recoat propertie~ are comparable to that of conventional porch and floor paints. Importantly, polymer solubility i8 ob-tained using acids like lactic or acetic acid which are less toxic than anionic systems solubilized with a~ines, and generally less than 10% of non-objectionable alcoholic solvents are needed which is advantageous from sev-eral 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 two copolymerized mono-ethylenically unsaturated components, namely: (1) nonreactive monomeri and
Aqueous coating compositions of the general type under considera-tion are in commerce, being produced under the disclosure of United States Patent 3,719,629 issued March 6, 1973. These known compositions are not only expensive, but they exhibit poor chalking resistance, and poor tint reten-tion. They are also marginal from the standpoints of (1) applicability toporches; (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 for-mula:
-C - 0 - cH2- CH2- N~H
and the cure is between the oxirane (epoxy) group in the epoxy resin and the amino hydrogen atoms in the aminoethyl group pictured. In the present inven-tion, the amino hydrogen atoms which are essential in the prior art are not present Moreover, the production of the pendant aminoethyl groups in the prior art required the use of expensive and hazardous ethylene imine, and thi~ is avoided in this invention.
From the broader standpoint, and in addition to the aqueous epoxy ~ystem noted previously, other resin systems have been employed to provide air drying porch and floor paints. Thus, the systems of this invention are intended to replace two existing aqueous systems, one based on an alkyd resin " ~
~12913Z
and another based on an aqueous copolymer latex, and also to replace an or-ganic solvent-based epoxy system. The invention exhibits significant supe-riority to all three as will be documented hereinafter.
In one aspect, the present invention provides a method of providing a thermosetting aqueous epoxy resin-ethylenically unsaturated amine 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 copolymerized monomers substantially free of hydroxy functionality and comprising at least about 60% of nonreactive monoethylenic monomer, and from 15-~0% of mono-ethylenic tertiary amine monomer selected from the group consisting of ter~
tiary amino esters and tertiary amino 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 so-lution in at least partially watermiscible organic solvent.
In another aspect, the invention provides a thermosetting aqueous epoxy resin-acrylic copolymer coating composition consisting essentially of water having dissolved therein an acid-neutralized organic solvent soluble tertiary amine copolymer of copolymerized monomers substantially free of hydroxy functionality and comprising at least about ~0% of nonreactive mono-ethylenic monomer, and from 15-40% of monoethylenic tertiary amine monomer selected from the group consisting of esters and amides of monoethylenic car-boxylic acias, said water further having emulsified therein with the aid of a surfactant a resinous polyepoxide.
In yet another aspect, the invention provides a two component pack for preparing a thermosetting aqueous epoxy resin-ethylenically unsaturated amine copolymer coating system which pack comprises a first component con-stituted by acid-neutralized organic solvent soluble tertiary amine copolyer ~129132 of copolymerized monomer substantially free of hydroxy functionality and com-prising at least about 60% of non-reactive monoethylenic monomer; and from 15 - 40% of monoethylenic tertiary amine monomer selected from the group con-sisting of tertiary amino esters and tertiary ~mino amides of monoethylenic acids, said copolymer being in solution in a watermiscible inert organic sol-vent, and a second component constituted by a resinous polyepoxide in solu-tion in an at least partially watermiscible 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 aque-ous epoxy resin-ethylenically unsaturated amine copolymer coating system.
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 watermiscible alcoholic solvent. The other component contains the epoxy resin, desirably together with a catalyst for the epoxy-tertiary amine reac-tion, 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. ~he water which is present in the aqueous mixture is normally added to the first compocent prior to admixture of the two com-ponents, but all or a portion of the water can be added after the mixture is formed. The first component also desirably includes a surfactant for main-taining the epoxy resin in relatively stable emulsion in the aqueous mixture which is provided.
Typical coatings produced by the present invention have a pot life of at least about ô 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 , - 3 -, :, l~Z9132 resistant in about 8-12 days. Recoat propertie~ are comparable to that of conventional porch and floor paints. Importantly, polymer solubility i8 ob-tained using acids like lactic or acetic acid which are less toxic than anionic systems solubilized with a~ines, and generally less than 10% of non-objectionable alcoholic solvents are needed which is advantageous from sev-eral 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 two copolymerized mono-ethylenically unsaturated components, namely: (1) nonreactive monomeri and
(2) tertiary amine monomer. ~1hile small amounts of other monomers may be present, such as monoethylenic carboxylic acids, monoethylenic amides or N-methylol derivatives thereof, or polyethylenic hydroxyfunctional materials such as polyesters, these are not necessary.
The nonreactive monoethylenically unsaturated (monoethylenic) monomer should constitute at least about 60% of the copolymer in order to provide desirably physical characteristics. Styrene is the preferred non-reactive monoethylenic monomer, but vinyl toluene is also useful. Methyl methacrylate, acrylonitrile, and vinyl acetate will further illustrate the nonreactive monomers which are useful. A portion of a flexibilizing non-reactive monomer is also desirably present, such as ethyl acrylate or meth-acrylate or butyl acrylate or methacrylate. These flexibilizing monomers can be more generally defined as C2 - C18 alkanol esters of monoethylenic car-boxylic acids.
In preferred practice, the nonreactive monomer component will con-stitute from about 60% to about 85% of the weight of the tertiary amine co-polymer, typically about 73%.
Our copending application Serial No. 317,715, filed December 11, 1978 is concerned with thermosetting aqueous epoxy resin-acrylic copolymer ~129~3Z
coating compositions consisting essentially of water having dissolved therein an acid-neutralized organic solvent soluble tertiary amine copolymer of co-polymerized monomers comprising at least about 40% of nonreactive monoethyl-enic monomer, and from 5-35% of monoet~ylenic hydroxyfunctional 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 o~ a surfactant a resinous polyepoxide.
In that application, monoethylenic hydro~yfunctional monomer was used in an amount of from 5-35% of the weight of the tertiary amine copolymer for various reasons. First, the hydroxy functionality assists in achieving water solubility with the aid of a solubilizing acid, but with an increased proportion of the amine monomer, this is not essential. Second, the presence of the primary hydroxy group provided by the hydroxy functional monomer helps the ultimate cure. It has now been found that with enough amine monomer, the secondary hydroxyl groups provided by the epoxy component provides a satis-factory cure. Also, sufficient reaction involving the tertiary amine group adequately couples the acrylic copolymer and the epoxy resin in the film which is formed.
The crucial component of the tertiary amine copolymer is t~e mono-ethylenic tertiary amine monomer. Typical tertiary amine monomers are di-methyl aminoethyl acrylate or methacrylate, dimethyl aminopropyl acrylate or methacrylate, diethyl aminomethyl acrylate or methacrylate, and diethyl amino-ethyl or aminopropyl acrylate or methacrylate. The corresponding crotonates ~nd tertiary amino esters of other monoethylenic carboxylic acids are also useful. Additionally, the corresponding amides are useful such as dimethyl aminoethyl methacrylamide.
The proportion of the tertiary amine monomer can vary in the same 112~13Z
way as the hydroxy monomer, namely, from 15-40% by weight of the copoly~er, preferably from 20-30% by weight.
Water miscible organic solvents whicb are useful in this invention are preferably alcoholic and are illustrated by ethanol, propanol, iso-propanol, n-butanol, isobutanol, 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. Propionic acid is also useful.
The solubili~ing acid is used in an amount to provide a colloidal dispersion having a preferred pX in the range of pH 6.o - 7.o, though a pH
in the ran8e of pH3 - 8 is broadly useful.
The epoxy resins which are used in this i-nvention can be broadly referred to as resinous polyepoxides, and those which possess a 1, 2-epoxy equivalency in the range of about 1.4 to about 2.0 are preferred. Poly-epoxides 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 i6 itself conventional, as discussed in patent 3,719,629 referred to previou~ly.
The polyepoxide is desirably used in an amount providing approx-imate stoichiometry between epoxy groups in the polyepoxide and tertiary nitroger atoms in the amine copolymer~ + 50%, more preferably + 20%.
The organic solvent component of the package containing the poly-epoxide is intended to provide desirably liquidity, particularly since the llZ9132 polyepoxide is normally a viæcous liquid or a solid at room temperature.Since it i8 clesired 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 wit~ the ultimate stable dispersion which is contemplated, and it is most accurate to refer to the form of the disper-sion aæ an emulsion since the presence of the polyepoxide component in the aqueous mixture which is formed is such as to induce considerably opacity to the liquid mixture.
A surfactant is normally included in the polyepoxide solution in order to stabilize the aqueous emulsions which are formed. Appropriate sur-factants may be nonionic or anionic and the selection of surfactants appro-priate 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 tertiary amine-epoxy curing reaction. ~his reaction is itself well known, and thus the se-lection of catalysts for the reaction is not of primary concern. Appropriate catalysts are Lewis acids, such as dibutyl tin dilaurate. Indeed, no cat-alyst is needed, and none is used in the preferred form of the invention.
The systems of this invention can be applied clear or pigmented, but pigmented systems containing titanium dioxide rutile at a pigment to binder ratio of 0.3:1.0 are preferred.
The invention is illustrated in the following examples.
Pre~aration of solvent soluble tertiary amine copol~mer in solution in water miscible organic solvent.
~50 parts of 2-butoxy ethanol are heated to 120C. in a reactor l~Z9~32 equipped with an agitator, a reflux condenser, a thermometer, and a nitrogen inlet tube for sparging the reaction mixture.
~ onomers and catalysts are premixed in an addition tank. 900 parts of styrene, 630 parts of butyl acrylate, 560 parts oY dimethyl a~inoethyl methacrylate and 30 parts of azobisisobutyronitrile are thus premixed and slowly added to the reactor over a period of 3 hours. The temperature in the reactor is maintained at 120C. during the period of addition and for one hour thereafter.
To complete monomer conversion, 2 parts of azobisisobutyronitrile are added and the reaction continued for one hour at 120 C. and then 2 more parts of the same catalyst and the reaction continued for 2 additional hours at the same temperature.
The product is then cooled to about 70 C. and 250 parts of 2-butoxy ethanol are added together with 700 parts of 2-ethoxy ethanol and the final copolymer solution is filtered to provide a solution having a Gardner vis-cosity of Zl~ a Gardner-Holdt color of 1-2 and a nonvolatile solids content of 58.~%.
Preparation of pigmented acidified copolymer aqueous solution.
Parts Component 223.6 solution of Example 1
The nonreactive monoethylenically unsaturated (monoethylenic) monomer should constitute at least about 60% of the copolymer in order to provide desirably physical characteristics. Styrene is the preferred non-reactive monoethylenic monomer, but vinyl toluene is also useful. Methyl methacrylate, acrylonitrile, and vinyl acetate will further illustrate the nonreactive monomers which are useful. A portion of a flexibilizing non-reactive monomer is also desirably present, such as ethyl acrylate or meth-acrylate or butyl acrylate or methacrylate. These flexibilizing monomers can be more generally defined as C2 - C18 alkanol esters of monoethylenic car-boxylic acids.
In preferred practice, the nonreactive monomer component will con-stitute from about 60% to about 85% of the weight of the tertiary amine co-polymer, typically about 73%.
Our copending application Serial No. 317,715, filed December 11, 1978 is concerned with thermosetting aqueous epoxy resin-acrylic copolymer ~129~3Z
coating compositions consisting essentially of water having dissolved therein an acid-neutralized organic solvent soluble tertiary amine copolymer of co-polymerized monomers comprising at least about 40% of nonreactive monoethyl-enic monomer, and from 5-35% of monoet~ylenic hydroxyfunctional 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 o~ a surfactant a resinous polyepoxide.
In that application, monoethylenic hydro~yfunctional monomer was used in an amount of from 5-35% of the weight of the tertiary amine copolymer for various reasons. First, the hydroxy functionality assists in achieving water solubility with the aid of a solubilizing acid, but with an increased proportion of the amine monomer, this is not essential. Second, the presence of the primary hydroxy group provided by the hydroxy functional monomer helps the ultimate cure. It has now been found that with enough amine monomer, the secondary hydroxyl groups provided by the epoxy component provides a satis-factory cure. Also, sufficient reaction involving the tertiary amine group adequately couples the acrylic copolymer and the epoxy resin in the film which is formed.
The crucial component of the tertiary amine copolymer is t~e mono-ethylenic tertiary amine monomer. Typical tertiary amine monomers are di-methyl aminoethyl acrylate or methacrylate, dimethyl aminopropyl acrylate or methacrylate, diethyl aminomethyl acrylate or methacrylate, and diethyl amino-ethyl or aminopropyl acrylate or methacrylate. The corresponding crotonates ~nd tertiary amino esters of other monoethylenic carboxylic acids are also useful. Additionally, the corresponding amides are useful such as dimethyl aminoethyl methacrylamide.
The proportion of the tertiary amine monomer can vary in the same 112~13Z
way as the hydroxy monomer, namely, from 15-40% by weight of the copoly~er, preferably from 20-30% by weight.
Water miscible organic solvents whicb are useful in this invention are preferably alcoholic and are illustrated by ethanol, propanol, iso-propanol, n-butanol, isobutanol, 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. Propionic acid is also useful.
The solubili~ing acid is used in an amount to provide a colloidal dispersion having a preferred pX in the range of pH 6.o - 7.o, though a pH
in the ran8e of pH3 - 8 is broadly useful.
The epoxy resins which are used in this i-nvention can be broadly referred to as resinous polyepoxides, and those which possess a 1, 2-epoxy equivalency in the range of about 1.4 to about 2.0 are preferred. Poly-epoxides 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 i6 itself conventional, as discussed in patent 3,719,629 referred to previou~ly.
The polyepoxide is desirably used in an amount providing approx-imate stoichiometry between epoxy groups in the polyepoxide and tertiary nitroger atoms in the amine copolymer~ + 50%, more preferably + 20%.
The organic solvent component of the package containing the poly-epoxide is intended to provide desirably liquidity, particularly since the llZ9132 polyepoxide is normally a viæcous liquid or a solid at room temperature.Since it i8 clesired 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 wit~ the ultimate stable dispersion which is contemplated, and it is most accurate to refer to the form of the disper-sion aæ an emulsion since the presence of the polyepoxide component in the aqueous mixture which is formed is such as to induce considerably opacity to the liquid mixture.
A surfactant is normally included in the polyepoxide solution in order to stabilize the aqueous emulsions which are formed. Appropriate sur-factants may be nonionic or anionic and the selection of surfactants appro-priate 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 tertiary amine-epoxy curing reaction. ~his reaction is itself well known, and thus the se-lection of catalysts for the reaction is not of primary concern. Appropriate catalysts are Lewis acids, such as dibutyl tin dilaurate. Indeed, no cat-alyst is needed, and none is used in the preferred form of the invention.
The systems of this invention can be applied clear or pigmented, but pigmented systems containing titanium dioxide rutile at a pigment to binder ratio of 0.3:1.0 are preferred.
The invention is illustrated in the following examples.
Pre~aration of solvent soluble tertiary amine copol~mer in solution in water miscible organic solvent.
~50 parts of 2-butoxy ethanol are heated to 120C. in a reactor l~Z9~32 equipped with an agitator, a reflux condenser, a thermometer, and a nitrogen inlet tube for sparging the reaction mixture.
~ onomers and catalysts are premixed in an addition tank. 900 parts of styrene, 630 parts of butyl acrylate, 560 parts oY dimethyl a~inoethyl methacrylate and 30 parts of azobisisobutyronitrile are thus premixed and slowly added to the reactor over a period of 3 hours. The temperature in the reactor is maintained at 120C. during the period of addition and for one hour thereafter.
To complete monomer conversion, 2 parts of azobisisobutyronitrile are added and the reaction continued for one hour at 120 C. and then 2 more parts of the same catalyst and the reaction continued for 2 additional hours at the same temperature.
The product is then cooled to about 70 C. and 250 parts of 2-butoxy ethanol are added together with 700 parts of 2-ethoxy ethanol and the final copolymer solution is filtered to provide a solution having a Gardner vis-cosity of Zl~ a Gardner-Holdt color of 1-2 and a nonvolatile solids content of 58.~%.
Preparation of pigmented acidified copolymer aqueous solution.
Parts Component 223.6 solution of Example 1
3 surfactant ~note 1) 150 titanium dioxide rutile amorphous silica ~ Attapulgus clay -Note 1 - The surfactant utilized is the American Cyanamide product Aerosol C-61 which is a cationic surfactant.
Surfactant selection is not critical.
The above is ground at high speed and then 510wly 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 37% aqueous formal-dehyde and 1.5 parts of a biocide. The formaldehyde and the 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 pol.YePoxide curing solution.
Pa Component 3.04 Diglycidyl ether of bisphenol 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 ô hours. Coating this emul-sion by brushing on a concrete surface followed by air drying at room temper-ature 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, O indicates a negative feature, and 1 indicates neither.
_ g _ 1129~32 TABLE
Competitive Materials in Commerce United States Example Two-Component Patent 3,719,629 Property I~ Latex Alkyd Epoxy (Dow) Water Based X X l X
Solvent Based O O
Price X X X O O
One Package X X
Two Package O ~ O O
Ease of Clean X X O O X
Up Use on Previous Paints X X X O X
Flammable X X O O 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 Resis- X X O X X
tance Abrasion Resistance X 1 1 X X
Chemical Resistance X 1 O X X
Hardness X O O 1 1 Good Adhesion X X X X X
Tire Track Adhesion X O 1 X X
Tint Retention 1 X 1 O O
Chalking Resis-tance 1 X 1 O O
Cracking Resis-tance 1 1 ?
Surfactant selection is not critical.
The above is ground at high speed and then 510wly 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 37% aqueous formal-dehyde and 1.5 parts of a biocide. The formaldehyde and the 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 pol.YePoxide curing solution.
Pa Component 3.04 Diglycidyl ether of bisphenol 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 ô hours. Coating this emul-sion by brushing on a concrete surface followed by air drying at room temper-ature 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, O indicates a negative feature, and 1 indicates neither.
_ g _ 1129~32 TABLE
Competitive Materials in Commerce United States Example Two-Component Patent 3,719,629 Property I~ Latex Alkyd Epoxy (Dow) Water Based X X l X
Solvent Based O O
Price X X X O O
One Package X X
Two Package O ~ O O
Ease of Clean X X O O X
Up Use on Previous Paints X X X O X
Flammable X X O O 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 Resis- X X O X X
tance Abrasion Resistance X 1 1 X X
Chemical Resistance X 1 O X X
Hardness X O O 1 1 Good Adhesion X X X X X
Tire Track Adhesion X O 1 X X
Tint Retention 1 X 1 O O
Chalking Resis-tance 1 X 1 O O
Cracking Resis-tance 1 1 ?
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of providing a thermosetting aqueous epoxy resin-ethylenically unsaturated amine 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 copolymerized monomers substantially free of hydroxy functionality and comprising at least about 60% of non-reactive mono-ethylenic monomer, and from 15-40% of monoethylenic tertiary amine monomer selected from the group consisting of tertiary amino esters and tertiary amino amides of monoethylenic carboxylic acids, said copolymer being in solu-tion in a water miscible inert organic solvent, and a second component con-stituted by a resinous polyepoxide in solution in at least partially water-miscible organic solvent.
2. A method according to claim 1 in which the polyepoxide is used in an amount providing approximate stoichiometry between epoxy groups in the polyepoxide and tertiary nitrogen atoms in the amine copolymer - 50%.
3. A method according to claim 1 in which said water miscible organic solvent is alcoholic.
4. A method according to claim 1 in which said amine copolymer con-sists essentially of from about 60% to about 85% of said nonreactive monomer, and from 20-30% of said tertiary amine monomer.
5. A method according to claim 4 in which said tertiary amine mon-omer is a dimethyl or diethyl amino aIkyl acrylate, methacrylate, acrylamide or methacrylamide.
6. A method according to claim 1 in which said component containing said polyepoxide includes a surfactant for emulsifying said polyepoxide in water.
7. A thermosetting aqueous epoxy resin-acrylic copolymer coating composition consisting essentially of water having dissolved therein an acid-neutralized organic solvent soluble tertiary amine copolymer of copolymerized monomers substantially free of hydroxy functionality and comprising at least about 60% of nonreactive monoethylenic monomer, and from 15-40% of mono-ethylenic tertiary amine monomer selected from the group consisting of esters and amides of monoethylenic carboxylic acids, said water further having emul-sified therein with the aid of a surfactant a resinous polyepoxide.
8. A thermosetting aqueous composition as recited in claim 7 in which said resinous polyepoxide is a diglycidyl ether of a bisphenol having an average molecular weight in the range of 350-4000.
9. A thermosetting aqueous epoxy resin-acrylic copolymer coating mixture which cures on air drying consisting essentially of an aqueous mix-ture constituted by an acid-neutralized organic solvent soluble tertiary amine copolymer of copolymerized monomers comprising at least about 40% of nonreactive monoethylenic monomer, and from 15-40% 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 mixture of water and a water miscible inert organic solvent, and a resinous poly-epoxide in solution in at least partially water miscible inert organic sol-vent emulsified in said copolymer solution.
10. A two component pack for preparing a thermosetting aqueous epoxy resin-ethylenically unsaturated amine copolymer coating system which pack comprises a first component constituted by acid-neutralized organic solvent soluble tertiary amine copolymer of copolymerized monomer substantially free of hydroxy functionality and comprising at least about 60% of non-reactive monoethylenic monomer, and from 15-40% of monoethylenic tertiary amine mon-omer selected from the group consisting of tertiary amino esters and tertiary amino amides of monoethylenic acids, said copolymer being in solution in a watermiscible inert organic solvent, and a second component constituted by a resinous polyepoxide in solution in an at least partially watermiscible sol-vent, the two components being present in the pack in such relative propor-tions that on mixing of the two components and the addition of water there is obtained a thermosetting aqueous epoxy resin-ethylenically unsaturated amine 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 stoi-chiometry between epoxy groups in the polyepoxide and tertiary nitrogen atoms in the amine copolymer - 50%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US001,749 | 1979-01-08 | ||
| US06/001,749 US4217261A (en) | 1976-12-20 | 1979-01-08 | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1129132A true CA1129132A (en) | 1982-08-03 |
Family
ID=21697660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA343,118A Expired CA1129132A (en) | 1979-01-08 | 1980-01-04 | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5592729A (en) |
| CA (1) | CA1129132A (en) |
| DE (1) | DE2948965A1 (en) |
| FR (1) | FR2445851A1 (en) |
| GB (1) | GB2039912A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1983001624A1 (en) * | 1981-11-09 | 1983-05-11 | Sandoz Ag | Lacquer composition and utilization thereof in the leather and textile fields |
| JPS6026061A (en) * | 1983-07-25 | 1985-02-08 | Fuji Photo Film Co Ltd | Paint for film cartridge made of metal |
-
1979
- 1979-12-05 DE DE19792948965 patent/DE2948965A1/en not_active Withdrawn
- 1979-12-26 JP JP17023079A patent/JPS5592729A/en active Pending
-
1980
- 1980-01-04 FR FR8000135A patent/FR2445851A1/en not_active Withdrawn
- 1980-01-04 CA CA343,118A patent/CA1129132A/en not_active Expired
- 1980-01-08 GB GB8000564A patent/GB2039912A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5592729A (en) | 1980-07-14 |
| FR2445851A1 (en) | 1980-08-01 |
| GB2039912A (en) | 1980-08-20 |
| DE2948965A1 (en) | 1980-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0048128B2 (en) | Coating compositions | |
| US4151143A (en) | Surfactant-free polymer emulsion coating composition and method for preparing same | |
| KR970001719B1 (en) | Ambient temperature curing compositions containing a hydroxy component and an anhydride component and an onium salt | |
| CA2124235C (en) | Aqueous coating composition | |
| TW416976B (en) | Process for producing multilayer coatings | |
| US4244850A (en) | Air curable latex | |
| EP0980408A1 (en) | Waterborne coating compositions for metal containers | |
| JPS5825388B2 (en) | Matsutannicarboxyrki | |
| JPH06248229A (en) | Coating medium and its use for production of acid-resistant coating | |
| JPH0692562B2 (en) | High solids coating composition containing polyepoxide and copolymer of α-olefin and olefinically unsaturated monoanhydride | |
| EP0414752B1 (en) | Water-based coating compositions | |
| JPS6287288A (en) | Method of feeding composite film to base material | |
| US4133790A (en) | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems | |
| EP0183463B1 (en) | Low temperature curing maintenance coatings | |
| US4906726A (en) | Water-based coating compositions containing hydroxides and oxides of calcium, strontium and barium | |
| US4049607A (en) | Heat convertible coating compositions | |
| CA1129132A (en) | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems | |
| US4104230A (en) | Two-package polymeric compositions | |
| US3136733A (en) | Highway marking composition | |
| US4217261A (en) | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems | |
| CA1301988C (en) | Process for preparing aqueous paint composition | |
| JPH0621275B2 (en) | Thermosetting coating composition | |
| JPH0673335A (en) | Water-base coating composition and its use for coating substrate | |
| US4560736A (en) | Water-thinnable coating compositions from aminoalkyl carboxylate hydrohalide polymers | |
| CA1129131A (en) | Air drying thermosetting aqueous epoxy-acrylic copolymer coating systems |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |