WO2018054687A1

WO2018054687A1 - Improved method for dyeing textiles containing synthetic materials in the washing machine using modified silicones

Info

Publication number: WO2018054687A1
Application number: PCT/EP2017/072407
Authority: WO
Inventors: Mareile Job; Anja VON KATHEN; Rainer Sorg; Laura FALENSKI; Frank Janssen
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2016-09-21
Filing date: 2017-09-07
Publication date: 2018-03-29
Also published as: DE102016218163A1

Abstract

The present invention relates to a method for machine-dyeing textiles, more particularly textiles which contain synthetic materials such as polyester.

Description

Improved coloring of textiles with synthetic materials in the washing machine due to modified silicones

The present invention relates to a process for the machine dyeing of textiles, in particular of textiles, comprising synthetic materials, such as polyester.

Means for dyeing textiles have been known for a long time. For example, in DE 195 45 585 A1 from 1995, an agent for dyeing textiles is described, which comprises a dye, a humectant and a thickener.

Means for dyeing textiles in the washing machine are also known in the market. Good coloration is achieved in particular with textiles made of cotton, linen or cellulose-containing fabrics. However, it is often the case that the textiles have synthetic materials in whole or in part. For example, seams are often made of polyester yarn, for example. These are not dyed by known dyes or only to a limited extent by the dye. Thus, after dyeing, the seam is often seen particularly clearly, since no dye was absorbed here, especially when dyed with a darker color. Even blended fabrics that have synthetic materials in addition to natural materials, are poorly colored and often not homogeneously colored.

The object of the present invention is therefore to overcome these known from the prior art disadvantages for the dyeing of textiles with synthetic materials in the

To avoid washing machine. Surprisingly, it has been shown that textiles which comprise synthetic materials can be dyed with at least one reactive dye if they are also brought into contact with at least one nucleophile-modified silicone. In a first embodiment, therefore, that of the present invention

underlying problem solved by a method for machine dyeing of textiles comprising synthetic materials, with at least one reactive dye, in which the textile to be dyed is brought into contact with the at least one reactive dye and at least one silicone, wherein the silicone terminally and / or in the side chain having an organic group having a nucleophile is modified, and the thus-modified silicone has an equivalent weight of the functional groups (FGEW) of 450 g / mol or more. The silicone is nucleophilically modified at one or more sites. In chemistry, nucleophilicity is a measure of the ability of an atom with a lone pair of electrons to attack a (partially) positively charged atom to form a covalent bond. Nucleophiles have a negative partial charge or have a free electron pair in a relatively high-energy atomic orbital.

It has now been found that the silicone according to the invention makes it possible to color all types of textiles with reactive dyes. Both synthetic textiles and natural textiles are dyed by the reactive dye. The silicone does not prevent the reaction of the reactive dye with, for example, cellulose, cotton, linen or other natural textile materials, so that a uniform color is also achieved in textiles made of blended fabrics. Textiles comprising synthetic materials according to the invention comprise such textiles which have a synthetic material over the entire surface. However, textiles are also included according to the invention, in which only the seam has a synthetic material. Synthetic materials within the meaning of the present invention are synthetic textile fibers or nonwovens. These textile fibers are for example made of polyester, polyamide, polyacrylic, polypropylene and elastane or mixtures of these. The inventive method now allows the coloring of these synthetic fibers or corresponding synthetic fibers or

Textiles containing materials. The coloring of natural fibers is not influenced by the method according to the invention. Thus, the inventive method allows a homogeneous coloring of textiles, which consist entirely of synthetic materials, but also of such textiles, in addition to synthetic materials and natural materials such as cotton, linen, viscose or wool.

The dyeing is carried out according to the invention with at least one reactive dye. Reactive dyes represent today the largest dye group for dyeing cellulose or fibers thereof. Reactive dyes form a covalent bond with the fiber, resulting in wet fast dyeings.

Textiles which can be dyed with the method according to the invention can consist of any desired materials. They have a synthetic material, in particular polyester. The proportion of synthetic material is preferably 10 wt .-% or more or 30 wt .-% or more, in particular 50 wt .-% or more, particularly preferably 70 wt .-% or more. Even textiles which consist of 100% synthetic material, in particular polyester, can be homogeneously dyed with the process according to the invention, the color intensity being markedly improved compared to processes known in the prior art. Likewise, textiles in which only the seam consists of a synthetic material or identifies such according to the invention comprises. Textiles in the sense of The present invention includes all types of woven, knitted, knitted or nonwoven fabrics, including fibers or threads, such as those contained in textiles, for example, in the form of seams.

Chemically, the reactive dyes consist of two parts: a chromophore part (such as an azo compound N = N) and attached to a reactive group (in the case of bifunctional reactive dyes also several reactive groups). More precisely

Reactive dyes into four sub-components, namely a solubilizing group, the actual dye (chromophoric group), a bridge member and a reactive anchor. The solubilizing group is responsible for the water solubility of the reactive dye. The chromophoric group absorbs light and thereby gives the color impression. The linkage links the anchor to the chromophore moiety and the anchor is responsible for the covalent bond with the textile.

Examples of suitable reactive dyes are derivatives of 2,4,6-trichloro-1, 3,5-triazine, in which a chlorine atom is replaced by a chromophore group (eg Procion MX) and optionally a further chlorine atom by amino or Alkoxy groups is replaced (eg Procion H, Procion P and Cibacron). In further derivatives, the remaining Cl atom may be replaced by fluorine (e.g.

Cibacron F) or a tertiary amine, especially nicotinic acid, (e.g. Kayacelon React, Procion H-EG). Also suitable are halopyrimidine dyes in which am

Heterocycle is connected to a chromophoric group (for example, Drimaren) and the heterocycle further cyano (Reacton), fluorine (Levafix EA) or methylsulfone groups (Levafix P). Dichloroquinoxalines and dichlorophthalazines are also suitable, as are benzothiazole derivatives. The benzothiazole derivatives have a leaving group, for example a halogen, in the 2-position of the heterocycle. By way of example, C.I. Reactive Black 5 (Remazol Black B), Procion HE, Sumifix Supra Yello 3RF, Cibacron C, 2-sulfooxyethylsulfonyl is further preferred as the active group to which a chromophore moiety can attach. Suitable chromophoric groups are azzo dyes, anthraquinone dyes, phthalocyanine dyes or triphenodioxazine dyes.

The reactive dye may preferably be selected from Cl Reactive Yellow 4, Cl Reactive Yellow 17, Cl Reactive Orange 1, Cl Reactive Red 8, Cl Reactive Red 12, Cl Reactive Red 23, Cl Reactive Blue 16, Cl Reactive Black 5, Sumifix Supra Yellow 3RF, Cibacron C, 6-amino-1-hydroxynaphthalene-3-sulfonic acid, 7-amino-1-hydroxynaphthalene-3-sulfonic acid, 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, 8-amino-1-haydroxynaphthalene -3,5-disulfonic acid, copper complexes of ο, ο'-disubstituted azo compounds, CI Direct Blue 106, CI Direct Blue 109, CI Pigment Violet 23, CI Reactive Blue 163, CI Reactive Blue 172, CI Reactive Blue 187, Cl Reactive Blue 198, Cl Reactive Blue 204, Cl Reactive Blue 224, Reactive Blue 225, Reactive Reactive Yellow 15, Reactive Red 159, Reactive Red 123, Reactive Red 16, Reactive Red 123, Reactive Orange 12, Reactive Orange 16, Reactive Orange 21, Reactive Blue 21, Reactive Yellow 21, Reactive Yellow 1, Levafix Yellow CA, Reactive Orange 107, Reactive Yellow 201 and Everzol Orange GSP or Remazol Briliant Blue FB.

Suitable reactive dyes are described in Ullmann's Encyclopedia of Industrial Chemistry (Seventh Edition, 201 1) Volume A 22 on pages 277 to 289. This is hereby fully incorporated by reference.

Especially preferred are Reactive Black 5, Reactive Blue 225, Reactive Blue 1 16, Reactive Blue 224, Reactive Blue 203, Reactive Yellow 125, Reactive Yellow 27, Reactive Red 159, Reactive Red 123, Reactive Orange 64, Reactive Orange GR, Reactive Blue 21, Reactive Yellow 1 1 1, Levafix Yellow CA, Reactive Orange 107, Reactive Yellow 201 and Everzol Orange GSP as a reactive dye.

The reactive substances may be present alone or in mixtures. This allows the color to be adjusted as desired.

In the following, when using the term "reactive dye, mixtures of two or more reactive dyes should always be included according to the invention. Likewise, according to the invention, mixtures of two or more modified silicones are always to be included in the use of the term "modified silicone".

According to the invention, the at least one modified silicone preferably has a functional group equivalent weight (FGEW) equivalent weight of 450 g / mol or more. The FGEW indicates the number of functional groups in a molecule and thereby allows the characterization of the modified silicone. The FGEW is defined as the ratio of number average molecular weight (determined by gel permeation chromatography) and the number of functional groups in the polymer. For nucleophiles containing an -OH group, the hydroxyl group value is often given in [mg KOH / g]. The equivalent weight of the functional group in [g / mol] can be determined from the hydroxyl group equivalent according to the following equation:

FGEW [g / mol] = 56,000 / hydroxyl group equivalent [mg KOH / g]

It has been found that an equivalent weight of the functional groups of 450 g / mol is sufficient to achieve a homogeneous coloration both in blended fabrics and in purely synthetic textiles. Preferably, the equivalent mass of the functional Groups in the range of 450 g / mol to 60,000 g / mol. It is preferably at least 450 g / mol, in particular at least 470 g / mol, preferably 500 g / mol or more. Values of more than 60,000 g / mol do not lead to any further intensification of the color, so that larger values may be present, but lead to no improvement. It has been found that values of 50,000 g / mol or less, in particular 30,000 g / mol or less, in particular 10,000 g / mol or less are sufficient to allow a uniform, color-intensive, homogeneous coloration. The equivalent mass of the functional groups (FGEW) is preferably in the range from 500 to 9,000 g / mol, in particular from 750 to 8,000 g / mol, preferably from 1, 000 to 7,600 g / mol. The equivalent mass of the functional groups can be determined by titration

The silicone according to the invention has a nucleophilic organic group terminally and / or in the side chain. Typical anionic nucleophiles are, for example, the following radicals: hydroxide, alkoxide, thiolate, carbanions, halide, peroxide, cyanide or azide. Neutral nucleophiles are, for example, amines, phosphines, alcohols, aromatics or water amines can be present as primary, secondary or tertiary amines. The silicone particularly preferably has a structure according to the following general formula A:

in which each independently

A: -Si (CH ₃ ) _a (X) b, with a + b = 3, and

B: Si (CH ₃ ) c (X) d, where c + d = 3,

X is an organic radical selected from -RNH ₂ , -RN (H) R'NH ₂ , -OH, -R (C ₂ H 4) e (C ₃ H ₆ O) _f R ', -ROH, -RSH, -C (R-) OH) 2R 'and mixtures thereof,

in which

R, R 'are each independently a linear or branched, aromatic or

is aliphatic organic radical having 12 or fewer carbon atoms, in particular having 6 or fewer carbon atoms,

e, f are, independently of each other, integers from 0 to 15, where e + f> 1, and m and n are, independently, integers from 0 to 600, where n = 0 and m is always 0 and m + n = 10 to 600.

Preferably, m and n are selected such that the number average molecular weight is 1,000 to 40,000 g / mol, The silicone is present as a polymer. In the general formula A it is shown for simplicity as a block copolymer. According to the invention, of this representation, as far as n Φ 0, are also random copolymers, gradient copolymers, alternating copolymers and block copolymers.

The silicone according to the invention can thus be modified terminally and / or in the side chain. Particularly preferably, the silicone is either terminal or modified in the side chain.

Therefore, n = 0 is particularly preferred when b and / or d * 0. Here, a, b, c, d, e, f and m and n can be integer natural numbers, where a, b, c and d can be 0, 1, 2 or 3. For e and f, all values between 0 and 15, ie 1, 2, 3, 4, 5 and so on, are to be regarded as disclosed.

If n = 0, the silicone according to the invention is only terminal, but not modified in the side chain. In this case, there may be a modification to a chain end. However, it is also possible that the silicone is modified at both ends of the chain. If both chains are end-modified, b and d * are 0. If one end of the chain is modified, then either b or d = 0. Preferably, b and d are 0 or 1. Multiple modification at one chain end is not preferred.

R and R 'represent linking groups between the Si-O backbone of the siloxane and the functional nucleophiles. They may also be part of the nucleophilic group. In order to place the functionality of the nucleophilic group close to the fiber to which the siloxane binds, the length of these linking groups is minimized. R and R 'are preferably independently of one another linear or branched, aromatic or aliphatic, substituted or unsubstituted organic radicals having 12 or fewer carbon atoms, in particular 10 or less, preferably 8 or less, in particular 6 or fewer carbon atoms. R and R 'can therefore independently of each other be acyl (ene), alkenyl, alkynyl or aryl radicals having 12 or fewer carbon atoms.

R and R 'may be terminal or as a link. It may thus be, for example, an alkyl or an alkylene group. If in the present application alkyl is defined for R / R ', then this applies correspondingly to the alkylene radical, as far as R / R' is present as a link. The same applies to alkenyl. Alkynyl and aryl radicals, which may also be included as a link or terminal.

"Aryl" is the general name for an atomic group derived from an aromatic hydrocarbon by removal of a hydrogen atom bound to the ring. The aromatics further enhance the nucleophilicity of the organic X residue. R and R 'can thus, for example, independently of one another represent a phenyl radical, a 1-naphthyl radical or a 2-naphthyl radical. If they act as a link, then 2 hydrogen atoms are from the aromatic ring

In the present application, hereinafter "alkyl" refers to a saturated aliphatic hydrocarbon including straight and branched chain groups Preferably, the alkyl group has 1 to 10 carbon atoms (when a numerical range of, for example, "1 to 10" is given herein, it is meant that these In particular, the alkyl may be a middle alkyl having 1 to 6 carbon atoms or a lower alkyl, in this case the alkyl group, 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc. up to and including 10 carbon atoms. which has 1 to 4 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, etc., act.

"Alkenyl" refers to an alkyl group, as defined herein, consisting of at least two

Carbon atoms and at least one carbon-carbon double bond, z. Ethenyl, propenyl, butenyl or pentenyl and their structural isomers such as 1- or 2-propenyl, 1-, 2-, or 3-butenyl, etc.

"Alkynyl" refers to an alkyl group as defined herein which is at least two

Carbon atoms and at least one carbon-carbon triple bond exists, for. Ethynyl (acetylene), propynyl, butynyl or petinyl and their structural isomers as described above.

One or more hydrogen atoms, methyl groups, methylene groups, methine groups or quaternary carbon atoms in R and / or R 'may each independently be substituted by heteroatoms. Heteroatoms in the context of the present invention are selected from the group consisting of nitrogen, oxygen, sulfur, silicon, selenium, phosphorus, fluorine, chlorine, bromine or iodine, in particular nitrogen, sulfur, silicon, selenium or phosphorus. One or more methyl groups can be substituted by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, silicon, selenium, phosphorus, fluorine, chlorine, bromine or iodine, one or more methylene groups can be selected by a heteroatom selected from the group of nitrogen, Oxygen, sulfur, selenium, phosphorus, or silicon, one or more methine groups may be substituted by a heteroatom selected from the group consisting of nitrogen, phosphorus, or silicon, and one or more quaternary carbon atoms may be substituted by silicon. Preferably, R and R 'are unsubstituted. Particularly preferably, R and R 'independently of one another have radicals which have 6 or fewer carbon atoms, since in this case a particularly good attachment of the organic radical to the main chain of the siloxane is made possible.

Silicones modified in accordance with the invention may have, for example, the following structures:

Suitable silicones are described, inter alia, by Shin-Etsu Chemical Co., Ltd. (Tokyo, Japan) (exemplary product names: KF-860, KF-8005, X-22-3939A, KR-8012, KF-6001 to -6003, X-22-4952 and others) or by Wacker Chemie AG (Munich, Germany), for example, under the product line "Finish WR".

The process according to the invention now comprises the steps of contacting the textile to be dyed with the modified silicone and with the reactive dye. In this case, it is possible according to the invention that the textile is first brought into contact with the modified silicone and only subsequently with the reactive dye. In this case, first the silicone can react with the textile and the functional groups of the silicone are then ready for the reactive dye.

However, it is also preferred according to the invention to bring the textile to be treated simultaneously in contact with the modified silicone and the reactive dye.

The molecular weight (number-average molecular weight determined by gel permeation chromatography) of the modified silicone is in particular in the range from 1,000 to 40,000, preferably from 2,000 to 30,000 and in particular from 2,000 to 20,000.

According to the invention, the dyeing is done in a washing machine. The concentration of

Silicone according to the invention in the wash liquor is in particular 0.5 to 15 wt .-%, preferably 0.5 to 10 wt .-%, in particular 1 to 5 wt .-% based on the total weight of the wash liquor. It has been found that such an amount is sufficient to provide textiles with a silicone finish and then to color it. Washing liquor is the total amount of liquid contained in the washing machine, including all substances dissolved therein.

The inventive method is preferably carried out at temperatures in the range of 5 ° C to 60 ° C, in particular from 15 ° C to 40 ° C. Initially, contacting with the silicone, this can also be done at temperatures of 30 ° C or less. The contacting of the reactive dye with the textile is preferably carried out at temperatures of 20 ° C to 40 ° C. Thus, these temperatures are also preferred in the case where silicone and reactive dye are brought into contact with the textile at the same time.

In one embodiment of the method according to the invention, modified silicone and reactive dye are provided simultaneously in a washing machine. The wash liquor initially has a temperature of 10 ° C to 15 ° C and is then heated to a temperature of 30 ° C to 40 ° C. This allows the silicone to react with the textile first.

Subsequently, the reaction of the reactive dye with the textile takes place. This allows a particularly intense coloration compared to when silicone and reactive dye are simultaneously brought into contact with the textile at temperatures in the range of 30 ° C to 40 ° C.

Initially contacting only with the silicone, the duration of the

In contacting, preferably at least 5 minutes, especially at least 10 minutes or at least 15 minutes, more preferably 30 minutes or more before the so pretreated textile is brought into contact with the reactive dye. Accordingly applies to a controlled

Temperature history that the lower temperature is maintained for a period of time before it is then increased.

Thus, according to the invention, the following methods are preferred:

In a first step, only the silicone of the invention in a washing machine

brought in. The textiles are introduced into the drum. Subsequently, a

Wash at cold wash. This should have a duration of at least 5 minutes, in particular of at least 10 minutes or of at least 15 minutes, more preferably of 20 minutes or more, or of 30 minutes or more.

The textile thus treated is then removed from the washing machine and dried. After drying, the textiles are moistened and put back into the washing drum.

Also, the reactive dye is provided. Subsequently, a conventional washing program is started in the main wash at a temperature preferably from 30 ° C to 40 ° C. Usual laundry programs are those for cooking and coloreds, as they are pre-programmed in commercial washing machines. Subsequently, the textile is washed with a commercially available detergent at 40 ° C or less, usually at 20 ° C to 30 ° C in a suitable washing program for colored laundry. In this case, excess dye that has not reacted with the textile is removed.

The dyed textile is then removed from the machine. Preferably, then the empty machine at a temperature of 40 ° C or more, especially at 60 ° C, run with detergent in a conventional wash cycle for cooking and coloreds. Following this, preferably any paint residues on rubber parts of the washing machine are preferably removed with a damp cloth.

The textile is now dyed and the washing machine can be used as usual, without the risk that textiles are dyed in further washes.

The silicone used as well as the reactive dye may be in liquid form and / or solid form. The state of matter refers to room temperature. This is preferred Silicone liquid and the reactive dye solid and is in the form of a powder or granules. The provision can be carried out by placing silicone and / or reactive dye in the chamber usually provided for detergent. Preferably, however, the reactive dye is provided directly in the washing drum. More preferably reactive dye and silicone are provided in the washing drum.

In a further preferred embodiment, the procedure is as described above.

However, there is no drying of the textile between the first wash in which the silicone is applied and the second wash in which the reactive dye is applied to the textile. Here, immediately after the wash cycle in which the silicone is applied, the reactive dye is introduced into the drum and, as described above, a wash cycle is started at the end of which the textile is removed and the washing machine runs again empty in a wash cycle at a higher temperature. The empty wash cycle is used to clean the washing machine so that no unwanted coloration occurs during subsequent wash cycles.

Both the reactive dye and the silicone are preferably introduced directly into the washing drum. It is possible, for example, that dye and silicone are each present in their own suitable container, which are opened before use and the contents are then added without the container in the washing drum. It is according to the invention also possible and preferred that silicone and dye are added in the respective container in the washing drum. In this case, the container may be at least partially water-soluble, so that during the respective wash cycle, the container is partially or completely dissolved, so that the content is released. Suitable materials for water-soluble containers or closures are well described in the art. In such cases, the container and / or closure preferably comprises polyvinyl alcohol (PVA) and consists in particular thereof.

However, it is also possible that the container is not water-soluble, but has such a shape that the container is first opened by the user and then introduced as a whole into the drum together with the textile. The spatial configuration of a corresponding container is limited only by the fact that this should be done in the wash no damage to the drum of the washing machine. The container may be, for example, a bag. In the context of this embodiment, deformable plastic bags have proved to be particularly preferred, which immediately before

Application can be cut open and then opened with the contents put on the laundry. However, it may also be a dimensionally stable design, which has a round, oval or egg-shaped form. In this case, one or two sides can also be flattened, whereby a first stability is given and a filling or temporary Closing is enabled. By a corresponding temporary closure, which is then opened by the consumer before use, a release in the washing machine is ensured. A corresponding container can be made of a plastic.

Particularly preferably, a corresponding container comprises polypropylene (PP) and in particular consists thereof. To avoid a manual opening of the container, the closure can for example be made of water-soluble polyvinyl alcohol.

In a likewise preferred embodiment, the method according to the invention comprises the following steps:

Silicone and reactive dye are placed in the drum of a washing machine. A moistened textile is also added to the washing machine. Subsequently, a conventional washing program is started, which has a temperature of preferably at least 30 ° C, but not more than 40 ° C. Suitable here is a conventional washing program for

Multi Colored-wash.

Silicone and reactive dye are in two different containers. These are designed in such a way that first the silicone is released and only after a time delay of preferably 10 minutes or more, in particular 15 minutes or more or 20 minutes or more, is the reactive dye released from its container. This allows first the silicone and then the reactive dye is associated with the textile to be dyed.

It is also possible that reactive dye and silicone are placed in a container in the drum. In this case, silicone and reactive dye are preferably in different spatial areas of the container. Here, these areas may have a different water solubility, so that thereby a time-delayed

Release of silicone and reactive dye is made possible. It is also conceivable that, in particular in the case of a dimensionally stable formation of a container which is not water-soluble, reactive dye and silicone are introduced into the container in such a way that they are separated by a water-soluble wall. In this case, the silicone is in the direction of the side of the container, which is opened by the consumer before introduction into the drum. Thus, the silicone is first brought into contact with the textile in the wash cycle. Only when the silicone is released from the container, the water-soluble partition comes into contact with the liquor, so that it is dissolved, which then passes the reactive dye in the drum and thus in contact with the textile. The water-soluble wall can be formed, for example, in the form of a water-soluble film or membrane, which is permeable to neither the silicone nor the reactive dye and does not react with them.

According to the invention it is also possible to incorporate the reactive dye in microcapsules.

Corresponding microcapsules are well described in the prior art. The microcapsules are equipped so that they do not react with the silicone according to the invention and in this, should it be present as a liquid, also not solve or otherwise destroyed. Silicone and encapsulated reactive dye can then together in a container in the

Washing drum are introduced. In the subsequent wash cycle for dyeing the textile silicone and reactive dye or the capsules are released simultaneously from the container. The encapsulation, however, also makes it possible for the silicone modified according to the invention first to come into contact with the textile and only then, after dissolution of the capsules, does the reactive dye come into contact with the textile.

In a further embodiment, the present invention relates to the use of a silicone as described above for dyeing textiles comprising a synthetic material together with a reactive dye.

In yet another embodiment, the present invention relates to a kit for dyeing textiles comprising synthetic materials comprising a container and a container

Silicone according to the invention and a reactive dye.

In a next embodiment, the present invention comprises a means for dyeing textiles with synthetic materials comprising a reactive dye and a silicone, wherein the silicone terminal and / or in the side chain with an organic group, the

Nucleophile is modified, and the thus modified silicone has an equivalent weight of the functional groups (FGEW) of 450 g / mol or more. In the agent according to the invention, the reactive dye can be present, for example, in encapsulated form. Corresponding microcapsules or macrocapeins have been adequately described in the prior art.

The agent used in the process according to the invention may comprise further constituents, for example preservatives and / or surfactants. Preferably, however, the agent is free of preservatives and also free of surfactants.

If surfactants are present, the concentration of the surfactants is in such a range that it is below the critical micelle concentration in the wash liquor. The proportion of surfactants, if present, is preferably 5 ml or less per 5 l of water. The presence of surfactants in said concentration, salts or other in

Detergents contained detergents does not interfere with the inventive method, so that a pre-cleaning of the washing machine is not necessary.

The reactive substance can be present in a preparation which has not only the reactive dye but also other auxiliaries. Corresponding auxiliaries are, for example, water-soluble salts, such as an alkali metal. Alkaline earth, AI and / or Zn cation and sulfate, chloride, bromide, carbonate, bicarbonate, silicate, metasilicate, bisulfate, nitrate, acetate, carboxylate and / or formate anion, in particular Na salts such as NaCl, Na metasilicate, Na silicate, Na acetate, Na carbonate and Na carboxylate, in particular NaCl, Na metasilicate, Na carbonate and Na silicate. Further auxiliaries are, for example, pH regulators for adjusting a pH of> 7, enzymes or oils. PH adjusting agents, especially sodium hydroxide, sodium carbonate, sodium silicate, sodium bicarbonate, sodium metasilicate and mixtures thereof.

The enzyme may be selected from an amylase, a protease, a lipase, a

Cellulase, hemicellulase, peroxidase, xylanase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, a malanase, a β-lucanase, an arabinosidase, a hyaluronidase, a chondroitinase, a laccase, and combinations thereof.

The oil is a neutral oil having 10 to 40, especially 15 to 30, carbon atoms.

An exemplary preparation comprises the reactive dye in a proportion of 0.01 wt .-% to 10 wt .-%, in particular from 0, 1 wt .-% to 10 wt .-%, preferably from 0.5 wt .-% to 9% by weight, for example from 1 wt .-% to 8 wt .-%, preferably from 1, 5 wt .-% to 8 wt .-% to.

The neutral oil may be contained in a proportion of 0 wt% to 1 wt%, especially 0.05 wt% to 0.2 wt%.

The remaining weight fraction is brought to 100 wt .-% by water-soluble salts and pH adjuster.

Thus, a particularly preferred composition comprises NaCl in a proportion of from 3% by weight to 95% by weight. pH adjusting agents, such as, for example, sodium metasilicate or sodium silicate, may each be present in an amount of up to 10% by weight (corresponding in total up to 20% by weight).

As another pH adjuster, the formulations often contain sodium carbonate, preferably in an amount of 10 to 95% by weight.

A pH-adjusting agent combination of sodium carbonate and sodium metasilicate is particularly preferred according to the invention.

The aforementioned aids do not influence the method according to the invention. The silicone makes it possible to furnish textiles with a dye, wherein the presence of the named auxiliaries does not adversely affect the coloring.

The present invention is explained in the following exemplary embodiments in a non-limiting manner.

Exemplary embodiments: Embodiment 1

In the following embodiments, Dylon -Tulip ^® Red was used as a composition containing a reactive dye. Dylon -Tulip ^® Red is a composition Cl Reactive Red 159 percent (1 wt .-% to 5 wt .-%), Cl Reactive Red 123 (<1 wt .-%) and Cl Reactive Orange 64 (<. 1 -%) as a reactive dye and sodium carbonate (25 wt .-% to 50 wt .-% having.

A fabric sample consisting of 100% polyester (WFK 30A) was used as the test sample. To simulate the washing process in a smaller scale washing machine, a Linitest Atlas machine was used.

The dry sample was placed in a Linitest apparatus containing an aqueous solution of a liquid silicone modified according to the invention. The concentration of silicone was 5 wt .-% based on the total weight of the wash bath. The temperature was 40 ° C. Different silicones were tested.

After 30 minutes, the sample was removed and still in a wet state in a

commercially available washing machine dyed in a 40 ° C cooking / colored program. The dyeing was done with "Dylon ^® -Tulip Red" according to the instructions for use of the textile dye.

As a comparative example, samples were used, which were dyed without pretreatment with the silicone with "Dylon ^® -Tulip Red", also in accordance with the instructions in a

Commercially available washing machine in a 40 ° C cooking / coloring program.

For the staining, moistened samples were mixed with the reactive dye in the

Was given washing machine and dyed together with the colorant in 40 ° C cooking / Bunwaschprogramm. Following the dyeing run, the samples were left in the machine and a repeated wash at 40 ° C with the addition of detergent. Subsequently, the samples were dried in air.

After dyeing and drying, the L ab values of the samples were measured. The results are shown in the following table: Color value a ^* dE before staining -0,305

Comparative Example (without silicone) 3.571 4.9

Example 1 4.081 5.5

Example 2 8,946 1 1, 9

Example 3 1 1, 528 15.6

In Example 1, a silicone according to the general formula (IX) shown above was used. In Example 2, a silicone according to the general formula (VI) shown above and in Example 3 a silicone according to the general formula (IV) shown above was used.

The samples equipped with the silicones according to the invention showed improved colorings in comparison with water-only pretreated textiles.

Embodiment 2:

A textile sample (textile) consisting of 50% cotton and 50% polyester was used.

The textile was prepared according to the instructions for use and then dyed in a washing machine with "Dylon ^® -Tulip Red". The dyeing was carried out in a conventional washing machine in the cooking / colored wash program at 40 ° C according to the instructions.

In the washing machine was also at the same time with the dye composition

given silicone according to the invention. In this case, a silicone according to the general formula (VI) was used. The concentration of silicone in the wash bath was 0.5% by weight, based on the total weight of the wash bath.

The simultaneous treatment with dye and silicone was carried out at a temperature of 40 ° C and a duration of 60 minutes. It was then washed and dried as in Example 1.

The textile was dyed homogeneously

Embodiment 3

In the following embodiments, Dylon -Tulip ^® Red was used as a composition containing a reactive dye. Dylon -Tulip ^® Red is a composition Cl Reactive Red 159 (1% to 5% by weight), Cl Reactive Red 123 (<1% by weight) and Cl Reactive Orange 64 (<1% by weight) as a reactive dye and sodium carbonate (25% by weight). % to 50% by weight.

After 30 minutes, the sample was removed and dyed while still wet in a commercial washing machine in 40 ° C cooking / coloring program. The dyeing was done with "Dylon ^® -Tulip Red" according to the instructions for use of the textile dye.

Commercially available washing machine in a 40 ° C cooking / coloring program.

For the dyeing moistened samples were added together with the reactive dye in the washing machine and dyed together with the colorant in 40 ° C cooking / Bunwaschprogramm. Following the dyeing run, the samples were left in the machine and a repeated wash at 40 ° C with the addition of detergent. Subsequently, the samples were dried in air.

After dyeing and drying, the L a b values of the samples were measured. The results are shown in the following table:

Claims

claims:

1. A method of machine dyeing textiles containing a synthetic material

comprising at least one reactive dye in which the textile to be dyed is brought into contact with the at least one reactive dye and at least one silicone, wherein the silicone is terminally and / or in the side chain with an organic group having a nucleophile modified.

2. The method according to claim 1, characterized in that the equivalent mass of the functional group (FGEW) of 450 g / mol to 60,000 g / mol, in particular from 500 g / mol to 30,000 g / mol, preferably from 1,000 g / mol to 8,000 g / mol.

3. The method according to claim 1 or 2, characterized in that the nucleophile

is selected from - RN (H) R'NH ₂ , -OH, -R (C ₂ H 4 O) e (C ₃ H ₆ O) _f R ', -ROH, -RSH, -C (R-OH) ₂ R' and mixtures thereof .

in which

R, R 'are each independently an organic radical having 12 or less carbon atoms.

Atoms, in particular with 6 or fewer carbon atoms, and

e, f are, independently, integers from 0 to 15, where e + f> 1.

4. The method according to claim 1 to 3, characterized in that the silicone has a structure according to the following general formula A.

in which each independently

A: -Si (CH ₃ ) _a (X) b, with a + b = 3, and

B: Si (CH ₃ ) c (X) d, where c + d = 3,

X is an organic radical selected from -RNH 2, - RN (H) R'NH 2, -

OH, -R (C 2 H 4 O) e (C 3 H ₆ O) f R ', -ROH, -RSH, -C (R-OH) ₂ R' and mixtures thereof, wherein

R, R 'independently of one another are each an organic radical having 12 or fewer carbon atoms, in particular having 6 or fewer carbon atoms, and e, f are independently integers from 0 to 15, where e + f> 1, and

m and n are, independently of each other, integers from 0 to 600, where n = 0 and m is always 0 and m + n = 10 to 600.

5. The method according to any one of claims 1 to 4, characterized in that first brings the textiles with at least one modified silicone and subsequently with at least one reactive dye in contact.

6. The method according to any one of claims 1 to 4, characterized in that one brings the textiles simultaneously with at least one modified silicone and at least one reactive dye in contact.

7. The method according to any one of claims 1 to 6, characterized in that brings the at least one modified silicone in a washing machine at a temperature in the range of 5 ° C to 30 ° C with a textile in a conventional color-washing program in contact, then introducing the at least one reactive dye in the washing drum and brings in a conventional color-washing program at a temperature in the range of 20 ° C to 40 ° C in contact with the textile.

8. The method of claim 7, further comprising washing the dyed fabric with a commercial detergent and, in particular, thereafter cleaning the washing machine.

9. Use of at least one silicone to improve the coloration of textiles comprising a synthetic material with at least one reactive dye, wherein the at least one silicone is modified terminally and / or in the side chain with an organic group having a nucleophile

10. Use according to claim 9, characterized in that the nucleophile is selected from - RN (H) R'NH ₂ , -OH,

-ROH, -RSH, -C (R-OH) ₂ R 'and mixtures thereof,

in which

R, R 'independently of one another are each an organic radical having 12 or fewer carbon atoms, in particular having 6 or fewer carbon atoms, and

e, f are, independently, integers from 0 to 15, where e + f> 1.

1 1. An agent for dyeing textiles comprising synthetic materials, comprising at least one reactive dye and at least one silicone, wherein the at least one silicone is modified terminally and / or in the side chain with an organic group having a nucleophile.

12. Composition according to claim 1 1, wherein the at least one reactive dye as a preparation

is present, the at least one reactive dye and at least one adjuvant selected from water-soluble salt, pH adjuster, enzyme and neutral oil having.

A kit for dyeing textiles comprising synthetic materials comprising an agent according to claim 11 or 12 and a suitable container having one or more separate regions.