Claims:Claims:
Claim 1: An active ingredient aqueous dispersion comprising at least one active ingredient and a polytetramer D, wherein, the polytetramer D contains constitutional units derived from

a) an aromatic ring-containing hydrophobic monomer, represented by the Formula (1)

Formula (1)

where R1= phenoxybenzyl, o-phenylphenoxyethyl or biphenylmethyl; R2= H or C1-C4 alkyl;

b) hydrophilic non-ionic monomer represented by the Formula (2),

Formula (2)
where R3=H or C1-C4 alkyl; R4 = C1-C2 alkyl, R7 = H or Methyl and n = 1 to 40;

c) aliphatic group containing hydrophobic monomer represented by Formula (3)

Formula (3)
Where R5 = H or C1-C4 alkyl; R6 = C1-C10 alkyl; and

d) carboxylic acid forming anhydride monomer represented by Formula (4).

Formula (4)

where, the polytetramer D is in the form of a colourless aqueous emulsion having solid content of about 10 weight % to about 70 weight %, where, ranges of amounts of the monomers represented by Formula 1, Formula 2, Formula 3 and Formula 4 are 20 to 35 weight%, 30 to 70 weight%, 5 to 25 weight% and 5 to 20 weight% respectively based on total weight of the monomer composition of the polymer dispersant D.

Claim 2: The active ingredient aqueous dispersion of Claim 1 further comprises a polytetramer E, wherein the polytetramer E contains constitutional units derived from a) an aromatic ring-containing hydrophobic monomer represented by the Formula (5)

Formula (5)
where R8= H or methyl;
b) hydrophilic non-ionic monomer represented by the Formula (6),

Formula (6)
where R9=H or C1-C4 alkyl; R10 = hydroxyethyl

c) aliphatic group containing hydrophobic monomer represented by Formula (7)

Formula (7)
Where R5’ = H or C1-C4 alkyl; R6’= C1-C10 alkyl and

d) Carboxylic acid monomer represented by formula (8).

Formula (8)
where R11 = H or C1-C4 alkyl;

where, the polytetramer E is in the form of a colourless aqueous dispersion having solid content of about 10 weight % to about 70 weight %, where ranges of amounts of the monomers represented by Formula 5, Formula 6, Formula 7 and Formula 8 are 8 to 14 weight%, 5 to 16 weight%, 25 to 35 weight% and 20 to 35 weight% respectively based on total weight of the monomer composition of the polymer dispersant E.

3. The active ingredient aqueous dispersion of claim 1 or 2, further comprises a polymer dispersion selected from a group consisting of crosslinked polymer nanospheres, self-crosslinking acrylic polymer emulsion, grafted copolymer emulsion and shell/core polymer emulsion.

4. The active ingredient aqueous dispersion of Claim 1 or 2, wherein, the Polytetramer D or the Polytetramer E is prepared by free radical dispersion polymerization technique.

5. The active ingredient aqueous dispersion of Claim 1 wherein the active ingredient is selected from a group consisting of fluorescent dyes, UV-absorbers, whitening compositions, invisible dyes or a combination thereof.

6. The active ingredient aqueous dispersion of Claim 3, wherein the dispersion is useful for coating paper, leather, wood and textile fabrics such as cotton, nylon, polyester and wool.

, Description:DESCRIPTION
NOVEL POLYTETRAMERS AND AQUEOUS DISPERSIONS CONTAINING THEM
The invention relates to compositions of novel polytetramers and their use in preparation of aqueous dispersions of active ingredients for textile and coating applications.
BACKGROUND
Polymeric dispersants are generally used for providing stable aqueous dispersions of variety of water-borne active ingredients such as colour dyes, fluorescent dyes, optical brighteners, UV absorbers, whitening dyes and invisible dyes. The polymeric dispersants include either block or random copolymers, having number average molecular weights generally ranging from 5000 to 150000 Daltons and more preferably from 5000 to 30000 Daltons and are prepared by free radical dispersion or micro-emulsion or mini-emulsion or RAFT polymerisation methods. The preparation of these polymers is generally carried out using polymerizable unsaturated monomers in the concentration ranges of about 10 to 50 weight % of aqueous emulsion. Block polymeric dispersants provide some advantages over those made of random polymeric dispersants in terms of increased stability of dispersion of active ingredients and improved adhesion to fibre. On the other hand, the random addition polymers are more attractive in terms of cost and ease of manufacturing.
US6326449 discloses a process for polymer dispersants derived from polymerizable units of styrene, alkyl acrylates, hydroxyalkyl acrylate and dimethyl acrylamide for high solids non-aqueous coatings.
US20020019459A1 discloses the use of copolymers with vinyl-functionalized polyethers for preparing aqueous pigment dispersions.
US6642338B2 discloses polymer dispersants with number average molecular weight lying in the range 10000 – 100000 Daltons for water-based coating compositions. The composition of the polymer dispersants disclosed in ‘338 publication has two or more constituents from the group consisting of styrene, alkyl acrylate or alkyl methacrylate, polyethylene glycol acrylate, methyl ether of polyethylene glycol methacrylate and monomers containing phosphate groups.
US8163839B2 discloses polymer dispersants having number average molecular weight in the range 5000-30000 Daltons, the constituents of polymers coming from monomers such as styrene, methyl methacrylate, ethyl methacrylate, methacrylic acid, a long alkyl chain monomer, dodecyl methacrylate and monomethyl ether polyethylene glycol methacrylate.
WO2007006637A2, EP1904581B1 and US2003044707 disclose composition of polymer dispersants with pendant chromophore groups and processes for their preparation. Such polymer dispersants though suitable for dispersing water-soluble fluorescent dyes possess disadvantages such as tedious preparation process and high cost.
US9416280 discloses a paint or ink composition containing an organic medium, pigment particulates and a copolymer dispersant having constituents from styrene, a dicarboxylic acid, or anhydride thereof, a polyetheramine and an amine such as dialkylaminoalkylamine and a number average molecular weight in the range 1000 to 50000. These dispersants were aimed to be compatible with binders such as nitrocellulose, polyamide and polyurethane.
Society of Dyers and Colourists, Colour Technol., 124, 355–363, discloses dispersants made of one or more of the monomers, methacrylic acid, styrene, benzyl methacrylate, butyl methacrylate and methyl methacrylate.
Another reference, NIHON GAZO GAKKAISHI (Journal of the Imaging Society of Japan) -2005, Volume 44 Issue 5 Pages 332-341, discloses amphiphilic copolymer dispersants of weight average molecular weight ranging from 137500 to 293100, made of monomer having methyl ether of polyethylene glycol or polypropylene glycol methacrylate as hydrophilic portion and lauryl methacrylate as hydrophobic side chain for dispersing disperse-dye-inkjet inks.
In a prior art reference, Polymer 42 (2001) 2387–2394, methyl ethers of polyethylene glycol-grafted styrene maleic anhydride copolymers are disclosed with no reference to efficiency of their dye/pigment dispersion activity.
US4906684 discloses ambient temperature curing coating composition with acetoacetoxyethyl methacrylate (AAEMA), glycidyl methacrylate (GMA) or glycidyl acrylate and a polymerizable acid.
US5266322 and US5380520 reveal aqueous emulsions of sulfopolyesters and a copolymer of vinyl acetate, dialkyl maleate or fumerate and emulsion polymer of AAEMA.
EP0626397A1 discloses an emulsion of acrylic polymer or an acrylic styrene polymer coating with incorporation of monomer, AAEMA.
EP0555774A, WO9616998Aand EP0897399B1 reveal preparation of self-crosslinking copolymer dispersions made from acrylate copolymers having AAEMA, which are used in paints as binders and which crosslink at room temperature or at elevated temperatures.
JP2001329199A and JP200536202A disclose water-based pigment dispersions or composition of inkjet inks formed based on polymer particles A (water-insoluble polymer and/or a self-dispersible pigment) and polymer particles B (based on methoxypolyethylene glycol (meth)acrylate), exhibiting excellent water resistance, rub fastness and highlighter fastness.

JP2006282989 A discloses an aqueous dispersion containing polymer particles A (containing colorants) and polymer particles B (containing water-insoluble organic compound) exhibiting excellent light fastness.

JP201084116 A discloses a water-based pigment dispersion containing water-insoluble vinyl polymer particles and a water-soluble organic solvent exhibiting good quality of images suitable for high-speed printing.

US2010036045A1 discloses an aqueous pigment dispersion containing a copolymer prepared from a macro monomer based on styrene and a nitrogenous monomer such as vinyl imidazole for use in water-borne surface coatings.

EP3006519B1 discloses a water-based ink composition containing an organic solvent such as propylene glycol and two water-insoluble polymers, one of which is an aqueous dispersant polymer of weight average molecular weight of 10000-150000 Daltons. The dispersant polymer contains constituents from hydrophobic monomer such as styrene or styrene-based macromonomer and an aromatic group containing methacrylate monomer such as benzyl methacrylate, a carboxylic acid monomer, a hydrophilic non-ionic monomer such as polyethylene glycol acrylate or methacrylate.

Active ingredient dispersion compositions used in textile coatings contain polyol additives such as glycols or high molecular weight polyethylene glycols or propylene glycols or glycol ethers or ethoxylated non-ionic surfactants in addition to polymeric dispersants. The presence of the polyol additives at high concentrations in coating compositions often lead to inferior performance such as adhesion loss on multiple washings, colour migration during washing and rubbing, poor scratch resistance and poor light fastness which are challenging performance issues. Some of these performance issues are also seen with some polymeric dispersants especially at high concentrations of active ingredients such as fluorescent dyes.

The objective of the current invention is to design and develop new novel polytetramers to disperse a variety of active ingredients in aqueous phase. Another objective of the invention is to provide superior surface-adsorption of dispersed active ingredients over the surface of crosslinked polymeric nanospheres. Yet another objective of the invention is to obtain high-performance dispersions, in terms of resistance to colour migration during washing, rubbing and exposure to light.

SUMMARY OF THE INVENTION
The invention relates to compositions of novel water-borne polytetramers and their use in dispersing active ingredients for textile and coating applications.
The invention discloses an active ingredient aqueous dispersion comprising at least one active ingredient and a polytetramer D, wherein, the polytetramer D contains constitutional units derived from
a) an aromatic ring-containing hydrophobic monomer, represented by the Formula (1),

Formula (1)
Where R1= phenoxybenzyl, o-phenylphenoxyethyl or biphenylmethyl; R2= H or C1-C4 alkyl;

b) hydrophilic non-ionic monomer, represented by the Formula (2),

Formula (2)
where R3=H or C1-C4 alkyl; R4 = C1-C2 alkyl, R7 = H or Methyl and n = 1 to 40;

c) aliphatic group containing hydrophobic monomer, represented by Formula (3),

Formula (3)
Where R5 = H or C1-C4 alkyl; R6 = C1-C10 alkyl; and

d) carboxylic acid forming anhydride monomer, represented by Formula (4).

Formula (4)
where, the polytetramer D is in the form of a colourless aqueous emulsion having solid content of from about 10 weight % to about 70 weight %, where, ranges of amounts of the monomers represented by Formula 1, Formula 2, Formula 3 and Formula 4 are 20 to 35 weight%, 30 to 70 weight%, 5 to 25 weight% and 5 to 20 weight% respectively based on total weight of the monomer composition of the polymer dispersant D.

The active ingredient aqueous dispersion of the invention further comprises a polytetramer E, wherein the polytetramer E contains constitutional units derived from
a) an aromatic ring-containing hydrophobic monomer, represented by the Formula (5)

Formula (5)
where R8= H or methyl;
b) hydrophilic nonionic monomer represented by the Formula (6),

Formula (6)
where R9=H or C1-C4 alkyl; R10 = hydroxyethyl
c) aliphatic group containing hydrophobic monomer represented by Formula (7),

Formula (7)
Where R5’ = H or C1-C4 alkyl; R6’= C1-C10 alkyl and

d) Carboxylic acid monomer, represented by Formula (8).

Formula (8)
where R11 = H or C1-C4 alkyl;

where, the polytetramer E is in the form of a colourless aqueous emulsion having solid content of about 10 weight % to about 70 weight %, where ranges of amounts of the monomers represented by Formula 5, Formula 6, Formula 7 and Formula 8 are 8 to 14 weight%, 5 to 16 weight%, 25 to 35 weight% and 20 to 35 weight% respectively based on total weight of the monomer composition of the polymer dispersant E.
The active ingredient aqueous dispersion further comprises a polymer dispersion selected from a group consisting of crosslinked polymer nanospheres, self-crosslinking acrylic polymer emulsion, grafted copolymer emulsion and shell/core polymer emulsion.
The polytetramer D or the polytetramer E is prepared by free radical dispersion polymerization technique. The active ingredient is selected from a group consisting of fluorescent dyes, UV-absorbers, whitening compositions, invisible dyes or a combination thereof.
The active ingredient dispersion of the invention is useful for coating paper, leather, wood and textile fabrics such as cotton, nylon, polyester and wool.
The foregoing features of invention will be more readily understood by reference to the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
In the present disclosure, the expressions, polytetramers and poly(tetramers) are used interchangeably.
The present invention provides composition of novel polytetramers, their synthesis through free radical dispersion polymerization and preparation of aqueous dispersions of active ingredients. In addition, the invention discloses light and wash fastness performance of printed textile fabrics which are printed with dispersions which contain polytetramers, active ingredients and nanospheres of prior art inventions.
In the current invention, novel polytetramers are designed by incorporating four different types of unsaturated polymerizable monomers, in which one of the monomers contains biphenyl/diphenyl ether groups. The biphenyl/diphenyl ether groups aid in enhancing the solubility of the active ingredients. Incorporation of alkyl or branched alkyl chains in the backbone provide steric stability to the dispersions. Incorporating polar monomers such as maleic anhydride improves wetting property of the polytetramers and stability by electrostatic repulsion forces. Fourthly, incorporation of monomers containing multiple ethylene oxide or propylene oxide units confers hydrophilicity to the polytetramers.
Dispersion of an active ingredient in an aqueous medium, is affected by not only the structure, the size and the quantity of the active ingredient to be dispersed in aqueous phase but also the structure and the average molecular weight of polymeric dispersant used. Further, dispersing characteristics of a polymeric dispersant depends upon type and weight percentage of each functional group attached to the backbone of the polymer. Any improper balance in electrostatic or steric repulsion or hydrophilic and lipophilic balance (HLB) would lead to either the active ingredient precipitating out in the form of crystals or precipitating out along with polymeric dispersant from aqueous phase.
Definitions
Some of the key expressions related to the present invention have the meaning as given below.
Active ingredients: Fluorescent dyes, UV-absorbers, whitening compositions, colour dyes, invisible dyes or a combination thereof.
Dispersion: Refers to dispersion of one or more active ingredients in aqueous or non-aqueous medium.
Polymer dispersant: Refers to ‘polymeric dispersant’ and the two expressions are used interchangeably in this document.
Water-borne: Refers to water-soluble or water-insoluble forms
Constitutional unit: Refers to the structural portion of polymerizable unsaturated monomer which gets incorporated in addition polymers of the invention
Crosslinked polymer nanospheres: Refers to aqueous dispersion of polymer particles made of monomers and crosslinking monomers as disclosed in Indian patent application No: 202041034776,
self-crosslinking acrylic polymer emulsion, grafted copolymer emulsion or shell/core polymer emulsion.
In one embodiment, novel polytetramers of the invention have constitutional units derived from four monomers represented by Formula (1), Formula (2), Formula (3) and Formula (4).

Formula (1)

where R1= phenoxybenzyl, o-phenylphenoxyethyl or biphenylmethyl;
R2= H or C1-C4 alkyl;

Formula (2)
where R3=H or C1-C4 alkyl; R4 = C1-C2 alkyl, R7 = H or Methyl and n = 1 to 40;

Formula (3)
Where R5 = H or C1-C4 alkyl; R6 = C1-C10 alkyl;
and

Formula (4)

Monomers represented by Formula (1):
The monomers represented by Formula (1) are aromatic ring-containing hydrophobic monomers specifically as shown in the structures, M1122, M1142 and M1192 given below;

Other examples of monomers represented by Formula (1) are benzyl methacrylate, styrene, and styrene based macromers. The aryl/alkyl aryl/biphenyl/biphenyl ether based acrylic ester hydrophobic monomers are more preferred to constitute the polytetramer of the invention, as they are richer in pi-conjugation. The conjugated pi-bonds of these biphenyl/diphenyl groups interact with the pi-conjugation of the active ingredients to increase the solubility and as a result, the active ingredient molecules are dispersed uniformly and delivered smoothly to the surface of the cross-linked nanospheres.
Monomers represented by Formula (2):
The monomers represented by Formula (2) are hydrophilic nonionic monomers containing ethylene oxide and propylene oxide chains. In order to compensate the hydrophobicity imparted by the presence of structural units derived from Formula (1), polymerizable unsaturated polyethylene oxide monomers are selected and incorporated to improve hydrophilicity and enhance the dispersion of active ingredients. Examples of monomers represented by Formula (2) are PEG500MA, PEG2000MA and PPG5MA. In many polymer dispersants, polyethylene glycol monomethyl ether methacrylate of number of moles of ethylene oxide of around 10-23 were being used and in many references number of moles of 23 being preferred, when the ethylene oxide chains of around 10 to 22 molecules lead to form higher molecules weights and form glassy surface films. In this regard, PEG500MA is the preferred monomer represented by Figure 2. The structure of PEG500MA and that of PPG5MA are shown below.

PEG500MA PPG5MA
where R3=H, R4 = Methyl, and n = 10 to 23. where R3=H, R4=Methyl, R7=Methyl and n=5
Monomers represented by Formula (3):
The monomers represented by Formula (3) in the current invention are acrylates or methacrylates

Formula (3)
Where R5 = H or C1-C4 alkyl; R6 = C5-C18 linear or branched alkyl alkyl groups in the alkoxy part (R6O) of acrylic or methacrylate esters. The alkyl groups have more than five carbon atoms. The branched or long alkyl chains are deemed to stabilize active ingredient molecules sterically with the polytetramers. Examples of monomers having Formula (3) are ethylhexyl methacrylate, ethylhexyl acrylate, stearyl acrylate and dodecyl acrylate which create steric repulsion characteristic to the resultant polymer dispersants. Use of appropriate weight % of these monomers in the polytetramer is important to achieve steric stabilization.
Monomers represented by Formula (4):

Formula (4)
Formula (4) represents unsaturated anhydride monomers which can provide unsaturated anionic monomers when the anhydride functionality is hydrolyzed with a base. The preferred monomer is maleic anhydride monomer, which provides anionic carboxylate species on treatment with bases. Other examples of monomers which can provide anionic functionality are carboxylic acids, sulphonic acids and phosphoric acids when quenched with a base. Cationic monomers on the other hand are generated by reaction of tertiary amines having unsaturation with acids or they can be quaternary ammonium salts. Specific examples of carboxylic acids are acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, methacryloxymethyl succinic acid. Examples of sulphonic acid monomers are styrene sulphonic acid, 2-acrylamido-2-methylpropanesulphonic acid or sulphopropylmethacrylate. Examples of phosphoric acid monomers include vinylphosphoric acid, vinylphosphonic acid, bis(methacryloxyethyl)phosphate, diphenyl-2-acryloyloxyethyl phosphate and diphenyl-2-methacryloyloxyethyl phosphate. Examples of the unsaturated tertiary amines are N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-dimethylaminoaryl methacrylate. Anionic and cationic type monomers are generally not used in combination, but an anionic monomer can be used a comonomer or as a combination of two or more anionic monomers in the composition of polytetramer. Similarly, a cationic monomer can be used as a comonomer alone or as a combination of two or more cationic monomers. Among the various ionic monomers, maleic anhydride, methacrylic acid or a combination thereof is used in the current invention. When maleic anhydride is used as ionic monomer, the resultant polytetramer of the current invention is treated with aqueous solution of ammonium bicarbonate and heated to 70C to break the five membered rings to form carboxylate groups, which are essential to provide adequate wetting property to the polytetramer. In the active ingredient dispersions, the active ingredient molecules such as dye molecules when adsorbed over the surface of the crosslinked nanospheres, the polytetramer dispersant also is adsorbed along with the active ingredient molecules to generate surface electrostatic repulsion forces.
Polymer Dispersants: Polytetramer D, formed from constitutional units derived from monomers of Formula (1), Formula (2), Formula (3) and Formula (4):
The purpose of the invention is to develop polymeric dispersants based on polytetramers for effective dispersion of the active ingredients. Polytetramer D (polymeric dispersants of the invention) is in the form of a colourless aqueous emulsion having solid content of from about 10 weight % to about 70 weight %, where, ranges of amounts of the monomers represented by Formula 1, Formula 2, Formula 3 and Formula 4 are 20 to 35 weight%, 30 to 70 weight%, 5 to 25 weight% and 5 to 20 weight% respectively based on total weight of the monomer composition of the polymer dispersant D.
Preparation of Polytetramers:
The present invention also provides a process for preparation of polytetramers by carrying out a free radical dispersion polymerization in non-aqueous phase with continuous addition of AIBN and polymerizable unsaturated monomers. Out of the various solvents generally used in the dispersion polymerisation, EtOH, iso-PrOH, THF, methylethylketone or their combinations are common. In the current invention, iso-PrOH was used to carry out the free radical dispersion polymerisation to form polytetramers. Neutralizing the resultant polytetramer with aqueous solution containing ammonium bicarbonate, subjecting the resultant solution mixture to rotary evaporation to remove iso-PrOH under reduced partial vacuum of 600 mmHg and heating the resultant polytetramer solutions at 700C to 800C with addition of ammonium persulphate in order to remove traces of unreacted monomers. The final solid contents of the resultant polytetramers were adjusted by using rotary evaporation under high vacuum of 700 mmHg.
In the current invention, the polytetramers were formed by carrying out the free radical dispersion polymerization of monomers at much lower concentrations as compared to the conventional prior art inventions, where the polymerisations were conducted at concentrations of around 25 to 50 weight percent of the solution mixture. In the current invention, we have carried out the free radical dispersion polymerisation at around 4 weight percent over a period 10 hours. When the molecular weights of polytetramers decrease to lower values, its dispersant effect is affected and balance of hydrophobic, hydrophilic, steric and electrostatic repulsion forces have been required for optimum dispersing of organic dyes. In literature, the polymer dispersants obtained with number average molecular weights of around 30000 Daltons are being used in dispersing organic pigment dyes, which are being used in manufacturing of inkjet inks.
Performance Characteristics of polytetramers
In one aspect, the new innovative polytetramers of the current invention provides excellent wetting and dispersing ability to a variety of water-borne active ingredients. In another aspect, the polytetramer aqueous emulsion forms by heating to 1500C glassy films which possess very good compatibility to a variety of alkyd resins and acrylic resins. In yet another aspect, the dispersed water-borne active ingredients are adsorbed over the surface of crosslinked polymeric nanospheres of the prior art-invention disclosed in Indian Patent application 202041034776 to form aqueous nanosphere dispersions, which can be used for coloring surfaces such as textile fabric surfaces. The fabrics printed with these nanosphere dispersions, particularly of fluorescent nanosphere dispersions exhibit improved adhesion and improved colour migration resistance during washing and rubbing and exposure to light.
Co-dispersants
The inventors have additionally found an aspect which is part of the current invention and is with regard to co-dispersants which can be present along with Polytetramer, D. These co-dispersants are referred to as Polytetramer, E in the current disclosure.
The constituting units of Polytetramer, E are derived from monomers represented by Formula (5), Formula (6), Formula (7) and Formula (8).
a) an aromatic ring-containing hydrophobic monomer represented by the Formula (5)

Formula (5)
where R8= H or methyl; A typical example is styrene.

b) hydrophilic non-ionic monomer represented by the Formula (6),

Formula (6)
where R9=H or C1-C4 alkyl; R10 = hydroxyethyl. A typical example is hydroxyethyl methacrylate (HEMA).

c) aliphatic group containing hydrophobic monomer represented by Formula (7)

Formula (7)
Where R5’ = H or C1-C4 alkyl; R6’= C1-C10 alkyl and typical examples are butyl acrylate and hexyl acrylate

d) Carboxylic acid monomer (precursor of ionic monomer) represented by Formula (8).

Formula (8)
where R11 = H or C1-C4 alkyl; Typical examples are acrylic acid, methacrylic acid and the like.

where, the polytetramer E is in the form of a colourless aqueous emulsion having solid content of from about 10 weight % to about 70 weight %, where ranges of amounts of the monomers represented by Formula 5, Formula 6, Formula 7 and Formula 8 are 8 to 14 weight%, 5 to 16 weight%, 25 to 35 weight% and 20 to 35 weight% respectively based on total weight of the monomer composition of the polymer dispersant E.
.
The preparation process for the co-dispersant, Polytetramer E is akin to that of Polytetramer D.
The ratio of amount of the main dispersant Polytetramer D to that of the Co-dispersant, Polytetramer E can be varied.
Polytetramer E can replace Polytetramer D of the invention only partially as found in the examples.
When Polytetramer E from comparative examples are used as sole polymeric dispersants, the active ingredient precipitates out rapidly and satisfactory dispersions are not obtained.
Cosolvents
The active ingredient aqueous dispersion of the invention may contain further water-soluble organic solvents selected from the group consisting of ethylene glycol, propylene glycol and polyglycol monomethyl ethers. Such solvents are added in required amounts to enhance dispersion characteristics of dispersions containing certain active ingredients. A typical example of a cosolvent is dipropylene glycol monomethyl ether (DPGMME).

The amounts of polymeric dispersants such as polytetramer D, or its combination with co-dispersant, Polytetramer E generally ranges from 1 to 10 times of the weight% of the active ingredient to be dispersed.

Components of the aqueous dispersions
The purpose of the invention is to provide aqueous dispersions of active ingredients of acceptable performance on surfaces such as textile fabrics. The aqueous dispersions are easily prepared under ultrasonication as described in the Examples section. One of the key components apart from polytetramers of the invention and active ingredients is crosslinked polymer particles which are required to improve the adsorption and performance of active ingredient particles on the surfaces such as those of textile fabrics. Accordingly, the active ingredient dispersion of the invention further comprises a polymer dispersion selected from a group consisting of crosslinked polymer nanospheres, self-crosslink acrylic polymer emulsion, grafted copolymer emulsion and shell/core polymer emulsion. A preferred crosslinked polymer nanosphere particles are those disclosed in the inventive examples of the invention disclosed in Indian Patent Application 202041034776.

Substrates for application of aqueous dispersions of the invention
The dispersions of active ingredients are useful for coating surfaces of substrates such as paper, leather, wood and particularly, textile fabrics such as cotton, nylon, polyester and wool. The performance of active ingredients is realized in full in presence of polytetramers of the invention.

Active Ingredients
Active ingredients to be used in the inventive dispersions belong to the classes of Fluorescent dyes, Optical brighteners, Whitening compositions, UV absorbers and Invisible dyes. Any of the water-borne active ingredients of these classes can be dispersed well by the innovative polytetramers of the invention to form aqueous dispersions.
Fluorescence dyes: Fluorescence dyes/fluorescent dyes form an important class of dyes in textile applications. Fluorescent dyes used in this invention can be water soluble dyes or water insoluble organic dyes. Preferred dyes include but are not limited to dyes selected from the classes of benzothioxanthane, xanthane, coumarin, naphthalimide, benzoxanthane, perylene, and acridine. Examples of water-soluble dyes which may be used include the sulfonate and carboxylate dyes, specifically, those that are commonly employed in ink-jet printing. Specific examples include: Sulforhodamine B (sulfonate), Acid Blue 113 (sulfonate), Acid Blue 29 (sulfonate), Acid Red 4 (sulfonate), Rose Bengal (carboxylate), Acid Yellow 17 (sulfonate), Acid Yellow 29 (sulfonate), Acid Yellow 42 (sulfonate), Acridine Yellow G (sulfonate), Nitro Blue Tetrazolium Chloride Monohydrate or Nitro BT, Rhodamine 6G, Rhodamine 123, Rhodamine B, Rhodamine B Isocyanate, Safranine O, Azure B, Azure B Eosinate, Basic Blue 47, Basic Blue 66, Thioflacin T (Basic Yellow 1), and Auramine O (Basic Yellow 2), all available from Aldrich Chemical Company. Examples of water-insoluble dyes which may be used include azo, xanthene, methine, polymethine, and anthraquinone dyes. Specific examples of water-insoluble dyes include Ciba-Geigy Orasol Blue GN, Ciba-Geigy Orasol Pink, Ciba-Geigy Orasol Yellow, Lumogen™ fluorescent dyes from BASF, and the like.
Optical brighteners: The commercially available Ultraphor® (BASF), Leucophor® (Clariant) or Tinopal® (Ciba) or other products from the chemical categories of the stilbenes, distyrylbiphenyls, coumarins, naphthalic acid imides and the benzoxazole and benzimidazole systems linked via double bonds.
Whitening Compositions: The concept behind whitening compositions is based on the principle of color cancellation to mask or alter the initial fabric color appear whiter. In order for masking say the yellow color of a fabric, a blue dye and violet dye is mixed in some proportion, so that appropriate color cancellation is affected and emission of multiple colors that blend to form white light results. Because of obtaining high dispersity of these dyes in water and increasing the dispersity with increasing the concentration of the new innovative polytetramers result in high performance of whitening. The blue dye is selected from the group consisting of direct blue 1, direct blue 71, direct blue 80, direct blue 279, acid blue 15, acid blue 17, acid blue 25, acid blue 29, acid blue 40, acid blue 45, acid blue 75, acid blue 80, acid blue 83, acid blue 90, acid blue 113 (also known as and commercially available as Erionyl Navy R), basic blue 3, basic blue 16, basic blue 22, basic blue 47, basic blue 66, basic blue 75, basic blue 159, reactive blue 17, reactive blue 19 (also may be referred to as Remazol brilliant blue R, CI Reactive Blue 19, Remazol Br Blue BW, Remazol Navy Blue, Remazol Navy Blue RGB, and/or Remazol Br Blue BB), Cyan Blue WW-GS (also known and available as Terasil® Blue TC), and combinations thereof. The violet dye is selected from the group consisting of direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 48, direct violet 51, direct violet 66, direct violet 99, acid violet 9, acid violet 15, acid violet 17, acid violet 24, acid violet 43, acid violet 49, acid violet 50, basic violet 1, basic violet 3, basic violet 4, basic violet 10, basic violet 35, and combinations thereof. In a particular embodiment of the method, the violet dye is direct violet 9.
UV absorbers: The polytetramers of the invention are found suitable for dispersing UV absorbers in aqueous medium, thereby forming highly dispersed aqueous emulsions. The well dispersed UV absorbers absorb UV-radiation much more strongly and excites and relax to the ground state extremely rapidly and efficiently through radiation-less processes, which imparts high stabilization efficiency and excellent photostability. UV absorbers are categorized by chemical class, for example benzotriazoles, benzophenones, and triazines. Each class has its own UV absorbance characteristics. For example, benzophenone- and triazine-types tend to absorb more strongly in the short wavelength UV-B region than the benzotriazole-types. In one embodiment, any UV ray absorber that may withstand the process conditions described herein may be employed to form the polymeric UV ray absorbing composition. Suitable examples of UV ray absorber include: (a) 2-hydroxybenzophenones, (b) 2-hydroxybenzotriazoles and (c) substituted acrylonitrile and the like.
Invisible dyes or Fluorophores: The polytetramers of the invention are used for dispersing a variety of invisible dyes in aqueous phase in the presence of nanosphere dispersions. Dye-adsorbed nanospheres absorb light efficiently and thereafter emit fluorescent light in higher quantum yield. They are used as color markers, which show up as striking colors on exposure to UV light or in some cases IR and in some other cases Far IR rays,
Representative materials in each of these classes are as follows: (1) stilbenes: 4,4′-bis(triazin-2-ylamino)stilbene-2,2′-disulfonic acid; benzenesulfonic acid-2,2′-(1,2-ethenediyl)bis[5-[4-bis(2-hydroxyethyl)amino]-6-[(4-sulfophenyl)amino]-1,3,5-triazin-2yl]amino-tetrasodium salt; and 4,4-bis [4-diisopropanolamino-6-(p-sulfoanilino)-s-triazin-2-yl-amine]stilbene-sodium disulfonate; (2) pyrazolines: 1,2-diphenyl-2-pyrazoline; (3) coumarins: 7-diethylamino-4-methylcoumarin; 7-hydroxy-4-methylcoumarin; and 3-(2-benzimidazolyl)-7-(diethyl amino)coumarin; (4) carbostyrils: 2-hydroxyquinoline; and (5) pyrenes: N-(1-pyrenebutanoyl)cysteic acid. Also, of interest as an ultraviolet fluorophore is dibenzothiophene-5,5-dioxide, as well as C.I. (Color Index) Fluorescent Brightener 28; C.I. Fluorescent Brightener 220; and C.I. Fluorescent Brightener 264, with some or all of these C.I. compositions being comparable or structurally equivalent to the specific materials listed above. The foregoing ultraviolet fluorophores and others are commercially available from numerous sources including but not limited to the Aldrich Chemical Co. of Milwaukee, Wis. (USA); Bayer Corporation of Pittsburgh, Pa. (USA) under the names “BLANKOPHORE” or “PHORWHITE”; Ciba-Geigy Corporation of Greensboro, N.C. (USA)/Basil, Switzerland; Molecular Probes of Eugene, Oreg. (USA); Sandoz Chemicals of Charlotte, N.C. (USA) under the name “LEUKOPHOR”; and Sigma Co. of St. Louis, Mo. (USA). These materials are characterized by their ability to generate fluorescent light upon ultraviolet illumination and can be seen by the unaided eye.
Materials
-Basic Violet 11:1, Basic red 1:1 and basic violet 11 were procured from Susan | HUPC, Chemical Co., Ltd, Room 301, Building B2, No.206 Zhen Hua Road, Hang Zhou, China P.C.310030 and used as received.
-HEMA, 98% purity and styrene, 98% purity were procured from ChemPure Private Limited, Jigani 560105, Bangalore.
-Acrylic ester monomers, M1192, M1122 & M1142 were procured from Miwon, Head Quarters, 20, Poeum-Daero, 59Beon-Gil, Suji-gu, Yongin-Si, Gyeon-ggi; 16864; Korea and used as received.
-PEG500MA and Zetaspheres Z179 were procured from Evonik India Pvt. Ltd. Krislon House, Sakivihar Road, Sakinaka, Andheri (East), Mumbai 400 072, India Board No. +91 22 6723 8800.
-HPMA is procured from Sigma-Aldrich and used as received.
-Ethylhexyl acrylate (EHA), n-butyl acrylate (BuAc), methacrylic acid (MAA), maleic anhydride (MA), IsoPr-OH, AIBN and tetrahydrofuran (THF) were procured from SD Fine Chemicals. Chemicals, otherwise not specified are laboratory grade.
-DPGMME, synthesis grade, was procured from Pure Chemicals Co. Limited, Principal Place, No.32, H-Block, 15th Main Road, Anna Nagar, Chennai 600040.
-Textile cotton woven fabric (100%) having construction of 23.6 ends/cm2 with an area density of 112.2 g/m2 was used as fabric for printing. (Matic, PO Box 14760, Mumbai 400099).
-Detergent Surf excel, procured was used as received. The other chemicals, otherwise not specified, are of LR grade and are used as received.
EXAMPLES
Procedure for Synthesis of Polytetramers
Comparative Examples CE1 to CE6 and Inventive Examples E1 to E5
Unsaturated monomers as specified in Tables 1A and 1B were weighed into a screw-cap reagent Borosil bottles and mixed to form a monomer mixture. In another similar bottle, specified amount of THF and AIBN were weighed and mixed to obtain initiator solution. Specified amount of iso-PrOH was weighed into a four neck 500 mL round bottom glass flask and heated to 70oC under mechanical agitation at 210 rpm. Once the temperature reached 70oC in 30 minutes, two Borosilicate burettes (10 and 5 mL) were fixed to B24 Teflon glands, through which 5 g of monomer mixture and 2.2 g of the initiator solution were added continuously while maintaining the temperature at 70oC. After completion of addition of monomer mixture and initiator solution, the reactions were continued further for another 3 hours. The resultant reaction products, the polytetramers were neutralized with NaHCO3 aqueous solution, which was added slowly, while stirring continued for 20 min. Then the reaction mixture was subjected to rotary evaporation for removal of iso-PrOH. To the resultant polytetramer aqueous solution, a mixture of 0.8 g of ammonium persulphate and 0.1 g of sodium metabisulphite were added and the reactions were continued further at 70oC for another 2 hours and then cooled to room temperature. The composition of polytetramers of the comparative as well as inventive of the invention are given in Tables 1A and 1B respectively.

The resulting dispersant solutions were used to prepare active ingredient (example: fluorescent dye)-dispersions as given below.

Procedure for preparation of fluorescent aqueous nanosphere dispersions
Comparative Examples D-CE1 to D-CE6 (see Table 2A for amounts of ingredients) and Inventive Examples D-E1 to D-E5 (see Table 2B for amounts of ingredients)
To the polytetramer aqueous emulsion obtained as described in the experimental section on “Procedure for Synthesis of polytetramers” (see Tables 1A and 1B for compositions), fluorescent dyes were added as active ingredients and subjected to ultrasonication for 5 to 10 minutes at room temperature. To the resultant fluorescent emulsion, crosslinked nanosphere dispersions (synthesized in accordance to the procedure given in patent application filed in Indian Patent Application202041034776 (prior to addition, the solid contents were adjusted to around 18 percent through rotary evaporator) were added and the resulting fluorescent dispersions were subjected to rotary evaporation for removal of excess water to adjust the final solid contents to around 28%.
Preparation of dye dispersion of Example D-E1(l)
The preparation procedure of the fluorescent aqueous nanosphere dispersion D-E1(l) was identical to that of other inventive examples D-E1 to D-E5 given above, excepting that the amount of polytetramer E1 was increased as shown in Table 2B.
Preparation of dye dispersion of Example D-E6
The preparation procedure of the fluorescent aqueous nanosphere dispersion D-E6 was identical to that of other inventive examples D-E1 to D-E5 given above, excepting that the polytetramer used was a combination of two dispersants, namely E-1 and CE-1 in the relative proportions as shown in Table 2B, sample ID D-E6.

In all the dispersions given in Table 2A, organic dyes were rapidly precipitating out and therefore were found unsuitable for coating applications.

Cloth Prints:
The fluorescent dispersions given in Table 2B were evaluated by printing on cotton fabrics and measuring light and wash fastness properties (see Table 3). An acrylic thickener prepared in accordance to the procedure described in US Patent 2004/0102553A1 was used to prepare the printing paste. To 9 g of the thickener, around 3.6 g of fluorescent nanosphere dispersion (dispersions shown in 2B) was added and mixed thoroughly with glass rod and cloth prints were taken using printing pad method over the cotton fabric specimen of 10 x 5cm2 size.
Table 3: Performance of Cloth Prints

Dye Dispersion used Light Fastness Wash Fastness Colour Migration
Strength, % dE Strength, % dE Strength, % dE
D-E1 75 4.5 75 5 120 2
D-E2 85 4 80 5.4 130 3.5
D-E3 80 4.5 84 6 110 3.2
D-E4 80 3.5 85 4.1 125 3.2
D-E5 80 5 85 4.6 110 2.5
D-E1(I) 80 4.5 80 4.3 110 2.8
D-E6 90 3.5 80 6.5 112 2

As compared to the fluorescent dispersions obtained with comparative polymer dispersants, where the resultant dispersions were not suitable to take the cloth prints, the new polymer dispersants of Examples E1 to E5, which were found suitable for applications and hence used to take cloth prints that showed acceptable fastness properties related to colour migration and light fastness (See Table 3). Also, fluorescent dispersion D-E6 made with a combination of two dispersants, namely E1 and CE1 also showed low colour migration and acceptable light fastness properties. This indicates that all the polymer dispersants represented by inventive examples are effective in dispersing the organic dyes and thus they also stabilize the resultant dye adsorbed polymer nanospheres.