Description:FIELD OF THE INVENTION:
The present invention provides for rosin reinforced emulsion polymer and coating compositions thereof comprising emulsion polymer particles of silane crosslinked reaction product of rosin fatty acid additive, acrylate/vinyl functional monomers, polymerizable surfactant, hydrophobic monomers including Iso-bornyl methacrylate (IBOMA), tertiary butyl methacrylate (TBMA), cyclohexyl methacrylate, with enabled waterproof characteristics based on said hydrophobic monomers and rosin fatty acid additive uniformly distributed on the polymer particle.
BACKGROUND ART:
Styrene-acrylic emulsions are a versatile class of polymers, which find applications in architectural coating, protective coating, wood coating, paper coating, adhesive, sealant, etc. One of the main requirements of polymeric coating material is their capability to confer water resistance to substrates. Water sensitivity is a major concern for emulsion polymers as most of their raw materials tend to water-soluble and/or have tendency to move towards the surface of coating. Use of silanes, cross linkers are the known routes to achieve water repellency or water resistance in waterborne coatings.
JP1994157758 mentions blending of silicone resin along with emulsion polymer, however due to solubility problems, it separates out. Use of high amount of trialkoxy silane provides unstable dispersion. This patent describes about use of polyorganosilane, having a graft over agent alkyl methacrylates, which then has used for making a composite polymer.
JP2013121993 informs making emulsion polymer using two-stage addition of different Tgs and ratios using styrene as monomer, which can used as a sealer for inorganic building material.
CN109401503 discloses the preparation of water proofing material composition having RDP powder of VAE, and inorganic compounds like quartz etc.
CN110591009 mentions graphene oxide as material used in shell of polymer. Emulsion for reinforcement to provide good polymer emulsion with stability, strong adhesive force, tensile strength, wear resistance and excellent water resistance.
CA2661823 informs the preparation of emulsion polymer using three stages and Tg decreases from core towards surface of polymer particle. Such polymer demands lower volatile organic compound, having good water softening resistance.
CN 111909313 teaches in-situ enhanced styrene-butadiene latex prepared from the following raw materials: 50-120 parts by wt. of water; 0.3-4.8 parts by wt. of fatty acid; 0.1-0.9 parts by wt. of potassium hydroxide; 1-10 parts by wt. of disproportionated potassium rosin acid soap; 0.05-0.4 parts of stabilizer; 0.1-0.5 parts by wt. of electrolyte; 3-10 parts by wt. of reinforcing agent; 30-50 parts by wt. of styrene; 50-70 parts by wt. of butadiene; 0.01-0.1 parts by wt. of mol. wt. regulator; 0.01-0.5 parts by wt. of initiator; 0.05-0.1 parts of terminating agent; 0.2-1 parts by wt. of anti-aging agent; wherein the reinforcing agent is a Sasobit asphalt modifier. Does not involve any rosin fatty acid derivative based material incorporated in the latex that too teaches a different styrene butadiene based latex.
CN 108219676B teaches modified rosin prepared by performing addition reaction on rosin and dienophile at a mass ratio of 1:(0.1-0.45), esterifying with polyol to obtain modified rosin resin and dissolving in acrylate monomer to obtain modified rosin resin, the dienophile is a reactant capable of providing unsaturated bonds in Diels-Alder reaction and is selected from fumaric acid, maleic anhydride, acrylic acid and acrylate. It is thus taught by this prior art that modified rosin resin as an adduct together with a polymerization inhibitor and though involves hydrophobic monomers including Iso- bornyl methacrylate, tertiary butyl methacrylate, does not suggest any emulsion polymerized polymer comprising a reaction product of modified rosin fatty acid derivative together with acrylate/vinyl functional monomers, polymerizable surfactant to be further crosslinked with silane functional cross linker.
CN 107286740 teaches UV-LED offset printing ink that is epoxy acrylate based and made up of the following components by wt. parts: 20-35 parts of modified epoxy acrylate, 10-20 parts of rosin modified polyester acrylate, 5-15 parts of acrylic acid modified alkyd resin, 5-10 parts of vinyl-terminated rosin derivative, 1-10 part of polyfunctional crosslinking monomer, 1-10 part of monofunctional group diluting monomer, 5-10 parts of photoinitiator, 15-40 parts of pigment, 3-10 parts of filler, 1-3 part of wax powder, and 0.1-5 part of auxiliary agent. The ink is cured by UV-LED, has no solvent volatilization, meets VOC national discharging standards, and is environmentally friendly and energy- saving. In addition, the ink has advantages of fast curing speed, high production efficiency, excellent flexibility and adhesive force simultaneously, good wear resistance, heat resistance and solution resistance, is suitable for high-speed operation, and is especially suitable for the printing of paper such as composite gold and silver paperboard, white cardboard, copperplate paper, metal foil paper, synthetic paper, composite laser paper, transfer paper and packaging products thereof.
CN 102603957 teaches that the aqueous adhesive composition comprises acrylate monomer 40-50, vinyl acetate 5-15, emulsifier 0.5-2, initiator 0.2-1, tackifying resin 0.5-1.5 and aqueous medium 40-50%. The acrylate monomer is selected from Me acrylate, Et acrylate, Bu acrylate and isooctyl acrylate. The emulsifier is selected from allyl sulfonate, acrylamido sulfonate, maleic acid derivative and allylsuccinic acid alkyl ester sulfonate. The tackifying resin is selected from rosin and its derivative, terpene resin and its modified derivative, and petroleum resin. The aqueous adhesive composition may further contain acrylic functional monomer selected from acrylic acid and methacrylic acid, and crosslinking monomer selected from glycidyl methacrylate, acrylamide, hydroxymethyl acrylamide, dimethylacrylamide, isobornyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, N-hydroxymethyl acrylamide and ethylene glycol dimethacrylate. The aqueous pressure-sensitive adhesive is prepared by dissolving tackifying resin in acrylate monomer, mixing with aqueous medium, vinyl acetate and emulsifier to obtain pre-emulsion, mixing aqueous medium and initiator to obtain initiator aqueous solution, heating to 70-90°C, dropping pre-emulsion in initiator aqueous solution, reacting for 3-6 h, adjusting with ammonia water to pH 7-8, cooling and discharging. The aqueous pressure-sensitive adhesive has good adhesion to substrate (esp. PU foam) and bending-resisting property, and excellent water resistance. This prior art is not directed tp any emulsion polymerized polymer for coating compsitions comprising a reaction product of modified rosin fatty acid derivative together with acrylate/vinyl functional monomers, polymerizable surfactant further crosslinked with silane functional cross linker.
JP 2018009153 teaches that resin comprises a rosin ester which is a reaction product of (A) a rosin, (B) a, ß-unsaturated carboxylic acid-modified rosin, and (C) an alcohol and satisfies that (i) the content of the backbone derived from dehydroabietic acid is = 20 wt.% and (ii) the ratio of the peak area (S2) of the component having a wt. av. mol. wt. of = 1200 to the total peak area (S1) measured by gel permeation chromatography is 20-50%. Thus, 100 parts of Rondis R (disproportionated rosin), 8.1 parts of glycerin, and 5.7 parts of diethylene glycol were added, heated, and esterified; next, 100 parts of CG-WW (rosin) and 8.4 parts of maleic acid were mixed therein and reacted; further, 1.8 parts of glycerin and 17.9 parts of pentaerythritol were added therein, reacted, and esterified to obtain a rosin ester; then 100 parts of the obtained rosin ester, 70 parts of toluene, 3 parts of Neo High Tenol F-13 (anionic emulsifier), and 140 parts of water were admixed and emulsified to obtain the title tackifier resin emulsion; and thereafter, 100 parts of water, 3 parts of methacrylic acid, 0.1 part of sodium sulfite, 5 parts of Emulgen 430 (polyoxyethylene oleyl ether) as a nonionic surfactant, 97 parts of chloroprene, and 0.3 part of n-octylmercaptan were admixed and polymerized using potassium persulfate (initiator) to obtain a polychloroprene latex; and finally, 100 parts of the obtained latex, 50 parts of the obtained emulsion, 1 part of AZ-SW (zinc oxide emulsion) as a metal oxide, and 1 part of Adekanol UH-526 (water soluble polyurethane thickener) were added to obtain an aqueous adhesive composition. This prior art is not directed tp any emulsion polymerized polymer comprising a reaction product of modified rosin fatty acid derivative together with acrylate/vinyl functional monomers, polymerizable surfactant further crosslinked with silane functional cross linker.
WO 9618703 A1 teaches sheets, having good recyclability of the sheet substrates, comprise paper-based substrates and pressure-sensitive adhesives from copolymers comprising (a) (carboxylic acid-modified) rosin esters 5-40, (b) (poly)ethylene glycol (meth)acrylates 5-40, (c) C4-18 alkyl (meth)acrylates 30-60%, and optionally, (d) ethylenically unsaturated carboxylic acids =20% and (e) other monomers =20%. Thus, emulsion polymerization of 60 parts a reaction of methacrylic acid, epichlorohydrin, abietic acid and glutaric acid anhydride with 60 parts methoxydiethylene glycol methacrylate, 100 parts Bu acrylate, 100 parts 2- ethylhexyl acrylate, 40 parts acrylic acid and 40 parts dimethylaminoethyl methacrylate in an aqueous solution containing an anionic surfactant and additives gave an adhesive which was coated on a siloxane-treated laminate of polyethylene and paper to give an adhesive tape which showed good adhesion and good recyclability of the substrate.
US20040044124A1 relates to novel rosin-fatty acid vinylic polymer compositions and the process for preparing them via free-radical addition polymerization reaction. In particular, the prior invention relates to novel rosin-fatty acid vinylic polymer compositions that exhibit properties which make them useful as components of paper sizes, as components of coatings, and as support resins for producing polymer latices that can be employed in formulating water-based coatings and inks. More particularly, these rosin-fatty acid vinylic polymer compositions are mixtures that are produced by the addition polymerization reaction of vinylic monomers in the presence of saturated fatty acids, hydrogenated dimer acids, hydrogenated rosins, or mixtures thereof.
However, no prior art has disclosed any reinforcement/impregnation of water-resistant molecule in polymer particle and coating compositions thereof to enhance the hydrophobicity and hence improved water resistance upon drying thereby functioning as waterproof emulsion polymer for damp substrates.
OBJECTS OF THE INVENTION:
Thus, the primary object of the present invention is to provide for emulsion polymers and coating compositions thereof having reinforced/impregnated water-resistant molecule in-build and on polymer particle surface of said emulsion polymer.
Another object of the present invention is to provide for said emulsion polymers and coating compositions thereof and a stage wise process for synthesis of said emulsion polymers by including rosin fatty acid additive together with acrylic/vinyl functional monomers, polymerizable surfactant that is further crosslinked with silicone crosslinker to enable reinforced waterproof emulsion polymer.
Still another objective of the present invention is to provide coating composition based on said emulsion polymers with improved water resistance on dry and damp substrates.
SUMMARY OF THE INVENTION:
Thus according to the basic aspect of the present invention there is provided a rosin reinforced emulsion polymer and coating compositions thereof comprising emulsion polymer particles of silane crosslinked reaction product of rosin fatty acid additive, acrylate/vinyl functional monomers, polymerizable surfactant, hydrophobic monomers including Iso-bornyl methacrylate (IBOMA), tertiary butyl methacrylate (TBMA).

Preferably the rosin reinforced emulsion polymer and coating compositions thereof is provided wherein said reaction product includes following % ingredients
0.2 to 1.6% rosin fatty acid additive on polymer solid basis;
35 to 50 parts of acrylate/vinyl functional monomers;
2 to 5 % polymerizable surfactant on polymer solid basis;
9.0 to 15.0 % hydrophobic monomers including Iso-bornyl methacrylate, tertiary butyl methacrylate, cyclo hexyl methacrylate on polymer solid basis;
crosslinked with 1.2 to 2.0 % functional silane on polymer solid basis.
According to another preferred aspect of the present invention there is provided said rosin reinforced emulsion polymer and coating compositions thereof as wherein said emulsion polymer particles are rosin fatty acid additive reinforced/impregnated emulsion polymer particles having improved in-build and surface hydrophobicity due to said rosin fatty acid additive and said hydrophobic monomers enabling waterproof characteristics.
Preferably said rosin reinforced emulsion polymer and coating compositions thereof is provided wherein said silane cross linker is in the range of 1.2 to 2% on emulsion polymer solids that is a functional silane crosslinker comprising vinyl trimethoxysilane, vinyltriethoxysilane, methacryloxyproprytrimethoxysilane, methacryloxypropyltriethoxysilane; and wherein said polymerizable surfactant includes alkyl ether sulphate based anionic surfactant having radical polymerizable allylic group with 20 EO, 12 EO based polyoxyethylene ether phosphate with an allylic moiety.
More preferably the rosin reinforced emulsion polymer and coating compositions thereof is provided wherein said rosin fatty acid additive reinforced/impregnated emulsion polymer enabling improved water resistant characteristics of said emulsion polymer includes said rosin fatty acid additive that is fatty acid modified rosin including fatty acids of abietic acid, linoleic acid, oleic acid, and which reinforcement of water resistant attributes of the emulsion polymer is favoured by incorporation of said rosin additive in pre-emulsion separated from hydrophobic monomers.
According to yet another preferred aspect of the present invention there is provided said rosin reinforced emulsion polymer and coating compositions thereof wherein said hydrophobic monomers as water resistant molecules incorporated in emulsion polymer particle surface impregnated with rosin fatty acid derivative includes Iso-bornyl methacrylate (IBOMA), tertiary butyl methacrylate (TBMA), cyclo hexyl methacrylate, and,
wherein said acrylate/vinyl functional monomers includes Butyl Acrylate, Styrene, n-Butyl Methacrylate, Methacrylic Acid.
Preferably said rosin reinforced emulsion polymer and coating compositions thereof is provided wherein the coating compositions comprising 0.4% (based on polymer solids) rosin fatty acid additive reinforced TBMA based emulsion polymer gives decreased coating performance when combined with anti-efflorescing agents in respect of surface hydrophobicity and water resistance vs. same 0.4% (based on polymer solids) rosin fatty acid additive reinforced but IBOMA based emulsion polymer when combined with anti-efflorescing agents giving superior performance; and
wherein 0.2% (based on polymer solids) rosin fatty acid additive reinforced IBOMA based emulsion polymer when combined with anti-efflorescing agents gives inferior coating performance in respect of surface hydrophobicity and water resistance vs. 0.4% (based on polymer solids) rosin fatty acid additive reinforced TBMA based emulsion polymer when combined with anti-efflorescing agents giving superior performance.
According to yet another preferred aspect of the present invention there is provided said rosin reinforced emulsion polymer and coating compositions thereof wherein said coating composition comprise
mill base slurry including non-reactive hydrophobic additives, dispersing agent, pigment, biocide, coalescing agent, 0.2% anti-efflorescing agent; and
rosin fatty acid additive reinforced emulsion polymer including 0.148 % rosin fatty acid additive reinforced IBOMA based emulsion polymer, and/ or 0.148 % rosin fatty acid additive reinforced TBMA based emulsion polymer.
Preferably said rosin reinforced emulsion polymer and coating compositions thereof is provided wherein said coating composition comprise
mill base slurry involving 0-0.6% anti-efflorescing agent; and
0.148 % rosin fatty acid additive reinforced TBMA based emulsion polymer said emulsion polymer achieved of at least 0.2% rosin fatty acid additive enabling improved coating performance in respect of surface hydrophobicity and water resistance.
According to another aspect of the present invention there is provided a process for the synthesis of rosin reinforced emulsion polymer and coating compositions thereof comprising the steps of providing followings feeds for stage wise addition to reactor charge
(i) providing anionic polymerizable surfactant including phosphate based and/or sulphate-based surfactant and de-mineralized water heated to 80-90°C as reactor charge;
(ii) providing pre-emulsion seed including buffer and initiator in de-mineralized water in amounts of 3-10% of pre-emulsion;
(iii) providing ingredients for pre-emulsion including phosphate based and/or sulphate based polymerizable anionic surfactant, rosin fatty acid additive, acrylate/vinyl functional monomers, acid monomer, potassium per sulfate, chain transfer agent in de-mineralized water, for feeding to said reactor charge in stages;
(iv) providing hydrophobic monomers including Iso-bornyl methacrylate, tertiary butyl methacrylate, cyclo hexyl methacrylate in demineralized water with (a) silane crosslinker, (b) with wet adhesion promoters as separate feeds for stage wise addition to reactor charge while concurrently adding said pre-emulsion feed into reactor charge, polymerizing and digesting the same to obtain therefrom rosin reinforced emulsion polymer and coating compositions thereof.
Preferably in said process for the synthesis of rosin reinforced emulsion polymer and coating compositions thereof as claimed in claim 9 wherein said stage wise addition of feed includes
addition of said pre-emulsion seed of step (ii) as initial feed to said reactor charge of (i) followed by,
feeding 25% of said pre-emulsion of step (iii) into said reactor charge continuously for a period of 180-240 mins at uniform rate and thereafter adding hydrophobic monomer feed of (iv) into said reactor;
post 50% completion of pre-emulsion addition of step (iii) into reactor charge further adding hydrophobic monomer feed of step (iv) (a) involving silane functional crosslinker;
post 75% completion of pre-emulsion addition of step (iii) into reactor charge further adding hydrophobic monomer feed of step (iv)(c) involving adhesion promoter and continuing polymerization followed by digestion and addition of additives including biocides, defoamer to achieve rosin reinforced emulsion polymer and coating compositions thereof.
DETAILED DESCRIPTION OF THE INVENTION:
As discussed hereinbefore, the present invention provides for approaches for improving water resistance of emulsion polymer thereby achieving modified rosin reinforced waterproof emulsion polymer comprising a reaction product of rosin fatty acid additive, acrylate/vinyl functional monomers, polymerizable surfactant, hydrophobic monomers including Iso-bornyl methacrylate, tertiary butyl methacrylate. Preferably said emulsion polymer is further crosslinked with silane functional cross linker.
It is thus the surprising finding of the present invention that when the select ingredients of rosin fatty acid additive, acrylate/vinyl functional monomers, hydrophobic monomers including Iso-bornyl methacrylate, tertiary butyl methacrylate in select levels are reacted/ polymerized in the presence of sulphate/phosphate based polymerizable anionic surfactant as initial reactor charge, and processed based on controlled addition of hydrophobic monomers after various stages of addition of pre-emulsion containing rosin fatty acid additive into the reactor charge, and is further crosslinked with silane,
the same leads to an emulsion polymer with hydrophobic monomers including Iso-bornyl methacrylate, tertiary butyl methacrylate tending to populate on the surface of the polymer particles and enhance hydrophobicity of said emulsion polymer particle surface to thereby improve water resistance of such emulsion polymers due to such controlled addition advantageously favoring both in-build and surface hydrophobicity due to said rosin fatty acid additive and said hydrophobic monomers.
Such water resistance could not be attained when such select ingredients in select levels were not involved and when such stage wise processing was not performed giving the desired emulsion polymer allowing incorporation of such water resistant/ hydrophobic molecules in emulsion polymer particles favoring in-build and surface hydrophobicity of such polymer particles.
Additionally, rosin fatty acid additive as reinforcing material for impregnation and its incorporation during emulsion polymerization is favored by involving it as a pre-emulsion ingredient for adding into the reactor charge separated from said hydrophobic monomers including Iso-bornyl methacrylate, tertiary butyl methacrylate, thereby leading to uniform homogenous distribution of said rosin across the emulsion polymer particle allowing further incorporation of hydrophobic monomers in said emulsion polymer particle surface giving improved water resistance.
Also importantly, emulsion polymer comprising polymerizable surfactant, instead of conventional surfactant, favors covalent linking to the emulsion polymer backbone during polymer synthesis free of any tendency to migrate towards the surface of the polymer particles to negatively affect its water resistance/ surface hydrophobicity.
The enabled waterproof characteristics of the emulsion polymer based on said hydrophobic monomers and rosin fatty acid additive uniformly dispersed in emulsion polymer particle is noteworthy.
The particle size of the rosin fatty acid additive is around 250 micrometers. When it was incorporated during emulsion polymer synthesis, could be uniformly dispersed as the final particle size of processed emulsions lies between 100-200 nanometers. Particle size of processed emulsions have been measured on Malvern Zetasizer Nano ZS90 instrument. 1% diluted sample solution prepared in de-mineralized water and used to measure particle size.
EXAMPLES:
Rosin fatty acid additive employed in the present invention has the following characteristics that are conventionally available and fatty acid modified rosin having the following specifications.
Composition Rosin fatty acid additive
Appearance Free-flowing powder
Bulk Density 350-550 g/l
Particle Size < 250 microns
Residual moisture < 3.0%
pH (10% solution) 8-10
Storage Stability 6 months

In the present invention, rosin fatty acid additive is a solid material containing conventional fatty acid modified rosin including fatty acids of abietic acid, linoleic acid, oleic acid.
Reactive (non-migratory) surfactants: include sulfate based non-migratory anionic surfactant that is alkyl ether sulphate having radical polymerizable group with 20 EO.
The phosphate based non-migratory anionic surfactant employed in the present invention includes ˜12 EO based polyoxyethylene ether phosphate with an allylic moiety.

Procedure for emulsion synthesis:
Anionic polymerizable surfactant and de-mineralized water charged into a kettle fitted with a three-neck lid and the assembly heated to 80-90°C.
In a separate pre-emulsion flask filled with anionic polymerizable surfactant (phosphate based and/or sulphate based) dissolved in de-mineralized water, rosin fatty acid additive molecule has added and mix well till its complete dissolution in water. Acrylate/vinyl functional monomers have weighed and stirred to form a milky white pre-emulsion (as per Table 1 below). Unsaturated carboxylic acid and initiator added into pre-emulsion, just prior to addition of seed into the reactor kettle. Seed added into reactor followed by addition of buffer solution and initiator solution into the reactor. Once, the exotherm observed indicating the start of reaction, to this reaction mixture, the pre-emulsion added for a period of 180-270 minutes, by maintaining the temperature at 80°±10°C. After 25% completion of pre-emulsion, hydrophobic monomer added into the pre-emulsion and addition has continued. After 50% completion of pre-emulsion, silane functional crosslinker, and/or hydrophobic monomer, added into the pre-emulsion and addition has continued. 75% completion of pre-emulsion, hydrophobic monomer, adhesion promoter has added into the pre-emulsion and addition has continued. After the completion of pre-emulsion addition, de-mineralized water used to flush the peristaltic pump used to pump the pre-emulsion mixture into the reactor. Upon completion of addition, chaser catalysts dissolved in de-mineralized water and added in reactor. The digestion process has completed in one hour. Below 50°C temperature, in reactor vessel, in-can preservative added followed by the pH made alkaline by the addition of neutralizer like multifunctional amino alcohol, ammonia.
All the hydrophobic monomers and all the variants mentioned works equally effectively to provide for the desired water-resistant attributes in accordance with the present invention.

Table 1:
Sr. No. Chemical Example 1
(EM-NJP-016) Example 2
(EM-NJP-008) Example 3
(EM-NJP-011) Example 4
(EM-NJP-017) Example 5 (EM-NJP-083) Example 6 (EM-NJP-084)
1 Reactor charge-I (70-90 deg C)
Sulphate based Polymerizable anionic surfactant 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24
2 5% pre-emulsion seed
Buffer 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24
De-mineralized water 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60
Initiator 0.08-0.13 0.08-0.13 0.08-0.13 0.08-0.13 0.08-0.13 0.08-0.13
De-mineralized water 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60
3 Pre-emulsion
De-mineralized water 16.0-24.0 16.0-24.0 16.0-24.0 16.0-24.0 16.0-24.0 16.0-24.0
Sulphate based Polymerizable anionic surfactant 1.20-1.90 1.20-1.90 1.20-1.90 1.20-1.90 1.20-1.90 1.20-1.90
Rosin fatty acid additive 0.00 0.20 0.10 0.20 0.8 0.20
Butyl Acrylate 12.0-19.0 12.0-19.0 12.0-19.0 12.0-19.0 12.0-19.0 12.0-19.0
Styrene 19.0-29.0 19.0-29.0 19.0-29.0 19.0-29.0 19.0-29.0 19.0-29.0
n-Butyl Methacrylate 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20
Isobornyl Methacrylate 4.80-7.20
Methacrylic Acid 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20
Silane crosslinker 0.60-1.00
Wet Adhesion Promoter 0.04-0.06
Chain transfer agent 0.02-0.04 0.02-0.04 0.02-0.04 0.02-0.04 0.02-0.04 0.02-0.04
Coalescing solvent 0.60-1.00 0.60-1.00 0.60-1.00 0.60-1.00 0.60-1.00 0.60-1.00
Initiator 0.12-0.18 0.12-0.18 0.12-0.18 0.12-0.18 0.12-0.18 0.12-0.18
4 Pre-emulsion Addition stage (feed over 180-270 minutes at uniform rate)
5 After 25% pre-emulsion addition
Iso bornyl methacrylate 1.60-2.40 1.60-2.40 1.60-2.40 - 1.60-2.40
Tertiary butyl methacrylate - - - 1.60-2.40 - -
Cyclo hexyl methacrylate - - - - - -
De-mineralized water - - - - - -
6 After 50% pre-emulsion addition
Iso bornyl methacrylate 1.60-2.40 1.60-2.40 1.60-2.40 0.00 1.60-2.40
Tertiary butyl methacrylate - - - 1.60-2.40 -
Silane crosslinker 0.60-1.00 0.60-1.00 0.60-1.00 0.60-1.00 0.60-1.00
De-mineralized water 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24
7 After 75% pre-emulsion addition
Iso bornyl methacrylate 1.60-2.40 1.60-2.40 1.60-2.40 - 1.60-2.40
Tertiary butyl methacrylate - - - 1.60-2.40 -
Wet Adhesion promoter 0.04-0.06 0.04-0.06 0.04-0.06 0.04-0.06 0.04-0.06
De-mineralized water 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24
6 De-mineralized water for flushing 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20 0.80-1.20
7 Digestion catalysts
TBHP 0.08-0.12 0.08-0.12 0.08-0.12 0.08-0.12 0.08-0.12 0.08-0.12
De-mineralized water 0.60-1.00 0.60-1.00 0.60-1.00 0.60-1.00 0.60-1.00 0.60-1.00
SFS 0.08-0.12 0.08-0.12 0.08-0.12 0.08-0.12 0.08-0.12 0.08-0.12
De-mineralized water 1.20-1.80 1.20-1.80 1.20-1.80 1.20-1.80 1.20-1.80 1.20-1.80
8 Additives
Biocide 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24 0.16-0.24
Defoamer 0.01-0.03 0.01-0.03 0.01-0.03 0.01-0.03 0.01-0.03 0.01-0.03
Multifunctional Amino Alcohol/ Ammonia 0.50-0.90 0.50-0.90 0.50-0.90 0.50-0.90 0.50-0.90 0.50-0.90
De-mineralized water 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60 2.40-3.60
Preparation of coating composition:
Processed emulsions used to prepare coating as a binder. General coating composition preparation has conducted by following steps like addition of non-reactive hydrophobic additives, addition of dispersing agent, pigment loading and dispersion followed by biocide & coalescing agent addition. This mill base slurry was used for final paint preparation by mixing emulsion in it. These coating compositions used to check water resistance and solvent resistance performance on cementitious substrate.
To check negative capillary water resistance, two test methods were followed. In first test method, highly porous cementitious panels with approximate 70% moisture, have applied with the coating composition followed by topcoat application (double coat) & sealing of edges to avoid water penetration from sides of the panels. 6-8 hours curing time has given between each coat application. After overnight curing, panel exposure in saturated salt solution initiated to check negative water resistance via capillary action. This exposure study conducted until failure of panels with either visible dampness/salt deposition or increased moisture content.
In second test method instead of fresh panels, they were dipped in salt solution for 24 hours followed by single water wash. After attending 70% moisture level, same procedure followed like first test method. This aggravated test should give results in short duration. Negative water pressure test conducted for all samples applied on cement block as per ASTM D 7088 test method.
RESULTS & DISCUSSION:
To study the impact of rosin fatty acid additive reinforced emulsion polymer, following sample preparation and their characterization w has completed.
1. CC-NJP-016: Coating sample prepared with conventional polymer along with externally added rosin additive molecule (RAM) to equal concentration. Total qty of RAM = 0.2% in mill base
2. CC-NJP-017-A: Coating sample prepared with rosin additive reinforced, TBMA based emulsion polymer with externally added RAM. Total qty of RAM = 0.2% (0.148% through polymer + 0.052% through mill base)
3. CC-NJP-017-B: Coating sample prepared with rosin additive reinforced, TBMA based emulsion polymer with externally added RAM. Total qty of RAM = 0.348% (0.148% through polymer + 0.2% through mill base)
5. CC-NJP-008: Coating sample prepared with rosin additive reinforced, IBOMA based emulsion polymer with externally added RAM. Total qty of RAM = 0.348% (0.148% through polymer + 0.2% through mill base)
6. CC-NJP-011: Coating sample prepared with rosin additive reinforced, IBOMA based emulsion polymer with externally added RAM. Total qty of RAM = 0.348% (0.074% through polymer + 0.274% through mill base)
7. CC-NJP-083: Coating sample prepared without rosin additive reinforced, IBOMA based emulsion polymer with externally added RAM. Total qty of RAM = 0.592% (0.592% through polymer + 0% through mill base)
8. CC-NJP-084: Coating sample prepared with rosin additive reinforced, IBOMA based emulsion polymer with externally added RAM. IBOMA, wet adhesion promoter and silane crosslinker have added from the initial stage of monomer addition. Total qty of RAM= 0.2% (0.148% through polymer + 0.052% through mill base)
Table 2 shows CC-NJP-016 that was found to be inferior to CC-NJP-017-A. The total concentration of anti-efflorescing agent is 0.2%. When it has added in paint mill base, sample failed in 16 days. Whereas sample with polymer having rosin additive with TBMA has failed in 63 days with lower content of anti-efflorescing agent of 0.052%. Even though overall concentration of anti-efflorescing agent is more in CC-NJP-017-B than that in CC-NJP-017-A, 17-A is performing better than 17-B. It indicates, incorporation of rosin additive in polymer itself improved water resistance attributes due to its uniform distribution in polymer.
Table 2: Effect of Rosin additive molecule (RAM) on coating performance
Sample code Description % Of Rosin additive anti-efflorescing agent Total % Negative Capillary test, as specifically designed test method
Negative pressure test, ASTM D 7088

Polymer Mill base
CC-NJP-016 Conventional polymer + mill base with anti-efflorescing agent 0 0.2 0.2 Failed in 16 days 3.5
CC-NJP-017-A rosin additive reinforced polymer with TBMA + mill base with anti-efflorescing agent 0.148 0.052 0.2 Failed in 63 days 3.5
CC-NJP-017-B rosin additive reinforced polymer with TBMA + mill base with anti-efflorescing agent 0.148 0.2 0.4 Failed in 43 days 3.5

It has been observed that, prototype developed with tertiary butyl methacrylate TBMA (CC-NJP-017-B) failed in 43 days whereas that with IBOMA (CC-NJP-008) passed up to 90 days. It proves that polymer with IBOMA is showing better water resistance and anti-efflorescence better than TBMA.
Table 3 below shows difference in the performance when rosin additive was added during emulsion synthesis as against when it has added in coating composition. When rosin additive was incorporated during emulsion polymer synthesis (CC-NJP-008), it was dispersed very well in polymer particles resulting in homogeneous distribution of rosin molecules throughout the coating. In addition, it remains in polymer system for longer time due to its reinforcement. Whereas, after adding in final formulation (CC-NJP-011), it may dispersed & occupied in voids between pigment and polymer particles and remain in cluster form, resulted in inferior performance as compared to the earlier one. Being water soluble, this rosin additive may show more tendency to come out on surface and leach out from the system sooner than the system in which it has been incorporated through synthesis.
Table 3: Effect of different hydrophobic monomers on water resistance
Sample code Description % Of Rosin additive anti-efflorescing agent Total % Negative Capillary test Negative pressure test, ASTM D 7088

Polymer Mill base
CC-NJP-008 rosin additive reinforced polymer with IBOMA + mill base with anti-efflorescing agent 0.148 0.2 0.348 Failed in 91 days 2
CC-NJP-017-B rosin additive reinforced polymer with TBMA + mill base with anti-efflorescing agent 0.148 0.2 0.348 Failed in 43 days 3.5
CC-NJP-011 rosin additive reinforced polymer with IBOMA + mill base with anti-efflorescing agent 0.074 0.274 0.348 Failed in 21 days Not done

Example 5 of Table 1 represents the coating composition containing emulsion polymer processed with rosin additive molecule (RAM) at 1.6% on polymer solids (45-55% polymer solids generated in yields of 98-99%) during synthesis which contributes 0.592% in final coating composition, indicating the effects are desired when the concentration of RAM has increased within a desired level. Example 6 of Table 1 represents coating composition in which emulsion processed with addition of isobornyl methacrylate (IBOMA), silane crosslinker and wet adhesion promoter only in the initial stage of synthesis and not stage-wise.
Meanwhile accelerated test method was developed in which instead of applying coating on fresh cementitious substrates, it was applied on salt deposited cementitious substrates.
Table 4: Effect of Rosin additive molecule (RAM) through coating applied on salty substrate
Sample code Description % Rosin fatty acid additive as anti-efflorescing agent Total % Negative Capillary test on salty substrate Negative pressure test, ASTM D 7088

Polymer Mill base
CC-NJP-016 Conventional polymer + mill base with anti-efflorescing agent 0 0.2 0.2 Failed in 7 days 3.5
CC-NJP-008 Rosin additive reinforced polymer with IBOMA + mill base with anti-efflorescing agent 0.148 0.2 0.348 Failed in 17 days 2
Example 5 of Table 1; SAMPLE NO.
CC-NJP-083 Rosin additive reinforced polymer with IBOMA + mill base without anti-efflorescing agent 0.592 0.0 0.592 Failed in 23 days Not done
Example 6 of Table 1; SAMPLE NO.
CC-NJP-084 Rosin additive reinforced polymer with IBOMA (from initial stage) + mill base with anti-efflorescing agent 0.148 0.052 0.2 Failed in 10 days Not done
CC-NJP-016, CC-NJP-008, CC-NJP-083, CC-NJP-084 applied on salt deposited substrates for negative capillary test as per newly developed test method (Table 4). CC-NJP-016 showed premature failure in 7 days whereas CC-NJP-008 failed in 17 days. Efflorescence resistance has found need to improve when the rosin additive has incorporated during polymer synthesis instead of physical blend of the same in coating composition. Also, when concentration of rosin additive has increased from 0.4 to up to 1.6 wt.% on polymer solids during polymer synthesis, and stage-wise addition has made its impact has clearly seen in terms of efflorescence resistance improvement even in the accelerated test. CC-NJP-083 thus failed after 23 days during accelerated test. Syntheses have conducted to incorporate even higher concentration of rosin additive molecule where, heavy grit formation found for the experiments containing >0.8% rosin additive on polymer solids. When 2% of rosin additive based on polymer solids incorporated in synthesis, gelation has observed.
CC-NJP-084 was found to fail only after 10 days not due to incorporation of lower amounts of rosin additive molecule in mill base but mainly due to addition of IBOMA, silane crosslinker and wet adhesion promoter only in the initial stage of synthesis which proved that stagewise addition of hydrophobic monomers, silane crosslinker and wet adhesion promoter plays a crucial role to impart required hydrophobicity to the particle surface which eventually helped to improve negative capillary resistance. The addition of hydrophobic monomers, silane crosslinkers and wet adhesion promoter from the initial stage result in uniform distribution of the same across the polymer particle. Whereas if hydrophobic monomers have added in sequence and controlled manner, concentration of the same increases towards periphery of the polymer particle enabling improved water resistance. It therefore improves hydrophobicity resulting from improved water resistance, (Example CC-NJP-008).
It is thus possible by way of the present advancement to provide for emulsion polymer that is impregnated with rosin additive molecule and having hydrophobic monomers populating emulsion polymer particle surface and further crosslinked with silane taken in select levels that allows enhancement of inner polymer particle and surface hydrophobicity resulting in much improved water resistance, preferably when rosin additive and the sequential addition of hydrophobic monomer takes place. The negative capillary test performance deteriorates when either of the condition mentioned earlier has not applied during emulsion polymerization.
Thus, incorporation of rosin fatty acid additive and hydrophobic monomers stage wise in the process during emulsion polymerization has found to be highly effective in enabling the desired performance. Samples with external addition of same molecule found and without implementing any stage wise addition gave inferior performance on wet substrates when exposed to saturated salt solution even though with higher concentration. It eventually improved efflorescence resistance. Role of hydrophobic monomer to improve water resistance when involved in select range to give a stable emulsion polymer has proven with conducted experiments whereby emulsions stated in the examples in accordance with the invention all have shelf life of 6 months without any phase separation/floatation/colour change etc. Amongst the hydrophobic monomers explored, sample with IBOMA has found better in water & efflorescence resistance than that of sample with TBMA.
, Claims:We Claim:
1. Rosin reinforced emulsion polymer and coating compositions thereof comprising emulsion polymer particles of silane crosslinked reaction product of rosin fatty acid additive, acrylate/vinyl functional monomers, polymerizable surfactant, hydrophobic monomers including Iso-bornyl methacrylate (IBOMA), tertiary butyl methacrylate (TBMA).

2. The rosin reinforced emulsion polymer and coating compositions thereof as claimed in claim 1 wherein said reaction product includes following % ingredients
0.2 to 1.6% rosin fatty acid additive on polymer solid basis;
35 to 50 parts of acrylate/vinyl functional monomers;
2 to 5 % polymerizable surfactant on polymer solid basis;
9.0 to 15.0 % hydrophobic monomers including Iso-bornyl methacrylate, tertiary butyl methacrylate, cyclo hexyl methacrylate on polymer solid basis;
crosslinked with 1.2 to 2.0 % functional silane on polymer solid basis.

3. The rosin reinforced emulsion polymer and coating compositions thereof as claimed in claims 1 or 2 wherein said emulsion polymer particles are rosin fatty acid additive reinforced/impregnated emulsion polymer particles having improved in-build and surface hydrophobicity due to said rosin fatty acid additive and said hydrophobic monomers enabling waterproof characteristics.

4. The rosin reinforced emulsion polymer and coating compositions thereof as claimed in claims 1-3 wherein said silane cross linker is in the range of 1.2 to 2% on emulsion polymer solids that is a functional silane crosslinker comprising vinyl trimethoxysilane, vinyltriethoxysilane, methacryloxyproprytrimethoxysilane, methacryloxypropyltriethoxysilane; and wherein said polymerizable surfactant includes alkyl ether sulphate based anionic surfactant having radical polymerizable allylic group with 20 EO, 12 EO based polyoxyethylene ether phosphate with an allylic moiety.

5. The rosin reinforced emulsion polymer and coating compositions thereof as claimed in claims 1-4 wherein said rosin fatty acid additive reinforced/impregnated emulsion polymer enabling improved water resistant characteristics of said emulsion polymer includes said rosin fatty acid additive that is fatty acid modified rosin including fatty acids of abietic acid, linoleic acid, oleic acid, and which reinforcement of water resistant attributes of the emulsion polymer is favoured by incorporation of said rosin additive in pre-emulsion separated from hydrophobic monomers.

6. The rosin reinforced emulsion polymer and coating compositions thereof as claimed in claims 1-5 wherein said hydrophobic monomers as water resistant molecules incorporated in emulsion polymer particle surface impregnated with rosin fatty acid derivative includes Iso-bornyl methacrylate (IBOMA), tertiary butyl methacrylate (TBMA), cyclo hexyl methacrylate, and,
wherein said acrylate/vinyl functional monomers includes Butyl Acrylate, Styrene, n-Butyl Methacrylate, Methacrylic Acid.

7. The rosin reinforced emulsion polymer and coating compositions thereof as claimed in claims 1-6 wherein the coating compositions comprising 0.4% (based on polymer solids) rosin fatty acid additive reinforced TBMA based emulsion polymer gives decreased coating performance when combined with anti-efflorescing agents in respect of surface hydrophobicity and water resistance vs. same 0.4% (based on polymer solids) rosin fatty acid additive reinforced but IBOMA based emulsion polymer when combined with anti-efflorescing agents giving superior performance; and
wherein 0.2% (based on polymer solids) rosin fatty acid additive reinforced IBOMA based emulsion polymer when combined with anti-efflorescing agents gives inferior coating performance in respect of surface hydrophobicity and water resistance vs. 0.4% (based on polymer solids) rosin fatty acid additive reinforced TBMA based emulsion polymer when combined with anti-efflorescing agents giving superior performance.

8. The rosin reinforced emulsion polymer and coating compositions thereof as claimed in claims 1-7 wherein said coating composition comprise
mill base slurry including non-reactive hydrophobic additives, dispersing agent, pigment, biocide, coalescing agent, 0.2% anti-efflorescing agent; and
rosin fatty acid additive reinforced emulsion polymer including 0.148 % rosin fatty acid additive reinforced IBOMA based emulsion polymer, and/ or 0.148 % rosin fatty acid additive reinforced TBMA based emulsion polymer.

9. The rosin reinforced emulsion polymer and coating compositions thereof as claimed in claim 8 wherein said coating composition comprise
mill base slurry involving 0-0.6% anti-efflorescing agent; and
0.148 % rosin fatty acid additive reinforced TBMA based emulsion polymer said emulsion polymer achieved of at least 0.2% rosin fatty acid additive enabling improved coating performance in respect of surface hydrophobicity and water resistance.
10. A process for the synthesis of rosin reinforced emulsion polymer and coating compositions thereof as claimed in claims 1-9 comprising the steps of providing followings feeds for stage wise addition to reactor charge
(i) providing anionic polymerizable surfactant including phosphate based and/or sulphate-based surfactant and de-mineralized water heated to 80-90°C as reactor charge;
(ii) providing pre-emulsion seed including buffer and initiator in de-mineralized water in amounts of 3-10% of pre-emulsion;
(iii) providing ingredients for pre-emulsion including phosphate based and/or sulphate based polymerizable anionic surfactant, rosin fatty acid additive, acrylate/vinyl functional monomers, acid monomer, potassium per sulfate, chain transfer agent in de-mineralized water, for feeding to said reactor charge in stages;
(iv) providing hydrophobic monomers including Iso-bornyl methacrylate, tertiary butyl methacrylate, cyclo hexyl methacrylate in demineralized water with (a) silane crosslinker, (b) with wet adhesion promoters as separate feeds for stage wise addition to reactor charge while concurrently adding said pre-emulsion feed into reactor charge, polymerizing and digesting the same to obtain therefrom rosin reinforced emulsion polymer and coating compositions thereof.

11. The process for the synthesis of rosin reinforced emulsion polymer and coating compositions thereof as claimed in claim 9 wherein said stage wise addition of feed includes
addition of said pre-emulsion seed of step (ii) as initial feed to said reactor charge of (i) followed by,
feeding 25% of said pre-emulsion of step (iii) into said reactor charge continuously for a period of 180-240 mins at uniform rate and thereafter adding hydrophobic monomer feed of (iv) into said reactor;
post 50% completion of pre-emulsion addition of step (iii) into reactor charge further adding hydrophobic monomer feed of step (iv) (a) involving silane functional crosslinker;
post 75% completion of pre-emulsion addition of step (iii) into reactor charge further adding hydrophobic monomer feed of step (iv)(c) involving adhesion promoter and continuing polymerization followed by digestion and addition of additives including biocides, defoamer to achieve rosin reinforced emulsion polymer and coating compositions thereof.

Dated this the 21st day of December, 2022 Anjan Sen
Of Anjan Sen and Associates
(Applicants Agent)
IN/PA-199