EP3638840A1

EP3638840A1 - Composition and use thereof for finishing fibres and textiles

Info

Publication number: EP3638840A1
Application number: EP18729449.1A
Authority: EP
Inventors: Johann HEIMGREITER; Rainer Wilhelm BRAUN; Gunther Duschek
Original assignee: Rudolf GmbH
Current assignee: Rudolf GmbH
Priority date: 2017-06-14
Filing date: 2018-06-13
Publication date: 2020-04-22
Anticipated expiration: 2038-06-13
Also published as: EP3638840C0; EP3638840B1; KR102574332B1; JP2020523426A; KR20200016865A; WO2018229111A1; US20200216778A1

Abstract

The invention relates to compositions comprising at least one cationic polyelectrolyte, at least one anionic compound and at least one non-ionic surfactant as well as to their use for finishing fibres and textiles.

Description

Composition and use thereof for finishing fibers and

textiles

description

The present invention relates to compositions comprising at least one cationic polyelectrolyte, at least one anionic compound and at least one nonionic surfactant and their use for finishing fibers and textiles.

Ever-increasing demands are placed on textiles today. Depending on the field of application, textiles are to be used e.g. hydrophobic, hydrophilic, flame-retardant, antistatic, wrinkle resistant, olabweisend, weatherproof, etc. These requirements can no longer be satisfied by the mere selection of a suitable fiber material. In the art, therefore, the surface of the fibers and / or textiles is increasingly being chemically modified, i. equipped to tailor the property profile of the textile according to the area of application. Textiles are usually made of fibers, with between natural fibers, i. Fibers made without chemical alteration from vegetable fibers, e.g. Cotton, or animal fibers, e.g. Wool or silk, won, and artificial fibers is distinguished. Unlike natural fibers, most synthetic fibers have significant advantages:

- less creasing

- high tear and abrasion resistance

- High variability of the properties by choice of monomers

- low weight

- low production costs Therefore, more synthetic fibers than natural fibers are currently being processed into textiles worldwide. However, despite the advantages, synthetic fibers also have disadvantages. Thus, synthetic fibers are increasingly electrostatically charged to natural fibers. Also, the synthetic fibers hardly absorb moisture, which has a negative effect on the wearing comfort. Textiles made of synthetic fibers can therefore not be used in certain areas at all or only to a limited extent, eg by combination with natural fibers.

In order to impart antistatic and / or hydrophilizing properties to synthetic fibers, so-called finishing agents can be used which are applied to the surface of the fibers or textiles. However, it is usually difficult to machine-fix the finishing agents to synthetic fibers, as synthetic fibers have few or no functional groups which can be used in the finish, e.g. by covalent, ionic or v.d.Waals- interactions permanently bind to the fiber or textile. To solve the problem, in most cases finishing agents are used which are self-crosslinking or can be crosslinked by another component. While such finishing agents usually have higher washing permanence, the textile feel of such finished textiles is unsatisfactory. In addition, the crosslinking reaction is usually carried out at higher temperatures, e.g. at 150 ° C, takes place. Such reaction conditions are not suitable for all fibers and can lead to undesirable yellowing, chemical degradation reactions and changes in shape of fiber and / or textile. Also, for health reasons, crosslinkable finishing agents are objectionable because the functional groups of the crosslinking agents, e.g. Epoxy, chloro hydroxyl or (blocked) isocyanate groups, which are suspected of being hazardous or even toxic. After all, the high energy consumption for the equipment is ecologically questionable.

Alternatively, equipment with complexes of cationic and anionic preparations is proposed to achieve appropriate washing permanence on a fiber or textile. For this purpose, usually a two-stage Process in which cationic and anionic components are applied sequentially.

EP 0 603 987 A1 describes a two-stage process in which a layer of cations and anions is applied successively to a substrate. The best washing permanence is achieved at a stoichiometric ratio between anions and cations, under which circumstances the hydrophilicity is insufficient. Although the hydrophilicity can be improved by varying the charge ratio between anions and cations, the wash permanence is adversely affected to the same extent. Acceptable hydrophilic properties with acceptable wash permanence are not achieved by the systems described.

In WO 2006/015080 A1 substrates are alternately cationic and anionic. In order to avoid deposits in the individual baths, one washing step takes place between the steps. Disadvantage of this method is that the polymers do not grow quantitatively, so that form precipitations in the liquor, which deposit on the fibers or textiles and thereby cause stains. The washing step also involves a great deal of extra work and product loss.

In US Pat. No. 6,060,410 B, a solution of a strongly substoichiometric ratio of cationic and anionic molecules is applied to a substrate. The still free ionic groups are mixed in a second bath with an oppositely ionic hydrophobing component.

US 5,208,111 B and US 2004/0185284 A1 also propose two-stage processes for the formation of complexes. The described two-stage processes are associated with a high production cost, at the same time it is difficult to ensure process stability, since the formation of insoluble complexes in the fleet the risk of unwanted deposits on fiber or textile. Water-insoluble cation-anion complexes can also be used as solids. For this purpose, the complexes are usually precipitated in aqueous systems as ion pairs and then separated, dried and / or granulated. The products can be used in plastic moldings or other non-aqueous formulations. For aqueous media equipment, these dried, water-insoluble complexes are not suitable because they are not finely dispersed to avoid deposits and stains.

No. 6,596,678 B2 describes a powdered detergent composition with a polyelectrolyte complex of cationic and anionic polymers. The polyelectrolyte complex is present in the wash liquor as a particle which deposits on the textiles to be cleaned and protects them during the washing process. After rinsing, the complex is washed out again.

In WO 201 1/131728 A1, an anion-cation complex precipitated in water is dried after filtration and used as additive in plastic moldings.

The above-described anion-cation complexes are all not suitable for finishing textiles, since homogeneous application to the fiber or textile is not possible or even can cause stains on the textile.

No. 3,622,378 B describes mixtures of anionic and cationic surfactants and an amphoteric surfactant. The complexes precipitate as the mixture is diluted. Moreover, the treated fibers and textiles do not have the desired wash permanence.

DE 19 852 584 A1 and US Pat. No. 6,060,410 B describe aqueous dispersions of cation-anion complexes. The dispersions are mechanically homogenized, for example by ultrasound. However, the fleet is only metastable and has a strong tendency to agglomerate. Thus, the fleet is limited suitable for use as equipment, also because there is a risk that it comes to deposits and stains on the textile to be equipped.

EP 0 603 987 B1 relates to a permanent hydrophilic-cationic surface coating. The surface to be coated is dipped in an aqueous solution of a cationic surfactant and / or polymer. To form the ion complex, an anionic surfactant and / or polymer is applied to the surface. Alternatively, a dispersion of the anion-cation complex is proposed for the coating of filters. For the coating of fibers or textiles, the ion complex described is not suitable, since it is not possible to produce sufficiently stable liquors.

In summary, the prior art finishing agents have the following disadvantages:

- complex multi-step processes in the application

- handle hardening

- thermal yellowing

- Use of physiologically questionable starting materials

- lack of washing permanence

- Risk of staining due to uncontrolled deposits

Also, it has not yet been possible to provide an aqueous product with which a textile or a fiber permanently antistatic and hydrophilic properties can be imparted. The object underlying the invention is therefore to overcome the disadvantages of the prior art.

Surprisingly, the problem could be solved by providing a composition which

(A) at least one cationic polyelectrolyte,

(B) at least one anionic compound,

(C) at least one nonionic surfactant and

(D) optionally at least one liquid medium

includes. The composition may be in the liquid or solid state, preferably the composition is in the form of colloid, granules or powder. In a preferred embodiment, the composition is in the form of a colloid. The colloid particles preferably have an average diameter of 5 nm to 3 μηη, more preferably 10 nm to 2 μηι and even more preferably 40 nm to 1.5 μπι and even more preferably 40 nm to 500 nm. Preferred the composition optically transparent or opaque. Polyelectrolytes are polymers with side or chain ionic groups. Thus, the cationic polyelectrolyte (A) is a polymer having pendant and / or pendant cationic groups, especially pendant cationic groups. Preferably, the cationic group in the polyelectrolyte is permanently cationic, ie independent of the reaction conditions, for example independent of the pH.

The cationic group in the polyelectrolyte (A) is preferably an ammonium, pyridinium, imidazolium, pyrrolidonium or N-substituted heteroaromatic group, more preferably a quaternary ammonium group.

The polyelectrolyte (A) is preferably obtainable by (i) polymerization of at least three monomer units each having a permanent cationic charge and / or (ii) by condensation reactions leading to at least three cationic groups and / or (iii) by alkylation of at least three amino functions in a polymer to permanent cationic groups.

The polyelectrolyte (A) may be a homo- or a copolymer. In the case where the polyelectrolyte is a copolymer, the copolymer may comprise at least one recurring unit selected from the group consisting of styrene, acrylonitrile, (meth) acrylic acid ester, (meth) acrylamide, (meth) acrylic acid, vinyl acetate and a comonomer Allylalkoholderivat is due. If the comonomers contain a chemically ionizable group, this can after Polymerization are converted to a permanent cationic group. Preference is given to chemically ionizable groups, for example amino groups, which can be reacted, for example, by alkylation to quaternary ammonium ions. The permanent cationic charge in the monomer unit (i) is preferably an ammonium, pyridinium, imidazolium, pyrrolidonium or N-substituted heteroaromatic group, more preferably a quaternary ammonium group. Preferred monomer units (i) are α, β-unsaturated hydrocarbon compounds which have a permanently cationic charge. Particularly preferred monomer units (i) are selected from the group consisting of diallyldialkylammonium salt, in particular diallyldimethylammonium chloride (DADMAC), trialkylammoniumalkyl (meth) acrylate salt and trialkylammoniumalkyl (meth) acrylamide salt.

Particularly preferred monomer units (i) are shown structurally below:

Anion with

Ri = -Ci-4-alkyl, preferably -CH ₃ or

With

R ₂ = -H or -C ₄ alkyl, preferably -CH ₃ , and

R ₃ =

θ

Alternatively, the cationic polyelectrolyte (A) can be prepared by condensation reactions leading to at least three cationic groups. Such a condensation reaction (ii) preferably comprises a reaction of at least one dialkylamine, tertiary alkyl and / or (hetero) aryl-diamine with at least one epihalohydrin and / or bishalogenide. The epihalohydrin is preferably epichlorohydrin or epibromohydrin, more preferably epichlorohydrin. The bishalogenide is preferably an α, ω-bishalide, preferably α, ω-bisalkyl halide or α, ω-bishalogenalkyl ether. Preferred amino-functional compounds for the condensation reaction (ii) with epihalohydrin and / or bis-halide include: R4

NH

R4

With

Ri as defined above

R ₄ = -CH 3, -C 2 H 5, -C 3 H 7, -C ₄ H 9,

p = 2-6.

In a further alternative, the polyelectrolyte (A) can be obtained by polymerization of at least three monomer units, each having at least one chemically and / or physically ionizable group. Preferably, the chemically ionizable group is an amino group which can be reacted by alkylation to a quaternary ammonium ion. Preferably, therefore, in the alternative (iii), the polyelectrolyte (A) is obtained by alkylating at least three amino functions in a polymer to form permanent cationic groups.

Preference is given to polymers having at least three amino functions, selected from the group consisting of linear or branched polyalkyleneimine, in particular polyethyleneimine. Alternatively, polymers having at least three amino functions can be obtained by polymerization of at least three monomer units each having at least one amino function, in particular diallyldialkylamine, vinylamine, vinylpyrazole, vinylimidazole and / or aziridine. Preferred polymers having at least three amino functions are:

in which R _{2 is} independently as defined above and

n is 3-100,000.

The conditions and alkylating reagents for the alkylation of the amino functions in the polymer are well known to those skilled in the art. Preferred alkylating reagents are e.g. Dimethyl sulfate, diethyl sulfate, methyl halide, benzyl halide, methyl tosylate, or 3-chloro-2-hydroxypropyl-Ν, Ν, Ν-trimethylammonium chloride (CHPTAC). The polyelectrolyte (A) preferably has a number average molecular weight of 1, 000 to 5,000,000 g / mol, more preferably 1 to 1,000 to 1,000,000 g / mol, even more preferably 1 to 500 to 1,000,000 g / mol and even more preferably from 2,000 to 500,000 g / mol. The polyelectrolyte (A) is preferably constructed such that 30-100 mol%, preferably 50-100 mol%, of the repeating units have a cationic group.

In a preferred embodiment, the cationic charge density of the cationic polyelectrolyte (A) is 2.0-14.0 meq / g, more preferably 2.3-13 meq / g, and most preferably 2.5-12 meq / g.

The composition contains the polyelectrolyte (A) preferably at 4-62% by weight, more preferably 5-55% by weight, based on the total mass of the components A, B and C.

The anionic compound (B) preferably has at least one, more preferably 1 -3, i. 1, 2 or 3, anionic group (s). In another preferred embodiment, the anionic compound (B) is an anionic polyelectrolyte.

Preferably, the anionic compound (B) comprises at least one phosphate, phosphonate, sulfate, sulfonate, carboxylate, sulfoacetate, sulfosuccinate and / or taurate group. In a further preferred embodiment, the anionic compound (B) is selected from mono-, di- (C _-2, 2-alkyl (alkoxy)) phosphate, mono-, di- (C _4-2 alkyl 2-) phosphonate, C _{4 -2} -alkylaminophosphonate, C _-2 2-alkyl (alkoxy) sulfate, secondary alkylsulfonate, petroleum sulfonate, C _4-2 2-alkylsulfonate, C _4-22 -alkylarylsulfonate, fatty alcohol ether carboxylate, fatty acid salt, fatty alkyl sulfoacetate, fatty acid amide ether sulfate, fatty alcohol ether carboxylate, nonylphenol ether sulfate, Fatty alkyl ether sulfate, C _-22 alkyl polyalkoxylene phosphate and C _-22 alkyl polyalkoxylene sulfate.

Preferred mono- or dialkyl (alkoxy) phosphates or hydrogen phosphates are derived from the following acids:

R _{2 is} independently of one another as defined above,

R _A independently of one another is a saturated or unsaturated hydrocarbon radical having 4-18 carbon atoms,

n _{A is} independently 0-20.

A preferred alkyl alkoxy sulfate is derived from the following acid: in which

R _A 2 is a saturated or unsaturated hydrocarbon radical having 8-18 carbon atoms, and

n _A 2 is independently 0-10.

A preferred alkylaryl sulfonate is derived from the following acid:

in which

R _A 3 is a saturated or unsaturated hydrocarbon radical having 8-20 carbon atoms.

Alternatively, the compound (B) may be an anionic polyelectrolyte. The polyelectrolyte (B) is preferably a polymer having pendant anionic groups. Such polyelectrolytes are preferably obtainable by polymerization of at least three Ivlonomereinheiten (iv), each having at least one chemically ionizable group. The ionizable group in the monomer unit (iv) is preferably a group having an acidic proton, for example, an ionic group-bonded acid group. Such acid groups can be deprotonated in an acid-base reaction by adding a base. Preferred examples of the monomer unit (iv) are (meth) acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), allylsulfonic acid and styrenesulfonic acid. In a preferred embodiment, the polyelectrolyte (B) is a homo- or copolymer. The polyelectrolyte copolymer may comprise at least one repeat unit attributable to a comonomer, for example, selected from the group consisting of styrene, acrylonitrile, (meth) acrylic acid ester and (meth) acrylamide.

The anionic polyelectrolyte (B) is preferably constructed such that 30-100 mol%, preferably 50-100 mol%, of the repeating units have an anionic group.

The anionic compound (B) preferably constitutes 15-85% by weight, more preferably 20-80% by weight, based on the total mass of the components (A), (B) and (C). Component (A) and component (B) together form an ionic complex. This ionic complex forms a nucleus to which the nonionic surfactant (C) is bound via hydrophobic interactions.

In a preferred embodiment, the ratio of the net charge in component (A) to the net charge in component (B) is from 1:10 to 10: 1, more preferably from 1: 7 to 7: 1. The net charge of component (A) equals the sum of all positive charges minus the sum of any negative charges present. The net charge of component (B) corresponds to the sum of all negative charges less the sum of any positive charges present.

Component (C) is preferably an alkoxylation product of fatty acid, fatty acid ester, fatty acid amine, fatty acid amide, fatty alcohol, aliphatic mono-, di- or tri-alcohol, mono-, di- or tri-glyceride, alkylphenol, sorbitan fatty acid and sugar derivatives or trialkylphenol polyalkoxylene or Block copolymer, eg Poly (ethylene oxide-co-propylene oxide).

In a more preferred embodiment, the nonionic surfactant (C) is selected from the group consisting of alkoxylated C ₉ -C ₂ 5 fatty alcohols, alkoxylated C9-25 fatty acid amines, alkoxylated C9-C25 fatty acid amides, C-8-C25 fatty acids alkoxylated at the carboxylate function, alkoxylated C-8-C25 fatty acid esters, alkoxylated Ce-C5-alkylphenols and alkoxylated mono-, di- or triglycerides of C ₈ -C ₂ 5 fatty acids and / or their esterification products with C ₈ -C ₂ 5 fatty acids or trialkylphenyl polyalkoxylene or a block polymer, for example poly (ethylene oxide-co-propylene oxide), or fatty alcohol-poly (ethylene oxide-co-poly) propylene oxide) and mixtures thereof. The number of alkoxy groups in the nonionic surfactant is at least 8, preferably 8-85, more preferably 10-85, and most preferably 10-80 repeat units. The alkyl groups may each independently be branched or straight-chained, saturated or unsaturated.

Preferred nonionic surfactants (C) are as follows:

in which

R _{B is} a saturated or unsaturated hydrocarbon radical having 8-22 carbon atoms,

R _{5 are} independent of each other

is

R ₆ , R ₇ and R _8, independently of one another, are -H or a saturated or unsaturated hydrocarbon radical having 8-18 carbon atoms,

n _{B is} 8-80,

a + b + c 10-1 is 15 and

m is 10-200.

The composition preferably contains 8-60% by weight, more preferably 10-55% by weight, of component (C) based on the total weight of components (A), (B) and (C).

The composition of the invention may contain at least one liquid medium (D). The liquid medium is preferably a solvent, in particular water, or a polar organic solvent or a mixture thereof. Preferred polar organic solvents are alcohol, glycol, glycol ethers, ethers, ketone or mixtures thereof. The organic solvents are particularly preferably ethanol, isopropyl alcohol, glycerol, monoethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, butyl diglycol, dipropylene glycol monomethyl ether, mono-, di-ethylene glycol monobutyl ether, N-methylpyrrolidone, acetone or mixtures thereof.

The composition according to the invention preferably contains 40-99.9% by weight, more preferably 50-99.7% by weight, of component (D) based on the total composition. Component (D) may be incorporated into the composition separately or together with the components of (A), (B) and (C). The composition may be present as a concentrate (eg 50-70% by weight of component (D) based on the total composition) or in diluted form. Diluted compositions are also used as a liquor. By "liquor" is meant a composition ready for treatment of a textile or fiber The liquor preferably contains 0.001-1 wt%, more preferably at most 0.5 wt%, most preferably 0.1-0, 5% by weight of the components (A), (B) and (C) relative to the total mass of the liquor.

The composition may further comprise at least one textile auxiliaries, e.g. an antistatic agent, hydrophilizing agent, flame retardant, softening agent, de-caking agent, lubricant, UV resistance agent, corrosion inhibitor or fluorine-free or fluorine-containing hydrophobing agent.

To adjust the pH of the composition may optionally be used pH regulators. Suitable pH regulators are known to the person skilled in the art.

In a further aspect, the present invention relates to a process for the preparation of the above-described composition comprising the steps: a) providing the component (A), optionally in a liquid medium, b) providing the component (B), optionally in a liquid Medium, c) providing the component (C), optionally in a liquid medium, d) optionally providing the component (D) and

e) mixing the products obtained in steps a) -d).

For mixing the products obtained in steps a) to d) (step e)), methods known to the person skilled in the art can be used. Preferably, step e) is carried out with homogenizers known in the art, e.g. in the temperature range of 20-100 ° C.

In a further aspect of the invention, the composition according to the invention is used for the antistatic and / or hydrophilicizing finish of Fibers, textiles or (artificial) leather, in particular of linear or flat textiles used.

"Fibers" in the context of the present invention are natural fibers and synthetic fibers. "Natural fibers" are preferably cotton, wool or silk. "Synthetic fibers" or "synthetic fibers" are produced synthetically from natural or synthetic polymers and are preferably made of polyester, polyolefin, preferably polyethylene or polypropylene, more preferably polypropylene, polyamide, polyaramide, such as Kevlar ^® and Nomex ^®, polyacrylonitrile, elastane or viscose.

A "Textif in the context of the invention is made of several fibers. The textile is preferably linear or flat. By "linear Textif" is meant, for example, a yarn, a thread or a rope. "Flat Textiles" are preferably nonwovens, felts, woven, knitted and braided fabrics According to the invention, textiles may also contain blends of natural fibers and synthetic fibers.

"Antistatic" equipment and / or "antistatic equipment" in the sense of the present invention means the increase of the electrical conductivity at the surface of the material to be equipped, in order to counteract an electrostatic charge. The electrical resistance on the surface of the finished material is preferably 10 ⁹ to ⁹ × 10 ¹¹ ohms (measured in accordance with DIN EN 1 149-1). The hydrophilicity in the context of the present invention is the measure of the ability of a material to absorb water. A material is referred to as "hydrophilic" in the sense of the present invention if the absorbency of the material is 1 to 30 seconds according to the TEGEWA dripping test. A further aspect of the invention is a method for finishing fibers, textiles or (artificial) leather comprising the steps:

(i) providing fibers, textiles or (artificial) leather,

(ii) applying the composition according to the invention to the fibers, textiles or (artificial) leather, (iii) optionally at least partially removing the liquid medium (D) at temperatures above room temperature (RT = 20 ° C) and optionally at reduced pressure (eg at 0-1,000 mbar, preferably 50-800 mbar). The composition according to the invention is preferably applied to the textiles in liquid form. The application is preferably carried out at room temperature. The composition according to the invention can be applied in a variety of ways known to the person skilled in the art for finishing on the substrate, for example the textile, the fiber or the (artificial) leather. Suitable methods are, for example, spraying, dipping, soaking, brushing or sponge application. Furthermore, the composition according to the invention can be applied by means of forced application or exhaustion. In the case of forced application, a liquor is usually provided in the desired concentration and applied by means of a forced application of aqueous medium to the pad with liquor pick-ups of 40-100%. For the purposes of the present invention, "liquor pickup" is understood to mean the quantity of liquid taken up in percent, based on the weight of the dry goods.

The process is usually adjusted so that the finished material is about 0.1-7% by weight, preferably 0.3-5% by weight of the components (A), (B) and (C) based on the total mass fiber, textile or (art) leather.

The method according to the invention may further comprise a post-treatment step (iv) in which the textile is completely dried and / or fixed. Step (iv) may be carried out at 80-160 ° C, preferably at 100-130 ° C.

Accordingly, a further subject of the invention is a fiber, a textile or (artificial) leather which is obtainable by the method described above or which or which comprise the composition according to the invention. In the fiber, textile or (synthetic) leather according to the invention, the components (A), (B) and (C) of the composition make up about 0.1-7% by weight, preferably 0.3-5% by weight. % based on the total weight of the finished fiber, textile, or (artificial) leather. The composition according to the invention can also be used as an additive in a textile auxiliary formulation, for example a detergent formulation. For this purpose, the composition according to the invention is in liquid or solid form, preferably in liquid form. The proportion of components (A), (B) and (C) preferably constitutes 1-10% by weight, more preferably 2-8% by weight, based on the detergent formulation.

Surprisingly, it has been found that the compositions according to the invention are suitable for providing fibers, textiles or (artificial) leather with antistatic and hydrophilic properties. In addition, it has been shown that the equipment is wash-permanent. "Detergents" within the meaning of the present invention are understood to mean that the desired properties imparted by the finishing agent, for example antistatic and / or hydrophilic properties, are not or hardly diminished even after repeated washing in domestic washing machines. Preferably, the desired properties do not deteriorate after 10-20 or 5-10 washes in household washing machines or by no more than 20%. Surprisingly, the wash-permanent equipment could be achieved not only in natural fibers but also in particular in synthetic fibers such as PE, PA, PAN and PP, which are usually difficult to equip and hardly washable be equipped due to lack of functional groups. The compositions of the invention can be applied in a one-step process at room temperature or at ambient temperature. In addition, the composition of the present invention is stable in a broad concentration range. "Stabif within the meaning of the invention means that no sediment is formed. In the case of the concentrate, sediment formation is preferably observed after 3 months, more preferably after 6 months, even more preferably after 12 months, at 4 ° C, at 25-30 ° C or at 40 ° C. In the case of a liquor formulation, the composition preferably remains stable for up to 1, 5-2 hours, more preferably up to 4 hours, even more preferably up to 8 hours at 4 ° C, 25-30 ° C or 40 ° C, ie no sediment forms during this period. This property of the composition causes that the fibers and textiles can be equipped homogeneously and that no sediments or deposits form on the materials to be finished.

In the following the invention will be described by way of examples. These examples are not intended to be limiting.

materials

Poly-DADMAC: polydiallyldimethylammonium chloride, active substance 53%

Copolymer DADMAC / diallylamine: active substance 38%

Hostapur SAS 60: C13-C17 secondary alkanesulfonate, sodium salt, active substance 60%

Hostaphate 1306: C13 hydrocarbon radical, 6 EO, phosphate ester, active substance 100%

Ether sulfate: C12-C14 hydrocarbon radical, 4 EO, sulfate, sodium salt, active substance 70%

Hordaphos 222: C12-C14 hydrocarbon radical, 4 EO, phosphate, active substance 100%

Lutensol TO 20: C13 hydrocarbon radical, 20 EO, alkyl polyethylene glycol ether-based, active substance 100%

Lutensol TO 129: C13 hydrocarbon radical, 12 EO, alkyl polyethylene glycol ether-based, active substance 90%

Lutensol AT 80: C16-C18 hydrocarbon radical, 80 EO, alkyl polyethylene glycol ether-based, active substance 100%

Marlipal 16/18 - 25: C16-C18 hydrocarbon residue, 25 EO, alkylpolyethylene glycol ether-based, active substance 100%

Leunapone F 1 1 / 40E: C9-C1 1-hydrocarbon radical, 40 EO, active substance 100% Dowanol DPM: dipropylene glycol monomethyl ether Example 1

In a beaker with stirrer (stirrer) 48 g of water are submitted. With stirring, 15 g of the fatty alcohol "Lutensol TO-20" (C13, 20EO) are added and the mixture is heated to 80 ° C. and the surfactant is completely dissolved. Subsequently, 17 g of a secondary alkanesulfonate (Hostapur SAS 60) are added and dissolved therein. Successively, 10 g of Dowanol (dipropylene glycol monomethyl ether) and 10 g of aqueous poly-DADMAC (active substance 53%) are added. The initially turbid mixture is cooled with stirring. This forms a clear colloid solution.

A liquor is prepared by diluting 40 g of the resulting product to 1000 ml with water. The textiles to be finished are equipped with the product by dipping in the liquor and subsequent squeezing (padding). The pressure on the padder is chosen so that the wet pickup is 100%.

After 3, 5 and 10 household washes, the antistatic and hydrophilic properties are measured in accordance with DIN EN 1 149-1 or TEGEWA drip test.

Polyester (polyethylene terephthalate, knitted fabric): zero value antistatic 1, 0x10 ¹⁴ ohms, hydrophilicity> 180 sec.

Polyacrylonitrile (woven fabric): zero value antistatic 1, 0 x 10 ohms, hydrophilicity> 10 sec.

Example 2

In a beaker with stirrer (stirrer) 47.2 g of water are introduced. While stirring, 15 g of "Marlipal 16/18 - 25" are added, the mixture is heated to 80 ° C. and the surfactant is completely dissolved, then 17.8 g of ether sulfate are added and dissolved therein This is followed by the addition of a clean colloidal solution, the clear mixture being cooled with stirring.

After 5 and 10 household washes, the antistatic and hydrophilic properties are measured in accordance with DIN EN 1 149-1 or TEGEWA drip test.

Polyester (polyethylene terephthalate, knitted fabric): zero value antistatic 1, 0 x 10 ¹ ohm, hydrophilicity> 180 sec.

Polyamide 6,6, knitted fabric: zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 80 sec.

Example 3

In a beaker with stirrer (stirrer) 50 g of water are introduced. While stirring, 11 g of "Lutensol TO 20" are added, the mixture is heated to 80 ° C. and the surfactant is completely dissolved, then 20.0 g of "Hordaphos 222" (can also be used partially neutralized or completely neutralized) are added and solved in it. Successively, 10 g of butyldiglycol and 9 g of aqueous copolymer of dimethylamine and epichlorohydrin (active substance 50%) are added. This forms a clear colloid solution. The clear mixture is cooled with stirring. A liquor is prepared by diluting 40 g of the resulting product to 1000 ml with water. The textiles to be finished are equipped with the product by dipping in the liquor and subsequent squeezing (padding). The pressure on the padder is chosen so that the wet pickup is 100%.

After 3, 5 and 10 household washes, the antistatic and hydrophilic properties are measured according to DIN EN 1 149-1 or TEG EWA dripping test.

Antistatic antistatic antistatic

Sinking sinking sinking time after 3 to 5 after 10

after 3 to 5 after 10

Equipment washes washes washes

Washes washes washes 40 ° C 40 ° C 40 ° C

40 ° C [s] 40 ° C [s] 40 ° C [s] [ohm] [ohm] [ohm]

Example 3 2.3E + 10 6.5E + 10 6.5E + 10 2 6 6 Polyamide 6,6, knitted fabric: zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 80 sec.

Example 4

In a beaker with stirrer (stirrer) 57.9 g of water are introduced. With stirring, 5 g of "Lutensol AT 80" are added, the mixture is heated to 80 ° C. and the surfactant is completely dissolved, then 20.0 g of "Hordaphos 222" (can also be used partially neutralized or completely neutralized) are added and therein solved. Successively, 10 g of butyldiglycol and 7.1 g of aqueous poly (dichloroethylethertetramethylethylenediamine) (active substance 60%) are added. This forms a clear colloid solution. The clear mixture is cooled with stirring. A liquor is prepared by diluting 40 g of the resulting product to 1000 ml with water. The textiles to be finished are equipped with the product by dipping in the liquor and subsequent squeezing (padding). The pressure on the padder is chosen so that the wet pickup is 100%.

After 5 and 10 household washes, the antistatic and hydrophilic properties are measured in accordance with DIN EN 1 149-1 or TEGEWA drip test. Polyester (polyethylene terephthalate, knitted fabric): zero value antistatic 1, 0 x 10 ¹ ohm, hydrophilicity> 180 sec.

Example 5

In a beaker with stirrer (stirrer) 49.3 g of water are introduced. 16.7 g of "Lutensol TO 129" are added with stirring, the mixture is heated to 80 ° C. and the surfactant is completely dissolved, then 14 g of "Hostaphat 1306" (which can also be used partially neutralized or completely neutralized) are added and contained therein solved. Successively, 10 g of butyl diglycol and 10 g of aqueous poly-DADMAC are added. The initially turbid mixture is cooled with stirring. This forms a clear colloid solution.

A liquor is prepared by diluting 40 g of the resulting product to 1000 ml with water. The textiles to be finished by dipping in the fleet and then squeezing (padding) with the Product equipped. The pressure on the padder is chosen so that the wet pickup is 100%.

Polypropylene: zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 180 sec.

Example 6 55.3 g of water are placed in a beaker with stirrer (stirring fish). While stirring, 20 g of "Leunapon F 11 / 40E" are added, the mixture is heated to 80 ° C. and the surfactant is completely dissolved, then 4.7 g of homopolyacrylic acid (active substance 50%) are added and dissolved therein g of butyldiglycol and 10 g of aqueous poly-DADMAC, and the turbid mixture is cooled with stirring to form an opaque colloid solution.

Antistatic antistatic antistatic

Sinking sinking sinking time after 3 to 5 after 10

after 3 to 5 after 10

Equipment washes washes washes

Washes washes washes 40 ° C 40 ° C 40 ° C

40 ° C [s] 40 ° C [s] 40 ° C [s] [ohm] [ohm] [ohm]

Example 6 8.0E + 10 4.0E + 10 3.6E + 10 4 4 5 Polyamide 6,6, knitted fabric: zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 80 sec.

Example 7

In a beaker with stirrer (stirrer) 41.2 g of water are placed. With stirring, 15 g of "Marlipal 16 / 18-25" are added, the mixture is heated to 80 ° C. and the surfactant is completely dissolved, then 17.8 g of ether sulfate and 1 g of homopolyacrylic acid (active substance 50%) are added and dissolved therein 15 g of butyldiglycol and 10 g of aqueous polyDADMAC are added successively, the cloudy mixture is cooled with stirring to form an opaque colloid solution, and a liquor is prepared by diluting 40 g of the resulting product to 1000 ml with water. The textiles to be finished are going through Diving in the fleet and subsequent squeezing (padding) equipped with the product. The pressure on the padder is chosen so that the wet pickup is 100%. After 0, 5 and 10 household washes, the antistatic and hydrophilic properties are measured according to DIN EN 1 149-1 or TEG EWA dripping test.

Comparative Example 1, two-step process

A liquor containing 10 g / l of cationic surfactant, coconut di (2-hydroxyethyl) methylammonium chloride (active substance 100%) is "padded" onto the textile and then dried, in a second step a liquor containing 17.2 g g / L anionic surfactant, Hostapur SAS 60, "padded".

The pressure on the padder is selected in both equipment so that the wet pickup is 100%. After 0, 5 and 10 household washes, the antistatic and hydrophilic properties are measured according to DIN EN 1 149-1 or TEG EWA dripping test.

(no wash permanence) Comparative Example 2, two-step process

A liquor containing 10 g / l of cationic surfactant, C12-C16 alkyldimethylbenzylammonium chloride (active substance 50%) is "padded" onto the textile and then dried, in a second step a liquor containing 17.2 g / l of anionic Surfactant, Hostapur SAS 60, "padded".

The pressure on the padder is selected in both equipment so that the wet pickup is 100%. After 0, 5 and 10 household washes, the antistatic and hydrophilic properties are measured according to DIN EN 1 149-1 or TEG EWA dripping test. Polyester (polyethylene terephthalate, knitted fabric): zero value antistatic 1, 0x10 ¹⁴ ohms, hydrophilicity> 180 sec.

(no wash permanence) Comparative Example 3, two-step process

A liquor containing 10 g / L of cationic surfactant, coconut di (2-hydroxyethyl) methylammonium chloride (active substance 100%), is "padded" onto the textile and then dried, and in a second step, a liquor containing 19.2 g / L anionic surfactant, ether sulfate, "padded".

(no wash permanence) Comparative Example 4, two-step process

A liquor containing 10 g / l of cationic surfactant, alkyldimethylbenzylammonium chloride (active substance 50%) is "padded" onto the textile and then dried, followed by a liquor containing 21.5 g / l of anionic surfactant, Hordaphos 222. "padded".

(no wash permanence) Comparative Example 5: Preparation without nonionic surfactant.

In a beaker with stirrer (stirrer) 48 g of water are submitted. With stirring, 17 g of Hostapur SAS 60 are added and dissolved therein. Successively, 10 g of Dowanol DPM and 10 g of aqueous poly-DADMAC are added. The mixture forms insoluble precipitates and can not be used.

The following points are the subject of the invention:

1 . Composition comprising:

(A) at least one cationic polyelectrolyte, (B) at least one anionic compound

(C) at least one nonionic surfactant and

(D) optionally at least one liquid medium. 2. Composition according to item 1 in the form of a colloid.

3. Composition according to one of the items 1 or 2, wherein the colloid particles have a mean diameter of 5 nm to 3 μιη. 4. Composition according to any one of items 1 -3, wherein the composition is optically transparent or opaque.

5. The composition according to any one of the preceding points, wherein the polyelectrolyte (A) is a polymer having side and / or chain cationic groups.

6. Composition according to one of the preceding points, wherein the polyelectrolyte (A) is obtainable by (i) polymerization of at least three monomer units, each having a permanently cationic charge and / or (ii) by condensation reactions leading to at least three cationic groups , and / or (iii) by alkylating at least three amino functions in a polymer to form permanent cationic groups.

7. Composition according to one of the preceding points, wherein the polyelectrolyte (A) is a homo- or copolymer.

8. The composition of item 7 wherein the polyelectrolyte copolymer comprises at least one repeating unit derived from a comonomer selected from the group consisting of styrene, acrylonitrile, (meth) acrylic acid ester, (meth) acrylamide, (meth) acrylic acid, vinyl acetate and allyl alcohol derivative is.

9. A composition according to any one of items 6-8, wherein the monomer unit (i) comprises an ammonium, pyridinium, imidazolium, pyrrolidinium group or an N-substituted heteroaromatic group. 10. The composition of any one of items 6-9, wherein the monomer unit (i) is selected from the group consisting of diallyldialkylammonium salt, especially diallyldimethylammonium chloride (DADMAC), trialkylammoniumalkyl (meth) acrylate salt, and trialkylammoniumalkyl (meth) acrylamide salt.

1 1. A composition according to any one of items 6-8, wherein the condensation reaction (ii) comprises reacting at least one di-alkylamine, tertiary alkyl and / or (hetero) aryl-diamine with at least one epihalohydrin and / or bishalogenide.

12. The composition of any one of items 6-8, wherein the polymer having at least three amino functions in (iii) is selected from the group consisting of linear or branched polyalkyleneimine, especially polyethylenimine, or obtainable by polymerizing at least three monomer units selected from the group consisting of diallyldialkylamine, vinylamine, vinylpyrazole, vinylimidazole and / or aziridine. 13. Composition according to one of the preceding points, wherein the component (A) 4-62 wt .-%, preferably 5-55 wt .-%, based on the total mass of the components (A), (B) and (C) ,

14. Composition according to one of the preceding points, wherein component (A) has a number-average molecular weight of 1, 000

5,000,000 g / mol, preferably 1 .000-1 .000,000 g / mol.

15. Composition according to one of the preceding points, wherein 30-100 mol%, preferably 50-100 mol%, of the repeating units in the component (A) have a cationic group.

16. Composition according to one of the preceding points, wherein the anionic compound (B) has at least one, preferably 1 -3 anionic group (s), or is an anionic polyelectrolyte. A composition according to any one of the preceding items, wherein the anionic compound (B) comprises at least one phosphate, phosphonate, sulfate, sulfonate, carboxylate, sulfoacetate, sulfosuccinate and / or taurate group. Composition according to one of the preceding items, wherein the anionic compound (B) is selected from mono-, di- (C 22- alkyl _4- (alkoxy)) phosphate, mono-, di- (C _4-2 2-alkyl) phosphonate , C _4-2 2-alkylamino-phosphonate, C _4-2 2-alkyl (alkoxy) sulfate, secondary alkylsulfonate, petroleum sulfonate, C _-22- alkylsulfonate, C _4-2 2-alkylarylsulfonate,

Fatty alcohol ether carboxylate, fatty acid salt, fatty alkyl sulfoacetate,

Fatty acid amide ether sulfate, fatty alcohol ether carboxylate, nonylphenol ether sulfate, fatty alkyl ether sulfate, C _4-22 alkyl polyalkoxylene phosphate and C _-22 alkyl polyalkoxylene sulfate. Composition according to item 16, wherein the polyelectrolyte (B) is a polymer having pendent anionic groups. Composition according to item 19, wherein the polyelectrolyte is obtainable by polymerization of at least three monomer units (iv), each having at least one chemically ionizable group. The composition of item 20, wherein the monomer unit (iv) is selected from the group consisting of (meth) acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid and

Styrene. A composition according to any one of items 16, 17, 19, 20 or 21, wherein the polyelectrolyte (B) is a homo- or copolymer. The composition of item 22, wherein the polyelectrolyte copolymer comprises at least one repeating unit derived from a comonomer selected from the group consisting of styrene, acrylonitrile, (meth) acrylic acid ester, and / or (meth) acrylamide. 24. Composition according to one of the preceding points, wherein the component (B) 15-85 wt .-%, preferably 20-80 wt .-%, based on the total mass of the components (A), (B) and (C) ,

25. A composition according to any preceding item, wherein component (A) and component (B) form an ionic complex with each other. 26. The composition according to any one of the preceding points, wherein the ratio of the net charge in component (A) to the net charge in component (B) is 1: 10 to 10: 1, preferably 1: 7 to 7: 1.

27. A composition according to any preceding item, wherein component (C) is an alkoxylation product of fatty acid, fatty acid ester,

Fatty acid amine, fatty acid amide, fatty alcohol, aliphatic mono-, di- or tri-alcohol, mono-, di- or tri-glyceride, alkylphenol, sorbitan fatty acid and sugar derivatives or trialkylphenol polyalkoxylene or a block copolymer, e.g. Poly (ethylene oxide-co-propylene oxide).

28. Composition according to one of the preceding points, wherein component (C) 8-60 wt .-%, preferably 10-55 wt .-%, based on the total mass of the components (A), (B) and (C). 29. Composition according to one of the preceding points, wherein the liquid medium (D) is selected from water, an organic solvent, preferably alcohol, glycol (ether), ether, ketone or mixtures thereof. 30. Composition according to one of the preceding points, wherein component (D) constitutes 40-99.9% by weight, preferably 50-99.7% by weight, based on the total composition.

31. Composition according to one of the preceding points, further comprising at least one textile auxiliaries, for example an antistatic agent, Hydrophilizing agents, flame retardants, softening agents,

Anti-wrinkling agent, lubricant, UV-resistance agent, corrosion inhibitor or fluorine-free or fluorine-containing hydrophobing agent. A composition according to any one of the preceding claims, comprising:

(A) at least one cationic polyelectrolyte,

(B) at least one anionic compound,

(C) at least one nonionic surfactant and

(D) optionally at least one liquid medium,

wherein the composition is in the form of a colloid and the ratio of the net charge in component (A) to the net charge in component (B) is 1: 10 - 10: 1. 33. A process for the preparation of a composition according to any one of items 1 - 32, comprising the steps

a) providing component (A), if appropriate in a liquid medium, b) providing component (B), if appropriate in a liquid medium, c) providing component (C), if appropriate in a liquid medium, d) if necessary, providing the component (D) and

e) mixing the products obtained in steps a) -d).

34. Use of the composition according to any one of items 1 to 32 for antistatic and / or hydrophilizing finishing of fibers, textiles or (artificial) leather, in particular linear or flat textiles.

35. Use according to item 34, wherein the fiber or textile of synthetic fibers, in particular polyester, polyolefin, preferably polyethylene or polypropylene, more preferably polypropylene, polyamide, polyaramid, polyacrylonitrile, elastane or viscose, natural fibers, especially wool, cotton or silk , or mixtures thereof.

36. Use of the composition according to any one of items 1 to 32 as an additive in textile auxiliary formulations, for example detergent formulations. 37. Method of finishing fibers, textiles or (artificial) leather comprising the steps

i) providing fibers, textiles or (artificial) leather,

ii) applying a composition according to one of the items 1 to 32 to the fibers, textiles or the (artificial) leather,

iii) optionally at least partial removal of the liquid medium (D) at temperatures above room temperature and optionally at reduced pressure. 38. Fiber, textile or (artificial) leather obtainable by a method according to item 37.

39. fiber, textile or (artificial) leather, comprising a composition according to any one of items 1 -32.

40. fiber, textile or (artificial) leather according to item 38 or 39, wherein the components (A), (B) and (C) in the composition 0.1 to 7 wt .-% based on the total mass of the finished fiber , the textile or the (art) leather.

Claims

claims

1 . Composition comprising:

(A) at least one cationic polyelectrolyte,

(B) at least one anionic compound,

(C) at least one nonionic surfactant and

(D) optionally at least one liquid medium.

2. Composition according to claim 1 in the form of a colloid, wherein the colloid particles preferably have a mean diameter of 5 nm to 3 μιη.

3. A composition according to any one of the preceding claims, wherein the polyelectrolyte (A) is obtainable by (i) polymerization of at least three monomer units, each having a permanently cationic charge, and / or (ii) by condensation reactions leading to at least three cationic groups and / or (iii) by alkylating at least three amino functions in a polymer to form permanent cationic groups.

4. Composition according to one of the preceding claims, wherein the anionic compound (B) has at least one, preferably 1 -3, anionic group (s) or is an anionic polyelectrolyte.

5. The composition according to any one of the preceding claims, wherein the anionic compound (B) at least one phosphate, phosphonate, sulfate,

Sulfonate, carboxylate, sulfoacetate, sulfosuccinate and / or taurate group.

Composition according to any one of the preceding claims, wherein the ratio of the net charge in component (A) to the net charge in component

(B) is 1: 10 to 10: 1, preferably 1: 7 to 7: 1.

A composition according to any one of the preceding claims, comprising:

(A) at least one cationic polyelectrolyte,

(B) at least one anionic compound, (C) at least one nonionic surfactant and

(D) optionally at least one liquid medium,

wherein the composition is in the form of a colloid and the ratio of the net charge in component (A) to the net charge in component (B) is 1: 10 - 10: 1.

8. A composition according to any one of the preceding claims, wherein component (C) is an alkoxylation product of fatty acid, fatty acid ester, fatty acid amine, fatty acid amide, fatty alcohol, aliphatic mono-, di- or tri-alcohol, mono-, di- or tri-glyceride, alkylphenol , Sorbitan fatty acid and sugar derivatives or trialkylphenol polyalkoxylene or a block copolymer, eg Poly (ethylene oxide-co-propylene oxide).

9. Composition according to one of the preceding claims, wherein the liquid medium (D) is selected from water, an organic

Solvent, preferably alcohol, glycol (ether), ether, ketone or mixtures thereof.

10. A process for preparing a composition according to any one of claims 1-9 comprising the steps of:

(a) providing component (A), optionally in a liquid medium,

(b) providing component (B), optionally in a liquid medium,

(c) providing component (C), optionally in a liquid medium,

(d) optionally providing component (D), and

(e) mixing the products obtained in steps a) -d).

1 1. Use of the composition according to any one of claims 1 to 9 for the antistatic and / or hydrophilizing treatment of fibers, textiles or (artificial) leather, in particular of linear or flat textiles.

Use of the composition according to any one of claims 1-9 as an additive in textile adjuvant formulations, e.g. Detergent formulations.

13. A method of finishing fibers, textiles or (artificial) leather comprising the steps of: i) providing fibers, textiles or (artificial) leather,

ii) applying a composition according to any one of claims 1-9 to the fibers, textiles or the (artificial) leather,

iii) optionally at least partial removal of the liquid medium (D) at temperatures above room temperature and optionally at reduced pressure.

14. fiber, textile or (synthetic) leather obtainable by a process according to claim 13.

15. A fiber, textile or (synthetic) leather comprising a composition according to any one of claims 1-9.

16. A fiber, textile or (artificial) leather according to claim 14 or 15, wherein the components (A), (B) and (C) in the composition 0.1 to 7 wt .-% based on the total mass of the finished fiber , the textile or the (art) leather.