CA1152672A - Water reducible alkyd resin coating composition - Google Patents
Water reducible alkyd resin coating compositionInfo
- Publication number
- CA1152672A CA1152672A CA000347746A CA347746A CA1152672A CA 1152672 A CA1152672 A CA 1152672A CA 000347746 A CA000347746 A CA 000347746A CA 347746 A CA347746 A CA 347746A CA 1152672 A CA1152672 A CA 1152672A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- binder
- coating composition
- resin
- alkyd resin
- 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
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
Abstract
ABSTRACT OF THE DISCLOSURE
A water reducible coating composition that by the addition of a solution of water and an amine or ammonia forms a sprayable nonairpolluting coating composition that can be dried at ambient temperatures and is useful for coating metal or plastic substrates and in particular for finishing or repairing automobiles and trucks; the coating composition contains a water soluble organic solvent, a binder and pig-ments. The binder is of (1) an alkyd resin that is prefer-ably the esterification product of soya oil fatty acids, isophthalic acid and trimethylol propane; (2) an alkylated melamine formaldehyde resin; (3) an acrylic dispersing resin and (4) an organo metallic drier.
A water reducible coating composition that by the addition of a solution of water and an amine or ammonia forms a sprayable nonairpolluting coating composition that can be dried at ambient temperatures and is useful for coating metal or plastic substrates and in particular for finishing or repairing automobiles and trucks; the coating composition contains a water soluble organic solvent, a binder and pig-ments. The binder is of (1) an alkyd resin that is prefer-ably the esterification product of soya oil fatty acids, isophthalic acid and trimethylol propane; (2) an alkylated melamine formaldehyde resin; (3) an acrylic dispersing resin and (4) an organo metallic drier.
Description
11526'72 A Water Reducible Alkyd Resin Coating Composition BACKGROUND OF THE INVENTION
This invention is directed to a coating composition and in particular to a coating com-position that can be diluted with water to form a nonair polluting composition.
In view of stricter air pollution legislations and increased energy costs, it has become important for paint manufacturers to provide coating compositions that are nonair polluting and that dry under ambient temperature conditions. Along with the above, automotive and truck manufacturers and the automotive and truc~
repair industry require coating compositions that form finishes that are weatherable, durable, and have an excellent appearance. In particular, the repair industry requires finishes that have excellent adhesion to all types of painted or primed substrates. The novel coating composition of this invention meets the aforementioned requirements.
S~MMARY OF T~E INVENTION
A coating composition containing about 40-90% by weight of a film forming binder, about 10-60% by weight of a water soluble organic solvent ~15267Z
and pigments in a pigment to binder weight ratio of about 1:100-75:100, wherein the binder is of about (1) 50-90~ by weigl~t, based on the weight of the binder, of an alkyd resin which is the esterification product of soya oil fatty acids, isophthalic acid and tri-methylol propane and has an acid number of about 20-100 and a weight average molecular weight of about 800-15,000 determined by gel permeation chromotography;
This invention is directed to a coating composition and in particular to a coating com-position that can be diluted with water to form a nonair polluting composition.
In view of stricter air pollution legislations and increased energy costs, it has become important for paint manufacturers to provide coating compositions that are nonair polluting and that dry under ambient temperature conditions. Along with the above, automotive and truck manufacturers and the automotive and truc~
repair industry require coating compositions that form finishes that are weatherable, durable, and have an excellent appearance. In particular, the repair industry requires finishes that have excellent adhesion to all types of painted or primed substrates. The novel coating composition of this invention meets the aforementioned requirements.
S~MMARY OF T~E INVENTION
A coating composition containing about 40-90% by weight of a film forming binder, about 10-60% by weight of a water soluble organic solvent ~15267Z
and pigments in a pigment to binder weight ratio of about 1:100-75:100, wherein the binder is of about (1) 50-90~ by weigl~t, based on the weight of the binder, of an alkyd resin which is the esterification product of soya oil fatty acids, isophthalic acid and tri-methylol propane and has an acid number of about 20-100 and a weight average molecular weight of about 800-15,000 determined by gel permeation chromotography;
(2) 0.5-5% by weight,based on the weight of the binder, of an alkylated melamine formaldehyde resin;
(3) 9-20% by weight, based on the wieght of the binder,of an acrylic dispersing resin;
(4) 0.5-5% by weight, based on the weight of the binder,of an organo metallic drier.
The composition can be reduced to an aqueous based composition having an acceptable application viscosity with an aqueous composition containing sufficient base to provide a pH of about 6.5-9Ø
DETAILED DESCRIPTION OF THE IN~'ENTION
The coating composition contains about 40-90% by weight of a film forming binder and usually about 70-85% by weight of the film forming binder. The remainder of the compsition comprises a water soluble solvent. Minor amounts of water dispersible solvents can be added. For application, the composition is reduced to an application viscosity of about 16 to 50 seconds measured according to AST~-1084-63 with an aqueous reducer solutior.. This reducer 3S solution contains up to about 20~ by weight of a water ~152672 soluble solvent or solvents and sufficient ammonia or amine or a combination thereof to form a salt of the alkyd resin and the acrylic dispersing resin and pro-vide a pH of about 6.5-9. Usually a pH of about 7-8 is used.
Typical water soluble solvents that can be used to form the composition and the aqueous reducer solution are as follows: ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol propyl ether, isopropanol, ethanol, methanol, butanol and other alcohols, acetone, and the like. Small amounts of nonwater soluble sol-vents such as toluene, xylene, acetates and mineral spirits can be used. The amount of solvent added to the composition with the aqueous reducer solution can be adjusted to meet and comply with governmental regulations.
Ammonia or amine or a combination thereof used in the aqueous reducer solution reacts with free carboxyl groups of the alkyd resin and acrylic dispersing resin to form salt groups which allow the resins to be dispersed in an aqueous medium. The pH of the resulting composition can be adjusted to the aforementioned values. Typical amines that can be used are triethylamine, trimethylamine, ethanolamine, N,N-diethylethanolamine, N,N-dimethyl-ethanolamine, N-methylethanolamine, monoisopro-panolamine, butanolamine, ethylenediamine, diethyl-amine and the like.
The composition can be a clear but usually contains pigments in a pigment to binder weight ratio of about 1:100 to 75:100. Typical pigments that can be used are as follows: titanium dioxide, aluminum flake, red, yellow or orange iron oxide~ Irgazin* yellow and green, copper phthalocyanine *denotes trade mark ,~
~152672 green and blue, Monastral* red, extender pigments and a wide variety of other organic and inorganic pigments.
The alkyd resin used in the composition is the esterification product of drying oil fatty acids, an aromatic dicarboxylic acid and a polyhydric alcohol.
To prepare the alkyd resin, the above constituents along with an esterification catalyst are charged into a reaction vessel. Either a conventional fusion or solution process using conventional equipment can be used to prepare the alkyd resin. Generally reaction temperatures of about 200-275C. for 1 to 5 hours are used to prepare the resin. The resulting alkyd resin has an acid number of about 20-100 and a weight average molecular weight of about 800-15,000 and a number average molecular weight of about 800-4000 determined by gel permeation chromatography.
Typical solvents that can be used in the solution process for making the a~yd resin are water miscible or water soluble and are as follows: ethers, aliphatic alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, ethylene glycol monoalkyl ethers, such as ethylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoalkyl ether acetates, and the like.
Typical esterification catalysts that are used in the process for preparing alkyd resins are as follows: barium oxide, barium hydroxide, barium naphthenate, calcium oxide, calcium hy-droxide, calcium naphthenate, lead oxide, lithiumhydroxide, lithium napthenate, lithium ricinoleate, sodium hydroxide, sodium naphthenate, zinc oxide, and lead tallate.
Typical drying oil fatty acids that are used to prepare alkyd resins are as follows:
*denotes trade mark .~
dehydrated castor oil fatty acids,heat-bodied soya oil fattv acids, tung oil fatty acids, linseed oil fatty acids, oiticica oil fatty acids, safflower oil fatty acids, soya oil fatty acids, and the like. Soya oil fatty acids are preferred.
Typical aromatic dicarboxylic acids that can be used to prepare the alkyd resin are as follows: isophthalic acid, terephthalic acid, phthalic acid. Isophthalic acid is preferred.
Typical polyhydric alcohols that can be used to prepare alkyd resins are as follows:
ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol, neopentyl glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, methyl-glucoside, dipentaerythritol, and sorbitol.
Trimethylol propane is preferred.
Monobasic organic acids also can be used to prepare alkyd resins and are as follows: abietic acid, benzoic acid, p-tert-butylbenzoic acid, caproic acid, caprylic acid, crotonic acid, 2-ethyl-hexoic acid, lauric acid, pelargonic acid, rosin acids, and the like.
Monofunctional alcohols also can be used to prepare alkyd resins and are as follows :
butanol, pentanol, hexanol, isooctanol, ethoxy-ethanol, and butyl carbitol.
Drying oils also can be used to prepare the alkyd resin such as castor oil, heat bodied soya oil, soya oil, corn oil, dehydrated castor oil, linseed oil, oiticica oil, safflower oil and tung oil.
One particularly preferred alkyd rein that forms a high quality composition is the esteri-fication product of soya oil fatty acids/isophthalic ~152672 acid/trimethylol propane that has an acid number ofabout 20-100 and preferably 35-45 and a weight average molecular weight of about 800-3500.
The alkylated melamine formaldehyde resin used in the composition can contain 1-4 carbon atoms in the alkyl group and is water soluble or water dispersible. One preferred resin that forms a high quality product is a partially methylated melamine formaldehyde resin that has an equivalent weight of about 225-325. By equivalent weight is meant, the grams of alkylated melamine formaldehyde resin required to react with one gram mole of carboxyl, hydroxyl or amide groups of a polymer.
The acrylic dispersing resin used in the composition contains sufficient carboxyl groups to disperse resin and pigments.
Useful types of resin are disclosed in Jakubauskas U.S. Patent 3,980,602 issued September 14, 1976. One preferred resin that forms a high quality product is a polymer of methyl methacrylate/styrene/
butyl acrylate/ acrylic acid. The following ratio of constituent is particularly preferred 25/30/35/10.
The composition contains organo metallic driers. Typical driers are cobalt naphthenate, managanese naphthenate, nickel naphthenate, nickel octoate,zirconium octate, lead tallate and the like.
One preferred combination of driers comprises zirconium octoate, cobalt naphthenate and 1,10 phenanthroline.
One particularly useful coating compo-stition of this invention comprlses about 15-30~
by weight of water soluble solvents and 70-85~ by weight of a film forming binder. The binder is of about 80-85% by weight of the alkyd resin of soya 3S oil fatty acids, isophthalic acid and trimethylol propane having an acid number of 35-45 and a weight average molecular weight, determined as above, of 800-3500; 1-4% by weight of a partiallv methylated melamine formaldehyde resin having an equivalent weight of about 225-325, 13-17% by weight of an acrylic dispersing resin of styrene/methyl methacrylate/
butyl acrylate/acrylic acid; and 1-3~ by weight of an organo metallic drier of zirconium octoate, cobalt naphthenate and phenanthroline.
As aforementioned, the composition is pigmented for most uses. The pigments are formed into a mill base by grinding the pigment with the alkyd resin or acrylic dispersing resin and the resulting mill base is added to form a pigmented composition. The mill base is prepared by conven-tional grinding techniques such as sand grinding, ball milling, attritor grinding and the like.
After reduction to an application viscosity with an aqueous solution containing ammonia or amine as discussed above, the composition can be applied to a variety of substrates by any of the conventional application methods such as spraying, electrostatic spraying, dipping, brushing, flow coating, roller coating and the like. The resulting coatings can be dried at ambient temperatures or baked at relatively low temperatures up to about 140C. for about 5 minutes to 2 hours. The resulting coating is about 0.1-5 mils thick and is glossy, durable, weatherable, and has an excellent appearance.
The composition has excellent adhesion to all types of substrates such as wood, glass, bare metal, metal painted withthe following: acrylic enamel, acrylic lacquer, acrylic dispersion en~el, acrylic dispersion lacquer, ~152672 alkyd enamel, _onventional alkyd or epoxy primers;
fiberglass reinforced with polyester painted as above; acrylonitrile/butadiene/styrene plastics or other plastics 2ainted as above. The afore-mentioned characteristics make the composition partic--~lari~ useful as a finish or a refinish used for automobiles and truck bodies.
The following example illustrates the invention. All quantities are on a weight basis O unless otherwise indicated.
Example l The following pigment dispersions are prepared:
White Pigment Dispersion By fiaerght Alkyd resin solution(80% by 16.57 weight solids alkyd resin of soya oil fatty acids/isophthalic acid/trimethylol propane having an acid No. of about 40 and a weight average molecular weight of abo~t 900 determined by gel permeation chromatography) Ethylene glycol monoethyl ether 17.77 Titanium dioxide pigment 65.66 Total lO0.00 The above constituents are blended to-gether and charged into a conventional sand mill and ground to a 0.5 mil fineness.
Parts Black Pigment Dispersion By Weight Portion 1 Alkyd resin solution (des- 45.46 cribed above) Ethylene glycol monoethyl ether 18.91 Carbon Black Pigment S.45 Portion 2 _ Alkyd '-esin solution (des- 22.73 cribed above) Ethylene glycol monoethyl ether7.45 Total100.00 Portion 1 is charged into an attritor and ground to a 0.25 mil fineness. Portion 2 is charged with the portion 1 into the attritor and ground to a 0.25 mil fineness.
Parts Blue Pigment Dispersion By Weight Acrylic Resin Solution (76% 26.19 solids in isopropanol of an acrylic polymer of 2596 methyl methacrylate, 3096 styrene, 35% butyl acrylate and 10% acrylic acid) Ethylene glycol monoethyl ether29.32 Ethylene glycol monobutyl ether11.41 Blue Pigment (phthalocyanine 23.08 blue pigment) Total 100.00 TE~e a~ove constituents are charged into an attritor and ground to a 0.25 mil fineness.
The following tintings are prepared:
Parts White Tinting By Weight White pigment dispersion 41.82 (prepared above) Alkyd resin solution (des- 41.62 cribed above) ~ethylated melamine formaldehyde1.78 resin solution (80% weight solids of a partially methylated melam~ne formal-dehyde resin having an equivalent weight of 225-325 in a l:i isopropanol~
isobutanol solvent) Acrylic resin solution (des- 9.23 cribed above) Parts By Weight Toluene 0.58 Ethylene glycol monobutyl ether 4.73 Methyl ethyl ketoxime 0.24 Total 100.00 The above constituents are thoroughlv mixed together to rorm a tinting that has a pigment to binder weight ratio of about 57.97/100 and a volume solid content of 63.8%.
Parts Blac~ Tinting By Weight Black pigment dispersion 39.07 ~prepared above) Alkyd resin solution (des- 41.97 cribed above) ~ethylated Melamine Formalde- 2.35 hyde Resin Solution(described above) Methyl ethyl ketoxime 0.31 Ethylene glycol monobutyl ether 3.30 Acrylic resin solution ~des- 13.00 cribed above) Total100.00 The above constituents are thoroughly mixed together to form a tinting base that has a pigment to binder weight ratio of 3.2/100 and a volume solids content of about 63.84%.
Parts Blue Tinting By Weight Blue Pigment Dispersion (pre- 23.68 pared above) Alkyd resin solution (described 64.51 above) Methylated Melamine Formaldehyde 2.46 Resin Solution(descr~ above) Methyl ethyl ketoxime 0.33 Acrylic resin solution ~des- 6.5B
cribed above) Ethylene glycol monobutyl ether 2.44 Total100.00 The above constituents are thoroughly mixed together to f~m a tinting base that has a pigment to binder weight ratio of about 5/100 and a volume soli~s of about 63.71.
A drier ccmposition is prepared by blendir.g together the following:
Zirconium Octoate solution containing 37 79 6% by weight zirconium in mineral spirits Cobalt Hydrocure solution (55% solids 56.60 cobalt naththenate in ~ineral spirits) 1,10 phenanthroline ~ 61 Total 10~, 00 A thinner composition is prepared by blending together the following:
Parts By Weight Ammonia solution(25~ aqueous solution) 2.15 Deionized ~ater 97.85 Total100.00 A paint is formulated by blending together the following:
Parts By Weight White ttnting (prepared a~ove)99.68 Black tinting (prepared above) 0.27 Blue tinting (prepared above) 0.05 Drier composition (prepared above)2.50 Total 102.50 A sprayable coating composition is prepared by blending 1 part by volume of the above paint with 1.5 parts by volume of the thinner. The resulting paint i5 sprayed onto the following panels:
unprimed cold rolled steel, unprimed phosphatized steel, alkyd resin primed phosphatized steel, thermosetting acrylic enamel/alkyd resin primed steel, acrylic lacquer/alkyd resin primed steel.
The ?anels are dried at an ambient temperature for about two hours and a dust free film is formed that is about 1-3 mils thick. After twenty-four hours the films have a hardness of about l.l knoops, a gloss measured at 20 of 86 and at 60 of 95 and water spot resistance of about 7 based on a scaie of 0-10 where lO represents no water spotting. After 1 week at ambient temperatures, the films have excel-lent resistance to gasoline, good chip resistance and cold crack resistance and h~proved resistance to water spotting.
Example 2 A silver mill base is prepared as ~ollows:
Parts By Weight Alkyd resin solution (des- 67.57 cribed in Example 1) Aluminum Paste (16.19 parts 24.91 of aluminum flake in 24.91 parts mineral spirits) Ethylene glycol monoethvl ether7.52 Total lO0.00 The above constituents are thoroughly blended together to form a mill base.
A thinner solution is prepared by blending together the following constituents:
Parts By Weight Acetone 17.11 Diethylene glycol monobutyl ether 3.38 Deionized Water 77.34 Ammonia solution (29% aqueous solution) 2.17 Total 100.00 A silver paint is prepared by blending together the following constituents:
l~SZ67Z
Parts By Weight Silver ~ ase (prepared 22,oo above) Acrylic resin solution (des- 12.42 cribed in Example 1) Methyl ethyl ketoxime 0.32 Ethylene glycol monoethyl ether1.~6 Alkyd resin solution (described50.47 in ~xample 1) Methylated Melamine Formalde- 2.39 hyde Resin Solution (described in Example 1) Ethylene glycol monobutyl ether6.07 Toluene 1.09 Drier Composition(prepared in3.38 Example 1) Total lOo.oo A sprayable composition is prepared by blending about 1 part by volume of the above paint with about 1.5 parts by volume of the~above thinner 20 solution. The resulting paint is sprayed onto phosphate treated steel panels coated with an alkyd resin primer and dried at ambient temperatures for two hours to form a 1-3 mil thick film.
After about two weeks at ambient temperatures 25 the resulting films have a hardness of about 1.9 knoops, a gloss measured at 20 of 79 and a gloss measured at 60 of about 98. The films have excellent adhesion to the substrates and have an excellent appearance and good weatherability.
~L152672 Example 3 A red mill base is prepared as follows:
Parts By Weight Alkyd resin solution (described 23.45 in Example 1) Red Iron Oxide Pigment 56.29 Ethylene glycol monoethyl ether 20.26 Total 100.00 10The above constituents are cha~ged into a sandmi.ll and are ground in a sandmill to a 0-2.5 mil fineness to form a mill base.
A thinner solution is prepared by blending together the following constituents:
15Parts By Weight Methanol 3.44 Diethylene glycol monobutyl ether 1.72 Isopropanol 13.96 Ammonia solution (29~ aqueous2.21 solution) Deionized Water 78.67 Total 100.00 A red paint is prepared by blending together the following constituents:
Parts By Weight Red Mill Base (prepared above)16.38 Acrylic resin solution (des-11.61 cribed in Example 1) Methyl ethyl ketoxime 0.30 Ethylene glycol monoethyl ether 1.68 Alkyd resin solution (des- 57.21 cribed in Example 1) Methylated '5elamine Formalde-2.24 hyde ~esin Solution (described in Example 1) ~152672 1~
Toluene 1.~7 Ethylene glycol monobutyl ether 5.75 Drier Composition;prepared in Example 1) 5.16 Total 100.00 A sprayable composition is prepared by blending about 1 part by volume of the above paint with about 1.5 parts by volume of the above thinner solution. The resulting paint is sprayed onto phosphate treated steel panels primed with an alkyd resin primer and baked for 30 minutes at 150C.
The resulting film is about 1-3 mils thick. The panels are exposed to ambient temperatures for about 1 week. The resulting films have a hardness of about 1.7 knoops and a gloss measured at 20 of about 85.
The films have an excellent appearance and exhibit good weatherability.
The composition can be reduced to an aqueous based composition having an acceptable application viscosity with an aqueous composition containing sufficient base to provide a pH of about 6.5-9Ø
DETAILED DESCRIPTION OF THE IN~'ENTION
The coating composition contains about 40-90% by weight of a film forming binder and usually about 70-85% by weight of the film forming binder. The remainder of the compsition comprises a water soluble solvent. Minor amounts of water dispersible solvents can be added. For application, the composition is reduced to an application viscosity of about 16 to 50 seconds measured according to AST~-1084-63 with an aqueous reducer solutior.. This reducer 3S solution contains up to about 20~ by weight of a water ~152672 soluble solvent or solvents and sufficient ammonia or amine or a combination thereof to form a salt of the alkyd resin and the acrylic dispersing resin and pro-vide a pH of about 6.5-9. Usually a pH of about 7-8 is used.
Typical water soluble solvents that can be used to form the composition and the aqueous reducer solution are as follows: ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol propyl ether, isopropanol, ethanol, methanol, butanol and other alcohols, acetone, and the like. Small amounts of nonwater soluble sol-vents such as toluene, xylene, acetates and mineral spirits can be used. The amount of solvent added to the composition with the aqueous reducer solution can be adjusted to meet and comply with governmental regulations.
Ammonia or amine or a combination thereof used in the aqueous reducer solution reacts with free carboxyl groups of the alkyd resin and acrylic dispersing resin to form salt groups which allow the resins to be dispersed in an aqueous medium. The pH of the resulting composition can be adjusted to the aforementioned values. Typical amines that can be used are triethylamine, trimethylamine, ethanolamine, N,N-diethylethanolamine, N,N-dimethyl-ethanolamine, N-methylethanolamine, monoisopro-panolamine, butanolamine, ethylenediamine, diethyl-amine and the like.
The composition can be a clear but usually contains pigments in a pigment to binder weight ratio of about 1:100 to 75:100. Typical pigments that can be used are as follows: titanium dioxide, aluminum flake, red, yellow or orange iron oxide~ Irgazin* yellow and green, copper phthalocyanine *denotes trade mark ,~
~152672 green and blue, Monastral* red, extender pigments and a wide variety of other organic and inorganic pigments.
The alkyd resin used in the composition is the esterification product of drying oil fatty acids, an aromatic dicarboxylic acid and a polyhydric alcohol.
To prepare the alkyd resin, the above constituents along with an esterification catalyst are charged into a reaction vessel. Either a conventional fusion or solution process using conventional equipment can be used to prepare the alkyd resin. Generally reaction temperatures of about 200-275C. for 1 to 5 hours are used to prepare the resin. The resulting alkyd resin has an acid number of about 20-100 and a weight average molecular weight of about 800-15,000 and a number average molecular weight of about 800-4000 determined by gel permeation chromatography.
Typical solvents that can be used in the solution process for making the a~yd resin are water miscible or water soluble and are as follows: ethers, aliphatic alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, ethylene glycol monoalkyl ethers, such as ethylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoalkyl ether acetates, and the like.
Typical esterification catalysts that are used in the process for preparing alkyd resins are as follows: barium oxide, barium hydroxide, barium naphthenate, calcium oxide, calcium hy-droxide, calcium naphthenate, lead oxide, lithiumhydroxide, lithium napthenate, lithium ricinoleate, sodium hydroxide, sodium naphthenate, zinc oxide, and lead tallate.
Typical drying oil fatty acids that are used to prepare alkyd resins are as follows:
*denotes trade mark .~
dehydrated castor oil fatty acids,heat-bodied soya oil fattv acids, tung oil fatty acids, linseed oil fatty acids, oiticica oil fatty acids, safflower oil fatty acids, soya oil fatty acids, and the like. Soya oil fatty acids are preferred.
Typical aromatic dicarboxylic acids that can be used to prepare the alkyd resin are as follows: isophthalic acid, terephthalic acid, phthalic acid. Isophthalic acid is preferred.
Typical polyhydric alcohols that can be used to prepare alkyd resins are as follows:
ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol, neopentyl glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, methyl-glucoside, dipentaerythritol, and sorbitol.
Trimethylol propane is preferred.
Monobasic organic acids also can be used to prepare alkyd resins and are as follows: abietic acid, benzoic acid, p-tert-butylbenzoic acid, caproic acid, caprylic acid, crotonic acid, 2-ethyl-hexoic acid, lauric acid, pelargonic acid, rosin acids, and the like.
Monofunctional alcohols also can be used to prepare alkyd resins and are as follows :
butanol, pentanol, hexanol, isooctanol, ethoxy-ethanol, and butyl carbitol.
Drying oils also can be used to prepare the alkyd resin such as castor oil, heat bodied soya oil, soya oil, corn oil, dehydrated castor oil, linseed oil, oiticica oil, safflower oil and tung oil.
One particularly preferred alkyd rein that forms a high quality composition is the esteri-fication product of soya oil fatty acids/isophthalic ~152672 acid/trimethylol propane that has an acid number ofabout 20-100 and preferably 35-45 and a weight average molecular weight of about 800-3500.
The alkylated melamine formaldehyde resin used in the composition can contain 1-4 carbon atoms in the alkyl group and is water soluble or water dispersible. One preferred resin that forms a high quality product is a partially methylated melamine formaldehyde resin that has an equivalent weight of about 225-325. By equivalent weight is meant, the grams of alkylated melamine formaldehyde resin required to react with one gram mole of carboxyl, hydroxyl or amide groups of a polymer.
The acrylic dispersing resin used in the composition contains sufficient carboxyl groups to disperse resin and pigments.
Useful types of resin are disclosed in Jakubauskas U.S. Patent 3,980,602 issued September 14, 1976. One preferred resin that forms a high quality product is a polymer of methyl methacrylate/styrene/
butyl acrylate/ acrylic acid. The following ratio of constituent is particularly preferred 25/30/35/10.
The composition contains organo metallic driers. Typical driers are cobalt naphthenate, managanese naphthenate, nickel naphthenate, nickel octoate,zirconium octate, lead tallate and the like.
One preferred combination of driers comprises zirconium octoate, cobalt naphthenate and 1,10 phenanthroline.
One particularly useful coating compo-stition of this invention comprlses about 15-30~
by weight of water soluble solvents and 70-85~ by weight of a film forming binder. The binder is of about 80-85% by weight of the alkyd resin of soya 3S oil fatty acids, isophthalic acid and trimethylol propane having an acid number of 35-45 and a weight average molecular weight, determined as above, of 800-3500; 1-4% by weight of a partiallv methylated melamine formaldehyde resin having an equivalent weight of about 225-325, 13-17% by weight of an acrylic dispersing resin of styrene/methyl methacrylate/
butyl acrylate/acrylic acid; and 1-3~ by weight of an organo metallic drier of zirconium octoate, cobalt naphthenate and phenanthroline.
As aforementioned, the composition is pigmented for most uses. The pigments are formed into a mill base by grinding the pigment with the alkyd resin or acrylic dispersing resin and the resulting mill base is added to form a pigmented composition. The mill base is prepared by conven-tional grinding techniques such as sand grinding, ball milling, attritor grinding and the like.
After reduction to an application viscosity with an aqueous solution containing ammonia or amine as discussed above, the composition can be applied to a variety of substrates by any of the conventional application methods such as spraying, electrostatic spraying, dipping, brushing, flow coating, roller coating and the like. The resulting coatings can be dried at ambient temperatures or baked at relatively low temperatures up to about 140C. for about 5 minutes to 2 hours. The resulting coating is about 0.1-5 mils thick and is glossy, durable, weatherable, and has an excellent appearance.
The composition has excellent adhesion to all types of substrates such as wood, glass, bare metal, metal painted withthe following: acrylic enamel, acrylic lacquer, acrylic dispersion en~el, acrylic dispersion lacquer, ~152672 alkyd enamel, _onventional alkyd or epoxy primers;
fiberglass reinforced with polyester painted as above; acrylonitrile/butadiene/styrene plastics or other plastics 2ainted as above. The afore-mentioned characteristics make the composition partic--~lari~ useful as a finish or a refinish used for automobiles and truck bodies.
The following example illustrates the invention. All quantities are on a weight basis O unless otherwise indicated.
Example l The following pigment dispersions are prepared:
White Pigment Dispersion By fiaerght Alkyd resin solution(80% by 16.57 weight solids alkyd resin of soya oil fatty acids/isophthalic acid/trimethylol propane having an acid No. of about 40 and a weight average molecular weight of abo~t 900 determined by gel permeation chromatography) Ethylene glycol monoethyl ether 17.77 Titanium dioxide pigment 65.66 Total lO0.00 The above constituents are blended to-gether and charged into a conventional sand mill and ground to a 0.5 mil fineness.
Parts Black Pigment Dispersion By Weight Portion 1 Alkyd resin solution (des- 45.46 cribed above) Ethylene glycol monoethyl ether 18.91 Carbon Black Pigment S.45 Portion 2 _ Alkyd '-esin solution (des- 22.73 cribed above) Ethylene glycol monoethyl ether7.45 Total100.00 Portion 1 is charged into an attritor and ground to a 0.25 mil fineness. Portion 2 is charged with the portion 1 into the attritor and ground to a 0.25 mil fineness.
Parts Blue Pigment Dispersion By Weight Acrylic Resin Solution (76% 26.19 solids in isopropanol of an acrylic polymer of 2596 methyl methacrylate, 3096 styrene, 35% butyl acrylate and 10% acrylic acid) Ethylene glycol monoethyl ether29.32 Ethylene glycol monobutyl ether11.41 Blue Pigment (phthalocyanine 23.08 blue pigment) Total 100.00 TE~e a~ove constituents are charged into an attritor and ground to a 0.25 mil fineness.
The following tintings are prepared:
Parts White Tinting By Weight White pigment dispersion 41.82 (prepared above) Alkyd resin solution (des- 41.62 cribed above) ~ethylated melamine formaldehyde1.78 resin solution (80% weight solids of a partially methylated melam~ne formal-dehyde resin having an equivalent weight of 225-325 in a l:i isopropanol~
isobutanol solvent) Acrylic resin solution (des- 9.23 cribed above) Parts By Weight Toluene 0.58 Ethylene glycol monobutyl ether 4.73 Methyl ethyl ketoxime 0.24 Total 100.00 The above constituents are thoroughlv mixed together to rorm a tinting that has a pigment to binder weight ratio of about 57.97/100 and a volume solid content of 63.8%.
Parts Blac~ Tinting By Weight Black pigment dispersion 39.07 ~prepared above) Alkyd resin solution (des- 41.97 cribed above) ~ethylated Melamine Formalde- 2.35 hyde Resin Solution(described above) Methyl ethyl ketoxime 0.31 Ethylene glycol monobutyl ether 3.30 Acrylic resin solution ~des- 13.00 cribed above) Total100.00 The above constituents are thoroughly mixed together to form a tinting base that has a pigment to binder weight ratio of 3.2/100 and a volume solids content of about 63.84%.
Parts Blue Tinting By Weight Blue Pigment Dispersion (pre- 23.68 pared above) Alkyd resin solution (described 64.51 above) Methylated Melamine Formaldehyde 2.46 Resin Solution(descr~ above) Methyl ethyl ketoxime 0.33 Acrylic resin solution ~des- 6.5B
cribed above) Ethylene glycol monobutyl ether 2.44 Total100.00 The above constituents are thoroughly mixed together to f~m a tinting base that has a pigment to binder weight ratio of about 5/100 and a volume soli~s of about 63.71.
A drier ccmposition is prepared by blendir.g together the following:
Zirconium Octoate solution containing 37 79 6% by weight zirconium in mineral spirits Cobalt Hydrocure solution (55% solids 56.60 cobalt naththenate in ~ineral spirits) 1,10 phenanthroline ~ 61 Total 10~, 00 A thinner composition is prepared by blending together the following:
Parts By Weight Ammonia solution(25~ aqueous solution) 2.15 Deionized ~ater 97.85 Total100.00 A paint is formulated by blending together the following:
Parts By Weight White ttnting (prepared a~ove)99.68 Black tinting (prepared above) 0.27 Blue tinting (prepared above) 0.05 Drier composition (prepared above)2.50 Total 102.50 A sprayable coating composition is prepared by blending 1 part by volume of the above paint with 1.5 parts by volume of the thinner. The resulting paint i5 sprayed onto the following panels:
unprimed cold rolled steel, unprimed phosphatized steel, alkyd resin primed phosphatized steel, thermosetting acrylic enamel/alkyd resin primed steel, acrylic lacquer/alkyd resin primed steel.
The ?anels are dried at an ambient temperature for about two hours and a dust free film is formed that is about 1-3 mils thick. After twenty-four hours the films have a hardness of about l.l knoops, a gloss measured at 20 of 86 and at 60 of 95 and water spot resistance of about 7 based on a scaie of 0-10 where lO represents no water spotting. After 1 week at ambient temperatures, the films have excel-lent resistance to gasoline, good chip resistance and cold crack resistance and h~proved resistance to water spotting.
Example 2 A silver mill base is prepared as ~ollows:
Parts By Weight Alkyd resin solution (des- 67.57 cribed in Example 1) Aluminum Paste (16.19 parts 24.91 of aluminum flake in 24.91 parts mineral spirits) Ethylene glycol monoethvl ether7.52 Total lO0.00 The above constituents are thoroughly blended together to form a mill base.
A thinner solution is prepared by blending together the following constituents:
Parts By Weight Acetone 17.11 Diethylene glycol monobutyl ether 3.38 Deionized Water 77.34 Ammonia solution (29% aqueous solution) 2.17 Total 100.00 A silver paint is prepared by blending together the following constituents:
l~SZ67Z
Parts By Weight Silver ~ ase (prepared 22,oo above) Acrylic resin solution (des- 12.42 cribed in Example 1) Methyl ethyl ketoxime 0.32 Ethylene glycol monoethyl ether1.~6 Alkyd resin solution (described50.47 in ~xample 1) Methylated Melamine Formalde- 2.39 hyde Resin Solution (described in Example 1) Ethylene glycol monobutyl ether6.07 Toluene 1.09 Drier Composition(prepared in3.38 Example 1) Total lOo.oo A sprayable composition is prepared by blending about 1 part by volume of the above paint with about 1.5 parts by volume of the~above thinner 20 solution. The resulting paint is sprayed onto phosphate treated steel panels coated with an alkyd resin primer and dried at ambient temperatures for two hours to form a 1-3 mil thick film.
After about two weeks at ambient temperatures 25 the resulting films have a hardness of about 1.9 knoops, a gloss measured at 20 of 79 and a gloss measured at 60 of about 98. The films have excellent adhesion to the substrates and have an excellent appearance and good weatherability.
~L152672 Example 3 A red mill base is prepared as follows:
Parts By Weight Alkyd resin solution (described 23.45 in Example 1) Red Iron Oxide Pigment 56.29 Ethylene glycol monoethyl ether 20.26 Total 100.00 10The above constituents are cha~ged into a sandmi.ll and are ground in a sandmill to a 0-2.5 mil fineness to form a mill base.
A thinner solution is prepared by blending together the following constituents:
15Parts By Weight Methanol 3.44 Diethylene glycol monobutyl ether 1.72 Isopropanol 13.96 Ammonia solution (29~ aqueous2.21 solution) Deionized Water 78.67 Total 100.00 A red paint is prepared by blending together the following constituents:
Parts By Weight Red Mill Base (prepared above)16.38 Acrylic resin solution (des-11.61 cribed in Example 1) Methyl ethyl ketoxime 0.30 Ethylene glycol monoethyl ether 1.68 Alkyd resin solution (des- 57.21 cribed in Example 1) Methylated '5elamine Formalde-2.24 hyde ~esin Solution (described in Example 1) ~152672 1~
Toluene 1.~7 Ethylene glycol monobutyl ether 5.75 Drier Composition;prepared in Example 1) 5.16 Total 100.00 A sprayable composition is prepared by blending about 1 part by volume of the above paint with about 1.5 parts by volume of the above thinner solution. The resulting paint is sprayed onto phosphate treated steel panels primed with an alkyd resin primer and baked for 30 minutes at 150C.
The resulting film is about 1-3 mils thick. The panels are exposed to ambient temperatures for about 1 week. The resulting films have a hardness of about 1.7 knoops and a gloss measured at 20 of about 85.
The films have an excellent appearance and exhibit good weatherability.
Claims (9)
1. A coating composition comprising about 40-90% by weight of a film forming binder and about 10-60% by weight of a water soluble organic solvent and pigments in a pigment to binder weight ratio of about 1:100 to 75:100; wherein the binder consists essentially of about (1) 50-90% by weight, based on the weight of the binder, of an alkyd resin consisting essentially of the esteri-fication product of soya oil fatty acids, isophthalic acid and trimethylol propane having an acid number of about 20-100 and a weight average molecular weight of about 800-15,000 determined by gel permeation chromatography;
(2) 0.5-5% by weight, based on the weight of the binder, of an alkylated melamine formaldehyde resin;
(3) 9-20% by weight, based on the weight of the binder, of an acrylic dispersing resin consisting of styrene/methyl methacrylate/
butyl acrylate/acrylic acid; and (4) 0.5-5% by weight, based on the weight of the binder, of an organo metallic drier.
(2) 0.5-5% by weight, based on the weight of the binder, of an alkylated melamine formaldehyde resin;
(3) 9-20% by weight, based on the weight of the binder, of an acrylic dispersing resin consisting of styrene/methyl methacrylate/
butyl acrylate/acrylic acid; and (4) 0.5-5% by weight, based on the weight of the binder, of an organo metallic drier.
2. The coating composition of Claim 1 containing a sufficient amount of an aqueous reducer to provide an application viscosity of 16 to 50 seconds measured according to ASTM 1084-63; wherein the reducer comprises up to about 20% by weight of a water soluble solvent, water and sufficient base of amine or ammonia to provide the resulting compo-sition with a pH of about 6.5-9Ø
3. The coating composition of claim 2 in which the base is ammonia.
4. The coating composition of claim 1 in which the alkyd resin has an acid number of about 35-45 and a weight average molecular weight of about 800-3500.
5. The coating composition of Claim 1 in which the alkylated melamine formaldehyde resin is a partially methylated melamine formaldehyde resin.
6. The coating composition of Claim 1 in which the organo metallic drier consists essentially of zirconium octoate, cobalt naphthenate and phenanthroline.
7. The coating composition of Claim 1 in which comprises about 15-30% by weight of water soluble solvents and 70-85% by weight of a film forming binder.
8. The coating composition of Claim 1 which comprises about 15-30% by weight of water soluble solvents and 70-85% by weight of a film forming binder; wherein the binder consists essentially of (1) 80-85% by weight, based on the weight of the binder, of an alkyd resin having an acid number of about 35-45 and a weight average molecular weight of about 800-3500, (2) 1-4% by weight, based on the weight of the binder, of a partially methylated melamine formaldehyde resin having an equivalent weight of about 225-325.
(3) 13-17% by weight, based on the weight of the binder, of an acrylic dispersing resin consisting of styrene/methyl mehacrylate/butyl acrylate/acrylic acid, (4) 1-3% by weight, based on the weight of the binder, of an organo metallic drier consisting essentially of zirconium octoate, cobalt naphthenate and phenanthroline.
(3) 13-17% by weight, based on the weight of the binder, of an acrylic dispersing resin consisting of styrene/methyl mehacrylate/butyl acrylate/acrylic acid, (4) 1-3% by weight, based on the weight of the binder, of an organo metallic drier consisting essentially of zirconium octoate, cobalt naphthenate and phenanthroline.
9. A metal substrate coated with about 0.1-5 mil thick layer of the dried coalesced composition of Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2098479A | 1979-03-16 | 1979-03-16 | |
| US020,984 | 1979-03-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1152672A true CA1152672A (en) | 1983-08-23 |
Family
ID=21801691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000347746A Expired CA1152672A (en) | 1979-03-16 | 1980-03-14 | Water reducible alkyd resin coating composition |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS55144058A (en) |
| AU (1) | AU5651080A (en) |
| BE (1) | BE882227A (en) |
| BR (1) | BR8001414A (en) |
| CA (1) | CA1152672A (en) |
| DE (1) | DE3009874A1 (en) |
| ES (1) | ES8104372A1 (en) |
| FR (1) | FR2451390A1 (en) |
| GB (1) | GB2044780B (en) |
| IT (1) | IT1130968B (en) |
| ZA (1) | ZA801507B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408821A (en) * | 2010-09-21 | 2012-04-11 | 苏州美亚美建筑涂料有限公司 | Alkyd resin waterproof paint |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4517320A (en) * | 1982-08-20 | 1985-05-14 | Ciba-Geigy Corporation | Stoving lacquers containing graphite |
| US4477608A (en) * | 1982-08-20 | 1984-10-16 | Ciba-Geigy Corporation | Compositions containing graphite |
| US4783497A (en) * | 1985-12-16 | 1988-11-08 | Reynolds Metals Company | Water-based polyester coating compositions containing an alkylated amino resin |
| CN104231503B (en) * | 2014-08-15 | 2016-06-01 | 深圳市容大感光科技股份有限公司 | A kind of water soluble resin composite |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE573304A (en) * | 1957-11-26 | |||
| US3349050A (en) * | 1965-04-08 | 1967-10-24 | Mobil Oil Corp | Coating composition |
| AT319428B (en) * | 1972-07-10 | 1974-12-27 | Vianova Kunstharz Ag | Process for the production of paint binders |
| US3980602A (en) * | 1975-02-28 | 1976-09-14 | E. I. Du Pont De Nemours And Company | Acrylic polymer dispersant for aqueous acrylic coating compositions |
-
1980
- 1980-03-11 BR BR8001414A patent/BR8001414A/en unknown
- 1980-03-14 CA CA000347746A patent/CA1152672A/en not_active Expired
- 1980-03-14 ZA ZA00801507A patent/ZA801507B/en unknown
- 1980-03-14 BE BE0/199796A patent/BE882227A/en unknown
- 1980-03-14 DE DE19803009874 patent/DE3009874A1/en not_active Withdrawn
- 1980-03-14 ES ES489597A patent/ES8104372A1/en not_active Expired
- 1980-03-14 IT IT20659/80A patent/IT1130968B/en active
- 1980-03-14 JP JP3174580A patent/JPS55144058A/en active Pending
- 1980-03-14 GB GB8008714A patent/GB2044780B/en not_active Expired
- 1980-03-14 FR FR8005775A patent/FR2451390A1/en active Pending
- 1980-03-17 AU AU56510/80A patent/AU5651080A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408821A (en) * | 2010-09-21 | 2012-04-11 | 苏州美亚美建筑涂料有限公司 | Alkyd resin waterproof paint |
| CN102408821B (en) * | 2010-09-21 | 2014-03-12 | 苏州美亚美建筑涂料有限公司 | Alkyd resin waterproof paint |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2044780A (en) | 1980-10-22 |
| AU5651080A (en) | 1980-09-18 |
| BE882227A (en) | 1980-09-15 |
| IT8020659A0 (en) | 1980-03-14 |
| FR2451390A1 (en) | 1980-10-10 |
| GB2044780B (en) | 1983-04-20 |
| ES489597A0 (en) | 1981-04-16 |
| ZA801507B (en) | 1981-08-26 |
| ES8104372A1 (en) | 1981-04-16 |
| DE3009874A1 (en) | 1980-09-25 |
| JPS55144058A (en) | 1980-11-10 |
| BR8001414A (en) | 1980-11-11 |
| IT1130968B (en) | 1986-06-18 |
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