Paint manufacture
This is a division of application Ser. No. 242,803 filed Apr. 10, 1972, now abandoned. 
    
    
     This invention relates to the manufacture of paint. 
     Paints usually comprise as fundamental constituents a film-forming polymer and a pigment, although a wide range of other constituents are frequently present, for example volatile solvents, coalescing liquids, plasticisers, crosslinking agents and fillers. It is important that the pigment is satisfactorily dispersed throughout any film produced from a paint since only in this way can the pigment properties be utilised to the fullest extent. The pigment should preferably be present in such a form that it contributes the optimum opacity or colour to the film. It is therefore desirable, in order to make the best use of pigment, that the pigment is well dispersed throughout the paint when made and is stable towards storage, so that each particle of pigment will contribute fully towards the opacity or colour of any ultimate film produced from the paint. 
     Conventionally, the pigment to be used in a paint is first dispersed with only a portion of the total film-forming polymer of which the paint is to be comprised, together with appropriate solvents, diluents or other additives, in a ball mill or other type of mill such as is used in the paint industry. This resulting dispersion or &#34;millbase&#34; is then mixed with the remainder of the film-forming polymer and any other necessary ingredients to produce the paint. In the case of an alkyd resin-based paint, for example, the pigment is first dispersed by ball-milling with a portion of the alkyd resin in the presence of a hydrocarbon liquid, and the product is then further diluted with the remainder of the alkyd resin and any other necessary ingredient. Frequently mixtures of millbases are blended with the film-forming polymer to give the desired colour, and this method of manufacture is hereinafter referred to as &#34;loading&#34;. The colour of the final paint is also normally adjusted by small further additions of coloured millbases containing the same or similar film-forming polymer, which is referred to herein as &#34;tinting&#34;. 
     A wide range of different film-forming polymers is used in the manufacture of different paints and, using the conventional procedure described above, it is necessary to pre-disperse pigment with a portion of the film-forming polymer, or a polymer compatible therewith, which is appropriate to each type of paint. Thus, even though the pigmentation of two paints comprised of different film-forming polymers may be identical, it has hitherto been necessary to disperse each pigment or mixture of pigments separately with the appropriate film-forming polymer at the millbase stage, in order to avoid any problems of incompatibility in the final paints between the dispersant polymer and the film-forming polymer. Similarly, any tinting operation calls for the use of dispersants which are compatible with the film-forming polymer in question. 
     We have now found that a certain class of dispersant polymers have the surprising property that pigment millbases prepared with any one of them may be combined with a wide range of different film-forming polymers to produce paints. 
     According to the present invention we provide a pigment dispersant suitable for use in making a series of paints, the dispersant being a copolymer comprising units derived from the following ethylenically unsaturated monomers in the stated proportions by weight based on the total weight of the copolymer:- 
     a. 0 - 50% of a hydroxy group-containing monomer, and/or 
     b. 0 - 20% of an amide group-containing monomer, provided that there is always present at least 5% of (a) or (b); 
     c. 20 - 80% of a monomer free from carboxyl groups and containing a straight or branched chain alkyl group of from 7 to 22 carbon atoms, and 
     d. 0 - 50% of one or more monomers free from the groups mentioned in (a), (b) or (c), the total of monomers being 100%. 
     It is essential that there is always a minimum proportion, namely 5%, of either the hydroxy group-containing monomer (a) or the amide group-containing monomer (b). Preferably both types of monomer are present, since the range of film-forming polymers with which millbases prepared with the dispersant copolymer may be combined is thereby increased, and since these groups also improve pigment dispersion, but when limited ranges of film-forming polymers are involved it may suffice to use only either (a) or (b). Suitable hydroxy-group-containing monomers include hydroxyethyl methacrylate, hydroxy isopropyl methacrylate and the corresponding acrylates. Suitable amide-group containing monomers include acrylamide and methacrylamide. 
     The comonomer (c), the presence of which in the copolymer is essential, may be, for example, an alkyl methacrylate or acrylate in which the alkyl group contains from 7 to 22 carbon atoms, such as lauryl methacrylate or 2-ethylhexyl acrylate, or an alkene containing from 7 to 22 carbon atoms. 
     The comonomers (d) are optional components of the copolymers of the invention, but at least one such comonomer is normally desirable in order to permit spacing of the functional groups carried by monomers (a), (b) and (c) in the copolymer. Suitable such monomers include, for example, styrene, vinyl toluene, acrylonitrile and alkyl acrylates and methacrylates in which the alkyl group contains from 1 to 6 carbon atoms, such as butyl methacrylate. The monomer (d) may be free from all reactive groups; it is essential that it is free from groups which will tend to react with the hydroxy or amide groups present in the other components of the copolymer under the conditions of formation of the copolymer. 
     Particularly suitable combinations of monomer to provide the dispersant polymer are:- 
     a. 15 - 30% of a hydroxy alkyl methacrylate, or corresponding acrylate, e.g. where alkyl is ethyl, propyl, isopropyl or butyl, 
     b. 1 - 10% of acrylamide or methacrylamide, 
     c. 20 - 80% of C 7  or higher alkyl acrylate or methacrylate, and 
     d. 10 - 50% of styrene or vinyl toluene, although many other combinations of monomers are possible. 
     The dispersant copolymers of the invention may conveniently be made by conventional solution polymerisation of the mixture of constituent monomers in an inert solvent, such as xylene, in the presence of a suitable initiator. A technique in which the monomers are gradually fed into the polymerising material is preferred to a &#34;one-shot&#34; procedure in which the whole of the monomers are present at the start of the polymerisation. 
     Whilst the dispersant copolymers as defined above are useful dispersants for a wide range of pigments and film-forming polymers, their performance can be improved by the presence therein of modifying chemical groups which are known to improve affinity for the pigment surface. According to a preferred embodiment of the invention, therefore, the dispersant copolymers hereinbefore defined are modified by the incorporation into the copolymer of a grouping which is capable of promoting association of the copolymer with the surface of a pigment. Such a modifying group may be introduced after copolymerisation of the monomers specified, for example by reaction of a compound containing the associating group, or a precursor thereof, with functional groups present in the copolymer as defined above. Alternatively, the dispersant copolymer may be prepared by including as a comonomer (d) a further monomer which contains a group having pigment dispersant characteristics. As a further alternative, in the preparation of the dispersant copolymer there may be employed a minor proportion of a comonomer (d) which contains a group capable of reacting with a compound which contains a complementary reactive group and which also provides the desired group having pigment dispersant characteristics. Preferably there is used not more than. 20% of this further comonomer based on the total weight of copolymer. 
     A particularly suitable further comonomer for use in the preparation of the dispersant polymer is a monomer which bears an epoxide groups, for example glycidyl acrylate, glycidyl methacrylate or allyl glycidyl ether. The epoxide groups thus introduced into the copolymer may be then reacted with a compound bearing both a carboxyl group and a group having pigment dispersant characteristics, in order to introduce into the dispersant polymer the desired dispersant group. Preferably the copolymer contains not more than 10% of the epoxide-containing monomer based on the total weight of copolymer. Particularly suitable pigment dispersant groups which can be introduced into the dispersant copolymer in this way are those obtained by reacting an epoxide groups present in the copolymer with a compound of structure ##STR1## wherein Ar is an aromatic group and n is 1 or 0, in the presence of a tertiary amine. The group Ar is preferably phenyl and may contain a wide range of substituents, such as nitro and amino groups; examples of suitable compounds include p-amino benzoic acid and p-nitro benzoic acid. Further details of these dispersant groups are provided in our U.S. Pat. No. 3,433,753, the description of which is incorporated herein by reference. Similarly, as described in our U.S. Pat. No. 3,505,268, the description of which is also incorporated herein by reference, the introduction of suitable pigment dispersant groups can be effected by reacting an epoxide group in the copolymer with a compound of structure ##STR2## wherein R is an aliphatic radical which may contain one or more additional hydroxyl groups, in the presence of a tertiary amine. 
     The aforementioned pigment dispersant groups may with advantage be modified by reaction with an organic monoisocyanate, as described in our British Patent Applications Nos. 42760/70 and 54130/70. 
     Other suitable comonomers (d) which may be used in the preparation of the dispersant copolymer, in order to introduce therein either directly or by subsequent reaction a group having pigment dispersant characteristics, include the following, the percentages stated being based on the total weight of the copolymer:- 
     i. up to 10% of an epoxide group-bearing monomer which is subsequently reacted with a polybasic inorganic acid which may or may not thereafter be partially neutralised with a suitable base, or with a partial ester of a polybasic organic acid, or with an amine; 
     ii. up to 20% of an amine group-bearing monomer; 
     iii. up to 20% of an amine group-bearing monomer which is at least partially reacted with propane sultone; 
     iv. up to 20% of an amine group-bearing monomer which is at least partially reacted with an alkyl halide; 
     v. up to 20% of a carboxylic acid group-bearing monomer; 
     vi. up to 10% of a carboxylic acid group-bearing monomer at least partially neutralised with a base; 
     vii. up to 10% of a carboxylic acid group-bearing monomer at least partially reacted with ethylene imine; 
     viii. up to 20% of an amide group monomer reacted with formaldehyde and esterified with a lower aliphatic alcohol. 
     The dispersant copolymers of the invention permit the prior preparation of dispersions of pigments or pigment mixtures used in paint manufacture, each of which dispersions may subsequently be employed for the direct pigmentation of paints based on a wide range of different film-forming polymers. The pigment dispersions may be prepared at any convenient time and stored for future use in whichever particular paint formulation within that range may be required. 
     Thus according to a further feature of the present invention, we provide a method of manufacturing a series of paints all of which have a pigment or a mixture of pigments in common and at least two of which comprise different film-forming polymers, the method comprising first dispersing the pigment or mixture of pigments in the presence of a dispersant copolymer as hereinbefore defined, and subsequently combining the dispersion so obtained with the film-forming polymer appropriate to each paint of the series. 
     The method of the invention offers the possibility of rationalising the manufacture of a range of paints by substantially reducing the number of different types of millbase which it is necessary to produce both for loading and for tinting operations. 
     Film-forming polymers used in the paint industry, for example in the formulation of automotive, refinish and industrial paints, which may be loaded and/or tinted according to the method of the invention include thermosetting acrylic/melamine-formaldehyde resin blends, thermosetting acrylic resins based on acrylamide or methacrylamide, coconut oil alkyd/melamine-formaldehyde and urea-formaldehyde blends, blends of coconut oil alkyds with melamine-formaldehyde and thermosetting acrylamide or methacrylamide-based resins, alkyd/nitrocellulose blends with or without melamine-formaldehyde resins, acrylic polymers of both lacquer and non-aqueous dispersion types, alkyd (dehydrated castor oil/tall oil)/melamine-formaldehyde low bake resins, alkyd (dehydrated castor oil/tall oil)/melamine-formaldehyde/hydroxyacrylic low bake resins, thermosetting acrylic/epoxy blends, alkyd (soya, dehydrated castor or coconut)/melamine-formaldehyde and/or urea-formaldehyde blends, alkyd (soya, dehydrated castor or coconut)/melamine-formaldehyde/urea-formaldehyde/epoxy resin blends, butylated melamine-formaldehyde and urea-formaldehyde resins, epoxy-polyamide blends, chlorinated rubber, short oil alkyds with oil lengths in the range 25 - 45% based on linseed, dehydrated castor or soya oils, short oil alkyds with oil lengths in the range 25 - 50% based on castor oil, hydrogenated castor oil or coconut oils, thermosetting acrylic copolymers based on hydroxy monomers, nitrocellulose finished plasticised with short oil alkyds or with ester plasticisers, epoxy esters and epoxy resins. 
     Whilst the paints made by the present process may be based on aliphatic or aromatic hydrocarbons or other solvents, it is preferred that they are based on solvents which are predominantly aromatic, e.g. xylene or toluene. Minor amounts of other solvents will often be used in addition. 
     The pigments employed in the paints manufactured by the present process are those conventionally used industrially and include, for example, the iron oxides, whether black, yellow, red or brown; transparent iron oxides; lead chromate; basic lead silico chromate; strontium chromate; chrome green; chrome oxide green; thio-indigo red; quinacridone; phthalocyanine blue; phthalocyanine green; red lead; cobalt blue; graphite; vegetable carbon black; mineral carbon black; metallic aluminium; metallic lead; metallic zinc; white lead sulphate; white lead carbonate; zinc oxide; rutile titanium dioxide; anatase titanium dioxide; zinc sulphide and zirconium oxide. 
     In addition to the dispersant polymer and pigment, the millbase may contain additionally other additives, for example, solvents, diluents, and flow control agents. 
     In combining the pigmented millbases with the various film-forming polymers according to the method of the invention, it is advisable to ensure efficient mixing in order to avoid the risk of &#34;shock&#34; flocculation of the pigment, as is the normal practice in the paint manufacturing industry. 
    
    
     The invention is illustrated by the following Examples, in which parts and percentages are by weight unless otherwise stated. 
     EXAMPLE 1 
     a. Preparation of dispersant copolymer 
     A copolymer of styrene/lauryl methacrylate/butyl methacrylate/hydroxypropyl methacrylate/methacrylamide in the ratios of 28/27/15/25/5 was prepared in xylene as a solution of 50% solids by a conventional addition polymerisation process. 
     b. Preparation of millbase 
     A white pigment millbase was prepared by first premixing 8.3 parts of the dispersant copolymer solution as described above, 12.9 parts of xylene and 70.5 parts of titanium dioxide (commercially available as Titanox RA 45, &#34;Titanox&#34; is a Registered Trade Mark) with a Torrance stirrer and then grinding in a Sussmeyer sand mill. Finally a further 3.3 parts of dispersant copolymer solution and 5.0 parts of xylene were added with stirring. 
     c. Preparation of a series of paints using the millbase (b) 
     i. The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
White millbase (b)      35.6    parts                                     
Butylated melamine-formaldehyde                                           
resin solution (50% solids in                                             
xylene/butanol)         21.7    parts                                     
Alkyd resin of 25% oil length                                             
prepared from lauric acid/benzoic                                         
acid/trimethylol propane/phthalic                                         
anhydride (60% solids in xylene)                                          
                        34.3    parts                                     
Butanol                 6.0     parts                                     
Xylene                  2.35    parts                                     
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     From the resulting paint there was produced a stoved finish which had a gloss level meeting the standard appropriate when a portion of the alkyd resin (and optionally of the butylated M/F resin) was used in the millbase rather than the dispersant copolymer (a). 
     ii. The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
White millbase (b)      38.4    parts                                     
Methylolated acrylamide thermosetting                                     
acrylic resi (50% solids in                                               
xylene/butanol)         45.80   parts                                     
&#34;Epikote&#34; 1001 (60% solids solution                                       
in xylene/butyl &#34;Cellosolve)                                              
(&#34;Epikote&#34; is a Registered Trade                                          
Mark)                   4.75    parts                                     
Butyl &#34;Cellosolve&#34; (&#34;Cellosolve&#34;                                          
is a Registered Trade Mark)                                               
                        3.0     parts                                     
Butanol                 1.8     parts                                     
Xylene                  5.5     parts                                     
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     The resulting paint was a thermosetting acrylic appliance finish from which there was produced a coating film having a gloss level which met the standard appropriate when a portion of the methylolated acrylamide acrylic resin was used in the millbase rather than the dispersant copolymer (a). 
     iii. The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
White millbase (b)      30.1    parts                                     
Isobutylated melamine-formaldehyde                                        
resin (67% solids solution in                                             
isobutanol)             11.0    parts                                     
Styrene/ethyl hexyl acrylate/hydroxy                                      
propyl methacrylate/acrylic acid                                          
copolymer (50% solids solution in                                         
xylene)                 45.9    parts                                     
Methyl ethyl ketone     3.7     parts                                     
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     The resulting paint was a thermosetting acrylic automotive finish from which there was produced a coating film having a gloss level which met the standard appropriate when a portion of the copolymer was used in the millbase rather than the dispersant copolymer (a). 
     iv. The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
Isopropanol             7.4     parts                                     
Butanol-damped Nitro cellulose                                            
(70% solids nitrocellulose)                                               
                        14.4    parts                                     
Methyl ethyl ketone     4.35    parts                                     
Ethyl acetate           4.0     parts                                     
Ester gum               19.5    parts                                     
Toluene                 25.4    parts                                     
White millbase (b)      12.1    parts                                     
Sextol phthalate plasticiser                                              
                        3.0     parts                                     
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     The resulting paint was a nitrocellulose-based wood finish which provided a coating film having a gloss level which met the standard appropriate when a portion of the nitrocellulose was used in the millbase rather than the dispersant copolymer (a). 
     v. The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
White millbase (b)      19.0    parts                                     
Poly(methyl methacrylate) (40%                                            
solids solution in toluene/acetone)                                       
                        42.8    parts                                     
Cellulose acetate butyrate (25%                                           
solids solution in toluene/butyl                                          
acetate)                6.25    parts                                     
Butyl benzyl phthalate  8.50    parts                                     
Acetone                 2.6     parts                                     
&#34;Cellosolve&#34; acetate    9.4     parts                                     
Toluene                 4.4     parts                                     
______________________________________                                    
 
    
     The resulting paint was an acrylic lacquer automotive finish which provided a coating film having a gloss level which met the standard appropriate when a portion of the poly(methyl methacrylate) was used in the millbase rather than the dispersant copolymer (a). 
     EXAMPLE 2 
     a. Preparation of dispersant copolymer 
     A copolymer of styrene/lauryl methacrylate/butyl methacrylate/hydroxyisopropyl methacrylate/methacrylamide/glycidyl methacrylate in the ratios 24/27/15/25/5/4 was prepared by conventional addition polymerisation in xylene to give a 50% solids solution. The copolymer was then modified by esterification with p-amino benzoic acid in the presence of dimethyl dodecyl tertiary amine. 
     b. Preparation of millbase 
     A white pigment millbase was prepared according to the procedure described in Example 1 (b) but using the modified dispersant copolymer described above in place of the copolymer of Example 1 (a). 
     c. Preparation of a series of paints from millbase (b) 
     A series of paints of composition analogous to those described in Example 1 (c) (i) - (v) was prepared, and it was observed that there was some improvement in the gloss of coating films produced from these paints in each case when using the above modified dispersant copolymer instead of the unmodified dispersant polymer of Example 1 (a). 
     EXAMPLE 3 
     Similar results to those stated in Example 2 were observed when paints were prepared in an analogous fashion from a white millbase which contained as dispersant a copolymer of styrene/ethyl hexyl acrylate/hydroxy isopropyl methacrylate/methacrylamide/glycidyl methacrylate in the ratios 26/40/25/5/4, modified by esterification with p-amino benzoic acid in the presence of dimethyl dodecyl tertiary amine. 
     EXAMPLE 4 
     This Example illustrates the preparation of various coloured millbases and their use in the manufacture of a series of paints: 
     a. Red oxide millbase 
     The following constituents: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
of Example 2 (a)        7.3     parts                                     
Xylene                  17.1    parts                                     
Red oxide pigment       60.0    parts                                     
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     were dispersed for 24 hours in a ball mill; there were then added with stirring: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
                        13.4    parts                                     
Xylene                  2.2     parts                                     
______________________________________                                    
 
    
     b. Copper phthalocyanine blue millbase 
     The following constituents: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
of Example 2 (a)        21.4    parts                                     
Xylene                  50.0    parts                                     
Phthalocyanine blue pigment                                               
                        14.4    parts                                     
______________________________________                                    
 
    
     were dispersed for 24 hours in a ball mill; there were then added with stirring: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
                        12.2    parts                                     
Xylene                  2.0     parts                                     
______________________________________                                    
 
    
     c. Black millbase 
     The following constituents: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
of Example 2 (a)        30.8    parts                                     
Xylene                  46.5    parts                                     
Lamp black pigment      17.7    parts                                     
______________________________________                                    
 
    
     were dispersed for 24 hours in a ball mill; there were then added with stirring: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
                        2.5     parts                                     
Xylene                  2.5     parts                                     
______________________________________                                    
 
    
     d. Yellow oxide millbase 
     The following contituents: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
of Example 2 (a)        8.26    parts                                     
Xylene                  19.60   parts                                     
Yellow oxide pigment    49.90   parts                                     
______________________________________                                    
 
    
     were dispersed for 24 hours in a ball mill; there were then added with stirring: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
                        20.04   parts                                     
Xylene                  2.20    parts                                     
______________________________________                                    
 
    
     e. Copper phthalocyanine green millbase 
     The following constituents: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
of Example 2 (a)        15.40   parts                                     
Xylene                  32.70   parts                                     
Phthalocyanine green    16.40   parts                                     
______________________________________                                    
 
    
     were dispersed for 4 hours in an attritor; there were then added with stirring: 
     
         ______________________________________                                    
Dispersant copolymer solution                                             
                        27.20   parts                                     
Xylene                  8.30    parts                                     
______________________________________                                    
 
    
     1. Blue stoving Car Finish 
     The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
Butylated melamine formaldehyde resin                                     
solution (62% solids in butanol)                                          
                        11.20   parts                                     
White millbase (Example 1 (b)                                             
                        3.15    parts                                     
Phthalocyanine blue millbase (Example                                     
4 (b))                  6.65    parts                                     
Black millbase (Example 4 (c))                                            
                        0.10    parts                                     
Phthalocyanine green millbase                                             
(Example 4 (e)          1.20    parts                                     
Isobutylated urea formaldehyde resin                                      
solution (60% solids in isobutanol)                                       
                        5.60    parts                                     
Alkyd resin of 39% oil length prepared                                    
from coconut oil/pentaerythritol/                                         
glycerol/phthalic anhydride (55%                                          
solids solution in toluene/xylene)                                        
                        56.60   parts                                     
Dipentene               10.00   parts                                     
Isobutanol              3.40    parts                                     
2% solution of a silicone oil in xylene                                   
                        0.10    parts                                     
Xylene                  2.00    parts                                     
______________________________________                                    
 
    
     2. Dark Grey General Industrial Finish 
     The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
Butylated urea formaldehyde resin                                         
solution (53% solids in xylene/                                           
butanol)                40.00   parts                                     
White millbase (Example 1 (b))                                            
                        7.40    parts                                     
Black millbase (Example 4 (c))                                            
                        2.00    parts                                     
Yellow oxide millbase (Example 4 (d))                                     
                        0.70    parts                                     
Alkyd resin solution of 43% oil                                           
length prepared from soyabean oil/                                        
glycerol/phthalic anhydride (60%                                          
solids solution in xylene)                                                
                        33.50   parts                                     
2% solution of a silicone oil in xylene                                   
                        0.05    part                                      
Butanol                 3.00    parts                                     
Xylene                  13.35   parts                                     
______________________________________                                    
 
    
     3. Beige Thermosetting Acrylic Car Finish 
     The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
Butylated melamine formaldehyde resin                                     
solution (67% solids in butanol)                                          
                        26.6    parts                                     
White millbase (Example 1 (b))                                            
                        7.05    parts                                     
Yellow oxide millbase (Example 4 (d))                                     
                        0.90    part                                      
Black millbase (Example 4 (c))                                            
                        0.20    part                                      
Red oxide millbase (Example 4 (a))                                        
                        0.05    part                                      
Styrene/ethyl hexyl acrylate/hydroxy-                                     
ethyl methacrylate/acrylic acid                                           
copolymer (50% solids solution in                                         
xylene)                 52.10   parts                                     
Isobutanol              3.00    parts                                     
Dipentene               8.00    parts                                     
Xylene                  2.00    parts                                     
______________________________________                                    
 
    
     4. Green Thermosetting Acrylic Domestic Appliance Finish 
     The following paint constituents were added to a stirred container in the order given: 
     
         ______________________________________                                    
White millbase (Example 1 (b))                                            
                        13.60   parts                                     
Yellow oxide millbase (Example 4 (d))                                     
                        3.00    parts                                     
Red oxide millbase (Example 4 (a))                                        
                        0.30    part                                      
Red oxide millbase (Example 4 (a))                                        
                        0.30    part                                      
Phthalocyanine blue millbase                                              
(Example 4 (b))         0.50    part                                      
&#34;Epikote&#34; 1001 (60% solids solution                                       
in xylene/butyl &#34;Cellosolve&#34;)                                             
                        5.90    parts                                     
Butyl &#34;Cellosolve&#34;      3.00    parts                                     
(&#34;Epikote&#34; and &#34;Cellosolve&#34; are                                           
Registered Trade Marks)                                                   
Methylolated acrylamide thermosetting                                     
acrylic resin (50% solids solution                                        
in xylene/butanol)      58.40   parts                                     
Butanol                 3.25    parts                                     
Xylene                  9.70    parts                                     
______________________________________