Solid paints

Solid paint compositions having dimensional stability based on ion bonding of discrete particles are obtained by reacting stabilized non-aqueous dispersions of certain resins having acid group functionality with 100-500 mole percent of metallic hydroxide, based on acid, dissolved in a high dielectric polar solvent.

The present invention relates to a new type of paint product, namely, a 
solid paint having dimensional stability based on ion bonding. 
Various resin compositions consisting of homopolymers and co-polymers 
having partially neutralized carboxylic acid groups are known. These 
contain between 3% and 20% of carboxylic acid residues of which less than 
50 percent of the carboxylic acid groups are neutralized with mono-valent, 
di-valent or tri-valent cations. The prior art resins, known as Ionomers, 
are desirable in industry because they combine the utility of a thermoset 
polymer with the mobility and workability of the thermoplastic resin. 
Ionomers have lower densities than vinyl or cellulosic plastics and 
because of their similarity to polyethylenes find use as protective films 
in the food packaging industry. Ethylene-methacrylic acid co-polymers are 
discussed in U.S. Pat. Nos. 3,266,272, 3,338,739; and in Belgium Patents 
674,595 and 600,397. Ethylene-sodium acrylate copolymers are described in 
Netherlands Pat. No. 6,511,920. Many of the desirable properties of these 
polymers such as stress-crack resistance, transparency, grease and 
abrasion resistance, low permeability, high elongation, high tensile 
strength, and low modulus are attributed in part to a type of ionic 
bonding. 
It has now been discovered that solid paints having effective gel 
properties necessary to provide dimensional stability can be prepared by 
cross-linking certain reactive polymers with "ion clusters" having polar 
molecule components. This type of ion bonding differs substantially from 
the solvent-free ionic bonding of the prior art compounds. 
One object of the present invention is to provide a solid paint composition 
having dimension stability based on ion bonding, i.e., ion cluster 
cross-linking of polymers, comprising the admixture of: 
I. A. A solution of a curable polymer having a molecular weight ranging 
from 1,000 to 7,000 and sufficient reactive acid functional groups 
selected from the group consisting of carboxylic, sulfonic and phosphonic 
to provide an acid number from 20 to 80, said resin dissolved in a 
non-polar solvent to provide a 25 to 90 weight percent solution; or 
B. a stabilized dispersion of a polymer having a molecular weight ranging 
from 25,000 to 1,000,000 and sufficient reactive functional groups 
selected from the group consisting of carboxylic, sulfonic, and phosphonic 
to provide an acid number from 25 to 60, said resin suspended in a 
non-polar non-solvent as a 25 to 90 weight percent suspension; or 
C. a mixture of a non-bonding NAD resin comprising a stabilized dispersion 
of a polymer having a molecular weight ranging from 25,000 to 1,000,000 
dispersed as a 25 to 90 weight percent suspension in a non-polar 
non-solvent, said resin having no reactive functional group sites, with an 
ion-bonding resin solution as defined in (IA), the proportion of 
non-bonding NAD resin to ion-bonding being from 2:1 to 8:1; and 
II. A solution of a metal hydroxide in a polar solvent of high dielectric 
strength to provide a 10-50 weight percent solution, said metal hydroxide 
selected from the group consisting of sodium, potassium, lithium, barium, 
calcium, manganese and magnesium; and 
III. Optionally a metallic drier in amounts from about 0.1 to 5 weight 
percent based on the total weight of polymer; 
wherein said composition contains from about 100 to 500 mole percent of 
metal hydroxide per mole of acid functional group. 
An additional object is to provide a process for preparing a solid paint 
having dimensional stability based on ion bonding and a gel strength from 
about 100 to 200 millimeter penetration which comprises: 
(a) dissolving or suspending a curable polymer resin of the type shown in 
IA or IB or IC above to form the respective polymer composition or 
mixtures thereof in such proportion to provide sufficient reactive acid 
functional groups necessary for the indicated dimensional stability when 
cross-linked by ionic cross-linking agents; 
(b) mixing pigments, fillers, colorants and 0 to 5 weight percent of an 
organic acid metal salt drier into the resin solution or dispersion; 
(c) adding thereto under vigorous stirring a 20 to 30 weight percent 
solution of metal hydroxide in a C.sub.1-8 aliphatic alcohol containing 
100 to 600 mole percent of the amount of metal hydroxide required to 
neutralize said reactive acid groups of the resin; 
(d) ageing the mixture for 3 to 25 hours at a temperature between 15 and 70 
degrees Centigrade. 
A further object is to provide paint sticks or bars based on the above 
compositions and processes. 
Solid paint compositions having dimensional stability and desirable paint 
characteristics result from the interaction of certain polymers, having 
reactive functional groups, with certain cross-linking agents formed by 
dissolving a metal hydroxide in a high dielectric polar solvent. 
Cross-linking of the polymer chains takes place through "ion clusters" 
composed of multiple ions associated with polar solvent molecules. By the 
term solid paint is meant a paint which has sufficient dimensional 
stability under storage conditions, i.e., is self-supporting, yet could be 
utilized as a stick of paint (analogous to a segment of hard butter or 
cheese). Such solid paint can advantageously be applied by hand to the 
surfaces usually protected by paint and coating products without the use 
of a brush or roller. For practical and protective purposes, such stick of 
paint will generally be contained in a skin or covering suitable for 
storage. Advantageously such protective cover will have a closeable 
opening, said covering being distinct from the nature of an applicator in 
the usual sense. The solid paint can be used by placing the paint stick in 
contact with the surface to be painted followed by the usual vertical and 
lateral movements across the substrate whereby a non-sagging, air-curable 
paint film is deposited thereon. The shear provided by drawing the paint 
stick over the surface to be painted is sufficient to cause the solid 
paint to deform to a flowable coating at the point of contact. Such a 
solid paint coating is one that possesses the desirable properties of 
adhesion, flow and uniform coverage of the surface. It is assumed that the 
solid paint of the present invention will contain the usual pigments, 
fillers, driers, bonding agents, and other additives to provide films 
having desirable properties of gloss, color, and hiding power. It is 
anticipated that such a solid paint could be fabricated in blocks or 
sticks having widths ranging from 1/8" to about 8 feet or larger, thus, 
also allowing use in industrial applications such as, for example, coil 
coating of metal. 
When the curable resin is a solution of a curable polymer in a non-polar 
solvent as shown in I.S. above, the resins useful in the present invention 
include homopolymers and copolymers and mixtures thereof having 
appropriate functional groups either built into the polymer chain or 
grafted thereto by the usual graft techniques. Useful resins include but 
are not limited to polyethers, polyesters, unsaturated polyesters, 
polyurethanes, polyolefins, polyacrylates, polyhydrocarbons derived from 
aliphatic and aromatic hydrocarbons having .alpha.,.beta.-unsaturation, 
vinyl resins and chlorine-substituted vinyls as well as other combinations 
known to the art. The particular reactants and quantities are chosen to 
produce resins having pendant and/or terminal functional substituents 
which are capable of further reaction with ionic reagents to form gels of 
proper dimensional stability and gel strength. Desirable application 
properties result when the gel strength is from about 100 to 190 and 
preferably from 135 to 180 when measured 25 hours after gelling. Gel 
strength is recorded in millimeter units using a Universal 
Penetrometer--the lower the penetrometer reading, the higher the gel 
strength. 
Regardless of the type of resin used in the practice of this invention, it 
is essential that the particular resin be soluble in a non-polar solvent 
and that the resin have pendant and/or terminal functional reactive groups 
which are readily ionizable. Such ionizable groups include both cationic 
and anionic reactive functions. Preferably, anionic functional groups used 
to modify the resin are the sulfonic, phosphonic and carboxylic types. The 
carboxylic acid functionality is especially preferred since a variety of 
polymers having such reactive ionizable groups can be readily purchased or 
synthesized. Preferred reaction products are those obtained from the 
combination of carboxylic acid substituted polyesters and alkyd polyesters 
having molecular weights in the range of from about 1000 to 7000 which 
contain from about 1 to 4 reactive functional groups per each 2,000 unit 
of molecular weight. Polyesters and polyethers having molecular weights in 
the range of 400-2000 and which yield solid paints of desirable gel 
properties are especially preferred. Alkyd resins modified with fatty acid 
groups and having terminal carboxylic functionality are exemplified in the 
best mode Examples. In the case of polyolefins, polyacrylates and other 
systems where no air-curing will occur, a higher molecular weight of the 
order of 100,000 is usually necessary. However, 1 to 4 reactive functional 
groups are still required per 2,000 unit of molecular weight. The alkyd 
resins useful in the practice of this invention are prepared by 
polymerizing the polymer monomers and other intermediates in a fusion cook 
at a temperature of about 400.degree.-600.degree. F. to yield resins 
having an acid value (A.V.) ranging from 30 to 55 and preferably 41.+-.2. 
Certain "longer" oil resins as exemplified hereafter in Examples 1 and 2 
are polymerized at 450.degree. F. to an A.V. of 43.0. 
The above described polymers having ionizable reactive groups are dissolved 
in sufficient non-polar solvents to provide solutions having non-volatile 
(N.V.) contents of from about 10 to 90 and preferably from 35 to 60 weight 
percent. Especially preferred are solutions of 50% N.V. Suitable non-polar 
solvents for dissolving the polymer include both aromatic and 
aliphatic-type hydrocarbons and are selected based on the particular resin 
used, the functionality on said resin, and the nature of the ionic 
reactant. In general, suitable solvents are hydrocarbons having a boiling 
point of about 125.degree. to 400.degree. F. and which contain up to 
twelve carbon atoms. These include hexane, heptane, octane, nonane, decane 
and mixtures thereof. Preferred hydrocarbons are the various octanes 
because of their suitable evaporation rates. Mineral spirits is an 
especially preferred solvent because of its availability and the desirable 
properties of the resultant solid paint. In certain cases aromatic 
hydrocarbons such as toluene and xylene can advantageously be used and are 
especially valuable in dissolving the higher molecular polymers. 
It is understood that the solvent, resin and proportions of each will vary 
and depend on the type of resins, the type of solvent, the fillers and 
other additives needed for a particular end-product solid paint. The 
additives, driers and other usual dispersant aids can be blended with the 
resin solution using a Cowles agitator. The order of addition is usually 
not critical. If desired, the pigments and other additives may be blended 
with the resin material prior to the solution of the resin in the 
non-polar solvent. After the additives are thoroughly mixed, the resulting 
composition is advantageously allowed to age for 12 to 20 hours before 
reacting with the ionic component. 
When the curable resin is a stabilized dispersion of a polymer in a 
non-polar non-solvent medium as shown in I.B. above, the resins useful in 
the present invention include homopolymers and copolymers and mixtures 
thereof having appropriate functional groups either built into the polymer 
chain or grafted thereto by the usual graft techniques. Such resins 
include but are not limited to polyethers, unsaturated polyesters, 
polyurethanes, polyacrylates, vinyl resin and chlorine-substituted vinyls 
as well as other combinations known to the art. The particular reactants 
and quantities are chosen to produce a resin having pendant functional 
substituents which are capable of further reactions with ionic reagents to 
form gels of proper dimensional stability and gel strength. Desirable 
application properties result when the gel strength is from about 130 to 
210 and preferably from 150 to 195 mm when measured 25 hours after 
gelling. Gel strength is recorded in millimeter units using a Universal 
penetrometer-the lower the penetrometer reading, the higher the gel 
strength. 
For the I.B. type of resin formulation used in the practice of this 
invention, it is essential that the particular resin be insoluble or only 
lightly swelled by the non-solvent, as is necessary for any non-aqueous 
dispersion, and that the resin have pendant reactive groups which are 
readily ionizable. Such ionizable groups include both cationic and anionic 
reactive functions. Preferably, anionic functional groups used to modify 
the resin are the sulfonic, phosphonic, and carboxylic types. The 
carboxylic acid functionality is especially preferred since a variety of 
polymers having such reactive ionizable groups can be readily purchased or 
synthesized. Preferred resins are copolymers of unsaturated hydrocarbons 
and unsaturated acids having molecular weights in the range of 100,000 to 
300,000. Especially useful resins for the practice of this invention are 
acrylic acid esters and vinyl polymers having a particle size range of 
from 0.01 to 30 microns. Acrylate and methacrylate copolymers having 
terminal carboxy functionality are especially preferred and are 
illustrated in the best mode examples. Non-aqueous dispersions (NADs) 
known to the art and particularly useful in the practice of this invention 
(if these are modified to have ionizable sites on the surface) include 
those described by Dowbenko and Hart, Ind. Eng. Chem. Prod. Res. Develop., 
Vol. 12, No. 1, 1973 at pages 14-28. The polymers and stabilizers 
described therein are hereby incorporated by reference. In the formation 
of such NADs the choice and level of stabilizer is eminently important to 
provide solid paints having desirable application flow and coalescence 
characteristics. Other useful NAD resin include those derived from poly 
(methyl methacrylate), polyacrylate and polymethacrylate resin and 
copolymers of these derived through addition polymerization with 
polyolefins, such as polyethylene, poly (vinyl ethyl ether), vinyl 
acetate, hydroxyethyl acrylate and 2 hydroxypropyl methacrylate. 
The polymer resins useful in this aspect of the invention can be prepared 
by solution polymerization followed by dispersion in a non-solvent or by 
dispersion polymerization. The first method involves polymerizing the 
monomer or comonomers and other intermediates under free radical 
conditions at a temperature of about -50.degree. to +250.degree. F. to 
yield a resin having an acid value (AV) ranging from 20 to 80 and 
preferably from 25 to 60. The second and preferred method involves 
polymerizing the monomer or comonomers and other intermediates in a 
non-solvent under free radical conditions at a temperature of about 31 
50.degree. to +250.degree. F. to yield a resin dispersion with the 
desirable acid value. 
The above described polymers having ionizable reactive groups are dispersed 
in a non-polar non-solvent to provide a dispersion having non-volatile 
(N/V) content of from about 10 to 90 and preferably from 30 to 60 weight 
percent. Especially preferred are dispersions of 50% N/V. Suitable 
non-solvents include both aromatic and aliphatic type hydrocarbons which 
are selected based on the particular resin, the functionality on said 
resin and the nature of the ionic reactant. In general suitable 
non-solvents are hydrocarbons having a boiling point of about 100.degree. 
to 400.degree. F. and which contain up to twelve carbon atoms. These 
include hexane, heptane, octane, nonane, decane, dodecane and mixtures 
thereof. Preferred hydrocarbons are the various octanes because of their 
suitable evaporation rates. Mineral spirits is an especially preferred 
solvent because of its availability and the desirable properties of the 
resultant solid paint. For some resin systems aromatic hydrocarbons such 
as toluene or xylene may be used. 
It is recognized that NAD resins can be suitably formulated with various 
stabilizers known to the art. The function of these stabilizers is 
primarily to prevent the resin particle from coalescing on storage and 
during formulation into solid paint products. Useful stabilizers include 
those described and referenced in the above noted article by Dowbenko and 
Hart. Polyene stabilizers which are useful for certain solid paint 
compositions include low molecular weight polybutadiene, grafted to a 
backbone of an acrylic copolymer. For the instant solid paints NAD resin 
stabilized by copolymers of methyl methacrylate and glycidyl methacrylate 
and further reacted with 12-hydroxy-stearic acid and/or poly (lauryl 
methacrylate) are especially preferred. 
It is understood that the non-solvent, resin and proportions of each will 
vary and depend on the type of resins, stabilizers, non-solvent, fillers 
and other additives needed for a particular end-product solid paint. The 
additives, driers and other usual dispersant aids are preferably blended 
with the resin dispersion using a Cowles agitator. The order of addition 
is usually not critical. The typical solid paint formulations as described 
herein are of the latex type non-aqueous resin dispersion and do not 
usually require specific drier components to give suitable film 
properties; when driers are added they are used in quantities less than 2 
percent and preferably less than 1 percent per weight of total 
composition. The driers are added for the small amount of oil or alkyd 
that is normally added to the formulation to aid dispersion of the pigment 
and to aid in the coalescence of the film. After application the resin 
particles coalesce and fuse to give a dry film in a matter of minutes. 
The polymer formulations shown in I.A. (solution of polymer in a non-polar 
hydrocarbon) or the formulation of I.B. (stabilized dispersion in a 
non-polar non-solvent) are next combined with the ionic cross-linking 
agents dissolved in a high dielectric polar solvent. 
Suitable ionic cross-linking reactants are usually of the inorganic salt 
variety which produce on solution specific cations or anions capable of 
combining with the terminal reactive groups of the resin to form ion 
clusters responsible for gel formation. Such clusters, which contain the 
high dielectric polar solvent molecules, act as reversible cross-links to 
join the reactive resin molecules in webs thus imparting gel strength and 
dimensional stability to the resultant solid paint. When the reactive 
terminal sites on the polymer are carboxylic acid groups (--COOH), the 
preferred cross-linking reactants are alcoholic solutions of mono, di and 
trivalent metal hydroxides. Such cross-linking reactants include the 
oxides and hydroxides of sodium, potassium, lithium, barium, calcium, 
manganese and magnesium. Equally effective cross-linking agents are the 
corresponding metal alkoxides, i.e., sodium methylate. In some cases 
ammonium hydroxide and organic cation formers such as tetramethyl-ammonium 
hydroxide can be used as cross-linking reactants. The cross-linking 
gelation derived by reacting sodium hydroxide with the above described 
resin molecules having terminal or pendant carboxyl groups is especially 
preferred. Suitable gels result when an effective amount of the cationic 
base combines with the free carboxylic acid functionality. In every case 
an amount of base substantially in excess of the amount required for 
neutralization is necessary to be effective. By substantial excess is 
meant from about 100-600 mole percent of ionic reactant dissolved in the 
polar solvent. Although the amount of excess varies with each particular 
resin system and depends upon the molecular weight of the resin, the 
number and type of the ionizable functional group and on the valence of 
the metal hydroxide, satisfactory gels result when the ionic reagent is 
used at 100-600 mole percent excess. When amounts less than 100 mole 
percent are used the resins do not exhibit the required dimensional 
stability. When amounts greater than 600 mole percent are used the resins 
do not exhibit the desired flow and surface characteristics. For gel 
formation the metal hydroxide or other ionic cross-linking reactant is 
added as a 10-50 weight percent solution in the high dielectric polar 
solvent to the polymer resin formulations. Preferred solid paints were 
obtained by using 100 to 250 mole percent sodium hydroxide based on the 
molar content of the reactive functional group, i.e., moles free COOH. 
The polar solvents useful in dissolving the ionic cross-linking agents are 
generally those solvents having a dielectric constant greater than 10, 
include aliphatic alcohols containing one to ten carbon atoms and one to 
two hydroxy groups. Although C.sub.1-8 aliphatic alcohols are usually 
preferred, glycols containing the similar carbon chains are sometimes 
useful in producing desirable gel properties in the resultant solid paint. 
Useful alcohols include methanol, ethanol, isopropanol, n-propanol, the 
normal and isomeric butanols, pentanols, hexanols, heptanols, octanols, as 
well as the corresponding glycols derived therefrom. Methanol is the 
preferred alcohol because of its costs, availability and the favorable 
solubility of the ionic reagents therein. In certain applications it is 
preferred to use glycols or mixtures of glycols and alcohols as the 
plasticizer carrier for the ionic reactant. Preferred glycols are ethylene 
glycol and propylene glycol although for certain resins the higher glycols 
such as pentanediol and hexanediol act in the nature of a plasticizer and 
provide desirable lubricity. Additional high dielectric polar solvents 
useful in the practice of this invention include, water, formamide, 
dimethylformamide, and dimethylsulfoxide. 
The metal driers suitable for the instant solid paint compositions are 
those known to the art and include the metal salts and/or esters of 
various organic carboxylic acids containing up to 30 carbon atoms and 
mixtures thereof. The metal salts of cobalt, zinc, zirconium, magnesium, 
aluminum and manganese prepared from branched chain C.sub.8-12 carboxylic 
acids are preferred driers. The typical paint formulations, as described 
herein, required unusually high amounts of metal drier of the order of 
about 0.5 to 5 percent based on the weight of the resin. The amount of 
drier needed depends to some extent on the oil or other source of double 
bonds used in the paint system, i.e. number and type of double bonds 
available. 
A further aspect of this invention includes the use of resins having 
pendant and/or terminal functional reactive groups other than the acid or 
carboxylate groups. When the ionizable group on the polymer is a cationic 
group precursor instead of an acid or carboxylate group, the ionic 
cross-linking reactant will be an anion precursor. Examples of cation 
formers are (1) primary, secondary, tertiary and cyclic amines, which 
react with hydrogen halides and hydrocarbon halides to give quaternary 
halides to give quaternary salts; (2) substituted phosphines which combine 
with halides to give phosphonium salts; (3) sulfides which react with 
alkyl halides to give sulfonium salts; (4) cyclic ethers which react with 
acids to give oxonium salts. Examples of anion source cross-linking agents 
include acetic acid, nitric acid, hydrochloric acid, sulfuric acid, and 
relatively short chain organic multibasic acids such as oxalic, malic, 
succinic, maleic, adipic acids and corresponding anhydrides. 
For industrial coating purposes, the block of solid paint is advantageously 
contained in conventional holding and applicator devices. Such devices, 
which will vary with the nature of the substrate to be coated and will be 
adaptable to continuous application, usually include a device for holding 
the solid paint and a mechanism for adjusting the pressure placed on the 
paint block to allow proper deformation to provide a fluid coating and 
film of required thickness. Increasing the pressure applied to the solid 
paint will result in the deposit of a heavier coating. Although the 
instant solid paints are capable of air drying, it is contemplated that 
for industrial coating applications curing of the film may be accelerated 
by the use of heat, and other energy techniques known to the art. 
The following specific examples illustrate only a limited number of 
embodiments; accordingly, the invention is not limited thereto. All parts 
and percentages being by weight unless otherwise indicated. The driers 
used were commercially available conventional driers. The "mineral 
spirits" and the "odorless mineral spirits" had a boiling range of 
300.degree.-400.degree. F. and 345.degree.-410.degree. F. respectively. 
Molecular weights reported are number average molecular weights unless 
otherwise specified. Examples 1 through 12 exemplify the I.A. type of 
polymer solution formulations whereas Examples 13 through 19 exemplify the 
I.B. type polymer dispersion formulations. Examples 20 through 23 
exemplify mixtures of the I.A. type of polymer solution formulations used 
in conjunction with non-bonding (no reactive acid functionality) 
non-aqueous dispersions.

EXAMPLES 1 
Resin A was prepared by polymerizing a mixture (in amounts shown below) of 
trimethylolethane (TME), dehydrated castor fatty acid (DCOFA), Azelaic 
dimer acid (AZELAIC 1110) and dimer acid (EMPOL 1014) at 460.degree. F. as 
a fusion cook to an acid value of 41 (41.+-.2 normal range). 
Resin B, a "longer" oil resin, was prepared in a fashion similar to Resin A 
by polymerizing at 450.degree. F. to an acid value of 42.0 
Resin C, prepared using Pentaerythritol (PE) in place of trimethylolethane 
(TME), was polymerized at 460.degree. F. to an acid value of 42.0 
Resin D, prepared using a combination of DCOFA and Tung Oil instead of 
simply DCOFA, was polymerized at 460.degree. F. to an acid value of 43.0. 
TABLE I 
______________________________________ 
Material Mols Wt. Acid Value 
______________________________________ 
Resin A TME 2.46 295 41 
DCOFA 2.46 690 
AZELAIC 1110 1.78 340 
EMPOL 1014 0.74 423 
Resin B TME 2.0 240 43 
DCOFA 2.4 672 
AZELAIC 1110 1.42 270 
EMPOL 1014 0.59 337 
Resin C PE 1.0 136 42 
DCOFA 2.0 560 
AZELAIC 1110 0.72 135 
EMPOL 1014 0.29 168 
Resin D TME 1.0 120 43 
DCOFA 0.6 168 
TUNG OIL 0.19 168.5 
AZELAIC 1110 0.48 91.6 
EMPOL 1014 0.97 555 
______________________________________ 
EXAMPLE 2 
The polyester Resin A (25 parts) was formulated into a hydrocarbon solution 
by mixing with 12 parts tung oil, 13 parts mineral spirits, 2.0 parts of a 
cobalt drier (12.0 percent metal), 2.0 parts manganese drier (9.0 percent 
metal) and 3.5 parts zirconium drier (12.0 percent metal) and the 
resultant composition was allowed to mature at room temperature for 16 
hours. Titanium dioxide (40 parts) and calcium carbonate (10 parts) were 
blended with the resin solution under Cowles agitation to yield a #6 
Hegman grind. Various weights of sodium hydroxide were then added as a 25 
weight percent solution in methyl alcohol to form the solid paints 
identified in Table II. Solid Paint 2A exhibited a streaky film 
appearance, the paint was slightly too hard requiring too much effort to 
apply, i.e. exhibited too much drag on application, and application 
characteristics which were too hard. 
The solid paints 2B and 2C with gel strength of 147 and 161 respectively 
exhibited satisfactory application characteristics and film appearance, 
i.e. the paint didn't require too much force to apply and the resultant 
film was uniform. All three solid paints exhibited dimensional stability 
and gave a satisfactory dry coating on application to a test panel 
surface. 
TABLE II 
______________________________________ 
Percent 
Neutralization 
Calculated 
Exp. Parts NaOH on Moles Gel Strength* 
No. Resin Added Carboxylic Acid 
(24 hours) 
______________________________________ 
2A A 6.65 225 119 
2B A 6.35 215 147 
2C A 6.05 205 161 
3A C 7.2 240 160 
3B C 7.2 240 155 
3C C 6.0 200 178 
4A C 4.75 160 176 
4B C 5.0 170 138 
8A C 6.1 200 165 
8B C 6.5 220 155 
______________________________________ 
*Average of three determinations. 
EXAMPLE 3 
Resin C was formulated into paints 3A and 3B using the procedure outlined 
in Example 2 and the same relative amounts of resin, tung oil, mineral 
spirits, cobalt drier, manganese drier, zirconium drier, titanium dioxide, 
and calcium carbonate. A third paint formulation 3C was similarly prepared 
from Resin C but contained 1.3 parts of cobalt drier (12% metal), 0.5 
parts manganese drier (9.0% metal), 3.0 parts zirconium drier (12% metal) 
and 0.19 parts aluminum stearate. The solid paints formed on the addition 
of 25% methanolic sodium hydroxide identified as 3A, 3B and 3C each 
exhibited satisfactory gel strengths, application characteristics, film 
appearance and drying quality. 
EXAMPLE 4 
Polyester Resin C (25 parts) was formulated into a hydrocarbon solution by 
mixing with 12 parts tung oil, 13 parts mineral spirits, 0.95 parts cobalt 
drier and 2.1 parts zinc drier (16 percent metal). A second resin 
formulation for Resin C was identical to the above except it contained 
only 0.9 parts of cobalt drier and additionally contained 0.45 parts of 
manganese drier. These resins and paints made therefrom which contained 50 
parts titanium dioxide and no calcium carbonate are identified 
respectively as 4A and 4B in Table II. It is seen that paints 4A and 4B 
with neutralization values of 160 and 170 exhibit gel strengths of 176 and 
138 respectively. The application characteristics of 4A were slightly 
inferior, the solid paint tended to be too soft. The film appearance and 
drying quality of both paints were acceptable. 
EXAMPLE 5 
Repeating the experiments 2A, 2B, 3A, 3B and 3C but adding the driers 
subsequent to the addition of pigment to the resin will result in 
essentially similar acceptable gel strengths, applications characteristics 
and drying rates. 
EXAMPLE 6 
Paint blocks of approximate size 4" .times. 6" were stored using a thin 
SARAN (Trademark of the Dow Chemical Company) envelope for a period of six 
months. Application of these paints to a test panel after the storage 
period showed no detectable deterioration of the application and film 
characteristics. Additionally, solid paints prepared from the same resins 
but having acid values in the range of from 30 to 60 gave acceptable solid 
paint characteristics. Equally good results were obtained when oiticica 
fatty acid, safflower fatty acid, soya fatty acid, or linseed fatty acid 
was used instead of dehydrated castor oil fatty acid. The best application 
properties were obtained when the gel strength as measured by the 
Universal penetrometer was between 130 and 180 mm. Gel strengths of from 
100 to 130 and 180-190 gave effective solid paints with somewhat less 
desirable characteristics. 
EXAMPLE 7 
Resin D was prepared by first esterifying the dehydrated castor fatty acid 
(168 parts) with trimethylolethane (120 parts) at a temperature ranging up 
to 480.degree. F. to yield a product of acid value 4.0. Thereafter an 
ester exchange was effected by further reaction with tung oil (168.5) in 
the presence of 2.0 parts of litharge catalyst until the product was 
completely miscible in methanol. The resulting product was combined with 
Azelaic 1110 (91.6 parts) and Empol 1014 (555 parts) and cooked to an acid 
value of 43.0. The resulting resin had an approximate molecular weight of 
1300. 
A cationic Resin E was prepared by condensing Resin D (1040.4 parts) with 
N,N-diethylaminoethanol in the presence of litharge (2.0 parts) catalyst 
using reaction conditions such that the predominant reaction was 
esterification rather than amide formation. After removal of water and 
excess N,N-diethylaminoethanol, Resin E had a molecular weight of 1500. 
Gelation of Resin E was effected by neutralizing (100 and 300%) an 50/50 
weight percent solution of Resin E in mineral spirits with 37% 
hydrochloric acid. The resultant solid paints had properties inferior to 
those of a corresponding gel neutralized to 200 percent with 32 N-sulfuric 
acid and resulting in gel strengths of from 100-150. 
EXAMPLE 8 
Polyester resin C (25 parts) was formulated into a hydrocarbon solution by 
mixing with 12 parts tung oil, 13 parts mineral spirits, 0.6 parts cobalt 
drier (12.0 percent metal), 0.6 parts manganese drier (9.0 percent metal) 
and 6.0 parts zirconium drier (12.0 percent metal) and the resultant 
composition was allowed to mature at room temperature for 16 hours. 
Titanium dioxide (40 parts) and calcium carbonate (10 parts) were blended 
with the resin solution under Cowles agitation to yield a #6 Hegman grind. 
Various weights of sodium hydroxide were then added as a 25 weight percent 
solution in methanol under reduced pressure in a "vacuum Cowles" to form a 
solid paint (Table II). This manner of addition diminishes the chance of 
entrapping air into the "final" solid paint. Paints 8A and 8B (of Table 
II) exhibited superior film appearance and application properties. Both 
paints were dimensionally stable and exhibited good dry on application to 
a test panel surface. 
EXAMPLE 9 
Resin F was prepared under free radical conditions as follows: 10 parts 
methacrylic acid, 90 parts lauryl methacrylate, 1 part Bis 
(4-t-butyl-cyclohexyl) peroxycarbonate (initiator), and 300 parts mineral 
spirits were added to the kettle. Polymerization was accomplished by 
heating to 60.degree. C. and holding at this temperature for 2 hours while 
the mass in the kettle was being agitated. Conversion of 99% was achieved; 
acid value of the polymer was 65.0. Approximately 100 parts of the mineral 
spirits were removed by vacuum distillation. 
Various weights of sodium hydroxide were added as a 25 weight percent 
solution in methanol to 75 parts of the 33 percent N/V resin with 
agitation as shown: 
______________________________________ 
Percent 
Neutralization 
Calculated on 
Exp. No. 
Parts NaOH Added Carboxylic Acid 
______________________________________ 
A 6.9 150 
B 9.2 200 
______________________________________ 
The two "clear" paints can be described as follows: Experiment A resulted 
in a product that was just barely dimensionally stable and exhibited poor 
application characteristics, i.e. on applying the paint laid down too 
thick a film and too much force (relative to the previous examples) was 
required to draw the sample across the test panel. 
Experiment B resulted in a stronger product that exhibited good dimensional 
stability (gel strength of approximately 160 mm penetration) and good 
application characteristics. Paint B exhibited very little drag on 
application. Both these products resulted in a "dry" film on the test 
panel. 
EXAMPLE 10 
Resin G, a 100 percent N/V dicarboxypolybutadiene having a molecular weight 
of 1410 and an acid value of 65.0, was formulated into the following solid 
paint systems: 
______________________________________ 
Exp. No. A B C D 
______________________________________ 
Resin G (parts) 50 50 50 17 
Resin A -- -- -- 33 
Mineral spirits 50 50 50 50 
Cobalt drier .5 .5 .5 .5 
(12 percent metal) 
Zirconium drier 1.7 1.7 1.7 1.7 
(12 percent metal) 
Titanium dioxide -- 130 110 90 
Calcium carbonate 
-- 70 50 40 
NaOH (25 parts in 
18.0 20.2 36 24 
metahanol) 
Percent Neutralization 
200 300 400 350 
Gel Strength (mm.) 
250 180 110 160 
______________________________________ 
Paint A having a gel strength of 250 did not exhibit dimensional stability. 
Paints B, C and D were dimensionally stable. Under application action 
Paint B tended to put down too thick a film and was a little too elastic, 
i.e. tended to be slightly taffy like. Paint C was too hard and for this 
reason it resulted in poor quality application. Paint D exhibited 
dimensional stability and acceptable application. All the paints resulted 
in a dry film on the test panel. 
EXAMPLE 11 
Alkyd Resin H was prepared by polymerizing a mixture of 146 parts 
trimethylolpropane, 146 parts pentaerythritol, 908 parts dehydrated castor 
oil fatty acid, and 413 parts Azelaic dimer acid (AZELAIC 1110) at 
480.degree. F., as a fusion cook to an acid value of 42. The resulting 
resin exhibited a viscosity of Z.sub.2 as determined using the 
Gardner-Holt Bubble Tube Test method ASTM D1545. 
Alkyd Resin I was prepared by polymerizing a mixture of 116.5 parts 
trimethylolpropane, 116.5 parts pentaerythritol, 296 parts dehydrated 
castor oil fatty acid, and 821 parts Azelaic dimer acid (AZELAIC 1110) at 
a temperature of 460.degree. F. to an acid value of 30. The resulting 
resin exhibited a viscosity of Z.sub.2 +(Gardner-Holt). 
EXAMPLE 12 
Solid paints were prepared from Resins H and I according to the procedure 
of Example 2 with the exception that driers were allowed to mature at room 
temperature for 1/2 hour, the order of addition of ingredients being as 
given in the following table with blending to a #51/2 Hegman grind. 
______________________________________ 
Material Parts 
Experiment No. 1 2 3 4 
______________________________________ 
Resin I -- -- -- 50 
Resin H 50 50 37 -- 
AC 100.sup.a) 30 30 54 30 
Dramatone Blue tinting base.sup.b) 
2.5 -- -- -- 
Titanium Dioxide 100 100 100 100 
Min-u-Sil 10.sup.c) 10 10 10 10 
Celite 499.sup.d) 10 10 10 10 
Rheox 1.sup.e) 1.0 -- 1.0 1.0 
Odourless mineral spirits 
50 55 44 50 
Cobalt drier (12.0 percent metal) 
0.3 0.3 0.3 0.3 
Manganese drier (9.0 percent metal) 
0.15 0.15 0.15 0.15 
Zirconium drier (12.0 percent metal) 
3.0 3.0 3.0 3.0 
Methyl ethyl Ketoxime 
0.2 -- 0.2 -- 
sodium hydroxide - methanol 
8.0 8.0 8.0 8.0 
(24 percent sodium hydroxide) 
% neutralization 130 130 180 160 
gel strength (mm) 170 170 160 180 
______________________________________ 
.sup.a) a diluent alkyd resin not capable of direct participation in ioni 
bonding -- Reichhold Chemicals Canada Ltd. 
.sup.b) DRAMATONE is trademarked product of GLIDDEN-DURKEE, Division of 
SCM Corporation. 
.sup.c) Crystalline silica product of Pennsylvania Glass Sand Corp. 
.sup.d) Diatomaceous silica product of Johns-Manville Co. 
.sup.e) Bodying agent product of N L Industries. 
The solid paints 1, 2, and 3 exhibited dimensional stability and 
characteristics equivalent or superior to the solid paint products of the 
previous Examples. When applied to a substrate by contact and hand 
pressure desirable surface films were obtained which air cured overnight. 
PREATION OF NAD RESINS 
The NAD resins 1, 2, 2A, 3 and 4 were prepared by addition polymerization 
of various monomers in the presence of non-solvents, free radical 
initiators and various stabilizers in the relative proportions shown in 
Table III. A small portion of the monomers is charged to the 
polymerization kettle with the non-solvent and about 50 percent of the 
desired stabilizer and polymerization is initiated by heating to a reflux 
temperature in the order of 70.degree.-80.degree. C. Thereafter the 
remaining monomers, stabilizer (30%) and free radical initiator are added 
with ethyl acrylate in one feed stream while the acidic component, i.e. 
methacrylic acid and remaining stabilizer (20%) is added in a separate 
feed stream over a two to three hour addition period at the reflux 
temperature. Additional initiator (1/4 total amount) is introduced in 
ethyl acetate in two portions over a further reaction period of 2 hours. 
After refluxing for an additional two hours, low boiling solvent is 
removed by heating to approximately 90.degree. C. For this present 
invention it is important that the NAD be prepared with the carboxylic 
sites (or other ionizable sites) at the surface of the particle (or at 
least the majority be available to the surface) in order to provide the 
external acid sites on the suspended polymer particles. In this case the 
acid feed was started 10 minutes after the other monomer feed was 
commenced; and the acid feed was completed approximately 10 minutes after 
the other monomer feed was terminated. 
Variants of the conditions shown in this example may be used as long as a 
stable NAD is produced where the acid sites are available for gelling and 
not buried in the body of the particle. It is recommended that an acid 
value determination be made on the NAD. 
TABLE III 
______________________________________ 
GENERAL MAKEUP OF NAD POLYMERS 
(TS BY WEIGHTS) 
NAD-1 NAD-2 NAD-2A NAD-3 NAD-4 
______________________________________ 
Vinyl Acetate 
227 142 142 142 142 
Ethyl Acrylate 
104 212 237 237 212 
NAD Stabilizer 
76.4 76 76 57.5 58 
Methacrylic Acid 
28 26 38 30 18 
Mineral Spirits 
300 300 300 300 300 
Hexane 300 300 300 300 300 
Azobisisobutyronitrile 
7.5 7.5 7.5 7.5 6 
Ethylacetate 25 25 25 25 25 
Non-Volatile Content 
(final) 42.4 47.5 49 49.8 58.1 
Acid Value NAD 
44.7 39.5 55.5 43.7 28.5 
______________________________________ 
PREATION OF NAD STABILIZER 
1000 parts 12-hydroxystearic acid, 3.5 parts tetraisopropyl titanate and 60 
parts xylene were heated together at 200.degree. C. under a nitrogen 
atmosphere. The reaction was monitored by collecting the by-product water. 
The resulting product had an acid value of 34.2 (calculated 33). This 
product was further reacted at 90.degree. C. under nitrogen with 82.3 
parts glycidyl methacrylate using 400 parts methyl ethyl ketone and 10 
parts triethylamine to yield a second intermediate having an acid value of 
4.3 and a non-volatile content of 93.4 (The methyl ethyl ketone is 
stripped off at the end of the reaction). This second intermediate (321 
parts) was polymerized under free radical conditions with 225 parts methyl 
methacrylate in the presence of ethyl acetate (500 parts), dodecyl 
mercaptan (1.5 parts) and azobisisobutyronitrile (3.0 parts) free-radical 
initiator. The stabilizer was obtained in 98 percent yield. 
PREATION OF ALKYD MODIFIER 
A polyester alkyd condensation polymer was prepared by condensing 136 parts 
pentaerythritol, 560 parts dehydrated castor oil fatty acid, 135 parts 
Azelaic 1110 dimer acid, and 168 parts Empol 1014 dimer acid in a fusion 
cook at 460.degree. F. to produce an alkyd resin having reactive 
carboxylic acid functionality, acid value of 41, and a molecular weight of 
1500. 
EXAMPLE 13 
Resin NAD-2 (87 parts of 50 N/V suspension in mineral spirits) was 
formulated and blended to a #6 Hegman grind with 30 parts of alkyd 
modifier and 120 parts titanium dioxide. No driers were used in the 
formulation. In a similar fashion resin NAD-2A (94 parts of 50 N/V in 
mineral spirits) was blended with 25 parts alkyd modifier and 115 parts 
titanium dioxide. Various weights of sodium hydroxide (25% solution in 
methanol) were then added to form the solid paints identified in Table IV 
as Experiment 1A, and 1B. Solid paints IA and IB with respective gel 
strengths of 164 and 185 exhibited dimensional stability, had good 
application characteristics and gave a satisfactory dry coating on 
application to a test panel. By good application characteristics it is 
implied that on drawing the paint across the test panel a uniform film of 
paint is transferred to the panel and the work required to accomplish this 
is not excessive. 
In a third paint, resin NAD-2 (94 parts of 50 N/V in mineral spirits) was 
blended with 25 parts alkyd modifier, 115 parts titanium dioxide, 0.5 
parts cobalt drier (12 percent cobalt), 0.5 parts manganese drier (8 
percent metal), 4.0 parts zirconium drier (12 percent metal); the driers 
are added for the alkyd modifier. 16.1 parts sodium hydroxide (25% 
solution in methanol) were then added to form the solid paint identified 
in Table IV as experiment IC. This product exhibited dimensional 
stability, had good application characteristics and exhibited an excellent 
dry on application to a test panel. 
TABLE IV 
______________________________________ 
Percent 
Neutralization 
Calculated 
Exp. Parts NaOH on Moles Gel Strength* 
No. Resin Added Carboxylic Acid 
(24 hours) 
______________________________________ 
IA NAD-2 15.8 175 164 
IB NAD-2A 16.1 175 185 
IC NAD-2A 16.1 175 183 
IIA NAD-1 12.8 200 135 
IIB NAD-1 12.8 200 195 
IIC NAD-1 12.8 200 221 
IIIA NAD-2 11.2 200 240 
IIIB NAD-2 14.0 250 190 
IVA NAD-3 14.0 225 150 
IVB NAD-3 16.2 225 200 
VIA NAD-2 15.3 175 160 
______________________________________ 
*Average of three readings. 
EXAMPLE 14 
Resin NAD-1 (110 parts) was formulated and blended to a #6 Hegman grind 
with 100 parts titanium dioxide, 0.015 parts cobalt drier (12% cobalt), 
0.10 parts zirconium drier (12% zirconium) in three formulations A, B and 
C containing 5, 10 and 15 parts of tall oil alkyd (100% solids) 
respectively. Various weights of sodium hydroxide were then added as a 25 
weight percent solution in methyl alcohol to form the solid paints 
identified in Table IV as Experiment IIA, and IIC. Solid paints IIA and 
IIB with gel strengths of 135 and 195 respectively exhibited satisfactory 
application characteristics. Solid paint IIC exhibited poor application 
characteristics. All three solid paints exhibited dimensional stability 
and gave a satisfactory dry coating on application to a test panel. 
EXAMPLE 15 
Resin NAD-2 (105 parts) was formulated and blended to a #6 Hegman grind 
with 100 parts titanium dioxide, 0.015 parts cobalt drier (12% cobalt), 
0.10 parts zirconium drier (12% zirconium) and 10 parts tall oil alkyd 
(100%). Various weights of sodium hydroxide were added as a 25 weight 
percent solution in methyl alcohol to form the solid paints identified in 
Table IV as Experiments IIIA and IIIB. Solid paint IIIA with a gel 
strength of 240 had inferior application characteristics (too soft, heavy 
drag) as opposed to the good characteristics of solid paint IIIB having a 
gel strength of 190. Although the paints exhibited dimensional stability 
the film appearance was poor due to unsatisfactory coalescence. 
EXAMPLE 16 
Resin NAD-3 (101 parts) was formulated as indicated for NAD-2 in Example 13 
above using 10 parts tall oil in one case and replacing the tall oil with 
15 parts of the polyester alkyd modifier in the second case. The 
corresponding solid paints prepared by the addition of a 25 weight percent 
solution of sodium hydroxide in methanol are identified in Table IV as 
solid paints IVA and IVB respectively. Solid paints IVA and IVB with gel 
strengths of 150 and 200 exhibited dimensional stability and satisfactory 
application and film characteristics. 
EXAMPLE 17 
Paint blocks of approximate size 4".times.6" formed from the above 
described solid paints were stored using a thin Saran (Trademark of the 
Dow Chemical Company) envelope for a period of six months. Application of 
these paints to a test panel after the storage period showed no detectable 
deterioration of the application and film characteristics. Additionally 
solid paints prepared from the same resins but having acid values in the 
range of from 25 to 60 gave acceptable solid paint characteristics. The 
best application properties were obtained when the gel strength as 
measured by the Universal penetrometer was between 130 and 195 mm. 
although formulations having gel strength of from 100-130 and 195-200 gave 
effective solid paints with somewhat less desirable characteristics. 
EXAMPLE 18 
Resin NAD-4 (94 parts of 50 N/V suspension in mineral spirits) was 
formulated and blended to a #6 Hegman grind with 30 parts of alkyd 
modifier, 100 parts titanium dioxide, 15 parts calcium carbonate, 0.65 
parts cobalt drier (12 percent cobalt), 0.65 parts manganese drier (8 
percent metal), and 6.0 parts zirconium drier (12 percent zirconium). 
Sodium hydroxide (25% solution in methanol) was then added to form the 
solid paint identified in Table IV as experiment VI A. This solid paint 
had good application characteristics, exhibited dimensional stability and 
gave a dry film on a test panel. 
EXAMPLE 19 
A "non-aqueous dispersion" was prepared without using added stabilizer. A 
monomer system was chosen so that it would be partially swelled in the 
non-polar solvent, this being enough to maintain stability of the 
dispersion. 
In this case, 780 parts butyl acrylate, 100 parts methacrylic acid, 8 parts 
dodecyl mercaptan, 12 parts azobisisobutyronitrile, and 600 parts mineral 
spirits were charged to a reactor. The charge was brought to and held at 
80.degree. C. for 5 hours. Conversion was 97%, the acid value of the 
dispersion was 43.7. The theoretical acid value is 72, i.e. a certain 
amount of the acid is buried when this method of preparation is used. 
Two aliquots each of 180 parts (60 percent N/V resin) were mixed with 25.0 
parts (200% neutralization) and 37.5 parts (300% neutralization) of sodium 
hydroxide as a 25 percent solution in methanol. Both products exhibited 
dimensional stability; however, the application characteristics were poor. 
This product is not a true NAD and could best be described as a very coarse 
dispersion. This does point out, however, the possibility of internal 
stabilization through a judicious choice of monomers. This system is not 
as stable and many of the ionizable sites are buried. 
EXAMPLE 20 
PREATION OF NON-BONDING NAD RESIN NON-AQUEOUS DISPERSION 
NAD resins of the non-bonding type (i.e. without reactive functional sites 
- no gelling sites) were prepared by the addition polymerization of 
various monomers in the presence of non-solvents, free radical initiators 
and stabilizers, one example of which is given in the table shown below. A 
small portion of the monomers is charged to the polymerization kettle with 
the non-solvent (mineral spirits etc.) and about 50 percent of the desired 
stabilizer and polymerization is initiated by heating to 
75.degree.-80.degree. C. After approximately 15-30 minutes, feeding of the 
remaining monomers, stabilizers, etc., is commenced and continued over 3-4 
hours. The batch, held at reacting temperature for an additional hour, is 
then cooled to yield a milky dispersion having a low viscosity (100-200 
cps) and a 46 percent by weight non-volatile content. 
______________________________________ 
Material Charge Feed 
______________________________________ 
ethyl acrylate 46 253 
methyl methacrylate 
9 64 
odourless mineral spirits.sup.a 
300 76 
mineral spirits.sup.b 
40 10 
stabilizer (38%) 37.5 37.5 
azobis isobutyronitrile 
1.5 4.0 
______________________________________ 
.sup.a boiling range 174.degree.-210.degree. C. 
.sup.b boiling range 149.degree.-204.degree. C. 
EXAMPLE 21 
Although a wide variety of NAD Stabilizers of the type exemplified in 
Examples 13-19 are suitable for the preparation of Non-bonding NAD resins 
the following illustrates the preparation of a particularly desirable and 
useful stabilizer: 
900 parts 12-hydroxystearic acid, 3.1 parts tetraisopropyl titanate and 90 
parts odourless mineral spirits were heated together at 210.degree. C. 
under a nitrogen atmosphere. The reaction was monitored by collecting the 
by-product water. The resulting product had an acid value of 36 
(calculated 33). The product was further reacted at 190.degree. F. under 
nitrogen with 97.6 parts glycidyl methacrylate using 10 parts 
triethylamine as a catalyst. This reaction product had an acid value of 
1.8 and a non-volatile content 91.0. This second intermediate (440 parts) 
was polymerized under free radical conditions at 85.degree. C. using 2.0 
parts azobis isobutyronitrile with 300 parts methyl methacrylate in the 
presence of odourless mineral spirits (800 parts). The product was reduced 
with 300 parts odourless mineral spirits. The final non-volatile content 
by weight was 38%. 
EXAMPLE 22 
Alkyd Resin J, having bonding sites and particularly useful in preparing 
solid paints in combination with the non-bonding NAD Resin NON-AQUEOUS 
DISPERSIONS shown in Example 20, was prepared by polymerizing a mixture of 
295 parts trimethylol propane, 690 parts dehydrated castor oil fatty acid, 
340 parts Azelaic dimer (AZELAIC 1110) and 423 parts EMPOL 1014 at a 
temperature of 250.degree. C. to an acid value of 42. The resulting resin 
gives a Gardner-Holt viscosity of Z.sub.2. 
EXAMPLE 23 
Solid paints were prepared from Resin J using the following formulations: 
______________________________________ 
Materials Parts 
Experiment No. 1 2 
______________________________________ 
Non-Bonding NAD Resin 
100 100 
Ion-Bonded Resin J 25 30 
AC 100 5 -- 
Rheox 1 1 1.2 
Titanium Dioxide 100 100 
Min-U-Sil 10 10 10 
Celite 499 10 10 
Cobalt drier (12.0 percent metal) 
0.65 0.70 
Manganese drier (9.0 percent metal) 
0.25 0.3 
Zirconium drier (12.0 percent metal) 
2.5 3.0 
Methanol 2.0 1.0 
Sodium hydroxide - methanol 
6.0 7.0 
(24 percent sodium hydroxide) 
% neutralization 195 195 
gel strength (mm.) 160 150 
______________________________________ 
The materials were added in the order shown, except that half of the 
quantity of NAD (50 parts) were held out until after the grind was 
achieved (i.e. all the pigments were added). Grind was 51/2 Hegman. After 
the remaining NAD was added and the batch cooled, the driers were added. 
The driers were allowed to mature for 1/2 hour before the sodium 
hydroxide-methanol was added with agitation under reduced pressure in a 
"vacuum Cowles" to form a solid paint. This manner of addition diminishes 
the chances of entrapping air into the "final" solid paint. 
Both paints exhibited dimensional stability. When rubbed (by hand) on a 
substrate, paint was transferred to the substrate forming a film. Both 
films exhibited dry over night. 
The solid paints formed by combining Non-Bonding NAD resins with lesser 
quantities of ION-bonded resins of the IA type exemplified in Examples 
1-12 and 22 are particularly for the trade sales (consumer) segment of the 
coating industry as well as for commercial coating applications such as 
for maintenance coatings and coil coating. The particular advantage of 
such combination and intercombination of ion-bonding and NAD resins (both 
bonding and non-bonding types) is that dimensional stability is retained 
with less bonding sites while application and film characteristics are 
greatly improved. 
EXAMPLE 24 
The change in the proportion of Non-Bonding NAD resins shown in Example 23 
from 75 to 200 parts NAD resin per 25 parts of ion-bonded resin will yield 
equally satisfactory dimensionally stable solid paints. 
EXAMPLE 25 
PREATION OF NON-BONDING NAD RESIN NB-2 
NAD Resin NB-2 is prepared by addition polymerization according to the 
procedure given in Example 20 using the same reactants except that the 
feed and charge were as follows: 
______________________________________ 
Material Charge Feed 
______________________________________ 
ethyl acrylate 10 75 
methyl methacrylate 
40 275 
odourless mineral spirits 
250 30 
mineral spirits 70 5 
stabilizer (38%) 25 50 
azobis isobutyronitrile 
1.5 4 
______________________________________ 
The stabilizer used was prepared according to Example 21. A low viscosity 
(100-200 cps), milky dispersion having a 53 percent by weight non-volatile 
content was obtained. 
EXAMPLE 26 
Solid paints were prepared from Alkyl Resin J (having bonding sites) using 
the following formulation: 
______________________________________ 
Materials Parts 
Experiment No. 3 4 
______________________________________ 
Non-Bonding NAD Resin NB-2 
35.0 50.0 
Ion-Bonded Resin J 55.0 55.0 
AC 100 26.0 26.0 
Rheox 1 1.0 1.0 
Titanium Dioxide 100.0 100.0 
Min-U-Sil 10.0 10.0 
Celite 499 10.0 10.0 
Odourless mineral spirits 
35.0 35.0 
Cobalt drier (12.0 percent metal) 
0.25 0.25 
Manganese drier (9.0 percent metal) 
0.15 0.15 
Zirconium drier (12.0 percent metal 
2.5 2.5 
Sodium hydroxide - methanol 
8.0 8.0 
(24 percent sodium hydroxide) 
Gel strength (mm.) 160 175 
______________________________________ 
The materials were added in the order shown. Grind was 51/2 Hegman. After 
mineral spirits and the non-bonding NAD resin were added to the grind, 
temperature was adjusted to below 40.degree. C. and the driers added. The 
batch was allowed to mature for 1/2 hour and then the sodium 
hydroxide-methanol was added with agitation under reduced pressure in a 
"vacuum Cowles" to form a solid paint. 
Both paints exhibited dimensional stability giving the above noted gel 
strengths determined 24 hours after gelling. When rubbed (by hand) on a 
substrate, paint was transferred to the substrate forming a film. Both 
films were dry to touch in approximately one hour. 
All gel strengths were determined using a solid magnesium penetrometer with 
stainless steel point and penetration cone weighing 102 gm. .+-.50 mg. All 
test readings were taken 5 seconds after the cone was released. 
The solid paint films of the present invention can be applied to the 
substrate workpieces to which paints and coatings are usually applied for 
protective or decorative purposes. The instant solid paints will be useful 
for consumer orientated artistic and household products as well as for 
industrial purposes. The substrate being coated can be metal, mineral, 
glass, wood, paper, plastic and fabric subject to the particular art 
skills in these areas. The instant solid paints are particularly useful 
for indoor decoration of walls and structural components including wood, 
wall board, plaster, plasterboard, and similar surfaces. 
The above Examples are illustrative of the best mode for the practice of 
this invention and are not to be construed as limitations thereon.