Claims:We Claim:
1. Solid waste based texturizing filler comprising ground and pulverized biocide fortified emulsion polymer skin based texturizing filler, ground at temperatures below the glass transition temperature of said emulsion polymer.
2. Solid waste based texturizing filler as claimed in claim 1 wherein said emulsion polymer skin is cryogenically ground preferably involving dry ice and/or liquid nitrogen and includes acrylic, styrene-acrylic emulsion polymer.
3. Solid waste based texturizing filler as claimed in claims 1 or 2 wherein said biocide fortified emulsion polymer skin based texturizing filler in powder form has gel content upto 95 wt. % preferably cross-linked gel content and 5-25 wt. % of thermoplastic non-gel content and particle size in the range of 10 microns to 5 mm preferably in the range of 300 to 400 microns (passing 100% through 0.85 mm sieve).
4.Solid waste based texturizing filler as claimed in claims1-3 wherein said cryogenically ground and pulverized biocide fortified emulsion polymer skin based texturizing filler that is cryogenically ground attains fineness (less than 20 mesh) as compared to filler ground by normal ice involving similar quantity of ground material.
5.Solid waste based texturizing filler as claimed in claims 1-4 wherein said cryogenically ground and pulverized biocide fortified emulsion polymer skin based texturizing filler is suitable for powder coating and water based decorative/texture paint formulations and comprises:
1-10 wt.% preferably 5-10 wt.% of said dry ground pulverized emulsion skin powder (DGPES) in powder coating and water based decorative/ architectural paint formulations providing for low-cost powder coating and water based decorative paint formulations having appearance and mechanical performance comparable to standard formulations.
6. Solid waste based texturizing filler as claimed in claims 1-5 wherein said (DGPES) in levels of about 5 wt.% (18#/30#) as texturizing filler in architectural coating formulations is comparable to conventional silica/dolomite filer.
7. Solid waste based texturizing filler as claimed in claims 1-6 wherein said (DGPES) suitable as colour texturing fillers/agent comprises
90-97 wt.% dry ground pulverized emulsion skin powder (DGPES) of >18 mesh;
1-4 wt.% colour filler;
0.1- 0.3% flow leveling additive;
5-8% resin.

8. Solid waste based texturizing filler as claimed in claims 1-7 wherein
said colour fillers include Red Oxide 105M, Yellow Oxide 3920 Sudafast Blue 2684, Hostaperm Green GNX, Carbon Black Pearl 120, Titanium dioxide R 902;
said flow leveling additive includes RESIFLOW P-67, P–88 including polyacrylic flow leveling additives on silica carrier having active content 60-70%;
said resin having glass transition temperature >50 degree centigrade to avoid any lump formation at room temperature and preferably includes polyester resin based on MP Diol (2-Methyl 1,3- Propane Diol) and PTA (Purified Terephthalic Acid) or EG (Ethylene Glycol), TMP (Trimethylolpropane) and PTA (Purified Terephthalic Acid), Ketonic Resin SRK 100.
9. A process for manufacturing said solid waste based texturizing filler as claimed in claims 1-8 comprising the steps of
(i) providing emulsion polymer skin based solid waste and decontaminating with bio-pack fortified water to provide for washed emulsion skin;
(ii) drying the washed emulsion skin at room temperature for removal of moisture;
(iii) (A) cryogenic grinding of dried emulsion skin by dry CO2 followed by sieving for desired particle size generation; OR
(iii) (B) cryogenic grinding of dried emulsion skin by liquid N2 followed by sieving for desired particle size generation.
10. A process for manufacturing said solid waste based texturizing filler as claimed in 9 wherein said
Step (i) involves decontamination of emulsion skin by bio-pack fortified water by taking about 40% Emulsion Skin (ES), 60% Water, 0.2% Bactericide mixed for 5 to 10 minutes using HSD (High speed disperser)followed by filtration to remove water;
Step (ii) involves drying of the washed emulsion skin for complete removal of moisture;
Step (iii) (A) involves cryogenic grinding using dry CO2 and sieving for desired particle size of filler by involving 80 wt.% Dry ES, 5% anticaking agent preferably marble powder of 500 # mesh size + about 20 wt.% dry CO2 to thereby attain usable fillers of various sizes; OR
Step (iii) (B) involves cryogenic grinding using liquid N2 and sieving for desired particle size of filler involving 80 wt.% Dry ES, 5 wt.% Marble powder 500 # mesh size, about 20 wt.% Liq. N2to thereby attain usable fillers of various sizes.
11. A process for manufacturing said solid waste based texturizing filler as claimed in claims 9-10 wherein said reutilizable solid waste based texturizing filleris sourced from including waste emulsion that sticks in internal reactor wall and stirrer, filtration residue collected in the filtration device as grit particlesand skin formed in storage tank, polymerization waste from emulsion skin of acrylic or styrene acrylic polymers of emulsion polymerization process synthesized in a water media that is converted into usable filler by subjecting to treatment with water containing a biocide free of solvents being water based system to be thus being more environmentally friendly.
12. A process for manufacturing said solid waste based texturizing filler as claimed in claims 9-11 wherein said anti caking agents include pyrogenic silica, finer calcium carbonate, finer dolomite, finer barium sulphate, said preferred anti caking agents has the size in the range of 5 to 25 microns.
13. A process for manufacturing said solid waste based texturizing filler as claimed in claims 9-12as colour texturing fillers/agent
wherein said emulsion skin filler in the range of 90-96 wt.% (<18# mesh size) is combined with 1-4 wt.% Colour Filler, 0.3% flow leveling additive, 5-8 wt.% polyester followed by extruding through twin screw extruder;
further grinding & sieving the extruded material to attain colour filler of desired particle sizes.

Dated this the 17th day of October, 2019 Anjan Sen
Of Anjan Sen and Associates
(Applicants Agent)
IN/PA-199
, Description:FIELD OF INVENTION
The present invention provides for solid waste based texturizing filler and paint/ powder coating formulations and colour texturing fillers/agents attained thereof involving solid polymerization waste based filler/ extender made usable and reutilizable. Said solid polymerization waste is emulsion skin made usable and reutilizable thereby serving as good replacement of conventional inorganic fillers and texturizing agent.

BACKGROUND ART
The present polymer emulsion manufacturing at plant generates significant amount of waste polymer in the form of dry skin or solid gel particles in the form of grit polymer, reactor wall sticking etc. This amounts to few metric tons of waste polymer generation as solid hazardous waste which is usually incinerated incurring environment pollution/ energy consumption and adding carbon foot print.
Some of the efforts seen in the prior art are as below:
US 6,248,809 B1 and US 7,967,988 B1 describes the methods of separating the latex solid from white water and thus providing the reusable filtrate for the environmental benefit. There is no specific process that is described to convert the solid sludge in usable form.
Moreover, US 8,597,563 B2 describes the process of coagulating the latex sludge from the waste white water of latex manufacture and using this sludge along with the thermosetting materials like GTR (ground tire rubber) for making thermoplastic articles.
In all these prior art, the key difference is they uses the waste white water waste of the emulsion manufacturing and coagulate /filter out the polymer solids to primarily use the latex filtrate to be reused in the polymer manufacturing.
Reference is drawn to US 8,597,563 B2, that teaches methods for making shape able composite materials or shaped articles from recycled materials comprising forming a crumb slurry by, in any order, increasing the particle size of a composition comprising white water waste from one or more emulsion or dispersion polymer and combining the white water waste polymer with one or more waste thermoset material, preferably, ground tire rubber (GTR), and, then processing the combined material wet or dry as a thermoplastic to form the composite material or article. This prior art uses the white-water waste of emulsion polymer reactor after batch discharge and concentrate the same by coagulation and other purification methods to use it along with the ground tire rubber (GTR) or other waste thermoset material for making thermoplastic articles by conventional plastic processing techniques.
US 6,248,809 B1, discloses polymer recovered by ultrafiltration from a whitewater waste stream generated during the production of a polymer latex. The whitewater Stream is circulated through an ultra-filtration System in laminar flow, under conditions of Shear insufficient to destabilize the whitewater emulsion, and therecovered polymer is in the form of an emulsion which may be blended at significant levels into the original polymer latex without degrading its performance properties. Hence teaches a method of recovering the polymer from white water waste generated during production of latex, which is recycled back in original polymer latex without compromising the performance.
US 7,967,988 B1, 2011, also teaches method for treatment of waste latex, and apparatus for treating a liquid volume containing latex waste so as to get the latex filtrate and the solid waste. The filtrate can be reused in the latex manufacturing process. This prior art also mentions (page 10 section 5 lower left corner) the possible use of the discharged latex solid as supplemental fuel or as a recycled pigment in the manufacture of paints or coatings or as a filler in composite material in concrete and other construction applications.
US8597563, US6248809 & US7967988 all teaches a process of reutilisation of liquid filtrate generated in emulsion, and describes a method of separation of emulsion polymer solid from waste water by means of different set of process like coagulation and sedimentation using different coagulum additives, ultrafiltration technique etc. but is not directed to reutilization of solid waste which sticks in reactor wall, filtration residue and skin form in storage tank, converting those to solid waste into usable form of filler.
US4299952Adescribes a process for generation of solid thermoplastic latex particles from latex solution having %NVM in the range of 10–50% by mechanical shear sufficient to transform the latex into a paste-like mass, admixing the paste-like mass with steam under a pressure of about 25 to 400 pounds per square inch, but is not about re-utilization of solid waste generated during emulsion polymer synthesis sticking in reactor wall, filtration residue and skin form in storage tankwith the waste emulsion skin undergoing a cryo grinding to be pulverized for use in powder coating.
EP0460284A2 teaches to increase the efficiency of coagulation and washing of hydrocarbon polymer particles by partly replacing mechanical energy with thermal energy, in particular the coagulation and washing of such particles formed by an emulsion polymerization process, and is not related to any re-utilization of solid waste generated during emulsion polymer synthesis by cyro-grinding followed by sieving and application in coating.
US8304463B relates to the recovery of waste latex used in the manufacture of carpeting and the utilization of waste latex in the manufacture of carpeting and does not teach about any re-utilization of waste emulsion skin stick on reactor wall, filtration residue and skin formed during storage of emulsion.

WO2002018453A1 teaches a method to reduce the polymer content in the effluent in the dewatering of two-phase liquid mixture of a thermoplastic plastic melt and an aqueous phase, by coagulating the plastic melt and squeezing the water out of the melt cake in an extrusion apparatus but is not directed to any residue treatment left in filtration assembly in the form of polymer grit during filtration of emulsion polymer and re-utilization of that waste residue in coating.
EP0683028B1describes a process of dewatering a two-phase fluid mixture of a thermoplastic melt and an aqueous phase in a counter-rotating twin-screw extruder and removing the aqueous phase from the extruder in liquid form. In this prior patent counter-rotating twin-screw extruder for dewatering is employed and is not directed to any multi-mill for pulverization of waste emulsion skin.
CN103692574A is related to mechanically crushing of waste plastics and separation of plastic enriched with same charges through electrostatic separation method and does not teach any cryo-grinding of waste emulsion skin followed by sieving.
US20050209439A relates to carpet waste material, consists of thermoplastic resin and calcium carbonates, and is distanced form any acrylic emulsion polymer waste containing almost 60% gel thermoset polymer minus any filler.
US4096061Adescribes a chemical method of separation of latex particles from paint waste water, using cationic flocculent for separation of the latex particles further adjusting the pH to alkaline condition and adding anionic dispersant for reuse of the sludge in the latex paint base formulation, but is not directed to any mechanical grinding of waste emulsion polymer not involving any chemical treatment.
WO2012095520A3 teaches recycling of liquid degraded paint and paint precursor by giving some chemical treatment and is distanced from treatment of solid acrylic emulsion polymer waste that involves mechanical grinding method to convert it into form of filler.
WO2007072502A2 deals with reusing sludge formed due to coagulation with flocculants of spray-paint which is mainly solvent borne paint including alkyd based paint sludge, epoxy paint sludge, acrylic basedpaint sludge, polyester melamine based paint sludge, aminopolyester paint basedsludge, thermosetting acrylic sludge, urea based sludge, silicone or modified silicone based paint sludge and acrylated alkyd paint sludge or any mixture thereofalkyd/ amino/ epoxy based,and is not related to any treatment of emulsion skin of acrylic or styrene acrylic polymers of emulsion polymerization process synthesized in a water media with water containing a biocide free of solvents being water based system thus being more environmentally friendly.
US6311906B1 teaches recycling of liquid waste paint contains filler, pigments, resin and additives in paste form and not related to any solid and highly cross linked thermosetting acrylic emulsion polymer.
US5166272A&WO2008009649A1 discloses a method of preparation of stable emulsion polymer to avoid/reduce formation of polymer grit, and not related to any reutilization of grit formed during emulsion polymerization process.
US6776364B2 teaches a process and processor for reusing liquid waste paint, rolling the waste paint between a pair of heated rotating drums and not related to any solid and highly cross linked thermosetting acrylic emulsion polymer.
US5,490,907 is related to recovery of volatile organics present in the paint sludge.
U.S. 5,765,293 mainly teaches paint sludge from the automotive industry which is mostly uncured epoxy based paint sludge that needs heat treatment (for curing) and not related to any waste polymer obtained from emulsion manufacturing plants that is structurally a acrylic or styrene acrylic polymer and incurable.
WO2014037954A1 is related to solvent recovery from paint sludge using fluidization and heat treatment.
US2004/0029511A1 mainly teaches abrasive materials that are usually comprised of thermally curable binders include phenolic resins (e.g., resol phenolic resin), urea-formaldehyde resins, urethane resins, melamine-formaldehyde resins, epoxy resins, and alkyd resins that are all solvent borne binders knitted on to a backing cloth (woven or non-woven) , hence abrasive texture not related to any texture forms of decorative paints to beautify walls or in polyester resins as a filler.
EP 2794983 B1 relates to carpet backing formulations and hence not related to any making of decorative paints with a textured appearance utilizing waste polymer.
Development of Waste Polystyrene as a binder for emulsion paint formulation related prior arts are usually dissolved in a solvent and hence are not water based systems.
US 5,026,782 describesa process to make core-shell morphologies using emulsion polymerization and not any reuse of any grit/waste polymer.
US 5,284,894 describes the normal emulsion polymerization process that uses surfactants and inspite of using any amount of surfactant – grit formation occurs in every batch, whose reuse is not tackled in this prior art.
Hence it is the need in the art to avoid generation of solid waste and even if the solid waste generates the key focus of the present invention is to explore reutilization of solid waste opposed to the reutilization of the liquid filtrate. The source of the solid waste is the sticking of the reactor walls, filter residues which are typically the polymer grit formed during the manufacture of polymer, emulsion skin formed during storage of the emulsion. All these are usually thrown out as solid hazardous waste, and hence a requirement to explore for provisions that focuses on conversion of this solid waste into usable filler/ extender by set of processessuch that the resulting fillers/ extenders would be good replacement of conventional inorganic fillers that are regularly used, which would not only reduce the overall density of the paint but would also reduce the cost and as well as provideimproved functional properties of the texture paint/ powder coatings.

OBJECTS OF THE INVENTION
Thus the primary object of the present invention is to provide for paint/ powder based coating formulations involving solid polymerization waste based usable filler/ extender as a good replacement of conventional inorganic fillers and texturizing agent.
Another object of the present invention is to provide for paint/ powder based coatings as water-based texture paintsinvolving said solid polymerization waste based usable filler/ extender that would have low overall density, would provide for improved functional properties of said texture/coatings and at the same time would be cost effective with enhanced performance.
Yet another object of the present invention is to provide for a process for processing/ utilizingthe solid waste that would provide said waste in usable form of extender/filler of varied sizes to be used in water-based texture paints as well as powder coatings.
Still another object of the present invention is to provide for re-utilization of said solid waste in the form of emulsion polymer skin generated during the emulsion polymerization process in water-based deco paint and powder coatings application.

SUMMARY OF THE INVENTION
Thus according to the basic aspect of the present invention there is provided solid waste based texturizing filler comprising ground and pulverized biocide fortified emulsion polymer skin based texturizing filler, ground at temperatures below the glass transition temperature of said emulsion polymer.
Preferably said solid waste based texturizing filler is provided wherein said emulsion polymer skin is cryogenically ground preferably involving dry ice and/or liquid nitrogen and includes acrylic, styrene-acrylic emulsion polymer.
According to a preferred aspect of the present invention there is provided said solid waste based texturizing filler wherein said biocide fortified emulsion polymer skin based texturizing filler in powder form has gel content upto 95 wt. % preferably cross-linked gel content and 5-25 wt. % of thermoplastic non-gel content and particle size in the range of 10 microns to 5 mm preferably in the range of 300 to 400 microns (passing 100% through 0.85 mm sieve).
Advantageously said solid waste based texturizing filler is provided wherein said cryogenically ground and pulverized biocide fortified emulsion polymer skin based texturizing filler that is cryogenically ground attains fineness (less than 20 mesh) as compared to filler ground by normal ice involving similar quantity of ground material.
Preferably said solid waste based texturizing filler is provided wherein said cryogenically ground and pulverized biocide fortified emulsion polymer skin based texturizing filler is suitable for powder coating and water based decorative/texture paint formulations and comprises:
1-10 wt.% preferably 5-10 wt.% of said dry ground pulverized emulsion skin powder (DGPES) in powder coating and water based decorative/ architectural paint formulations providing for low-cost powder coating and water based decorative paint formulations having appearance and mechanical performance comparable to standard formulations.
More preferably said solid waste based texturizing filler is provided wherein said (DGPES) in levels of about 5 wt.% (18#/30#) as texturizing filler in architectural coating formulations is comparable to conventional silica/dolomite filer.
According to another preferred aspect of the present invention there is provided said solid waste based texturizing filler wherein said (DGPES) suitable as colour texturing fillers/agent comprises
90-96 wt.% dry ground pulverized emulsion skin powder (DGPES) of >18 mesh;
1-4 wt.% colour filler;
0.1- 0.3% flow leveling additive;
5-8% resin.

Preferably, said solid waste based texturizing filler is provided wherein
said colour fillers include Red Oxide 105M, Yellow Oxide 3920 Sudafast Blue 2684, Hostaperm Green GNX, Carbon Black Pearl 120, Titanium dioxide R 902;
said flow leveling additive includesRESIFLOW P-67, P–88 including polyacrylic flow leveling additives on silica carrier having active content 60-70%;
said resin having glass transition temperature >50 degree centigrade to avoid any lump formation at room temperature and preferably includes polyester resin based on MP Diol (2-Methyl 1,3- Propane Diol) and PTA (Purified Terephthalic Acid) or EG (Ethylene Glycol), TMP (Trimethylolpropane) and PTA (Purified Terephthalic Acid), Ketonic Resin SRK 100.
According to another aspect of the present invention there is provided a process for manufacturing said solid waste based texturizing filler comprising the steps of
(i) providing emulsion polymer skin based solid waste and decontaminating with bio-pack fortified water to provide for washed emulsion skin;
(ii) drying the washed emulsion skin at room temperature for removal of moisture;
(iii) (A) cryogenic grinding of dried emulsion skin by dry CO2 followed by sieving for desired particle size generation; OR
(iii) (B) cryogenic grinding of dried emulsion skin by liquid N2 followed by sieving for desired particle size generation.
Preferably in said process for manufacturing said solid waste based texturizing filler wherein said
Step (i) involves decontamination of emulsion skin by bio-pack fortified water by taking about 40% Emulsion Skin (ES), 60% Water, 0.2% Bactericide mixed for 5 to 10 minutes using HSD (High speed disperser)followed by filtration to remove water;
Step (ii) involves drying of the washed emulsion skin for complete removal of moisture;
Step (iii) (A) involves cryogenic grinding using dry CO2 and sieving for desired particle size of filler by involving 80 wt.% Dry ES, 5% anticaking agent preferably marble powder of 500# mesh size + about 20 wt.% dry CO2to thereby attain usable fillers of various sizes; OR
Step (iii) (B) involves cryogenic grinding using liquid N2 and sieving for desired particle size of fillerinvolving 80 wt.% Dry ES, 5 wt.% Marble powder 500 # mesh size, about 20 wt.% Liq. N2to thereby attain usable fillers of various sizes.
According to another preferred aspect of the present invention there is provided a process for manufacturing said solid waste based texturizing filler wherein said reutilizable solid wastebased texturizing filleris sourced from including waste emulsion that sticks in internal reactor wall and stirrer, filtration residue collected in the filtration device as grit particlesand skin formed in storage tank, polymerization waste from emulsion skin of acrylic or styrene acrylic polymers of emulsion polymerization process synthesized in a water media that is converted into usable filler by subjecting to treatment with water containing a biocide free of solvents being water based system to be thus being more environmentally friendly.
Preferably in said process for manufacturing said solid waste based texturizing filler said anti caking agents include pyrogenic silica, finer calcium carbonate, finer dolomite, finer barium sulphate, said preferred anti caking agents has the size in the range of 5 to 25 microns.
According to another preferred aspect of the present invention there is provided a process for manufacturing said solid waste based texturizing filler as colour texturing fillers/agent
wherein said emulsion skin filler in the range of 90-96 wt.% (<18# mesh size) is combined with 1-4 wt.% Colour Filler, 0.3% flow leveling additive, 5-8 wt.% polyester followed by extruding through twin screw extruder;
further grinding &sieving the extruded material to attain colour filler of desired particle sizes.

DETAILED DESCRIPTION OF THE INVENTION
As described hereinbefore, the present invention provides for solid waste based texturizing filler and paint/ powder based coating formulations attained thereof involving solid polymerization waste based filler/ extender made usable and reutilizable. Said solid polymerization waste is emulsion skin that was otherwise incinerated and/or used for landfilling. Such said waste basedcoating formulations of the present invention involves said solid polymerization waste based usable filler/ extender as a good replacement of conventional inorganic fillers and texturizing agent.
Preferably, paint/ powder based coating formulations as water-based texture paint formulation is provided involving said solid polymerization waste based usable filler/ extender having low overall density, provides for improved functional properties of said texture/coatings and at the same time is cost effective with enhanced performance.
The present invention is explained hereunder in greater details in relation to the non-limiting exemplary illustrations and figures.

BRIEF DESCRIPTION OF FIGURES
Figure 1: illustrates lab scale process flow of converting the emulsion skin waste into usable fillers;
Figure 2: illustrates imagesrevealing the resulting usable product/ filler appearance at various stages of the process;
Figure 3: illustrates microscopic images showing the particles size and shape of the DGPES and dolomite powder for size and shape comparison;
Figure 4: illustrates picture of tested powder coating panels;
Figure 5: illustrates application as texturizing agent in low cost texture emulsion paint;
Figure 6: illustrates process flow of converting the emulsion skin filler into colour texturing Agent;
Figure 7: illustrates images of colour texturizing agent prepared using emulsion skin;
Figure 8: illustrates textured paint containing 0.5% coloured Emulsion skin 18/30# in formulation;
Figure 9: illustrates images of the industrial scale multi-mill conventional grinder for emulsion skin grinding.

EXAMPLES:
A process for processing/ utilizing the solid waste in usable form of extender/filler of varied sizes is thus provided that can be employed in water-based texture paints as well as powder coatings.Apart from what is described in Figure 1, cryogenic grinding using liquid N2, and sieving for desired particle size of filler80% Dry ES + 5% Marble powder 500 # + 20% Liq. N2, and wherein for 90% emulsion skin, 10% liquid N2, is required and the Liquid N2 is inoculated at 0.5 bar pressure having a relief valve in the system thereby generating usable fillers of various sizes.
Two specific applications for the emulsion skin of the present invention:
1. The purified dry ground emulsion skin is used as texturizing material in powder coating with variable proportion. The initial test results show that uses of 5% & 10% on weight basis is technically feasible.
2. The emulsion skin-based filler alone was studied at the level of up to 5 % in duracast texture in place of silica/ dolomite filler in architectural coating (decorative water based paint application)
This document provides the formula/recipe and the processing details for the said applications:
Processing Technology:
The emulsion skin based waste is not in a form which can be used directly in any of the current products or can be used in any new products using the same.
Hence the process followed by the present invention is for converting these non-standard/ non usable materials into usable standard material which can be produced consistently at plant. The flow chart under Figure 1 depicts the process followed for purification of these wastes.
STEP 1involves decontamination of emulsion skin by bio-pack fortified water by taking about 40% Emulsion Skin (ES)+ 60% Water + 0.2% Bactericide and mixed it for 5 to 10 minutes using HSD. Then filtered to remove the water;
STEP 2 involves drying of the washed emulsion skin and was allowed to dry the washed emulsion skin at room temperature to remove the moisture completely;
STEP 3A involves cryogenic grinding using dry CO2 and sieving for desired particle size of filler 80% Dry ES + 5% Marble powder 500 # + 20% dry CO2 after which usable fillers of various sizes was attained;
STEP 3B involves cryogenic grinding using liquid N2 and sieving for desired particle size of filler80% Dry ES + 5% Marble powder 500 # + 20% Liq. N2after which usable fillers of various sizes was attained.
The wt.% of each of the component mentioned above plays critical role in attaining the required particles size and hence its utility either in powder coating or as specific sized texturizing agent/ filler for textured paint. The content of liquid N2 or Dry CO2 is thus selective for best efficiency of grinding using pulverizer like multimill and the quality of the filler in terms of sizes. The use of marble powder at 5wt.% level ensures the non sticking of the ground particles (anti caking agent) due to lower glass transition temperature of the emulsion skin. Other anti caking agents like pyrogenic silica, finer calcium carbonate, finer dolomite, finer barium sulphate also enables achievement of fillers.

Figure 2 reveals the resulting usable product/ filler appearance at various stages of the process.
Table 1: Characterization/ Specification of the prepared fillers prepared as above
Sr. No. Parameter Result/ specification range Remark
1 Glass transition temperature By DSC 20 to 30 °C Since it is a mix composition of all emulsions, the Tg may vary.
2 % Moisture Max. 1 %
3 % Water soluble Max 1%
4 Gel content Max 95 % The general observations when done by soxhlet solvent extraction method, it selectively contains about 5 to 25 % of thermoplastic (non-gel) content and rest is crosslinked (gel) polymer, which was only found to be suitable.
5 Particle size (d50) 300 to 400 microns (passing 100% through 0.85 mm sieve) The pulverized material was passed through 0.85 mm sieve
6 Microbial growth No (Biocide fortified material) The wet emulsion skin had shown microbial growth when tested in lab, however, the biocide treated emulsion skin when ground and pulverized passed the test.
7 Heavy metal content
(ppm) Lead - 2.05PPM;
Cadmium - < 1PPM
Chromium - < 1PPM
Arsenic - < 2 PPM
Mercury - < 1 PPM Done by ICP-OES( Inductively Coupled Plasma -Optical Emission Spectrometry) method at APL lab.

It was found by way of the present invention that Soxhlet solvent extraction method provides easy tool to characterize the waste polymer and its suitability to provide for the desired fillers for use in texture paints as well as powder coatings.
The method of generating the solid polymer waste including from reactor walls results into crosslinking of polymer chains to the tune of upto 95 % which means this polymer waste contains about 5 to 25 % of polymer which is not crosslinked and hence thermally sensitive which facilitates the thermal processing using extruder making it processable for powder coating application. Moreover, the higher crosslinked portion of the waste also makes it less solvent sensitive hence stable as texturizing material for water borne paints where co-solvents and coalescing agents does not affect their dimensional stability.
Hence if the processed waste polymer does not have crosslinking in the above range it either does not have good processability on extruder for making powder coatings or does not enable a stable texturizing agent /filler in water borne texture paints.
The Soxhlet solvent extraction method thus provides an easy tool to characterize the waste polymer and hence ensures the required performance as above. The other methods like solvent swelling methods can also be employed however may not be very easy to perform when compared to above method.
Figure 3 illustrates microscopic images showing the particles size and shape of the DGPES and dolomite powder for size and shape comparison.
Characterisation of Emulsion Skin: Key characterization techniques used to characterize the dry ground pulverized emulsion skin powder (DGPES)
1. DSC analysis to understand glass transition temperature (Tg) of polymer skin;
2. Microbiology analysis of the polymer skin to optimize bio-pack doses to arrest initial microbial growth;
3. Sieve analysis the particle size distribution of the dried ground emulsion skin;
4. ICP – OES for heavy metal content determination;
5. Soxhlet extraction to find the gel content in emulsion skin;
6. Microscopic Analysis (pictures to compare with conventional fillers like Dolomite.

The experimental designs of black topcoat powder coating paint with varied dosages of the dry ground pulverized emulsion skin powder (DGPES) (5% & 10% on wt. basis) were prepared. The experimental designs were evaluated along with commercial PC (POWDER COATING) benchmark. under Table 2 below:

Table 2:Experimental designs of black topcoat powder coating paint with varied dosages of the dry ground pulverized emulsion skin powder (DGPES) (5% & 10% on wt. basis)

Sr. No. Initial Film Properties Standard
(Commercial PC benchmark) Batch 1 Batch 2
Experiment Standard STD + 5% Emulsion Skin STD + 10% Emulsion Skin
1 Film Thickness (µ) 50 - 60 50 - 60 50 - 60
2 Gloss @ 60° 17 - 20 16- 18 15 - 17
3 Finish Fine Texture Fine Texture Fine Texture
4 Impact (Direct) 160 Kg.cm 160 Kg.cm 160 Kg.cm
5 Impact (Reverse) 160 Kg.cm 160 Kg.cm 160 Kg.cm
6 Bending (5 mm) Pass Pass Pass
7 Cross Cut Adhesion Pass Pass Pass
8 PSD – D 50
(Finish Powder) 38 (µ) 45 (µ) 52 (µ)

9 Tg 54.98 °C 55.98 °C 58.30 °C
10 Remarks (If any specific) Improve film toughness;
Good grind ability
Improve film toughness
Limited grind ability at higher dosage

The workability of experimental designs under Table 2 above at the time extrusion was also found to be suitable. Initial performance in terms of appearance and mechanical performance were found comparable with standard. The slight shift in PSD towards coarser side observed with increase dosage of emulsion skin which is also acceptable.Figure 4 also shows the picture of tested powder coating panels.
Significantly, based on above performance data, the powder coating plant in Sarigam had taken 100 Kg batch of hybrid Black Powder coating at shop floor, where the processability and performance was found to conform to the laboratory results, thus proving easy and facile scalability.

Application as texturizing agent in low cost texture emulsion paint
The prototype designs of low-cost texture paint (in line with Apextex) prepared based on above filler (prepared from waste emulsion skin). Here the filler (16#/18#) was used as texturizing material in tune of 4% in the formulation. The performance data was found to be encouraging with the potential of new product in this segment as illustrated under Figure 5.
The performance of this texture paint was found comparable with commercial Apextext Texture Paint and based on the results a consumption of about 0.30 MT /Years of emulsion skin based filler.
Application as filler in duracast texture
The prototype designs of Duracast CrossTex prepared based on above filler. Here the filler (18#/30#) when used in the levels of about and upto 5% in the formulation is able to replace conventional inorganic fillers like silica, dolomite calcium carbonate etc. The laboratory performance was found comparable with standard Duracast CrossTex.
Application as colour texturizing agent for specialty textures (stone finishes etc.)
The process flow chart in Figure 6 depicts the description of the process and the process flow to prepare the colored texturizing process. The process standardization for preparing colour texturizing material is done and then experimental designs were prepared and explored the application of this colour material as texturizing agent.
Solid waste based texturizing filler could be prepared wherein said dry ground pulverized emulsion skin powder (DGPES) suitable as colour texturing fillers/agent comprises
90-96 wt.% dry ground pulverized emulsion skin powder (DGPES) of <18 mesh; higher doses had a negative impact on extrusion and grinding friability of the solid material whereas lower dosage helps in extrusion but negatively impact on cost of final fillers;
1-4 wt.% colour filler: Red Oxide 105M, Yellow Oxide 3920 from LANXESS. Sudafast Blue 2684 from Sudarshan-Hostaperm Green GNX fromClariant, Carbon Black Pearl 120 from cabot, Titanium dioxide R 902 from Dupont, etc.; Lower or higher doses will change the desired shade of the final fillers;
0.1-0.3% flow leveling additive: RESIFLOW P-67 from Estron, P – 88 (Polyacrylic flow leveling additives on silica carrier, active content 60-70%), If higher doses of additives were incorporated it flattens the final film and lower doses are associated with surface defects (pin holes and cratering) on paint film;
5-8% Resin:Resin with glass transition temperature >50 degree centigrade (so that no lump formation at room temperature takes place) Polyester resin based on MP Diol and PTA or EG,TMP and PTA; Ketonic Resin SRK 100 procured from local market in Indiacan generally used for the experiments. Lower doses has a negative impact on extrusion & grinding of the solid materials while higher doses enables ease of extrusion & grinding but cost of final fillers increases.
The process of making the colored powder/ colored texturizing agent (to be used as colored filler) is adapted for extruding through twin screw extruder followed by grinding and sieving to reach to desired particle sized colour fillers.
The process flow of converting the emulsion skin Filler into Colour Texturing Agent:
STEP 1 involves extrusion process by taking 90-96 % emulsion skin filler (<18#) +1-4% Colour Filler + 0.3% Flow leveling additive + 5-8% Polyester. Then extruded through the Twin Screw Extruder.
STEP 2 involves Grinding & Sieving wherein the extruded material was grinded followed by sieving to get desired particle size colour filler, as clearly shown in Figure 6.
Figure 7 shows photos of colour texturizing agent prepared using emulsion skin.
Figure8 shows textured paint containing 0.5% coloured Emulsion skin 18/30# in formulation.
The process is provided under Figure 1 above for grinding of emulsion skin (60 MT cap/year) and Figure 9 shows the machinery involved.
Table 3 :- Emulsion skin grinding efficiency study using various grinding media (Dry CO2, Liq. N2, With Ice)
Comparative data of Emulsion Polymer Skin Grinding using various grinding media
Grinding Media Emulsion Skin : Grinding Media < 20# >20# &<80# >80# &<120# >120# TOTAL Remarks
With Dry Ice (CO2) 90 : 10 37.78 56.94 3.50 1.78 100 - Each Mixture was ground for 2 mins in domestic mixture machine
- 5 Mins Sieving on Shaker
80 : 20 28.05 65.38 4.59 1.98 100
70 : 30 22.07 70.26 5.56 2.11 100
With Liq. Nitrogen (N2) 90 : 10 51.09 46.43 2.13 0.34 100 - Each Mixture was ground for 2 mins in domestic mixture machine
- 5 Mins Sieving on Shaker
80 : 20 24.11 68.18 6.67 1.05 100
70 : 30 21.14 70.64 6.89 1.33 100.00
With Ice (H2O) 80 : 20 69.46 30.11 0.34 0.10 100 - Each Mixture Grind for 2 mins in domestic mixture machine.
-Material gets re-agglomerated during drying
- 5 Mins Sieving on Shaker
70 : 30 70.96 28.40 0.48 0.16 100
60 : 40 70.28 29.13 0.43 0.17 100

Select grinding conditions: -
The grinding efficiency with respect to fineness and quantity of grind material (less than 80 preferably above 20 mesh) of polymer skin with Dry Ice and Liquid Nitrogen is seen to be better and comparable than normal Ice.
Texturing formulations usually prefer a particle size range between 20 to 80 # size to be used for water borne texture paints. As seen in the sieve analysis mentioned in above table dry ice and liquid nitrogen are able to provide a large quantity of finer material in comparison with the grinding with ice (water).
Another aspect is the involvement of ground material in powder coating. Powder coating requires <120# for better homogeneity of the composition to be extruded for uniform coating. This is achieved only in the case of using of dry ice or liquid nitrogen. It was surprisingly found that low temperature (<-4 to 5 deg C) grinding achievable by dry ice and liquid nitrogen during the grinding process, makes the polymer waste brittle which thus gets grinded efficiently, in involving reduced temperature below the glass transition temperature of the waste polymer. In case of only ice the temperature is higher than 5 degree centigrade where still certain polymers are soft and not able to get grinded efficiently.
The present invention is based on the utilization of the polymer emulsion skin generated during manufacture of the emulsion polymer, whereas solvent borne solid waste was not found useful for the study. Compositionally solvent borne solid wastes includes polymers/ polymer composition as paints which are significantly different with respect to their molecular weights, glass transition temperatures, the polymer back bone including polyester to epoxy to alkyd to amino to polyurenthane, hence the treatment process of the present invention does not suit such solvent borne solid wastes but only emulsion skin waste that is mainly acrylic or styrene-acrylic.

Additional details for the polymer waste classified as emulsion skin
The major sources of generation of emulsion skin is the Asian Paints Ltd. plant itself.
? The solid polymer deposits on the internal wall of reactor and on the stirrer
? The residues collected in the filtration device as grit particles; usually the polymer gel
? The separated dry skin formation in the storage tank of the emulsion.
The emulsion skin collected from all the above sources is preserved in barrels for one month and disposed after one month if not utilized. The total amount of emulsion skin generated at APL plants (all six plants) amounts to Approximately 134 MT/year.

It is thus possible by way of the present invention to provide for solid waste emulsion skin into reusable emulsion skin of various size/ shape and morphologies that could be gainfully used in select products including low-cost powder coating and water based decorative paint formulations, as colour texturing fillers/agent.
Therefore the solid waste based texturizing fillerof the present invention finds end use and application as fillers in Powder coating & Duracast range Texture Paint, texturizing agent in Apex texture paint and colour texturizing agent in texture paint such as “Graniza Texture”. These are broadly known as water based architectural texture paints.
Thus advantageously waste polymer in the form of solid waste generated as sticking on the reactor wall or stirrers etc or the filter residues which are typically contributing as hazardous solid waste and sent outside the plant as waste, could be made processable and converted to re-usable form by way of providing for extender/filler of varied sizes for use in water-based texture paints as well as powder coatings.
Thus it serves two purposes:
1. The re-utilization of the solid waste in products which are manufactured in the same plant hence reducing the total solid waste generation.
2. The extenders/ fillers produced from this solid waste can serve as texturizing agent/ low density filler comprising a substantially cross-linked polymer has a minimum of 60% gel content, Tg of 10 to 50 degree centigrade and the final size of the filler in the range of 10 microns to 5 mm to be used in waterborne texture paints or powder coating to replace the conventional fillers and pigments. Thus providing the cost benefit and some performance enhancement.
The solution with regard to the solid waste management differs from the conventional knowledge based on the following:
i. The key focus is to avoid generation of the solid waste as opposed to reutilization of the liquid filtrate as per the prior knowledge;
ii. The source of the solid waste is the sticking of the reactor walls, filter residues which are typically the polymer grit formed during the manufacture of polymer, emulsion skin formed during storage of the emulsion. All these are usually thrown out as solid hazardous waste wherein the present invention deals with the conversion of this solid waste into usable filler/ extender by set of processes as hereinbefore described.
The resulting fillers/ extenders of the present invention thus proves to be good replacement of the conventional inorganic fillers thus also reducing the overall density of the paint and hence the cost as well as provides some improvement in functional properties of the texture paint/ powder coatings thereby finding end use and application as filler /extender/ texturizing agent in water based exterior/interior texture paints formulations, and as a filler/ extender/ texturizing agent in powder coating formulations.