DE102005018315B4 - Aqueous preparations based on carboxy-functional organopolysiloxane-polyammonium copolymers and their use on cellulosic substrates - Google Patents

Abstract

Aqueous preparations, characterized by a content, based on the total composition, of (1) 10 to 80% by weight of a linear or branched carboxy-functional organopolysiloxane-polyammonium copolymer (β) which can be prepared: I. By reacting an organopolysiloxane of the formula (α) wherein R1, R2 and R4 independently have the structure provided that at least one of R1, R2 and R4 has a primary or secondary amino group and R1, R2 and R4 are not simultaneously but also trimethylsiloxy, R6, R8 are independently hydrogen or a linear or branched alkyl radical having 1 to 4 carbon atoms, R7 has one of the meanings given for R5, or is, a is an integer from 5-200, b is an integer from 0-5, ...

Description

The invention relates to aqueous preparations based on carboxy-functional organopolysiloxane-polyammonium copolymers and their use on cellulosic substrates.

The use of cationic aftertreatment agents to improve the contact and wash fastnesses of direct and reactive dyeings to cellulosic fibers is known. In practice, aqueous solutions of polymeric compounds which are functionalized with a plurality of quaternary ammonium groups are frequently used. The cationic charges provide a high affinity of the polymer for the fiber, which has anionic character due to its negative zeta potential, and fix anionic dye and dye hydrolyzate via the formation of a water-insoluble electroneutral salt. Important representatives of such known aftertreatment agents are, for. Polydimethyldiallylammonium chloride, quaternized polyalkyleneamines and amine-formaldehyde condensation products.

In its application, the aftertreatment agent for improving the color fastness is usually applied to the textile substrate in a separate step following the dyeing process. The application can take place both in the exhaust process and by forced application on the padder.

If a softener agent finish is additionally desired on the textile substrate, this can be carried out in a single-stage process with the co-use of soft-grip-imparting substances in the padding process. B. amino-functional organopolysiloxanes. In most cases, however, a two-stage application is preferred, wherein the aftertreatment agent is applied in a first foulard passage and the softener agent is applied in a second foulard passage.

In the exhaust process due to the high Aufziehgeschwindigkeit of the aftertreatment means a simultaneous equipment of the goods with a slower pulling on the textile substrate softening agent is not possible. The cationic polymer generates a high positive charge density on the fiber surface and thereby prevents the addition of the usually also positively charged softener agents, which thus remain in the aqueous treatment liquor.

In practice, attempts are made to circumvent this problem by applying the softener agent before the aftertreatment agent. However, a disadvantage of this procedure, in addition to poor reproducibility and the extended process time is often caused by side reactions deterioration of the soft touch. For example, amine-formaldehyde condensation products block the amino groups of amino functional organopolysiloxanes responsible for good softness, thereby suppressing the desired smooth and soft surface feel. Another disadvantage of this procedure is the masking of the fiber surface and the unfixed dye particles with the softener agent, whereby the access of the applied in the second stage after-treatment agent to the dye and thus the desired reaction of the aftertreatment agent is prevented with the dye to be fixed. This results in significant disadvantages in the color fastness properties.

It was therefore an object to develop a preparation in which an aftertreatment agent and a softener agent combined in an active component are present, which can be used in a single-stage application process in the exhaust on the modern Jetfärbemaschinen. It should be ensured by the combination of the two active components in a polymer, that they simultaneously and uniformly apply to the fiber during application. In this way, a good soft feel with good hydrophilicity and low tendency to yellowing is to be achieved on the textile substrates in addition to optimal dye fixation.

This object is achieved by the claimed preparations and their use.

In the prior art, amino-functional organopolysiloxanes for the treatment of textile substrates are often used in the form of aqueous emulsions in order to give them a soft feel. Frequently, organopolysiloxanes are used which are laterally or terminally modified in the polymer chain with aminoethylaminopropyl or aminopropyl radicals. These amino-functional organopolysiloxanes are formulated by protonation with weak acids and with the aid of emulsifiers to form aqueous microemulsions. Disadvantages of these emulsions are the low stability under alkaline conditions of use, a poor resistance to shearing, a pronounced yellowing tendency Under temperature stress as well as a strong foaming during the application on modern finishing machines.

Many textile finishing processes require the application of high pH values in the aqueous treatment baths. Thus, the pretreatment, bleaching and dyeing of cellulosic substrates always requires the use of high amounts of alkalis. If not sufficiently neutralized and carefully washed out after such steps, it may in the subsequent treatment with z. As soft-grip agents based on amino-functional organopolysiloxanes to destabilize the microemulsions and thus come to significant deposits of water-insoluble organopolysiloxane in the treatment device. These deposits can then be reflected directly in the form of stains on the textile, which are difficult or impossible to remove.

Aminofunctional organopolysiloxanes, when applied to finishing machines which exert high shear forces on the treatment liquor, often exhibit insufficient stability of the formulation and thus cause similar negative consequences, such as caused by a sharp increase in pH. Particularly on the modern fully or partly flooded jet dyeing machines, high shear stresses occur during the pumping operations, which is why, for example, emulsion separation with the undesired organopolysiloxane deposits on the textile substrate can again occur during use in the exhaust process.

Another disadvantage of the softener agents based on amino-functional organopolysiloxanes is the strong tendency to yellowing, which can occur in the treated, white and light-colored textile substrates at drying temperatures above 120 ° C.

Soft-grip agents based on amino-functional organopolysiloxanes usually contain relatively large amounts of nonionic emulsifiers, as a result of which the foam tendency of the application liquors increases greatly. As a result, the universal applicability is limited to the fast-running textile equipment machines, such as the Düsenfärbeapparaten because the foam produced in these devices by the strong mechanics significantly hindered the transport of the product to be treated in the machine, as well as the mass transfer between the treatment liquor and textile substrate.

In order to avoid these disadvantages, microemulsions of organopolysiloxanes which carry quaternary ammonium groups are frequently used in practice. These preparations are stable under alkaline conditions. Depending on the preparation method, organopolysiloxanes bearing quaternary ammonium groups are obtained, in which the quaternary functions are positioned laterally (lateral), terminally (terminally) or polymer backpressure.

Mixed forms of these different structural units within a polymer can also be prepared.

In WO 02/18528 Preparations are described which contain linear, polyquaternary modified organopolysiloxanes. These preparations are used in household linen, where they give the treated textiles a soft touch, crease, elasticity, advantageous ironing and perfuming properties and dimensional and dimensional stability.

DE-OS 10036533 describes a process for the preparation of polyquaternary organopolysiloxanes and their use as wash resistant hydrophilic softening agents for textiles. The synthesis is carried out by reacting α, ω-diepoxypolysiloxanes with a mixture of a tertiary amine and a di-tertiary diamine. The organopolysiloxanes obtained in this way have polymer-internal diammonium groups.

In GB 1,006,729 describes the preparation of silanes and siloxanes containing a quaternary ammonium group. In this case, haloalkyl-containing silanes or siloxanes are reacted with tertiary amines. The haloalkyl groups are bonded directly to the silane or siloxane via an Si-C bond. The silanes and siloxanes described can be used as defoamers, sizing agents for fibrous glass surfaces or as additives in silicone oils, lubricants, gums and resins.

DE 3340708 describes the preparation of a polyquaternary polysiloxane polymer in which polysiloxane groups and bisquaternary (or diquaternary) diamine groups are alternately arranged. The preparation is carried out either by reacting a Dihalogenalkylpolysiloxans with tertiary alkylenediamines or by the reaction of a bisteric diaminopolysiloxane with a dihalo, Dimesylat- or Ditosylate connection. These polysiloxane polymers are used in cosmetics for the treatment of hair and nails.

In WO 96/27557 describes a copolymer of DADMAC and vinyltrialkoxysilane as flocculants for wastewater treatment.

Quaternized polyalkyleneamines are in DE-A1 19849190 . DE-A1 2521960 . DE-A1 2629922 and DE-A1 2838878 described. The preparation is usually carried out by reacting di-tertiary amines with alkylene dihalides. For example, in DE-A1 2629922 reacted a diamine and an alkylene dihalide in the presence of methanol for 60 to 100 hours under reflux conditions. Characteristic of the synthesis of these compounds are the very long reaction times. The quaternized polyalkyleneamines thus obtained are mainly used as hair treatment agents.

In US 6,025,322 are described polycationic compounds which are prepared by reacting piperazine derivatives with dihalides, Epihalohydrinen or Bisepoxyverbindungen. The polymers thus prepared are used as aftertreatment agent for colored textiles to improve the color fastness. Although they cause a color fastness improvement, but are not suitable for softening textile substrates.

DE 103 16 662 A1 discloses reactive functionalized amino and / or ammonium polysiloxane compounds and salts thereof and their use for surface treatment of synthetic fibers as wash resistant hydrophilic plasticizers.

DE 102 59 291 discloses self-emulsifying formulations containing organopolysiloxanes and alkylammonium compounds, and their use in aqueous systems on textile substrates.

DE 100 36 694 discloses a process for treating organic fibers with aqueous formulations of amino functional organosilicon compounds. The organosilicon compounds are prepared by graft copolymerization of ethylenically unsaturated, amino-containing monomers on mercaptosiloxanes.

DE 10 2005 014 311 discloses polyamino and / or polyammonium polysiloxane copolymer compounds having comb-like polyalkylene oxide units and their use in particular for treating textiles and fibrous materials.

DE 10 2005 014 312 A1 discloses compositions comprising at least one polyamino and / or polyammonium polysiloxane compound on a substrate and their use for textile treatment, in particular for the treatment of wet textiles after washing.

DE 10 2004 034 266 A1 relates to phyllosilicate-containing polysiloxane compositions, to processes for their preparation, and to their use for treating substrates.

US 2006/0223939 is directed to linear polyamino and / or polyammoniumpolysiloxane copolymers, especially hydrophilic polyquaternary polysiloxane copolymers, as well as their use in cosmetics and for surface treatment.

Unexpectedly, the inventors have now found that the adverse effects of heretofore known textile auxiliaries can be avoided by using the claimed linear or branched carboxy-functional organopolysiloxane-polyammonium copolymers (β).

• (1) 10 bis 80 Gewichtsprozent eines linearen oder verzweigten, carboxyfunktionellen Organopolysiloxan-Polyammonium-Copolymers (β), welches herstellbar ist: I. durch Umsetzung eines Organopolysiloxans der Formel (α)
  
  worin die Reste R¹, R² und R⁴ unabhängig voneinander die Struktur
  
  aufweisen, mit der Maßgabe, dass mindestens einer der Reste R¹, R² und R⁴ eine primäre oder sekundäre Aminogruppe aufweist und R¹, R² und R⁴ jedoch nicht gleichzeitig, auch Trimethylsiloxygruppen sind,
  
  R⁶, R⁸ = unabhängig voneinander Wasserstoff oder ein Linearer oder verzweigter, vorzugsweise in linearer Alkylrest mit 1 bis 4 Kohlenstoffatomen, vorzugsweise mit einem Kohlenstoffatom sind, R⁷ eine der für R⁵ genannten Bedeutungen besitzt, oder
  
  ist, a eine ganze Zahl von 5–200, vorzugsweise 15–100, b eine ganze Zahl von 0–5, vorzugsweise 0–2, c die ganz Zahl 2 oder 3, vorzugsweise 2, d eine ganze Zahl von 1–10, vorzugsweise 2–4, e eine ganze Zahl von 1–10, vorzugsweise 2–4, f eine ganze Zahl von 1–10, vorzugsweise 1 ist und wobei die mit den Indices a und b versehenen Einheiten statistisch verteilt sind, mit mindestens einer Dicarbonsäure oder einem Dicarbonsäureanhydrid, ausgewählt aus Maleinsäure, Fumarsäure, Citraconsäure, Mesaconsäure, Itaconsäure, 2-Methylenglutarsäure, trans, trans-2,4-Hexadiendisäure, Maleinsäureanhydrid, Citraconsäureanhydrid, Itaconsäureanhydrid, Methyl-5-norbornen-2,3-dicarbonsäureanhydrid, 4,10-Dioxatricyclo[5.2.1.0-2,6-]dec-8-en-3,5-dion, cis-5-Norbornen-endo-2,3-dicarbonsäureanhydrid, cis-5-Norbornen-exo-2,3-dicarbonsäureanhydrid, Bicyclo[2.2.2]oct-5-en-2,3-dicarbonsäureanhydrid, 3-(2-Neopentylallyl)tetrahydrofuran-2,5-dion, Nonenylbernsteinsäureanhydrid, 3-(2-Methyl-2-propenyl)dihydro-2,5-furandion, 5-Methyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dion, 3-(3-Methyl-2-butenyl)dihydro-2,5-furandion, 5,6-Dimethyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dion, 2-Octen-1-ylbernsteinsäureanhydrid und 3-[(2E)-2-decenyl]dihydro-2,5-furandion, bevorzugt Maleinsäureanhydrid, Citraconsäureanhydrid, Itaconsäureanhydrid und Methyl-5-norbornen-2,3-dicarbonsäureanhydrid, besonders bevorzugt Maleinsäureanhydrid, wobei das molare Verhältnis von amino-funktionellem Organopolysiloxan (α) zu Dicarbonsäure oder Dicarbonsäureanhydrid so gewählt wird, dass nach der Reaktion noch freie Carboxylgruppen im Organopolysiloxanmakromonomer vorhanden sind, und wobei pro Mol reaktive Aminogruppe im Organopolysiloxan (α) 0,2 bis 1 Mol Dicarbonsäure oder Dicarbonsäureanhydrid eingesetzt wird, zu einem olefinisch ungesättigten Organopolysiloxanmakromonomeren und II. durch anschließende radikalische Copolymerisation dieses olefinisch ungesättigten Organopolysiloxanmakromonomeren mit einem oder mehreren Comonomeren des Types (γ) ausgewählt aus Diallyldimethylammoniumchlorid, Diallylmethylamin, Diallylamin, [(2-Methacryloyloxi)-ethyl]trimethylammoniumchlorid, [(2-Methacryloyloxi)-ethyl]Trimethylammoniummethosulfat, [(2-Acryloyloxi)-ethyl)]trimethylammoniumchlorid, [(2-Acryloyoxi)-ethyl]trimethylammoniummethosulfat, (3-Acrylamidopropyl)trimethylammoniumchlorid, Dimethylaminoethylmethacrylat, Dimethylaminopropylmethacrylamid, N-Methyl-2-vinylpyridiniumchlorid und N-Methyl-4-vinlypyridiniumchlorid, bevorzugt Diallyldimethylammoniumchlorid, Diallylmethylamin und Diallylamin, besonders bevorzugt Diallyldimethylammoniumchlorid zu dem linearen oder verzweigten, carboxyfunktionellen Organopolysiloxan-Polyammonium-Copolymer (β), wobei der Gesamtstickstoffgehalt des linearen oder verzweigten, carboxyfunktionellen Organopolysiloxan-Polyammonium-Copolymers (β) 3–9 Gewichtsprozent, vorzugsweise 4–8 Gewichtsprozent beträgt, und der Stickstoffgehalt in dem Organopolysiloxan der Formel (α) 0,2–4,5 Gewichtsprozent, vorzugsweise 0,5–3,0 Gewichtsprozent beträgt und wobei die herstellungsbedingt vorhandenen Carboxylgruppen stets auf dem Polymerrücken und benachbart zu den Amidofunktionen des Organopolysiloxanmakrocomonomeren angeordnet sind, und
• (2) bevorzugt 0,1 bis 20 Gewichtsprozent eines Emulgators und/oder
• (3) bevorzugt 0,1 bis 25 Gewichtsprozent eines Hydrotroplikums und
• (4) 20 bis 90 Gewichtsprozent Wasser, bezogen auf die Gesamtzusammensetzung.

The first subject of the invention are aqueous preparations characterized by a content based on the total composition

• (1) 10 to 80% by weight of a linear or branched carboxy-functional organopolysiloxane-polyammonium copolymer (β) which can be prepared: I. by reacting an organopolysiloxane of the formula (α)
  
  wherein the radicals R ¹ , R ² and R ⁴ independently of one another have the structure
  
  with the proviso that at least one of R ¹ , R ² and R ^{4 has} a primary or secondary amino group and R ¹ , R ² and R ⁴ are not simultaneously but also trimethylsiloxy,
  
  R ⁶ , R ⁸ = independently of one another are hydrogen or a linear or branched one, preferably in linear alkyl radical having 1 to 4 carbon atoms, preferably with one carbon atom, R ^{7 has} one of the meanings given for R ⁵ , or
  
  is a is an integer of 5-200, preferably 15-100, b is an integer of 0-5, preferably 0-2, c is the integer 2 or 3, preferably 2, d is an integer of 1-10, preferably 2 -4, e is an integer of 1-10, preferably 2-4, f is an integer of 1-10, preferably 1 and wherein the units provided with the indices a and b are randomly distributed, with at least one dicarboxylic acid or a Dicarboxylic acid anhydride selected from maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 2-methyleneglutaric acid, trans, trans-2,4-hexadienedioic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, methyl 5-norbornene-2,3-dicarboxylic anhydride, 4,10- Dioxatricyclo [5.2.1.0-2,6-] dec-8-ene-3,5-dione, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, cis-5-norbornene exo-2,3-dicarboxylic anhydride , Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 3- (2-neopentylallyl) tetrahydrofuran-2,5-dione, nonenyl succinic anhydride, 3- (2-methyl 1- (2-propenyl) dihydro-2,5-furandione, 5-methyl-3a, 4,7,7a-tetrahydro-2-benzofuran-1,3-dione, 3- (3-methyl-2-butenyl) dihydro 2,5-furandione, 5,6-dimethyl-3a, 4,7,7a-tetrahydro-2-benzofuran-1,3-dione, 2-octene-1-ylsuccinic anhydride and 3 - [(2E) -2- decenyl] dihydro-2,5-furandione, preferably maleic anhydride, citraconic anhydride, itaconic anhydride and methyl-5-norbornene-2,3-dicarboxylic anhydride, most preferably maleic anhydride, wherein the molar ratio of amino-functional organopolysiloxane (α) to dicarboxylic acid or dicarboxylic acid anhydride so it is chosen that after the reaction still free carboxyl groups are present in Organopolysiloxanmakromonomer, and wherein per mole of reactive amino group in organopolysiloxane (α) 0.2 to 1 mol of dicarboxylic acid or dicarboxylic anhydride is used, to an olefinically unsaturated organopolysiloxane macromonomer and II. by subsequent radical copolymerization this olefinically unsaturated organopolysiloxane macromer omonomers with one or more comonomers of the type (γ) selected from diallyldimethylammonium chloride, diallylmethylamine, diallylamine, [(2-methacryloyloxy) ethyl] trimethylammonium chloride, [(2-methacryloyloxy) -ethyl] trimethylammonium methosulfate, [(2-acryloyloxy) -ethyl) ] trimethylammonium chloride, [(2-acryloyloxy) ethyl] trimethylammonium methosulfate, (3-acrylamidopropyl) trimethylammonium chloride, dimethylaminoethyl methacrylate, dimethylaminopropylmethacrylamide, N-methyl-2-vinylpyridinium chloride and N-methyl-4-vinylpyridinium chloride, preferably diallyldimethylammonium chloride, diallylmethylamine and diallylamine, more preferably Diallyldimethylammonium chloride to the linear or branched, carboxy-functional organopolysiloxane-polyammonium copolymer (β), wherein the total nitrogen content of the linear or branched, carboxy-functional organopolysiloxane-polyammonium copolymer (β) 3-9 weight percent, preferably 4-8 weight percent, and the nitrogen content in the Organopolysiloxane of the formula (α) is 0.2-4.5 weight percent, preferably 0.5-3.0 weight percent, and wherein the carboxy groups produced by the preparation are always arranged on the polymer back and adjacent to the amido functions of Organopolysiloxanmacrocomonomeren, and
• (2) preferably 0.1 to 20 weight percent of an emulsifier and / or
• (3) preferably 0.1 to 25 weight percent of a hydrotroplicum and
• (4) 20 to 90% by weight of water, based on the total composition.

All weights of the components (1) to (4) of the preparations according to the invention relate to the total composition of the preparation according to the invention. Preferred ranges for the component (1) are a range of 10-40, especially 15-30 weight percent. If component (2) is added, its concentration is preferably in the range of 0.1 to 20, especially 0.3 to 10, percent by weight. If component (3) is added, its concentration is preferably in the range of 0.1-20% by weight. The preferred range of component (4) is 40-90, but especially between 50-80 weight percent.

The preparation of the carboxy-functional organopolysiloxane-polyammonium copolymers (β) is carried out by methods which are known to the person skilled in the art. First, amino-functional organopolysiloxanes of the formula (α) such as. In EP 1136513 Example 1, prepared by equilibration of terminal or lateral amino-functional organopolysiloxanes in the presence of known equilibration catalysts. Subsequently, the amino-functional organopolysiloxanes with olefinically unsaturated dicarboxylic acids or dicarboxylic anhydrides analogous to US4777277 Example 2 is converted to the corresponding olefinically unsaturated organopolysiloxane macromonomers. In this amidation reaction, only the primary and secondary amino groups of the organopolysiloxane react. The molar ratio of amino-functional organopolysiloxane to dicarboxylic acid or dicarboxylic anhydride is chosen such that free carboxyl groups are still present in the organopolysiloxane macromonomer after the reaction. In general, 0.2 to 1.0 mol of dicarboxylic acid or dicarboxylic anhydride per mole of reactive amino group of organopolysiloxane used. The reactions are usually carried out in solvents such as tetrahydrofuran or toluene at reflux temperature. The degree of conversion of the reactive primary and secondary amino groups is monitored titrimetrically.

In a further reaction step, the organopolysiloxane macromonomers thus obtained, which carry amidofunctional, olefinically unsaturated groups in the terminal and / or lateral position, are free-radically copolymerized with the comonomers of type (γ). Depending on the terminal or lateral positioning of the olefinically unsaturated groups of the organopolysiloxane macromonomer, linear or branched, carboxy-functional organopolysiloxane-polyammonium copolymers (β) are formed during the polymerization. Monofunctional, olefinically unsaturated organopolysiloxane macromonomers lead to linear carboxy-functional organopolysiloxane-polyammonium copolymers (β), while polyunsaturated unsaturated organopolysiloxane macromonomers lead to branched, carboxy-functional organopolysiloxane-polyammonium copolymers (β).

The free-radical copolymerization takes place by the methods of solution or emulsion polymerization in aqueous medium which are generally known to the person skilled in the art (component (4) explained below) (see, for example, US Pat. DE 10059826 , Process 3), optionally with the concomitant use of optionally used emulsifiers (component (2) explained below) and / or a hydrotrope (component (3) explained below).

As initiators organic peroxides, z. B. benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauryl peroxide or azo initiators such. As azobisisobutyronitrile (AIBN) can be used. Also suitable are inorganic peroxy compounds, such as. B. (NH ₄ ) ₂ S ₂ O ₅ , K ₂ S ₂ O ₈ or H ₂ O ₂ , preferably (NH ₄ ) ₂ S ₂ O ₈ , optionally in combination with reducing agents (eg., Sodium hydrogen sulfite, ascorbic acid, iron (II) sulfate, etc.) or redox systems which contain as reducing component an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.).

In the case of the carboxy-functional organopolysiloxane-polyammonium copolymers (β), the term "carboxy-functional" is understood to mean the presence of the atomic group -COOH in the copolymer. In this case, the carboxy groups present in the preparation are always arranged on the polymer back and adjacent to the amido functions of the organopolysiloxane macrocomonomer.

The carboxy-functional organopolysiloxane-polyammonium copolymers (β) thus formed produce good soft feel and good dye fixation on textile substrates.

As emulsifiers (component (2)) optionally present in the preparations according to the invention, those based on cationic, nonionic or amphoteric bases or mixtures of these compounds can be used. Preferably, cationic emulsifiers or ethoxylation products of aliphatic alcohols containing from 6 to 22 carbon atoms are used which contain up to 50 moles of ethylene oxide. The alcohols preferably contain 8 to 16 carbon atoms; they may be saturated, linear or branched, preferably branched, and may be used alone or in admixture. Above particular advantage in terms of low foaming in the application liquors are alcohols of the type mentioned, when the alkylene oxide is composed of ethylene oxide and 1,2-propylene oxide in random distribution and preferably in a block-like distribution. Nonionic emulsifiers from the group of ethoxylated, branched aliphatic alcohols have proven particularly useful due to their favorable overall properties. Therefore z. B. Ethoxilate of 2,6,8-trimethyl-4-nonanol, of isodecyl alcohol or Isotriedecylalkoholes with in each case 2 to 50 moles, in particular 3 to 15 moles of attached ethylene oxide for the preparation of the inventive preparations preferred. Preferred cationic emulsifiers are, for example, quaternary ammonium salts, such as di (C ₁₀ -C ₂₄ ) -alkyldimethylammonium chloride, (C ₁₀ -C ₂₄ ) -alkyldimethylethylammonium chloride or bromide, (C ₁₀ -C ₂₄ ) -alkyltrimethylammonium chloride or bromide, (C ₁₀ -C ₂₄ ) -alkyldimethylbenzylammonium chloride, N- (C ₁₀ -C ₁₈ ) -alkylpyridinium chloride or bromide, N- (C ₁₂ -C ₁₈ ) isoquinolinium chloride, bromide or monoalkylsulfate, N- (C ₁₂ -C ₁₈ ) - alkyl N-methyl ammonium morpholinium chloride, bromide or monoalkyl sulfate, N- (C ₁₂ -C ₁₈ ) alkyl N-ethyl ammonium morpholinium chloride, bromide or monoalkyl sulfate; N- (C ₁₂ -C ₁₈ ) -alkylmethlypolyoxyethyleneammonium chloride, bromide or monoalkyl sulfate and salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms with organic or inorganic acids.

The optionally present in the inventive preparations component (3), a hydrotrope, can be selected from the group of polyfunctional alcohols. Thus, dialcohols having 2-10, preferably 2-6, but especially 2-4 carbon atoms per molecule can be used. Also suitable are their mono- and diethers and the mono- and diesters of these dialcohols. As particularly preferred examples of component (3) to be used are butyl diglycol, 1,2-propylene glycol and dipropylene glycol.

The claimed linear or branched, carboxy-functional organopolysiloxane-polyammonium copolymers (β) usually already have good water solubility due to their structure. In some cases it may be convenient to prepare preparations of components (1) to (4) with stirring at 70 ° C in the presence of small amounts of organic acids (for example, acetic acid or lactic acid) to convert the polymer into the form usable from an aqueous medium to bring an emulsion.

Another object of the invention is the use of the preparations of the invention as a post-treatment agent to improve the softness and color fastness, in particular the contact and wash fastness of direct and reactive dyeings on cellulosic substrates, and their use in the exhaust process and in the forced application process.

The term "cellulosic substrates" is the collective term for fabrics of natural or regenerated cellulose. Natural cellulose fibers are, for example, cotton and linen, regenerated cellulose can be found, for example, under the terms viscose, acetate, rayon or modal fibers.

In the application, the aftertreatment agent is preferably applied to the substrate in a separate step following the dyeing process. In this case, the application can be carried out both by the dry-in-wet as well as the wet-in-wet process by forced application on the padder. The compulsory application of the claimed preparation on the padder can be carried out in one stage under weakly acidic conditions. After the padder passage, the substrate is then dried in the subsequent step.

A particularly preferred and advantageous application of the preparations according to the invention takes place in the exhaust process by treating the substrate with the application liquor. This makes it possible that their application can be carried out in a single stage in the exhaust process on the modern Jetfärbemaschinen. In this case, preference is given to working under weakly acidic conditions, with uniform application of the claimed linear or branched carboxy-functional organopolysiloxane-polyammonium copolymer (β) from the application liquor to the fiber being achieved. This is followed by a pre-drying by centrifuging or squeezing on the padder and a final drying passage.

The concentration of the preparations according to the invention in the application liquors is selected so that the substrates contain, after their treatment, between 0.2 and 2.0 percent by weight of the claimed linear or branched, carboxy-functional organopolysiloxane-polyammonium copolymers (β), based on the weight of the substrate ,

The application fleets show a high stability in a wide pH range (in particular between pH 7 and 12) and only a slight tendency to foam on fast-running textile finishing machines, such. B. the modern Jetfärbeapparaten.

The textile substrates treated with the preparations according to the invention have, in addition to the good soft-grip and color-fastness properties, a high yellowing resistance with light shades. Furthermore, the treated textiles, especially bath and hand towels and underwear and sportswear are characterized by high absorbency.

The invention is explained in more detail in the following examples. The polymer chain lengths (number indices) given in the formulas of the preparation examples are average values in each case.

Preparation Example 1 (not according to the invention)

ist,
hergestellt und anschließend mit 5 Gramm Isotridecylalkohol mit 6 Ethylenoxidgruppen, 5 Gramm Isodecylalkohol mit 7 Ethylenoxidgruppen und 7 Gramm Butyldiglykol in 63 Gramm Wasser bei 30°C verrührt. Man erhält 100 Gramm einer Mikroemulsion mit einem Gesamtstickstoffgehalt von 0,22 Gewichtsprozent, bezogen auf die Gesamtzusammensetzung der Zubereitung.Analogous to US 4,891,166 Example 1 is 20 grams of an organopolysiloxane having terminally positioned and quaternized amino groups of the general formula

is
and then stirred with 5 grams of isotridecyl alcohol with 6 ethylene oxide groups, 5 grams of isodecyl alcohol with 7 ethylene oxide groups and 7 grams of butyldiglycol in 63 grams of water at 30 ° C. This gives 100 grams of a microemulsion having a total nitrogen content of 0.22 percent by weight, based on the total composition of the preparation.

Preparation Example 2 (not according to the invention)

Analogously to Example 1 of WO 99/47574 500 grams of an aqueous solution of polydiallyldimethylammonium chloride are produced, the polymer content being 14 percent by weight.

Preparation Example 3 (Inventive)

mit einem Stickstoffgehalt von 1,3 Gewichtsprozent, mit 0,05 Mol Maleinsäureanhydrid analog zu US 4777277 , Beispiel 2. Nach dem Zusatz von 0,8 Mol Diallyldimethylammoniumchlorid, 15 Gramm eines quaternierten Talgfettaminethoxilates mit 15 Ethylenoxidgruppen, 20 Gramm Butyldiglykol, 575 Gramm Wasser und 4 Gramm Ammoniumperoxodisulfat wird bei ca. 80°C während 2 Stunden die radikalische Polymerisation (II.) analog zu DE 10059826 , Verfahren 3 durchgeführt. Es bildet sich eine dünnflüssige Emulsion mit 28 Gewichtsprozent eines linearen oder verzweigten, carboxyfunktionellen Organopolysiloxan-Polyammonium-Copolymers mit einem Gesamtstickstoffgehalt von 5,2 Gewichtsprozent.The preparation of the olefinically unsaturated organopolysiloxane macromonomer is carried out by (I.) reaction of 0.05 mol of an organopolysiloxane of the formula .alpha..sub.1:

with a nitrogen content of 1.3% by weight, with 0.05 mol of maleic anhydride analogous to US 4777277 Example 2 After the addition of 0.8 mol of diallyldimethylammonium chloride, 15 grams of a quaternized tallow fatty amine with 15 ethylene oxide groups, 20 grams of butyldiglycol, 575 grams of water and 4 grams of ammonium peroxodisulfate at about 80 ° C for 2 hours, the radical polymerization (II. ) analogous to DE 10059826 , Method 3 performed. A low viscosity 28 weight percent emulsion of a linear or branched carboxy-functional organopolysiloxane-polyammonium copolymer having a total nitrogen content of 5.2 weight percent is formed.

Preparation Example 4 (Inventive)

mit einem Stickstoffgehalt von 2,0 Gewichtsprozent, mit 0,05 Mol Maleinsäureanhydrid analog zu US 4777277 , Beispiel 2. Nach dem Zusatz von 1,0 Mol Diallyldimethylammoniumchlorid, 30 Gramm eines quaternierten Talgfettaminethoxilates mit 15 Ethylenoxidgruppe, 30 Gramm Butyldiglylkol, 720 Gramm Wasser und 5 Gramm Ammoniumperoxodisulfat wird bei ca. 80°C während 4 Stunden die radikalische Polymerisation (II.) analog zu DE 10059826 , Verfahren 3 durchgeführt. Es bildet sich eine dünnflüssige Emulsion mit 28 Gewichtsprozent eines linearen oder verzweigten, carboxyfunktionellen Organopolysiloxan-Polyammonium-Copolymers mit einem Gesamtstickstoffgehalt von 5,5 Gewichtsprozent.The preparation of the olefinically unsaturated organopolysiloxane macromonomer is carried out by reacting 0.05 mol of an organopolysiloxane of the formula α 2:

with a nitrogen content of 2.0% by weight, with 0.05 mol of maleic anhydride analogous to US 4777277 Example 2. After the addition of 1.0 mole of diallyldimethylammonium chloride, 30 grams of a quaternized Tallow fatty amine ethoxylates with 15 ethylene oxide group, 30 grams of butyldiglycol, 720 grams of water and 5 grams of ammonium peroxodisulfate at about 80 ° C for 4 hours, the radical polymerization (II.) Analogously to DE 10059826 , Method 3 performed. A low viscosity 28 weight percent emulsion of a linear or branched carboxy-functional organopolysiloxane-polyammonium copolymer having a total nitrogen content of 5.5 weight percent is formed.

Preparation Example 5 (Inventive)

The preparation of the olefinically unsaturated organopolysiloxane macromonomer is carried out by reaction (I.) of 0.02 mol of an organopolysiloxane of the formula .alpha..sub.3:

With a nitrogen content of 2.0% by weight, with 0.02 mole of maleic anhydride analogous to US 4777277 EXAMPLE 2 Following the addition of 0.6 mol of diallyldimethylammonium chloride, 25 grams of a quaternized tallow fatty amine ethoxylate with 15 ethylene oxide groups, 20 grams of butyldiglycol, 500 grams of water and 4 grams of ammonium peroxodisulfate, free radical polymerization (II. ) analogous to DE 10059826 , Method 3 performed. A low viscosity 28 weight percent emulsion of a linear or branched carboxy-functional organopolysiloxane-polyammonium copolymer having a total nitrogen content of 5.1 weight percent is formed.

applications

The equipments with the products of Formulation Examples 1-5 were exhausted and paddled.

I. Evaluation of color fastness, softness and hydrophilicity in the exhaust process

For the evaluation of color fastness, softness and hydrophilicity, test fabrics (cotton mesh 200 g / m ² ) were first dyed according to the formulations described below and subsequently aftertreated by exhaustion. Staining with substantive dye laboratory dyeing: Labortaumelbecherfärbeapparat substrate: Cotton nettle, boiled and bleached to color white dye bath: -2% of the weight of goods Sirius Light Blue BRR (CI 34140) -20 g / l sodium sulfate anhydrous 2 g / l commercial wetting agent Liquor ratio: 1:25 dyeing: - heat up to 98 ° C at 10 ° C per minute, - hold at this temperature for 60 minutes, - Rinse for 10 minutes. Staining with reactive dyes laboratory dyeing: Labortaumelbecherfärbeapparat substrate: Cotton jersey, boiled and bleached to color white dye bath: - 4% of the product weight Procion Red HE-7B (CI 15620) - 2% of the product weight Procion Yellow HE-4R (CI Reactive Yellow 84) - 70 g / l sodium sulfate anhydrous - 25 g / l soda anhydrous - 1 g / l commercial wetting agent Liquor ratio: 1:25 dyeing: - heat up to 80 ° C at 10 ° C per minute, - hold at this temperature for 60 minutes, - Rinse for 10 minutes. Equipment in exhaustion Laboratory equipment apparatus: Labortaumelbecherfärbeapparat Equipment Fleet: The amounts of the respective products of Preparation Examples 1-5 are given in Table 1. The equipment fleet contains 4 g / l Na ₂ SO ₄ . The pH is adjusted to 5-6. Liquor ratio: 1:15 Equipment conditions: - treat for 20 minutes at 20 ° C, - rinse for 2 minutes, - spin off, - Dry at 80 ° C in a warming cabinet.

Table 1 - Amounts used in the exhaust process

The respective amounts used of the products of Preparation Examples 1-5 in Application Examples 1-6 depends on the weight of the product and are given in Table 1 in percent by weight of the weight of the product. Preparation according to Example 1 Preparation according to Example 2 Preparation according to Example 3 (according to the invention) Preparation according to Example 4 (according to the invention) Preparation according to Example 5 (according to the invention) Application example 1 3 Application Example 2 3 Application example 3 3 3 Application Example 4 (Inventive) 3 Application example 5 (according to the invention) 3 Application example 6 (according to the invention) 3

Color fastness evaluation - exhaust method

Table 2 - Wash fastness - exhaust process Wash fastness according to DIN EN ISO 105-C05, 30 minutes at 40 ° C cotton, dyed with substantive dye Bleeding of the cotton-accompanying tissue Bleeding of the wool-accompanying tissue Application example 1 1 4-5 Application Example 2 3 4-5 Application example 3 2-3 4-5 Application Example 4 (Inventive) 3 4-5 Application example 5 (according to the invention) 3 4-5 Application example 6 (according to the invention) 3 4-5 untreated 1 4-5 Table 3 - Wash fastness - exhaust process Wash fastness according to DIN EN ISO 105-C05, 30 minutes at 60 ° C cotton, dyed with reactive dyes Bleeding of the cotton-accompanying tissue Bleeding of the wool-accompanying tissue Application example 1 2 1-2 Application Example 2 4 4-5 Application example 3 4 4-5 Application Example 4 (Inventive) 4-5 4-5 Application example 5 (according to the invention) 4-5 4-5 Application example 6 (according to the invention) 4-5 4-5 untreated 1 1-2 Table 4 - Waterfastness - exhaustion process Waterfastness according to DIN 54006 cotton, dyed with substantive dye Bleeding of the cotton-accompanying tissue Bleeding of the wool-accompanying tissue Application example 1 1 2 Application Example 2 5 4-5 Application example 3 4-5 4-5 Application Example 4 (Inventive) 5 4-5 Application example 5 (according to the invention) 5 4-5 Application example 6 (according to the invention) 5 4-5 untreated 1 2 Table 5 - Waterfastness - exhaustion process Waterfastness according to DIN 54006 cotton, dyed with reactive dyes Bleeding of the cotton-accompanying tissue Bleeding of the wool-accompanying tissue Application example 1 2-3 3 Application Example 2 5 4-5 Application example 3 5 4-5 Application Example 4 (Inventive) 5 4-5 Application example 5 (according to the invention) 5 4-5 Application example 6 (according to the invention) 5 4-5 untreated 1 2 Table 6 - perspiration fastness - exhaustion Fastness to perspiration according to DIN 54020 cotton, dyed with substantive dye Bleeding of the cotton-accompanying tissue Bleeding of the wool-accompanying tissue Application example 1 1 2 Application Example 2 5 5 Application example 3 4-5 5 Application Example 4 (Inventive) 5 5 Application example 5 (according to the invention) 4-5 5 Application example 6 (according to the invention) 5 5 untreated 1 2 Table 7 - perspiration fastness - exhaustion Fast to perspiration according to DIN 54020 cotton, dyed with reactive dyes Bleeding of the cotton-accompanying tissue Bleeding of the wool-accompanying tissue Application example 1 2-3 3 Application Example 2 5 4-5 Application example 3 4-5 4-5 Application Example 4 (Inventive) 5 4-5 Application example 5 (according to the invention) 5 4-5 Application example 6 (according to the invention) 5 4-5 untreated 1 1-2

Hand assessment

The evaluation of the handle character of the treated substantive dye-stained test fabric is subject to variously different subjective criteria. Nevertheless, in order to obtain meaningful results, an assessment by at least 5 test persons is required. The evaluation of the results was carried out according to statistical methods, where grade 1 represents the softest, most comfortable grip, grade 6 the hardest, least smooth and uncomfortable. Table 8 - Handle Evaluation - Extraction Procedure Grip evaluation grade within the test series Application example 1 3 Application Example 2 6 Application example 3 4 Application Example 4 (Inventive) 1 Application example 5 (according to the invention) 2 Application example 6 (according to the invention) 1 untreated 6

Hydrophilicity - exhaust method

The evaluation of the hydrophilicity was carried out on the treated, substantive dye-stained test fabric according to the TEGEWA dropping test (Melliand Textilberichte 68 (1987), 581-583). Table 9 - Hydrophilicity - exhaust process Sinking time (sec) Application example 1 5 Application Example 2 <2 Application example 3 4 Application Example 4 (Inventive) <2 Application example 5 (according to the invention) <2 Application example 6 (according to the invention) <2 untreated <2

II. Evaluation of color fastness, softness and hydrophilicity in the padding process

For the evaluation of color fastness, softness and hydrophilicity, test fabrics (cotton mesh 200 g / m ² ) according to the formulations described above were first dyed and then aftertreated by padding. Equipment in the padding process Laboratory equipment apparatus: laboratory padder Equipment Fleet: The amounts of the respective products of Preparation Examples 1-5 are given in Table 10. The pH of the equipment fleet is set to 5-6. Liquor ratio: 1:15 Equipment conditions: - Fleet intake 80% - Dry at 150 ° C for 5 minutes in a drawer dryer

Table 10 - Levels of padding

The respective amounts used of the products of Preparation Examples 1-5 in Application Examples 7-12 are given in grams per liter of equipment liquor. Preparation according to Example 1 Preparation according to Example 2 Preparation according to Example 3 (according to the invention) Preparation according to Example 4 (according to the invention) Preparation according to Example 5 (according to the invention) example 20 Application Example 8 20 Application Example 9 20 20 Application Example 10 (Inventive) 40 Application example 11 (according to the invention) 30 Application example 12 (according to the invention) 30

Color fastness rating - padding method

This is not listed separately in tabular form, since the results obtained according to the invention are identical or gradually better than those of the test fabrics treated in the exhaust process. This applies both to the dyeings with the reactive and substantive dyes.

Hand assessment

This was carried out in the same manner as indicated above in Table 8. Table 11 - Handle assessment - padding procedure Grip evaluation grade within the test series Application example 7 3 Application Example 8 6 Application Example 9 4 Application Example 10 (Inventive) 1 Application example 11 (according to the invention) 2 Application example 12 (according to the invention) 1 untreated 6

Hydrophilicity - padding process

The evaluation of the hydrophilicity was carried out on the treated, substantive dye-stained test fabric according to the TEGEWA dropping test (Melliand Textilberichte 68 (1987), 581-583). Table 12 - Hydrophilicity - padding procedure Sinking time (sec) Application example 7 9 Application Example 8 <2 Application Example 9 4 Application Example 10 (Inventive) <2 Application example 11 (according to the invention) <2 Application example 12 (according to the invention) <2 untreated <2

Yellowing on white goods - padding procedure

Sections of a bleached, non-optically brightened cotton modal knit fabric were impregnated with the equipment liquors according to Application Examples 7-12 on a laboratory tampon having a wet pickup of 80%, dried at 120 ° C for 2 minutes and then heat set at 170 ° C for 2 minutes. Subsequently, the whiteness of the samples was measured whole on the whiteness meter "texflash 2000" from the company "datacolor international" (Switzerland). Table 13 - Yellowing Whiteness to whole Application example 7 179 Application Example 8 180 Application Example 9 180 Application Example 10 (Inventive) 186 Application example 11 (according to the invention) 191 Application example 12 (according to the invention) 177 untreated 195

Claims (5)

Aqueous preparations, characterized by a content, based on the total composition, of (1) 10 to 80% by weight of a linear or branched carboxy-functional organopolysiloxane-polyammonium copolymer (β) which can be prepared: I. By reacting an organopolysiloxane of the formula (α)

wherein the radicals R ¹ , R ² and R ⁴ independently of one another have the structure

with the proviso that at least one of R ¹ , R ² and R ^{4 has} a primary or secondary amino group and R ¹ , R ² and R ⁴ are not simultaneously but also trimethylsiloxy,

R ⁶ , R ⁸ = independently of one another are hydrogen or a linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{7 has} one of the meanings given for R ⁵ , or

a is an integer of 5-200, b is an integer of 0-5, c is the integer 2 or 3, d is an integer of 1-10, e is an integer of 1-10, f is an integer and wherein the units provided with the indices a and b are randomly distributed, with at least one dicarboxylic acid or a dicarboxylic anhydride selected from maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 2-methyleneglutaric acid, trans, trans-2, 4-hexadiene diacid, maleic anhydride, citraconic anhydride, itaconic anhydride, methyl 5-norbornene-2,3-dicarboxylic anhydride, 4,10-dioxatricyclo [5.2.1.0-2,6-] dec-8-ene-3,5-dione, cis-5 Norbornene-endo-2,3-dicarboxylic anhydride, cis-5-norbornene exo-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 3- (2-neopentylallyl) tetrahydrofuran-2,5-dione, nonenyl succinic anhydride, 3- (2-methyl-2-propenyl) dihydro-2,5-furandione, 5-methyl-3a, 4,7,7a-tetrahydro-2-benzofuran-1,3 dione, 3- (3-methyl-2-butenyl ) dihydro-2,5-furandione, 5,6-dimethyl-3a, 4,7,7a-tetrahydro-2-benzofuran-1,3-dione, 2-octene-1-ylsuccinic anhydride and 3 - [(2E) - 2-decenyl] dihydro-2,5-furandione, wherein the molar ratio of amino-functional Organopolysiloxane (α) to dicarboxylic acid or dicarboxylic anhydride is chosen so that after the reaction is still free carboxyl groups in Organopolysiloxanmrocomonomer present, and wherein per mole of reactive amino group in the organopolysiloxane (α) 0.2 to 1 mol of dicarboxylic acid or dicarboxylic anhydride is used, to an olefinic unsaturated organopolysiloxane macromonomers and II. by subsequent free radical copolymerization of this olefinically unsaturated organopolysiloxane macromonomer with one or more comonomers of type (γ) selected from diallyldimethylammonium chloride, diallylmethylamine, diallylamine, [(2-methacryloyloxy) ethyl] trimethylammonium chloride, [(2-methacryloyloxy) -ethyl trimethyl ammonium methosulfate, [(2-acryloyloxy) ethyl] trimethyl ammonium chloride, [(2-acryloyloxy) ethyl] trimethyl ammonium methosulfate, (3-acrylamidopropyl) trimethyl ammonium chloride, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, N-methyl-2-vinylpyridinium chloride loride and N-methyl-4-vinylpyridinium chloride, to the linear or branched, carboxy-functional organopolysiloxane-polyammonium copolymer (β) wherein the total nitrogen content of the linear or branched carboxy-functional organopolysiloxane-polyammonium copolymer (β) is 3-9% by weight; the nitrogen content in the organopolysiloxane of formula (α) is 0.2-4.5 weight percent and wherein the carboxyl groups produced are always located on the polymer back and adjacent to the amido functions of the organopolysiloxane macrocommerin, and (4) 20 to 90 weight percent water. Aqueous preparations according to claim 1, characterized by an additional content of (2) 0.1 to 20% by weight of an emulsifier and / or (3) 0.1 to 25% by weight of a hydrotrope based on the total composition. Use of the preparations according to claim 1 or 2 as a post-treatment agent on cellulosic substrates. Use according to claim 3 in the exhaust process. Use according to claim 3 in the forced application method.