EP3638841A1

EP3638841A1 - Composition and use thereof for finishing fabrics

Info

Publication number: EP3638841A1
Application number: EP18729452.5A
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: WO2018229116A1; EP3638841B1; US20200173098A1

Abstract

The invention relates to compositions comprising at least one cationic polyelectrolyte, at least one anionic compound and at least one non-ionic surfactant. Also disclosed is the use of said compositions for finishing fabrics.

Description

Composition and use thereof for equipping

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 textiles.

Ever-increasing demands are placed on textiles today. Depending on the field of application, textiles are to be used e.g. hydrophobic, hydrophilic, flameproof, antistatic, crease resistant, oil repellent, 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. The equipment usually takes place directly at the manufacturers on an industrial scale.

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 provide appropriate To achieve wash permanence on a fiber or textile. For this purpose, a two-stage process is usually carried out in which cationic and anionic components are applied successively. 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 Pat. No. 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 an 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, e.g. by ultrasound, homogenized. However, the fleet is only metastable and has a strong tendency to agglomerate. Thus, the fleet is only limited for use as a finishing agent, 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 applied to the surface. Alternatively, a dispersion of the

Anion-cation complex proposed for the coating of filters. For the coating of fibers or textiles, the ion complex described is not suitable because it is not sufficiently stable

Fleets can be produced.

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

- complex multi-step processes in the application

- Equipment can not be carried out by the end user

- Handle hardening

- thermal yellowing

- Use of physiologically questionable starting materials

- lack of washing permanence

- Risk of staining due to uncontrolled deposits Frequently, there is also a desire on the part of the end user to impart certain properties to already existing textiles or to refresh certain properties of textiles. Thus, additives are known which are simply added to the wash liquor during the wash cycle, eg in (domestic) washing machines. Textiles treated in this way should, for example, have improved water-repellent effect after washing. The additives can be used as a substitute or additive to conventional detergents. Alternatively, the additives may also be added to the washload in metering units. The dosing unit ensures a controlled release of the additive during use, ie during the wash cycle. The metering units allow the controlled release of the additive, for example, continuously over the entire wash cycle or gradually under certain conditions, eg when reaching a predetermined temperature or under mechanical load (eg during spin). Such dosing units are known to the person skilled in the art and include, for example, so-called wash cloths, dosing balls, tabs, pods or caps. So far, it has not yet been possible to provide additives for the end consumer market with which a textile can be given permanent antistatic and / or hydrophilic properties. In particular, in the application of the additive in the domestic field, ie hand washing and (household) washing machines, beyond the highest requirements are made in terms of environmental compatibility and toxicity, since the contaminated with the additive wash usually enter the wastewater untreated.

Surprisingly, the problem can 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

(D) optionally comprises at least one liquid medium.

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 from 5 nm to 3 μm, more preferably from 10 nm to 2 μm, even more preferably from 40 nm to 1.5 μm and even more preferably from 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, i. regardless 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 be converted after polymerization to a permanently 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:

With

Ri = C _1-4 alkyl, preferably -CH _3,

or

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

R ₃ =

Θ

ion

Θ

ion

Θ

anion 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-bis-halide, preferably α, ω-bisalkyl halide or α, ω-bishaloalkyl. Preferred amino-functional compounds for the condensation reaction (ii) with epihalohydrin and / or bis-halide include:

NH

With

Ri as defined above

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:

or

in which

R2 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, for example, 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 1,000,000 to 5,000,000 g / mol, more preferably from 1,000 to 1,000,000 g / mol, even more preferably from 1,500 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 _4- 22 alkyl (alkoxy)) phosphate, mono-, di- (C _4-2 alkyl 2-) phosphonate, C _{4 -2} 2-Alkylaminophosphonat, C _-2, 2-alkyl (alkoxy) sulphate, secondary alkyl sulfonate, petroleum sulfonate, C ₄ _ ₂ 2-alkylsulfonate, C ₄ _ ₂₂ - alkylaryl, Fettalkoholethercarboxylat, fatty acid salt,

Fettalkylsulfoacetat, Fettsäureamidethersulfat, Fettalkoholethercarboxylat, Nonylphenolethersulfat, fatty alkyl ether sulfate, C _4-2 Alkylpolyalkoxylenphosphat 2- and C ₄ 2 ₂ -Alkylpolyalkoxylensulfat.

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

in which

R2 is independently defined as above,

R _A independently of one another 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 monomer units (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, e.g. an acid group with ionogenically bound hydrogen. 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.

In a particularly preferred embodiment, the composition according to the invention comprises:

(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.

The 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 a block copolymer, for example poly (ethylene oxide-co-propylene oxide). In a more preferred embodiment, the nonionic surfactant (C) is selected from the group consisting of alkoxylated Cg-C 25 fatty alcohols, alkoxylated C ₉ -25 fatty amines, alkoxylated Cg-C-25 fatty acid amides, alkoxylated at the carboxylate function Cs C ^ s fatty acids, alkoxylated Cs-C ^ s fatty acid esters, alkoxylated C ₈ -C ₂ 5-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 Trialkylphenylpolyalkoxylen or a block polymer, for example poly (ethylene oxide-co-propylene oxide), or fatty alcohol-poly (ethylene oxide-co-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 repeating units. The alkyl groups may each independently be branched or straight-chained, saturated or unsaturated. Preferred nonionic surfactants (C) are as follows:

in which

RB is a saturated or unsaturated hydrocarbon radical 8-22

Carbon atoms,

R5 independently

is

R ₀ , R 7 and Re independently of one another are -H or a saturated or unsaturated hydrocarbon radical having 8-18 carbon atoms, n _{B is B} 8-80,

a + b + c 10-1 is 15 and

m is 10-200.

The composition preferably contains 20-80% by weight, more preferably 30-60% 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 40-80% by weight, more preferably 50-80% 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 40-75% by weight of component (D) based on the total composition) or in diluted form.

The composition may further comprise at least one textile auxiliaries, e.g. an antistatic agent, hydrophilizing agent, flame retardants, soft-grip agent, Entknitterungsmittel, lubricants, UV-resistance agents, corrosion inhibitors or fluorine-free or fluorine-containing hydrophobing agents.

If necessary, pH regulators may be used to adjust the pH of the composition. 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 composition described above 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).

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) takes place with homogenizers known in the art, for example 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 finishing of textiles, in particular of linear or flat textiles, more preferably of flat textiles.

A "Textif in the context of the invention is made of several fibers. For the purposes of the present invention, "fibers" are natural fibers and synthetic fibers. "Natural fibers" are preferably cotton, wool or silk. "Synthetic fibers" or "synthetic fibers" are synthetically produced 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 spandex, or viscose , According to the invention, textiles may also contain mixtures of natural fibers and synthetic fibers.

Preferably, the textile is flat. "Flat textiles" are preferably knits, fleeces, felts, woven fabrics, knitted fabrics and braids. "Antistatic" finish and / or "antistatic finish" within the meaning of the present invention means increasing the electrical conductivity at the surface of the material to be finished Preferably, the electrical resistance at the surface of the finished material is 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. Surprisingly, it has been found that textiles can already be finished by adding the composition according to the invention into the wash liquor, for example in (domestic) washing machines or in hand washing. For this purpose, the composition may be added as a concentrate or in diluted form. Preferably, the concentration of components (A), (B), (C) and optionally (D) in the wash liquor is 0.1-10 g / L, more preferably 0.3-8 g / L.

Alternatively, the composition according to the invention may be provided in a dosing unit by which the composition according to the invention is washed during the wash cycle, e.g. in a (household) washing machine, can be released controlled. Such dosing units are known in the art and include so-called wash cloths, tabs, caps, pods and dosing devices, e.g. Dosing balls.

In one aspect, the invention therefore relates to a metering unit comprising a composition according to the invention, in particular in the form of a washing cloth, tablets, caps, pods or a metering device. In the case of tabs, the composition - preferably in solid form - compressed into tablets (so-called tabs). The tabs gradually dissolve in the course of the wash cycle, thus allowing a continuous delivery of the composition to the laundry. In the case of caps, the - preferably liquid - composition, for example, packed in bags. The package is preferably such that it will leak at a predetermined temperature in the presence of water, and thus the timing of release of the composition during the wash cycle can be controlled. Alternatively, the package is designed so that it is leaking under mechanical stress, eg in the spin cycle. The packaging is preferably made of polyethylene or polypropylene. In the case of pods, the - preferably liquid - composition is packaged, for example, in bags, analogously to the caps. The packaging is preferably such that it dissolves without residue under the given washing conditions. The packaging is therefore preferably made of degradable or soluble polymers, such as polyvinyl alcohol or polylactide.

When washing cloth is preferably a substrate impregnated with the composition of the invention. The washing cloth is added to the laundry in the drum of the (household) washing machine preferably at the beginning of the wash cycle. During the wash cycle, the composition migrates in a controlled manner into the wash liquor.

In a preferred embodiment, the substrate is a nonwoven, woven, knitted or felt. The substrate is preferably cellulose, e.g. Cotton or viscose, polyethylene terephthalate, polyamide, polyolefin, in particular polypropylene or polyethylene and / or polyacrylonitrile. The substrates of the wash cloths are preferably made of polyolefins, particularly preferably polypropylene, due to their favorable price and their low fluff tendency.

The washcloth preferably has an area of <1600 cm ² , more preferably 10-1600 cm ² , even more preferably 20-1000 cm ² . The mass ratio of the components (A), (B) and (C) in the composition to the substrate of the washing cloth is preferably 1: 1 or 10: 1 to 0.5: 1.

The high local concentration of the composition as well as the ratio of the active substances (A), (B) and (C) allows a continuous migration of the composition into the wash liquor. For all metering units according to the invention, the amount of the composition should be selected such that the concentration of components (A), (B), (C) and optionally (D) in the wash liquor during the finish cycle is 0.1-10 g / l 0.3 - 8 g / l. Preferably, the fabric after washing is about 0.01-1 wt%, more preferably 0.01-0.8 wt%, of the components (A), (B) and (C) based on the total mass equipped of textile.

The wash wipes of the invention may be used for one or more washes, preferably for at least 1, 2, 5 or 10 washes, e.g. be used at 95 ° C. The washcloths may also be combined with other active substances, e.g. Detergent, softener, fabric softener, fragrances, etc. be equipped. The washing sheets according to the invention can be produced according to the following steps:

(i) providing a substrate,

(i) application of the preparation according to the invention to the substrate and (iii) optionally at least partial removal of the liquid medium (D) at temperatures above room temperature and optionally at reduced

Print.

The composition according to the invention can preferably be prepared according to the known methods, for example by spraying, dipping, impregnating, brushing or sponge application or forced application, or exhaustion method. The washing cloths are preferably produced by treating the substrate with the concentrate of the composition according to the invention. The method according to the invention may further comprise an after-treatment step (iv) in which the impregnated substrate 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 the use of the dosing unit according to the invention for the antistatic and / or hydrophilicizing finishing of textiles, preferably in washing machines, in particular in household washing machines.

Surprisingly, it has been found that the compositions according to the invention are suitable for providing textiles with antistatic and hydrophilic properties. In addition, it has been shown that the equipment is wash-permanent. "Washing permanence" in the sense of the present invention is understood to mean that the desired properties conferred by the finishing agent, for example antistatic and / or hydrophilic properties, are not or hardly reduced even after repeated washing in household washing machines 10-20 or 5-10 washes in household washing machines or not more than 20%.

Surprisingly, the wash-permanent equipment could be achieved not only with natural fibers but also in particular with synthetic fibers such as PE, PA, PAN and PP, which are usually difficult to equip and hardly washable due to lack of, less or inert functional groups. The compositions according to the invention can be applied in a simple process, for example in (household) washing machines. In addition, the composition according to the invention is stable over a wide concentration range. "Stabif according to 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. Also in the wash liquor no sediment forms. This property of the composition means that the textiles can be equipped homogeneously and that no sediments or deposits form on the materials to be finished. The invention will now be illustrated by way of example. 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%

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%

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

Dowanol DPM: dipropylene glycol monomethyl ether

Example 1 48 g of water are placed in a beaker with stirrer (stirring fish). With stirring, 15 g of the fatty alcohol "Lutensol TO-20" (C13, 20EO) are added, the mixture is heated to 80 ° C., completely dissolving the surfactant, then 17 g of a secondary alkanesulfonate (Hostapur SAS 60) are added and dissolved 10 g of Dowanol (dipropylene glycol monomethyl ether) and 10 g of aqueous poly-DADMAC (active substance 53%) are added in succession, The initially cloudy mixture is cooled with stirring to form a clear colloid solution A liquor is prepared by dissolving 40 g of the resulting The textiles to be finished are dipped in the liquor and then squeezed (padded) with water Product equipped. 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.

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

Polyacrylonitrile (woven fabric): zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 10 sec.

Antistatic Antistatic Antistatic Eininkzeit Eininkzeit Decline after 3 to 5 to 10 to 3 to 5 to 10

Equipment washes washes washes washes washes washes washes

40 ° C 40 ° C 40 ° C 40 ° C 40 ° C 40 ° C

[Ohm] [ohm] [ohm] [s] [s] [s]

Example 1 3.40E + 10 6.00E + 10 1 .40E + 10 3 3 5 Example 2: washcloth

Preparation of the composition 47.4 g of water are placed in a beaker with stirrer (stirring bar). With stirring, 15 g of the fatty alcohol "Lutensol TO-20" (C13, 20EO) are added, then 5 g of butyldiglycol are added, the mixture is heated to 90 ° C., the surfactant is completely dissolved, then 13.8 g of an alkoxylated (4EO) Phosphoric acid ester (Hordaphos 222) was added and dissolved 1.66 g of sodium hydroxide solution (50%) and 9.2 g of aqueous poly-DADMAC (active substance 53%) were added in succession, The initially turbid mixture was cooled while stirring Forms a clear colloid solution

The washcloth comprises a substrate of polypropylene spun fiber fabric with an area of 900 cm ² . The substrate has a mass of 17.3 g. The substrate is equipped by dipping in the resulting composition and then squeezing (padding). The pressure on the padder is chosen so that the wet pickup is 200%. Subsequently, the finished substrate is dried at 120 ° C for 2 minutes. Application of washcloth and results

The washing cloth thus obtained is washed together with 0.6 kg of accessories (household washing at 40 ° C). The accessory pack consists of 0.3 kg of polyester (polyethylene terephthalate, knitted fabric) and of 0.3 kg of polyamide (nylon 6,6; knitwear)

After household washing, the package is dried for 2 days in air and conditioned for 3 days in a climate room. Subsequently, antistatic and Hydrophilicity measured. In order to check a homogenous equipment, the accessory pack is tested in four different places.

Polyester (polyethylene terephthalate, knitted fabric):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 180 sec.

Polyamide 6,6; Knitwear:

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 80 sec.

Example 3: Washcloth Preparation of the composition

In a beaker with stirrer (stirrer) 43.0 g of water are introduced. With stirring, 30 g of the fatty alcohol "Lutensol TO-20" (C13, 20EO) are added, the mixture is heated to 90 ° C., the surfactant is completely dissolved, and then 17.0 g of a secondary alkanesulfonate sodium salt (Hostapur SAS 60 , Active substance 60%) was added and dissolved.The mixture is cooled to 60 ° C. At this temperature, 9.2 g of aqueous poly-DADMAC (active substance 53%) are added. added. The initially turbid mixture is cooled with stirring. This forms a clear colloid solution.

Production of the washing cloth

Analogously to Example 2, the same proportions are used on a scale of 1:10.

The washcloth comprises a polypropylene spun fiber fabric substrate of 90 cm ^{2 area} . The substrate has a mass of 1.0 g.

The substrate is equipped by dipping in the resulting composition and then squeezing (padding). The pressure on the padder is chosen so that the wet pickup is 240%. Subsequently, the finished substrate is dried at 120 ° C for 2 minutes.

Application of washcloth and results

The washing cloth thus obtained is washed together with 60 g of accessory pack (household washing at 40 ° C.). The accessory pack consists of 30 g polyester (polyethylene terephthalate, knitted fabric) and 30 g polyamide (polyamide 6,6; knitwear). The accessory pack simulates the textiles to be finished by the end user.

After household washing, the package is dried for 2 days in air and conditioned for 3 days in a climate room. Subsequently, antistatic and hydrophilic properties are measured. In order to check a homogeneous equipment, the accessory pack is tested in three different places. Polyester (polyethylene terephthalate, knitted fabric):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 180 sec.

Polyamide 6,6; Knitwear):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 80 sec.

In order to test the washing permanence of the goods equipped by this method (= accessory pack), the accessory pack was washed again 3, 5 and 10 times. The mean values of the measurements are shown as results.

Polyester (polyethylene terephthalate, knitted fabric):

Equipment washes washes washes washes washes washes washes

40 ° C 40 ° C 40 ° C 40 ° C 40 ° C 40 ° C

[Ohm] [ohm] [ohm] [s] [s] [s]

Accessory kit

PES in 5.50E + 10 9.50E + 10 5.50E + 10 4 5 7

Example 3

Polyamide 6,6; Knitwear):

Equipment washes washes washes washes washes washes washes

40 ° C 40 ° C 40 ° C 40 ° C 40 ° C 40 ° C

[Ohm] [ohm] [ohm] [s] [s] [s]

Accessory pack PA

in the example 3.40E + 10 9.00E + 10 1 .00E + 1 1 13 8 21 3 Example 4: Washcloth

Preparation of the composition

In a beaker with stirrer (stirrer) are presented 58.0 g of water. With stirring, 15 g of the fatty alcohol "Lutensol TO-20" (C13, 20EO) are added, the mixture is heated to 90 ° C., the surfactant is completely dissolved, and then 17.0 g of a secondary alkanesulfonate sodium salt (Hostapur SAS 60 , Active substance 60%) is added and dissolved.The mixture is cooled to 60 ° C. At this temperature, 9.2 g of aqueous poly-DADMAC (active substance 53%) are added.The initially cloudy mixture is cooled with stirring clear colloid solution.

Production of the washing cloth

The substrate is equipped by dipping in the resulting composition and then squeezing (padding). The pressure on the padder is chosen so that the wet pickup is 240%. Subsequently, the finished substrate is dried at 120 ° C for 2 minutes. Application of washcloth and results

The washing cloth thus obtained is washed together with 60 g of accessory pack (household washing at 40 ° C.). The accessory pack consists of 30 g polyester (polyethylene terephthalate, knitted fabric) and 30 g polyamide (polyamide 6,6; knitwear). The accessory pack simulates the textiles to be finished by the end user. After household washing, the package is dried for 2 days in air and conditioned for 3 days in a climate room. Subsequently, antistatic and hydrophilic properties are measured. In order to check a homogeneous equipment, the accessory pack is tested in three different places.

Polyester (polyethylene terephthalate, knitted fabric):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 180 sec.

Polyamide 6,6; Knitwear):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 80 sec.

In order to test the washing permanence of the product equipped by this method (= accessory pack), the accessory pack was washed again 3, 5 and 10 times. The mean values of the measurements are shown as results.

Polyester (polyethylene terephthalate, knitted fabric):

Equipment washes washes washes washes washes washes washes

40 ° C 40 ° C 40 ° C 40 ° C 40 ° C 40 ° C

[Ohm] [ohm] [ohm] [s] [s] [s]

Accessory kit

PES in 1 .40E + 1 1 1 .10E + 1 1 9.50E + 10 3 4 8

Example 4 Polyamide 6,6; Knitwear):

Example 5: Washcloth

Preparation of the composition

In a beaker with stirrer (stirrer) 55.37 g of water are introduced. While stirring, 15 g of the fatty alcohol "Lutensol TO-20"

(C13, 20EO). Subsequently, 5 g of butyldiglycol are added.

The mixture is heated to 90 ° C while the surfactant completely dissolved.

Subsequently, 13.8 g of an alkoxylated (4EO) phosphoric acid ester

(Hordaphos 222) added and solved. The mixture is cooled to 60 ° C. At this temperature, successively 1.66 g of sodium hydroxide solution

(50%) and 9.2 g of aqueous poly-DADMAC (active substance 53%) was added. The initially turbid mixture is cooled with stirring. This forms a clear colloid solution. Production of the washing cloth

The washing cloth thus obtained is washed together with 60 g of accessory pack (household washing at 40 ° C.). The accessory pack consists of 30 g polyester (polyethylene terephthalate, knitted fabric) and 30 g polyamide (polyamide 6,6; knitwear). The accessory pack simulates the textiles to be finished by the end user. After household washing, the package is dried for 2 days in air and conditioned for 3 days in a climate room. Subsequently, antistatic and hydrophilic properties are measured. In order to check a homogeneous equipment, the accessory pack is tested in three different places. Polyester (polyethylene terephthalate, knitted fabric):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 180 sec.

Polyamide 6,6; Knitwear):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 80 sec.

In order to test the washing permanence of the product equipped by this method (= accessory pack), the accessory pack was again 3, 5 and 10 times washed. The mean values of the measurements are shown as results.

Polyester (polyethylene terephthalate, knitted fabric):

Example 6: Washcloth

Preparation of the composition

In a beaker with stirrer (stirrer) 50.37 g of water are introduced. While stirring, 15 g of "Marlipal 16 / 18-25" (C16-C18, 25EO) are added, then 10 g of Dowanol DPM are added and the mixture is heated to 90 ° C, completely dissolving the surfactant The mixture is cooled to 60 ° C. At this temperature, 1.66 g of sodium hydroxide solution (50%) and 9.2 g of aqueous poly-DADMAC (active substance 53%) was added, and the initially turbid mixture was cooled while stirring to form a clear colloid solution. Production of washing cloth

After household washing, the package is dried for 2 days in air and conditioned for 3 days in a climate room. Subsequently, antistatic and hydrophilic properties are measured. In order to check a homogeneous equipment, the accessory pack is tested in three different places.

Polyester (polyethylene terephthalate, knitted fabric):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 180 sec.

Accessory pack PES

Antistatic sinking time

[Ohm] [s]

5.00 E + 1 1 3

1.80 E + 1 1 2

1.70 E + 1 1 2 Polyamide 6,6; Knitwear):

Zero value antistatic 1, 0 x 10 ¹⁴ ohms, hydrophilicity> 80 sec.

Polyester (polyethylene terephthalate, knitted fabric):

Equipment washes washes washes washes washes washes washes

40 ° C 40 ° C 40 ° C 40 ° C 40 ° C 40 ° C

[Ohm] [ohm] [ohm] [s] [s] [s]

Accessory kit

PES in 2.60E + 1 1 6.50E + 1 1 8.00E + 1 1 23 29 180

Example 6

Polyamide 6,6; Knitwear):

Equipment washes washes washes washes washes washes washes

40 ° C 40 ° C 40 ° C 40 ° C 40 ° C 40 ° C

[Ohm] [ohm] [ohm] [s] [s] [s]

Accessory pack PA

in Example 4.80E + 1 1 8.00E + 1 1 1.10E + 12 20 12 62 6

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.

3. The composition according to any one of claims 1 or 2, wherein the colloid particles have an average diameter of 5 nm to 3 μιη.

A composition according to any one of claims 1-3, wherein the composition is optically transparent or opaque.

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

6. The 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 alkylation of at least three amino functions in a polymer to permanent cationic groups. 7. A composition according to any one of the preceding claims, wherein the polyelectrolyte (A) is a homo- or copolymer.

The composition of claim 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, (eth) acrylic acid, vinyl acetate and allyl alcohol derivative.

A composition according to any one of claims 6-8, wherein the monomer unit (i) comprises an ammonium, pyridinium, imidazolium, pyrrolidinium group or an N-substituted heteroaromatic group.

A composition according to any one of claims 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 claims 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. A composition according to any one of claims 6-8, wherein the polymer having at least three amino functions in (iii) is selected from the group consisting of linear or branched polyalkyleneimine, in particular polyethylenimine, or obtainable by polymerization of at least three monomer units selected from the group consisting of diallyldialkylamine, vinylamine, vinylpyrazole, vinylimidazole and / or aziridine.

13. A composition according to any one of the preceding claims, wherein the component (A) 4-62 wt .-%, preferably 5-55 wt .-%, based on the total mass of the components (A), (B) and (C) ,

14. The composition according to any one of the preceding claims, wherein the 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. The composition according to any one of the preceding claims, wherein 30-100 mol%, preferably 50-100 mol%, of the repeating units in the component (A) have a cationic group.

16. A composition according to any 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.

17. A composition according to any one of the preceding claims, wherein the anionic compound (B) comprises at least one phosphate, phosphonate, sulfate, sulfonate, carboxylate, sulfoacetate, sulfosuccinate and / or taurate group.

18. A composition according to any one of the preceding claims, wherein the anionic compound (B) is selected from mono-, di- (C _4-22 -

Alkyl (alkoxy)) phosphate, mono-, di- (C _ ₂₂ alkyl) phosphonate, C ₄ _ ₂₂ - Alkylaminophosphonat, sulfate C _4-2 2-alkyl (alkoxy), secondary alkyl sulfonate, petroleum sulfonate, C _4-2 2 Alkyl sulfonate, C _4-22 alkylaryl sulfonate, 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 _4-22 alkyl polyalkoxylene sulfate.

The composition of claim 16, wherein the polyelectrolyte (B) is a polymer having pendent anionic groups.

20. The composition of claim 19, wherein the polyelectrolyte is obtainable by polymerization of at least three monomer units (iv), each having at least one chemically ionizable group.

21. The composition of claim 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 styrenesulfonic acid.

22. The composition according to any one of claims 16, 17, 19, 20 or 21, wherein the polyelectrolyte (B) is a homo- or copolymer.

23. The composition of claim 22, wherein the polyelectrolyte copolymer comprises at least one repeating unit, which is due to a comonomer selected from the group consisting of styrene, acrylonitrile, (meth) acrylic acid ester and / or (meth) acrylamide.

24. The composition according to any one of the preceding claims, wherein the component (B) 15-85 wt .-%, preferably 20-80 wt .-%, based on the total mass of the components (A), (B) and (C) ,

25. The composition according to any one of the preceding claims, wherein the component (A) and the component (B) together form an ionic complex.

Composition according to any one of the preceding claims, in which 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 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.

28. 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, e.g. Poly (ethylene oxide-co-propylene oxide).

29. The composition according to any one of the preceding claims, wherein component (C) 20-80 wt .-%, preferably 30-60 wt .-%, based on the total mass of the components (A), (B) and (C).

30. A composition according to any 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.

31. Composition according to one of the preceding claims, wherein component (D) constitutes 40-80% by weight, preferably 50-80% by weight, based on the total composition.

A composition according to any one of the preceding claims, further comprising at least one textile auxiliaries, e.g. an antistatic,

Hydrophilizing agents, flame retardants, softening agents,

Wrinkling agent, lubricant, UV resistance agent, Corrosion inhibitor or fluorine-free or fluorine-containing hydrophobing agent.

33. Dosing unit comprising a composition according to one of claims 1 to 32, in particular in the form of a washing cloth, tabs, caps,

Pods or a dosing device.

The metering unit of claim 33, wherein the washcloth comprises a substrate, e.g.

Knitted fabric, a nonwoven, woven, knitted or felt covers.

35. The dosing unit of claim 34, wherein the substrate is made of cellulose, e.g.

Cotton or viscose, polyethylene terephthalate, polyamide, polyolefin, in particular polypropylene or polyethylene and / or polyacrylonitrile.

36. A dosing unit according to claim 34 or 35, wherein the substrate is impregnated with the composition according to any one of claims 1-32.

The metering unit of any of claims 34-36, wherein the mass ratio of components (A), (B) and (C) in the composition to the substrate is 1: 1 or 10: 1 to 0.5: 1.

38. A dosing unit according to any one of claims 34-37, wherein the substrate has an area of 10-1600 cm ² .

39. Dosing unit according to claim 33, wherein the composition is packaged, preferably in a bag, preferably made of polyethylene, polypropylene, polyvinyl alcohol or polylactide.

A method of making a wash sheet according to any of claims 34-38 comprising the steps

(i) providing a substrate,

(ii) applying the composition of any of claims 1-32 to the substrate and (iii) optionally at least partial removal of the liquid medium (D) at temperatures above room temperature and optionally at reduced pressure.

41. Use of the dosing unit according to any one of claims 33-39 or the composition according to any one of claims 1-32 for antistatic and / or hydrophilizing finishing of textiles.

42. Use according to claim 41 in washing machines, in particular household washing machines.