EP1871863A2

EP1871863A2 - Composition containing polyamino-polysiloxane and/or polyammonium-polysiloxane compounds on a substrate

Info

Publication number: EP1871863A2
Application number: EP06742529A
Authority: EP
Inventors: Roland Wagner; Sabine Nienstedt; Christopher Roos; Annette Moeller; Karl-Heinz Sockel; Karl-Heinz Staghulla; Anita Witossek; Horst Lange
Original assignee: Momentive Performance Materials GmbH; Momentive Performance Materials Inc
Current assignee: Momentive Performance Materials GmbH; Momentive Performance Materials Inc
Priority date: 2005-03-30
Filing date: 2006-03-30
Publication date: 2008-01-02
Also published as: JP2008537985A; US20080194785A1; WO2006103076A3; CN101151358A; DE102005014312A1; WO2006103076A2

Abstract

The invention concerns compositions comprising a composition containing a polyamino-polysiloxane and/or polyammonium-polysiloxane compound on a substrate. The invention also concerns methods for producing said compounds as well as their use for treating wet textiles after washing.

Description

COMPOSITION COMPRISING POLYAMINO AND / OR POLYAMOMONOJM POLYSILOXAN COMPOUNDS ON ONE

Substrate

DESCRIPTION:

The invention relates to compositions which comprise at least one polyamino and / or polyammonium-polysiloxane compounds on a substrate, processes for their preparation and their use for textile treatment, in particular for the treatment of wet textiles after washing. From US 3,442,692 a method for conditioning laundry is known, wherein the wet laundry articles under heat in a clothes dryer together with a conditioning agent containing ^'substrate with agitation mixed, the transition of the conditioning agent on the laundry articles during the drying takes place. As conditioners, for example, softening and antistatic agents, bacteriostats, fungus and moth repellent are used. As softening and antistatic agents, mention is generally made of cationic compounds such as ammonium compounds.

The said ammonium compounds, however, are disadvantageous since they generally do not have sufficient substantivity, i. their ability to permanently grow on the fiber during conventional laundry drying is low. Attempting to improve substantivity by, for example, increasing the content of ammonium groups is usually accompanied by a deterioration of the softening properties. Furthermore, relatively high amounts of conditioning agents are required because the conditioners under the conditions of laundry drying repeatedly detach from the laundry and get into the environment by means of the dryer exhaust air.

There was therefore an urgent desire to improve the substrate-based conditioners of the prior art in terms of substantivity and plasticizing properties and thus to improve the effectiveness and the effectiveness of the substrate-based Kon¬itiitungsmittelungsmittel. It has surprisingly been found that compositions containing a substrate and at least one polyamino and / or polyammonium-polysiloxane compound coated on the substrate are capable of solving the above described problem. The polyamino and / or polyammonium

Polysiloxane compounds are characterized in that they comprise on average at least one organopolysiloxane group and at least one amino and / or ammonium group. Preferably, the polyamino and / or polyammonium-polysiloxane compounds contain on average at least two, more preferably at least three organopolysiloxane grappenes and at least two, more preferably at least three, amino and / or ammonium clusters. An organopolysiloxane according to the invention is a group having at least ^■ two connected via an oxygen atom silicon atoms, wherein at least one of the silicon atoms having at least one bound via a carbon atom of the organic radical.

In a preferred embodiment of the invention, the polyamino and / or polyammonium-polysiloxane compounds are selected from polyamino and / or polyammonium-polysiloxane copolymer compounds. Such copolymer compounds are characterized by a content of linear molecular segments with alternating organopolysiloxane Grappen and amino and / or ammonium groups. This does not exclude that the copolymer compound may be branched.

In a preferred embodiment of the invention, the polyamino- and / or polyammonium-polysiloxane copolymer compounds are characterized in that they have at least one, preferably on average at least two, more preferably on average at least three repeat units of the formula (I) :

- [Q-V] - (I)

wherein Q is selected from the group consisting of: -NR.-, -N ⁺ R ₂ -

a saturated or unsaturated diaminofunctional heterocycle of the formulas:

, such as

an aromatic diaminofunctional heterocycle of the formula:

a trivalent radical of the formula:

-N

a trivalent radical of the formula: - A -

/

--NT

^, or

a tetravalent radical of the formula

where each R is hydrogen or a monovalent organic radical,

where Q does not bind to a carbonyl carbon atom,

V is selected from the group consisting of V ¹ , V ² and V ³ , wherein

V ^{2 is} selected from 2-valent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic

Hydrocarbon radicals having up to 1000 carbon atoms (wherein the carbon atoms of the polysiloxane radical Z ² defined below are not included), optionally one or more groups selected from

-CÖNR ² - in which R ^{2 represents} hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms and having one or more groups selected from -O-, -NH-, -C (O) - and -C (S) -, and optionally by one or more substituents selected from the group consisting of a hydroxyl group, an optionally substituted, preferably containing one or more nitrogen atoms heterocyclic group, amino, alkylamino,

Dialkylamino, ammonium, polyether radicals and

Polyetheresterresten may be substituted, wherein when several groups -CONR ² , they may be the same or different,

-C (O) - and -C (S) - may contain

the radical V ² optionally by one or more hydroxyl groups and / or by

wherein a is an integer of 0 to 2 and R and R 'may be the same or different and each represents an organic group, may be substituted, and

the radical V ^{2 is} at least one group -Z ² - of the formula

contains, in which

R ^{1 may be the} same or different and is selected from the group consisting of: Ci to C ₂₂ alkyl, fluoro (Ci-Ci ₀ ) alkyl, C ₆ -C ₀ -aryl and -W-Si (OR) 3- _a (R ') a, wherein R, R' and V are as defined above, and W is -O- or a divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical up to 100 carbon atoms, which may contain one or more groups - C (O) -, -O-, -NH-, -S-, and may optionally be substituted by hydroxy groups, and

m = 20 to 1000 means

V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms, optionally one or more groups selected from

-CONR ² -, wherein R ^{2 is} as defined above, wherein the groups R ² in the groups V ¹ and V ^{2 may be the} same or different,

-C (O) -, -C (S) - and -Z ¹ - may contain, wherein -Z ¹ - a group of the formula

is in which

RR ¹¹ wwiiee oobb «en is defined, wherein the groups R ¹ in the groups V ¹ and V ^{2 may be the} same or different, and n2 = 0 to 19 means

and the radical V ¹ optionally by one or more hydroxyl groups and / or by

wherein a is an integer of 0 to 2 and R and R 'may be the same or different each other and each represents an organic group, may be substituted, and

V ^{3 is} a trivalent or higher, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 1000 carbon atoms, optionally one or more groups selected from

-O-, -CONH-, , -CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) -, -Z ¹ -, which is as defined above, -Z ² - which is as defined above, and Z ³ , wherein Z ^{3 is} a tri- or higher organopolysiloxane unit, may contain, and

optionally substituted by one or more hydroxyl groups and / or by

wherein a is an integer from 0 to 2 and R and R 'may be the same or different and each represents an organic radical, may be substituted, may be substituted, with the proviso that said polysiloxane compound contains at least one group -Z ¹ -, -Z ² - or Z ³ , that the tri- and tetravalent radicals Q serve either the branching of the main chain formed from Q and V such that the Valences that do not serve for attachment in the backbone, further branches formed from [QV] units, or the tri- and tetravalent residues Q saturate with residues V ³ within a linear backbone without forming a branch, and wherein the from ammonium groups resulting positive charges are neutralized by organic or inorganic acid anions. These copolymer compounds have a particularly high substantivity with high plasticizing effect.

In a particularly preferred embodiment of the invention, the substituents R in the groups Q comprise one or more radicals R ⁰ , where R ^{0 is} a polyalkylene oxide-containing organic radical. The use of these radicals R ⁰ leads to an increased hydrophilicity of the polyamino and / or polyammonium-polysiloxane copolymer compounds, which thus accumulate more quickly on the wet garments resulting from the textile washing. In a preferred embodiment, the inventive

Polyamino and / or polyammonium-polysiloxane copolymer compounds characterized in that the molar ratio R ⁰ : Q from 0.001 to 2, more preferably from 0.01 to 1, more preferably 0.05 to 0.8. If the molar ratio is less than 0.001, the hydrophilicity is too low. An optimal coordination of softness and hydrophilicity succeeds in the range from 0.05 to 0.8. The radical R ° preferably represents a group of the formula (III):

-X-E-Y (III),

wherein X represents a single bond or a divalent, straight-chain, branched or cyclic hydrocarbon radical having up to 20 carbon atoms, which may optionally contain nitrogen and / or oxygen, and X is connected via a carbon atom to the nitrogen atom of Q,

E is a polyalkylene oxide radical of the formula

- [(C _a H _2a ) O] _y -

wherein a = 2 to 4, and y = 2 to 10,000,

which is connected via a carbon atom to the group X and via an oxygen atom to the group Y,

Y represents hydrogen or a monovalent, straight-chain, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon radical having up to 24 carbon atoms, which may contain oxygen and / or nitrogen and / or halogen and is bonded to the group E via a carbon atom.

Preferably, R ^{0 is} a group of the formula (III) in which - E - represents a group of the formula (IV):

CH ₃ - (CH ₂ CH ₂ O) V (CHCH ₂ O) WY ^

which may be static and block-like sequences of the ethylene and propylene oxide units and the bond to E can take place via an ethylene or propylene oxide unit, the representation of the group (IV) is therefore only quantitative,

with v = 0 to 200, w = 0 to 200, v + w ≥ l.

In the group of the formula (III), furthermore, Y is preferably selected from H or straight-chain, cyclic, branched C 1 - to C ₂₂ -alkyl, alkenyl, alkynyl, fluoro (C 1 -C 10) -alkyl and C 6 -C ₁₀ -aryl aryl radicals.

Further preferred alkylene oxide units R ⁰ preferably have the structure:

CH ₃ CH ₃

-CHCH2θ- (CH2CH2θ) _v (CHCH2θ) _W -iY

with v = 0 to 200, w = 0 to 200, v + w ≥ 1, Y = H or straight-chain, cyclic, branched C 1 to C ₂₂ alkyl, alkenyl,

Alkynyl, fluoro (Ci-Ci ₀ ) alkyl and C ₆ -C ₀ aryl radical.

In the above general polyalkylene oxide formulas, preference is given to: v 0 to 100, more preferably 0 to 70, especially 0 to 40, especially 0 to 20, w 0 to 100, particularly preferably 0 to 70, especially 0 to 40, especially 0 to 20, Y is a straight-chain, cyclic, branched Ci to Cn alkyl, alkenyl, alkynyl, or C _ö -Cio aryl group, especially methyl, ethyl, isopropyl, butyl, hexyl, dodecyl,

AUyl ₃ oleyl, phenyl.

Another preferred alkylene oxide unit R ⁰ has the structure - (C 1 -C 12) alkylene-N ⁺ R ₂ EY, where C 1 -C 12 alkylene is a straight-chain, cyclic or branched one

Alkylene unit having 1 to 12 carbon atoms, and R, E and Y are as defined above.

The polysiloxane compounds which contain on average preferably at least two, preferably at least three, more preferably at least four units of the formula (I), wherein preferably on average at least two, more preferably at least three, even more preferably at least four units R ⁰ can be contained, and in Agents preferably at least one unit V ¹ , V ² and / or V ^{3 are} included are preferably terminated by monofunctional groups -QR and / or -VR, ie for example by amino groups. These result from saturation of one of the two binding sites of Q or V by a monovalent group R or hydrogen, which is as defined above, and are also referred to below as V * or Q ^st . Instead of V *, other, unreacted reactive groups, such as epoxy or Halogenalkylgmppen stand.

In the case of the polysiloxane compounds according to the invention which contain on average preferably at least two units of the formula (I), wherein on average preferably at least two units R ⁰ may be present, and on average preferably at least one unit V ¹ , V ² and / or V ³ are, for example, linear polysiloxane copolymers of the general formula (P):

- [Q-V] - (P)

wherein Q is as defined above, and

V and at least one group V ¹ or group V ² , wherein V ¹ and V ^{2 are} as defined above. In addition, V can also represent trivalent or higher valency, especially trivalent radicals V ³ . In this case, there are preferably also trivalent or tetravalent units Q, as defined above, and the saturation of the trivalent or higher-valued radicals V ³ and the tri- or tetravalent units Q preferably takes place exclusively with one another within the linear main chain with the formation of cyclic structures, as explained in more detail below. However, this case is less preferred. In the general formulas (I) and (P), the molar ratio of

Groups V ¹ and V ² in the polysiloxane compounds Wv ^{1 take} on any value per se. Thus, according to the invention, the case is also included in which the polysiloxane compound of the formulas (I) or (P) contains only V ² units, ie the polysiloxane compound has the formula - [QV ² ] -. Also, the case where the polysiloxane compound contains only V 1 units is included in the invention. In this case, however, the V ¹ units must contain Z 1 siloxane units. However, in a preferred embodiment of the invention, the polysiloxane compound of formulas (I) or (P) contains both V ² and V ¹ units.

In a further preferred embodiment of the present invention, the molar ratio of the groups V ¹ and V ² in the polysiloxane compounds of the general formulas (I) or (P) is:

V ² ^ = I.

In a further embodiment of the linear polysiloxane compounds of the formula (I) b2w. (P) is V ² A ^ ¹ other than I ₅ V ² / V ^{x is} preferably <1, more preferably <0.9, more preferably, Wv ¹ satisfies the relationship

0.0005 <WV ¹ <0.5, more preferably

0.0005 <VW <0.3.

The group R is preferably selected from the groups R ² . Preferred embodiments of Q are:

For radicals of the formula

a quaternized imidazole moiety of the structure

a quaternized pyrazole unit of the structure

For radicals of the formula

a doubly quaternized piperazine moiety of structure

R2 R2

-N + + N-

For radicals of the formula

a mono-quaternized piperazine moiety of the structure

a monoquaternized piperazine unit of Strulctur

For radicals of the formula

-N ⁺ R ₂ -

a doubly quaternized unit of structure

a monoquaternized unit of the structure

a doubly quaternized unit of structure

and a monoquaternized unit of the structure

For radicals of the formula

-NO-

a monoquaternized unit of the structure

Wherein:

t is from 2 to 10,

R as defined above, preferably R ^2, R ² is as defined above, and the meaning of R from the meaning of the above group R may be identical or different,

R ^{3 has} the meaning of R ² , wherein R ² and R ^{3 may be the} same or different, or

R ² and R ³ together with the positively charged nitrogen atom form a five- to seven-membered heterocycle which may optionally additionally have one or more nitrogen, oxygen and / or sulfur atoms, R ⁵ , R ⁶ , R ^{7 may be the} same or different and are selected from the group consisting of: H, halogen, hydroxyl, nitro, cyano, thiol, carboxyl, alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl, acetyloxy, cycloalkyl, aryl, alkylaryl, and Groups of the type -NHR ^W , in which R ^{w is} H, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, acetyl group, ureido group, and in each case two of the adjacent radicals R ⁵ , R ⁶ and R ⁷ with the them to the heterocycle-binding carbon atoms aromatic five to Can form seven rings, and R ^{8 has} the meaning of R ² , wherein R ⁸ and R ^{2 are the} same or different can be eden. In particular, R8 may be a polyoxyalkylene-containing radical, resulting in the formation of an R ° -containing radical Q.

In the case that Q is a trivalent residue of the formulas or or a tetravalent radical, these radicals in the case of the linear copolymers of the formula (P) as mentioned above preferably do not serve the branching of the polysiloxane copolymers but these radicals are exclusively bonded to particularly trivalent radicals V ³ , forming cyclic structures which form part of the linear main chain, such as a structural element of the formula:

In a preferred embodiment of the polysiloxane compounds of

Formula (I) or (V) V ^{2 represents} a group of the formula

_V ² * -Z ² -V ² * -

in which Z ^{2 is} as defined above and V ² * - represents a bivalent straight, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms, optionally containing one or more groups selected from -O-, -CONH -, -CONR ² -, wherein R ^{2 is} as defined above, -C (O) - and -C (S) - may contain, and the radical V ² * may optionally be substituted by one or more hydroxyl groups.

In the above-mentioned embodiment, the linear polysiloxane copolymer according to the invention may have the following repeating units:

- [V ² * -Z ² -V ² * -QJ- preferably together with - [V'-Q] -.

The molar ratio of repeating units - [V ² * -Z ² -V ² * -Q] - to - [V ^1- Q] "_> ^a l ^so that the ratio V ² Af ¹ , as mentioned above, about 1 However, in one embodiment, is preferably not equal to 1, more preferably> 1, more preferably> 1 and less than 1.5. The comb-like introduction of hydrophilic side groups R ⁰ makes it possible to increase the proportion of the plasticizing properties contributing group V ² with constant hydrophilicity. Conversely, given a proportion of plasticizing groups V ^{2, it is} possible to increase the hydrophilicity by introducing the group R ⁰ .

As will be explained in detail below in connection with the process for the preparation of the above-described linear polysiloxane copolymers, the block-like sequences which have more than one - [V ^ -Q] unit linked to one another regularly with the V ² depending on the preparation -Q units or irregularly connected to the V ² -Q units. This means the following:

In the regular compound in which, for example, one of the group -Q-JV'-QJ _x -responding prepolymer with V ² corresponding monomer units in a molar ratio of 1: 1 is reacted, the linear polysiloxane copolymers can be represented as follows:

x may be 2 to 2000 and is the mean of the distribution and y is also an average and is 2 to 1000.

In general, therefore, the polysiloxane polymers according to the invention preferably have the formula

where y 'is from 2 to 1000, more preferably from 3 to 500, even more preferably from 4 to 200.

The through the formula represented linear

Polysiloxane copolymers are characterized by having substantially no interlinked -V ² -Q units, or with others

In other words, two -V ² -Q units are always interrupted by at least one -V ^ Q unit. In the case of the irregular compound in which, for example, Q units are monomers corresponding to monomer units corresponding to V ¹ and monomer units corresponding to V ² in the ratio Qf (V ¹ + V ² ), with, for example

V ² / V ^J > 1, the linear polysiloxane copolymers can be prepared as follows:

-Q- (V ^ V ² ) -,

where V is the ratio V ² / V ^! then> 1 is. The groups V ¹ and V ^{2 are} statistically distributed over the copolymer chain. In contrast to the linear polysiloxane copolymers prepared by the regular compound, this

Copolymer also have adjacent -QV ² units.

In a preferred embodiment of the invention used

Polysiloxane compound of the formula (I) or (P), the group V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 600, preferably up to 400, carbon atoms which optionally have one or more groups,

selected from -O-, -CONH-, , -CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) - and -Z ¹ - may contain, wherein -Z ¹ - a group of the formula

wherein R ^{1 is} Ci-Cis-alkyl, which may be optionally substituted with one or more fluorine atoms, or phenyl, and Ό. ₂ as defined above. In a further preferred embodiment of the polysiloxane compounds of the formula (I) or (F), the group Q is selected from:

wherein R ^{2 is} preferably H or alkyl, preferably having 1 to 6 carbon atoms, and R ^{3 is} preferably H, alkyl, preferably having 1 to 6 carbon atoms, or R ⁰ .

Preference is given in the formulas (I) and (F):

R ¹ = Ci to Cis-alkyl, in particular methyl, ethyl, trifluoropropyl and phenyl,

ni = 20 to 400, more preferably 20 to 300, especially 20 to 200. In a further preferred embodiment, ni is between 20 and 50 or between 80 and 200. The number ni is the average degree of polymerization of M _{n of} the diorganosiloxy units in the Group Z ² .

Ώ. ₂ = 0 to 15, more preferably 0 to 10, especially 0 to 5, more particularly 0. The number Ώ. ₂ is the average degree of polymerization of M _{n of} the diorganosiloxy units in the group Z ¹ .

Particularly preferred is

R ^z

R ³

for -NH ₂ ⁺ -, -N (CHs) ₂ ⁺ -, - (NHR °) ⁺ -.

V ^{2 *} for a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical with up to 16 Carbon atoms which may contain one or more groups selected from -O-, -CONH-, -CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) - and having a or more hydroxyl groups may be substituted. Even more preferably, -V ² * - is selected from groups of the formulas:

- (CH ₂ ) SOCH ₂ CHCH ₂ - - (CH ₂ ) 3θCH ₂ CH-

OH CH ₂ OH

- (CHa) ₂ -, - (CHi) ₃ -, - (CHa) ₄ -, - (CHa) ₅ -, - (CHa) ₆ -,

-CH = CHCH ₂ -, -CH = CHCH ₂ CH ₂ -,

-CH ₂ CH ₂ CH ₂ OC (O) CH ₂ -, -CH ₂ CH ₂ CH ₂ OC (O) CH ₂ CH ₂ -,

-CH = CHCH ₂ OC (O) CH ₂ -, -CH = CHCH ₂ OC (O) CH ₂ CH ₂ -,

CH ₃ -CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) V (OCH ₂ CH) WOC (O) CH ₂ -

CH ₃ -CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) V (OCH ₂ CH) WOC (O) CH ₂ CH ₂ -

CH ₃ -CH = CHCH ₂ (OCH ₂ CH ₂ ) V (OCH ₂ CH) WOC (O) CH ₂ -

CH ₃ -CH = CHCH ₂ (OCH ₂ CH ₂ ) V (OCH ₂ CH) WOC (O) CH ₂ CH ₂ - CH ₃ -CH = CHCH ₂ CH ₂ (OCH ₂ CH ₂ ) v (OCH ₂ CH) _w OC (O) CH 2 -

CH ₃ -CH = CHCH ₂ CH 2 (OCH 2 CH 2) v (OCH 2 CH) _w OC (O) CH ₂ CH ₂ -

CH ₃ - (CH ₂ ) IOC (O) (OCH ₂ CH ₂ ) V (OCH ₂ CH) WOC (O) CH ₂ CH ₂ -

CH ₃ - (CH ₂ ) IOC (O) (OCH ₂ CH ₂ ) V (OCH ₂ CH) WOC (O) CH ₂ -

- (CH ₂ ) 3θCH ₂ CHCH ₂ - - (CH ₂ ) 3 OCH ₂ CH-

OH CH ₂ OH

- (CH ₂ ) S-, - (QHb) ₄ -, - (CH ₂ ) S-, - (CH ₂ ) ₆ -,

-CH = CHCH ₂ -, -CH = CHCH ₂ CH ₂ -,

-CH ₂ CH ₂ CH ₂ OC (O) CH ₂ -, - CH ₂ CH ₂ CH ₂ OC (O) CH ₂ CH ₂ -.

V ¹ preferably represents ■ -R ⁹ -, in which R ^{9 represents} a divalent, saturated or mono- or polyunsaturated, straight-chain or branched hydrocarbon radical having from 2 to 25 carbon atoms, - (CH ₂ ) _u C (O) O - [(CH ₂ CH ₂ O) _q - (CH ₂ CH (CH ₃ ) O) _r ] -C (O) (CH ₂ ) _u -

^■ - (CH ₂ ) _u C (O) OR ⁹ -OC (O) (CH ₂ ) u-, wherein R ^{9 is} as previously defined,

■ - (CH ₂ ) _u -R ¹⁰ - (CH ₂ ) _u -, where R ^{10 is} an aromatic group, - [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH ₂ -, ^■ -CH (CH 3) CH ₂ O [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃₎ O] _r -CH ₂ CH (CH 3) -

-CH ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) (CH ₂ ) ₂ CH (OH) CH ₂ -,

-CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ - and -CH ₂ CH (OH) CH ₂ O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (OH) CH ₂ - wherein u is from 1 to 3, q and r is from 0 to 200, preferably from 0 to 100, more preferably from 0 to 70 and particularly preferably 0 to Is 40, and q + r> 0. Preferred variants of V ¹ are structures of the formula:

-CH ₂ C (O) O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -C (O) CH ₂ - ₅

-CH ₂ CH ₂ C (O) O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -C (O) CH ₂ CH ₂ -,

-CH ₂ CH ₂ CH ₂ C (O) O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH 3) O] _^ -C (O) CH ₂ CH ₂ CH ₂ -, esterified alkylene, alkenylene , Alkynylene units, especially the structures

-CH ₂ C (O) O- [CH _2] ₀ -OC (O) CH ₂ -,

-CH ₂ CH ₂ C (O) O- [CH ₂ ] _O -OC (O) CH ₂ CH ₂ -,

-CH ₂ CH ₂ CH ₂ C (O) O- [CH ₂ ] _O -OC (O) CH ₂ CH ₂ CH ₂ -

-CH ₂ C (O) O-CH ₂ C = CCH ₂ -OC (O) CH ₂ -, -CH ₂ CH ₂ C (O) O-CH ₂ C = CCH ₂ -OC (O) CH ₂ CH ₂ -

-CH ₂ CH ₂ CH ₂ C (O) O-CH ₂ C = CCH ₂ -OC (O) CH ₂ CH ₂ CH ₂ -,

-CH ₂ C (O) O-CH ₂ CH = CHCH ₂ -OC (O) CH ₂ -,

-CH ₂ CH ₂ C (O) O-CH ₂ CH = CHCH ₂ -OC (O) CH ₂ CH ₂ -,

-CH ₂ CH ₂ CH ₂ C (O) O-CH ₂ CH = CHCH ₂ -OC (O) CH ₂ CH ₂ CH ₂ , alkylene, alkenylene, alkynylene and aryl units, especially the structures:

- [CH ₂ ] o- with o = 2 to 6, NOT SUBMITTED ON REGISTRATION DATE

NOT SUBMITTED ON REGISTRATION DATE

wherein a, b and c may be the same or different and from 1 to 40,

with v + w> 0, where the arrangement of the ethylene and propylene oxide units can be random or block-like and the attachment to Q via ethylene and propylene oxide units via a carbon atom can take place.

The branching unit V ³ may contain a trivalent or higher organopolysiloxane unit, such as: wherein R ^{1 is} as defined above, m = 0 to 1000, and m is ¹ > 1 and m ² > 3,

wherein R ^{1 is in} each case as defined above.

An example of a Z ³ -containing branching unit V ³ is, for example:

The polysiloxanes used according to the invention may contain units R °, which are preferably incorporated into the polymer by suitable alkylation reactions of primary, secondary or tertiary monoamino-functionalized polyalkylene oxides with reactively functionalized siloxane precursors. The primary mono functionalized Jeffamine ^® M series (Huntsman Corp.) are preferably used.

In a preferred embodiment, the primary mono-amino-functionalized polyalkylene oxides are first alkylated in an upstream reaction with the reactive-functionalized siloxanes, preferably epoxysiloxanes, to form tertiary amines. These precursors are incorporated into the siloxane block copolymer in the subsequent polymer formation reaction. In the context of another preferred variant, it is possible to dispense with this upstream reaction and to use the primarily mono-amino-functionalized polyalkylene oxides directly in the polymer formation reaction.

For the less preferred case in which the polyalkylene oxide units are intended to terminate the siloxane block polymers in a controlled manner, it is possible to start from secondary or tertiary amino-functionalized polyalkylene oxide units. If not directly available, these can be prepared by pre-reaction of the primarily monofunctionalized polyalkylene oxides with alkylating agents, for example monoepoxides such as isopropyl glycidyl ether or dimethyl sulfate.

The monofunctionally bonded hydrophilic element R ⁰ can be introduced into the polyquaternary polysiloxane copolymers used according to the invention in order to increase the hydrophilicity in a targeted manner. This leads to both Increased hydrophilicity of the polysiloxane copolymers themselves according to the invention, so that, for example, a facilitated transition into the moisturizing takes place, as well as to increase the hydrophilicity of the treated with the compositions of the invention textiles, which leads for example to an improved moisture absorption of textiles.

Examples of alternating polysiloxane-quat block copolymers which can be used according to the invention are described, for example, in DE OS 3340708, US Pat. No. 6,240,929, EP 282720, DE OS 10036533, WO 02/10257, WO 02/10259, WO 03/078504, WO 2004/041912, WO 2004 / 042136 and application PCT / EP 2004/050472.

The polyamino used in the invention and / or polyammonium-polysiloxane compounds may be solid or liquid at 25 ⁰ C. In the event that they are liquid at 25 ⁰ C, the viscosities of said polysiloxanes are preferably between 500 to 50,000,000 mPa.s at 25 ° C, preferably 1000 to 2,500,000 mPa.s at 25 ⁰ C and a Shear rate gradient of D = 1 s ^"1 .

In the composition according to the invention, the substrate is generally a solid support material (at room temperature (25 ^° C.) and preferably up to the decomposition temperature) which is capable of absorbing the polyamino and / or polyammonium-polysiloxane compounds and, in particular, among them Discharge conditions of laundry drying again. Therefore, it is preferably a porous material. The substrates may be, for example, layered, bag-like, or in compact layers. Also, solid non-deformable, porous substrates are applicable, such as granules, which in turn may be enclosed in wipes. Particularly preferably, the substrate is in the form of a layered material. According to the invention, for example, spongy or fibrous materials such as fiber fabrics, non-woven fabrics, paper towels are preferred. With respect to the materials used, there are no particular limitations, as long as the substrate material can accommodate the polyamino and / or polyammonium-polysiloxane compounds. Preferred materials are natural or synthetic fibers, such as those based on cellulose, such as cotton, furthermore wool, sisal, linen, cellulose esters, polyols. vinyl compounds, polyolefins, polyamides, polyurethanes, polyesters. Sponge-like materials may for example consist of polyurethanes.

The compositions according to the invention suitably contain from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, more preferably from 0.3 to 5% by weight, of the polyamino and / or polyammonium-polysiloxane compounds, based on the total weight of the composition.

The composition according to the invention may contain at least one further textile treatment agent. Such fabric treatment agents include, for example, other softening and antistatic agents other than those used in the present invention, bacteriostats, antifungal and mothproofing agents, deodorants, fragrances, ironing aids, anti-caking agents, etc. These may be used in amounts of up to 20% by weight .-% be contained in the composition of the invention.

Furthermore, the composition of the invention may contain one or more solvents, such as water or alcohols.

The invention further relates to a process for the preparation of the composition according to the invention, which comprises applying at least one polyamino and / or polyammonium-polysiloxane compound to the substrate. The application can be carried out in a manner known per se (see, for example, US Pat. No. 3,442,692), for example by impregnation, spraying, etc., if appropriate using solvents. According to the invention, the case is also included in that the end user is provided with the polyamino and / or polyammonium-polysiloxane compounds optionally in admixture with further ingredients in liquid form for application to a separately provided solid substrate, and the end user the inventive Composition by impregnation of the solid substrate with the provided liquid composition immediately before the application itself manufactures.

The invention further relates to a method for the treatment of textiles, which comprises contacting the inventive composition with the textiles. Preference is given to the composition of the invention with the still moist, resulting from the textile laundry textiles preferably at temperatures of more than 25 ⁰ C, preferably brought using commercial clothes dryer in contact. Accordingly, the invention further relates to the use of the composition according to the invention for the treatment of textiles made of natural or synthetic fibers. The invention further relates to the use of polyamino and / or polyammonium-polysiloxane copolymer compounds for the production of solid textile treatment agents, in particular for the production of substrate-based textile treatment agents. Here, as above, solid means that the outer application form does not substantially change during application to the textiles, which is ensured in particular by the use of a solid support, as defined above. Preferably, the above-described use of polyamino and / or polyammonium-polysiloxane copolymer compounds in liquid form at room temperature, optionally with the addition of further functional constituents, such as those mentioned above, and solvents.

Examples

example 1

Ia) Synthesis of a Chloroacetic Ester 384 g (0.384 mol) of a commercially available polyethylene glycol PEG 1000 are initially charged under nitrogen at room temperature. The material is heated to 70 ⁰ C and thereby melted. With intensive stirring 104 g (0.92 mol) of chloroacetyl chloride are added dropwise within 15 minutes. During the dropping, the temperature rises without heating to 90 ⁰ C and a HCl evolution begins. After completion of the dropwise addition, the batch is heated to 120 ^° C. for 1.5 hours. Finally, all components boiling to 120 ° C./5 hPa are distilled off. There are obtained 424 g of a colorless wax, which determines the composition determined by ¹ H-NMR

CICH ₂ C (O) O [CH ₂ CH ₂ O] _2I C (O) CH ₂ Cl. The solids are 99.7%.

Example Ib) Synthesis of a block copolymer

In a 500 ml three-necked flask under nitrogen 100 g (17.27 mmol) of a

Siloxane epoxides of the structure

3.46 g (34.54 mmol) of N-methylpiperazine and 50 g of n-butanol are mixed together and heated to 100 ⁰ C for 6 hours.

19.61 g (17.27 mmol) of the ester according to Beispiella dissolved in in 73 g n-butanol are added to the batch and heat the entire mixture for another 12 hours at 100-106 ⁰ C. Finally, the batch is heated to 117 ^° C. for 8 hours. A yellow biphasic product is obtained which when shaken turns into a viscous opaque mass. The solids are 49.8% by weight. According to ¹ H-NMR data, the conversion of the epoxide at the end of the reaction is 95.1%, the conversion of the chloroacetic acid ester 93.9%. The polymer has the following structure:

Example 2

Washing tests are carried out in a Miele Novotronic W526. Washing conditions: 95 ⁰ C, short cycle, 2x rinse, soft dosage of the freshener in the second rinse, spin at 1200 U / min Drying: 24 hours drying canvas.

Ariel Hydractive® Trade name of Procter & Gamble GmbH Lenor® Trade name of Procter & Gamble GmbH Hand assessment

There are formed 5 pairs of lobes, each consisting of an inventively and not inventively treated terry cloth. These pairs of flaps are judged by 4 offenders in terms of grip. There are a total of 20 comparative handle assessments.

For each handle better lobes is a rating of 1 to 4 possible. As a result of the assessment, the cloths equipped according to the invention receive an overall grade of +0.58.

hydrophilicity

On each one according to the invention and not equipped according to the invention

Frotteelappen 10 drops of water (50 .mu.l) placed on it, while the times measured to sink. The sinking of the drops on the inventively equipped cloth takes place immediately at the moment of placement.

The sinking of the drops onto the cloth not equipped according to the invention takes place on average after 1 second and is visibly delayed with respect to the cloths provided according to the invention.

Overall

The data show that despite a reduction of the standard amount of plasticizer to 25% and only partial replacement by the siloxane block copolymers according to the invention, an improvement in the handle can be achieved. At the same time, the hydrophilicity of the finished textile material increases significantly.

Claims

CLAIMS;

A composition comprising a substrate and at least one polyamino and / or polyammonium-polysiloxane compound coated on the substrate.

2. A composition according to claim 1, wherein the polyamino and / or polyammonium polysiloxane compounds comprise at least one organopolysiloxane group and at least one amino and / or ammonium group.

3. A composition according to claim 1 or 2, wherein the polyamino and / or polyammonium polysiloxane compounds comprises at least two organopolysiloxane groups and at least two amino and / or ammonium groups.

A composition according to any one of claims 1 to 3, wherein the polyamino and / or polyammonium-polysiloxane compounds are selected from polyamino and / or polyammonium-polysiloxane copolymer compounds comprising linear molecular segments having alternating organopolysiloxane groups and amino and / or ammonium groups.

5. The composition according to any one of claims 1 to 4, wherein the polyamino and / or polyammonium-polysiloxane copolymer compounds have at least one repeating unit of the formula (I):

- [Q-V] - (I)

wherein Q is selected from the group consisting of: -NO-,

-N ⁺ R ₂ -

a saturated or unsaturated diaminofunctional heterocycle of the formulas:

, such as

an aromatic diaminofunctional heterocycle of the formula:

a trivalent radical of the formula:

-N

a trivalent radical of the formula: /

-N ⁺ l \

, or

a tetravalent radical of the formula

i + - N-

wherein each R is hydrogen or a monovalent organic radical,

where Q does not bind to a carbonyl carbon atom,

V is selected from the group consisting of V ¹ , V ² and V ³ , wherein

V ^{2 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms (wherein the carbon atoms of the polysiloxane radical Z ² defined below are not counted) which optionally have one or more groups selected from

-CONR ² - in which R ^{2 is} hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms and having one or more groups selected from -O-, -NH-,

-C (O) - and -C (S) -, and optionally by one or more substituents selected from the group consisting of a hydroxyl group, an optionally substituted, preferably one or more nitrogen atoms containing heterocyclic group, amino, alkylamino, dialkylamino, ammonium, polyether radicals and polyether radicals may be substituted, where if several groups -CONR ² , these may be the same or different,

-C (O) - and -C (S) - may contain

the radical V ² optionally by one or more hydroxyl groups and / or by

-Si (OR) ₃ - (R ').

the radical V ^{2 is} at least one group -Z ² - of the formula

contains, in which

R ^{1 may be the} same or different and is selected from the group consisting of: C 1 to C ₂₂ alkyl, fluoro (C ₁ -C 10) alkyl, C ₆ -C 10 aryl and -W-Si (OR) ₃ , _a (R ') _a , wherein R, R' and a are as defined above and W is -O- or a bivalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups -C (O) -, -O-, -NH-, -S-, and may optionally be substituted by hydroxy groups, and

ni = 20 to 1000 means

is in which

R ^{1 is} as defined above, where the groups R ¹ in the groups V ¹ and V ^{2 may be} identical or different, and n ₂ = 0 to 19, and the radical V ¹ optionally by one or more hydroxyl groups and / or by

-Si (OR) ₃ .. (R ').

-O-, -CONH-, -CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) -, -Z ¹ -, which is as defined above, -Z ² - which is as defined above, and Z ³ , wherein Z ^{3 is} a tri- or higher organopolysiloxane unit may contain, and

optionally substituted by one or more hydroxyl groups and / or by

wherein a is an integer from 0 to 2 and R and R 'may be the same or different and each represents an organic radical, may be substituted, may be substituted,

with the proviso in that said polysiloxane compound contains at least one group -Z ¹ -, -Z ² - or Z ³ such that the tri- and tetravalent radicals Q serve either to branch the main chain formed from Q and V such that the valencies that are not serve the bond in the main chain, further from - [QV] -

Carry units formed branches, or the tri- and tetravalent radicals Q become saturated with residues V ³ within a linear main chain without formation of a branch, and

wherein the positive charge resulting from ammonium groups is neutralized by organic or inorganic acid anions.

6. The composition according to claim 5, characterized in that V comprises repeating units of the formula V ¹ and V ² .

A composition according to any one of claims 1 to 6, wherein the substrate is a solid support material capable of receiving and releasing the polyamino and / or polyammonium-polysiloxane compounds.

A composition according to any one of claims 1 to 7, wherein the substrate is a porous material.

A composition according to any one of claims 1 to 8, wherein the substrate is a spongy or fibrous material.

A composition according to any one of claims 1 to 9, wherein the composition contains from 0.01% to 20% by weight of the polyamino and / or polyammonium-polysiloxane compounds, based on the total weight of the composition.

11. The composition according to any one of claims 1 to 10, which contains at least one further textile treatment agent.

12. A process for the preparation of the composition according to any one of claims 1 to 11, that the application of at least one polyamino and / or

Polyammonium-polysiloxane compound comprises on the substrate.

A method of treating textiles which comprises contacting the composition of any one of claims 1 to 11 with the textiles.

14. A method according to claim 13, wherein the contacting of the composition according to any one of claims 1 to 11 with wet textiles optionally at temperatures of more than 25 ⁰ C includes.

15. Use of the composition according to any one of claims 1 to 11 for the treatment of textiles.

16. Use of polyamino and / or polyammonium-polysiloxane copolymer compounds for the production of solid textile treatment agents.