WO2019115392A1

WO2019115392A1 - Soil release formulations for textile applications

Info

Publication number: WO2019115392A1
Application number: PCT/EP2018/083995
Authority: WO
Inventors: Helmut Sieber
Original assignee: HeiQ mATERIALS AG
Current assignee: HeiQ mATERIALS AG
Priority date: 2017-12-13
Filing date: 2018-12-07
Publication date: 2019-06-20
Anticipated expiration: 2020-06-13

Abstract

Textile treatment formulation to lastingly impart anti-staining properties to fibers or garments, in particular to cotton or cotton based fibers or garments, said formulation containing an effective amount of a block-copolymer (I) or a mixture thereof. The block- copolymer (I) comprises at least one or a plurality of blocks of the following structure or consists of the following structure: (HO)-(HI)-(HO_RT) (I) wherein (HO_RT) is a hydrophobic reactive tail block, based on or formed exclusively from at least one monomeric hydrophobic building block as well as at least one bifunctional reactive monomeric acrylate or acrylamide building block; (HO) is a hydrophobic block, based on or formed exclusively from at least one monomeric hydrophobic building block; (HI) is a hydrophilic block, based on or formed exclusively from at least one monomeric hydrophilic acrylate building block.

Description

TITLE

SOIL RELEASE FORMULATIONS FOR TEXTILE APPLICATIONS

TECHNICAL FIELD

The present invention relates to textile fiber finishing fabric care formulations imparting improved soil release properties to the corresponding textile fiber product. The present invention furthermore relates to methods of making corresponding textile fiber finishing formulations and uses thereof.

PRIOR ART

Fabric, especially clothing, can become soiled by a range of substances including hydrophobic stains (grease, oil) but also hydrophilic stains. Avoiding lasting stain attachment as well as removal of soils and in particular oily stains is a continuing aim for textile manufacturing and for cleaning detergent manufacturers. Despite the use of many- different surfactants and combinations thereof, the products do not achieve complete removal in particular of greasy/oily stains independent of the textile basic material. A further requirement in the textile field is instant or at least rapid stain removal at the moment of the staining.

Treating the fabric during manufacturing of the fibres or the clothing so that stains and soils do not effectively bind to the fabric or fiber surface may on the one hand avoid attachment of the staining substances in the first place and further provide improved cleaning of fabrics. According to this approach, the staining substances do not bind or form strong physicochemical interactions with the fabric surface and can be more easily removed from the fabric surface upon laundering or another treatment process.

So one approach is to treat the fabric or rather the fiber surface during the manufacturing process to form the desired fabric or fiber surface exhibiting the desired stain repellency. With this approach, one drawback may be the reduced stain repellency over time due to exposure to adverse environmental effects and washing. A second approach may be to repeatedly treat the fabric or fiber surface during the laundering or other fabric treatment process. With this approach, the stain repellency characteristics may be renewed with each treatment or after a specific time, however repeated application leads to increased costs and treatment material waste. One state-of-the-art molecular system providing anti-staining properties to textile surfaces are perfluorinated hydrocarbon systems with for example 6 or 8 carbon atoms. The systems at the time provide for water repellency, oil repellency as well as soil release, i.e. ease of removal of oily stains. However, in particular for environmental reasons the perfluorinated hydrocarbon systems, in as far as not banned already, need to be replaced by other chemistries.

Development of improved deposition aids which provide for uniform application of stain repellency formulations are required.

DE 1719359 proposes a method for improving the soil-release properties of textiles. Acidic hydrophilic acrylate based fabric care formulations are described to impart soil release properties to fabrics, however at the same time to impart an undesired feel of stiffness. The document proposes to solve that problem by adding to such an acidic hydrophilic acrylate based fabric care formulation in a mixture long chain fatty acid compounds or the corresponding alcohols, thereby achieving anti-staining properties as well as soft feel. The effect is reduced if in addition to that known soft feel agents such as quaternary fatty acid esters or amino-functional siloxanes or common textile crosslinkers such as dimethylol ethylene urea (DMEU) or dimethylol dihydroxy ethylene urea (DMDHEU) are added. US-A-2006116495 discloses silicone-containing polymers having numerous uses which are prepared by polymerizing one or more ethylenically unsaturated monomers in the presence of a branched organopolysiloxane having at least one lipophilic branched siloxane portion and at least one optionally branched hydrophilic portion.

WO-A-03054284 discloses a perfluoroalkyl based copolymer comprising monomers copolymerized in the following percentages by weight: (a) from about 40% to about 75% of a monomer of formula I: Rf-CH2CH2-0C(0)-C(R)=CH2, (b) from about 15% to about 55% of a monomer of formula II: R2-0C(0)-C(R)=CH2, (c) from 1.5% to about 5% of a monomer of the formula III: H0-CH2CH2-0C(0)-C (R) =CH2, (d) from 1.5% to about 5% of a monomer of the formula IV: H-(0CH2CH2)m-0-C(0)-C(R)=CH2, (e) from 1% to about 3% of a monomer of the formula V: HO-CH2-NH-C(0)-C (R)=CH2, (f) from 0% to about to about 9.8% of vinylidene chloride, vinyl acetate, or a mixture thereof, (g) from 0% to about 2% of a blocked isocyanate, wherein Rf is a straight or branched-chain perfluoroalkyl group of from 2 to about 20 carbon atoms, each R is independently H or CH3, R2 is an alkyl chain from 2 to about 18 carbon atoms; and m is 2 to about 10.

US 5763022 provides a process for improving the resistance to solvents in finishing and stabilizing fiber materials with textile binders, wherein the textile binder used is an aqueous copolymer dispersion or a redispersible copolymer powder of acrylamide based copolymers, containing (a) one or more monomer units from the group consisting of vinyl esters of unbranched or branched carboxylic acids with 1 to 12 carbon atoms, esters of acrylic acid and methacrylic acid with unbranched or branched alcohols with 1 to 12 carbon atoms, vinyl aromatics, vinyl halides and alpha-olefins, and (b) 0.3 to 10 wt %, relative to the total weight of the copolymer, of one or more N-(alkoxymethyl)- acrylamides or N-(alkoxymethyl)methacrylamides with a C1-C6 alkyl residue, or mixtures of these N-(alkoxymethyl)-meth(acrylamides with N-methylolacrylamide and/or N- methylolmethacrylamide in a weight ratio of N-methylol compound to N-(alkoxymethyl) compound of at most 5:1. No soil release properties are disclosed.

JPS5040897 and correspondingly GB 1473362 disclose how cellulosic fibre products are rendered resistant to wet and dry creasing, shrinkage and surface abrasion, rendered soft to the touch and given increased tensile strength by treatment with a solution or dispersion of a filmforming glycidyl-containing thermoplastic random polymer, drying the product and then heating it to clear the oxirane bond of the glycidyl group. The polymer is a random copolymer of 1 to 55% of one or more monoethylenically unsaturated monomers containing a glycidyl group with one or more other ethylenically unsaturated monomers. The glycidyl monomers are glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl crotonate, dichloro glycidyl acrylate, vinyl glycidyl ether or other ester or ether. The other monomer is preferably 2-ethylhexyl acrylate but many other olefins, vinyl compounds and unsaturated acids, esters and amides are specified. The oxirane bond is cleared by heating in the presence of an acid catalyst to 120 to 190 C for 0.5 to 15 minutes, preferably whilst being pin centred 15% in the weft direction. No block copolymers are disclosed and no soil release properties.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide new fabric care formulations to impart anti-staining properties to fabrics, avoiding the use of perfluorinated hydrocarbon systems. Therefore the proposed systems are free from halogenated in particular perhalogenated building blocks, preferably free from perfluoro building blocks.

The proposed formulation systems shall be efficient as concerns the anti-staining, in the sense that the fabric gets less prone to get stained, and that once it is stained it is easy to remove the corresponding staining during the laundry process. The proposed formulations shall in addition to that be stable and easy to apply for the actual fabric treatment process, and also be stable for the storage, i.e. for the time between manufacturing and actual use. Furthermore, the active ingredient of the corresponding formulation to be deposited on the fibers shall be resistant to be removed during laundry cycles, so it shall have a lasting effect on the fabric and should not have to be renewed.

The present invention thus relates to a textile treatment formulation to impart anti-staining properties to fibers or garments. The proposed formulation contains an effective amount of a block-copolymer (I) or a mixture thereof, wherein the block-copolymer (I) has the following structure (and preferably consists only of these building blocks):

(HO)-(HI)-(HO_RT) (I)

In this block-copolymer structure the following definitions apply:

(HO) is a hydrophobic block, based on or formed exclusively from at least one monomeric hydrophobic building block. This block typically forms the innermost core of a resulting core-shell particle.

(HI) is a hydrophilic block, based on or formed exclusively from at least one monomeric hydrophilic acrylate building block. This block typically forms an intermediate water- swellable core layer of a resulting core-shell particle. The swellablitity is believed to contribute to the anti-soiling property imparted by the system: during the washing cycle the core-shell particle swells and releases the soling substances.

(HO_RT) is a hydrophobic reactive tail block, based on or formed exclusively from at least one monomeric hydrophobic building block as well as at least one bifunctional reactive monomeric acrylate or acrylamide building block. The reactive tail is adapted to either react with functional groups on the surface of the fiber, or to react with functional groups of other chemicals on the surface of the fiber. The attachment by way of the reactive tails can also be by way of electrostatic interaction, van der Waals interactions or hydrogen bonding instead of or in addition to the chemical bond. This block typically forms the outermost shell of a resulting core-shell particle.

As used herein the term "fabric care compositions" includes compositions and formulations designed for treating textiles and fabrics, such as, but not limited to, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions.

In the present context, the term "containing" means various components conjointly employed in the preparation of the formulation, so it does not exclude the presence of other chemicals in the formulation. Equally, in the present context, the terms "include", "includes" and "including" are meant to be non- limiting.

According to one possible embodiment the formulation is a dispersion of the block- copolymer (I) and water without additional constituents or just with a deposition aid, typically such a master formulation is then, before use, supplemented with additional ingredients for the actual application step to the fabric.

In the present context, the articles including "the", "a" and "an" when used in a claim or in the specification, are understood to mean one or more of what is claimed or described.

In the present context, the term "plurality" means more than one.

In the present context, the terms "fabric", "textile", and "cloth" as well as "garment" are used non-specifically and may refer to any type of flexible material consisting of a network of natural or artificial fibers, including natural, artificial, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, silk, hemp, flax, lyocell, rayon, jute, polyamide, modacrylic, olefmic, acrylic, or a mixture and/or blend thereof.

In the present context, the term "deposition aid" means a compound or composition that assists in deposition of a substance, in particular of the block-copolymer (I), typically as a core-shell particle, on a surface, such as the surface of a fabric or fiber during a treatment process. Deposition aids may allow for or at least assist complete and uniform deposition of the substance on the fabric surface.

In the present context, the expression "monomeric building block" refers to a monomer forming the corresponding block.

In the present context, the term "hydrophobic" means that the corresponding block has the tendency to mix with and/or contact alkanes, oils, fats, and greasy substances, this at least to an extent which is more pronounced than a block that is designated hydrophilic in the present context. It is therefore a block whose interactions with oil or other hydrophobic solvents substances are more thermodynamically favorable than their interactions with water and other polar substances.

In the present context, the term "hydrophilic" means that the corresponding block has the tendency to mix with and/or contact water and other polar substances, this at least to an extent which is more pronounced than a block that is designated hydrophobic in the present context. It is therefore a block whose interactions with water and other polar substances are more thermodynamically favorable than their interactions with oil or other hydrophobic solvents. Preferably the proposed block-copolymer (I) is free from halogen containing building blocks, in particular free from perhalogen building blocks and/or from siloxane or polysiloxane building blocks.

According to a first preferred embodiment, the bifunctional reactive monomeric acrylate or acrylamide building block in (HO_RT) is selected from the group consisting of N-alkylol acrylamide, epoxy-acrylate, or mixtures thereof. The alkyl group in the N-alkylol acrylamide is typically a linear saturated alkyl chain with 1 - 10, preferably 1 - 3 carbon atoms.

Preferably the bifunctional reactive monomeric acrylate or acrylamide building block in (HO_RT) is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, or mixtures thereof. To avoid release of formaldehyde the use of glycidyl based systems is preferred.

Most preferably it is selected to be glycidyl methacrylate alone or N-methylol methacrylamide alone, most preferably glycidyl methacrylate is used.

The average number of monomeric acrylate or acrylamide building blocks within (HO_RT) is preferably in the range of 1-20, more preferably in the range of 2-15.

According to yet another preferred embodiment the at least one monomeric hydrophobic building block in (HO_RT) is selected from at least one hydrophobic acrylate and/or hydrophobic vinylester monomer.

The at least one monomeric hydrophobic building block in (HO RT) can also be based on or formed exclusively from at least two different hydrophobic acrylate and/or hydrophobic vinylester monomers.

Preferably the weight ratio between the two different hydrophobic acrylate and/or hydrophobic vinylester monomers in (HO_RT) is in the range of 2:1 - 1 :2, preferably in the range of 1.25:1 - 1 : 1.25.

Further preferably the two different hydrophobic acrylate and/or hydrophobic vinylester monomers in (HO RT) differ in their hydrophobicity.

The monomeric hydrophobic building block in (FIO_RT) can be based on or formed exclusively from at least one hydrophobic acrylate and/or hydrophobic vinylester monomer as well as at least one more hydrophilic acrylate and/or more hydrophilic vinylester monomer.

The monomeric hydrophobic building block in (FIO_RT) can also be based on or formed exclusively from at least two different hydrophobic acrylate and/or hydrophobic vinylester monomers as well as at least one hydrophilic acrylate and/or hydrophilic vinylester monomer.

The at least one monomeric hydrophobic building block in (HO_RT) may also be preferably selected from alkyl acrylate and alkyl methacrylate monomers, wherein the alkyl chain is a saturated branched or linear alkyl group with 3-12 carbon atoms, preferably with 4-8 carbon atoms, most preferably with 6 carbon atoms, wherein preferably the at least one hydrophobic acrylate building block is selected as 2-ethylhexyl acrylate.

The at least one monomeric hydrophobic building block in (HO RT) can further be preferably a saturated branched, cyclic and/or linear alkyl vinyl ester, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 5-20 carbon atoms, preferably with 4-17 carbon atoms, most preferably with 7-12 carbon atoms, wherein preferably the at least one hydrophobic vinylester monomer is selected as vinylneodecanoat.

The at least one monomeric hydrophilic building block in (HO RT) is preferably selected from a hydrophilic acrylate and/or methacrylate, preferably as a hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 1-5 carbon atoms, preferably with 2-4 carbon atoms, wherein preferably the hydrophilic acrylate monomer is selected from the group consisting of: 2- hydroxyethyl acrylate, 2 -hydroxy ethyl methacrylate or a mixture thereof. Most preferably the hydrophilic acrylate is selected as 2 -hydroxy ethyl methacrylate.

Most preferably (HO_RT) is based on or formed exclusively from

one monomeric hydrophobic building block selected as saturated branched, cyclic and/or linear alkyl vinyl ester, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 5-20 carbon atoms, preferably with 4-17 carbon atoms, most preferably with 7-12 carbon atoms, preferably vinylneodecanoat, as well as one monomeric hydrophobic building block selected as alkyl acrylate and alkyl methacrylate, wherein the alkyl chain is a saturated branched or linear alkyl group with 3-12 carbon atoms, preferably with 4-8 carbon atoms, most preferably with 6 carbon atoms, in particular 2-ethylhexyl acrylate

as well as at least one bifunctional reactive monomeric acrylate or acrylamide building block selected as glycidyl methacrylate alone or N-methylol methacrylamide alone

In this case preferably but also generally the mass proportion of the sum of the monomeric hydrophobic building blocks to the bifunctional reactive monomeric acrylate or acrylamide building block can be in the range of 3:1 to 15:1, preferably 5:1 - 10:1, and/or the mass proportion of the two monomeric hydrophobic building blocks is in the range of 2: 1 - 1 :2, preferably 1.2:1 - 1 :1.2.

The weight ratio of the sum of the at least one monomeric hydrophobic building blocks and the sum of the at least one bifunctional monomeric acrylate or acrylamide building blocks in (HO R.T) can be in the range of 15: 1 - 2:1, preferably in the range of 10:1 - 5:1. The block (HO) can be based on or formed exclusively from at least one hydrophobic acrylate and/or hydrophobic vinylester monomer.

(HO) can be based on or formed exclusively from at least two different hydrophobic (meth)acrylate and/or hydrophobic vinylester monomers, and wherein further preferably the two different hydrophobic (meth)acrylate and/or hydrophobic vinylester monomers differ in their hydrophobicity.

Also (HO) can be based on or formed exclusively from at least one hydrophobic (meth)acrylate and/or hydrophobic vinylester monomer as well as at least one hydrophilic (meth)acrylate and/or hydrophilic vinylester monomer.

(HO) can also be based on or formed exclusively from at least two different hydrophobic (meth)acrylate and/or hydrophobic vinylester monomers, preferably differing in their hydrophobicity, as well as at least one hydrophilic (meth)acrylate and/or hydrophilic vinylester monomer.

The at least one hydrophobic acrylate monomer in (HO) is preferably selected from alkyl acrylate and alkyl methacrylate monomers, wherein the alkyl chain is a saturated branched or linear alkyl group with 3-12 carbon atoms, preferably with 4-8 carbon atoms, most preferably with 6 carbon atoms, wherein preferably the at least one hydrophobic acrylate building block is selected as 2-ethylhexyl acrylate.

The at least one hydrophobic vinylester monomer in (HO) is preferably a saturated branched, cyclic and/or linear alkyl vinyl ester, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 5-20 carbon atoms, preferably with 4-17 carbon atoms, most preferably with 7-12 carbon atoms, wherein preferably the at least one hydrophobic vinylester monomer is selected as vinylneodecanoat.

The at least one hydrophilic (meth)acrylate monomer in (HO) is preferably selected hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 1 -5 carbon atoms, preferably with 2-4 carbon atoms, wherein preferably the hydrophilic acrylate monomer is selected from the group consisting of: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or a mixture thereof, wherein preferably the hydrophilic acrylate is selected as 2-hydroxyethyl methacrylate.

The average number of monomeric building blocks within (HO) can be in the range of 2- 20, preferably in the range of 3-15.

(HO) is most preferably based on or formed exclusively from

at least two different hydrophobic acrylate and/or hydrophobic vinylester monomers, preferably differing in their hydrophobicity,

as well as at least one hydrophilic acrylate and/or hydrophilic vinylester monomer, and

wherein the mass proportion of the sum of the monomeric hydrophobic building blocks to the hydrophilic acrylate and/or hydrophilic vinylester monomer can be in the range of 5:1 to 1 :1, preferably 3:1 - 2:1, and/or the mass proportion of the two monomeric hydrophobic building blocks is in the range of 2: 1 - 1 :2, preferably 1.2: 1 - 1 : 1.2.

The block (HI) is preferably formed from at least one hydrophilic (meth)acrylate monomer selected to be hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 1-5 carbon atoms, preferably with 2-4 carbon atoms.

Preferably the hydrophilic (meth)acrylate monomer is selected from the group consisting of: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or a mixture thereof, wherein preferably the hydrophilic acrylate is selected, preferably exclusively, as 2-hydroxyethyl methacrylate.

The average number of monomeric building blocks within (HI) is preferably in the range of 2-20, more preferably in the range of 3-15.

The weight proportion of the blocks in the block-copolymer (I) is, according to a preferred embodiment, selected to be as follows

(HO) / (HI) is in the range of 1 :5 - 1 : 1 , preferably in the range of 1 :3 - 1 : 1.5, or in the range of 1 :2;

and/or (HO_RT) / (HI) is in the range of 1 :5— 1 : 1, preferably in the range of 1 :3 - 1 : 1.5, or in the range of 1 :2;

and/or (HO) / (HO_RT) is in the range of 1 :2 - 2:1 , preferably in the range of 1.5:1 - 1 :1.5, or in the range of 1 : 1. A particularly preferred embodiment of (I) is as follows:

(HO) is based exclusively on vinylneodecanoat, 2-ethylhexyl acrylate and 2-hydroxyethyl methacrylate, preferably in a weight proportion of in the range of 1 : 1 : 1 ;

(HI) is based exclusively on 2-hydroxyethyl methacrylate;

(HO RT) is based exclusively on vinylneodecanoat, 2-ethylhexyl acrylate and either glycidyl methacrylate alone or N-methylol methacrylamide alone,

wherein preferably the weight ratio of the blocks is according to the preceding paragraph. The block-copolymer (I) can be and typically is present in the formulation as a core shell particle, the (HO) block forming an innermost core, the (HI) block forming an intermediate, preferably water swellable shell and the (HO_RT) block forming an outer reactive shell.

The block-copolymer (I) can be present in the formulation as an emulsion or dispersion in water and at least partially embedded in a micellar structure, wherein the micellar structure is preferably formed by at least one surfactant, preferably formed by at least one of an alkylbenzene sulfonic acid, preferably dodecylbenzene sulfonic acid and/or an polyoxyethylene (EO) and/or polyoxypropylene (PO) non-ionic surfactant, preferably ethoxylated fatty systems such as alcohol iso-tridecyl alcohol 6 (EO) (which is an alpha- tridecyl-omega-hydroxy-poly(oxy-l,2-ethanediyl) with on average 6 oxy-l,2-ethanediyl blocks).

Furthermore, the present invention relates to a use of a formulation as detailed above or a treatment liquor comprising a formulation as detailed above for the coating of fibers and/or textiles, wherein preferably the fibers and/or textiles are based on cotton, hemp, flax, lyocell, rayon, jute, wool, polyester, polyamide, modacrylic, olefinic, acrylic, or a mixture and/or blend thereof, preferably cellulose based fibres such as cotton, in particular to impart a soil release effect.

Preferably before treatment with the formulation of the fibers and/or textiles, in particular in case of cotton, are treated with a softener formulation and/or cationic fixer formulation, preferably based on quaternary polyamine systems.

Also the invention relates to a method for treatment of fibers and/or textiles, wherein preferably the fibers and/or textiles are based on cotton, hemp, flax, lyocell, rayon, jute, wool, polyester, polyamide, modacrylic, olefinic, acrylic, or a mixture and/or blend thereof, preferably cellulose based fibres such as cotton, with a formulation according to any of claims 1-11, or with a treatment liquor comprising a formulation as given above, in particular to impart a soil release effect.

The fibers and/or textiles can be treated by the formulation or using a treatment liquor based on such a formulation during a time span of 10 to 40 minutes, preferably in the range of 15 to 30 minutes, at a temperature in the range of 20 to 60 °C, preferably at a temperature in the range of 30 to 50 °C or by forced application.

Subsequent to the treatment with the formulation the fibers and/or textiles are typically subjected to at least one of the following post-treatments after drying: compacting, calendaring, decatizing, raising, emerizing, condensation of crosslinkers or selfcrosslinking polymers.

Last but not least the invention relates to a fiber or textile treated with such a formulation or resulting from a method as given above, in particular garment, article of clothing, including underwear, outerwear, protective clothing, sports clothing, in particular based on cellulose fibres.

Also, the invention relates to a method of making the block-copolymer (I) of the formulation as given above, wherein

in a first step, in an emulsion polymerization in water, in the presence of at least one surfactant, preferably formed by at least one of an alkylbenzene sulfonic acid, preferably dodecylbenzene sulfonic acid and/or an polyoxyethylene (EO) and/or polyoxypropylene (PO) non-ionic surfactant, preferably ethoxylated or propoxylated fatty alcohol systems, including iso-tridecyl alcohol 6 (EO) at least one hydrophobic monomer for the formation of the (HO) block is polymerized, in a second subsequent step, if need be after addition of catalyst and/or activator, in an emulsion polymerization, the monomer forming the (HI) block, in one or several repeated steps, is added to form a structure of the type:

(HI)-(HO)

in a third subsequent step, in an emulsion polymerization, monomers forming the (HO_RT) are added.

If need be, this can be followed by addition of catalyst and/or activator and after- polymerization, e.g. at elevated temperature.

Further embodiments of the invention are laid down in the dependent claims.

DESCRIPTION OF PREFERRED EMBODIMENTS

Preferred embodiments of the invention are described in the following with reference to the examples, which are for the purpose of illustrating the present preferred embodiments of the invention and not for the purpose of limiting the same.

EXAMPLE 1: Oily Soil Release Polymer, MMA based:

The aim is to synthesize a soil release polymer having good results especially with hydrophobic (oily) stains on cellulose fibers. This is achieved by a three-step sequential copolymerization.

Laboratory Equipment:

One liter four-necked round bottom glass flask with parallel side necks; 200 ml dropping funnel with pressure compensation; KPG-stirrer with moveable blades with KPG-bearing sleeve; Flexible glass agitator coupling; Electronic laboratory stirrer; Thermometer with scaling -50 up to +l50°C; Thermometer adapter; 2 glass plugs; Glass funnel; Various 100 and 250 ml glass beakers; Various pipettes; Heating device.

List of Ingredients:

Dodecylbenzene sulfonic acid, sodium salt

Iso-tridecyl alcohol with 6EO (e.g. Lutensol TO 6, BASF SE)

Demineralized water

CSL (Caustic soda 50% in water)

Ammonium persulfate, 10% solution in water

Bruggolite FF6 M (Briiggemann KG), reducing agent, containing ascorbic acid (AA), sodium formaldehyde sulfoxylate (SFS) along with t-butyl hydroperoxide (TBHP), 10% solution in water

2EHA (2-Ethylhexyl acrylate)

VeoVa 10 (Vinyl ester of versatic acid, neodecanoic acid vinyl ester), available from Hexion

HEMA (2-Hydroxyethyl methacrylate)

Visiomer N-MMAA (Evonik AG; N-Methylol methacrylamide)

Synthesis:

First step: Fill the four-necked glass flask with 200 g (= 40%) demineralized water. Add 30 g (= 6%) sodium salt of dodecylbenzene sulfonic acid, 7.5 g (= 1.5%) iso-tridecyl alcohol 6 EO and 62.5 g (= 12.5%) demineralized water.

Close the flask. Heat to 60 - 65°C. The suspension becomes a clear solution at about 50°C Add via the dropping funnel

15 g (= 3%) VeoVa 10 (MW: 198.31) 15 g (= 3%) 2EHA (MW: 184.28)

15 g (= 3%) HEM A (MW: 130.14)

Stir for 20 minutes whilst maintaining 60 - 65°C.

Then add drop-by-drop: 5 g (= 1%) Ammonium persulfate, 10% solution in water, followed by 2.5 g = 0.5%) Bruggolite FF6 M, 10% solution in water

Stir for 60 minutes whilst keeping the temperature between 55 and 60°C. The emulsion becomes clear. The reaction enthalpy keeps the temperature from dropping too fast, but does not lead to a temperature increase.)

Second step : Add via the dropping funnel over 20 min: 90 g (= 18%) FIEMA (MW: 130.14)

Stir for 20 minutes whilst keeping the temperature between 55 and 65°C.

Check pH and correct to pH 5.5 - 6.0 with CSL (usually 25 drops for pH6)

Stir for 60 minutes whilst keeping the temperature between 55 and 65°C.

The emulsion becomes turbid. The reaction enthalpy keeps the temperature from dropping too fast, but does not lead to a temperature increase.

Third step·. Add via the dropping funnel over 20 min

20 g (= 4%) VeoVa 10 (MW: 198.31)

20 g (= 4%) 2EHA (MW: 184.28)

5 g (= 1%) Visiomer N-MMAA (MW: 115.10)

Stir for 90 minutes whilst keeping the temperature between 55 and 66°C.

After-polymerization : Then add drop-by-drop: 2.5 g (= 0.5%) Ammonium persulfate, 10% solution in water, followed by: 2.5 g (= 0.5%) Bruggolite FF6 M, 10% solution in water. Stir for 90 minutes; enthalpy will let the temperature rise by about 5°C; let the temperature drop to 50 and maintain between 45 and 55°C. When reaching 50°C check pFI to be 5.5 - 6.0; if necessary, correct by adding slowly CSL. Then check final pH (target 5.5 - 6.0) and dry substance (target 37 +/- 2%); stir without heating until 30°C is reached;

Stir for another 20 minutes whilst letting the temperature fall. The pH should be maintained; at too low a pH the product tends to self-crosslink during storage; at too high a pH it may turn brown. Discharge. Yield: 500g Product

EXAMPLE 2: Oily Soil Release Polymer, GMA based:

Laboratory Equipment:

As in Example 1. List of Ingredients:

As in example 1, but instead of N-MMAA the system GMA (Glycidyl methacrylate) is used.

Synthesis:

First step Fill the four-necked glass flask with 200 g (= 40%) demineralized water. Add 30 g (= 6%) sodium salt of dodecylbenzene sulfonic acid, 7.5 g (= 1.5%) iso-tridecyl alcohol 6 EO and 62.5 g (= 12.5%) demineralized water.

15 g (- 3%) VeoVa 10 (MW: 198.31)

15 g (= 3%) 2EHA (MW: 184.28)

15 g (= 3%) HEM A (MW: 130.14)

Stir for 20 minutes whilst maintaining 60 - 65°C.

Then add drop-by-drop: 7.5 g (= 1.5%) Ammonium persulfate, 10% solution in water, followed by 5.0 g = 1.0%) Bruggolite FF6 M, 10% solution in water

Second step·. Add via the dropping funnel over 20 min: 90 g (= 18%) HEMA (MW: 130.14)

Stir for 20 minutes whilst keeping the temperature between 55 and 65°C.

Check pH and correct to pH 5.5 - 6.5 with CSL (usually 25 drops for pH6)

Stir for 60 minutes whilst keeping the temperature between 55 and 65°C.

The emulsion becomes turbid. The reaction enthalpy keeps the temperature front dropping too fast, but does not lead to a temperature increase.

Third step : Add via the dropping funnel over 20 min

20 g (= 4%) VeoVa 10 (MW: 198.31 )

20 g (= 4%) 2EHA (MW: 184.28)

5 g (= l%) GMA (MW: 142.15)

Stir for 90 minutes whilst keeping the temperature between 55 and 66°C.

After-polymerization: Then add drop-by-drop: 2.5 g (= 0.5%) Ammonium persulfate, 10% solution in water, followed by: 2.5 g (= 0.5%) Bruggolite FF6 M, 10% solution in water. Stir for 90 minutes; enthalpy will let the temperature rise by about 5°C; let the temperature drop to 50 and maintain between 45 and 55°C. When reaching 50°C check pH to be 5.5 - 6.0; if necessary, correct by adding slowly CSL. Then check final pH (target 5.5 - 6.0) and dry substance (target 37 +/- 2%); stir without heating until 30°C is reached;

Stir for another 20 minutes whilst letting the temperature fall. The pH should be maintained; at too low a pH the product tends to self-crosslink during storage; at too high a pH it may turn brown. Discharge. Yield: 500g Product.

APPLICATION RECIPE 1:

A 97% cotton/3 % elastomer twill is padded with

80 g/1 product as per EXAMPLE 1

10 g/1 Magnesium chloride hexahydrate

2 g/1 Citric acid 50% solution

1 g/1 non-ionic rapid wetting agent

Liquor add-on (pick-up) of 60%.

The fabric is dried for 2 minutes at 120°C and cured for 5 minutes at 150°C

APPLICATION RECIPE 2:

A 100% cotton interlock is padded with

60 g/1 product as per EXAMPLE 2

2 g/1 Citric acid 50% solution

1 g/l non-ionic rapid wetting agent

Liquor add-on (pick-up) of 80%.

The fabric is dried for 2 minutes at 120°C and cured for 1 minute at 170°C

APPLICATION RECIPE 3:

A 100% cotton shirting fabric is padded with

100 g/l product as per EXAMPLE 1

100 g/l Low formaldehyde modified DMDHEU resin

30 g/1 Magnesium chloride hexahydrate

2 g/1 Citric acid 50% solution

1 g/1 non-ionic rapid wetting agent

Liquor add-on (pick-up) of 60%.

The fabric is dried for 2 minutes at l20°C and cured for 5 minutes at l50°C APPLICATION RECIPE 4 (reference):

A 97% cotton/3 % elastomer twill is padded with

50 g/1 C6 Perfluorocarbon resins (HeiQ Barrier STAR)

2 g/1 Citric acid 50% solution

1 g/1 non-ionic rapid wetting agent

Liquor add-on (pick-up) of 60%.

The fabric is dried for 2 minutes at l20°C and cured for 5 minutes at l50°C

APPLICATION RECIPE 5 (reference):

A 100% cotton interlock is padded with

50 g/l C6 Perfluorocarbon resins (HeiQ Barrier STAR)

2 g/1 Citric acid 50% solution

1 g/1 non-ionic rapid wetting agent

Liquor add-on (pick-up) of 80%.

The fabric is dried for 2 minutes at l20°C and cured for 1 minute at 170°C

APPLICATION RECIPE 6 (reference):

A 100% cotton shirting fabric is padded with

70 g/1 C6 Perfluorocarbon resins (HeiQ Barrier STAR)

100 g/l Low formaldehyde modified DMDHEU resin

30 g/l Magnesium chloride hexahydrate

2 g/1 Citric acid 50% solution

1 g/l non-ionic rapid wetting agent

Liquor add-on (pick-up) of 60%.

The fabric is dried for 2 minutes at l20°C and cured for 5 minutes at l50°C

APPLICATION RECIPE 7 (reference):

A 97% cotton/3 % elastomer twill is padded with

60 g/l Self-crosslinking acrylic ester copolymer

10 g/1 Magnesium chloride hexahydrate

2 g/1 Citric acid 50% solution

1 g/1 non-ionic rapid wetting agent Liquor add-on (pick-up) of 60%.

The fabric is dried for 2 minutes at 120°C and cured for 5 minutes at 150°C

APPLICATION RECIPE 8 (reference):

A 100% cotton interlock is padded with

20 g/l Amino-modified polysiloxane textile softener

2 g/l Citric acid 50% solution

1 g/l non-ionic rapid wetting agent

Liquor add-on (pick-up) of 80%.

The fabric is dried for 2 minutes at 120°C and cured for 1 minute at 170°C

APPLICATION RECIPE 9 (reference):

A 100% cotton shirting fabric is padded with

20 g/l Amino-modified polysiloxane textile softener

130 g/l Low formaldehyde modified DMDHEU resin

30 g/l Magnesium chloride hexahydrate

2 g/l Citric acid 50% solution

1 g/l non-ionic rapid wetting agent

Liquor add-on (pick-up) of 60%.

The fabric is dried for 2 minutes at l20°C and cured for 5 minutes at l50°C

DOMESTIC WASHING of the finished textiles:

The fabrics finished with the application recipes 1 to 9 were divided into 4 parts, one part was left as is, one part subjected to 1 domestic laundry operation ISO 6330 4N and tumble dried, one part subjected to 10 domestic laundry operations ISO 6330 4N and tumble dried, and one part subjected to 30 domestic laundry operations ISO 6330 4N and tumble dried.

SOIL-RELEASE TESTING as per AATCC TM 130-2010:

The textile samples were tested for soil-release property by carrying out the AATCC (American Association of Textile Chemists and Colorists) Test Method 130-2010; i.e. they were stained with corn (maize) oil, the stain squeezed into the textile by placing a defined weight for a defined time onto it, and then the stained textile swatches were subjected to the washing process III of the said test method. After air drying the samples were evaluated using the scale of the AATCC TM 130-2010.

Stain release ratings were determined by placing the stained, washed, and dried fabric flat in the center of a non-glare blacktop table with one edge of the table touching a Stain Release Replica (available from the AATCC). The fabric was viewed from a distance of ca.. 75 cm and the residual stain was compared to the Stain Release Replica to the nearest 0.5 rating. Ratings are given from 1 (minimum) to 5 (maximum). In the United States, a normally accepted level of stain release is a rating of 3.

TEST RESULTS (AATCC TM 130-2010 Ratings)

LIST OF REFERENCE SIGNS

CSL caustic soda HEMA 2-hydroxyethyl methacrylate

DMEU dimethylol ethylene urea HI hydrophilic block

DMDHEU dimethylol dihydroxy HO hydrophobic block

ethylene urea VeoVa 10 HO RT hydrophobic reactive tail Vinyl ester of versatic block

acid, neodecanoic acid vinyl PFOA perfluororoctanoic acid ester PO polyoxypropylene

EO polyoxyethylene RT reactive tail

GMA glycidyl methacrylate SR soil release

2EHA 2-ethylhexylactrylate

Claims

1. Textile treatment formulation to lastingly impart anti-staining properties to fibers or garments, in particular to cotton or cotton based fibers or garments, said formulation containing an effective amount of a block-copolymer (I) or a mixture thereof, wherein the block-copolymer (I) comprises at least one or a plurality of blocks of the following structure or consists of the following structure:

(HO)-(HI)-(HO_RT) (I) wherein

(HO_RT) is a hydrophobic reactive tail block, based on or formed exclusively from at least one monomeric hydrophobic building block as well as at least one bifunctional reactive monomeric acrylate or acrylamide building block;

(HO) is a hydrophobic block, based on or formed exclusively from at least one monomeric hydrophobic building block;

(HI) is a hydrophilic block, based on or formed exclusively from at least one monomeric hydrophilic acrylate building block.

2. Formulation according to claim 1 , wherein

the bifunctional reactive monomeric acrylate or acrylamide building block in (HO_RT) is selected from the group consisting of N-alkylol acrylamide, epoxyacrylate, or mixtures thereof, wherein the alkyl group in the N-alkylol acrylamide is a linear saturated alkyl chain with 1 - 10, preferably 1 - 3 carbon atoms, wherein preferably the bifunctional reactive monomeric acrylate or acrylamide building block in (HO_RT) is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, or mixtures thereof, wherein it is preferably selected to be glycidyl methacrylate alone or N-methylol methacrylamide alone;

and/or wherein the average number of monomeric acrylate or acrylamide building blocks within (HO_RT) is in the range of 1-20, preferably in the range of 2-15.

3. Formulation according to any of the preceding claims, wherein

the at least one monomeric hydrophobic building block in (HO_RT) is selected from at least one hydrophobic acrylate and/or hydrophobic vinylester monomer, and/or wherein the at least one monomeric hydrophobic building block in (HO_RT) is based on or formed exclusively from at least two different hydrophobic acrylate and/or hydrophobic vinylester monomers, wherein preferably the weight ratio between the two different hydrophobic acrylate and/or hydrophobic vinylester monomers in (HO_RT) is in the range of 2:1 - 1 :2, preferably in the range of 1.25: 1 - 1 :1.25, and wherein further preferably the two different hydrophobic acrylate and/or hydrophobic vinylester monomers differ in their hydrophobicity,

and/or wherein the monomeric hydrophobic building block in (HO_RT) is based on or formed exclusively from at least one hydrophobic acrylate and/or hydrophobic vinylester monomer as well as at least one more hydrophilic acrylate and/or more hydrophilic vinylester monomer,

and/or wherein the monomeric hydrophobic building block in (HO RT) is based on or formed exclusively from at least two different hydrophobic acrylate and/or hydrophobic vinylester monomers as well as at least one hydrophilic acrylate and/or hydrophilic vinylester monomer,

and/or wherein the at least one monomeric hydrophobic building block in (HO_RT) is preferably selected from alkyl acrylate and alkyl methacrylate monomers, wherein the alkyl chain is a saturated branched or linear alkyl group with 3-12 carbon atoms, preferably with 4-8 carbon atoms, most preferably with 6 carbon atoms, wherein preferably the at least one hydrophobic acrylate building block is selected as 2-ethylhexyl acrylate,

and/or wherein the at least one monomeric hydrophobic building block in (HO_RT) is preferably a saturated branched, cyclic and/or linear alkyl vinyl ester, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 5-20 carbon atoms, preferably with 4-17 carbon atoms, most preferably with 7-12 carbon atoms, wherein preferably the at least one hydrophobic vinylester monomer is selected as vinylneodecanoat,

and/or wherein the at least one monomeric hydrophilic building block in (HO_RT) is preferably selected as an acrylate, preferably as a hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 1-5 carbon atoms, preferably with 2-4 carbon atoms, wherein preferably the hydrophilic acrylate monomer is selected from the group consisting of: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or a mixture thereof, wherein preferably the hydrophilic acrylate is selected as 2-hydroxyethyl methacrylate,

and/or wherein most preferably (HO_RT) is based on or formed exclusively from one monomeric hydrophobic building block selected as saturated branched, cyclic and/or linear alkyl vinyl ester, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 5-20 carbon atoms, preferably with 4-17 carbon atoms, most preferably with 7-12 carbon atoms, preferably vinylneodecanoat,

as well as one monomeric hydrophobic building block selected as alkyl acrylate and alkyl methacrylate, wherein the alkyl chain is a saturated branched or linear alkyl group with 3-12 carbon atoms, preferably with 4-8 carbon atoms, most preferably with 6 carbon atoms, in particular 2- ethylhexyl acrylate

as well as at least one bifunctional reactive monomeric acrylate or acrylamide building block selected as glycidyl methacrylate alone or N- methylol methacrylamide alone

wherein preferably the mass proportion of the sum of the monomeric hydrophobic building blocks to the bifunctional reactive monomeric acrylate or acrylamide building block is in the range of 3: 1 to 15: 1, preferably 5:1 - 10:1, and/or the mass proportion of the two monomeric hydrophobic building blocks is in the range of 2: 1 - 1 :2, preferably 1.2:1 - 1 :1.2.

4. Formulation according to any of the preceding claims, wherein

the weight ratio of the sum of the at least one monomeric hydrophobic building blocks and the sum of the at least one bifunctional monomeric acrylate or acrylamide building blocks in (HO_RT) is in the range of 15: 1 - 2: 1, preferably in the range of 10:1 - 5:1.

5. Formulation according to any of the preceding claims, wherein

(HO) based on or formed exclusively from at least one hydrophobic acrylate and/or hydrophobic vinylester monomer,

and/or wherein (HO) is based on or formed exclusively from at least two different hydrophobic acrylate and/or hydrophobic vinylester monomers, and wherein further preferably the two different hydrophobic acrylate and/or hydrophobic vinylester monomers differ in their hydrophobicity,

and/or wherein (HO) is based on or formed exclusively from at least one hydrophobic acrylate and/or hydrophobic vinylester monomer as well as at least one hydrophilic acrylate and/or hydrophilic vinylester monomer,

and/or wherein (HO) is based on or formed exclusively from at least two different hydrophobic acrylate and/or hydrophobic vinylester monomers, preferably differing in their hydrophobicity, as well as at least one hydrophilic acrylate and/or hydrophilic vinylester monomer,

wherein the at least one hydrophobic acrylate monomer in (HO) is preferably selected from alkyl acrylate and alkyl methacrylate monomers, wherein the alkyl chain is a saturated branched or linear alkyl group with 3-12 carbon atoms, preferably with 4-8 carbon atoms, most preferably with 6 carbon atoms, wherein preferably the at least one hydrophobic acrylate building block is selected as 2- ethylhexyl acrylate,

and/or wherein the at least one hydrophobic vinylester monomer in (HO) is a saturated branched, cyclic and/or linear alkyl vinyl ester, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 5-20 carbon atoms, preferably with 4-17 carbon atoms, most preferably with 7-12 carbon atoms, wherein preferably the at least one hydrophobic vinylester monomer is selected as vinylneodecanoat,

and/or wherein at least one hydrophilic acrylate monomer in (HO) is selected as an acrylate, preferably as hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 1-5 carbon atoms, preferably with 2-4 carbon atoms, wherein preferably the hydrophilic acrylate monomer is selected from the group consisting of: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or a mixture thereof, wherein preferably the hydrophilic acrylate is selected as 2-hydroxyethyl methacrylate,

and/or wherein the average number of monomeric building blocks within (HO) is in the range of 2-20, preferably in the range of 3-15.

6. Formulation according to claim 5, wherein (HO) is based on or formed exclusively from

wherein the mass proportion of the sum of the monomeric hydrophobic building blocks to the hydrophilic acrylate and/or hydrophilic vinylester monomer is in the range of 5: 1 to 1 :1, preferably 3:1 - 2: 1, and/or the mass proportion of the two monomeric hydrophobic building blocks is in the range of 2:1 - 1 :2, preferably 1.2: 1 - 1 :1.2.

7. Formulation according to any of the preceding claims, wherein

(HI) is formed from at least one hydrophilic acrylate monomer selected to be a hydrophilic acrylate, preferably hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate, wherein the alkyl chain is a saturated branched, cyclic or linear alkyl group with 1-5 carbon atoms, preferably with 2-4 carbon atoms, wherein preferably the hydrophilic acrylate monomer is selected from the group consisting of: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or a mixture thereof, wherein preferably the hydrophilic acrylate is selected, preferably exclusively, as 2-hydroxyethyl methacrylate,

and/or wherein the average number of monomeric building blocks within (HI) is in the range of 2-20, preferably in the range of 3-15.

8. Formulation according to any of the preceding claims, wherein the weight proportion of the blocks in the block-copolymer (I) is selected to be

(HO) / (HI) is in the range of 1 :5— 1 :1 , preferably in the range of 1 :3 - 1 : 1.5, or in the range of 1 :2;

and/or (HO_RT) / (HI) is in the range of 1:5 - 1 :1, preferably in the range of 1 :3 - 1 : 1.5, or in the range of 1 :2;

and/or (HO) / (HOJR.T) is in the range of 1 :2 - 2: 1, preferably in the range of

1.5:1 - 1 : 1.5, or in the range of 1 :1.

9. Formulation according to any of the preceding claims, wherein

(HO) is based exclusively on vinylneodecanoat, 2-ethylhexyl acrylate and 2- hydroxyethyl methacrylate, preferably in a weight proportion of in the range of 1 : 1 : 1 ;

(HI) is based exclusively on 2-hydroxyethyl methacrylate;

(HO_RT) is based exclusively on vinylneodecanoat, 2-ethylhexyl acrylate and either glycidyl methacrylate alone or N-methylol methacrylamide alone, wherein preferably the weight ratio of the blocks is according to claim 8.

10. Formulation according to any of the preceding claims, wherein block-copolymer (I) is present in the formulation as a core shell particle, the (HO) block forming an innermost core, the (HI) block forming an intermediate, preferably water swellable shell and the (HO_RT) block forming an outer reactive shell.

11. Formulation according to any of the preceding claims, wherein block-copolymer (I) is present in the formulation as an emulsion or dispersion in water and at least partially embedded in a micellar structure, wherein the micellar structure is preferably formed by at least one surfactant, preferably formed by at least one of an alkylbenzene sulfonic acid, preferably dodecylbenzene sulfonic acid and an polyoxyethylene (EO) and/or polyoxypropylene (PO) non-ionic surfactant, preferably iso-tridecyl alcohol 6 (EO).

12. Use of a formulation according to any of the preceding claims or a treatment liquor comprising a formulation according to any of the preceding claims for the coating of fibers and/or textiles, wherein preferably the fibers and/or textiles are based on cotton, hemp, flax, lyocell, rayon, jute, wool, polyester, polyamide, modacrylic, olefmic, acrylic, or a mixture and/or blend thereof, preferably cellulose based fibres such as cotton, in particular to impart a soil release effect wherein preferably before treatment with the formulation of the fibers and/or textiles, in particular in case of cotton, are treated with a softener formulation and/or cationic fixer formulation, preferably based on quaternary polyamine systems.

13. Method for treatment of fibers and/or textiles, wherein preferably the fibers and/or textiles are based on cotton, hemp, flax, lyocell, rayon, jute, wool, polyester, polyamide, modacrylic, olefmic, acrylic, or a mixture and/or blend thereof, , preferably cellulose based fibres such as cotton, with a formulation according to any of claims 1-11, or with a treatment liquor comprising a formulation according to any of the preceding claims 1 - 1 1 , in particular to impart a soil release effect wherein preferably the fibers and/or textiles are treated by the formulation according to any of claims 1-1 1 or using a treatment liquor based on such a formulation according to any of claims 1-11 during a time span of 10 to 40 minutes, preferably in the range of 15 to 30 minutes, at a temperature in the range of 20 to 60 °C, preferably at a temperature in the range of 30 to 50 °C or by forced application

wherein further preferably subsequent to the treatment with the formulation according to any of claims 1-11 the fibers and/or textiles are subjected to at least one of the following post-treatments after drying: compacting, calendaring, decatizing, raising, emerizing, condensation of crosslinkers or self-crosslinking polymers.

14. Fiber or textile treated with a formulation according to any of claims 1-11 or resulting from a method according to claim 13, in particular garment, article of clothing, including underwear, outerwear, protective clothing, sports clothing, in particular based on cellulose fibres.

15. Method of making the block-copolymer (I) of the formulation according to any of claims 1-1 1, wherein

in a first step, in an emulsion polymerization in water, in the presence of at least one surfactant, preferably formed by at least one of an alkylbenzene sulfonic acid, preferably dodecylbenzene sulfonic acid and an polyoxyethylene (EO) and/or polyoxypropylene (PO) non-ionic surfactant, preferably iso-tridecyl alcohol 6 (EO) at least one hydrophobic monomer for the formation of the (HO) block is polymerized, in a second subsequent step, if need be after addition of catalyst and/or activator, in an emulsion polymerization, the monomer forming the (HI) block, in one or several repeated steps, is added to form a structure of the type:

(HI)-(HO)

in a third subsequent step, in an emulsion polymerization, monomers forming the (HO RT) are added,

if need be followed by addition of catalyst and/or activator and after polymerization.