CA2099860A1 - Aqueous coating composition and its use for coating substrates - Google Patents
Aqueous coating composition and its use for coating substratesInfo
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- CA2099860A1 CA2099860A1 CA 2099860 CA2099860A CA2099860A1 CA 2099860 A1 CA2099860 A1 CA 2099860A1 CA 2099860 CA2099860 CA 2099860 CA 2099860 A CA2099860 A CA 2099860A CA 2099860 A1 CA2099860 A1 CA 2099860A1
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- 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
- 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
- C08G59/145—Compounds containing one epoxy group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Wood Science & Technology (AREA)
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- General Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
AN AQUEOUS COATING COMPOSITION AND
ITS USE FOR COATING SUBSTRATES
ABSTRACT OF THE DISCLOSURE
The present invention relates to aqueous coating compositions containing an aqueous solution and/or dispersion of a) a polyacrylate component which contains at least one copolymer having carboxylic and/or sulphonic acid groups which may be at least partially present in salt form, is based on the reaction product of olefinically unsaturated monomers and has an acid number of 30 to 240 mg KOH/g, a hydroxyl number of O to 180 mg KOH/g, and a molecular weight (Mn) of 500 to 50,000, b) an epoxide component which contains b1) at least one aliphatic or cycloaliphatic epoxy resin having an average of at least 2 epoxide groups per molecule and containing 0.2 to 2.0 equivalents of epoxide per 100 g of resin and b2) up to 20 wt.%, based on the weight of b1), of at least one aliphatic monoepoxide with 7 to 25 carbon atoms, c) up to 10 wt.%, based on the total weight of components a) to e), of one or more organic, water-miscible solvents, d) up to 5 wt.%, based on the total weight of components a) to e), of one or more external emulsifiers and e) optionally other known coatings additives, wherein the equivalent ratio of unneutralized acid groups of component a) to epoxide groups of component b) is 1:0.5 to 1:3.
The present invention also relates to the use of these coating compositions for the production of coatings for curing at 5 to 140°C on any desired substrates.
ITS USE FOR COATING SUBSTRATES
ABSTRACT OF THE DISCLOSURE
The present invention relates to aqueous coating compositions containing an aqueous solution and/or dispersion of a) a polyacrylate component which contains at least one copolymer having carboxylic and/or sulphonic acid groups which may be at least partially present in salt form, is based on the reaction product of olefinically unsaturated monomers and has an acid number of 30 to 240 mg KOH/g, a hydroxyl number of O to 180 mg KOH/g, and a molecular weight (Mn) of 500 to 50,000, b) an epoxide component which contains b1) at least one aliphatic or cycloaliphatic epoxy resin having an average of at least 2 epoxide groups per molecule and containing 0.2 to 2.0 equivalents of epoxide per 100 g of resin and b2) up to 20 wt.%, based on the weight of b1), of at least one aliphatic monoepoxide with 7 to 25 carbon atoms, c) up to 10 wt.%, based on the total weight of components a) to e), of one or more organic, water-miscible solvents, d) up to 5 wt.%, based on the total weight of components a) to e), of one or more external emulsifiers and e) optionally other known coatings additives, wherein the equivalent ratio of unneutralized acid groups of component a) to epoxide groups of component b) is 1:0.5 to 1:3.
The present invention also relates to the use of these coating compositions for the production of coatings for curing at 5 to 140°C on any desired substrates.
Description
2 0 ~
Mo3923-us LeA ~9,157 AN AQUEOUS COATING COMPOSITION AND
BACKGROUND ~F THE INVENTION
Field of the Invention The present invention relates to a new aqueous coating composition containing polyacrylate resins which have carboxylic and/or sulphonic acid functionality and are dissolved and/or dispersed in water as an essential binder component and (cyclo)aliphatic epoxy resins as curing agents, and the use of the coating compositions for the production of coatings.
Description of the Prior Art Today aqueous coating compositions are gaining increasing importance for ecological and economic reasons. The replacement of coating compositions conventionally dissolved in organic solvents is, however, technically difficult for various reasons.
Aqueous binders based on alkyd resins and polyesters have a marked tendency to saponification. The saponification causes a reduction of molecular weight, which leads to a loss of quality of the binder and the coatings obta1ned therefrom. In addition, the storability of such binders is considerably reduced.
Frequently, therefore, binders dissolved in purely organic solvents are produced or sold, and are then diluted further with water for application. During application these systems release, in addition to water, the organic solvents contained in the system. The ability to dilute these anionic binders with water is obtained only by neutralization with bases, usually organic amines. During curing, these amines are also released. As a rule, complicated incinerators are then necessary industrially in order to remove the organic constituents from the waste air, while in do-it-yourself 35376TWR2g 1 9 2~
applications, these constituents are emitted into the ambient air.
Another problem of these water-based coating compositions is the distinctive viscosity anomaly. On dilution of the aqueous lacquer solutions, the viscosity initially increases and then decreases rapidly after passing a maximum. Because the coating compositions react to small water additions with considerable viscosity changes, they require particularly careful handling.
A further disadvantage, in particular for stoving systems containing polyester or alkyd resins in combination with melamine resins as crosslinkers, is the relatively high curing temperature, which is usually at least 120C. This requires a high expenditure of energy for curing the system. For many applications, such as the repair coating of automobiles, curing is not possible under such temperature conditions. As a rule, coating compositions are required that are curable at the lowest possible temperatures and yet have suffic;ent water- and solvent-resistance after curing. Ideal binders would be usable, e.g., in the automobile field, both at temperatures below 100C for repair coating and at higher temperature for original equipment manufacture (OEM).
Other crosslinking mechanisms, such as the crosslinking of OH-functional polymers with polyisocyanates, have some advantages when compared to crosslinking with melamine resins.
Thus, the curing can be carried out at room temperature or, accelerated, at 80 to 120-C. The coatings obtained in this way possess a good mechanical property profile and are generally resistant to gasoline and water. However, there are problems when it is intended to apply this crosslinking principle to aqueous formulations, since the isocyanates are reactive with water. It was previously common to apply such systems in purely organic solution resulting in the disadvantages mentioned with regard to the emission of organic solvents.
Mo3923 Only recently have special aqueous coating compositions become known (e.g. DE-OS 3,8291587) to overcome these problems.
These compositions contain combinations of polyhydroxy compounds and polyisocyanates with free isocyanate groups as binders which are dissolved and/or dispersed in water. Yet the difficulty remains that the side reactions of NCO groups with water can interfere with the actual cross-linking reaction, e.g., when detailed instructions about the composition of the lacquer recipe and the curing conditions are not followed.
B;nders based on a polymer containing amino or ammonium groups and epoxides also have a high reactivity and can be cured at temperatures below 100C. However, the basic groups needed for compatibility with water render the crosslinked coatings highly hydrophilic, which has a negative effect on their water resistance.
Accordingly, it is an obiect of the present invention to provide a new coating composition which may be applied an aqueous phase substantially free of co-solvent, is dilutable without the viscosity anomaly, can be cured over a wide temperature range (in particular at only moderately elevated temperatures or room temperature), has a long processing time and possesses good water resistance water resistance.
These objects may be achieved with the preparation of the coating compositions according to the invention which are described in more detail below.
SUMMARY OF THE INVENTION
The present invention relates to aqueous coating compositions containing an aqueous solution and/or dispersion of a) a polyacrylate component which contains at least one copolymer having carboxylic and/or sulphonic acid groups which may be at least partially present in salt form, is based on the reaction product of oleflnically unsaturated monomers and has an acid number of 30 to 240 mg KOH/g, a Mo3923 2~99~
hydroxyl number of 0 to 180 mg KOH/g, and a molecular weight (Mn) of 500 to SO,OOO, b) an epoxide component which contains bl) at least one aliphatic or cycloaliphatic epoxy resin having an average of at least 2 epoxide groups per molecule and containing 0.2 to 2.0 equivalents of epoxide per 100 g of resin and b2) up to 20 wt.%, based on the weight of bl), of at least one aliphatic monoepoxide with 7 to 25 carbon atoms, c) up to 10 wt.%, based on the total weight of components a) to e), of one or more organic, water-miscible solvents, d) up to 5 wt.%, based on the total weight of components a) to e), of one or more external emulsifiers and e) optionally other known coatings additiv~s, wherein the equivalent ratio of unneutralized acid groups of component a) to epoxide groups of component b) is 1:0.5 to 1:3.
The present invention also relates to the use of these coating compositions for the production of coatings for curing at 5 to 140C on any desired substrates.
DETAILED DESCRIPTION OF THE INVENTION
Component a) is selected from copolymers having carboxylic or sulphonic acid groups, acid numbers of about 30 to 240 mg KOH/g and hydroxyl nUmbersof o to about 180 mg KOH/g. The acid number includes both free, i.e., unneutralized, acid groups, particularly carboxyl groups, and also neutralized acid groups, in particular carboxylate groups. Preferably, 0 to 30 wt.% of the ac~d groups are present in neutralized form. In particular, ammonia or aliphatic amines are used as neutralizing agents, particularly those having a molecular weight of 31 to 200. Examples include methylamine, dimethyl-amine, trimethylamine, triethylamine, ethanolamine, 2-amino-2-methyl-1-propanol and N,N-dimethylethanolamine. The copolymers generally have a molecular weight (Mn~ determined by Mo3923 2~g~
gel permeation chromatography using polystyrene as standard) of 500 to 50,000, preferably 1,000 to 25,000.
Preferred copolymers for use as component a) are those prepared from al) 0 to 70, preferably 0 to 50, wt.% styrene, a2) 0 to 70, preferably 0 to 50, wt.% methyl methacrylate, a3) 0 to 70, preferably 0 to 50, wt.% of an acrylate component selected from one or more Cl to C8-alkyl acrylates, a4) 0 to 30, preferably 0, wt.% of at least one component lo having hydroxyl groups selected from hydroxyalkyl (meth)acrylatès having 1 to 4 carbon atoms in the hydroxyalkyl group, a5) 5 to 40, preferably 10 to 30, wt.% of an acid component, selected from acrylic acid, methacrylic acid and v;nylsulphonic acid, preferably methacrylic acid, a6) 0 to 30, preferably 0, wt.% of other ethylenically unsaturated monomers, provided that the sum of the percentages of components al) to a6) is 100 and 0 to 30 mol% of the incorporated acid groups are neutralized with aliphatic amines or ammonia.
Suitable monomers a3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate and 2-ethylhexyl acrylate. Preferred monomers a3) are n-butyl acrylate, n-hexyl acrylate and 2-ethylhexyl acrylate; n-butyl and/or n-hexyl acrylate are especially preferred.
Suitable hydroxy-functional (meth)acrylates a4) include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and mixtures of these monomers. Preferred are 2-hydroxyethyl methacrylate and the technical mixture of 2- and 3-hydroxy-propyl methacrylate.
Acid-containing monomer a5) is most preferably present in an amount of 15 to 25% by weight. Methacrylic acid is especially preferred as monomer a5).
Mo3923 -6- 2 ~ ~ 9 ~ 6 9 Suitable monomers a6), which may optionally be present, include sub~tituted styrene derivatives such as the isomeric vinyltoluenes, ~-methylstyrene, propenylbenzene, C5-CI2-cycloalkyl (meth)acrylates, vinyl esters (such as vinyl acetate, propionate or versatate) and N-methoxymethyl (methJacrylamide.
The ability to emulsify copolymers a) depends above all on the concentration of an incorporated anionic group and on the presence or absence of external emulsifiers. Preferably, the hydrophilicity of component a) is adjusted via the incorporation of acid groups, their degree of neutralization and/or the concomitant use of external emulsifiers d), such that at least 20 wt.%, preferably at least 80 wt.%, of component a) is present in a form emulsified in water; the remainder is present in water-dissolved form. Especially preferred agueous copolymers a) are those which have been produced by emulsion polymerization in the aqueous medium and consequently are present essentially in a form emulsified in water.
Methods of production of such aqueous emulsions are known.
Extensive descriptions can be found, e.g., in Houben-Weyl, Methoden der organischen Chemie, volume E20, Makromolekulare Stoffe I, 4th Edition, 1987, p. 218 ff., Georg Thieme Verlag.
Epoxy resins suitable as component b) include low-molecular (cyclo)aliphatic compounds bl) that have good solubility or emulsifiability in water, 1f necessary in the presence of emulsifiers d). These compounds have an average of at least 2, preferably 2 to 5, epoxide groups per molecule and a viscosity at 25C of 50 to lO,000 mPa.s. They also contain 0.2 to 2.0 epoxide groups per 100 9 of resin solids. A very suitable example of such epoxy resin is "Glycidether 100", a commercial product of the Raschig AG company. Glycidether 100 is an epoxide mixture based on a glycidyl glycerol ether, with an epoxide value of 0.67 to 0.70 equivalents of epoxide/100 9 and a viscosity at 25C of 140 to 175 mPa.s. It also has good Mo3923 2~8~
compatibility with water. Another commercial product suitable as component bl) is Epikote 877 of the Shell Company.
Component b) can optionally contain aliphatic monoepoxides b2) as reactive diluents in amounts of up to 20 wt.%, based on the weight of component bl). Suitable components b2) include glycidyl ethers of aliphatic C4-C22 alcohols, such as butyl glycidyl ether; and epoxidized olefins, such as epoxidized ~-olefins, for example reactive diluent Edenol 817 RV of the Henkel company.
In the coating compositions according to the invention, components a) and b) are present in an amount such that the molar ratio of unneutralized acid groups of component a) to epoxide groups of component b) is 1:3 to 1:0.5, preferably 1:1.5 to 1:0.75.
The coating compositions according to the invention may also contain up to 10 wt.%, based on the weight of components a) to e), of water-miscible organic solvents c). Examples of these solvents include butoxyethanol, methoxypropanol, ethanol and acetone.
In the coating compositions according to the invention, external emulsifiers d) may be present to assist the emulsifiability of components a) and b). These external emulsifiers, if used at all, are used in amounts of up to 5 wt.%, based on the total weight of components a) to e).
Suitable external emulsifiers include 3-benzyl-4-hydroxy-biphenyl polyglycol ether and the sodium salt of di-sec.-butyl naphthalenesulphonic acid.
The coating compositions may also contain additives d) which are known from coatings technology. Examples include 3~ pigments, antifoaming agents, levell;ng agents, dispersion aids for p;gment distribution, fillers, catalysts for the epoxide addition reaction or also other non-water miscible (hydrophobic) auxiliary solvents, which are different from component c), but which are emulsifiable in the total system due to the presence of the emulsifiers.
Mo3923 20~6a To prepare the coating compositions it is possible to emulsify or dissolve the epoxide component b) in the aqueous or aqueous-organic emulsion of component a) (that may contain hydrophilic solvents c), the previously mentioned hydrophobic solvents and/or emulsifiers d)). The good water compatibility of the component b), at least in presence of the emulsifiers d), ensures good mixing by simply stirr;ng at room temperature.
If additives are to be present, they are preferably added to the system preferably before the addition of component b).
The coating compositions according to the invention in general have a water content of 20 to 75 wt.% and a total content of hydrophilic solvents c) and other possible volatile solvents, that can be part of component e), of no more than 10 wt.%, wherein these percentages are based on the total weight f the coatiny composition.
The coating compositions according to the invention have a processing time at room temperature of at least 10 h, often of more than 24 h.
The coating compositions according to the invention can be applied to suitable substrates by known methods, for example, by spray;ng, dipping and brushing. The curing of the coatings can be carried out within a wide temperature range of 5 to 160C, preferably 5 to 140C. Preferably the curing takes place at room or ambient temperature. At elevated curing temperatures, for example 80 to 140-C, stoving times of 15 to 45 minutes are usually sufficient. Irrespective of the curing temperature, coatings are obtained which possess scratch resistance, water resistance, solvent resistance and high gloss.
The coating compositions according to the inventlon are also distinguished by the lack of a the previously discussed viscosity anomaly, i.e., on dilution with water no initial rise in viscosity occurs.
The coating compositions according to the invention are suitable in particular for the production of primary coats or Mo3923 2~9~
g top coats on any desired substrates, but particularly on concrete, wood, metal and plastics. The coating compositions are suitable for the production of fillers, base coats and clear coats for both original equipment manufacture and for the repair coating of motor vehicles. They are also suitable for furniture coating, industrial coatings and for building protection.
In the following examples all parts and percentages are by weight unless otherwise indicated.
lo EXAMPLES
In the examples the following epoxy resins bl) and polyacrylate resins a) were used.
Glvcidvl ether A
An epoxide mixture containing glycidyl glycerol ether, flash point 118 to 135DC (Abel-Penski), Hazen color no more than 200, epoxide value about 0.68 equivalents of epoxide/100 9, viscosity (25C) about 155 mPa.s ~commercial product of the Raschig company, Ludwigshafen, trade name: Glycidether 100).
GlvcidYl ether B
Low-viscosity, aliphatie diepoxide, viscosity 40 to 90 mPa.s. Epoxide value: about 0.308 equivalents of epoxide/100 9 (commercial product of the Shell company, trade name: Epikote 877).
Polvacrvlate Example 1 In a stirred apparatus equipped with reflux condenser, internal thermometer and dropping funnel, while 3 liters of N2/h were passed over, 554.4 parts of distilled water, 3.9 parts of emulsifier 1 (3-benzyl-4-hydroxybiphenyl polyglycol ether) and 0.75 parts of emulsifier 2 (di-sec.-butyl naphthalene sulphonate) were charged and heated to 80-C with intensive stirring. Then at 80C a solution of 1.25 parts of ammonium peroxodisulphate and 11.25 parts of water was added and the mixture was stirred for exactly 5 minutes. 10 vol% of a monomer mixture containing 72.7 parts of styrene, 134.8 parts of methyl methacrylate, 78.5 parts of n-butyl acrylate, 85.7 Mo3923 2 ~
parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at 80C at the same time. After 15 minutes stirring at 80C, the remainder of the monomer mixture was added dropwise over a period of 2 hours.
After the addition was complete, a solution of 0.25 parts of ammon;um peroxodisulphate in 12.25 parts of water was added dropwise ;n 10 minutes and the mixture was stirred for a further 2 hours at 80'C. The emulsion obtained had a polymer content of 40.3 wt.%. The acid number of the polymer was 115.1 ~o mg KOH/g. By dropwise addition of a 20% solution of N,N-dimethylethanolamine in butoxyethanol, the solution was 15%
neutralized, based on the indicated acid number. The emulsion obtained had a polymer content of 38.9 wt.%.
PolYacrYlate Example 2 In the stirred apparatus described in Polyacrylate Example 1, while 3 liters of N2/h were passed over, 542.7 parts of distilled water, 3.9 parts of emulsifier 1 and 0.75 parts of emulsifier 2 were charged, and the mixture was heated to 80C
with intensive stirring. At 80C, a solution of 1.25 parts of ammonium peroxodisulphate and 11.25 parts of water was added and the mixture was stirred for exactly 5 minutes. 10 vol% of a monomer mixture containing 41.6 parts of styrene, 90 parts of methyl methacrylate, 113.3 parts of n-butyl acrylate, 39.0 parts of hydroxyethyl methacrylate, 80 parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at the same time at 80'C. After 15 minutes stirring at 80C, the remainder of the monomer mixture was added dropwise in 2 hours.
After the addition was complete, a solution of 0.25 parts of ammonium peroxodisulphate in 12.25 parts of water was added dropwise in 10 minutes and the mixture was stirred for a further 2 h at 80'C. The emulsion obtained had a polymer content of 40.0 wt.%. The acid number of the polymer was 141.8 mg KOH/g. By dropwise addition of a 20 % solution of N,N-dimethy1ethanolamine in butoxyethanol, the emulsion was 15%
neutralized, based on the acid number. The emulsion obtained Mo3923 -~1- 2~
was filtered through a Seitz clarifying bed T5500. The polymer content of the filtered solution was 40.9 wt.%.
PolYacrYlate Example 3 In the stirred apparatus described in Polyacrylate Example 1s while 3 liters of N2/h were passed over, 544.8 parts of distilled water, 3.9 parts of emulsifier 1 and 0.75 parts of emulsifier 2 were charged and the mixture was heated to 80C
with intens;ve stirring. Then at 80C a solution of 1.25 parts of ammonium peroxodisulphate in 11.25 parts of distilled water lo was added and the mixture was stirred for exactly 5 minutes.
10 vol% of a monomer mixture containing 41.6 parts of styrene, 100 parts of methyl methacrylate, 113.3 parts of n-butyl acrylate, 39 parts of hydroxyethyl methacrylate, 71.4 parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at the same time at 80C. After 15 m;nutes stirring at 80C, the remaining monomer mixture was added dropwise in 2 hours.
After the addition, was complete a solution of 0.25 parts of ammonium peroxodisulphate and 12.25 parts of distilled water was added dropwise. The mixture was allowed to react for a further 2 h at 80C with intensive stirring. The emulsion obtained had an acid number of 52.4 mg KOH/g and a polymer content of 40 wt.%, which results in a calculated acid number, based on solids, of 131 mg KOH/g. After cooling to room temperature the emulsion was 15% neutralized, based on the measured acid number, with a 20% solution of N,N-dimethyl-ethanolamine in butoxyethanol. The emulsion obtained was filtered through a Seitz clarify;ng bed T5500. The solids content of the filtered solution was 39.2 wt.%.
PolYacrvlate Example 4 In the stirred apparatus described in Polyacrylate Example 1, while 3 liters of N2/h were passed over, 557.8 parts of distilled water, 3.9 parts of emulsifier 1 and 0.75 parts of emulsifier 2 were charged and the mixture then heated with intensive stirring to 80C. Then at 80C a solution of 1.25 parts of ammonium peroxodisulphate in 11.25 parts of water were Mo3923 added and the mixture was stirred for exactly 5 minutes. 10 vol% of a monomer mixture containing 62.4 parts of styrene, 100 parts of methyl methacrylate, 113.3 parts of n-butyl acrylate, 39.0 parts of hydroxyethyl methacrylate, 63.96 parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at the same time at 80C. After 15 minutes stirring at 80C, the remaining monomer mixture was then added dropwise in 2 hours.
After the addition was complete, a solution of 0.25 parts lo of ammonium peroxodisulphate in 12.25 parts of water was then added dropwise in 10 minutes, followed by further stirring for 2 hours at BOC. The emulsion obtained had a polymer content of 40.0 wt.%. The acid number of the polymer was 146.8 mg KOH/g. By dropwise addition of a 20% solution of N,N-dimethylethanolamine butoxyethanol, the emulsion was 15%
neutralized, based on the given acid number. The emulsion obtained was filtered through a Seitz clarifying bed T5500.
The polymer content of the filtered solution was 39.3 wt.%.
Polvacrvlate Example 5 In the stirred apparatus described in Polyacrylate Example 1, while 3 liters of N2/h were passed over, 590.25 parts of distilled water, 3.9 parts of emulsifier and 0.75 parts of Emulsifier 1 were charged and then heated to 80C with intensive stirring. A solution of 1.25 parts of ammonium peroxodisulphate in 11.25 parts of distilled water was added and the mixture was stirred for exactly 5 minutes. 10 vol% of a monomer m~xture containing 65.5 parts of styrene, 52.5 parts of methyl methacrylate, 141.3 parts of n-butyl acrylate, 72.3 parts of hydroxyethyl methacrylate, 63.96 parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at the same time at 80-C. After 15 minutes stirring at 80C, the rest of the monomer mixture was then added dropwise in 2 hours.
After the addition was complete, a solution of 0.25 parts of ammonium peroxodisulphate and 12.25 parts of distilled water was then added dropwise. The mixture was allowed to react Mo3923 6 ~
further for another 2 h at 80C with intensive st;rring. The emulsion obtained had an acid number of 42.8 mg KOH/g and a polymer content of 40 wt.%, resulting in a calculated acid number, based on solids, of 107 mg KOH/g. After cooling to room temperature the emulsion was 15% neutralized, based on the measured acid number, with a 20% solution of N,N-dimethyl-ethanolamine in butoxyethanol. The emulsion obtained was filtered by a Seitz clarifying bed T5500. The solids content of the filtered solution was 38.6 wt.%.
Lacquer ExamDles Coating compositions were prepared by mixing the emulsions from Polyacrylate Examples 1, 4 and 5 with glycidyl ether A.
The components were mixed in a ratio of copolymer to glycidyl ether of 100:50 and 100:30, respectively. Glycidyl ether A was stirred by hand into the aqueous emulsion. The crosslinkable coating compositions obtained had the following compositions (Examples 1 to 6):
Example 1 Copolymer:glycidyl ether A ratio - 100:30, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.
34.8 wt.% copolymer according to Polyacrylate Example 1 1.0 wt.% N,N-dimethylethanolamine 3.8 wt.% butoxyethanol 0 3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 10.5 wt.% glycidyl ether A
49.5 wt.% water 100.0 wt.%
Example 2 Copolymer:glycidyl ether A ratio - lOO:SO, corresponding to an equlvalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.55.
Mo3923 2~99~
32.5 wt.% copolymer according to Polyacrylate Example 1 0.9 wt.% N,N-dimethylethanolamine 3.6 wt.% butoxyethanol 0.3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 16.3 wt.% glycidyl ether A
46 3 wt % water 100.0 wt.%
Examole 3 lo Copolymer:glycidyl ether A ratio - 100:30, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.27.
34.7 wt.% copolymer according to Polyacrylate Example 1 1.2 wt.% N,N-dimethylethanolamine 4.7 wt.% butoxyethanol 0.3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 10.5 wt.% glycidyl ether A
48.5 wt.% water 1OO.O wt.%
Example 4 Copolymer:glycidyl ether A ratio - 100:50, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.23.
32.4 wt.% copolymer according to Polyacrylate Example 4 1.1 wt.% N,N-dimethylethanolamine 4.4 wt.% butoxyethanol 0.3 wt.% emulsifier I
0.1 wt.% emulsifier 2 16.4 wt.% glycidyl ether A
45.3 wt.% water 100.0 wt.%
Mo3923 2 ~
Example 5 Copolymer:glycidyl ether A ratio - 100:30, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.07.
34.6 wt.% copolymer according to Polyacrylate Example 5 0.9 wt.% N,N-dimethylethanolamine 3.5 wt.% butoxyethanol 0.3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 10.4 wt.% glycidyl ether A
50.2 wt.% water 100.0 wt.%
Example 6 Copolymer:glycidyl ether A ratio - 100:50, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.67 32.2 wt.% copolymer according to Polyacrylate Example 5 0.8 wt.% N,N-dimethylethanolamine 3.3 wt.% butoxyethanol 0.3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 16.2 wt.% glycidyl ether A
47.0 wt.% water 100.0 wt.%
Each of these coating compositions were spread at a wet film thickness of 180 ~m onto glass plates and then were each cured for 30 minutes at 80 and 120-C. Glossy, crosslinked films were obtained which possessed good scratch resistance.
The films cured at 80 C showed an advantageous post-curing at room temperature, so that after 2 to 3 days, partial solubility was no longer observed. The films dried at 120C were completely resistant to solvent immediately after cooling.
Water resistance was carried out by laying a wet cotton ball, covered with a Petri dish on the films cured at 120C.
Mo3923 2 ~
The film was then tested hourly for changes at the point of contact. After 6 hours, no changes were observed.
Example 7 100 parts of the resin from Polyacrylate Example 1 having a solids content of 39.7 wt.% were intensively stirred with 11.7 parts of glycidyl ether A. A transparent two-component coating composition was formed with a ratio of carboxyl to epoxide groups of 1:1. The processing time of the batch exceeded 24 h. The coating composition had the following lo composition:
Binder solid: 46.02 wt.%
Water: 50.40 wt.%
Organic solvent:3.58 wt.%
100.00 wt.%
The film was applied in a wet film thickness of 200 ~m (= 50 to 60 ~m dry) and dried overnight to a hard, completely transparent film. The curing reaction was completely finished after about 14 days at room temperature. The properties of the liquid coating composition and the fully cured film were as 20follows:
Liquid Coatinq Composition Processing time (without loss of film properties) > 24 h Dust free drying (sand drying) 1.5 h Pressure drying (pressure with finger-tip) 5 h 25Coatinq Film optics: gloss very good transparency very good Pendulum hardness (DIN 53157): 146 sec.
Solvent resistance:
3o - White Spirit very good - solvent naphtha 100 very good - methoxypropyl acetate very good - acetone moderate - ethanol good-moderate Water resistance (24 h action) good Mo3923 2 ~
Example 8 Example 7 was repeated with the exception that to accelerate the reaction 0.23 parts of tris-(dimethylamino-methyl)-phenol (Accelerator DMP 30, Rohm and Haas company, Frankfurt/M.) were added. The properties of the liquid coating composition and the fully cured film were as follows:
Liquid Coating Compo tion Processing time: > 24 h Dust free drying: 0.5 h lo Pressure dry;ng: 1.0 h Coating Film optics: gloss very good transparency very good Pendulum hardness (DIN 53157) 150-160 sec Solvent resistance:
- White Spirit very good - solvent naphtha 100 very good - methoxypropyl acetate very good - acetone moderate - ethanol very good Water resistance (24 h. action) good Example 9 Example 7 was repeated with the exceptlon that the coating composition was hardened for 30 min. at 120-C instead of at room temperature. The properties of the fully cured film were as follows:
Film optics: gloss very good transparency very good Pendulum hardness 160-170 sec.
Mo3923 `` 2~ 6~
Solvent resistance:
- White Spirit very good - solvent naphtha 100 very good - methoxypropyl acetate very good - acetone very good - ethanol good Water resistance good Example 10 100 parts of the resin from Polyacrylate Example 2 having lo a solids content of 40.8 wt.% were stirred with 21.32 parts of a commercial titan;um diox;de, rutile type (Bayert;tan R-KB-4, Bayer AG Leverkusen) and then subjected to dispersion in a dissolver for 30 minutes at a rotation speed of 15 to 20 m/sec.
The resulting dispersion component was suitable for use in a two-component white coating composition and had practically unlimited storability. The use of further dispersing additives was unnecessary. To 121.32 9 of this dispersion component was added 12.30 9 of glycidyl ether A and the mixture was stirred until homogeneous. The ratio of carboxyl to epoxide groups was 20 1:1. The coating composition had the following composition:
Binder, solid39.74 wt.%
Pigment15.95 wt.%
Water 40.19 wt.%
Organic solvent4.12 wt.%
100.00 wt.%
The coating composition was applied in a wet film thickness of 200 ~m (= 50 to 60 ~m dry). After drying overnight, a hard, glossy coating was obtained. The curing reaction was completely finished after a drying time of 10 to 3o 14 days. The properties of the llquid coating composition and of the completely cured film were as follows:
Mo3923 2~99$~
Liquid Coating Composition Processing time (without loss of film properties) 10-15 h ~ustfree drying (sand drying): 0.5 h Pressure drying (pressure with finger tip) 1-1.5 h Coating Film optics: gloss very good Pendulum hardness 150-160 sec.
Solvent resistance:
- White Spirit very good lo - solvent naphtha 100 very good - methoxypropyl acetate very good - acetone good - ethanol very good Water resistance (24 h action) good Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3923
Mo3923-us LeA ~9,157 AN AQUEOUS COATING COMPOSITION AND
BACKGROUND ~F THE INVENTION
Field of the Invention The present invention relates to a new aqueous coating composition containing polyacrylate resins which have carboxylic and/or sulphonic acid functionality and are dissolved and/or dispersed in water as an essential binder component and (cyclo)aliphatic epoxy resins as curing agents, and the use of the coating compositions for the production of coatings.
Description of the Prior Art Today aqueous coating compositions are gaining increasing importance for ecological and economic reasons. The replacement of coating compositions conventionally dissolved in organic solvents is, however, technically difficult for various reasons.
Aqueous binders based on alkyd resins and polyesters have a marked tendency to saponification. The saponification causes a reduction of molecular weight, which leads to a loss of quality of the binder and the coatings obta1ned therefrom. In addition, the storability of such binders is considerably reduced.
Frequently, therefore, binders dissolved in purely organic solvents are produced or sold, and are then diluted further with water for application. During application these systems release, in addition to water, the organic solvents contained in the system. The ability to dilute these anionic binders with water is obtained only by neutralization with bases, usually organic amines. During curing, these amines are also released. As a rule, complicated incinerators are then necessary industrially in order to remove the organic constituents from the waste air, while in do-it-yourself 35376TWR2g 1 9 2~
applications, these constituents are emitted into the ambient air.
Another problem of these water-based coating compositions is the distinctive viscosity anomaly. On dilution of the aqueous lacquer solutions, the viscosity initially increases and then decreases rapidly after passing a maximum. Because the coating compositions react to small water additions with considerable viscosity changes, they require particularly careful handling.
A further disadvantage, in particular for stoving systems containing polyester or alkyd resins in combination with melamine resins as crosslinkers, is the relatively high curing temperature, which is usually at least 120C. This requires a high expenditure of energy for curing the system. For many applications, such as the repair coating of automobiles, curing is not possible under such temperature conditions. As a rule, coating compositions are required that are curable at the lowest possible temperatures and yet have suffic;ent water- and solvent-resistance after curing. Ideal binders would be usable, e.g., in the automobile field, both at temperatures below 100C for repair coating and at higher temperature for original equipment manufacture (OEM).
Other crosslinking mechanisms, such as the crosslinking of OH-functional polymers with polyisocyanates, have some advantages when compared to crosslinking with melamine resins.
Thus, the curing can be carried out at room temperature or, accelerated, at 80 to 120-C. The coatings obtained in this way possess a good mechanical property profile and are generally resistant to gasoline and water. However, there are problems when it is intended to apply this crosslinking principle to aqueous formulations, since the isocyanates are reactive with water. It was previously common to apply such systems in purely organic solution resulting in the disadvantages mentioned with regard to the emission of organic solvents.
Mo3923 Only recently have special aqueous coating compositions become known (e.g. DE-OS 3,8291587) to overcome these problems.
These compositions contain combinations of polyhydroxy compounds and polyisocyanates with free isocyanate groups as binders which are dissolved and/or dispersed in water. Yet the difficulty remains that the side reactions of NCO groups with water can interfere with the actual cross-linking reaction, e.g., when detailed instructions about the composition of the lacquer recipe and the curing conditions are not followed.
B;nders based on a polymer containing amino or ammonium groups and epoxides also have a high reactivity and can be cured at temperatures below 100C. However, the basic groups needed for compatibility with water render the crosslinked coatings highly hydrophilic, which has a negative effect on their water resistance.
Accordingly, it is an obiect of the present invention to provide a new coating composition which may be applied an aqueous phase substantially free of co-solvent, is dilutable without the viscosity anomaly, can be cured over a wide temperature range (in particular at only moderately elevated temperatures or room temperature), has a long processing time and possesses good water resistance water resistance.
These objects may be achieved with the preparation of the coating compositions according to the invention which are described in more detail below.
SUMMARY OF THE INVENTION
The present invention relates to aqueous coating compositions containing an aqueous solution and/or dispersion of a) a polyacrylate component which contains at least one copolymer having carboxylic and/or sulphonic acid groups which may be at least partially present in salt form, is based on the reaction product of oleflnically unsaturated monomers and has an acid number of 30 to 240 mg KOH/g, a Mo3923 2~99~
hydroxyl number of 0 to 180 mg KOH/g, and a molecular weight (Mn) of 500 to SO,OOO, b) an epoxide component which contains bl) at least one aliphatic or cycloaliphatic epoxy resin having an average of at least 2 epoxide groups per molecule and containing 0.2 to 2.0 equivalents of epoxide per 100 g of resin and b2) up to 20 wt.%, based on the weight of bl), of at least one aliphatic monoepoxide with 7 to 25 carbon atoms, c) up to 10 wt.%, based on the total weight of components a) to e), of one or more organic, water-miscible solvents, d) up to 5 wt.%, based on the total weight of components a) to e), of one or more external emulsifiers and e) optionally other known coatings additiv~s, wherein the equivalent ratio of unneutralized acid groups of component a) to epoxide groups of component b) is 1:0.5 to 1:3.
The present invention also relates to the use of these coating compositions for the production of coatings for curing at 5 to 140C on any desired substrates.
DETAILED DESCRIPTION OF THE INVENTION
Component a) is selected from copolymers having carboxylic or sulphonic acid groups, acid numbers of about 30 to 240 mg KOH/g and hydroxyl nUmbersof o to about 180 mg KOH/g. The acid number includes both free, i.e., unneutralized, acid groups, particularly carboxyl groups, and also neutralized acid groups, in particular carboxylate groups. Preferably, 0 to 30 wt.% of the ac~d groups are present in neutralized form. In particular, ammonia or aliphatic amines are used as neutralizing agents, particularly those having a molecular weight of 31 to 200. Examples include methylamine, dimethyl-amine, trimethylamine, triethylamine, ethanolamine, 2-amino-2-methyl-1-propanol and N,N-dimethylethanolamine. The copolymers generally have a molecular weight (Mn~ determined by Mo3923 2~g~
gel permeation chromatography using polystyrene as standard) of 500 to 50,000, preferably 1,000 to 25,000.
Preferred copolymers for use as component a) are those prepared from al) 0 to 70, preferably 0 to 50, wt.% styrene, a2) 0 to 70, preferably 0 to 50, wt.% methyl methacrylate, a3) 0 to 70, preferably 0 to 50, wt.% of an acrylate component selected from one or more Cl to C8-alkyl acrylates, a4) 0 to 30, preferably 0, wt.% of at least one component lo having hydroxyl groups selected from hydroxyalkyl (meth)acrylatès having 1 to 4 carbon atoms in the hydroxyalkyl group, a5) 5 to 40, preferably 10 to 30, wt.% of an acid component, selected from acrylic acid, methacrylic acid and v;nylsulphonic acid, preferably methacrylic acid, a6) 0 to 30, preferably 0, wt.% of other ethylenically unsaturated monomers, provided that the sum of the percentages of components al) to a6) is 100 and 0 to 30 mol% of the incorporated acid groups are neutralized with aliphatic amines or ammonia.
Suitable monomers a3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate and 2-ethylhexyl acrylate. Preferred monomers a3) are n-butyl acrylate, n-hexyl acrylate and 2-ethylhexyl acrylate; n-butyl and/or n-hexyl acrylate are especially preferred.
Suitable hydroxy-functional (meth)acrylates a4) include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and mixtures of these monomers. Preferred are 2-hydroxyethyl methacrylate and the technical mixture of 2- and 3-hydroxy-propyl methacrylate.
Acid-containing monomer a5) is most preferably present in an amount of 15 to 25% by weight. Methacrylic acid is especially preferred as monomer a5).
Mo3923 -6- 2 ~ ~ 9 ~ 6 9 Suitable monomers a6), which may optionally be present, include sub~tituted styrene derivatives such as the isomeric vinyltoluenes, ~-methylstyrene, propenylbenzene, C5-CI2-cycloalkyl (meth)acrylates, vinyl esters (such as vinyl acetate, propionate or versatate) and N-methoxymethyl (methJacrylamide.
The ability to emulsify copolymers a) depends above all on the concentration of an incorporated anionic group and on the presence or absence of external emulsifiers. Preferably, the hydrophilicity of component a) is adjusted via the incorporation of acid groups, their degree of neutralization and/or the concomitant use of external emulsifiers d), such that at least 20 wt.%, preferably at least 80 wt.%, of component a) is present in a form emulsified in water; the remainder is present in water-dissolved form. Especially preferred agueous copolymers a) are those which have been produced by emulsion polymerization in the aqueous medium and consequently are present essentially in a form emulsified in water.
Methods of production of such aqueous emulsions are known.
Extensive descriptions can be found, e.g., in Houben-Weyl, Methoden der organischen Chemie, volume E20, Makromolekulare Stoffe I, 4th Edition, 1987, p. 218 ff., Georg Thieme Verlag.
Epoxy resins suitable as component b) include low-molecular (cyclo)aliphatic compounds bl) that have good solubility or emulsifiability in water, 1f necessary in the presence of emulsifiers d). These compounds have an average of at least 2, preferably 2 to 5, epoxide groups per molecule and a viscosity at 25C of 50 to lO,000 mPa.s. They also contain 0.2 to 2.0 epoxide groups per 100 9 of resin solids. A very suitable example of such epoxy resin is "Glycidether 100", a commercial product of the Raschig AG company. Glycidether 100 is an epoxide mixture based on a glycidyl glycerol ether, with an epoxide value of 0.67 to 0.70 equivalents of epoxide/100 9 and a viscosity at 25C of 140 to 175 mPa.s. It also has good Mo3923 2~8~
compatibility with water. Another commercial product suitable as component bl) is Epikote 877 of the Shell Company.
Component b) can optionally contain aliphatic monoepoxides b2) as reactive diluents in amounts of up to 20 wt.%, based on the weight of component bl). Suitable components b2) include glycidyl ethers of aliphatic C4-C22 alcohols, such as butyl glycidyl ether; and epoxidized olefins, such as epoxidized ~-olefins, for example reactive diluent Edenol 817 RV of the Henkel company.
In the coating compositions according to the invention, components a) and b) are present in an amount such that the molar ratio of unneutralized acid groups of component a) to epoxide groups of component b) is 1:3 to 1:0.5, preferably 1:1.5 to 1:0.75.
The coating compositions according to the invention may also contain up to 10 wt.%, based on the weight of components a) to e), of water-miscible organic solvents c). Examples of these solvents include butoxyethanol, methoxypropanol, ethanol and acetone.
In the coating compositions according to the invention, external emulsifiers d) may be present to assist the emulsifiability of components a) and b). These external emulsifiers, if used at all, are used in amounts of up to 5 wt.%, based on the total weight of components a) to e).
Suitable external emulsifiers include 3-benzyl-4-hydroxy-biphenyl polyglycol ether and the sodium salt of di-sec.-butyl naphthalenesulphonic acid.
The coating compositions may also contain additives d) which are known from coatings technology. Examples include 3~ pigments, antifoaming agents, levell;ng agents, dispersion aids for p;gment distribution, fillers, catalysts for the epoxide addition reaction or also other non-water miscible (hydrophobic) auxiliary solvents, which are different from component c), but which are emulsifiable in the total system due to the presence of the emulsifiers.
Mo3923 20~6a To prepare the coating compositions it is possible to emulsify or dissolve the epoxide component b) in the aqueous or aqueous-organic emulsion of component a) (that may contain hydrophilic solvents c), the previously mentioned hydrophobic solvents and/or emulsifiers d)). The good water compatibility of the component b), at least in presence of the emulsifiers d), ensures good mixing by simply stirr;ng at room temperature.
If additives are to be present, they are preferably added to the system preferably before the addition of component b).
The coating compositions according to the invention in general have a water content of 20 to 75 wt.% and a total content of hydrophilic solvents c) and other possible volatile solvents, that can be part of component e), of no more than 10 wt.%, wherein these percentages are based on the total weight f the coatiny composition.
The coating compositions according to the invention have a processing time at room temperature of at least 10 h, often of more than 24 h.
The coating compositions according to the invention can be applied to suitable substrates by known methods, for example, by spray;ng, dipping and brushing. The curing of the coatings can be carried out within a wide temperature range of 5 to 160C, preferably 5 to 140C. Preferably the curing takes place at room or ambient temperature. At elevated curing temperatures, for example 80 to 140-C, stoving times of 15 to 45 minutes are usually sufficient. Irrespective of the curing temperature, coatings are obtained which possess scratch resistance, water resistance, solvent resistance and high gloss.
The coating compositions according to the inventlon are also distinguished by the lack of a the previously discussed viscosity anomaly, i.e., on dilution with water no initial rise in viscosity occurs.
The coating compositions according to the invention are suitable in particular for the production of primary coats or Mo3923 2~9~
g top coats on any desired substrates, but particularly on concrete, wood, metal and plastics. The coating compositions are suitable for the production of fillers, base coats and clear coats for both original equipment manufacture and for the repair coating of motor vehicles. They are also suitable for furniture coating, industrial coatings and for building protection.
In the following examples all parts and percentages are by weight unless otherwise indicated.
lo EXAMPLES
In the examples the following epoxy resins bl) and polyacrylate resins a) were used.
Glvcidvl ether A
An epoxide mixture containing glycidyl glycerol ether, flash point 118 to 135DC (Abel-Penski), Hazen color no more than 200, epoxide value about 0.68 equivalents of epoxide/100 9, viscosity (25C) about 155 mPa.s ~commercial product of the Raschig company, Ludwigshafen, trade name: Glycidether 100).
GlvcidYl ether B
Low-viscosity, aliphatie diepoxide, viscosity 40 to 90 mPa.s. Epoxide value: about 0.308 equivalents of epoxide/100 9 (commercial product of the Shell company, trade name: Epikote 877).
Polvacrvlate Example 1 In a stirred apparatus equipped with reflux condenser, internal thermometer and dropping funnel, while 3 liters of N2/h were passed over, 554.4 parts of distilled water, 3.9 parts of emulsifier 1 (3-benzyl-4-hydroxybiphenyl polyglycol ether) and 0.75 parts of emulsifier 2 (di-sec.-butyl naphthalene sulphonate) were charged and heated to 80-C with intensive stirring. Then at 80C a solution of 1.25 parts of ammonium peroxodisulphate and 11.25 parts of water was added and the mixture was stirred for exactly 5 minutes. 10 vol% of a monomer mixture containing 72.7 parts of styrene, 134.8 parts of methyl methacrylate, 78.5 parts of n-butyl acrylate, 85.7 Mo3923 2 ~
parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at 80C at the same time. After 15 minutes stirring at 80C, the remainder of the monomer mixture was added dropwise over a period of 2 hours.
After the addition was complete, a solution of 0.25 parts of ammon;um peroxodisulphate in 12.25 parts of water was added dropwise ;n 10 minutes and the mixture was stirred for a further 2 hours at 80'C. The emulsion obtained had a polymer content of 40.3 wt.%. The acid number of the polymer was 115.1 ~o mg KOH/g. By dropwise addition of a 20% solution of N,N-dimethylethanolamine in butoxyethanol, the solution was 15%
neutralized, based on the indicated acid number. The emulsion obtained had a polymer content of 38.9 wt.%.
PolYacrYlate Example 2 In the stirred apparatus described in Polyacrylate Example 1, while 3 liters of N2/h were passed over, 542.7 parts of distilled water, 3.9 parts of emulsifier 1 and 0.75 parts of emulsifier 2 were charged, and the mixture was heated to 80C
with intensive stirring. At 80C, a solution of 1.25 parts of ammonium peroxodisulphate and 11.25 parts of water was added and the mixture was stirred for exactly 5 minutes. 10 vol% of a monomer mixture containing 41.6 parts of styrene, 90 parts of methyl methacrylate, 113.3 parts of n-butyl acrylate, 39.0 parts of hydroxyethyl methacrylate, 80 parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at the same time at 80'C. After 15 minutes stirring at 80C, the remainder of the monomer mixture was added dropwise in 2 hours.
After the addition was complete, a solution of 0.25 parts of ammonium peroxodisulphate in 12.25 parts of water was added dropwise in 10 minutes and the mixture was stirred for a further 2 h at 80'C. The emulsion obtained had a polymer content of 40.0 wt.%. The acid number of the polymer was 141.8 mg KOH/g. By dropwise addition of a 20 % solution of N,N-dimethy1ethanolamine in butoxyethanol, the emulsion was 15%
neutralized, based on the acid number. The emulsion obtained Mo3923 -~1- 2~
was filtered through a Seitz clarifying bed T5500. The polymer content of the filtered solution was 40.9 wt.%.
PolYacrYlate Example 3 In the stirred apparatus described in Polyacrylate Example 1s while 3 liters of N2/h were passed over, 544.8 parts of distilled water, 3.9 parts of emulsifier 1 and 0.75 parts of emulsifier 2 were charged and the mixture was heated to 80C
with intens;ve stirring. Then at 80C a solution of 1.25 parts of ammonium peroxodisulphate in 11.25 parts of distilled water lo was added and the mixture was stirred for exactly 5 minutes.
10 vol% of a monomer mixture containing 41.6 parts of styrene, 100 parts of methyl methacrylate, 113.3 parts of n-butyl acrylate, 39 parts of hydroxyethyl methacrylate, 71.4 parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at the same time at 80C. After 15 m;nutes stirring at 80C, the remaining monomer mixture was added dropwise in 2 hours.
After the addition, was complete a solution of 0.25 parts of ammonium peroxodisulphate and 12.25 parts of distilled water was added dropwise. The mixture was allowed to react for a further 2 h at 80C with intensive stirring. The emulsion obtained had an acid number of 52.4 mg KOH/g and a polymer content of 40 wt.%, which results in a calculated acid number, based on solids, of 131 mg KOH/g. After cooling to room temperature the emulsion was 15% neutralized, based on the measured acid number, with a 20% solution of N,N-dimethyl-ethanolamine in butoxyethanol. The emulsion obtained was filtered through a Seitz clarify;ng bed T5500. The solids content of the filtered solution was 39.2 wt.%.
PolYacrvlate Example 4 In the stirred apparatus described in Polyacrylate Example 1, while 3 liters of N2/h were passed over, 557.8 parts of distilled water, 3.9 parts of emulsifier 1 and 0.75 parts of emulsifier 2 were charged and the mixture then heated with intensive stirring to 80C. Then at 80C a solution of 1.25 parts of ammonium peroxodisulphate in 11.25 parts of water were Mo3923 added and the mixture was stirred for exactly 5 minutes. 10 vol% of a monomer mixture containing 62.4 parts of styrene, 100 parts of methyl methacrylate, 113.3 parts of n-butyl acrylate, 39.0 parts of hydroxyethyl methacrylate, 63.96 parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at the same time at 80C. After 15 minutes stirring at 80C, the remaining monomer mixture was then added dropwise in 2 hours.
After the addition was complete, a solution of 0.25 parts lo of ammonium peroxodisulphate in 12.25 parts of water was then added dropwise in 10 minutes, followed by further stirring for 2 hours at BOC. The emulsion obtained had a polymer content of 40.0 wt.%. The acid number of the polymer was 146.8 mg KOH/g. By dropwise addition of a 20% solution of N,N-dimethylethanolamine butoxyethanol, the emulsion was 15%
neutralized, based on the given acid number. The emulsion obtained was filtered through a Seitz clarifying bed T5500.
The polymer content of the filtered solution was 39.3 wt.%.
Polvacrvlate Example 5 In the stirred apparatus described in Polyacrylate Example 1, while 3 liters of N2/h were passed over, 590.25 parts of distilled water, 3.9 parts of emulsifier and 0.75 parts of Emulsifier 1 were charged and then heated to 80C with intensive stirring. A solution of 1.25 parts of ammonium peroxodisulphate in 11.25 parts of distilled water was added and the mixture was stirred for exactly 5 minutes. 10 vol% of a monomer m~xture containing 65.5 parts of styrene, 52.5 parts of methyl methacrylate, 141.3 parts of n-butyl acrylate, 72.3 parts of hydroxyethyl methacrylate, 63.96 parts of methacrylic acid and 7.4 parts of dodecyl mercaptan, were added at the same time at 80-C. After 15 minutes stirring at 80C, the rest of the monomer mixture was then added dropwise in 2 hours.
After the addition was complete, a solution of 0.25 parts of ammonium peroxodisulphate and 12.25 parts of distilled water was then added dropwise. The mixture was allowed to react Mo3923 6 ~
further for another 2 h at 80C with intensive st;rring. The emulsion obtained had an acid number of 42.8 mg KOH/g and a polymer content of 40 wt.%, resulting in a calculated acid number, based on solids, of 107 mg KOH/g. After cooling to room temperature the emulsion was 15% neutralized, based on the measured acid number, with a 20% solution of N,N-dimethyl-ethanolamine in butoxyethanol. The emulsion obtained was filtered by a Seitz clarifying bed T5500. The solids content of the filtered solution was 38.6 wt.%.
Lacquer ExamDles Coating compositions were prepared by mixing the emulsions from Polyacrylate Examples 1, 4 and 5 with glycidyl ether A.
The components were mixed in a ratio of copolymer to glycidyl ether of 100:50 and 100:30, respectively. Glycidyl ether A was stirred by hand into the aqueous emulsion. The crosslinkable coating compositions obtained had the following compositions (Examples 1 to 6):
Example 1 Copolymer:glycidyl ether A ratio - 100:30, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.
34.8 wt.% copolymer according to Polyacrylate Example 1 1.0 wt.% N,N-dimethylethanolamine 3.8 wt.% butoxyethanol 0 3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 10.5 wt.% glycidyl ether A
49.5 wt.% water 100.0 wt.%
Example 2 Copolymer:glycidyl ether A ratio - lOO:SO, corresponding to an equlvalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.55.
Mo3923 2~99~
32.5 wt.% copolymer according to Polyacrylate Example 1 0.9 wt.% N,N-dimethylethanolamine 3.6 wt.% butoxyethanol 0.3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 16.3 wt.% glycidyl ether A
46 3 wt % water 100.0 wt.%
Examole 3 lo Copolymer:glycidyl ether A ratio - 100:30, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.27.
34.7 wt.% copolymer according to Polyacrylate Example 1 1.2 wt.% N,N-dimethylethanolamine 4.7 wt.% butoxyethanol 0.3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 10.5 wt.% glycidyl ether A
48.5 wt.% water 1OO.O wt.%
Example 4 Copolymer:glycidyl ether A ratio - 100:50, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.23.
32.4 wt.% copolymer according to Polyacrylate Example 4 1.1 wt.% N,N-dimethylethanolamine 4.4 wt.% butoxyethanol 0.3 wt.% emulsifier I
0.1 wt.% emulsifier 2 16.4 wt.% glycidyl ether A
45.3 wt.% water 100.0 wt.%
Mo3923 2 ~
Example 5 Copolymer:glycidyl ether A ratio - 100:30, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.07.
34.6 wt.% copolymer according to Polyacrylate Example 5 0.9 wt.% N,N-dimethylethanolamine 3.5 wt.% butoxyethanol 0.3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 10.4 wt.% glycidyl ether A
50.2 wt.% water 100.0 wt.%
Example 6 Copolymer:glycidyl ether A ratio - 100:50, corresponding to an equivalent ratio of unneutralized carboxyl groups to epoxide groups of 1:1.67 32.2 wt.% copolymer according to Polyacrylate Example 5 0.8 wt.% N,N-dimethylethanolamine 3.3 wt.% butoxyethanol 0.3 wt.% emulsifier 1 0.1 wt.% emulsifier 2 16.2 wt.% glycidyl ether A
47.0 wt.% water 100.0 wt.%
Each of these coating compositions were spread at a wet film thickness of 180 ~m onto glass plates and then were each cured for 30 minutes at 80 and 120-C. Glossy, crosslinked films were obtained which possessed good scratch resistance.
The films cured at 80 C showed an advantageous post-curing at room temperature, so that after 2 to 3 days, partial solubility was no longer observed. The films dried at 120C were completely resistant to solvent immediately after cooling.
Water resistance was carried out by laying a wet cotton ball, covered with a Petri dish on the films cured at 120C.
Mo3923 2 ~
The film was then tested hourly for changes at the point of contact. After 6 hours, no changes were observed.
Example 7 100 parts of the resin from Polyacrylate Example 1 having a solids content of 39.7 wt.% were intensively stirred with 11.7 parts of glycidyl ether A. A transparent two-component coating composition was formed with a ratio of carboxyl to epoxide groups of 1:1. The processing time of the batch exceeded 24 h. The coating composition had the following lo composition:
Binder solid: 46.02 wt.%
Water: 50.40 wt.%
Organic solvent:3.58 wt.%
100.00 wt.%
The film was applied in a wet film thickness of 200 ~m (= 50 to 60 ~m dry) and dried overnight to a hard, completely transparent film. The curing reaction was completely finished after about 14 days at room temperature. The properties of the liquid coating composition and the fully cured film were as 20follows:
Liquid Coatinq Composition Processing time (without loss of film properties) > 24 h Dust free drying (sand drying) 1.5 h Pressure drying (pressure with finger-tip) 5 h 25Coatinq Film optics: gloss very good transparency very good Pendulum hardness (DIN 53157): 146 sec.
Solvent resistance:
3o - White Spirit very good - solvent naphtha 100 very good - methoxypropyl acetate very good - acetone moderate - ethanol good-moderate Water resistance (24 h action) good Mo3923 2 ~
Example 8 Example 7 was repeated with the exception that to accelerate the reaction 0.23 parts of tris-(dimethylamino-methyl)-phenol (Accelerator DMP 30, Rohm and Haas company, Frankfurt/M.) were added. The properties of the liquid coating composition and the fully cured film were as follows:
Liquid Coating Compo tion Processing time: > 24 h Dust free drying: 0.5 h lo Pressure dry;ng: 1.0 h Coating Film optics: gloss very good transparency very good Pendulum hardness (DIN 53157) 150-160 sec Solvent resistance:
- White Spirit very good - solvent naphtha 100 very good - methoxypropyl acetate very good - acetone moderate - ethanol very good Water resistance (24 h. action) good Example 9 Example 7 was repeated with the exceptlon that the coating composition was hardened for 30 min. at 120-C instead of at room temperature. The properties of the fully cured film were as follows:
Film optics: gloss very good transparency very good Pendulum hardness 160-170 sec.
Mo3923 `` 2~ 6~
Solvent resistance:
- White Spirit very good - solvent naphtha 100 very good - methoxypropyl acetate very good - acetone very good - ethanol good Water resistance good Example 10 100 parts of the resin from Polyacrylate Example 2 having lo a solids content of 40.8 wt.% were stirred with 21.32 parts of a commercial titan;um diox;de, rutile type (Bayert;tan R-KB-4, Bayer AG Leverkusen) and then subjected to dispersion in a dissolver for 30 minutes at a rotation speed of 15 to 20 m/sec.
The resulting dispersion component was suitable for use in a two-component white coating composition and had practically unlimited storability. The use of further dispersing additives was unnecessary. To 121.32 9 of this dispersion component was added 12.30 9 of glycidyl ether A and the mixture was stirred until homogeneous. The ratio of carboxyl to epoxide groups was 20 1:1. The coating composition had the following composition:
Binder, solid39.74 wt.%
Pigment15.95 wt.%
Water 40.19 wt.%
Organic solvent4.12 wt.%
100.00 wt.%
The coating composition was applied in a wet film thickness of 200 ~m (= 50 to 60 ~m dry). After drying overnight, a hard, glossy coating was obtained. The curing reaction was completely finished after a drying time of 10 to 3o 14 days. The properties of the llquid coating composition and of the completely cured film were as follows:
Mo3923 2~99$~
Liquid Coating Composition Processing time (without loss of film properties) 10-15 h ~ustfree drying (sand drying): 0.5 h Pressure drying (pressure with finger tip) 1-1.5 h Coating Film optics: gloss very good Pendulum hardness 150-160 sec.
Solvent resistance:
- White Spirit very good lo - solvent naphtha 100 very good - methoxypropyl acetate very good - acetone good - ethanol very good Water resistance (24 h action) good Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3923
Claims (6)
1. An aqueous coating composition containing an aqueous solution and/or dispersion comprising a) a polyacrylate component which contains at least one copolymer having carboxylic and/or sulphonic acid groups, which may be at least partially present in salt form, is based on the reaction product of olefinically unsaturated monomers and has an acid number of 30 to 240 mg KOH/g, a hydroxyl number of 0 to 180 mg KOH/g, and a molecular weight (Mn) of 500 to 50,000, b) an epoxide component which contains b1) at least one aliphatic or cycloaliphatic epoxy resin having an average of at least 2 epoxide groups per molecule and containing 0.2 to 2.0 equivalents of epoxide per 100 g of resin and b2) up to 20 wt.%, based on the weight of b1), of at least one aliphatic monoepoxide with 7 to 25 carbon atoms, c) up to 10 wt.%, based on the total weight of components a) to e), of one or more organic, water-miscible solvents, d) up to 5 wt.%, based on the total weight of components a) to e), of one or more external emulsifier and e) optionally other known coatings additives, wherein the equivalent ratio of unneutralized acid groups of component a) to epoxide groups of component b) is 1:0.5 to 1:3.
2. The aqueous coating composition of Claim 1 wherein component a) comprises one or more copolymers prepared from a1) 0 to 70 wt.% styrene, a2) 0 to 70 wt.% methyl methacrylate, a3) 0 to 70 wt.% of an acrylate component selected from the group consisting of C1 to C8 alkyl acrylates, a4) 0 to 30 wt.% of a component having hydroxyl groups selected from the group consisting of hydroxyalkyl (meth)acrylates having 1 to 4 carbon atoms in the hydroxyalkyl group, a5) 5 to 40 wt.% of an acid component selected from the group consisting of acrylic acid, methacrylic acid and vinylsulphonic acid and a6) 0 to 30 wt.% of other ethylenically unsaturated monomers, provided that the sum of the percentages of components a1) to a6) is 100 and 0 to 30 mol% of the incorporated acid groups are neutralized with aliphatic amines or ammonia.
3. The aqueous coating composition of Claim 1 wherein characterized in that component a) is prepared by emulsion polymerization in an aqueous medium.
4. The aqueous coating composition of Claim 2 wherein characterized in that component a) is prepared by emulsion polymerization in an aqueous medium.
5. A substrate coated with the aqueous coating composition of Claim 1.
6. A wood, metal, plastic or mineral substrate coated with the aqueous coating composition of Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4222256.7 | 1992-07-07 | ||
| DE19924222256 DE4222256A1 (en) | 1992-07-07 | 1992-07-07 | Aqueous coating agent and its use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2099860A1 true CA2099860A1 (en) | 1994-01-08 |
Family
ID=6462657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2099860 Abandoned CA2099860A1 (en) | 1992-07-07 | 1993-07-05 | Aqueous coating composition and its use for coating substrates |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0578068A1 (en) |
| JP (1) | JPH0673335A (en) |
| CA (1) | CA2099860A1 (en) |
| DE (1) | DE4222256A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5780117A (en) * | 1996-02-26 | 1998-07-14 | Rohm And Haas Company | Dual-cure latex compositions |
| WO2022147082A1 (en) * | 2020-12-29 | 2022-07-07 | Ppg Industries Ohio, Inc. | Waterborne acid-epoxy coating composition |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4324322B4 (en) * | 1993-07-20 | 2005-11-24 | Delo Industrieklebstoffe Gmbh & Co. Kg | Flexible, light-initiated curing epoxy resin compositions, their preparation and use |
| DE4403318C1 (en) * | 1994-02-03 | 1994-11-17 | Westdeutsche Farbengesellschaf | Coating system |
| US5922410A (en) * | 1995-01-18 | 1999-07-13 | Rohm And Haas Company | Wood coating composition |
| CN101842417B (en) * | 2007-07-30 | 2013-07-31 | 巴斯夫公司 | Water-based dispersions of highly-branched polymers |
| DE102016006694B4 (en) | 2015-05-31 | 2018-07-12 | Karim El Kudsi | Interior coatings of drinking water pipes based on epoxy resin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE25880E (en) * | 1958-03-26 | 1965-10-12 | Ethoxyline besin emulsions | |
| US3492252A (en) * | 1963-10-07 | 1970-01-27 | Scm Corp | Emulsion coating comprising neutralized latex of acidic polymer and an epoxy component |
| US3403088A (en) * | 1964-05-18 | 1968-09-24 | Ppg Industries Inc | Electrodeposition of water-dispersed acrylic interpolymers |
-
1992
- 1992-07-07 DE DE19924222256 patent/DE4222256A1/en not_active Withdrawn
-
1993
- 1993-06-24 EP EP93110110A patent/EP0578068A1/en not_active Withdrawn
- 1993-07-05 JP JP19097293A patent/JPH0673335A/en active Pending
- 1993-07-05 CA CA 2099860 patent/CA2099860A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5780117A (en) * | 1996-02-26 | 1998-07-14 | Rohm And Haas Company | Dual-cure latex compositions |
| WO2022147082A1 (en) * | 2020-12-29 | 2022-07-07 | Ppg Industries Ohio, Inc. | Waterborne acid-epoxy coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4222256A1 (en) | 1994-01-13 |
| JPH0673335A (en) | 1994-03-15 |
| EP0578068A1 (en) | 1994-01-12 |
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