Description:FIELD OF INVENTION
The present invention provides for compatible pigment dispersion resin as pigment vehicle suitable as a universal tinting system/ formulation towards blending pigment in polymer paint/ coatings and comprises high solid acrylated polyester polyols adapted for said universal tinting formulation and also provides a method of manufacture thereof.
High solid polyester polyols of the present invention is obtained of polyols, (including Pentaerythritol, Trimethylol propane) carboxylic acid anhydrides, (including hexahydro phthalic anhydride, phthalic anhydride) and glycidyl ester of versatic acid (Cardura E10) to give resultant polyester polyol that is further reacted with distilled soya fatty acid to give branched polyester in different molar ratios, adapted to compatibilize with select levels of acrylate monomers not only to enable complete conversion into stable high solid acrylated polyester polyol but also such that the high solid acrylated polyester polyol thus attained is suitable as compatibilizer resin facilitating universal tinter system.

Thus, said resultant polyester polyol when is further reacted with distilled soya fatty acid gives branched polyester having infinite mineral spirit solubility, and said resultant branched polyester polyol when reacted with acrylic monomers (methyl methacrylate, butyl acrylate, isobutyl methacrylate etc.) through free radical polymerization, enables said high solid acrylated polyester polyol suitable as said compatibilizer resin.

Said high solid acrylated branched polyester polyol designed at % NVM of 70-95, fatty acid content of 30-60% and hydroxyl value from 60-140 mg KOH/gm and acid value of 5-15 mg KOH/gm is of low molecular weight having weight average molecular weight, Mw in the range of 2000-15000. These polyols have excellent compatibility with a variety of polymers including alkyds, polyesters, acrylics, epoxies, polyurethanes and have very good solubility in both polar and non-polar solvents including mineral spirits.

Such high solid acrylated branched polyester polyols have been used in tint paste composition mean for universal tinting system.

Background Art

A lot has been achieved on acrylic polyester polyols, and in reference to colorant compositions for coatings, the coatings are prepared by blending pigment particles with a dispersion resin that is dissolved in a solvent, and the resulting pigment vehicle is then blended with a resin, a carrier liquid, and other components. The dispersion resin of the pigment vehicle must be compatible with the carrier liquid. Generally acrylic based dispersion resins are soluble in solvents such as water, ketones, acetates, or aromatics, but such dispersion resins are insoluble or have limited solubility in mineral spirits. There are many commercially available resins such as solid acrylic resins and Ketone-aldehyde resins which are soluble in certain conventional solvents but have limited solubility in mineral spirits. Such limited solubility in mineral spirits is also an indicator of in-compatibility with different polymer or resin systems.
Some coating compositions, such as those intended for metal coating industrial applications, may include materials such as epoxies, urethanes, and short oil alkyds, and these compositions generally include a carrier liquid having a polar character. Other compositions, such as industrial coating of wood, metal may include materials such as medium and long oil alkyds and may include a carrier liquid having a non- polar character, such as mineral spirits. While preparing a coating composition with mineral spirits as the carrier liquid, it is generally necessary to use a pigment vehicle with a dispersion resin that is different from the pigment dispersion resin that would be used for coating compositions with polar carriers. It would be highly desirable to provide a pigment dispersion resin that is compatible with polar carrier liquids such as alcohols, ketones, esters, and non-polar carrier liquids such as aliphatic and aromatic hydrocarbons including mineral spirits. Such a pigment dispersion resin would work for multiple types of coating compositions, including paints having polar carrier liquids and paints having nonpolar carrier liquids enabling simplification of the production processes for a manufacturer that produces various types of paint.

On this reference is drawn to WO2001085820 that teaches about multi-component coatings, adhesives and sealing materials that contain (A) an adduct, producible from a diisocyanate and a compound of the formula I, that has an isocyanate-reactive group and wherein R1 and R2 represent hydrogen atoms or alkyl groups, U and V represent oxygen atoms, sulfur atoms or NR6, wherein R6 is an alkyl group or aryl group, R3 is an alkylene group and R4 and R5 represent hydrogen atoms, isocyanate-reactive groups or groups R6; wherein if 1 of R4, R5 or R6 contains an isocyanate-reactive group or R4 or R5 represents an isocyanate-reactive functional group, the others groups of R4, R5 or R6, if available, have no isocyanate-reactive groups and the molar ratio of isocyanate groups in the diisocyanate to the isocyanate-reactive groups in I is 1.0; and (B) a thermally curable polyol reactive diluent selected from the group of the hyperbranched polyols that have a tetrafunctional central group, cyclic and/or acyclic C9-C16 alkanes that are functionalized with at least two hydroxy groups, and/or those polyols that are obtainable by metathesis of olefins and hydroformylation and reduction of the resulting oligomers. Curable products containing (A), (B), and, optionally, binders and crosslinkers exhibit good reflow and polishing ability. A typical clear varnish composition contained 25.82 parts (B) (number-average mol. weight 1684, weight-average mol. weight 3280) prepared by stirring 136 parts pentaerythritol 6.5 h with 616 parts phthalic anhydride at 120° and reaction of the intermediate with 904 parts glycidyl versatate until the acid number was 0.7 mg KOH/g, 19.92 parts binder solution prepared by radical polymerization of 75 parts Veova 10 with styrene 225, tert-butylcyclohexyl acrylate 150, Bu methacrylate 450, and hydroxypropyl methacrylate 600 parts in 2,4-diethyl-1,5-octanediol (II) 150, amyl Me ketone 217.5, and ethoxyethyl propionate 132.4 parts, 6.67 parts II, 25.04 parts Desmodur 3600, 3.28 parts Desmodur N3390, 0.08 parts defoamer, 0.02 parts dibutyltin dilaurate, 0.82 parts Basilon oil OL44, 0.78 parts light stabilizer, 17.2 parts BuOAc, and 14.02 parts (A) prepared by reaction of N-(2-hydroxyethyl)-2-isopropyl-1,3-oxazolidine with HDI in a 1:1 mol ratio. While part B of this prior art is a hyperbranched polyol, fatty acid modification of the polyol is not taught to further chemically react with acrylic/ vinylic monomers through unsaturation of fatty acid.

JP58222158 A teaches acrylic monomer mixtures that are polymerized in the presence of e-caprolactone (I)-modified unsaturated polyester polyols and mixed with an isocyanate or amino resin to prepare coating materials. Thus, 60 parts PhMe and 50 parts solution (60.5% non-volatiles) containing a polyester polyol prepared from trimethylolpropane 37.2, phthalic anhydride 38.0, maleic anhydride 3, Cardura E 25.3 (glycidyl ester of Versatic acid), and I 42.8 parts were heated to 100°, mixed with a solution containing styrene (II) 7, Bu methacrylate (III) 40, Bu acrylate (IV) 10, ß-hydroxyethyl methacrylate (V) 13, PhMe 20, AIBN 1.5, and tert-Bu2O2 0.5 part during 4 h, kept for 10 h, mixed (100 parts) with 65 parts TiO2 and 30 parts Super Beckamine L-117-60, thinned, sprayed on soft steel, and baked 20 min at 140° to prepare a coating having hardness H, Ericksen test >7 mm, very good contamination resistance, very good weather and gasoline resistance, and very good low-temperature bending and impact resistance, compared with H-2H, <1 mm, very good, good, and poor, respectively for a coating prepared from a 10:49:27.2:22.8 II-III-IV-V copolymer. This prior art teaches about unsaturated polyester resin and its acrylation through maleic anhydride (diene) meant for baking finishes and does not suggest about branched high solid polyester grafted with fatty acid backbone and further modified with acrylic/ vinyl monomers through fatty acid unsaturation that would be adapted to provide for very good compatibility across polymer systems including long oil alkyds, polyesters, epoxy, polyurethane etc. and excellent solubility in polar as well as non-polar solvents including mineral spirits for preparing universal tinting system.

CN113845720 teaches about composite material comprises 60-90 parts of polypropylene base resin (homopolymer and/or copolymer), 1-15 parts of filler (talc, calcium carbonate, etc.), 1-15 parts of toughening agent (ethylene-octene copolymer and/or ethylene-butene copolymer), 0.1-1.5 parts of auxiliary agent (antioxidant and/or lubricant) and 1-5 parts of coloring masterbatch; wherein the coloring masterbatch is composed of polypropylene carrier resin, colorant (organic pigment) and hyperbranched resin (aromatic hyperbranched polyamide polyester, hydroxyl-terminated aliphatic hyperbranched polyester, etc.) in the mass ratio of (60-80): (20-40): (0.2-2.0).

CN111303458 teaches about preparation method includes (1) preparing color paste from (by weight%) dye 20-30, polyester polyol 60-70, color development agent 0.5-1, defoamer 0.1-1 and dispersant 1-5 by mixing and grinding; (2) Adding the prepared color paste 10-30, carrier resin 30-95 and thickener 1-3 in a mixer, heating and stirring to form a mixture; (3) Mixing the mixture 85-95, polylactic acid 3-8, dispersant 0.5-2, stabilizer 0.5-1, coupling agent 0.1-0.5, and fragrance agent 1-2, and grinding; (4) Performing molten co-extrusion, cooling, cutting into particles, and drying. The inventive color masterbatch is light resistant, antibacterial, flame retardant, and environmentally friendly, and has improved dispersion, stability, and tinting strength.

CN109762501 teaches about a sealant that comprises component A and B; component A is composed of 10-25 parts of polycarbodiimide, 0-20 parts of polymer containing at least two acidic functional groups (dimerized fatty acids, trimerized fatty acids, carboxyl acrylic resin, etc.), 0-10 parts of thixotropic agent (nano-calcium carbonate, fumed white carbon black, carbon black, etc.), 0-20 parts of plasticizer (acetyl tri-Bu citrate, TXIB, diisononyl cyclohexane-1,2-dicarboxylate, etc.) and 0-30 parts of filler (light/heavy calcium carbonate, barium sulfate, magnesium oxide, etc.); component B is composed of 5-40 parts of polymer containing at least two acidic functional groups, 10-30 parts of filler, 0.1-0.5 parts of catalyst (organozinc catalyst (zinc isooctanoate), organobismuth catalyst (neodecanoic acid bismuth salt), organotin catalyst (dibutyltin dilaurate)), 0-10 parts of chain extender (maleic anhydride, tetrahydromethyl-1,3-isobenzofurandione, glutaric anhydride, etc.), 0-20 parts of plasticizer, 0-10 parts of thixotropic agent, 0-5 parts of pigment (titanium dioxide, iron oxide black, iron oxide red, etc.) and 0-5 parts of auxiliary agent (0-2 parts of dispersing agent 0-2 parts of silane coupling agent). Thus, 10 parts of polycarbodiimide and 20 parts of polyether polyol 1000LM were added to reaction kettle, stirred evenly at room temperature, 20 parts of light calcium carbonate was added, stirred and bubbles were removed in a vacuum to get component A; 20 parts of dimerized fatty acid (HY 005), 5 parts of acetyl tri-Bu citrate, 23.5 parts of light calcium carbonate, 1 part of carbon black and 0.5 parts of dibutyltin dilaurate were added and stirred evenly at room temperature to obtain component B; wherein the polycarbodiimide was prepared by condensation reaction of toluene diisocyanate under the catalysis of an organic phosphine and blocked with monoisocyanate; component A and B were mixed in 1:1 ratio, injected into previously sealed expansion joint.

JP2006022216 discloses polyester polyols that are prepared by reaction of (a-1) polyhydric alcohols, (a-2) polycarboxylic acids and/or their anhydrides, and (a-3) monoepoxides having long-chain hydrocarbon groups, and show OH value 30-350 mgKOH/g, acid value 10-100 mg KOH/g, and Mn 300-3000. Thus, a coated steel plate was coated with a composition containing a polyester polyol prepared from trimethylolpropane, hexahydrophthalic anhydride, and Cardura E 10P (neodecanoic acid monoglycidyl ester), Cymel 325 (melamine resin), and allyl methacrylate-Bu acrylate-hydroxyethyl acrylate-methacrylic acid-Me methacrylate copolymer dimethylethanolamine salt, preheated, coated with Magicron TC 71 (acrylic melamine resin clear coating), and baked to give a coated product with good metallic appearance and surface smoothness. It also goes to state that in addition to the polyester resin, sesame oil fatty acid, coconut oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, eno oil fatty acid, hemp oil fatty acid, toll oil fatty acid, dehydrated castor oil fatty acid, etc. (half) A fatty acid-modified polyester resin modified with a dry oil fatty acid or the like can also be used. In general, the amount of modification with these fatty acids is preferably 30% by weight or less in terms of oil length. Further, a product obtained by partially reacting a monobasic acid such as benzoic acid may be used. Further, for example, in order to introduce an acid group into a polyester resin, after the esterification reaction of the polybasic acid and the polyhydric alcohol, a polybasic acid such as trimellitic acid or trimellitic anhydride and an anhydride thereof are further added. It can also be reacted. This prior art thus teaches about thermosetting aqueous coating compositions comprising of polyester polyol (part A) which has very high hydroxyl value (30-350 mg KOH/gm) and acid value (10-100 mg KOH/gm) and acrylic emulsion latex particles (part B) and cross-linking agent like blocked polyisocyanate (part C). In aqueous coating composition, Part A (polyester polyol) is mixed with melamine resin (Cymel 325) and blended with part B (water based acrylic emulsion latex) and part C (blocked polyisocyanate) to prepare a base coat and top coat paint system.

NO340741 discloses nontoxic and biodegradable low dosage gas hydrate inhibitor comprising hyperbranched polyester polyols having hydroxyl end groups which are chemically modified. Further, this prior art relates to a method for controlling gas hydrate formation and plugging of gas hydrate forming fluids and the use of the gas hydrate inhibitors for this purpose. In said hyperbranched polyester polyols wherein all or parts of the hydroxyl end groups are esterified with at least one hydrophobic group for increased ampiphilicity and hydrate interaction and/or increased oil solubility, said hydrophobic group is introduced by reaction of the hyperbranched polyester polyol with a carboxylic acid and/or a carboxylic anhydride, wherein the carboxylic acid is selected from pivalic acid, dimethylbutyric acid, trimethylpentanoic acid, tert-butyl-trimethylpentanoic acid, diethylhexanoic acid or cyclopentanoic acid, and carboxylic anhydride is pivalic anhydride.

WO2015171433 directed to polyester polyols are made from thermoplastic polyesters that are disclosed. The polyols can be made by heating a thermoplastic polyester such as virgin PET, recycled PET, or mixtures thereof, with a glycol to give a digested intermediate, which is then condensed with a dimer fatty acid to give the polyol. The polyester polyol comprises recurring units of a glycol-digested thermoplastic polyester and a dimer fatty acid. The polyester polyol can also be made in a single step by reacting the thermoplastic polyester, glycol, and dimer acid under conditions effective to produce the polyol. High-recycle-content polyols having desirable properties are for formulating polyurethane products, including aqueous polyurethane dispersions or coatings. The polyols provide a sustainable alternative to bio- or petrochemical-based polyols.

In view of the above prior knowledge on various polyester polyols and coating compositions thereof, and for the purpose of providing colorant composition for coatings that enables blending pigment particles in paints/coatings there is a long felt requirement of a compatible pigment dispersion resin as pigment vehicle suitable for blending varied pigments in varied polymer paint/ coatings that would not only be compatible with polymer paint/ coatings but would also be compatible with polar, non-polar carrier liquid of said polymer coatings including mineral spirits/ mineral turpentine oil to enable such pigment dispersion resin as pigment vehicle to work for or easily disperse in multiple types of polymer coating/paint compositions, including coatings/paints having polar carrier liquids and polymer paints having non-polar carrier liquids to thereby enable simplification of the production processes for a manufacturer that produces various types of paint.

Objects of the Invention

It is thus the primary object of the present invention to provide for a compatible pigment dispersion resin as pigment vehicle suitable as universal tinting system/formulation for blending varied pigments in varied polymer paint/ coatings that would selectively comprise a high solid acrylated polyester polyol compatible with polar, non-polar carrier liquid of said polymer coatings including mineral spirits/ mineral turpentine oil to enable such pigment dispersion resin of pigment vehicle to work for or easily get dispersed in multiple types of polymer coating/paint compositions.

Another object of the present invention is to provide for said compatible pigment dispersion resin of pigment vehicle adapted as an universal tinting system/formulation/pigment concentrates that would be compatible with polymer coatings/paints having polar carrier liquids and polymer paints having non-polar carrier liquids to thereby enable simplification of the production processes for a manufacturer that produces various types of polymer paints.

Yet another object of the present invention is to provide for said compatible pigment dispersion resin that would not only be soluble in carrier solvents of polymer paints/ coatings including water, ketones, acetates, or aromatics, but would also be soluble in mineral spirits including mineral turpentine oil (MTO).

Still another object of the present invention is to provide for said compatible pigment dispersion resin and a process of its manufacture that would not only be compatible with acrylic polymer, ketone-aldehyde coatings/ paints but would also be compatible with metal coatings for industrial applications, including polymer materials such as epoxies, urethanes, and short oil alkyds, which all generally include a carrier liquid having a polar character, but would also be compatible with industrial coating of wood, metal including polymer materials such as medium and long oil alkyds including a carrier liquid having a non- polar character, such as mineral spirits.

It is yet another object of the present invention to provide for said compatible pigment dispersion resin including high solid acrylated polyester polyol as a reaction product of high solid branched polyester polyol with fatty acid pendant chains grafted with acrylic/ vinyl monomers via free radical polymerization in a solvent medium enabling select hydroxy value of ˜30-120 mg KOH/gm and acid value of ˜5-20 mg KOH/gm providing excellent solubility and compatibility free of any phase separation, overnight stability also favouring good drying time across various polymer paints/ coatings including varied carrier liquids/solvents therein.

Summary of the Invention

Thus according to the basic aspect of the present invention there is provided said high solid acrylated polyester polyols comprising acrylic grafted fatty acid modified monoepoxide compound based polyester polyol having % NVM (non-volatile matter) of 70-95, hydroxyl value from 60-140 mg KOH/gm and acid value of 5-15 mg KOH/gm.

Preferably said high solid acrylated polyester polyols is provided having low molecular weight levels of weight average molecular weight, Mw in the range of 2000-15000 and adapted as a compatibilizer pigment dispersion resin/ pigment vehicle suiting blending of pigments in polymer paint/ coatings thereby providing for excellent solubility based compatibility in polymer paint/ coatings of varied polymers including alkyds, polyesters, acrylics, epoxies, polyurethanes and polar, non-polar solvents including mineral spirits as carrier liquids therein.

According to another preferred aspect of the present invention there is provided said high solid acrylated polyester polyols wherein said acrylic grafted fatty acid modified monoepoxide compound based polyester polyol is a 50:50 to 60:40 acrylic/vinylic grafted branched polyester polyol facilitating acrylic/vinylic monomer conversion in the range of 78-100%, when said branched polyester polyol is a reaction product of polyols including Pentaerythritol, Trimethylol propane, carboxylic acid anhydrides including hexahydro phthalic anhydride, phthalic anhydride, and glycidyl ester of versatic acid, distilled soya fatty acid involved in molar ratio ranges of 1:0.81-1.6:1.5-1.64:1.2-1.5:1.2-2.0 for Mono pentaerythritol (98%): Hexahydrophthalic anhydride: Phthalic anhydride: glycidyl ester of versatic acid: Distilled soybean oil fatty acid respectively, and
said acrylic/vinylic monomers include Isobutyl methacrylate, n-Butyl Methacrylate, Methyl methacrylate, Hydroxy ethyl methacrylate monomers.
Preferably said high solid acrylated polyester polyols are provided as a compatibilizer resin of pigment concentrate/universal tinting formulation whereby base polymer resin/paints including Alkyd, Epoxy, Polyurethane, Polysiloxane, Polyesters is combined with lower dosage of compatibilizer resin at 12:1 sufficing incorporation of maximum dosage of tinter/pigment in said base polymer resin/paints.

According to another preferred aspect of the present invention there is provided said high solid acrylated polyester polyols suitable as said compatibilizer resin of said pigment concentrate includes inorganic and organic pigment concentrate based universal tinting formulation wherein said high solid acrylated polyester polyol compatibilizer resin is tolerant to inorganic pigment loading of 40-70% by weight and organic pigment loading ranging from 3-28% by weight.
Preferably said high solid acrylated polyester polyols are provided suitable as said inorganic and organic pigment concentrate based universal tinting formulation comprising
16 wt.% of 70% solution of said high solid acrylated polyester polyol compatibilizer resin; 68 wt.% Titanium dioxide pigment; 5 wt % of an Anionic dispersant; 2 wt. % of butyl acetate; 7 wt. % of Xylol; 1 wt. % of Methoxy propyl acetate; 0.5 wt. % Bentone SD2 & 0.5 wt. anti-settling agent having solid content 78-80 wt. % with pigment to said compatibilizer resin/binder ratio ˜4:1.

More preferably said high solid acrylated polyester polyols suitable as said inorganic and organic pigment concentrate based universal tinting formulation are provided comprising
25.5 wt.% of 70% solution of said high solid acrylated polyester polyol compatibilizer resin; 56 wt.% yellow iron Oxide pigment by weight, 5 wt % of an Anionic dispersant, 1 wt. % of butyl acetate, 9.5 wt. % of Xylol & 1 wt. % of Methoxy propyl acetate, 1 wt. % Bentone SD2 & 1 wt. % antisettling agent, having solid content of 75-78 wt. % with pigment to said compatibilizer resin/binder ratio ˜1:2.6.

Preferably said high solid acrylated polyester polyols suitable as said inorganic and organic pigment concentrate based universal tinting formulation comprise
63 wt.% of 70% solution of said high solid acrylated polyester polyol compatibilizer resin; 16.5% phthalocyanine green pigment by weight, 5 wt. % of a polyester modified dispersant, 6 wt. % of Xylol & 3 wt. % of Methoxy propyl acetate, 0.5 wt. % Bentone SD2 & 6 wt. % Ethyl Carbitol acetate, having solid content of 60-62 wt. % with pigment to said compatibilizer resin/binder ratio ˜ 0.25.:1.

According to another aspect of the present invention there is provided a process for manufacturing high solid acrylated polyester polyols comprising the steps of providing fatty acid modified monoepoxide compound based polyester polyol and grafting acrylic monomers thereon by free radical polymerization and obtaining therefrom said high solid acrylated polyester polyols.

Preferably said process for manufacturing of high solid acrylated polyester polyols are provided wherein said step of providing fatty acid modified monoepoxide compound based polyester polyol is carried out based on step 1 of involving reactants for esterification reaction including polyol, carboxylic acid/ anhydride in a reactor equipped with a temperature controller, nitrogen sparger, overhead stirrer and dean Stark assembly and is heated to temperature of about 150-155°C for 1 hour, followed by adding glycidyl ester of versatic acid as the monoepoxide compound with the temperature maintained at 150 to 155oC for 1 hour, and thereafter adding distilled soya fatty acid, di-butyl tin oxide and mixed xylene and heated to 210-215 °C and reaction continued until final acid value of the reaction mass reaches to 5-15 mg KOH/g, whereby mixed xylene is used as azeotropic solvent in the aforesaid esterification reaction and obtaining therefrom resultant branched polyol with percent non-volatile matter ranging from 70-95 %, acid value in the range of 5-15 mg KOH/gm, hydroxyl value in the range of 40-140 mg KOH/gm and weight average molecular weight (Mw) in the range of 1500-4000; and
wherein grafting acrylic monomers on said resultant branched polyol of step 1 by free radical polymerization is performed based on step 2 by involving said branched polyester polyol that is reacted with acrylic/vinyl monomers in presence of solvent medium in the ratio of 60:40 to 50:50 of polyester polyol: acrylic via free radical polymerization by employing peroxide initiators including di-tertiary butyl peroxide (DTBP), tert-butyl peroxy benzoate (TBPB) enabling monomer conversion of in the range of 78-100% and obtaining therefrom said high solid acrylated branched polyester polyol having % non-volatile matter in the range of 60-80%, acid value in the range of 5-15 mg KOH/gm, hydroxyl value in the range of 40-100 mg KOH/gm and weight average molecular weight (Mw) in the range of 5000-10000.

Brief Description of Figures
Figure 1: illustrating Impact resistance, Scratch hardness & crosscut adhesion test Example 9 resin-based pigment concentrate;
Figure 2: illustrating initial panel before QUV exposure and after 750hrs of QUV exposure Example 9 resin-based pigment concentrate in Acrylic PU;
Figure 3: illustrating Panel after 750hrs of QUV exposure in Alkyd PU Example 9 resin-based pigment concentrates;
Figure 4: illustrates reducing strength in MTO based long oil Alkyd pastel base & Mass tone on the right side in MTO based long oil Alkyd clear base with Example 9 resin-based pigment concentrate;
Figure 5: illustrates reducing strength in Mineral turpentine oil-based water containing Alkyd pastel base with Example 9 resin-based pigment concentrate that shows good compatibility.

Detailed description of the invention
As discussed hereinbefore, the present invention provides for a compatible pigment dispersion resin as pigment vehicle adapted as universal tinting system/ formulation/ pigment concentrates suiting blending of pigments in polymer paint/ coatings and comprises high solid acrylated polyester polyols and also provides a route for synthesizing such high solid acrylated polyester polyols.
First and foremost for the present invention a branched polyol is prepared by employing select levels of polyol, polyacid and monoepoxide compound (Cardura E10), which branched polyol is further modified/reacted with fatty acids to get high solid fatty acid modified branched polyester polyol with hydroxyl value in the range of 30-140 mg KOH/gm, acid value in the range of 5-20 mg KOH/ gm and % non-volatile matter in the range of 70-90%. Such fatty acid modified branched polyol is further chemically grafted with acrylic/ vinylic monomers through unsaturation on fatty acid chain via free radical polymerization to finally attain high solid acrylated polyester polyols, which thereby achieves significant compatibility with variety of polymer resin based coatings/paints including alkyd, acrylic, epoxy, polyurethane, polysiloxane polymers having polar and non-polar solvents including mineral spirit as liquid carriers.
The synthesis of high solid acrylated polyester polyol involves two steps:
Step 1 involves synthesis of high solid branched polyester polyol. Reactants (polyol, carboxylic acid/ anhydride) are charged into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and dean Stark assembly and is heated to temperature of about 150-155°C for 1 hour and thereafter Cardura E10 is charged in reactor and temperature is maintained at 150 to 155oC for 1 hour. After this, distilled soya fatty acid, di-butyl tin oxide and mixed xylene is charged into the reactor and reactor mass is heated to 210-215 deg C and reaction is carried out till the final acid value of the reaction mass reaches to 5-15 mg KOH/g. Mix Xylene is used as azeotropic solvent in the aforesaid esterification reaction. The percent non-volatile matter of the resultant branched polyol ranges from 70-95 %, acid value in the range of 5-15 mg KOH/gm, hydroxyl value in the range of 40-140 mg KOH/gm and weight average molecular weight (Mw) in the range of 1500-4000.

Step 2 involves synthesis of high solid acrylated branched polyester polyol. The branched polyester polyol obtained in step 1 is reacted with acrylic/vinyl monomers in presence of solvent medium via free radical polymerization using peroxide initiators like di-tertiary butyl peroxide (DTBP), tert-butyl peroxy benzoate (TBPB) etc. The said high solid acrylated branched polyester polyol thus obtained has % non-volatile matter in the range of 60-80%, acid value in the range of 5-15 mg KOH/gm, hydroxyl value in the range of 40-100 mg KOH/gm and weight average molecular weight (Mw) in the range of 5000-10000.

Key feature and surprising finding of the present invention is that the low molecular weight high solid acrylated branched polyester polyol of the present invention provides for high solids, renewable content, and excellent compatibility with polymer binder coatings/ paints including that of alkyds, acrylics, polyester, epoxies, polyurethane, polysiloxanes and compatible with either polar or non-polar solvents including mineral spirits present as liquid carriers in such coatings/paints thereby adapted for universal tinting/tint paste formulation suiting variety of applications.
Pigment concentrates (tint pastes) were prepared using the compatibilizer resins (low molecular weight high solid acrylated branched polyester polyol) of the present invention. The pigment concentrates are then tested for tinting various types of base polymer paints including Alkyd, Epoxy, Polyurethane, Polysiloxane, Polyesters as well as combinations thereof as hybrid polymer paints. The physical, mechanical & performance properties of tinter formulated on compatibilizer resins (polyols) were evaluated.
The following examples illustrate certain embodiments and aspects of the present invention and not to be construed as limiting the scope thereof. All parts and percentages are by weight basis unless otherwise stated.
Example 1
High solid polyester polyol is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Mono pentaerythritol (98%) 8.86
2 Hexahydrophthalic anhydride 19.68
3 Mixed Xylene 5.68
4 Cardura E10 30.00
5 Distilled soybean oil fatty acid 35.76
6 Dibutyl tin oxide 0.02
TOTAL 100.00

Process:
Charge item no 1, 2 and 3 in the reaction flask. Heat the reaction mixture up to 150-155° C and hold the temperature at 150-155° C for 1 hour. Then turn off the heating and cool the batch to 130° C and add item number 4 dropwise with the help of addition funnel within 20-25 minutes in the reaction flask. After addition, check for exotherm if any, then turn on the heating, and raise the temperature up to 150-155° C and hold it for 1 hour. After that charge item number 5 & 6 in the reaction flask. Raise temperature slowly up to 215° C maximum and collect the water as a by-product of esterification reaction and maintain the temperature until an acid <20 mg KOH/g obtained. Turn off the heating and discharge & filter the batch < 180° C in clean container.
Final constants of resin are, % Nonvolatile (@150° C/30 minutes): 94.25, Gardner Viscosity @ 25° C: Z-, Gardner color: 7, Acid value (mg KOH/gm): 15.48, Mineral turpentine oil tolerance: 1: Infinite and Weight average molecular weight: 1668.

This resin was tested in alkyd and polyurethane base tint paste. Compatibility with alkyd was okay but drying was slow and overnight phase separation observed in both systems.
Molar ratios of (Mono pentaerythritol (98%): Hexahydrophthalic anhydride: carduraE10: Distilled soybean oil fatty acid is 1:2:2:2).

Example 2
High solid polyester polyol is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Mono pentaerythritol (98%) 9.50
2 Hexahydrophthalic anhydride 8.00
3 Phthalic anhydride 10.50
4 Mixed Xylene (I) 3.00
5 Cardura E10 27.00
6 Distilled soybean oil fatty acid 40.00
7 Dibutyl tin oxide 0.02
8 Mixed Xylene (II) 1.98
TOTAL 100.00

Process:
Charge item no 1, 2, 3 and 4 in the reaction flask. Start heating the reaction mixture up to 150-155° C and hold the temperature for 1 hour. Then turn off the heating and cool the batch to 130° C and add item number 5 dropwise with the help of addition funnel within 20-25 minutes in the reaction flask. After addition, check for exotherm if any, then turn on the heating, and raise the temperature up to 150-155° C and hold it for 1 hour. After that charge item number 6, 7 & 8 in the reaction flask. And raise temperature slowly up to 215° C maximum and collect the water as a byproduct of esterification reaction and maintain the temperature until an acid <20 mg KOH/g obtained. Turn off the heating and discharge & filter the batch at less than 180° C in clean container.
Final constants are, % Nonvolatile (@150° C/30 minutes): 94.95, Gardner Viscosity @ 25° C:Y-Z, Gardner color: 8-9, Acid value(mg KOH/gm): 15.2, Mineral turpentine oil tolerance: 1:Infinite and Weight average molecular weight: 2294.
Incorporation of Phthalic anhydride did not show any difference in results as compared to example 01.
Molar ratios of (Mono pentaerythritol (98%): Hexahydrophthalic anhydride: Phthalic anhydride: carduraE10: Distilled soybean oil fatty acid is 1:0.7:1:1.6:2.0).
Example 3
High solid polyester polyol is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Mono pentaerythritol (98%) 8.90
2 Hexahydrophthalic anhydride 8.20
3 Phthalic anhydride 9.15
4 Mixed Xylene (I) 1.83
5 Cardura E10 25.05
6 Distilled soybean oil fatty acid 29.07
7 Phthalic anhydride 5.13
8 Dibutyl tin oxide 0.018
9 Mixed Xylene (II) 3.62
10 Mixed Xylene (III) 9.032
TOTAL 100.00

Process:
Charge item no 1, 2, 3 and 4 in the reaction flask. Start heating and heat the reaction mixture up to 150-155° C and hold it for 1 hour. Then turn off the heating and cool the batch to 130° and add item number 5 dropwise with the help of addition funnel within 20-25 minutes in the reaction flask. After addition check for exotherm if any, then turn on the heating, and raise the temperature up to 150-155° C and hold it for 1 hour. After that charge item number 6, 7, 8, & 9 in the reaction flask. Raise temperature slowly up to 215° C maximum and collect the water as a byproduct of esterification reaction and maintain the temperature until an acid <15 mg KOH/g obtained. Turn off the heating and dilute batch with item number 10 and discharge & filter the batch at less than 130° C in clean container.
Final constants are: % Nonvolatile (@150° C/30 minutes): 85.0, Gardner Viscosity @ 25° C: Y+, Gardner color: 6-7, Acid value (mg KOH/gm): 10.1, Mineral turpentine oil tolerance: 1: Infinite,
This formula was modified with increase in molecular weight (Practical data of Mw for example 01 is 1668 and example 02 is 2294 and for example 03 it was 3806). overnight separation was improved in Polyurethane base.
Molar ratios of (Mono pentaerythritol (98%): Hexahydrophthalic anhydride: Phthalic anhydride: carduraE10: Distilled soybean oil fatty acid is 1:0.81:1.48:1.61:1.60.
Example 4
High solid acrylated polyester polyol is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Example 03 68.00
2 Mixed Xylene (I) 13.00
3 isobutyl methacrylate 10.00
4 n-Butyl methacrylate 6.00
5 Di-tert-butyl peroxide 0.80
6 Di-tert-butyl peroxide 0.10
7 Mixed Xylene (II) 1.00
8 Di-tert-butyl peroxide 0.10
9 Mixed Xylene (III) 1.00
TOTAL 100.00

Process:
Prepare a mixture of item number 3, 4 and 5 in premix vessel. Then Charge item number 1 & 2 into the reaction flask and start stirring, heating and nitrogen gas purging and raise the temperature up to 137° C. Start addition of mixture of 3, 4 & 5 through peristaltic pump into the reaction flask within 180+/- 15 minutes. After 15+/-5 minutes of completion of addition, add item number 6 and 7. Then raise the temperature up to 140° C and maintain it for1 hour. Add item number 8 and 9 and process till conversion of monomers reached 79-81%. This was the design with 80:20 ratio of base resin (Exp 03) to acrylic monomers respectively. Initiator was taken 6.25 % of monomer amount.
Final constants are: %NVM (@150° C/30 minutes): 76.3 Gardner Viscosity @ 25° C:X-Y11.7, Mineral turpentine oil tolerance: 1:5.
Acrylation of resin example 03 carried out to improve properties but incomplete conversion of monomers was the issue. Resin was not tested in product.

Example 5
High solid acrylated polyester polyol is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Example 03 59.57
2 Mixed Xylene (I) 13.63
3 isobutyl methacrylate 11.00
4 n-Butyl methacrylate 6.00
5 Methyl methacrylate 6.00
6 Tert- butyl peroxy benzoate 1.60
7 Tert- butyl peroxy benzoate 0.10
8 Mixed Xylene (II) 1.00
9 Tert- butyl peroxy benzoate 0.10
10 Mixed Xylene (III) 1.00
TOTAL 100.00

Process:
Prepare a mixture of item number 3, 4, 5 and 6 in premix vessel. Then Charge item number 1 & 2 into the reaction flask and start stirring heating and nitrogen gas purging and raise the temperature up to 137° C. Start addition of mixture of 3, 4, 5 and 6 through peristaltic pump into the reaction flask within 180+/- 15 minutes. After 15+/-5 minutes of completion of addition, add item number 7 and 8 and raise the temperature up to 140° C and maintain it. After completion of 1 hour, add item number 9 and 10 and process till conversion of monomers reached 79-81%. This was the design with 70:30 ratio of base resin (Exp 03) to acrylic monomers respectively. And initiator was taken 8.0% of monomer amount and additional monomer MMA added.
Final constants: % Nonvolatile (@150° C/30 minutes): 76.5, Gardner Viscosity @ 25° C: Z1, Mineral turpentine oil tolerance: 1:4.2
Still the conversion was not complete. Resin was not tested in product.

Example 6
High solid polyester polyol is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Example 03 51.33
2 Mixed Xylene (I) 12.57
3 Isobutyl methacrylate 15.00
4 n-Butyl methacrylate 8.00
5 Methyl methacrylate 8.00
6 Tert- butyl peroxy benzoate 2.90
7 Tert- butyl peroxy benzoate 0.10
8 Mixed Xylene (II) 1.00
9 Tert- butyl peroxy benzoate 0.10
10 Mixed Xylene (III) 1.00
TOTAL 100.00
Process:
Prepare a mixture of item number 3, 4, 5 and 6 in premix vessel. Then Charge item number 1 & 2 into the reaction flask and start stirring heating and nitrogen gas purging and raise the temperature up to 137° C. Start addition of mixture of 3, 4, 5 and 6 through peristaltic pump into the reaction flask within 180+/- 15 minutes. After 15+/-5 minutes of completion of addition, add item number 7 and 8 and raise the temperature up to 140° C and maintain it. After completion of 1 hour, add item number 9 and 10 and process till conversion of monomers reached 79-81%. This was the design with 60:40 ratio of base resin (Exp 03) to acrylic monomers respectively. And initiator was increased to 10.0 % of monomer amount. This is the first design which have got conversion up to 78.4%.
Final constants: % Nonvolatile (@150° C/30 minutes): 78.4, Gardner Viscosity @ 25° C: Z5+, Gardner color: 6-7, Acid value (mg KOH/gm): 11.7, Mineral turpentine oil tolerance: 1: Infinite
This resin was tested in Alkyd and Polyurethane base. Drying and hardness was slightly improved. And Overnight stability show better results in alkyd and Polyurethane base.
Example 7
High solid polyester polyol free of acrylic grafting is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Mono pentaerythritol (98%) 10.24
2 Hexahydrophthalic anhydride 18.55
3 Mixed Xylene (I) 1.75
4 Cardura E10 25.73
5 Distilled soybean oil fatty acid 21.08
6 Hexahydrophthalic anhydride 6.95
7 Dibutyl tin oxide 0.017
8 Mixed Xylene (II) 3.493
9 Mixed Xylene (III) 12.19
TOTAL 100.00

Process:
Charge item no 1, 2, and 3 in the reaction flask. Start heating the reaction mixture up to 150-155° C and hold the temperature at 150° C for 1 hour. Then turn off the heating and cool the batch upto 130° C and add item number 4 dropwise with the help of addition funnel within 20-25 minutes in the reaction flask. After addition check for exotherm if any, then turn on the heating, and raise the temperature up to 150-155° C and hold it for 1 hour. After that charge item number 5, 6, 7 & 8 in the reaction flask. Raise temperature slowly up to 215° C maximum and collect the water as a byproduct of esterification reaction and maintain the temperature until an acid <15 mg KOH/g obtained. Turn off the heating and add item no. 9 below 180° C and mix it for 15 minutes and discharge & filter the batch at less than 130° C in clean container.

Final constants: % Nonvolatile (@150° C/30 minutes): 82.02, Gardner Viscosity @ 25° C: Z, Gardner color: 3-4, Acid value (mg KOH/gm): 14.2, Mineral turpentine oil tolerance: 1: Infinite.
Molar ratios of (Mono pentaerythritol (98%): Hexahydrophthalic anhydride (I): carduraE10: Distilled soybean oil fatty acid: Hexahydrophthalic anhydride (II) is 1:1.6:1.5:1:0.6).
This design shows slight improvement in drying in alkyd system and no overnight separation in alkyd system, but separation observed in Polyurethane base.

Example 8
High solid polyester polyol free of acrylic grafting is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Mono pentaerythritol (98%) 10.33
2 Hexahydrophthalic anhydride 18.72
3 Mixed Xylene (I) 2.73
4 Cardura E10 26.00
5 Distilled soybean oil fatty ac 25.97
6 Hexahydrophthalic anhydride 4.43
7 Dibutyl tin oxide 0.018
8 Mixed Xylene (II) 2.73
9 Mixed Xylene (III) 9.072
TOTAL 100.00

Process:
Charge item no 1, 2, and 3 in the reaction flask. Start heating and heat the reaction mixture up to 150-155° C and hold the temperature at 150° C for 1 hour. Then turn off the heating and cool the batch upto 130° C and add item number 4 dropwise with the help of addition funnel within 20-25 minutes in the reaction flask. After addition check for exotherm if any, then turn on the heating and raise the temperature up to 150-155° C and hold it for 1 hour. Charge item number 5, 6, 7 & 8 in the reaction flask and raise temperature slowly up to 215° C maximum and collect the water as a byproduct of esterification reaction and maintain the temperature until an acid <15 mg KOH/g obtained. Turn off the heating and add item no. 9 below 180° C and mix it for 15 minutes and discharge & filter the batch at less than 130° C in clean container.

Final constants: % Nonvolatile (@150° C/30 minutes): 86.12, Gardner Viscosity @ 25° C: Y-, Gardner color: 3-4, Acid value (mg KOH/gm): 10.64, Mineral turpentine oil tolerance: 1:Infinite
No improvement observed in properties, like example 07 results.

Molar ratios of (Mono pentaerythritol (98%): Hexahydrophthalic anhydride (I): carduraE10: Distilled soybean oil fatty acid: Hexahydrophthalic anhydride (II) is 1:1.6:1.5:1.2:0.3).

Example 9
High solid acrylated polyester polyol is prepared by charging the following constituents into a four- necked reactor flask equipped with a temperature controller, heating mantle, nitrogen sparger, overhead stirrer and Dean Stark assembly.
Formulation:
Sr No. Raw material Parts By Weight

1 Example 08 40.22
2 Mixed Xylene (I) 19.58
3 Isobutyl methacrylate 15.00
4 n-Butyl methacrylate 10.00
5 Methyl methacrylate 3.00
6 Hydroxy ethyl methacrylate 5.00
7 Tert- butyl peroxy benzoate 4.00
8 Mixed Xylene (II) 1.00
9 Tert- butyl peroxy benzoate 0.10
10 Mixed Xylene ((III) 1.00
11 Tert- butyl peroxy benzoate 0.10
12 Mixed Xylene (IV) 1.00
TOTAL 100.00

Process:
Prepare a mixture of item number 3, 4, 5, 6 and 7 in premix vessel. Then Charge item number 1 & 2 into the reaction flask and start stirring heating and nitrogen gas purging and raise the temperature up to 137° C. Start addition of mixture of 3, 4, 5, 6 and 7 through peristaltic pump into the reaction flask within 180+/- 15 minutes. After completion, flush the tube with item number 8. Then after 15+/-5 minutes of completion of addition, add item number 9 and 10 and raise the temperature up to 140° C and maintain it. After completion of 1 hour, add item number 11 and 12 and process till conversion of monomers reached 69-71%. This was the design with 50:50 ratio of base resin (Exp 08) to acrylic monomers respectively. This is the first design which have got complete conversion.
Final constants: % Nonvolatile (@150° C/30 minutes): 69.82, Gardner Viscosity @ 25° C: W-, Gardner color: 2-3, Acid value (mg KOH/gm): 8.5, Mineral turpentine oil tolerance: 1:3.6
Example 9 was the final design in which we have observed best results in terms of drying, compatibility, overnight separation. Then it was tested in epoxy base as well and observed excellent results. This was achieved by optimizing oil length and polybasic acid content in base resin, which was initially having low molecular weight, then incorporation of polybasic acid in third stage acted as bridging molecule which caused to increase molecular weight as mentioned in example 03 and improved the drying and compatibility upto a mark. But to achieve good drying, compatibility and mechanical properties acrylation was carried out in different base and acrylic monomer ratios (e.g. 80:20, 70:30, 60:40) and with different initiator (Di-tert-butyl peroxide and Tert- butyl peroxy benzoate) and monomers (Isobutyl methacrylate, Methyl methacrylate, Hydroxy ethyl methacrylate, n-Butyl methacrylate) and their percentage. Finally, 50:50 ratio of Example 08: acrylic monomers carried out with Initiator amount 12.0% of monomers observed the optimum value to achieve all improved properties.
Evaluation of Compatibility for examples 1-9
The high solid polyester/ acrylated polyester polyols of the present invention also known as compatibilizer resins were evaluated in various base paint systems except example 4 and 5 as the monomer conversion rate for these resins were poor. The compatibility of the compatibilizer resins of examples 1, 2, 3, 6, 7, 8, 9 with a range of base paint systems were evaluated. The mixing ratio for base resin (e.g. Alkyd, Epoxy, Polyurethane, Polysiloxane, Polyesters) to compatibilizer resin was fixed at 12:1 based on the maximum dosage of a tinter in base paint. Approximately 0.5g of compatibilizer resin of examples 1, 2, 3, 6, 7, 8, 9 was weighed in 7 different glass test tubes. 6g of base resin is added into each test tube followed by 3g mixture of solvent & diluent. (Methoxy propyl acetate, Ethyl Carbitol acetate, Butyl acetate & Xylol) The samples were mixed till complete dissolution of binder. Then films were applied on 6x4” glass panels as a wet film by 300-micron applicator & stored at controlled temperature of 27 deg for 24hrs. The remaining homogeneous solution in test tube was also kept under observation. The process is repeated for each base resin system & compatibilizer resin examples 1,2,3,6,7,8,9. After storage, the compatibility is evaluated visually as either OK (clear film) or slightly cloudy/ cloudy film.
The solutions of examples 1, 2, 3, 6 shows slight haziness in test tube along slight cloudiness in film when applied on the glass panel. The solution & films of example 7, 8, 9 remained clear & no cloudiness was observed. The homogeneous clear solutions of compatibilizer resins 7, 8, 9 confirms that they are fully compatible with each base resin system. The compatibilizer resins 7, 8, 9 have been used to formulate Universal tinters.

Materials
The dispersing agents having pigment-affinitive groups are for e.g. anionic, non-ionic, polyester modified dispersants, etc. were used for the preparation of pigment concentrates. The quantity of dispersants used for different pigment concentrates ranges from 2 to 100% by pigment weight.
To achieve the sufficient viscosity & flow properties in Pigment concentrates, various aromatic & aliphatic solvents have been used. Aromatic solvents include Mix xylene, Xylol, O-xylene while aliphatic hydrocarbon solvents such as Methoxy propyl acetate, Ethyl carbitol acetate, Butyl acetate were used. At least two solvents/ diluents have been used for the preparation of pigment concentrates.

Pigment concentrates
The pigment concentrates were prepared using organic & inorganic pigments. The organic pigments include azo pigments, red dyes, ketopyroles, pthalocyanines, quinacridones while inorganic includes Titanium dioxide, barium sulphide, Zinc Oxide, Red Iron oxide, Furnace carbon black, Yellow Iron oxides & other metal oxides.
Fillers/extenders like barytes & talc are used to adjust the weight per litre & improve the cost effectiveness of the pigment concentrates. Dispersions with inorganic pigments had a pigment loading of 40-70% by weight while organic pigment concentrates had a pigment loading ranging from 3-28% by weight.
1) A pigment concentrate was formulated using 68% Titanium dioxide pigment by weight, compatibilizer resin 16 wt.% of 70% solution of the high solid acrylated polyester in example 9, 5 wt % of an Anionic dispersant, 2 wt. % of butyl acetate, 7 wt. % of Xylol & 1 wt. % of Methoxy propyl acetate, 0.5 wt. % Bentone SD2 & 0.5 wt. anti-settling agent. The solid content was about 78-80 wt. %. The pigment to binder ratio was about 4:1.
2) A pigment concentrate was formulated using 56% yellow iron Oxide pigment by weight, compatibilizer resin 25.5 wt.% of 70% solution of the high solid acrylated polyester in example 9, 5 wt % of an Anionic dispersant, 1 wt. % of butyl acetate, 9.5 wt. % of Xylol & 1 wt. % of Methoxy propyl acetate, 1 wt. % Bentone SD2 & 1 wt. % antisettling agent. The solid content was about 75-78 wt. %. The pigment to binder ratio was about 1:2.6.
3) A pigment concentrate was formulated using 16.5% phthalocyanine green pigment by weight, compatibilizer resin 63 wt.% of 70% solution of the high solid acrylated polyester in example 9, 5 wt. % of a polyester modified dispersant, 6 wt. % of Xylol & 3 wt. % of Methoxy propyl acetate, 0.5 wt. % Bentone SD2 & 6 wt. % Ethyl Carbitol acetate. The solid content was about 60-62 wt. %. The pigment to binder ratio was about 0.25.:1.
Initially, the colorants/ tinters / pigment concentrates have been prepared at lab scale using a 1.2L stainless steel jacketed vessel. The compatibilizer resin is charged along with a suitable solvent & diluent combination in vessel followed by a combination of dispersants. The solution is then uniformly mixed under high-speed stirrer & then pigment is added gradually allowing it to wet properly. The chilling is provided to the vessel through jacked coils. The grinding is carried out by using Zirconium oxide (800-1200g) beads of 1-1.2 mm in size. After achieving the finish of 7 on Hegmann gauge, the grinding is stopped. The composition is thinned to 100% using solvent & resin.
The same experiments were replicated at large scale using a high-speed mixer (HSM) & Dyno mill. The premixing is being carried out on HSM followed by Dyno mill passes ranging from 1-4 depending upon the nature of pigment.
The pigment concentrates are then tested for tinting various types of base paints e.g. Alkyd, Epoxy, Polyurethane, Polysiloxane, polyesters as well as the mixture of above hybrids. The physical, mechanical & performance properties of white tinter formulated on compatibilizer resin 7, 8, 9 were evaluated. As the formulations with compatibilizer resin 7, 8 showed phase separation when kept for overnight stability while there was no phase separation observed in tinter prepared on compatibilizer resin 9. It was found comparable to tinter formulation based on aldehyde resin. Hence, only tinter prepared on compatibilizer resin example 9 was considered for physical, mechanical & performance properties.
Preparation of Pigment concentrates
Pigment concentrates were prepared using the compatibilizer resins of Examples 1, 2, 3, 6, 7, 8, and 9. A comparative test was carried out using aldehyde resin. In the pigment concentrates anionic dispersing agent & Polyester modified dispersing agent were used. The evaluation was carried out with the following pigments: titanium dioxide rutile, yellow iron oxide pigment, phthalocyanine green pigment, carbon black pigment, red iron oxide.

Example 1 & 2 showed good compatibility in alkyd system but poor compatibility in polyurethane system. Also, the drying time was inferior. Example 3 showed good compatibility in both alkyd & polyurethane system, but drying time was still inferior higher for alkyd system. Separation found in PU system when kept for overnight. Example 6 showed good compatibility in both alkyd & polyurethane system with slight improvement in drying time as compared to example 3. Example 7 & 8 showed good compatibility in both alkyd & polyurethane system & improvement in drying time as compared to example 6 but phase separation observed in overnight stability in PU system. Example 9 showed best results in terms of compatibility in alkyd, polyurethane system & epoxy system with very good drying time. No separation observed in overnight stability.

Formulation of pigment concentrate (in percentages by weight)

Sr No. Materials Percentage
Industrial White colorant Ex. 1 Ex. 2 Ex. 3 Ex. 6 Ex. 7 Ex. 8 Ex. 9
1 Compatibilizer Resin 16 16 16 16 16 16 16
2 Anionic dispersing agent 5 5 5 5 5 5 5
3 1-methoxy-2-propyl acetate 1 1 1 1 1 1 1
4 Xylol 7 7 7 7 7 7 7
5 Butyl Acetate 2 2 2 2 2 2 2
6 Titanium dioxide pigment 68 68 68 68 68 68 68
7 Bentone SD2 0.5 0.5 0.5 0.5 0.5 0.5 0.5
8 Ant settling agent 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Total 100 100 100 100 100 100 100

Based on the initial results obtained from Example 9, detail testing was being conducted for the pigment concentrate. The pigment concentrate showed excellent results under QUV B exposure @ 313 nm when exposed for 650hrs. The results for colorant prepared using compatibilizer resin of the present invention example 9 are as follows.
Physical & Coloristic Properties
Example 9
Viscosity 83.4
Finish, Hegmann Gauge 7+
Specific gravity, kg/ltr 2.045
NVM, % 79.02%
Humectancy of drying 1.5hr
Tinting strength in Polyurethane system (By Volume) Acrylic PU clear
0.217/-0.099/0.003/0.239
CR- 89.369
Acrylic PU pastel
-0.34/0.15/0.028/0.047
RS- 100.02%
Tinting strength in Epoxy system (By Volume) High build epoxy clear -0.26/0.26/-0.07/0.37
CR- 92.88
High build epoxy pastel
-0.09/-0.10/0.11/0.18
RS- 100.77%
Tinting strength in Alkyd system (By Volume) Medium oil alkyd clear
-0.001/-0.27/-0.08/0.29
CR- 92.75
Medium oil alkyd pastel
-0.04/-0.56/-0.39/0.69
RS- 100.14%
Accelerated Stability at 55°C for 30 days No separation & settling observed, No viscosity pickup
Accelerated stability, Oven (90 days @ 55 °C) No separation & settling observed, No viscosity pickup, No change in product compatibility & performance.

As seen in the above table, it was found that the compatibilizer resin-based on example 9 showed excellent compatibility in polyurethane, epoxy and alkyd based pigment concentrates hence example 9 was taken for long term testing’s & QUV exposure.
Mechanical Properties of White tinter
Properties PU
Acrylic PU Alkyd PU
Example 9 Example 9
Finish, HG scale 7+ 7+
Pot life (Hrs) 4 6
Gel Time (Hrs) 8 12
Drying Time 60 60
(Surface Dry), Min
Drying Time 8 12
(Hard Dry), Hrs
Gloss, GU @ 60° angle 95-96 96
Adhesion (DTM) 5B 4B
Scratch Hardness (Kg) 1.2 1
Impact (Direct), 7.1 Joule Passes Passes

Industrial colorant white prepared using example 9 was tested for above mechanical properties in polyurethane (PU) system i.e. Acrylic PU & Alkyd PU and showed very good impact resistance, drying time, adhesion, gloss, etc.
Figure 1 illustrates Impact resistance, Scratch hardness & crosscut adhesion test Example 9 resin-based pigment concentrate is shown and as visible from Figure 1, sample is passing in direct & reverse impact resistance test with the impact of 7.1.
Joules. It also passes Scratch hardness of 1.2 Kg & crosscut adhesion test as no film removal observed on adhesion tape.

Epoxy
High build epoxy 2 pack Epoxy
Properties Example 9 Example 9
Finish (Hegman gauge scale) 3+ 6.5+
Pot life (Hrs) 6 6
Gel Time (Hrs) 48 24
Surface Dry time (mins) 60 60
Hard Dry time (hrs) 16 16
Gloss, GU @ 60° angle 30 50
Adhesion (DTM) 4B 5B
Scratch Hardness (kg) 2.0 Kg 2.0 Kg
Impact (Direct), 7.1 Joule min Passes Passes

Industrial colorant white prepared using example 9 was tested for above mechanical properties in epoxy system i.e. high build epoxy & 2 pack Epoxy and showed good impact resistance, drying time, adhesion, gloss, etc.

Alkyd
Medium oil alkyd
Properties Example 9
Finish on (Hegman gauge scale) 7+
Surface Dry (hrs) 4 hrs
Hard Dry time (hrs)
23 hours
Gloss, GU @ 60° angle 93-95
Adhesion (DTM) 4B
Scratch Hardness (kg) 0.7 Kg
Impact (Direct), 7.1 Joule min Passes
Industrial colorant white prepared using example 9 was tested for above mechanical properties in medium oil-based alkyd system and showed excellent impact resistance, drying time, adhesion, gloss, etc.
During the QUV exposure, various properties such as coloristic properties, gloss, yellowing tendency have been checked. The color difference has also been recorded during the exposure.
The gloss values have been measured before exposing the panels for QUV. Also, the gloss is being checked at the intervals of 100-250hrs. The exposed panels were also evaluated for occurrence of any surface defects during exposure. No surface defects observed in both the backbones.
It has been found that the pigment concentrates on Example 9 shows lesser tendency for yellowing. The gloss retention is also found better for pigment concentrate on Example 9.
QUV GLOSS @ 20deg
DESCRIPTION Example 9

Gloss in Acrylic PU @ initial 95
Gloss in Alkyd PU @ initial 96.6

Gloss in Acrylic PU @ 250hrs 93.1
Gloss in Alkyd PU 1 @ 250hrs 94.2

Gloss in Acrylic PU @ 500hrs 90.2
Gloss in Alkyd PU @ 500hrs 93.8

Gloss in Acrylic PU @ 650hrs 90.8
Gloss in Alkyd PU @ 650hrs 89.9

Gloss in Acrylic PU @ 750hrs 87.0
Gloss in Alkyd PU @ 750hrs 86.5

The color difference is being measured as DE compared to unexposed panel for 250hrs, 500hrs, 650hrs, 750hrs in Polyurethane bases Acrylic PU & Alkyd PU.

QUV RESULTS IN Acrylic PU
Example 9
DE in Acrylic PU @ 250 HRS 0.05
DE in Acrylic PU @ 500HRS 0.19
DE in Acrylic PU @ 650HRS 0.32
DE in Acrylic PU @ 750HRS 0.42

The above table shows that when the panels are exposed under QUV B @313 nm, the pigment concentrate prepared using example 9 shows slightly better color retention-based pigment concentrate in Acrylic Polyurethane base at each stage of exposure i.e. Color difference DE is 0.42 for example 9 after 750 hours of QUV exposure.

QUV RESULTS IN Alkyd PU
Example 9
DE in Alkyd PU @ 250 HRS 0.34
DE in Alkyd PU @ 500HRS 0.76
DE in Alkyd PU @ 650HRS 1.31
DE in Alkyd PU @ 750HRS 2.05

Similarly, example 9 shows much better color retention-based pigment concentrate in another Alkyd Polyurethane base at each stage of exposure i.e. Color difference DE is 2.05 for example 9 after 750hrs of QUV exposure. This shows that the example 9 performs better under QUV exposure in terms of colour retention as well.
Figure 2 illustrates initial panel before QUV exposure and after 750hrs of QUV exposure Example 9 resin-based pigment concentrate in Acrylic PU
Figure 3 illustrates panel after 750hrs of QUV exposure in Alkyd PU Example 9 resin-based pigment concentrate

Based on the above findings, pigment concentrates prepared on Example 9 high solid acrylated polyester polyols was found to be good in most of the coloristic, mechanical properties & long-term exposure properties as it was significant from the gloss & color difference data that Example 9 was performing better. Similarly, the yellowing tendency was also lower in example 9.

Apart from the above observations, the major distinguishing parameter was based on the compatibility in Mineral turpentine oil based long oil alkyd systems & Mineral turpentine oil-based water containing alkyd system. Example 9 shows good compatibility in both the systems, unlike the available prior arts based on acrylic and aldehyde-based chemistries. Hence, the present invention on high solid acrylated polyester polyol is adapted as compatibilizer resin of pigment concentrates including inorganic and organic pigment concentrate based universal tinting formulation having universal tinting capability. Also, it has fatty acid component to extent of 30-40% on polymer solids.

Figure 4 illustrates reducing strength in MTO based long oil Alkyd pastel base & Mass tone in MTO based long oil Alkyd clear base with Example 9 resin-based pigment concentrate, to elaborate further Figure 4 shows that Example 9 shows no rub out issue in pastel base. Similarly, the contrast ratio & whiteness index for example 9 is very good.

Figure 5 illustrates reducing strength in Mineral turpentine oil-based water containing Alkyd pastel base with Example 9 resin-based pigment concentrate that shows good compatibility.

Formulation for Industrial Colorants Yellow Oxide & Phthalocyanine Green pigments

Formulation of pigment concentrate (in percentages by weight)
Sr No. Materials Percentage
Industrial Yellow Oxide colorant Example 9
1 Compatibilizer Resin 25.5
2 Anionic dispersing agent 5
3 1-methoxy-2-propyl acetate 1
4 Xylol 9.5
5 Butyl Acetate 1
6 Micronized yellow Iron Oxide 56
7 Bentone SD2 1
8 Anti-settling agent 1
Total 100

Formulation of pigment concentrate (in percentages by weight)
Sr No. Materials Percentage
Industrial Phthalocyanine Green colorant Example 9
1 Compatibilizer Resin 63
2 Polyester modified dispersing agent 5
3 1-methoxy-2-propyl acetate 3
4 Xylol 6
6 Phthalocyanine green pigment 16.5
7 Bentone SD2 0.5
8 Ethyl Carbitol acetate 6
Total 100

It is thus possible for the present invention to provide for high solid acrylated polyester polyols adapted as a compatibilizer pigment dispersion resin/ pigment vehicle and providing for universal tinting formulation suiting blending of pigments in polymer paint/ coatings thereby providing for excellent solubility based compatibility in polymer paint/ coatings of varied polymers including alkyds, polyesters, acrylics, epoxies, polyurethanes and polar, non-polar solvents including mineral spirits as carrier liquids therein.
, Claims:We Claim:

1. High solid acrylated polyester polyols comprising acrylic grafted fatty acid modified monoepoxide compound based polyester polyol having % NVM (non-volatile matter) of 70-95, hydroxyl value from 60-140 mg KOH/gm and acid value of 5-15 mg KOH/gm.

2. The high solid acrylated polyester polyols as claimed in claim 1 having low molecular weight levels of weight average molecular weight, Mw in the range of 2000-15000 and adapted as a compatibilizer pigment dispersion resin/ pigment vehicle suiting blending of pigments in polymer paint/ coatings thereby providing for excellent solubility based compatibility in polymer paint/ coatings of varied polymers including alkyds, polyesters, acrylics, epoxies, polyurethanes and polar, non-polar solvents including mineral spirits as carrier liquids therein.

3. The high solid acrylated polyester polyols as claimed in claims 1 or 2 wherein said acrylic grafted fatty acid modified monoepoxide compound based polyester polyol is a 50:50 to 60:40 acrylic/vinylic grafted branched polyester polyol facilitating acrylic/vinylic monomer conversion in the range of 78-100%, when said branched polyester polyol is a reaction product of polyols including Pentaerythritol, Trimethylol propane, carboxylic acid anhydrides including hexahydro phthalic anhydride, phthalic anhydride, and glycidyl ester of versatic acid, distilled soya fatty acid involved in molar ratio ranges of 1:0.81-1.6:1.5-1.64:1.2-1.5:1.2-2.0 for Mono pentaerythritol (98%): Hexahydrophthalic anhydride: Phthalic anhydride: glycidyl ester of versatic acid: Distilled soybean oil fatty acid respectively, and
said acrylic/vinylic monomers include Isobutyl methacrylate, n-Butyl Methacrylate, Methyl methacrylate, Hydroxy ethyl methacrylate monomers.
4. The high solid acrylated polyester polyols as claimed in claims 1-3 as a compatibilizer resin of pigment concentrate/universal tinting formulation whereby base polymer resin/paints including Alkyd, Epoxy, Polyurethane, Polysiloxane, Polyesters is combined with lower dosage of compatibilizer resin at 12:1 sufficing incorporation of maximum dosage of tinter/pigment in said base polymer resin/paints.

5. The high solid acrylated polyester polyols as claimed in claims 1-4 suitable as said compatibilizer resin of said pigment concentrate includes inorganic and organic pigment concentrate based universal tinting formulation wherein said high solid acrylated polyester polyol compatibilizer resin is tolerant to inorganic pigment loading of 40-70% by weight and organic pigment loading ranging from 3-28% by weight.
6. The high solid acrylated polyester polyols as claimed in claims 1-5 suitable as said inorganic and organic pigment concentrate based universal tinting formulation comprising
16 wt.% of 70% solution of said high solid acrylated polyester polyol compatibilizer resin; 68 wt.% Titanium dioxide pigment; 5 wt % of an Anionic dispersant; 2 wt. % of butyl acetate; 7 wt. % of Xylol; 1 wt. % of Methoxy propyl acetate; 0.5 wt. % Bentone SD2 & 0.5 wt. anti-settling agent having solid content 78-80 wt. % with pigment to said compatibilizer resin/binder ratio ˜4:1.

7. The high solid acrylated polyester polyols as claimed in claims 1-5 suitable as said inorganic and organic pigment concentrate based universal tinting formulation comprising
25.5 wt.% of 70% solution of said high solid acrylated polyester polyol compatibilizer resin; 56 wt.% yellow iron Oxide pigment by weight, 5 wt % of an Anionic dispersant, 1 wt. % of butyl acetate, 9.5 wt. % of Xylol & 1 wt. % of Methoxy propyl acetate, 1 wt. % Bentone SD2 & 1 wt. % antisettling agent, having solid content of 75-78 wt. % with pigment to said compatibilizer resin/binder ratio ˜1:2.6.

8. The high solid acrylated polyester polyols as claimed in claims 1-5 suitable as said inorganic and organic pigment concentrate based universal tinting formulation comprising
63 wt.% of 70% solution of said high solid acrylated polyester polyol compatibilizer resin; 16.5% phthalocyanine green pigment by weight, 5 wt. % of a polyester modified dispersant, 6 wt. % of Xylol & 3 wt. % of Methoxy propyl acetate, 0.5 wt. % Bentone SD2 & 6 wt. % Ethyl Carbitol acetate, having solid content of 60-62 wt. % with pigment to said compatibilizer resin/binder ratio ˜ 0.25.:1.

9. A process for manufacturing high solid acrylated polyester polyols as claimed in claims 1-5 comprising the steps of providing fatty acid modified monoepoxide compound based polyester polyol and grafting acrylic monomers thereon by free radical polymerization and obtaining therefrom said high solid acrylated polyester polyols.

10. The process for manufacturing high solid acrylated polyester polyols as claimed in claim 9 wherein said step of providing fatty acid modified monoepoxide compound based polyester polyol is carried out based on step 1 of involving reactants for esterification reaction including polyol, carboxylic acid/ anhydride in a reactor equipped with a temperature controller, nitrogen sparger, overhead stirrer and dean Stark assembly and is heated to temperature of about 150-155°C for 1 hour, followed by adding glycidyl ester of versatic acid as the monoepoxide compound with the temperature maintained at 150 to 155oC for 1 hour, and thereafter adding distilled soya fatty acid, di-butyl tin oxide and mixed xylene and heated to 210-215 °C and reaction continued until final acid value of the reaction mass reaches to 5-15 mg KOH/g, whereby mixed xylene is used as azeotropic solvent in the aforesaid esterification reaction and obtaining therefrom resultant branched polyol with percent non-volatile matter ranging from 70-95 %, acid value in the range of 5-15 mg KOH/gm, hydroxyl value in the range of 40-140 mg KOH/gm and weight average molecular weight (Mw) in the range of 1500-4000; and
wherein grafting acrylic monomers on said resultant branched polyol of step 1 by free radical polymerization is performed based on step 2 by involving said branched polyester polyol that is reacted with acrylic/vinyl monomers in presence of solvent medium in the ratio of 60:40 to 50:50 of polyester polyol: acrylic via free radical polymerization by employing peroxide initiators including di-tertiary butyl peroxide (DTBP), tert-butyl peroxy benzoate (TBPB) enabling monomer conversion of in the range of 78-100% and obtaining therefrom said high solid acrylated branched polyester polyol having % non-volatile matter in the range of 60-80%, acid value in the range of 5-15 mg KOH/gm, hydroxyl value in the range of 40-100 mg KOH/gm and weight average molecular weight (Mw) in the range of 5000-10000.

Dated this the 15th day of March, 2024 Anjan Sen
(Applicants Agent)
IN/PA-199