CA1124435A - Acrylic lacquer composition - Google Patents
Acrylic lacquer compositionInfo
- Publication number
- CA1124435A CA1124435A CA370,577A CA370577A CA1124435A CA 1124435 A CA1124435 A CA 1124435A CA 370577 A CA370577 A CA 370577A CA 1124435 A CA1124435 A CA 1124435A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- methyl methacrylate
- binder
- polymer
- coating composition
- 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
Landscapes
- Paints Or Removers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A coating composition for finishing the exterior of automobile and truck bodies having a film forming binder of the following constituents:
(a) polymethyl methacrylate;
(b) a copolymer of methyl methacrylate and an alkyl amino alkyl methacrylate such as diethyl amino ethyl methacrylate;
(c) a copolymer of methyl methacrylate and an alkyl acrylate such as butyl acrylate;
(d) cellulose acetate butyrate;
(e) a polyester plasticizer;
(f) a polymer of methyl methacrylate, an alkyl acrylate and an .alpha.-.beta. ethylenically unsatu-rated monocarboxylic acid such as acrylic acid or methacrylic acid reacted with an alkkylene imine such as propylene imine;
the composition has good adhesion to lacquer and enamel finishes used on automobiles and truck bodies and is excellent for refinishing automobile and truck bodies.
A coating composition for finishing the exterior of automobile and truck bodies having a film forming binder of the following constituents:
(a) polymethyl methacrylate;
(b) a copolymer of methyl methacrylate and an alkyl amino alkyl methacrylate such as diethyl amino ethyl methacrylate;
(c) a copolymer of methyl methacrylate and an alkyl acrylate such as butyl acrylate;
(d) cellulose acetate butyrate;
(e) a polyester plasticizer;
(f) a polymer of methyl methacrylate, an alkyl acrylate and an .alpha.-.beta. ethylenically unsatu-rated monocarboxylic acid such as acrylic acid or methacrylic acid reacted with an alkkylene imine such as propylene imine;
the composition has good adhesion to lacquer and enamel finishes used on automobiles and truck bodies and is excellent for refinishing automobile and truck bodies.
Description
,t ,..
4~
BACKGROUND O~ THE INVENTION
This lnvention is related to coatlng compositions and in particular to acrylic lacquer coating compositions.
To refinish or repair acrylic lacquer and acrylic enamel Pinishes of automobile and truck bodies, different coating compositions have been utilized for the enamel and for the lacquer finishes. Willey U.S. 3,711,433 issued January 16, 1973 illustrates a typical composition utilized to re-finish or repair acrylic lacquer finishes and Walus et al., U.S. 3,488,307 issued January 6, 1970 illustrates a typical composition utilized to refinish or repair acrylic enamel finishes. These aforementioned compositions are excellent refinish compositiOns. However, to reduce costs and.simplify inventories for both suppliers and users which typically are auto body repair shops, a single composition is desired that could be used to refinish or repai~ both eriamel and lacquer finishes.
The novel canposition of this invention can be used to refinish or repair enamel and lacquer finishes of autc~nobile and truck bodies and has excellent adhesion to these finishes, good appearance, good durability and weatherability. me ccmposition can also be used as an o~iginal equipment finish that is applied by a manufacturer to automobile and truck bodies.
SUMMARY OF THE INVENTION
The coating canposition comprises about 5-40~ by weight of a film fo~ng binder and about 60-95% by weight of volatile organic solvents; wherein the binder consists essentially of (a) 15-25% by weight~ based on the weight of the binder, of polymethyl methacrylate having a relative viscosity of about 1.17-1.20 measured ~ i at 25C on a 0.5% polymer 5O11~5 solutlon using dichloroethylene as the solvent;
tb) 5-15% by weight, based on the weight of the binder, of a copolymer of methyl methacrylate and alkyl amino alkyl methacrylate having 1-4 carbon atoms ln the alkyl group and having a relatlve viscosity of about 1.17-1.20 measured as above;
; 10 tc) 20-40% by weight, based on the weight of the binder, of a copolymer of methyl methacrylate and an alkyl acrylate having 2-8 carbon atoms in the alkyl group and having a relatlve viscosity of 1.17-1.20 measured as above;
(d) 5-25% by weight, based on the . weight of the binder, of cellulose acetate butyrate having a viscosity of about 1-20 seconds and a butryl .
content of about 30-55~ by weight;
(e) 15-30% by weight, based on the weight of the binder, of a polyester plasti-cizer of a saturated fatty oil, a polyol and an organic dicarboxylic acid or an anhydrideof an organic dicarboxylic acid having an acid number of about 0.1-10; and (f) 1-10% by weight, based on the weight of the binder , of a polymer of methyl methacrylate,an alkyl acrylate having 2-12 carbon atoms in the alkyl group and an ;~
~ L~.Z~;35 drB unsaturated monocarboxylic acid and in which the polymer ls reacted wlth an alkylene imine and havlng a relatlve viscoslty of about 1.17-1.20 measured as above;and wherein the total of (a), (b), (c), (d) (e) and (f) are 100%.
DESCRIPTION OF THE INVENTION
~he coatlng composltion has a binder content Or film-forming constituents of about 5-40% by weight.
The remainder of the constituents in the composition is a solvent blend for the binder. In addition, the compo-sition optionally contains pigment in a pigment to binder ratio of about 1.0/100 to 100/100.
The acrylic polymers utilized in the coating composition are prepared by solution polymerization in which the monomers are blended with a solvent, polymeri-- zation catalyst and heated to about 75-150C for 2-6 hours to form a polymer that has a relative viscosity of about 1.17-1.20 measured at 0.5% polymer solids at 25C uslng dlchloroethylene as the solvent.
Typical solvents which are used to prepare the acrylic polymers are the following: toluene, ethyl acetate, acetone, ethylene monoethylether acetate,methyl-ethyl ketone, lsopropyl alcohol, and other allphatic, cyclo-allphatlc and aromatic hydrocarbon, esters, ethers, ketones and alcohols which are conventionally used.
About 0.1-4% by welght, based on the weight of the monomers, of the polymerization catalyst is used to prepare the acrylic polymer. Typlcal catalysts are:
az~-bis-isobutyronltrile, azo-bis(-~-gamma dlmethyl) valeronitrile), benzoyl peroxide, t-butyl plvalate and the like.
A chain transfer agent can be used to control the molecular weight of the acryllc polymers.
Typical chain transfer agents are 2-mercapto ethanol, dodecyl mercaptan, benzene thioethanol, mercapto succinic acid, butyl mercaptan, mercapto proprionic acid and the like.
The coating composition contains about 15-25% by weight, based on the weight of the binder, of polymethyl methacrylate havlng the aforementioned relative viscosity. Preferably, about 17-20% by weight, based on the weight of the binder, of polymethyl metha-crylate is used in the coating composition.
The coating composition contains about 5-15%
by weight, based on the weight of the binder, of a copolymer of methyl methacrylate and an alkyl amino alkyl methacrylate having the aforementioned relative viscosity. Typical alkyl amino alkyl methacrylates are dimethylaminoethyl methacrylate,diethylaminoethyl methacrylate, tertiary butyl aminoethyl methacrylate and the like. Preferably, the copolymer contains about 90-99.5% by weight of methyl methacrylate~and 0.5-10%
by weight of the alkyl amino alkyl methacrylate such as diethyl amino ethyl methacrylate. One preferred coating composition contains about 8-12% by weight of the above copolymer.
~.244~5 The coating composition contains about 20-40%
by weight, based on the weight of the binder, of a copolymer of methyl methacrylate and an alkyl acrylate having
4~
BACKGROUND O~ THE INVENTION
This lnvention is related to coatlng compositions and in particular to acrylic lacquer coating compositions.
To refinish or repair acrylic lacquer and acrylic enamel Pinishes of automobile and truck bodies, different coating compositions have been utilized for the enamel and for the lacquer finishes. Willey U.S. 3,711,433 issued January 16, 1973 illustrates a typical composition utilized to re-finish or repair acrylic lacquer finishes and Walus et al., U.S. 3,488,307 issued January 6, 1970 illustrates a typical composition utilized to refinish or repair acrylic enamel finishes. These aforementioned compositions are excellent refinish compositiOns. However, to reduce costs and.simplify inventories for both suppliers and users which typically are auto body repair shops, a single composition is desired that could be used to refinish or repai~ both eriamel and lacquer finishes.
The novel canposition of this invention can be used to refinish or repair enamel and lacquer finishes of autc~nobile and truck bodies and has excellent adhesion to these finishes, good appearance, good durability and weatherability. me ccmposition can also be used as an o~iginal equipment finish that is applied by a manufacturer to automobile and truck bodies.
SUMMARY OF THE INVENTION
The coating canposition comprises about 5-40~ by weight of a film fo~ng binder and about 60-95% by weight of volatile organic solvents; wherein the binder consists essentially of (a) 15-25% by weight~ based on the weight of the binder, of polymethyl methacrylate having a relative viscosity of about 1.17-1.20 measured ~ i at 25C on a 0.5% polymer 5O11~5 solutlon using dichloroethylene as the solvent;
tb) 5-15% by weight, based on the weight of the binder, of a copolymer of methyl methacrylate and alkyl amino alkyl methacrylate having 1-4 carbon atoms ln the alkyl group and having a relatlve viscosity of about 1.17-1.20 measured as above;
; 10 tc) 20-40% by weight, based on the weight of the binder, of a copolymer of methyl methacrylate and an alkyl acrylate having 2-8 carbon atoms in the alkyl group and having a relatlve viscosity of 1.17-1.20 measured as above;
(d) 5-25% by weight, based on the . weight of the binder, of cellulose acetate butyrate having a viscosity of about 1-20 seconds and a butryl .
content of about 30-55~ by weight;
(e) 15-30% by weight, based on the weight of the binder, of a polyester plasti-cizer of a saturated fatty oil, a polyol and an organic dicarboxylic acid or an anhydrideof an organic dicarboxylic acid having an acid number of about 0.1-10; and (f) 1-10% by weight, based on the weight of the binder , of a polymer of methyl methacrylate,an alkyl acrylate having 2-12 carbon atoms in the alkyl group and an ;~
~ L~.Z~;35 drB unsaturated monocarboxylic acid and in which the polymer ls reacted wlth an alkylene imine and havlng a relatlve viscoslty of about 1.17-1.20 measured as above;and wherein the total of (a), (b), (c), (d) (e) and (f) are 100%.
DESCRIPTION OF THE INVENTION
~he coatlng composltion has a binder content Or film-forming constituents of about 5-40% by weight.
The remainder of the constituents in the composition is a solvent blend for the binder. In addition, the compo-sition optionally contains pigment in a pigment to binder ratio of about 1.0/100 to 100/100.
The acrylic polymers utilized in the coating composition are prepared by solution polymerization in which the monomers are blended with a solvent, polymeri-- zation catalyst and heated to about 75-150C for 2-6 hours to form a polymer that has a relative viscosity of about 1.17-1.20 measured at 0.5% polymer solids at 25C uslng dlchloroethylene as the solvent.
Typical solvents which are used to prepare the acrylic polymers are the following: toluene, ethyl acetate, acetone, ethylene monoethylether acetate,methyl-ethyl ketone, lsopropyl alcohol, and other allphatic, cyclo-allphatlc and aromatic hydrocarbon, esters, ethers, ketones and alcohols which are conventionally used.
About 0.1-4% by welght, based on the weight of the monomers, of the polymerization catalyst is used to prepare the acrylic polymer. Typlcal catalysts are:
az~-bis-isobutyronltrile, azo-bis(-~-gamma dlmethyl) valeronitrile), benzoyl peroxide, t-butyl plvalate and the like.
A chain transfer agent can be used to control the molecular weight of the acryllc polymers.
Typical chain transfer agents are 2-mercapto ethanol, dodecyl mercaptan, benzene thioethanol, mercapto succinic acid, butyl mercaptan, mercapto proprionic acid and the like.
The coating composition contains about 15-25% by weight, based on the weight of the binder, of polymethyl methacrylate havlng the aforementioned relative viscosity. Preferably, about 17-20% by weight, based on the weight of the binder, of polymethyl metha-crylate is used in the coating composition.
The coating composition contains about 5-15%
by weight, based on the weight of the binder, of a copolymer of methyl methacrylate and an alkyl amino alkyl methacrylate having the aforementioned relative viscosity. Typical alkyl amino alkyl methacrylates are dimethylaminoethyl methacrylate,diethylaminoethyl methacrylate, tertiary butyl aminoethyl methacrylate and the like. Preferably, the copolymer contains about 90-99.5% by weight of methyl methacrylate~and 0.5-10%
by weight of the alkyl amino alkyl methacrylate such as diethyl amino ethyl methacrylate. One preferred coating composition contains about 8-12% by weight of the above copolymer.
~.244~5 The coating composition contains about 20-40%
by weight, based on the weight of the binder, of a copolymer of methyl methacrylate and an alkyl acrylate having
2-8 carbon atoms in the alkyl group and having the afore-mentioned relative viscosity. The polymer usually con-tains 80-9Q% by weight methyl methacrylate and 10-20%
by weight butyl acrylate. Other alkyl acrylates that can be used are ethyl acrylate, propyl acrylate, hexyl acrylate, lsobutyl acrylate, 2 ethylhexyl acrylate and the like. Preferably, the coating compositon contains about 25-35% by weight of the above polymer.
The coating composition contains about 1-10%
by weight, based on the weight of the binder, of a poly-mer of methyl methacrylate, an alkyl acrylate having 2-12 carbon atoms in the alkyl group and an ~,~ unsatu-rated monocarboxylic acid in which the polymer is reacted with an alkylene imine. Any of the aforementioned alkyl acrylates can be used to prepare the polymer including nonyl acrylate, decyl acrylate and lauryl acrylate.
Preferably, ethyl acrylate, butyl acrylate, butyl acrylate or 2 ethyl acrylate is used. Typically useful acids used to prepare this polymer are acrylic acid and methacrylic acid. Alkylene imines such as propylene imine or ethylene imine or hydroxy ethyl ethylene imine are reacted with the carboxyl groups of the acid of the polymer. Generally, about 90-100% of the carboxyl groups are reacted with an alkylene imine. About 2-5% by weight, based on the weight of the binder, of one particularly useful polymer can be used in the composition in which the polymer is of 70-90% by weight of methyl methacrylate, 9-20% by weight of ethyl acrylate and 1-10% by wei~ht of methacrylic acid which is reacted with propylene imine.
~ 2~4~i About 5-25% by weight, based on the welght of the blnder, of cellulose acetate butyrate (CAB~ ls used ln the coatlng composition. The CAB has a butyryl content of about 30-55% by weight and a viscosity of about 1-20 seconds measured according to ASTMD 1343-56 a blend of a high viscosity CAB and a low viscosity CAB
can be used in the composition in a weight ratio of about l:l.to 1:6. The high viscosity CAB has a butyryl content of about 35-40% by weight and a viscosity of 15-20 seconds and the low viscosity CAB has the same butyryl content and a viscosity of about ~-3 seconds.
In one preferred composition of 3-15% of the low vlscosity CA~ is used in combination with about 3-10% by weight of the high viscosity CAB.
The composition contains about 15-30% by weight, based on the weight of the binder, of a polyester plasticizer of a saturated fatty oil, a polyol and an organic dicarboxylic acid or an anhydride thereof having an acid number of about 0.1-10. The polyester is pre-pared by conventional polymerization techniques in whichthe constituents and a conventional esterification catalyst such as lead tallate, sodium naphthenate, barium oxide, barium hydroxide, lithium hydroxide are reacted at 80-200C for about 0.5-6 hours. A typical saturated fatty oil that can be used to prepare the poly-ester is coconut oil: Polyesters of a polyol and an organic dicarboxylic acid or anhydride thereof without a saturated fatty oil can also be used.
Typical polyols that can be used to prepare the polyester are ethylene glycol, propylene glycol, dipropylene glycol, butane diol, diethylene glycol, neopentyl glycol and the like.
Z L~4 3 S
Other polyols that can be used are glycerol, trimethylol propane, trimethylol ethanej pentaery thritol, dlpentaerytrhrito~ sorbitol and the like.
Typical organic dicarboxyllc acids or anhydrides that can be used to prepare the polyester are adipic acid, azelaic acid ? chlorendic acid, chlorendic anhydride, phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, succinic acid, succinic anhydride trimelletic acid, trimelletic anhydride and the like.
One particularly useful polyester.used in the coating composition is of coconut oil, ethylene glycol and phthalic anhydride. ~bout 20-25% by weight, based on the weight of the binder, of the alkyd resin is used in the composition.
Another aspect of this invention is a coating composition comprising 5-40% by weight of a film-forming binder and 95-60% by weight of a volatile organic solvent, wherein the binder consists essentially of about ta) 30-50% by weight, based on the weight ~ 20 ofthe binder, of polymethyl methacrylate having a relative viscosity of about 1.17 to 1.20 measured at 25C on a 0.5~ polymer solids solution using a dichloroethylene .. . . _ . _ : solvent; -_.
(b) 20-40% by weight, based on the weight of the binder, of cellulose acetate butyrate having a viscosity of about 1-3 seconds and a butyryl content of 30-55% by weight;
4;35 -(c) 5-15% by weight, based on the weight of the binder, of a phthalate ester plasticlzer, (d) 10-30% by weight, based on the weight of the binder, of a~polyester plasticizer of a saturated fatty oil, a polyol and an organic dicarboxylic acid or an anhydride of a dicarboxylic acid and having an acid number of about 0.1-10; and (e) 1-10% by weight, based on the weight of the binder, of a polymer of methyl methacrylate, an alkyl acrylate having 2-12 carbon atoms in the alkyl group and ~ ;
an ~,~-unsaturated monocarboxylic acid and in which the polymer is reacted with an alkylene lmine and having a relative ViSGosity of about 1.17 to 1.20 measured as above, wherein the total of (a), (b), (c), (d) and (e) are 100%.
The aforementioned polymethyl methacrylate, cellulose acetate butyrate and high and low viscosity blends thereof or cellulose acetate butyrate having a 1-3 second viscosity and a butyryl content of 35-40% by weight, the polyester and the acrylic resin reacted ~ith an alkylene imine can be used the above coating composition. Preferred phthalate ester plasticizers are butyl cyclohexyl phthalate.
and butyl benzyl phthalate.
As mentioned before, the composition can contain pigments. These pigments can be introduced into the compositlon by ~lrst ~orming a mill base wlth any of the above polymers utillzed in the coating composltion or with other compatible polymers by conventional techniques, such as s&nd-grinding, ball milling, attritor grinding, or two roll milling to disperse the pigments. The mill base is blended with the film-~orming constituents as shown in the following Ex&mples.
Any of the conventional pigments used in the coating compositions can be utilized in this composition.
Examples of typical pigments that can be used are as follows: metallic oxide, such as tit&nium dioxide, zinc oxide, iron oxide and the like, metal hydroxide, metal - flakes such as aluminum flake, sulfide, sulfates, carbonates, carbon black, silica, talc, china clay, phthalocyanine blues and greens, organo reds, organo maroons &nd other organic dyes.
The coating composition of this invention can be applied over a variety of substrates, such as metal, primed metal, metal coated with en&mels or lacquers, wood, glass, plastics, and the like, by any of the conventional application methods, such as spraying,electrostatic spraying, dipping, brushing, flow-coating and the like. The viscosity of the compo-sition can be adjusted ~or any of these methods by adding solvents if necessary.
The applied coatings can be dried at ambient temperatures or baked at relatively low temperatures of about 35-100C. ~or about 15 minutes-2 hours. The resulting finish is about 0.1-5 mils thick but ~or most uses, a 1-3 mil thick finish is used. The resulting 2 4~ 5 finish has good appearance and can be rubbed or pollshed wlth con~entional techniques to improve the smoothness or gloss or both. The finish has good adhesion to substrates of all types particularly industrial lacquers or enamel finished substrates. The finish is hard and resistant to weathering, staining,scratches and the like. These charac-teristics make the composition particularly useful for finishing or refinish automobile and truck bodies. The coating composition can also be used on aircraft, farm equipment such as tractors, appliances, vending machines, bridges, water tanks, gas tanks and the like.
The following Examples illustrate the invention.
All quantities are shown on a weight ba,sis unless other-wise indicated ~ 2~35 - An iminated ac~ylic polymer solutlon prepared by charging the following constituents lnto a reaction vessel equipped with a thermometer,a stirrer, a reflux condenser and a heating mantel;
Parts by Portion 1. Weight Toluene 54-79 Isopropanol 110.83 Ethyl Acetate 148.05 Methyl methacrylate monomer 254.08 Ethyl acrylate monomer 45.80 Met;hacrylic acid monomer 13.80 Azobisisobutyronitrile 0.73 Portion 2 Azobisisobutyronitrile 0.83 Ethyl acetate 6.70 Toluene 4.80 Portion 3 Azobisiobutyronitrile 1.26 Ethyl acetate 7.32 Toluene 13.60 Portion 4 Isopropanol 19.86 Toluene 104.55 Portion 5 Propylene imine 9.20 Isopropanol 13.80 Total810.00 Por~ion 1 is premixed and then is charged into the reaction ~essel with constant mixing and heated.
_ 12 -and then the heat is turned off. The temperature of the resulting reaction mixture rises to a reflux temperature of about 82-84C and ls maintained at this temperature by slightly refluxlng the mixture for about 60 minutes. Portion 2 is premixed and added to the reaction vessel and the resulting reaction mixture is held at about 81-83C by s~i~htly.refluxing the mixture for about 90 minutes.. Portion 3 is premixed and.added to the reaction vessel and the resulting reaction mixture is held at about 81-83C at; a slight reflux for about 45 minutes. Portion 4 is added with mixing and then Portion 5 is premixed and added and the reaction mixture is thoroughly mixed for about 15 minutes and held at about 76-80C for about 2 hours or until the acid number of the reaction ~
mixture reaches about 0.1-3.5 and then cooled to room temperature.
The resulting polymer solution has a solids content of about 39% by weight, a Gardner Holdt Viscosity measured at 25C of about W-Y and the polymer has the following compo-.sition: methyl methacrylate/~thyl acrylate/methacrylic acid/
propylenimine in a weight ratio of 81.0/14.6/4.4/2.9 in which all of the propyleneimine has reacted with the metha-crylic acid. The polymer has a relative viscosity of about 1.2 measured on a 0.5% polymer ~solids solutio~Q using a dichloroethylene solvent at 25C.
A butyl acrylate/methyl methacrylate polymer solution is prepared by char.ging the following constituents into a reaction vessel equipped as above:
Parts by Portlon 1 Weight Acetone 81.61 Toluene 82.00 Butyl acrylate monomer 58.7?
s - Methylmethacrylate mQnomer 267.61 Benz~yl peroxide 1.61 Po~tlon 2 Benzoyl peroxlde ,0.72 Toluene 6.72 Portion 3 Toluene 317.12 Total 816.11 Portion 1 ls charged into the reactlon vessel and heated to about 100C and held at thls temperature for about 1 hour and 20 minutes. Portlon 2 ls premlxed and added to the reaction vessel and the resultlng reaction mixture ls held at about 100C for about 20 minutes and then Portion
by weight butyl acrylate. Other alkyl acrylates that can be used are ethyl acrylate, propyl acrylate, hexyl acrylate, lsobutyl acrylate, 2 ethylhexyl acrylate and the like. Preferably, the coating compositon contains about 25-35% by weight of the above polymer.
The coating composition contains about 1-10%
by weight, based on the weight of the binder, of a poly-mer of methyl methacrylate, an alkyl acrylate having 2-12 carbon atoms in the alkyl group and an ~,~ unsatu-rated monocarboxylic acid in which the polymer is reacted with an alkylene imine. Any of the aforementioned alkyl acrylates can be used to prepare the polymer including nonyl acrylate, decyl acrylate and lauryl acrylate.
Preferably, ethyl acrylate, butyl acrylate, butyl acrylate or 2 ethyl acrylate is used. Typically useful acids used to prepare this polymer are acrylic acid and methacrylic acid. Alkylene imines such as propylene imine or ethylene imine or hydroxy ethyl ethylene imine are reacted with the carboxyl groups of the acid of the polymer. Generally, about 90-100% of the carboxyl groups are reacted with an alkylene imine. About 2-5% by weight, based on the weight of the binder, of one particularly useful polymer can be used in the composition in which the polymer is of 70-90% by weight of methyl methacrylate, 9-20% by weight of ethyl acrylate and 1-10% by wei~ht of methacrylic acid which is reacted with propylene imine.
~ 2~4~i About 5-25% by weight, based on the welght of the blnder, of cellulose acetate butyrate (CAB~ ls used ln the coatlng composition. The CAB has a butyryl content of about 30-55% by weight and a viscosity of about 1-20 seconds measured according to ASTMD 1343-56 a blend of a high viscosity CAB and a low viscosity CAB
can be used in the composition in a weight ratio of about l:l.to 1:6. The high viscosity CAB has a butyryl content of about 35-40% by weight and a viscosity of 15-20 seconds and the low viscosity CAB has the same butyryl content and a viscosity of about ~-3 seconds.
In one preferred composition of 3-15% of the low vlscosity CA~ is used in combination with about 3-10% by weight of the high viscosity CAB.
The composition contains about 15-30% by weight, based on the weight of the binder, of a polyester plasticizer of a saturated fatty oil, a polyol and an organic dicarboxylic acid or an anhydride thereof having an acid number of about 0.1-10. The polyester is pre-pared by conventional polymerization techniques in whichthe constituents and a conventional esterification catalyst such as lead tallate, sodium naphthenate, barium oxide, barium hydroxide, lithium hydroxide are reacted at 80-200C for about 0.5-6 hours. A typical saturated fatty oil that can be used to prepare the poly-ester is coconut oil: Polyesters of a polyol and an organic dicarboxylic acid or anhydride thereof without a saturated fatty oil can also be used.
Typical polyols that can be used to prepare the polyester are ethylene glycol, propylene glycol, dipropylene glycol, butane diol, diethylene glycol, neopentyl glycol and the like.
Z L~4 3 S
Other polyols that can be used are glycerol, trimethylol propane, trimethylol ethanej pentaery thritol, dlpentaerytrhrito~ sorbitol and the like.
Typical organic dicarboxyllc acids or anhydrides that can be used to prepare the polyester are adipic acid, azelaic acid ? chlorendic acid, chlorendic anhydride, phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, succinic acid, succinic anhydride trimelletic acid, trimelletic anhydride and the like.
One particularly useful polyester.used in the coating composition is of coconut oil, ethylene glycol and phthalic anhydride. ~bout 20-25% by weight, based on the weight of the binder, of the alkyd resin is used in the composition.
Another aspect of this invention is a coating composition comprising 5-40% by weight of a film-forming binder and 95-60% by weight of a volatile organic solvent, wherein the binder consists essentially of about ta) 30-50% by weight, based on the weight ~ 20 ofthe binder, of polymethyl methacrylate having a relative viscosity of about 1.17 to 1.20 measured at 25C on a 0.5~ polymer solids solution using a dichloroethylene .. . . _ . _ : solvent; -_.
(b) 20-40% by weight, based on the weight of the binder, of cellulose acetate butyrate having a viscosity of about 1-3 seconds and a butyryl content of 30-55% by weight;
4;35 -(c) 5-15% by weight, based on the weight of the binder, of a phthalate ester plasticlzer, (d) 10-30% by weight, based on the weight of the binder, of a~polyester plasticizer of a saturated fatty oil, a polyol and an organic dicarboxylic acid or an anhydride of a dicarboxylic acid and having an acid number of about 0.1-10; and (e) 1-10% by weight, based on the weight of the binder, of a polymer of methyl methacrylate, an alkyl acrylate having 2-12 carbon atoms in the alkyl group and ~ ;
an ~,~-unsaturated monocarboxylic acid and in which the polymer is reacted with an alkylene lmine and having a relative ViSGosity of about 1.17 to 1.20 measured as above, wherein the total of (a), (b), (c), (d) and (e) are 100%.
The aforementioned polymethyl methacrylate, cellulose acetate butyrate and high and low viscosity blends thereof or cellulose acetate butyrate having a 1-3 second viscosity and a butyryl content of 35-40% by weight, the polyester and the acrylic resin reacted ~ith an alkylene imine can be used the above coating composition. Preferred phthalate ester plasticizers are butyl cyclohexyl phthalate.
and butyl benzyl phthalate.
As mentioned before, the composition can contain pigments. These pigments can be introduced into the compositlon by ~lrst ~orming a mill base wlth any of the above polymers utillzed in the coating composltion or with other compatible polymers by conventional techniques, such as s&nd-grinding, ball milling, attritor grinding, or two roll milling to disperse the pigments. The mill base is blended with the film-~orming constituents as shown in the following Ex&mples.
Any of the conventional pigments used in the coating compositions can be utilized in this composition.
Examples of typical pigments that can be used are as follows: metallic oxide, such as tit&nium dioxide, zinc oxide, iron oxide and the like, metal hydroxide, metal - flakes such as aluminum flake, sulfide, sulfates, carbonates, carbon black, silica, talc, china clay, phthalocyanine blues and greens, organo reds, organo maroons &nd other organic dyes.
The coating composition of this invention can be applied over a variety of substrates, such as metal, primed metal, metal coated with en&mels or lacquers, wood, glass, plastics, and the like, by any of the conventional application methods, such as spraying,electrostatic spraying, dipping, brushing, flow-coating and the like. The viscosity of the compo-sition can be adjusted ~or any of these methods by adding solvents if necessary.
The applied coatings can be dried at ambient temperatures or baked at relatively low temperatures of about 35-100C. ~or about 15 minutes-2 hours. The resulting finish is about 0.1-5 mils thick but ~or most uses, a 1-3 mil thick finish is used. The resulting 2 4~ 5 finish has good appearance and can be rubbed or pollshed wlth con~entional techniques to improve the smoothness or gloss or both. The finish has good adhesion to substrates of all types particularly industrial lacquers or enamel finished substrates. The finish is hard and resistant to weathering, staining,scratches and the like. These charac-teristics make the composition particularly useful for finishing or refinish automobile and truck bodies. The coating composition can also be used on aircraft, farm equipment such as tractors, appliances, vending machines, bridges, water tanks, gas tanks and the like.
The following Examples illustrate the invention.
All quantities are shown on a weight ba,sis unless other-wise indicated ~ 2~35 - An iminated ac~ylic polymer solutlon prepared by charging the following constituents lnto a reaction vessel equipped with a thermometer,a stirrer, a reflux condenser and a heating mantel;
Parts by Portion 1. Weight Toluene 54-79 Isopropanol 110.83 Ethyl Acetate 148.05 Methyl methacrylate monomer 254.08 Ethyl acrylate monomer 45.80 Met;hacrylic acid monomer 13.80 Azobisisobutyronitrile 0.73 Portion 2 Azobisisobutyronitrile 0.83 Ethyl acetate 6.70 Toluene 4.80 Portion 3 Azobisiobutyronitrile 1.26 Ethyl acetate 7.32 Toluene 13.60 Portion 4 Isopropanol 19.86 Toluene 104.55 Portion 5 Propylene imine 9.20 Isopropanol 13.80 Total810.00 Por~ion 1 is premixed and then is charged into the reaction ~essel with constant mixing and heated.
_ 12 -and then the heat is turned off. The temperature of the resulting reaction mixture rises to a reflux temperature of about 82-84C and ls maintained at this temperature by slightly refluxlng the mixture for about 60 minutes. Portion 2 is premixed and added to the reaction vessel and the resulting reaction mixture is held at about 81-83C by s~i~htly.refluxing the mixture for about 90 minutes.. Portion 3 is premixed and.added to the reaction vessel and the resulting reaction mixture is held at about 81-83C at; a slight reflux for about 45 minutes. Portion 4 is added with mixing and then Portion 5 is premixed and added and the reaction mixture is thoroughly mixed for about 15 minutes and held at about 76-80C for about 2 hours or until the acid number of the reaction ~
mixture reaches about 0.1-3.5 and then cooled to room temperature.
The resulting polymer solution has a solids content of about 39% by weight, a Gardner Holdt Viscosity measured at 25C of about W-Y and the polymer has the following compo-.sition: methyl methacrylate/~thyl acrylate/methacrylic acid/
propylenimine in a weight ratio of 81.0/14.6/4.4/2.9 in which all of the propyleneimine has reacted with the metha-crylic acid. The polymer has a relative viscosity of about 1.2 measured on a 0.5% polymer ~solids solutio~Q using a dichloroethylene solvent at 25C.
A butyl acrylate/methyl methacrylate polymer solution is prepared by char.ging the following constituents into a reaction vessel equipped as above:
Parts by Portlon 1 Weight Acetone 81.61 Toluene 82.00 Butyl acrylate monomer 58.7?
s - Methylmethacrylate mQnomer 267.61 Benz~yl peroxide 1.61 Po~tlon 2 Benzoyl peroxlde ,0.72 Toluene 6.72 Portion 3 Toluene 317.12 Total 816.11 Portion 1 ls charged into the reactlon vessel and heated to about 100C and held at thls temperature for about 1 hour and 20 minutes. Portlon 2 ls premlxed and added to the reaction vessel and the resultlng reaction mixture ls held at about 100C for about 20 minutes and then Portion
3 ls added.
The resulting polymer solution has a sollds content of about 40% by welght and Gardner Holdt Viscosity measured at 25~C of V-1/2 to W. The polymer contains about 82% methyl methacrylate and 18% butyl acrylate and has a relative vlscoslty measured as above of about 1.19.
A methyl methacrylate/diethyl amino ethyl methacrylate copolymer solution is prepared by charging the followlng constituents into a reaction vessel equipped as above:
Parts by Portlon 1 Weight Methyl methacrylate monomer 322.15 Diethylaminoethyl methacrylate 3.25 monomer Ace~one 115.40 Toluene 48.80 ~ 2~4~5 Azobisisobutyronltrlle 1.09 Portion 2 Acetone 5-00 Azobisisobutyronitrile 0.55 Portion 3 Acetone 27.65 Toluene 293.10 Total 816.99 Port,lon 1 ls changed into a reaction vessel equipped as above and heated to about 100C and held at this temperature for about 1 hour. Portion 2 is added and the resulting reaction mixture is held at 100C for another hour. Portion 3 is added and the reaction mixture is cooled.
The resulting polymer solution has a polymer solids content of about 40% by weight and a Gardner Holdt Viscoslty measured at 25C of about X-~2. The polymer is ~9% by weight methyl methacrylate and 1~ butyl acrylate and has a relative viscosity measured as above of about 1.2.
A methyl methacrylate polymer solution is prepared by charging the following constituents into a reaction vessel equipped as above:
Parts by Portlon 1 _ Weight Methyl methacrylate monomer322.28 Acetone 112.71 Toluene 48.33 Benzoyl peroxlde 2.18 Portion 2 Acetone 32.29 Toluene 290.2g_ 808.08 Portion 1 is premixed and charged into a reaction : vessel and heated to about 100C and held at this temperature ~or about 1-1/2 hours and then Portion 2 is added and the resulting pol~mer solution is cooled to room temperature.
The polymer solution has a polymer solids content of about 40% by weight and the polymer has a relative viscosity of about l,i9 measured as above.
A ~oconut 0il/ethylene glycol/phthalic anhydride es~er resin solution is prepared by charging the following constituents in a reaction vessel equipped as abo.ve:
Parts by Portion 1 weight Coconut oil 275.70 Ethylene glycol 185.00 Dibutyltin oxide 0. 26 : Lead tallate drier 0.23 Portion 2 Phthalic Anhydride 394.70 Portion 3 Toluene 63.74 Portion 4 Toluene 75.36 Total 994.99 ~L~ 2~43~
Portion 1 is charged into the reaction Vessel and heated to 188C and held at this temperature for about 1 hour. Portlon 2 is then added and then the temperature of the resulting reaction mixture is brought to 150C. Portion 3 is added and the reaction mixture is held at its reflux temperature of about 190C for about 30 minutes and then the temperature OL the reaction mixture is increased to about 200C and held at this temperature for 30 minutes. The reaction mixture is heated to 232C and held for 2 hours at this tempera-ture and then heated to 245C and held until the acid numberof the reaction mixture is below about 10 which usually takes about 1 hour. The reaction mixture is heated to 250C and held at this temperature for about 2 hours. During the above reaction, water is removed from the reaction mixture.
Portion 4 is added and the resulting alkyd resin solution is cooled to room temperature.
The ester resin solution has a solids content of about 85% by weight and a Gardner Holdt Viscosity measured at 25C of about Y-~l and the alkyd resin has an acid number of about 7-10.
A white mill base is prepared by charging the following constituents into a mixing vessel and then grinding the mixture in a sand mill:
Parts by Portion 1 weight Methyl methacrylate/diethylamino ethyl methacrylate copolymer 7.00 solution (prepared above) Cellulose acetate butyrate(CAB)6.00 solution (25% CAB having a 38%
butyryl content and a 1 second viscosi'y ir. a solvent of 5 parts toluene/2 parts acetone) Toluene 18.05 Ethylene glycol monoethyl ether acetate 10.00 ~ ~fl4~5 Portion 2 Tltanlum dioxide pigment 55.00 Portion 3 Ester resin solution (prepared ~ 3.95 above) Total 100.00 Portion 1 is mixed for 15 minutes and then portion 2 is added and mixed for 1 hour and portion 3 is added and mixed for 1 hour. The resulting mixture is ground 3n a .sandmill.
An aluminum flake mill base is prepared by mixing the following constituents.
- Parts by PortiGn 1 Weight Methyl methacrylate polymer 56.64 solution(prepared above) Aluminum Paste (67% aluminum 12.12 flake in an aliphatic hydro-carbon.) Portion 2 Methyl methacrylate polymer 21.35 solution(prepared above) Toluene 11.89 Total100.00 Portion 1 is added to a mixer and slowly mixed for 3 hours and then portion 2 is added and mixed for 1 hour.
A white acrylic lacquer coating composition is prepared as follows:
Parts by Portion 1 Weight Acetone 12.97 Ethylene glycol monoethyl 25.28 ethyl acetate Toluene 33.18 Ester: resin solution 56.48 (prepared above) ~ 4~ S
Portion 2 ~llicone solution (1% 0.25 solids silicone SF69 in xylene) Methyl methacrylate polymer solution 107.32 tprepared above) Methyl methacrylate/diethyl 45.69 aminoethyl methacrylate copoly-mer solution (prepared above) Butyl acrylate/methylmethacrylate148.75 copolymer solution (prepared above) Imi~ated acrylic polymer solution17.50 (prepared above) Cellulose Acetate Butyrate solution 101.88 (described above) High Molecular Wei~ht Cellulose124.45 Acetate Butyrate (CAB) solution (15%
solids CAB having a 38% butyryl content and a 20 second viscosity measured according to ASTMD-1343-56 at 25C in a solvent blend of 60 parts acetone/25 parts toluene.) Portion 3 White Mill base (prepared ab?ve)168.47 Total 842.22 The constituents of Portion 1 are added 20 in the order shown and mixed until uniform. Portion 2 is added and thoroughly mixed before Portion 3 is added and mixed until uniform.
The resulting lacquer has a pigment to binder ratio of 40/100. The binder is of 18.5 parts parts polymethyl metha-crylate, 10.0 parts methyl methacrylate/diethylamino ethyl methacrylate copolymer, 25.5 parts butyl acrylate/methyl methacrylate copolymer, 23.0 parts of ester resin, 12.0 parts CAB having a 1 second viscosity, 8.0 parts CAB having a 20 second viscosity and 3.0 parts of an iminated acrylic polymer.
l~ Z9L435 A whlte acrylic lacquer B ls prepared identlcal to the above lacquer A except the iminated acrylic polymer is omitted and the butyl acrylate/methyl methacrylate copolymer is substituted therefore.
A silver metallic acrylic lacquer C is prepared by mi~ing together the following constituents.
Parts by Portion 1 Weight Acetone 22.11 Ethy~ene glycol aminoethyl 39.21 ether acetate Toluene 51.60 Ester resin solution 59.09 (prepared above) Portion 2 -Silicone solution (1% 0.24 solids silicone SF69 in xylene)
The resulting polymer solution has a sollds content of about 40% by welght and Gardner Holdt Viscosity measured at 25~C of V-1/2 to W. The polymer contains about 82% methyl methacrylate and 18% butyl acrylate and has a relative vlscoslty measured as above of about 1.19.
A methyl methacrylate/diethyl amino ethyl methacrylate copolymer solution is prepared by charging the followlng constituents into a reaction vessel equipped as above:
Parts by Portlon 1 Weight Methyl methacrylate monomer 322.15 Diethylaminoethyl methacrylate 3.25 monomer Ace~one 115.40 Toluene 48.80 ~ 2~4~5 Azobisisobutyronltrlle 1.09 Portion 2 Acetone 5-00 Azobisisobutyronitrile 0.55 Portion 3 Acetone 27.65 Toluene 293.10 Total 816.99 Port,lon 1 ls changed into a reaction vessel equipped as above and heated to about 100C and held at this temperature for about 1 hour. Portion 2 is added and the resulting reaction mixture is held at 100C for another hour. Portion 3 is added and the reaction mixture is cooled.
The resulting polymer solution has a polymer solids content of about 40% by weight and a Gardner Holdt Viscoslty measured at 25C of about X-~2. The polymer is ~9% by weight methyl methacrylate and 1~ butyl acrylate and has a relative viscosity measured as above of about 1.2.
A methyl methacrylate polymer solution is prepared by charging the following constituents into a reaction vessel equipped as above:
Parts by Portlon 1 _ Weight Methyl methacrylate monomer322.28 Acetone 112.71 Toluene 48.33 Benzoyl peroxlde 2.18 Portion 2 Acetone 32.29 Toluene 290.2g_ 808.08 Portion 1 is premixed and charged into a reaction : vessel and heated to about 100C and held at this temperature ~or about 1-1/2 hours and then Portion 2 is added and the resulting pol~mer solution is cooled to room temperature.
The polymer solution has a polymer solids content of about 40% by weight and the polymer has a relative viscosity of about l,i9 measured as above.
A ~oconut 0il/ethylene glycol/phthalic anhydride es~er resin solution is prepared by charging the following constituents in a reaction vessel equipped as abo.ve:
Parts by Portion 1 weight Coconut oil 275.70 Ethylene glycol 185.00 Dibutyltin oxide 0. 26 : Lead tallate drier 0.23 Portion 2 Phthalic Anhydride 394.70 Portion 3 Toluene 63.74 Portion 4 Toluene 75.36 Total 994.99 ~L~ 2~43~
Portion 1 is charged into the reaction Vessel and heated to 188C and held at this temperature for about 1 hour. Portlon 2 is then added and then the temperature of the resulting reaction mixture is brought to 150C. Portion 3 is added and the reaction mixture is held at its reflux temperature of about 190C for about 30 minutes and then the temperature OL the reaction mixture is increased to about 200C and held at this temperature for 30 minutes. The reaction mixture is heated to 232C and held for 2 hours at this tempera-ture and then heated to 245C and held until the acid numberof the reaction mixture is below about 10 which usually takes about 1 hour. The reaction mixture is heated to 250C and held at this temperature for about 2 hours. During the above reaction, water is removed from the reaction mixture.
Portion 4 is added and the resulting alkyd resin solution is cooled to room temperature.
The ester resin solution has a solids content of about 85% by weight and a Gardner Holdt Viscosity measured at 25C of about Y-~l and the alkyd resin has an acid number of about 7-10.
A white mill base is prepared by charging the following constituents into a mixing vessel and then grinding the mixture in a sand mill:
Parts by Portion 1 weight Methyl methacrylate/diethylamino ethyl methacrylate copolymer 7.00 solution (prepared above) Cellulose acetate butyrate(CAB)6.00 solution (25% CAB having a 38%
butyryl content and a 1 second viscosi'y ir. a solvent of 5 parts toluene/2 parts acetone) Toluene 18.05 Ethylene glycol monoethyl ether acetate 10.00 ~ ~fl4~5 Portion 2 Tltanlum dioxide pigment 55.00 Portion 3 Ester resin solution (prepared ~ 3.95 above) Total 100.00 Portion 1 is mixed for 15 minutes and then portion 2 is added and mixed for 1 hour and portion 3 is added and mixed for 1 hour. The resulting mixture is ground 3n a .sandmill.
An aluminum flake mill base is prepared by mixing the following constituents.
- Parts by PortiGn 1 Weight Methyl methacrylate polymer 56.64 solution(prepared above) Aluminum Paste (67% aluminum 12.12 flake in an aliphatic hydro-carbon.) Portion 2 Methyl methacrylate polymer 21.35 solution(prepared above) Toluene 11.89 Total100.00 Portion 1 is added to a mixer and slowly mixed for 3 hours and then portion 2 is added and mixed for 1 hour.
A white acrylic lacquer coating composition is prepared as follows:
Parts by Portion 1 Weight Acetone 12.97 Ethylene glycol monoethyl 25.28 ethyl acetate Toluene 33.18 Ester: resin solution 56.48 (prepared above) ~ 4~ S
Portion 2 ~llicone solution (1% 0.25 solids silicone SF69 in xylene) Methyl methacrylate polymer solution 107.32 tprepared above) Methyl methacrylate/diethyl 45.69 aminoethyl methacrylate copoly-mer solution (prepared above) Butyl acrylate/methylmethacrylate148.75 copolymer solution (prepared above) Imi~ated acrylic polymer solution17.50 (prepared above) Cellulose Acetate Butyrate solution 101.88 (described above) High Molecular Wei~ht Cellulose124.45 Acetate Butyrate (CAB) solution (15%
solids CAB having a 38% butyryl content and a 20 second viscosity measured according to ASTMD-1343-56 at 25C in a solvent blend of 60 parts acetone/25 parts toluene.) Portion 3 White Mill base (prepared ab?ve)168.47 Total 842.22 The constituents of Portion 1 are added 20 in the order shown and mixed until uniform. Portion 2 is added and thoroughly mixed before Portion 3 is added and mixed until uniform.
The resulting lacquer has a pigment to binder ratio of 40/100. The binder is of 18.5 parts parts polymethyl metha-crylate, 10.0 parts methyl methacrylate/diethylamino ethyl methacrylate copolymer, 25.5 parts butyl acrylate/methyl methacrylate copolymer, 23.0 parts of ester resin, 12.0 parts CAB having a 1 second viscosity, 8.0 parts CAB having a 20 second viscosity and 3.0 parts of an iminated acrylic polymer.
l~ Z9L435 A whlte acrylic lacquer B ls prepared identlcal to the above lacquer A except the iminated acrylic polymer is omitted and the butyl acrylate/methyl methacrylate copolymer is substituted therefore.
A silver metallic acrylic lacquer C is prepared by mi~ing together the following constituents.
Parts by Portion 1 Weight Acetone 22.11 Ethy~ene glycol aminoethyl 39.21 ether acetate Toluene 51.60 Ester resin solution 59.09 (prepared above) Portion 2 -Silicone solution (1% 0.24 solids silicone SF69 in xylene)
4-dodecyloxy-2-hydroxy 6.96 benzophenne(DOBP U.V. Screening agent) Methyl methacrylate polymèr solution 18.40 (prepared above) Methyl methacrylate/diethyl 62.16 aminoethyl methacrylate copolymer solution (prepared above) Butyl acrylate/methyl methacrylate 158.39 copolymer solution (prepared above) Iminated acrylic polymer solution 18.63 (prepared above) Cellulose Acetate Butyrate solution 169.08 (described above) High Molecular Welght Cellulose49.73 Acetate Butyrate (CAB) solution (1~% solids CAB having a 38% butyryl content and a 20 second viscosity measured according to ASTMD-1343-56 at 25C) in a solvent blend of 60 parts acetone/25 parts toluene).
Portion 3 Alurllinum flake mill base 124.40 (prepared above) 3 Total 780.00 .z~s~s The constituents of Portion l are added to a mixer in the order shown with constant mixing and Portion 2 is added and thoroughly m~ixed and then Portion 3 is added and : thoroughly mixed.
The resulting lacquer has a pigment to binder ratio of 4.07/100. The binder is of 18.5 parts polymethyl methacrylate monomer, 10.0 parts methyl methacrylate/diethylamino ethyl methacrylate copolymer, 2~.5 parts butyl acrylate~methyl methacrylate copolymer, 20.2 parts of ester resin, 2.8 parts DOBP, 17.0 parts CAB having a l second viscosity, 3.0 parts CAB having a 20 second viscosity and 3.0 parts of an iminated acrylic polymer.
A silver metallic acrylic lacquer D is prepared identical to the above lacquer C except the iminated acrylic polymer is omitted and the butyl acrylate/methylmethacrylate copolymer is subst`ituted therefore.
The above prepared lacquers A,B,C and D are each sprayed onto separate primed steel panels coated with baked acrylic enamels and baked for 24 hours at 43C. to provide a topcoat about 2 mils thick.
The adhesion of the topcoat to the substrate is determined on a set of these panels by scribing a rectangular grid through the topcoat to the metal with a knife and placing scotch tape over the grid and then removing the tape. A sub~ective rating of 10 means that none of the topcoat is removed while a rating of 0 indicates that all of the topcoat is removed.
The panels are tested for initial adhesion, wet adhesion after 96 hrs. exposure to 100% relative humid~ty at 38C and recovered adhesion, i.e. the panel sub~ected to the wet adhesion test is allowed to dry at room temperature for 24 hours and then tested as above.
Several sets of panels were subjected to outdoor s weathering in Florida for a 3 month period and then tested for adhesion as above. The results of these tests are s~mmarized ln the following table:
Table Initial Adhesior.* Wet Adhesion* Recovered Adhesion*
Start 3mo.Fla. Start 3mo.Fla. Start 3mo.Fla Lacquers A+C 7.4 7.8 1.9 2.2 6.3 4.6 B+D 2.0 2.9 0.5 0 1.7 0.9 *(average of 16 data points) The above results show that Lacquers A and C which contain only a s,mall precentage of an ~m~nated acrylic polymer have substantially better adheslon under all conditions that do Lacquers B and D which do not contain an iminated acrylic polymer.
The following constituents are blended together to form a clear lacquer that will dry at room temperatures:
Parts by Weight Isopropanol 386.0 Acetone 464.0 Toluene 156.0 Xylene 276.0 Cellulose Acetate Butyrate 220.3 (having a butyryl content of 38% and a viscosity of 2 seconds measured as in Example 1) Ethylene glycol monoethyl ether 232.0 acetate ~OBP U.V.~Screening agent 25.7 (described in Example 1) Silicone solution (described 7.8 in Example 1) 3o Butyl cyclohexylphthalate 73.3 Esterresin solution (prepared 197.0 ln Example 1) Imlnated Acrylic Polymer solution 94.4 (prepared in Example 1) Methyl methacrylate Polymer solution850.0 (prepared in Example 1) Total 2982.5 The above lacquer is sprayed onto primed steel panels coated with an acrylic lacquer ana primed steel panels coated with an acrylic enamel and in each case dried at 43C for 24 hours. The adheslon of the lacquer on each of the substrates is checked as in Example 1 and in each case the lacquer has an acceptable level of adhesion to the panel, i.e. an adhesion level of 7 and above when dry.
The application is a division of copending Canadian Serial No. 306 669, filed 1978-06-30.
_ 23 ~ .
Portion 3 Alurllinum flake mill base 124.40 (prepared above) 3 Total 780.00 .z~s~s The constituents of Portion l are added to a mixer in the order shown with constant mixing and Portion 2 is added and thoroughly m~ixed and then Portion 3 is added and : thoroughly mixed.
The resulting lacquer has a pigment to binder ratio of 4.07/100. The binder is of 18.5 parts polymethyl methacrylate monomer, 10.0 parts methyl methacrylate/diethylamino ethyl methacrylate copolymer, 2~.5 parts butyl acrylate~methyl methacrylate copolymer, 20.2 parts of ester resin, 2.8 parts DOBP, 17.0 parts CAB having a l second viscosity, 3.0 parts CAB having a 20 second viscosity and 3.0 parts of an iminated acrylic polymer.
A silver metallic acrylic lacquer D is prepared identical to the above lacquer C except the iminated acrylic polymer is omitted and the butyl acrylate/methylmethacrylate copolymer is subst`ituted therefore.
The above prepared lacquers A,B,C and D are each sprayed onto separate primed steel panels coated with baked acrylic enamels and baked for 24 hours at 43C. to provide a topcoat about 2 mils thick.
The adhesion of the topcoat to the substrate is determined on a set of these panels by scribing a rectangular grid through the topcoat to the metal with a knife and placing scotch tape over the grid and then removing the tape. A sub~ective rating of 10 means that none of the topcoat is removed while a rating of 0 indicates that all of the topcoat is removed.
The panels are tested for initial adhesion, wet adhesion after 96 hrs. exposure to 100% relative humid~ty at 38C and recovered adhesion, i.e. the panel sub~ected to the wet adhesion test is allowed to dry at room temperature for 24 hours and then tested as above.
Several sets of panels were subjected to outdoor s weathering in Florida for a 3 month period and then tested for adhesion as above. The results of these tests are s~mmarized ln the following table:
Table Initial Adhesior.* Wet Adhesion* Recovered Adhesion*
Start 3mo.Fla. Start 3mo.Fla. Start 3mo.Fla Lacquers A+C 7.4 7.8 1.9 2.2 6.3 4.6 B+D 2.0 2.9 0.5 0 1.7 0.9 *(average of 16 data points) The above results show that Lacquers A and C which contain only a s,mall precentage of an ~m~nated acrylic polymer have substantially better adheslon under all conditions that do Lacquers B and D which do not contain an iminated acrylic polymer.
The following constituents are blended together to form a clear lacquer that will dry at room temperatures:
Parts by Weight Isopropanol 386.0 Acetone 464.0 Toluene 156.0 Xylene 276.0 Cellulose Acetate Butyrate 220.3 (having a butyryl content of 38% and a viscosity of 2 seconds measured as in Example 1) Ethylene glycol monoethyl ether 232.0 acetate ~OBP U.V.~Screening agent 25.7 (described in Example 1) Silicone solution (described 7.8 in Example 1) 3o Butyl cyclohexylphthalate 73.3 Esterresin solution (prepared 197.0 ln Example 1) Imlnated Acrylic Polymer solution 94.4 (prepared in Example 1) Methyl methacrylate Polymer solution850.0 (prepared in Example 1) Total 2982.5 The above lacquer is sprayed onto primed steel panels coated with an acrylic lacquer ana primed steel panels coated with an acrylic enamel and in each case dried at 43C for 24 hours. The adheslon of the lacquer on each of the substrates is checked as in Example 1 and in each case the lacquer has an acceptable level of adhesion to the panel, i.e. an adhesion level of 7 and above when dry.
The application is a division of copending Canadian Serial No. 306 669, filed 1978-06-30.
_ 23 ~ .
Claims (9)
1. A coating composition comprising 5-40% by weight of a film forming binder and 60-95% by weight of volatile organic solvents; wherein the binder consists essentially of about (a) 30-50% by weight, based on the weight of the binder, of polymethyl methacrylate having a relative viscosity of about 1.17-1.20 measured at 25°C on a 0.5% polymer solids solution using dichloroethylene solvent;
(b) 20-40% by weight, based on the weight of the binder, of cellulose acetate butyrate having a viscosity of about 1-3 seconds and a butyryl content of 30-55% by weight;
(c) 5-15% by weight, based on the weight of the binder, of a phthalate ester plasticizer;
(d) 10-30% by weight, based on the weight of the binder, of a polyester plasticizer of a saturated fatty oil, a polyol and an organic di-carboxylic acid or an anhydride of an organic dicarboxylic acid and having an acid number of about 0.1-10; and (e) 1-10% by weight, based on the weight of the binder, of a polymer of methyl methacrylate, an alkyl acrylate having 2-12 carbon atoms in the alkyl group and an .alpha.,.beta.-unsaturated monocarboxylic acid and in which the polymer is reacted with an alkylene imine and having a relative viscosity of about 1.17 to 1.20 measured as above;
wherein the total of (a), (b), (c), (d) and (e) are 100%.
(b) 20-40% by weight, based on the weight of the binder, of cellulose acetate butyrate having a viscosity of about 1-3 seconds and a butyryl content of 30-55% by weight;
(c) 5-15% by weight, based on the weight of the binder, of a phthalate ester plasticizer;
(d) 10-30% by weight, based on the weight of the binder, of a polyester plasticizer of a saturated fatty oil, a polyol and an organic di-carboxylic acid or an anhydride of an organic dicarboxylic acid and having an acid number of about 0.1-10; and (e) 1-10% by weight, based on the weight of the binder, of a polymer of methyl methacrylate, an alkyl acrylate having 2-12 carbon atoms in the alkyl group and an .alpha.,.beta.-unsaturated monocarboxylic acid and in which the polymer is reacted with an alkylene imine and having a relative viscosity of about 1.17 to 1.20 measured as above;
wherein the total of (a), (b), (c), (d) and (e) are 100%.
2. The coating composition of Claim 1 containing pigment in a pigment to binder weight ratio of about 1/100 to about 100/100.
3. The coating composition of Claim 1 in which the methyl methacrylate and alkyl amino alkyl methacrylate copolymer consists essentially of methyl methacrylate and diethyl amino ethyl methacrylate.
4. The coating composition of Claim 3 in which the copolymer consists essentially of about 90-99.5% by weight of methyl methacrylate and 0.5-10% by weight diethyl amino ethyl methacrylate.
5. The coating composition of Claim 1 in which the phthalate plasticizer is butyl cyclohexyl phthalate or butyl benzyl phthalate.
6. The coating composition of Claim 1 in which the polyester plasticizer consists essentially of coconut oil, ethylene glycol and phthalic anhydride.
7. The coating composition of Claim 1 in which the methyl methacrylate, alkyl acrylate, .alpha.,.beta.-unsaturated monocarboxylic polymer reacted with an alkylene imine consists essentially of methyl methacrylate, ethyl acrylate, methacrylic acid and the alkylene imine is propylene imine.
8. The coating composition of Claim 1 in which the polymer consists essentially of about 70-90% by weight of methyl methacrylate, 9-20% by weight of ethyl acrylate and 1-10% by weight of methacrylic acid which is reacted with propylene imine.
9. The coating composition of Claim 1 in which the binder consists essentially of (a) polymethyl methacrylate;
(b) cellulose acetate butyrate having a viscosity of about 1-3 seconds and a butyryl content of about 35-40% by weight;
(c) a phthalate plasticizer or butyl cyclohexyl phthalate;
(d) a polyester plasticizer consisting essentially of coconut oil, ethylene glycol and phthalic anhydride; and (e) a polymer consisting essentially of about 70-90% by weight methyl methacrylate, 9-20%
by weight of ethyl acrylate and 1-10% by weight of methacrylic acid which is reacted with propylene imine.
(b) cellulose acetate butyrate having a viscosity of about 1-3 seconds and a butyryl content of about 35-40% by weight;
(c) a phthalate plasticizer or butyl cyclohexyl phthalate;
(d) a polyester plasticizer consisting essentially of coconut oil, ethylene glycol and phthalic anhydride; and (e) a polymer consisting essentially of about 70-90% by weight methyl methacrylate, 9-20%
by weight of ethyl acrylate and 1-10% by weight of methacrylic acid which is reacted with propylene imine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA370,577A CA1124435A (en) | 1977-07-01 | 1981-02-10 | Acrylic lacquer composition |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US812,335 | 1977-07-01 | ||
| US05/812,335 US4168249A (en) | 1977-07-01 | 1977-07-01 | Acrylic lacquer coating composition of polymethyl methacrylate, copolymers of methyl methacrylate, cellulose acetate butyrate and a polyester plasticizer |
| CA306,669A CA1111180A (en) | 1977-07-01 | 1978-06-30 | Acrylic lacquer composition |
| CA370,577A CA1124435A (en) | 1977-07-01 | 1981-02-10 | Acrylic lacquer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1124435A true CA1124435A (en) | 1982-05-25 |
Family
ID=27165733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA370,577A Expired CA1124435A (en) | 1977-07-01 | 1981-02-10 | Acrylic lacquer composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1124435A (en) |
-
1981
- 1981-02-10 CA CA370,577A patent/CA1124435A/en not_active Expired
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1111180A (en) | Acrylic lacquer composition | |
| US4020216A (en) | Coating composition for flexible substrates | |
| CA1152673A (en) | High solids coating composition of a low molecular weight acrylic polymer and an alkylated melamine cross-linking agent | |
| US4752532A (en) | Polyester primer composition | |
| US4525521A (en) | Coating composition of an acrylic polymer having amino ester groups and a glycidyl acrylic polymer | |
| CA1194646A (en) | High solids ambient temperature curing coatings of acrylic-fatty acid drying oil resins | |
| US3844993A (en) | Floor mop having pivotable handle for changing directions air-drying coating composition of an acrylic enamel and an isocyanate cross-linking agent | |
| JPH0246071B2 (en) | ||
| US4330458A (en) | High solids coating composition of a blend of a low molecular weight acrylic polymer and a medium molecular weight acrylic polymer and an alkylated melamine cross-linking agent | |
| GB2060661A (en) | Coating compositions of an alkyd-acrylic copolymer | |
| US4404248A (en) | Clear coat/color coat finish from a high solids coating composition of a blend of a low molecular weight acrylic polymer and a medium molecular weight acrylic polymer and an alkylated melamine cross-linking agent | |
| US4389502A (en) | Clear air-dry acrylic lacquer coating composition | |
| JPH07163943A (en) | Method of providing composite coating on base material | |
| US4407990A (en) | Acrylic coating compositions | |
| US3893960A (en) | Acrylic coating composition for finishing flexible substrates | |
| US3753935A (en) | Nonyellowing acrylic enamel containing an acid phosphate catalyst | |
| GB1583203A (en) | Oil-modified alkyd resin composition | |
| CA1124435A (en) | Acrylic lacquer composition | |
| US3878140A (en) | Acrylic coating composition for refinishing flexible substrates | |
| US3411941A (en) | Process for coating a metallic article with thermally reflowable cellulose acetate butyrate/melamine-formaldehyde resin/alkyd or acrylic resin coating compositions | |
| US3553124A (en) | Coating compositions comprising acrylic polymers containing an oxazoline drying oil constituent | |
| EP0043625B1 (en) | Motor car repair paint | |
| US3634347A (en) | Acrylic lacquer coating composition containing a controlled quantity of low molecular weight melamine-formaldehyde resin | |
| US3884852A (en) | Acrylic coating composition for finishing flexible substrates | |
| US2857344A (en) | Coating compositions comprising an oil modified alkyd resin and nitrocellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |