CA1082389A - Solid paint composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Solid paint composition having dimensional stability based on ion bonding and gel strengths ranging from 100 to 200 millimeter penetration are formed by interaction of certain polymers having acid group func-tionality with a substantial excess in the order of 100-600 mole percent of a cross-linking reactant formed by solution of a metal hydroxide in a high dielectric polar solvent said polymers being a curable resin 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.

Description

23~9 The present invention relates to a new type of pa-int product, namely, a solid paint having dimensional stability based on ion bonding.
Various resin compositions consisting of homo-polymers 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% of the carboxylic acid groups are neutralized with monovalent, divalent or trivalent cations. The prior art resins, known as ionomers, are desirable in ;ndustry 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 plas~ics and because of their similarity to - polyethylene find use as protectiv~ films in the food packaging industry.
Ethylene-methacryljc acid co-polymers are discussed in U.S. Patents 3,266,272 of William Fredericks issued on August 16, 1966, 3,338,739 of Richard W. Rees issued on August 29, 1g67, and in Belgium Patents 674,595 of Dunlop Rubber Co. issued December 31, 1965 and 600,397 of Barnes Engineering Co. issued February 20, 1961. Ethylene-sodium acrylate copolymers are described in Netherlands Patent 6,511,920 of Stamicarbon N.V.
issued March 5, 1967. 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 ~., 1 ' 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 react;ve polymers with "ion -clusters" having polar molecule components. This type of ion bonding ~ ~ : 1 3~
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~B~23~3!9 . -2-dlf:Eers substantially from the solvent-free ionic bonding of the prior ~rt compounds.
The present invention provides a solid paint composition having a gel strength ranging from 100 to 200 millimeter penetration and a dimensional stability based on ion bonding comprising the admixture of (a) a solution of a curable polymer having a molecular weight ranging from 1,000 to 7,000 and sufficient reactive 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; ~b) an ionic cross-linking agent selected from the group con-sisting of metal hydroxide, metal oxide, metal alkoxide, .. 15 ammonium hydroxide, or an organic cation former dissolved !~1 or suspended in a polar solvent of high dielectric strength to provide a 10-50 weight percent solution, said metal hydroxide, preferably selected from the group consisting of sodium, potassium, lithium, barium, calcium, manganese and magnesium; ~c) a metallic drier in amounts from :. about 0 to 5 weight percent based on the total weight ~;. of pol~mer7 and (d) an opacifying pigment or colorant, wherein said composition contains from about lO0 to 600 mole percent of ionic cross;linking agent per mole of aci.d functional group.
The invention further provides 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 the curable polymer resin to form the solution 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, or colorants and 0 to 5 ~r~
weight percent of a metallic drier into the resin solution . or dispersion; ~c) adding thereto under ~igorous stirring a 20 to 30 weight percent solution or suspension of an ~ I

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ionlc cross-linking agent as deirled above in a polar solvent of high dielectr~c strength to provide a 10~15 weight percent solutlon or suspension containing 100 to 600 mole percent of the amount o~ ionic cross~linking '!.
agent required 'o r.eutralize said reactive acid groups of the resinO The process may be ~ollowed by aging the mixture for 3 to 25 hours at a temperature between 15 and 70 degrees CentigradeO
' The invention further provides paint sticks encased in a removable skin or bars based on the above compositions and processes.
Solid paint compositions having dimensional sta~ility and desirable paint characteristics result from the interaction of certain polymers, having reactive functional groups, with certain cross-linking agents formed by dissolving an ionic cross-linking agent in a high dielectric polar solventO Cross-linking of the polymer chains takes place through "ion clusters" com-posed of multiple ions associated with polar solvent , molecules~ By the term solid paint is meant a paint which has sufficient d~mensional stability under storage conditions, iOeOI is self-supportingl yet could be utilized as a stick of paint (analogous to a segment of hard butter or cheese3. Such solid paint can advantageously be applied hy hand to the surfaces , usually protected by paint and coating products,,without the use of a brush or roller~ For practical and pro tective purposesl such stick of paint will generally be contained in a skin or covering suitable for storageO
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 ~.,.

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drawing the paint s-tick 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 prop-erties of adhesion, flow and uniform coverage, o~ thesurfaceO It is assumed that the solid paint of the present invention will contain the usual pigments, fillers, driers, bonding agents, and other additives to pro.~ide films having deslrable properties of gloss, color~ and hiding powerO It is anticipated that such a ~olld 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 o metalO
1 15 The resins useful in the present invention ; include homopolymers and co-polymers and mixtures thereof.
having appropr~ate functional groups either builk into the polymer chain or grafted thereto by the usual graft techniquesO Useul resins include but are not limited to polyethers, polyesters/ unsaturated polyesters, : polyurethanes, polyolefins, polyacrylates, polyhydro-carbons derived from aliphatic and aromatic hydrocarbons having ~,B unsaturation, vinyl resins and chlorine-substituted vinyls as well as other combinations known -~ 25 to the artO 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 propèr dimensional stability and gel strengthO Desirable application properties result when the gel strength is from about lO0 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 l~wer the penetrometer xeading, the higher the gel strengthO
Regardless of the type of resin used in the :: -practice of this invention~ it is essential that the ~ * Trademark ~:.
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particular resin be s~luble in a non-polar solvent and that the resin have pendant and/or terminal functional reactive groups which are readily ionizable. Such ion-izable groups include both cationic and anionic reactive unctions. Preferably, anionic functional groups used ~ to modify the resin ale the sulfonic, phosphonic and - carboxylic tnypes. The carbox~lic acid functionality is espe~ially preferred since a variety of polymers having such reactive ionizable groups can be readily purchased or synthesized. Preferred reaction produats are those ohtained from the co~ination o aarboxylic aaid sub-stituted polyesters an~ alkyd polyesters having molec-ular weights in the range of from about 1000 to 7000 which contain from about 1 to 4 reactive functional groups per each 2000 unit of molecular weight. Poly-- esters and polyethers having molecular weights in the range of 400-2000 and which yield solid paints o~ de-sirable gel properties are e~pecially preferred. Alkyd ;; xesins modi~ied with fatty acid groups and having terminal aarboxylic functionality are exemplified in the best mode Examples. In the case of polyolefins, polyacrylates and other systems where no air-curing will occltr, a higher molecular weight of the order of ~ 100,000 is usually necessary. However, 1 to 4 reactive ;; 25 functional groups are still required per 2000 unit of - molecular weight. The alkyd resins useful in the practice of this invention are prepared by polymeriz-ing the polymer monomers and other intermediates in a fusion cook at a temperature of a~out 400-6a0F. to yield resins having an acid value ~A.V.~ ranging from ~; 30 to 55 and preferably 41 ~ 2. Certain 'longer' oil ~ resins as exemplified hexeafter in Examples 1 and 2 are ;~ polymerized at 450F. to an A.V. of 43.0~
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The above described polymers having ioniz-able reactive ~roups are dissolved in sufficient non-polar solvents to provide solutions having non-volatile - (N.V.) contents of from about 10 to 90 and prefexably ~, ~
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~, 23~3 from 35 to 60 weight percent. Especially preferred are solutions of 50~ N.V. Suitable non-polar solvenks for dissolving the polymer include both aromatic and aliphatic--type hydrocarbons and are selected based on the particular resin us~d, the functionality on said resin, and the nature of the ionic reactant. In gsneral, suitable solvents are hydrocaxbons having a - bo.iling point of about 125 to 400~F. and which con-tain up to twelve carbon atoms. These include hex-ane, heptane, ootane, nonane, decane and mixtures thereof. Preferred hydrooarbons are the various octanes because of their suitable evaporation rates.
Mineral spirits is an especially preferred solvent beoause of its availability and the desirable prop-erties of the resultant solid paint. In certain case~
:~ aromatia 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 o~ each will vary and depend on thetype of resins, the types 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 solu--tion using a Cowles* agitator. The order of additionis 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 mix-ed, the resulting composition is advantageously allowedto age for 12 to 20 hours before reacting with the ; ioni~ component.
The solution of polymer in a non-polar solv-ent is next combined ~ith 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 : .
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on soluti.on speci~ic ca~ionsor anions capable of combining with th~ termillal reac~ive qroups of the resin to form ion clusters responsib].e for gel ~ormation. Such clusters, whicll contain the high dielectri.c polar solvent molecules, act as reversible cross-links to join the reactive resin molecules in webs thus impartin~ cfel strength and dimen- :
sion~l stability to the resultant solid paintO 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 hydroxidesO Such cross-linking reactants include the : oxides and hydroYides ~f sodium, pota~sium, lithium, :~ barium, calcium, manganese and magnesium Equally effective cross linking agents are the corresponding metal alkoxides : 15 i~e sodium methylateO In some cases ammon um hydroxide : and organic cation formers such as tetramethyl-ammonium hydroxide can be used as cross-linking reactantsO The cross~linking gelation derived by reacting sodium hydroxide with the above described resin molecules having terminal or pendant carboxyl groups is espec.ially preferred .: 20 Suitable gels result when an effective amount of the :: cationic base combines with the free carboxylic acid functionalityO In every case an amount of ~ase substan-tially in excess of the amount required for neutralization . is necessary to be effectiveO. By substantial excess is ~`: 25 meant f~om about 100-600 mole percent of ionic reac-tant . 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 100-6~0 . mole percent excessO When amounts less than 100 mo].e :.: percent are used the resins do not exhibit the required dimensional stabilityO When amoun~s greater than 600 mole percent are used the resins do not exhibit the desired flow and surface characteristicsO For gèl formation the metal hydroxide or other ionic cross-' , , ~,~ ' . .
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--8--linking reactant is added as a 10-50 weight percent solu-t:ion in the high dielectric polar solvent to the polymer resin formulations. Preferred solid paints were obtained by using lOO to 250 mole percent sodium hydroxide based on the molar content of the reactive functional group i.e. moles free COOHo The polar solvents useful in dissolving the ionic cro~s-linking agents are generally those solvents having a dielectric constant greater than lO, include aliphatic alcohols containing one to ten carbon atoms and one to two hydroxy groupsO Although Cl 8 aliphatic .- alcohols are usually preferred, glycols containing the similar carbon chains are sometimes useful in producing ~: desirable gel properties in the resultant solid paintO
-~ 15 Useful alcohols include methanol, ethanol, isopropanol, n-propanol, the normal and isomeric butanols, pentanols, hexanols, heptanols, octanols~ as well as the corres-: ponding glycols derived therefromO Methanol is the pre-ferred alcohol because of its costs, availability and the : 20 favorable solubility of the ionic reagents thereinO In : certain applications it is preferred to use glycols or mixtures of glycols and alcohols as the plasticizer carrier for the ionic reactantc Preferred glycols are ethylene ~-glycol and propylene glycol although for certain resins : 25 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 dimethylsulfoxideO
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 O The metal sal~s of cobalt, zinc, zirconium, magnesium, aluminum and manganese prepared from branched chain C8 12 carboxylic acids are preferred driersO The typical paint formulations, as described herein, re~uired usually high amounts o~

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g metal drie~ of the order oE about o. 5 to 5 percent based on the weight of the resin. The amount of drier needed depends to some extent on the oil or othar source o~
double bonds us~d in the paint system i~e. number and type of double bol~ds available.
A further aspect of this invention includes the use of resins having pendant and/or terminal func-tional reactive groups other than the acid or carboxylate groups. When the ionizable group on the polymer is a - 10 cationic group precursor instead of an acid or carboxylate group, the ionic ~ross-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 h~drocarbon halides to give quarternary halides to give quarternary salts; (2) ~ substituted phosphines which combine with halides to give - phosphonium salts; (3) sulfides which react with alkyl halides give sulfonium salts; ~4~ cyclic ethers which react with acids give oxonium salts. Examples of ~- 20 anion sburce 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 are ; corresponding anhydrides.
For industrial coating purposes, the block of solid paint is advantageously contained in con~
- ventional holding and applicator devicesO Such devices, ;~ which will vary with the nature of the substrate to be :;, coated and will be adaptable to contin~ous applicatlon, 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 ilm of re~uired thickness. In-creasing the pressure applied to the Colid 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 , . `

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applicatic,ns curlng of -the ~ilm may be accelerated by the used of heat~ and other energy techniques known to the art.
The following specific examples illu~trate only a limited number of embodiments; accordingly, the invention is not limited thereto. All parts and per-centages being by weight unless otherwise indicatedO The driers used were commercially available conventional driers. The "mineral spirits" and the "odorless minéral spirits" had a boiling range of 300 400F. and 345-410F. respec-tively. Molecular weights reported are n~r average molecular weights unless otherwise specifiedO E~LE 1 Resin A was prep~Gq~r~r polymerizing a mixture lS (in amounts shown below) of trimethylolethane (TME), de-hydrated castor fatty acid ~DCOFA), Azelaic dimer acid (AZELAIC 1110*) and dimer acid (EMPOL 1014*) at 460F.
as a fusion cook to an acid value of 41 ~41 ~ 2 normal range)~
Resin B, a "longer" oil resin, was prepared ln a fashion similar to Resin A ~y polymerizing at 450F~
to an acid value of 42.0~
Resin C~ prepared using Pentaerythritol (PE) ~, in place of trimethyloleth~ne ~TME)~ was polymerized at 460~F. to an acid value of 4200.
Resin D, prepared using a combination of DCOFA
and Tung Oil instead of simply DCOFA, was polymerized at 460F~ to an acid value of 43O0 TABLE I
, 30 Acid Material Mols Wt. Value, Resin A TME 2,46 295 41 AZELAIC 1110 1.78 340 ;~, 35 EMPOL 1014 0~74 423 Resin B TME 2,0 240 43 AZELAIC 1110 1,42 270 ~, ~ EMPOL 1014 0.59 337 Resin C PE lo0 136 42 DCOFA 2.0 560 -~ AZELATC 1110 0.72 135 *Trademark ~I~JB23~g ~ Acid Material Mols Wt~ Value ; _ _ __ Resin D TME 1,0 120 43 TUNG OIL Ool9 16805 AZELAIC 1110 0,48 91.6 EMPOL 10140,97 555 EXAMPLE i The polyester Resin A (25 parts) was formulated into a hydrocarbon solution by mixing with 12 parts tung 10 oil, 13 parts mineral spirits, 200 parts of a cobalt drier (1200 percent metal), 200 parts manganese drier (9.O 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 hoursO Titanium di-oxide ~40 parts) and calcium carbanate (10 parts) were blendea with the resin solution under Cowles agitation to yield a ~6 ~egman grindO 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 appear.ance, the paint was slightly too hard ` requiring tco much effort to apply i~e. exhibited too :~- much drag on application, and application characteristics :'-' which were too hardO The solid paints 2B and 2C with 25 gel strength of 147 and 161 respectively exhibited satisfactory application characteristics and film appearance i~eO 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 te,st panel surface, .

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rrABLE II

Parts Percent Neutralization Gel NaOH Calculated on Moles Strength*
Exp. No. Resin Added Carbo~ Acid _ (24 hours) 2A A 6.65 225 119 2B A 6~35 215 147 2C A 6.05 205 161 4A C 4~75 160 176 8B C 6 5 220 155 :~
:: 15 Average of three ~etermlnatlons 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 drierl zirconium drier, titanium dioxide, and calcium carbonate A third paint formulatlon 3C was s`imil-. arly prepared from Resin C but contained 1 3 parts of cobalt drier ~12% metall~ ~D5 parts manganese drier ~9O0%
metal], 3O~ parts zirconium drier C12% metal~ and 0 19 : 25 parts aluminum stearateO The solid paints fcrmed on the addition of 25~ methanolic sodium hydroxide identified :~:
: as 3A, 3B and 3C each exhibited satisactory gel strengths t application characteristics, film appearance and drying : quality~
; 30 EX~4PLE 4 Polyester Resin C ~25 parts) was ~ormulated 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 metallO 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 0O45 parts of manganese drier, These resins and paints made there~rom whlch contained 5Q parts :~

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tltdnium d~.oxide and no calclum car~onate are identifled respectlvely as 4A and 4B in Table I~, It is ~een that paints 4A and 4B with neutrali~ation values o~ 160 and 170 exhibit gel strengths of 176 and 138 respectivelyO
The application characteristics of 4A were slightly inferior~ the solid paint tended to be too softO The ~ilm appearance and drying quality of ~oth pa.~nts were acceptable.
EX~MPLE S
Repeating the experiments 2A, 2B, 3A, 3B and 3C ~ut adding the driers subsequent to the addition of : pigment to the resin will result in essentially similar acceptable gel strengths, application characteristics and drying rates, : Paint blocks ~ approximate size 4" x 6" were stored using a thin SARAN CTrademark of the DQW Chemical ; Companyl envelope for a period o~ six monthsO Applica-tion of these paints to a test panel after the storage period showed no detectable deterioration of the appli-catlon and film characteristicsO Addltionally~ solid paints prepared from the same resins but having acid values in the range of from 30 to 60 gave acceptable solid paint characteristics. E~ually good results were obtained when oiticica fatty acid~ safflower fatty : acid, soya fa,tty acid, or linseed fatty acid was used instead of dehydrated castor oil fatty acid, The :~ best application properties were obtained w.hen the gel strength as measured by the Universal penetrometer was between 130 and 180 mm~ Gel stren~ths o~ ~rom lO0 to 130 and 180-190 gave effective solid palnts with somewhat less desirable characteristlcsO
. EXAMPLE 7 Resin D was prepared ~y first esterl~ying .~ 35 the dehydrated castor fatty acld ~168 parts~ with trimethylo.lethane ~12Q paxts~ at a temperature xa~ging up to 480Fo to yield a product ~f acid value 4O~o ...
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Thereafter an ester exchange was ef~ected by furthex re action with tung oil (168~51 in the presence o~ 200 parts of litharge catalyst until the pr~duct wa~ com-pletely miscible in methanol~ The resulting product was combined with Azelaic 1110 (9106 partsl and Empol 1014 ~555 parts~ and cooked to an acid value of 43000 The resulting resin had an approximate molecular weight of 1300, A cationlc Resin E was prepared ~y condensing Resin D ~1040~4 partsl with N,N-diethylaminoethanol in the presence of litharge ~0 paxts~ catalyst using reaction conditions such that the predomlnant reaction : was esteri~ication rather than amide formationO After removal of water and excess N,N-diethylaminoethanol, Resin ~ had a molecular weight of 15000 Gelation of Resin E was ef~ected ~y neutralizing U00 and 300%) a 50/50 weight percent solution of Resin E in mlneral spirits with 37% hydrochloric acidO The ~ resultant solid paints had propertles lnferior to those ;, 20 of a corresponding gel neutralized to 200 percent with 32 N~sulfuric acid and ~esulting in gel strengths of from 1~0 1500 ' : ExaupLE 8 '; Polyester resin C ~25 parts~ was formulated - 25 into a hydrocarbon solution by m~xing with 12 parts ,~: tung oil~ 13 parts mineral spirits, 006 parts cobalt drier ~2 0 ~ percent metal~, 0 o 6 parts manganese drier : ~900 percent metal~ and 600 parts zirconium drler 12~0 percent metal~, and the xecultant composition :.' 30 was allowed to mature at room temperature ~or 16 hoursO
: Titanium dioxide (40 parts) and calcium car~onate ~10 parts~ were blended with the resin solution under Cowles agitation to yield a #6 ~egman grindO 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 CTable II~o This manner of addition diminishes the - . ..
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~0~3~39 chance of entrappiny air into the Ifinal' solid paint.
Paints ~A arld 8B ~o~ Table II) exhi~ited superior film appearance and application properties. soth paints were dimensionally stable and exhi~ited good dry on application to a test panel surface, EX~MPLE 9 Resin F was prepared under ~ree radical conditions as follows: 10 parts methacrylic acid, 90 parts lauryl methacrylate, 1 pa.rt Bis ~4-t-butylcyclo-hexyl~ peroxycarbonate Cinltiator~, and 300 parts mineral spirits ~ere added t~ the kettle~ Polylnerization was accomplished ~y heating to 60C, and holding at this temperature for 2 hours while the mass in the kettle was being agitatedO Conversion Gf 99% was :. 15 achieved; acid value of the polymer was 65~0O Approximately 100 parts of the mineral spirits ~ere removed by vacuum distillationO
Various weights of sodium hydroxide were addedas a 25 weight percent solution ln methanol to 75 part~
of the 33 percent N/V resin with agitation as shown:
Percent Neutralization Ex~ NoO Parts NaO~ Added Calculated ~n CarbQxvIic Acid : A 609 150 B 9~2 200 The two ~clear~ paints can ~e described as follows:
Experiment A resulted in a product that was just barely dimensionally stable and exhi~ited poor application characteristics, iOeO on applying the paint laid down too thick a film and too much force (relative to the . 30 previous examples~ was required to draw the sample across the test panel, Experiment B resulted in:a stronger pr~duct that : exhibited good dimensionalstabi-lity (gel strength of ap~o~Lmately 160 mm penetration~ and good application characteristics.
Paint B exhibited very little drag on application~ Both these 'products ~esulted in a ~dryl film on the test panelO
. EXAMPLE 10 . Resin G; a 100 percent N~V dicar~oxypoly~utadiene :;
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238g havin~ a molecular wei.c3ht a~ 1410 and an acld value o~
65.0, was formulated into the following solid paint systems:
No~ A B C D
5 Resin G ~parts~ 50 50 50 17 Resin A - - - 33 Mineral spirits 50 50 50 50 Cobalt drier ,5 O5 5 ~5 (12 percent metal~
10 Zirconium drier 1O7 1O71.7 1.7 ~12 percent metal:) Titanium dioxide - 130110 90 Calcium carbonate - 70 50 40 NaOH (25 parts in 18O0 20O2 36 24 15 methanoll Percent Neutralization 200 300 400 350 Gel Strength (mmOI 250 180 110 160 ~ Paint A having a gel strength of 250 did not exhibit di-- mensional stabilityO Paints B, C and D were dimensionally stableO 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 likeO Paint C was too hard and for this reason it resulted in poor quality applica-tionO Paint D exhibited dimensional stability and ;~ 25 acceptable applicationO All the paints resulted in a . dry film on the test panel.

` Alkyd Resin H was prepared by polymerizing :~ a mixture of 146 parts trimethylolpropane, 146 parts penta-: 30 erythritol~ 908 parts dehydrated castor oil fatty acid, and 413 parts Azelaic dimer acid (AZELAIC 1110) at 480F, as a fusion cook to an acid value of 42 The resulting resin exhibited a viscosity of Z2 as determined using . the Gardner-Holt Bubble Tube Test method ASTM D 1545.
Alkyd Resin I was prepared by polymerizing a mixture of 116O5 parts trimethylolpropane, 116O5 parts pentaerythritol, 296 parts dehydrated castor oil fatty acid, and 821 parts Azelaic dimer acid (AZELAIC
1110) at a temperature of 460F~ to an acid value of 30.
`~ 40 The resulting resin exhibited a viscosity of Z2 (Gardner-Holt~O

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8;~ 389 13_ MPI,E 1 2 Solld palnts were prepared from Resins H and I
accordiny ~o 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 #5 1/2 Hegman grind.
Material Parts Experiment No. 1 2 3 4 10 Resin I ~ ~ ~ 50 Resin H 50 50 37 AC 100 a~ b 30 30 54 30 Dramatone Blue tinting bas~ ) 2.5 - -Titanium ~ioxide 100 100 100 100 15 Min-u-Sil lp* 10 lG 10 10 Celite 499d) 10 10 10 10 Rheox le) -loO ~ L~O l~O
Odorless mineral spirits 50 55 44 50 Cobalt drier ~120 percent metal~ 0.3 003 0.3 003 20 Manganese drier (900 percent metal)0~15 0015 0015 0.15 Zirconium drier ~12.0 percent metal) 3~0 300 3rO 300 Methyl ethyl Ketoxime 002 _ 0.2 sodium hydroxide - methanol 300 8.0 8.0 8.0 (24 percent sodium hydroxide) 25 % neutralization 130 130 l~O 160 gel strength ~mm~ 170 170 160 180 .
.. a) a diluent alkyd resin not capable of direct participation . - in ionic bonding Reichold Chemicals (Canada) Ltdo b) DRAMATONE i.s trademarked product of GLIDDEN~DURKEE, Divison of SCL~ Corporation~
.; c) Crystalline silica product of Pennsylvania Class Sand : , :. Corp~
:~ d) Diatomaceous silica product of Johns~Manville CoO
e) Bodying agent product of N~Lo Industries~
The solid paints 1, 2 and 3 exhibited dimensional stability and characteristics equivalent or superior to : the solid paint products of the pxevious Examples. When : applied to a substrate by contact and hand pressure desirable surface films were obtained whlch air cured overnight~

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Claims (10)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A solid paint composition having a gel strength ranging from 100 to 200 millimeter penetration and a dimensional stability based on ion bonding comprising the admixture of:
a) a solution of a curable polymer resin 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 per cent solution;
b) an ionic cross-linking agent selected from the group consisting of metal hydroxide, metal oxide, metal alkoxide, ammonium hydroxide, or an organic cation former dissolved of suspended in a polar solvent of high dielectric strength to provide a 10-50 weight percent solution or suspension; and c) an opacifying pigment or colorant;
wherein said composition contains from about 100 to 600 mole percent of ion cross-linking agent per mole of acid functional group.

2. The composition of claim 1, wherein the cross-linking agent is metal hydroxide selected from the group consisting of sodium, potassium, lithium, barium, calcium, manganese and magnesium hydroxides, the polar solvent is selected from the group consisting of a C1-8 aliphatic alcohol, formamide and water; and the functional group.
is a carboxylic acid group.

3. The composition of claims 1 and 2, wherein the polar solvent is methanol and the cross-linking agent is sodium hydroxide.

4. The composition of claim 1, wherein the resin is a polyester resin having a molecular weight of 1500-3500 and acid number 38-48 and is dissolved in mineral spirits and the ionizing cross-linking agent is sodium hydroxide present at 220-280 mole percent excess basis the acid functional group.

5. The composition of claim 1, having from 0 to about 5 weight percent based on the weight of polymer of a metal drier.

6. The composition of claim 5, having from 1 to 3 weight percent of organic acid metal salt drier, said metal being selected from the group consisting of cobalt, zinc, magnesium, aluminum, manganese and zirconium.

7. A process for preparing a solid paint having dimensional stability based on ion bonding and a gel strength from 100 to 200 millimeter penetration which comprises:
(a) dissolving a curable polymer resin to form the solution 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 said curable polymer resin 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, (b) mixing thereto pigments, fillers, or color-ants and 0.5 to 5 weight percent of an organic acid metal salt drier into the resin solution, (c) adding thereto under vigorous stirring a 20 to 30 weight percent solution or suspension of metal hydroxide in a C1-8 aliphatic alcohol containing 100 to 600 mole percent of the amount of metal hydroxide required to neutralize said reactive acid group of the resin.

8. The process of claim 7, wherein the resin is a homopolymer or copolymer selected from the group consisting of alkyd resin, polyester, unsaturated polyester, polyolefin, polystyrene, polyvinylchloride, polymethacrylate, poly-acrylate, or mixtures thereof, wherein said reactive acid group is a carboxylic acid group.

9. The process of claim 8, wherein a polyester alkyd resin having a molecular weight of 1500 to 3500 and an acid number of 38 to 48 is reacted with an excess of sodium hydroxide in the range of 210-250 mole percent, over the amount required for neutralization basis mole of the carboxylic acid group, said sodium hydroxide added as a 25 weight percent solution in methanol.

10. A paint stick which comprises the solid paint according to claims 1 or 2, encased in a removable skin.