Zwitterionic polysiloxane

Abstract

To provide an improved polysiloxane which has high emulsion stability to an anion, a salt, a pH change, strong shearing force, and a combination of these influencing factors, is resistant to thermal yellowing and phenol yellowing, and is used for finishing a soft feeling.SOLUTION: Provided are polysiloxanes having zwitterionic groups, for example, as described below (Formula A), their preparation, compositions comprising such polysiloxanes, and these polysiloxanes or compositions for treating substrates.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polysiloxanes having zwitterionic groups, their preparation, compositions containing such polysiloxanes, and the use of these polysiloxanes or compositions to treat substrates. [Background technology]

[0002] Polysiloxanes are used in a variety of ways to finish textile materials, and because of their flexible structure and ease of functionalization, they can be customized for many different applications.

[0003] Amino-modified polysiloxanes have long been used as softening agents. They are usually applied to textiles as liquid preparations in the form of aqueous emulsions. With the addition of emulsifiers, amino-modified polysiloxanes form stable emulsions in water at acidic pH values.

[0004] However, the described formulations have a number of drawbacks, such as low stability under alkaline conditions, high sensitivity to salts and anions, and poor resistance to shear stress during application in modern finishing machines. Another drawback is the pronounced susceptibility of treated substrates to thermal yellowing, especially at drying temperatures above 120°C.

[0005] However, many textile pretreatment processes require the use of high pH values ​​in aqueous treatment baths. For example, pretreatment, bleaching, and dyeing of cellulose substrates routinely require the use of large amounts of alkali. If such process steps are not adequately neutralized and carefully washed, alkaline components can be carried over to subsequent treatment baths containing softeners, which can lead to destabilization of emulsions of amino-functional polysiloxanes. Emulsion destabilization under alkaline conditions is due to deprotonation of the amino functional groups of the polysiloxane. Without a cationic charge on the polysiloxane, the microemulsion will coagulate. The resulting coagulum can deposit unevenly on the textile being treated, causing staining of the textile.

[0006] Emulsions of polysiloxanes bearing quaternary ammonium groups can at least partially overcome the aforementioned drawbacks. The preparation of diquaternary polysiloxanes is described, for example, in U.S. Patent No. 5,623,999. They are synthesized by reacting a polysiloxane having terminal epoxide groups with a tertiary amine in a ratio such that each epoxide group corresponds to at least one tertiary amino group. The reaction is carried out at elevated temperatures in the presence of an acid in an amount equivalent to the nitrogen atoms to be quaternized. Due to this special preparation method, the resulting diquaternary polysiloxanes have quaternary ammonium groups located only at the terminals. Compounds prepared in this manner are recommended for use in hair treatment products and cosmetics.

[0007] Ammonium-modified polysiloxanes and polyether-modified polysiloxanes are described in Patent Document 2. These polysiloxanes are prepared from epoxy-functional polysiloxanes by reacting the epoxy-functional polysiloxanes with amines and alkyl alcohol alkoxylates. This is followed by quaternization with an alkylating agent. These polysiloxanes are used to finish textile substrates and are characterized by high resistance to thermal yellowing. Due to the terminal polyether and ammonium groups, they also have good pH stability.

[0008] However, the above-mentioned advantages of polysiloxanes containing quaternary ammonium groups are offset under practical conditions by the drawback that they often exhibit poor resistance to phenolic yellowing, to anionic textile auxiliaries, to the addition of salts, and to the shear effects in the presence of anions and with the addition of salts, especially in jet processes.

[0009] In a jet dyer, the finish is subjected to strong dynamic loads due to high shear forces, which can destabilize the treatment and lead to the formation of undesirable stains, as mentioned above.

[0010] In the softening of dyed or optically brightened fabrics in a jet dyeing machine, where the fabric has already been dyed or optically brightened, it is important that, on the one hand, there is no undesired separation from the destabilized softening emulsion, and, on the other hand, the respective dyeing or optically brightening is not impaired. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] U.S. Patent No. 4,891,166 [Patent Document 2] German patent no. 102005056864 Summary of the Invention [Problem to be solved by the invention]

[0012] The problem is therefore to provide an improved polysiloxane for soft-hand finishes that meets these requirements and overcomes the drawbacks of the prior art. In particular, polysiloxanes that have high emulsion stability against anions, salts, pH changes, and strong shear forces, as well as combinations of these influences, and that are resistant to thermal and phenolic yellowing, should be provided. [Means for solving the problem]

[0013] Surprisingly, this problem is solved by the polysiloxanes according to the invention which are modified with zwitterionic groups.

[0014] It has been surprisingly shown that the zwitterionic polysiloxanes according to the invention and their emulsions exhibit high shear stability, especially in the presence of salts, stability to anions, and resistance to phenolic yellowing. The polysiloxanes according to the invention are not only suitable as softening agents, but can also be added to paints, glazes, lacquers, and car care products, for example, to improve their wetting, spreading, and / or leveling properties.

[0015] Thus, a first aspect of the present invention provides compounds of general formula A: [ka] (In the formula, R 1 are, independently of each other, Methyl, [ka] However, in formula A, at least one R 1 corresponds to one of Formulas II to V, R 2 are, independently of each other, [ka] and R 3 are, independently of each other, [ka] or [ka] with the proviso that at least one R in Formula A is a zwitterionic group selected from 3 is a zwitterionic group, R 4are, independently of each other, unbranched or branched C 1~7 -Alkylene, preferably unbranched C 1~5 -alkylene, particularly preferably -(CH2)2-, R 5 are, independently of each other, branched or unbranched C 1~18 -alkyl, preferably unbranched C 1~8 - alkyl, particularly preferably methyl, R 6 are, independently of each other, unbranched C 2~5 -alkylene, preferably -(CH2)2- or -(CH2)3-, R 7 are, independently of each other, unbranched or branched C 1~18 -Alkylene, preferably unbranched C 1~8 -alkylene, particularly preferably -(CH2)2- or methylene, R 8 are independently H or OH, R 9 are, independently of each other, unbranched or branched C 1~18 -Alkylene, preferably unbranched C 1~8 - alkylene, particularly preferably methylene, R 11 are, independently of each other, [ka] and R 12 are, independently of each other, [ka] and R 13 are each independently an aliphatic or cyclic C 1~18 - alkylene or arylene, in each case optionally C 1~8 -substituted with alkyl or benzyl, preferably unbranched C 1~8 - alkylene, in particular -(CH2)4-, -(CH2)6-, [ka] and n is an integer of 20 to 2000, preferably 40 to 1000, particularly preferably 40 to 180; m is 0 or an integer greater than 0, preferably 0 or 1 to 2000, more preferably 0 or 1 to 55).

[0016] Preferably, R is 0% to 99.9%, more preferably 50% to 99.9%, even more preferably 80% to 99.9%, and particularly preferably 90% to 99.9%. 1 The substituent is methyl in the polysiloxanes according to the invention.

[0017] Alternatively, R is preferably 0% to 99.999%, more preferably 50% to 99.999%, even more preferably 80% to 99.999%, and particularly preferably 90% to 99.999%. 1 The substituent is methyl in the polysiloxanes according to the invention.

[0018] R according to Equations II to V 1 Zwitterionic embodiments of substituents can be located terminally and / or laterally on the polysiloxane backbone in polysiloxanes according to the present invention.

[0019] In a preferred embodiment, the polysiloxane according to the present invention has two terminal R 1 The substituent is methyl and at least one lateral R 1 The substituent corresponds to one of Formulas II to V.

[0020] In an alternative embodiment, in the polysiloxane according to the invention, all lateral R 1 The substituent is methyl, and the two terminal R 1 The substituents are selected from Formulas II to V.

[0021] In a preferred embodiment, all R of the polysiloxane according to the invention 1 The substituents are selected from methyl and Formula II, Formula III, and Formula V.

[0022] In a preferred embodiment, all R of the polysiloxane according to the invention 1 The substituents are selected from methyl and Formula II.

[0023] In an alternative embodiment, all R of the polysiloxane according to the present invention 1 The substituents are selected from methyl and formula III.

[0024] At least one R in the polysiloxane according to the present invention 1 When the substituent corresponds to formula IV, R 8 is preferably OH.

[0025] At least one R in the polysiloxane according to the present invention 12 When the substituent corresponds to formula XV, R 8 is preferably OH.

[0026] In the polysiloxane of the present invention, 10% to 100%, more preferably 40% to 99.9%, particularly preferably 50% to 95%, and most preferably 60% to 80% of R 3 is preferably present as a zwitterionic group. Surprisingly, at least 10% of R 3 It has been shown that when the substituents are present as zwitterionic groups, the polysiloxanes according to the invention already exhibit improved process stability compared to polysiloxanes without zwitterionic groups. 3 When the substituents are present as zwitterionic groups, in particular better emulsion stability in application to shear forces, especially in the presence of salts, better emulsion stability in application to anions, and resistance to phenolic yellowing are achieved.

[0027] In a preferred embodiment, all zwitterionic groups in the polysiloxane according to the present invention are present as formula VIa.

[0028] In an alternative embodiment, all zwitterionic groups in the polysiloxane according to the present invention are present as Formula VIb.

[0029] Preferably, R in the polysiloxane according to the invention 2 is the expression: [ka] is equivalent to

[0030] In a preferred embodiment, the polysiloxane of formula A is R 1 are, independently of each other, Methyl, [ka] However, in formula A, at least one R 1 corresponds to either formula II or formula III, R 2 are, independently of each other, [ka] and R 3 are, independently of each other, [ka] or [ka] with the proviso that at least one R in Formula A is a zwitterionic group selected from 3 is a zwitterionic group, R 11 are, independently of each other, [ka] and R 12 are, independently of each other, [ka] and R 4 , R 5 , R 6 , R 9 , R 13 , m and n are as defined above.

[0031] In a preferred embodiment, the lateral R 1 Substantially all of the substituents are methyl, and particularly when m is greater than 0, 90% to 99.999% of R 1 The substituent is methyl.

[0032] In a preferred embodiment, m=0, i.e., the polysiloxane has the formula I: [ka] (In the formula, R 1 are, independently of each other, Methyl, [ka] with the proviso that in formula I, at least one R 1 corresponds to one of Formulas II to V, R 2 are, independently of each other, [ka] and R 3 are, independently of each other, [ka] or [ka] with the proviso that at least one R in Formula I is a zwitterionic group selected from 3 is a zwitterionic group, R 4 are, independently of each other, unbranched or branched C 1~7-Alkylene, preferably unbranched C 1~5 -alkylene, particularly preferably -(CH2)2-, R 5 are, independently of each other, branched or unbranched C 1~18 -alkyl, preferably unbranched C 1~8 - alkyl, particularly preferably methyl, R 6 are, independently of each other, unbranched C 2~5 -alkylene, preferably -(CH2)2- or -(CH2)3-, R 7 are, independently of each other, unbranched or branched C 1~18 -Alkylene, preferably unbranched C 1~8 -alkylene, particularly preferably -(CH2)2- or methylene, R 8 are independently H or OH, R 9 are, independently of each other, unbranched or branched C 1~18 -Alkylene, preferably unbranched C 1~8 - alkylene, particularly preferably methylene, n is an integer of 20 to 2000, preferably 40 to 1000, and particularly preferably 40 to 180).

[0033] Preferably, 0% to 99.9%, more preferably 50% to 99.9%, even more preferably 80% to 99.9%, particularly preferably 90% to 99.9% of R in the polysiloxane according to the present invention. 1 The substituent is methyl.

[0034] In the polysiloxanes according to the present invention, R 1 Zwitterionic embodiments of the substituents can be located terminally and / or laterally on the polysiloxane backbone.

[0035] In a preferred embodiment, the two terminal R 1 The substituent is methyl and at least one lateral R 1The substituent corresponds to one of Formulas II to V.

[0036] In an alternative embodiment, in the polysiloxane according to the invention, all lateral R 1 The substituent is methyl, and the two terminal R 1 The substituents are selected from Formulas II to V.

[0037] In a preferred embodiment, all R of the polysiloxane according to the invention 1 The substituents are selected from methyl and Formula II, Formula III, and Formula V.

[0038] In a preferred embodiment, all R of the polysiloxane according to the invention 1 The substituents are selected from methyl and Formula II.

[0039] In an alternative embodiment, all R of the polysiloxane according to the present invention 1 The substituents are selected from methyl and formula III.

[0040] At least one R in the polysiloxane according to the present invention 1 When the substituent corresponds to formula IV, R 8 is preferably OH.

[0041] In the polysiloxane of the present invention, 10% to 100%, more preferably 40% to 99.9%, particularly preferably 50% to 95%, and most preferably 60% to 80% of R 3 is preferably present as a zwitterionic group. Surprisingly, at least 10% of R 3 It has been shown that when the substituents are present as zwitterionic groups, the polysiloxanes according to the invention already exhibit improved process stability compared to polysiloxanes without zwitterionic groups. 3When the substituents are present as zwitterionic groups, in particular better emulsion stability in application to shear forces, especially in the presence of salts, better emulsion stability in application to anions, and resistance to phenolic yellowing are achieved.

[0042] In a preferred embodiment, all zwitterionic groups in the polysiloxane according to the present invention are present as formula VIa.

[0043] In an alternative embodiment, all zwitterionic groups in the polysiloxane according to the present invention are present as Formula VIb.

[0044] Preferably, R in the polysiloxane according to the invention 2 is the expression: [ka] is equivalent to

[0045] In a preferred embodiment, the polysiloxane of formula I is R 1 are, independently of each other, Methyl, [ka] with the proviso that in formula I, at least one R 1 corresponds to either formula II or formula III, R 2 are, independently of each other, [ka] and R 3 are, independently of each other, [ka] or [ka] with the proviso that at least one R in Formula I is a zwitterionic group selected from 3 is a zwitterionic group.

[0046] R 4 , R 5 , R 6 , R 9 and n is as defined above.

[0047] Another aspect of the present invention is a process for preparing the polysiloxanes according to the present invention, comprising the steps of: (a) General formula VII: [ka] (In the formula, R 10 are, independently of each other, Methyl, [ka] with the proviso that in Formula VII, at least one R 10 corresponds to one of Formulas VIII to XI; (b) optionally, converting a polysiloxane of general formula VII into a polysiloxane of formula OCN-R 13 -NCO with a diisocyanate; (c) treating the polysiloxane of formula VII or the polysiloxane adduct obtained after step (b) with peroxide and / or a compound of general formula XII: [ka] wherein X is a halogen, in particular Cl or Br, or at least one salt thereof, wherein the peroxide is preferably hydrogen peroxide (H2O2), di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, meta-chloroperbenzoic acid, dibenzoyl peroxide, diacetyl peroxide, peroxides of the formula diacetyl peroxide, peracetic acid, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, sodium peroxide and / or barium peroxide, particularly preferably hydrogen peroxide (H2O2), The process includes:

[0048] R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 13 , n and m are as defined above.

[0049] Preferably, in step b) of the process according to the invention, a compound of the general formula OCN-R 13 The molar ratio of the --NCO diisocyanate to the polysiloxane of general formula VII is 0.1:1 to 1:1, more preferably 0.4:1 to 0.999:1, particularly preferably 0.5:1 to 0.95:1, and most preferably 0.6:1 to 0.9:1.

[0050] Preferably, in step b) of the process according to the invention, a compound of the general formula OCN-R 13 The molar ratio of isocyanate groups of the -NCO diisocyanate to isocyanate-reactive hydroxy groups of the polysiloxane of general formula VII is 0.1:1 to 1:1, more preferably 0.4:1 to 0.999:1, particularly preferably 0.5:1 to 0.95:1, and most preferably 0.6:1 to 0.9:1.

[0051] Preferably, in step b), a compound of the general formula OCN-R 13The -NCO diisocyanates are selected from the group consisting of toluene-2,4-diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), longer chain homologues of diphenylmethane diisocyanate (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate and / or isophorone diisocyanate.

[0052] Preferably, step b) is carried out with or in the absence of a solvent, more preferably in the absence of a solvent.

[0053] Preferably, step b) is carried out using a catalyst, in particular using a catalyst based on a tertiary amine, a bismuth compound, and / or an organotin compound.

[0054] Preferably, the course of the reaction in step b) can be monitored by titration or IR spectroscopy.

[0055] When a salt of a halocarboxylic acid according to formula XII is used as a reactant in step c), the salt is preferably an ammonium or sodium salt of the halocarboxylic acid.

[0056] Preferably, in the process according to the invention, the reactants are used in amounts such that the molar ratio between the reactants and the tertiary amino groups in the polysiloxane of formula VII or the tertiary amino groups in the polysiloxane adduct obtained after step (b) corresponds to the desired degree of conversion of amino groups to zwitterionic groups. Preferably, the molar ratio between the reactants and the tertiary amino groups in the polysiloxane of formula VII is 0.1:1 to 1:1, more preferably 0.4:1 to 0.999:1, particularly preferably 0.5:1 to 0.95:1, and most preferably 0.6:1 to 0.8:1.

[0057] Preferably, the reaction in step b) and / or step c) of the process according to the present invention is carried out at a temperature between 15°C and 150°C, more preferably between 20°C and 105°C, even more preferably between 25°C and 95°C, even more preferably between 40°C and 90°C, and most preferably between 70°C and 85°C.

[0058] Step c) of the process according to the invention is preferably carried out in a solvent, particularly preferably comprising water and / or at least one organic solvent. The organic solvent can be selected from the group consisting of monofunctional and polyfunctional alcohols, such as ethanol, 1-propanol, 2-propanol, butanol, 2-methyl-2-propanol, 3-methyl-1-butanol, and 2-hexyl-1-decanol, and / or their ether compounds, such as ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dipropylene glycol-n-butyl ether, propylene glycol monobutyl ether, propylene glycol-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, hexylene glycol, butyl glycol, butyl diglycol, and triethylene glycol dimethyl ether, and / or ketones, such as acetone, can be used. Preferably, the solvent is water and / or an organic solvent.

[0059] If desired, further steps such as distillation and / or filtration can be added to the process.

[0060] The preparation of the amino-functional polysiloxane of formula VII, which serves as starting compound in the process according to the present invention, is carried out according to methods known to those skilled in the art.Thus, in the first step, epoxy-functional polysiloxane can be obtained by hydrosilylation of Si-H-containing polysiloxane with α,β-unsaturated epoxy compound.The corresponding process is described, for example, in German Patent Application Publication No. 3705121.

[0061] In the second step, the epoxide group is reacted with a secondary amine to form a polysiloxane of formula VII. A corresponding process is described, for example, in WO 02 / 10256. If necessary, this can be followed by equilibration with, for example, octamethylcyclotetrasiloxane.

[0062] In a further aspect, the present invention relates to polysiloxanes obtainable by the process according to the invention described above.

[0063] In a preferred embodiment, the present invention provides a process for the preparation of polysiloxanes according to the present invention, which comprises a compound of general formula VII: [ka] (In the formula, R 10 are, independently of each other, Methyl, [ka] with the proviso that in Formula VII, at least one R 10 corresponds to one of the formulae VIII to XI), by treating a polysiloxane of the general formula XII: [ka] wherein X is a halogen, in particular Cl or Br, or at least one salt thereof, The peroxide in this regard is preferably hydrogen peroxide (H2O2), di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, meta-chloroperbenzoic acid, dibenzoyl peroxide, diacetyl peroxide, peracetic acid, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, sodium peroxide and / or barium peroxide, particularly preferably hydrogen peroxide (H2O2).

[0064] R 2 , R4 , R 5 , R 6 , R 7 , R 8 , R 9 and n is as defined above.

[0065] When a salt of a halocarboxylic acid according to formula XII is used as a reactant, the salt is preferably an ammonium or sodium salt of the halocarboxylic acid.

[0066] Preferably, in the process according to the invention, the reactants are used in amounts such that the molar ratio between the reactants and the tertiary amino groups in the polysiloxane of formula VII corresponds to the desired degree of conversion of amino groups to zwitterionic groups. Preferably, the molar ratio between the reactants and the tertiary amino groups in the polysiloxane of formula VII is 0.1:1 to 1:1, more preferably 0.4:1 to 0.999:1, particularly preferably 0.5:1 to 0.95:1, and most preferably 0.6:1 to 0.8:1.

[0067] Preferably, in the process according to the present invention, the reaction is carried out at a temperature of 15°C to 150°C, more preferably 20°C to 105°C, even more preferably 25°C to 95°C, and particularly preferably 70°C to 85°C.

[0068] The process according to the present invention is preferably carried out in a solvent, particularly preferably comprising water and / or at least one organic solvent. The organic solvent can be selected from the group consisting of monofunctional and polyfunctional alcohols, such as ethanol, 1-propanol, 2-propanol, butanol, 2-methyl-2-propanol, 3-methyl-1-butanol, and 2-hexyl-1-decanol, and / or their ether compounds, such as ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dipropylene glycol-n-butyl ether, propylene glycol monobutyl ether, propylene glycol-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, hexylene glycol, butyl glycol, butyl diglycol, and triethylene glycol dimethyl ether, and / or ketones, such as acetone, can be used. Preferably, the solvent is water and / or an organic solvent.

[0069] If desired, further steps such as distillation and / or filtration can be added to the process.

[0070] The preparation of the amino-functional polysiloxane of formula VII, which serves as starting compound in the process according to the present invention, is carried out according to methods known to those skilled in the art.Thus, in the first step, epoxy-functional polysiloxane can be obtained by hydrosilylation of Si-H-containing polysiloxane with α,β-unsaturated epoxy compound.The corresponding process is described, for example, in German Patent Application Publication No. 3705121.

[0071] In the second step, the epoxide group is reacted with a secondary amine to form a polysiloxane of formula VII. A corresponding process is described, for example, in WO 02 / 10256. If necessary, this can be followed by equilibration with, for example, octamethylcyclotetrasiloxane.

[0072] In a further aspect, the present invention relates to polysiloxanes obtainable by the process according to the invention described above.

[0073] A further aspect of the present invention is (i) at least one polysiloxane according to the present invention, and (ii) a solvent, in particular water and / or an organic solvent, more preferably water; The present invention relates to a composition comprising:

[0074] Preferably, the composition according to the present invention comprises, based on the total mass of the composition, 0.005% by weight to 99.9% by weight, more preferably 5% by weight to 99% by weight, particularly preferably 10% by weight to 90% by weight of component (i).

[0075] In a preferred embodiment, the composition according to the invention further comprises (iii) at least one emulsifier. The emulsifier can be anionic, cationic, nonionic, or amphoteric. Mixtures of such emulsifiers can also be used.

[0076] Preferably, the composition according to the invention comprises at least one nonionic emulsifier, particularly preferably an ethoxylated product of a fatty alcohol. Such an ethoxylated product of a fatty alcohol can be included in the composition according to the invention in pure form or as a mixture. For example, an aliphatic C ethoxylated product, which can be saturated, linear, or preferably branched, and contains up to 50 bonded ethylene oxide units, can be used. 6~22 -Alcohols, especially aliphatic C 8~18 Ethoxylation products of C-alcohols are preferred, for example isodecyl alcohol, isotridecyl alcohol or C-alcohols, each having 2 to 50, in particular 5 to 25, bonded ethylene oxide units per molecule. 16~18 The ethoxylated products of -alcohols are particularly advantageous.

[0077] In addition to the pure ethoxylation products, alcohols of the mentioned composition whose alkylene oxide radicals are composed of ethylene oxide and 1,2-propylene oxide distributed randomly or in blocks are also suitable.

[0078] Preferably, the composition according to the invention comprises from 2% to 100% by weight, more preferably from 10% to 80% by weight, particularly preferably from 20% to 70% by weight, of the emulsifier (iii) or mixture of emulsifiers, based on component (i).

[0079] When the solvent (ii) of the composition according to the invention comprises an organic solvent, it is preferably polar or non-polar. Monofunctional and polyfunctional alcohols, such as ethanol, 1-propanol, 2-propanol, butanol, 2-methyl-2-propanol, 3-methyl-1-butanol, and 2-hexyl-1-decanol, and / or their ether compounds, such as ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dipropylene glycol n-butyl ether, propylene glycol monobutyl ether, propylene glycol n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, hexylene glycol, butylene glycol, butyl diglycol, triethylene glycol dimethyl ether, and / or their ester compounds, such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 1-methoxy-2-propyl acetate, dibasic acid esters or amyl acetate, and / or ketones, such as acetone, methyl ethyl ketone, methyl propyl ketone, and / or saturated hydrocarbons, especially gasoline having 5 to 10 carbon atoms, more preferably gasoline having 6 to 8 carbon atoms, such as gasoline, hexane, heptane, octane, cyclohexane, and cycloheptane, especially n-pentane, n-hexane, n-heptane, or n-octane, isoparaffins, or organic solvents selected from the group consisting of petroleum ethers. Preferably, the solvent is water and / or an organic solvent. The composition according to the invention can also contain a mixture of polar and nonpolar solvents.

[0080] In a preferred embodiment, the composition according to the invention further comprises (iv) at least one additive, for example a diluent, such as polyethylene glycol having a molecular weight of 200 g / mol to 10,000 g / mol, preferably 400 g / mol to 6,000 g / mol, and / or glycerol, and / or urea, and / or at least one acid, in particular an organic acid such as acetic acid or lactic acid. The stability of the composition can be further improved by protonating any tertiary amino groups present in the polysiloxane.

[0081] In a particularly preferred embodiment, the composition according to the invention comprises (i) at least one polysiloxane according to the invention, (ii) a solvent, in particular water, and (iii) at least one emulsifier; Includes.

[0082] In this case, the composition according to the invention is preferably an emulsion, in particular an oil-in-water emulsion, or a treatment liquid, in particular an aqueous treatment liquid. The preparation of the emulsion according to the invention is carried out according to methods known to those skilled in the art, for example at temperatures between 15°C and 70°C.

[0083] The emulsion preferably contains 5 to 60% by weight, and particularly preferably 10 to 40% by weight, of component (i) based on the total weight of the emulsion. The treatment liquid preferably contains 0.005 to 3.0% by weight, and particularly preferably 0.01 to 1.2% by weight of component (i) based on the total weight of the emulsion.

[0084] In a particularly preferred embodiment, the composition according to the invention comprises (i) at least one polysiloxane according to the invention, (ii) a solvent, in particular water, and (iv) at least one additive, in particular an acid.

[0085] In a particularly preferred embodiment, the composition according to the invention comprises (i) at least one polysiloxane according to the invention, (ii) a solvent, in particular water, (iii) at least one emulsifier, and (iv) at least one additive, in particular an acid.

[0086] In a further preferred embodiment, the composition according to the invention comprises (i) at least one polysiloxane according to the invention, (ii) a solvent, in particular water, (iii) at least one emulsifier, and (iv) at least one additive, in particular an acid, and / or at least one softening agent, preferably an organically modified polysiloxane.

[0087] Suitable softening agents are, for example, polysiloxanes having amino groups, quaternary ammonium groups (quat), polyether groups, and / or (poly)urethane groups, and combinations thereof.

[0088] The organomodified polysiloxane is different from the polysiloxane according to Formula A.

[0089] Surprisingly, the compositions, especially emulsions, are particularly stable to shear stress and anions, especially in the presence of salts, and are resistant to phenolic yellowing.This facilitates the uniform treatment of substrates, especially the uniform finishing of textiles with these compositions.High process stability is a great advantage, especially when finishing using jet processing, because, in addition to the other factors mentioned above, high shear stress often acts, which can have a strong destabilizing effect on emulsions.

[0090] Without being bound by any theory, it is assumed that the zwitterionic groups in the polysiloxanes according to the invention contribute significantly to stabilization against these effects.

[0091] A further aspect of the present invention relates to the use of a polysiloxane according to the invention or a composition according to the invention in the treatment of substrates or as an additive in paints, glazes, varnishes and / or car care formulations. Preferred substrates for use according to the present invention are textiles, leather, metal, glass, wood or plastics.

[0092] In a preferred embodiment, the composition according to the invention is an additive for paints, glazes, varnishes and / or car care formulations comprising at least one polysiloxane (i) according to the invention and an organic solvent, in which case the composition preferably comprises 0.1% to 99.9% by weight, particularly preferably 0.5% to 99% by weight, and most preferably 10% to 90% by weight of component (i), based on the total weight of the composition.

[0093] In car care and coating compositions, component (i) may be present from 0.1% to 5% by weight based on the total weight of the composition.

[0094] The use according to the invention for finishing textile substrates is preferred. In particular, the textile substrates can be woven, knitted, nonwoven, fiber, and / or leather products, or mixtures thereof. According to the invention, the textile substrates can comprise natural fibers, in particular cotton and / or wool, and / or synthetic fibers, in particular viscose, polyester, polyamide, and / or polyacrylonitrile.

[0095] The emulsions or aqueous dilutions of these emulsions, also known as treatment solutions, are preferably used to finish textile substrates.

[0096] Surprisingly, it has been shown that the polysiloxanes according to the invention allow for uniform application under all conditions when treating substrates. Due to their high emulsion stability, they allow for uniform finishing of the substrate even under conditions that would otherwise have a destabilizing effect on the emulsion, such as high pH values, the presence of salts, the presence of anions, and / or strong shear forces.

[0097] In a preferred embodiment, the polysiloxanes or compositions according to the present invention can be used to improve the softness and handle of textile substrates. Surprisingly, finishing with the polysiloxanes according to the present invention has been shown to produce excellent softness and handle in treated textiles without compromising hydrophilicity. Fabrics treated in this manner have also been shown to be stable to thermal and / or phenolic yellowing.

[0098] The use of the present invention to finish dyed or optically brightened articles offers unique advantages: the finishing can even be carried out in the same jet dyeing machine in which the fabric was dyed or optically brightened. Surprisingly, it has been shown that finishing with the polysiloxane or composition according to the present invention does not impair the coloring or optically brightening effect, respectively, while at the same time significantly improving the softness and handle of the fabric.

[0099] In a further preferred embodiment, the polysiloxanes or compositions according to the present invention can be used to improve the wetting, spreading, leveling, and / or foaming behavior of paints, glazes, varnishes, and / or car care formulations. The use of polysiloxanes according to the present invention can reduce the surface tension of these formulations, depending on their application, thereby allowing the formulation to flow more uniformly and / or wet the substrate better, thereby avoiding cratering. Additionally, the presence of polysiloxanes according to the present invention in the formulations can improve the surface smoothness of the treated material. In car care products, the compositions, among other things, prevent so-called sheeting, i.e., the spreading of (rain) water on the treated surface. This accelerates the breakdown of the water film, allowing the water to run off more easily and accelerating drying. Furthermore, the polysiloxanes according to the present invention can have a degassing and / or defoaming effect.

[0100] A further aspect of the present invention relates to a substrate, in particular a textile substrate, treated with the polysiloxane according to the invention. Preferably, the substrate according to the invention comprises 0.04 to 2.4% by weight, particularly preferably 0.08 to 1.2% by weight, of the polysiloxane according to the invention, based on the total weight of the textile substrate. The substrate is preferably one of the substrates described above.

[0101] In a particularly preferred embodiment, the substrate is a textile substrate as described above.

[0102] In an alternative embodiment, the substrate is a metal substrate.

[0103] Another aspect of the present invention is a method for producing a semiconductor device comprising: (i) providing a substrate; (ii) applying a polysiloxane according to the invention or a composition according to the invention to a substrate; (iii) optionally treating the substrate obtained after step (ii) at an elevated temperature; The present invention relates to a process for treating a substrate, comprising:

[0104] The substrate in steps (i) to (iii) is preferably one of the substrates described above. In a particularly preferred embodiment, the substrate is a textile substrate as described above.

[0105] The application of the polysiloxane according to the invention or the composition according to the invention to the substrate in step (ii) can preferably be carried out by padding, spraying, brushing, dipping, patting and / or exhaust processes, for example, a textile substrate can be finished with the polysiloxane according to the invention or the composition according to the invention by exhaustion in a jet.

[0106] In a preferred embodiment, in step (iii) of the process according to the invention, water is removed, preferably at a temperature between 110° C. and 150° C., optionally under reduced pressure. DETAILED DESCRIPTION OF THE INVENTION

[0107] The following examples serve to explain the invention in more detail, without however limiting it. [Example]

[0108] Example 1 (not according to the invention): According to Example 3 of EP 0 294 642, 56.8 g (200 mmol) of lauryl(dimethylaminopropyl)amide was mixed with 80.0 g of H₂O, and 12.0 g (200 mmol) of glacial acetic acid was added at 20°C. After 30 minutes, the reaction mixture was heated to 50°C, and 590 g (100 mmol) of an epoxysiloxane having an epoxy content of 0.338 mol / kg and an average chain length of 75 was added dropwise. After adding 200 ml of isopropanol, stirring was continued under reflux for 6 hours. The H₂O / isopropanol mixture was distilled off at 100°C and 0.2 bar. 140 g of butyl diglycol was added, yielding a slightly yellow organopolysiloxane.

[0109] Example 2 (according to the invention): 500 g of a laterally Si-H modified poly(dimethylsiloxane-co-methylhydrosiloxane) having 0.089 wt % Si-bonded hydrogen (corresponding to 443 mmol of Si-H) and an average chain length of 75 was added over 60 minutes to a solution of 28.3 mg of Karstedt catalyst in 65.7 g (575 mmol) of allyl glycidyl ether previously adjusted to 135° C. After removal of excess allyl glycidyl ether by distillation, 44.4 g (443 mmol) of N-methylpiperazine was added slowly at 135° C. to give a clear, slightly yellowish organopolysiloxane (Intermediate A).

[0110] 76.5 g of the resulting intermediate A (corresponding to 114 mmol of tertiary nitrogen) was heated to 35°C together with 14.0 g of butyl diglycol. At this temperature, 6.46 g (57.0 mmol) of a 30% aqueous hydrogen peroxide solution was added with stirring. After the exothermic reaction had finished, stirring was continued at 75°C for 6 hours, yielding a slightly yellowish organopolysiloxane.

[0111] Example 3 (according to the invention): 76.5 g of Intermediate A from Example 2 (corresponding to 114 mmol of tertiary nitrogen) was heated to 35°C together with 8.50 g of butyl diglycol. At this temperature, 12.9 g (114 mmol) of 30% aqueous hydrogen peroxide solution was added with stirring. After the exothermic reaction had finished, stirring was continued at 75°C for 6 hours, yielding a slightly yellowish organopolysiloxane.

[0112] Example 4 (according to the invention): 500 g of an α,ω-dihydrogen polydimethylsiloxane having 0.035 wt % Si-bonded hydrogen (corresponding to 176 mmol of Si—H) and an average chain length of 75 was added over 60 minutes to a solution of 26.3 mg of Karstedt catalyst in 26.1 g (229 mmol) of allyl glycidyl ether, previously adjusted to 135° C. After removal of excess allyl glycidyl ether by distillation, 33.0 g (176 mmol) of bis[3-(dimethylamino)propyl]amine was added slowly at 135° C. to obtain a yellowish organopolysiloxane (Intermediate B).

[0113] 76.5 g of Intermediate B (corresponding to 48.7 mmol of tertiary nitrogen) was heated to 35°C together with 13.0 g of butyl diglycol. At this temperature, 5.52 g (48.7 mmol) of a 30% aqueous hydrogen peroxide solution was added with stirring. After the exothermic reaction had finished, stirring was continued at 75°C for 6 hours, yielding a slightly yellowish organopolysiloxane.

[0114] Example 5 (according to the invention): 7.04 g (74.5 mmol) of chloroacetic acid was dissolved in 5.00 g of HO and 10.0 g of butyl glycol. To this solution, 5.96 g (74.5 mmol) of 50% sodium hydroxide solution was added with stirring. After stirring for 15 minutes, 100 g of Intermediate A from Example 2 (corresponding to 149 mmol of tertiary nitrogen) was added, and the mixture was stirred at 75° C. for 4 hours to yield a slightly yellowish organopolysiloxane.

[0115] Example 6 (according to the invention): 5.41 g (57.3 mmol) of chloroacetic acid was dissolved in 6.00 g of HO and 12.0 g of butyl glycol. To this solution, 4.58 g (57.3 mmol) of 50% sodium hydroxide solution was added with stirring. After stirring for 15 minutes, 100 g of Intermediate B from Example 4 (corresponding to 63.6 mmol of tertiary nitrogen) was added, and the mixture was stirred at 75° C. for 4 hours to yield a slightly yellowish organopolysiloxane.

[0116] Example 7 (according to the invention): 500 g of an α,ω-dihydrogen polydimethylsiloxane having 0.035 wt % Si-bonded hydrogen (corresponding to 176 mmol of Si—H) and an average chain length of 75 was added over 60 minutes to a solution of 26.3 mg of Karstedt catalyst in 26.1 g (229 mmol) of allyl glycidyl ether, previously adjusted to 135° C. After removal of excess allyl glycidyl ether by distillation, 33.0 g (176 mmol) of bis[3-(dimethylamino)propyl]amine was added slowly at 135° C. The catalyst was then cooled to 50° C. Then, the mixture was cooled to 50°C, and 896 mg of 1,4-diazabicyclo[2.2.2]octane and 38.1 g (172 mmol) of isophorone diisocyanate were added. The mixture was stirred at 70°C until the NCO band in the IR spectrum disappeared, yielding a yellowish organopolysiloxane (Polysiloxane Adduct C).

[0117] 75.1 g of polysiloxane adduct C (equivalent to 46.6 mmol of tertiary nitrogen) was heated with 5.00 g of HO, 10.0 g of butyl glycol, 2.64 g (28.0 mmol) of chloroacetic acid, and 2.24 g (28.0 mmol) of 50% sodium hydroxide solution to 75° C. The mixture was stirred at 75° C. for 4 hours, yielding a slightly yellowish organopolysiloxane.

[0118] Emulsion example General emulsification instructions: The specified amount of emulsifier was added to the organopolysiloxane to be emulsified at room temperature and stirred with a wall-mounted anchor-type stirrer until a uniform mixture was obtained. H2O was added in portions to the mixture and stirred until all of the water was absorbed.

[0119] [Table 1]

[0120] Application Examples Soft grip evaluation Slices of non-optically brightened cotton terrycloth were finished in a Mathis Labomat at a bath ratio of 1:10 for 20 minutes at 40°C using an aqueous treatment solution containing 20 g / l of the emulsion prepared according to the examples and adjusted to pH 5 with 60% acetic acid. Excess treatment solution was then squeezed out using a laboratory padder at 3 bar, followed by drying at 140°C for 2 minutes. The circulation speed was 45 rpm.

[0121] The gripping properties of the emulsion-treated test fabrics were then evaluated. This is subject to subjective criteria that vary from person to person, and evaluations by at least five testers are required to obtain meaningful results. Results were analyzed using statistical methods, with a rating of 1 representing the softest, most comfortable grip in the test series and a rating of 3 representing the hardest, least soft, and most uncomfortable grip.

[0122] [Table 2]

[0123] hydrophilic The hydrophilicity of cotton terry fabrics finished for soft handling evaluation was evaluated according to the TEGEWA drop test method (Melliand Textilberichte 68 (1987), 581-583).

[0124] [Table 3]

[0125] Anion Stability 100 ml of the emulsion to be tested was prepared in each of two beakers at a concentration of 40 g / L in water. To the first beaker was added 100 ml of a 4 g / L solution of VEROLAN™ NEW (an organic dispersant containing polyacrylate and alkyl phosphonate, anionic active). To the second beaker was added 100 ml of a 12 g / L solution of RUCO-BLANC™ AMA (a whitening agent, stilbene derivative, anionic active). The treatment solution was adjusted to pH 5 with 60% acetic acid.

[0126] After a standing time of 6 hours, the evaluation was carried out according to the following grading system: 1. The processing solution is transparent 2 The treatment solution is cloudy or "slightly cloudy" 3 The treatment solution is flocculated or has a precipitate that can be reconstituted by stirring (does not flocculate again within 1 minute). 4 Formation of large flakes or precipitate that can no longer be stirred 5 Oily deposits on the surface of the treatment liquid or beaker

[0127] If the grade is no worse than "3", the exam is considered passed.

[0128] [Table 4]

[0129] heat yellowing Sections of bleached, non-fluorescently whitened cotton modal knit fabric were impregnated in a lab foulard with an aqueous treatment solution containing 20 g / l of the emulsion prepared according to the examples and 0.5 g / l of 60% acetic acid at 80% wet absorption, dried for 2 minutes at 120° C., and then heat-set for 2 minutes at 170° C. The whiteness of the samples was then measured with a whiteness meter "texflash 2000" from "datacolor international" (Switzerland) according to Ganz (Applied Optics 15 (1976) 9, 2039-2058).

[0130] [Table 5]

[0131] The preparations according to the invention do not cause yellowing of the textile substrates, and the whiteness of the substrates treated with the preparations according to the invention corresponds to the whiteness of the untreated textiles.

[0132] Phenol yellowing Sections of bleached, non-fluorescently whitened cotton Modal knitted fabric were impregnated in a laboratory foulard with an aqueous treatment solution containing 40 g / l of the emulsion prepared according to the examples and 0.5 g / l of 60% acetic acid at a wet absorption of 80% and then dried for 2 minutes at 120° C. Yellowing was then assessed using the sandwich test (DIN EN ISO 105-X18).

[0133] Each test sample and control tissue is individually placed between two horizontally stacked glass plates, between the folded test paper, and the stack of plates, test paper, test sample, and control tissue is then airtightly wrapped and incubated in a heating cabinet at 50°C for 16 hours.

[0134] After opening the packaging, any possible color changes are immediately assessed using a gray scale on a scale of 1 to 5 according to ISO 105-A01.

[0135] The higher the value on the grey scale, the less yellowing the textile.

[0136] [Table 6]

[0137] Jet Stability In a beaker, 400 mL of a treatment solution containing 4 g / L sodium sulfate and 5 g / L of the emulsion to be tested in water was adjusted to pH 4.5 with 60% acetic acid. The aqueous treatment solution was then heated to 40° C. and stirred at this temperature for 20 minutes at 2000 revolutions per minute using a pitched blade stirrer. At the end of this time, the stirrer was turned off and the solution was evaluated for separation after a one-hour settling period. This test is intended to simulate the mechanical forces of the jet process in the presence of textile auxiliaries remaining on the textile from the previous finishing step.

[0138] [Table 7]

[0139] The following sections summarize the invention.

[0140] 1. General formula A: [ka] (In the formula, R 1 are, independently of each other, Methyl, [ka] However, in formula A, at least one R 1 corresponds to one of Formulas II to V, R 2 are, independently of each other, [ka] and R 3are, independently of each other, [ka] or [ka] with the proviso that at least one R in Formula A is a zwitterionic group selected from 3 is a zwitterionic group, R 4 are, independently of each other, unbranched or branched C 1~7 -Alkylene, preferably unbranched C 1~5 -alkylene, particularly preferably -(CH2)2-, R 5 are, independently of each other, branched or unbranched C 1~18 -alkyl, preferably unbranched C 1~8 - alkyl, particularly preferably methyl, R 6 are, independently of each other, unbranched C 2~5 -alkylene, preferably -(CH2)2- or -(CH2)3-, R 7 are, independently of each other, unbranched or branched C 1~18 -Alkylene, preferably unbranched C 1~8 -alkylene, particularly preferably -(CH2)2- or methylene, R 8 are independently H or OH, R 9 are, independently of each other, unbranched or branched C 1~18 -Alkylene, preferably unbranched C 1~8 - alkylene, particularly preferably methylene, R 11 are, independently of each other, [ka] and R 12 are, independently of each other, [ka] and R 13 are each independently an aliphatic or cyclic C 1~18 - alkylene or arylene, in each case optionally C 1~8 -substituted with alkyl or benzyl, preferably unbranched C 1~8 - alkylene, in particular -(CH2)4-, -(CH2)6-, [ka] and n is an integer of 20 to 2000, preferably 40 to 1000, particularly preferably 40 to 180; m is 0 or an integer greater than 0, preferably 0 or an integer from 1 to 2000, and particularly preferably 0 or an integer from 1 to 55).

[0141] 2. R of 0% to 99.9%, preferably 50% to 99.9%, more preferably 80% to 99.9%, particularly preferably 90% to 99.9% 1 Substituent or R 0% to 99.999%, preferably 50% to 99.999%, more preferably 80% to 99.999%, particularly preferably 90% to 99.999% 1 Item 2. The polysiloxane according to item 1, wherein the substituent is methyl.

[0142] 3. Two terminal R 1 The substituent is methyl and at least one lateral R 1 A polysiloxane according to any one of the preceding paragraphs, wherein the substituents correspond to one of formulas II to V.

[0143] 4. All lateral R 1 The substituent is methyl, and the two terminal R 1 Item 3. The polysiloxane according to item 1 or 2, wherein the substituent is selected from the group represented by formula II to formula V.

[0144] 5. All R 1 4. The polysiloxane of any one of the preceding paragraphs, wherein the substituents are selected from methyl and Formula II.

[0145] 6. R in formula A is 10% to 100%, preferably 40% to 99.9%, more preferably 50% to 95%, and most preferably 60% to 80% 3

[0023] The polysiloxane of any one of the preceding paragraphs, wherein is a zwitterionic group.

[0146] 7. The polysiloxane of any one of the preceding paragraphs, wherein all zwitterionic groups are present as formula VIa.

[0147] 8. A polysiloxane according to any one of the preceding paragraphs, wherein all zwitterionic groups are present as formula VIb.

[0148] 9. R 2 is preferably [ka] Item 10. The polysiloxane of any one of the preceding items, wherein

[0149] 10. R 11 teeth, [ka] Item 10. The polysiloxane of any one of the preceding items, wherein

[0150] 11. R 12 Item 11. Polysiloxane according to item 10, which corresponds to either formula XIII or formula XIV:

[0151] 12. When m is greater than 0, substantially all, especially 90% to 99.999%, of the lateral R 1 Item 10. The polysiloxane of any one of the preceding items, wherein the substituent is methyl.

[0152] 13. General formula I: [ka] (In the formula, R 1 are, independently of each other, Methyl, [ka] with the proviso that in formula I, at least one R 1 corresponds to one of Formulas II to V, R 2 are, independently of each other, [ka] and R 3 are, independently of each other, [ka] or [ka] with the proviso that at least one R in Formula I is a zwitterionic group selected from 3 is a zwitterionic group, R 4 are, independently of each other, unbranched or branched C 1~7 -Alkylene, preferably unbranched C 1~5 -alkylene, particularly preferably -(CH2)2-, R 5 are, independently of each other, branched or unbranched C 1~18 -alkyl, preferably unbranched C 1~8 - alkyl, particularly preferably methyl, R 6 are, independently of each other, unbranched C 2~5 -alkylene, preferably -(CH2)2- or -(CH2)3-, R 7 are, independently of each other, unbranched or branched C 1~18 -Alkylene, preferably unbranched C 1~8 -alkylene, particularly preferably -(CH2)2- or methylene, R 8 are independently H or OH, R 9 are, independently of each other, unbranched or branched C1~18 -Alkylene, preferably unbranched C 1~8 - alkylene, particularly preferably methylene, Item 10. The polysiloxane according to any one of items 1 to 9, wherein n is an integer of 20 to 2000, preferably 40 to 1000, and particularly preferably 40 to 180.

[0153] 14. (a) General formula VII: [ka] (In the formula, R 10 are, independently of each other, Methyl, [ka] with the proviso that in Formula VII, at least one R 10 corresponds to one of Formulas VIII to XI; (b) optionally, converting a polysiloxane of general formula VII into a polysiloxane of formula OCN-R 13 -NCO with a diisocyanate; (c) treating the polysiloxane of formula VII or the polysiloxane adduct obtained after step (b) with peroxide and / or a compound of general formula XII: [ka] wherein X is a halogen, in particular Cl or Br, or at least one salt thereof, wherein the peroxide is preferably hydrogen peroxide (H2O2), di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, meta-chloroperbenzoic acid, dibenzoyl peroxide, diacetyl peroxide, peracetic acid, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, sodium peroxide and / or barium peroxide, particularly preferably hydrogen peroxide (H2O2), A process for preparing the polysiloxane of any one of the preceding paragraphs, comprising:

[0154] 15. The process according to item 14, wherein the molar ratio between the reactant and the tertiary amino groups in the polysiloxane of Formula VII or the tertiary amino groups in the polysiloxane adduct obtained after step (b) is 0.1:1 to 1:1, preferably 0.4:1 to 0.999:1, more preferably 0.5:1 to 0.95:1, and most preferably 0.6:1 to 0.8:1.

[0155] 16. In step b), a compound of the general formula OCN-R 13 Item 16. The process according to item 14 or 15, wherein the molar ratio of isocyanate groups of the -NCO diisocyanate to isocyanate-reactive hydroxy groups of the polysiloxane of general formula VII is 0.1:1 to 1:1, more preferably 0.4:1 to 0.999:1, particularly preferably 0.5:1 to 0.95:1, and most preferably 0.6:1 to 0.9:1.

[0156] 17. In step b), a compound of the general formula OCN-R 13 17. The process of any one of paragraphs 14 to 16, wherein the —NCO diisocyanate is selected from the group consisting of toluene-2,4-diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), longer chain homologues of diphenylmethane diisocyanate (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate, and / or isophorone diisocyanate.

[0157] 18. The process according to any one of items 14 to 17, wherein in step b) and / or step c), the reaction is carried out at a temperature of 15°C to 150°C, preferably 20°C to 105°C, more preferably 25°C to 95°C, even more preferably 40°C to 90°C, and particularly preferably 70°C to 85°C.

[0158] 19. The process according to any one of paragraphs 14 to 18, wherein step b) is carried out with or without a solvent, preferably in the absence of a solvent.

[0159] 20. The process according to any one of paragraphs 14 to 19, wherein step b) is carried out using a catalyst, in particular using a catalyst based on a tertiary amine, a bismuth compound, and / or an organotin compound.

[0160] 21. The process of any one of paragraphs 14 to 20, wherein the progress of the reaction in step b) is monitored by titration or IR spectroscopy.

[0161] 22. The process according to any one of paragraphs 14 to 21, wherein the reaction in step c) is carried out in a solvent preferably comprising water and / or at least one organic solvent.

[0162] twenty three. (i) at least one polysiloxane according to any one of items 1 to 13, and (ii) a solvent, in particular water and / or an organic solvent; A composition comprising:

[0163] 24. The composition according to item 23, wherein the composition contains 0.005% by weight to 99.9% by weight, preferably 5% by weight to 99% by weight, and particularly preferably 10% by weight to 90% by weight of component (i), based on the total weight of the composition.

[0164] 25. (iii) The composition according to item 23 or 24, further comprising at least one anionic, cationic, nonionic, or amphoteric emulsifier, preferably at least one nonionic emulsifier, particularly preferably an ethoxylation product of a fatty alcohol.

[0165] 26. The composition according to item 25, wherein the emulsifier (iii) is present in an amount of 2% by weight to 100% by weight, preferably 10% by weight to 80% by weight, and particularly preferably 20% by weight to 70% by weight, based on component (i).

[0166] 27. The composition according to any one of items 23 to 26, wherein the organic solvent is preferably selected from the group consisting of monofunctional alcohols and polyfunctional alcohols, and / or ether compounds thereof and / or ester compounds thereof.

[0167] 28. (iv) A composition described in any one of items 23 to 27, further comprising at least one additive, such as a diluent, glycerol, urea, and / or at least one acid, and / or at least one softener, preferably an organically modified polysiloxane.

[0168] 29. The composition according to any one of items 23 to 28, which exists as an emulsion, preferably as an oil-in-water emulsion.

[0169] 30. Use of a polysiloxane according to any one of paragraphs 1 to 13 or a composition according to any one of paragraphs 23 to 29 for treating a substrate, in particular for finishing a textile substrate, or as an additive in paints, glazes, lacquers and / or car care formulations.

[0170] 31. The use according to paragraph 30, wherein the textile substrate is a fabric, a knitted fabric, a nonwoven fabric, a fiber and / or leather.

[0171] 32. Use according to paragraph 30 or 31, wherein the textile substrate comprises natural fibers, in particular cotton and / or wool, and / or synthetic fibers, in particular viscose, polyester, polyamide and / or polyacrylonitrile.

[0172] 33. The use according to any one of items 30 to 32 for improving the softness and feel of a textile substrate.

[0173] 34. Use according to paragraph 30 for improving the wetting, spreading and / or levelling properties of paints, glazes, lacquers and / or car care formulations.

[0174] 35. A substrate, particularly a textile substrate, treated with the polysiloxane according to any one of items 1 to 13.

[0175] 36. The substrate according to item 35, comprising 0.04% to 2.4% by weight, preferably 0.08% to 1.2% by weight, of polysiloxane, based on the total weight of the textile substrate.

[0176] 37. (iii) providing a substrate; (iv) applying the polysiloxane according to any one of items 1 to 13 or the composition according to any one of items 23 to 29 to a substrate; (v) optionally treating the substrate obtained after step (ii) at an elevated temperature; A process for treating a substrate, comprising:

[0177] 38. The process for treating a substrate according to paragraph 37, wherein step (ii) is carried out by foularding, spraying, brushing, dipping, padding, and / or exhaustion.

[0178] 39. The process for treating a substrate according to item 37 or 38, wherein in step (iii), water is removed preferably at a temperature of 110°C to 150°C.

Claims

1. General formula A: 【Chemistry 1】 (In the formula, R １ are, independently of each other, Methyl, 【Chemistry 2】 where, in formula A, at least one R １ corresponds to one of Formulas II to V, R ２ are, independently of each other, 【Transformation 3】 and R ３ are, independently of each other, 【Chemistry 4】 or 【Transformation 5】 with the proviso that at least one R in Formula A is a zwitterionic group selected from ３ is a zwitterionic group, R ４ are, independently of one another, unbranched or branched C １～７ - alkylene, preferably unbranched C １～５ -alkylene, particularly preferably -(CH ２ ) ２ - and R ５ are each independently a branched or unbranched C １～１８ - alkyl, preferably unbranched C １～８ alkyl, particularly preferably methyl, R ６ are, independently of each other, unbranched C ２～５ -alkylene, preferably -(CH ２ ) ２ - or - (CH ２ ) ３ - and R ７ are, independently of one another, unbranched or branched C １～１８ - alkylene, preferably unbranched C １～８ -alkylene, particularly preferably -(CH ２ ) ２ - or methylene, R ８ are independently H or OH, R ９ are, independently of one another, unbranched or branched C １～１８ - alkylene, preferably unbranched C １～８ alkylene, particularly preferably methylene, R １１ are, independently of each other, 【Transformation 6】 and R １２ are, independently of each other, 【Transformation 7】 and R １３ are each independently an aliphatic or cyclic C １～１８ alkylene or arylene, in each case optionally C １～８ - alkyl or benzyl substituted, preferably unbranched C １～８ -Alkylene, especially -(CH ２ ) ４ -, -(CH ２ ) ６ -, 【Transformation 8】 and n is an integer of 20 to 2000, preferably 40 to 1000, particularly preferably 40 to 180; m is 0 or an integer greater than 0, preferably 0 or an integer from 1 to 2000, more preferably 0 or an integer from 1 to 55.

2. R of 0% to 99.9%, preferably 50% to 99.9%, more preferably 80% to 99.9%, particularly preferably 90% to 99.9% １ Substituent groups or 0% to 99.999%, preferably 50% to 99.999%, more preferably 80% to 99.999%, particularly preferably 90% to 99.999% of R １ 2. The polysiloxane of claim 1, wherein the substituent is methyl.

3. Two terminal R １ The substituent is methyl and at least one lateral R １ The substituent corresponds to one of Formulas II to V, or All lateral R １ The substituent is methyl, and the two terminal R １ The substituents are selected from Formula II to Formula V: The polysiloxane according to claim 1 or 2.

4. All R １ The substituents are selected from methyl and formula II, and / or R ２ teeth, 【Chemistry 9】 and / or R １１ teeth, 【Chemistry 10】 and / or R １２ corresponds to one of formula XIII or formula XIV: The polysiloxane according to any one of claims 1 to 3.

5. R in formula A is 10% to 100%, preferably 40% to 99.9%, more preferably 50% to 95%, and most preferably 60% to 80%. ３ is a zwitterionic group, and / or All zwitterionic groups are present as Formula VIa, or all zwitterionic groups are present as Formula VIb: The polysiloxane according to any one of claims 1 to 4.

6. General formula I: 【Chemistry 11】 (In the formula, R １ are, independently of each other, Methyl, 【Chemistry 12】 with the proviso that in formula I, at least one R １ corresponds to one of Formulas II to V, R ２ are, independently of each other, 【Chemistry 13】 and R ３ are, independently of each other, 【Chemistry 14】 or 【Chemistry 15】 with the proviso that at least one R in Formula I is a zwitterionic group selected from ３ is a zwitterionic group, R ４ are, independently of one another, unbranched or branched C １～７ - alkylene, preferably unbranched C １～５ -alkylene, particularly preferably -(CH ２ ) ２ - and R ５ are each independently a branched or unbranched C １～１８ - alkyl, preferably unbranched C １～８ alkyl, particularly preferably methyl, R ６ are, independently of each other, unbranched C ２～５ -alkylene, preferably -(CH ２ ) ２ - or - (CH ２ ) ３ - and R ７ are, independently of one another, unbranched or branched C １～１８ - alkylene, preferably unbranched C １～８ -alkylene, particularly preferably -(CH ２ ) ２ - or methylene, R ８ are independently H or OH, R ９ are, independently of one another, unbranched or branched C １～１８ - alkylene, preferably unbranched C １～８ alkylene, particularly preferably methylene, 6. Polysiloxane according to claim 1, wherein n is an integer from 20 to 2000, preferably from 40 to 1000, particularly preferably from 40 to 180.

7. (a) General formula VII: 【Chemistry 16】 (In the formula, R １０ are, independently of each other, Methyl, 【Chemistry 17】 with the proviso that in Formula VII, at least one R １０ corresponds to one of Formulas VIII-XI; (b) optionally, converting the polysiloxane of general formula VII into a compound of formula OCN-R １３ -NCO diisocyanate; (c) treating the polysiloxane of formula VII or the polysiloxane adduct obtained after step (b) with a peroxide and / or a compound of general formula XII: [Chemistry 18] wherein X is a halogen, in particular Cl or Br, or at least one salt thereof, Here, the peroxide is preferably hydrogen peroxide (H ２ O ２ ), di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, meta-chloroperbenzoic acid, dibenzoyl peroxide, diacetyl peroxide, peracetic acid, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, sodium peroxide and / or barium peroxide, particularly preferably hydrogen peroxide (H ２ O ２ ) and the molar ratio between the reactants and the tertiary amino groups in the polysiloxane of formula VII or in the polysiloxane adduct obtained after step (b) is preferably from 0.1:1 to 1:1, more preferably from 0.4:1 to 0.999:1, more preferably from 0.5:1 to 0.95:1, and most preferably from 0.6:1 to 0.8:1; A process for preparing the polysiloxane of any one of claims 1 to 6, comprising:

8. In step b), the general formula OCN-R １３ the molar ratio of isocyanate groups of the -NCO diisocyanate to the isocyanate-reactive hydroxy groups of the polysiloxane of general formula VII is from 0.1:1 to 1:1, more preferably from 0.4:1 to 0.999:1, particularly preferably from 0.5:1 to 0.95:1, most preferably from 0.6:1 to 0.9:1, and / or In step b), the general formula OCN-R １３ -NCO diisocyanates are selected from the group consisting of toluene-2,4-diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), longer chain homologues of diphenylmethane diisocyanate (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate and / or isophorone diisocyanate; The process of claim 7.

9. In step c), the reaction is preferably carried out in a solvent comprising water and / or at least one organic solvent, and / or Step b) is carried out with or without a solvent, and / or Step b) and / or step c) is carried out at a temperature of 15°C to 150°C, more preferably 20°C to 105°C, even more preferably 25°C to 95°C, even more preferably 40°C to 90°C, particularly preferably 70°C to 85°C; 9. The process according to claim 7 or 8.

10. (i) at least one polysiloxane according to any one of claims 1 to 6, and (ii) solvents, in particular water and / or organic solvents, preferably from the group of monofunctional and polyfunctional alcohols and / or their ether compounds and / or their ester compounds, (iii) optionally at least one anionic, cationic, nonionic or amphoteric emulsifier, preferably at least one nonionic emulsifier, particularly preferably an ethoxylation product of a fatty alcohol, an emulsifier, wherein the emulsifier (iii) is present in an amount of preferably 2% to 100% by weight, more preferably 10% to 80% by weight, particularly preferably 20% to 70% by weight, based on component (i), and / or (iv) optionally at least one additive, such as a diluent, glycerol, urea and / or at least one acid and / or at least one softening agent, preferably an organically modified polysiloxane; A composition comprising: the composition comprises, based on the total weight of the composition, 0.005% to 99.9% by weight, more preferably 5% to 99% by weight, and particularly preferably 10% to 90% by weight of component (i); composition.

11. 11. The composition according to claim 10, which is present as an emulsion, preferably as an oil-in-water emulsion.

12. for treating substrates, in particular textile substrates, preferably woven, knitted, nonwoven, fibre and / or leather, particularly preferably comprising natural and / or synthetic fibres, or As an additive in paints, glazes, lacquers, and / or car care formulations, Use of a polysiloxane according to any one of claims 1 to 6 or a composition according to claim 10 or 11.

13. in improving the soft handle of textile substrates; and / or In improving the wetting, spreading and / or leveling of paints, glazes, lacquers and / or car care formulations, 13. The use according to claim 12.

14. 7. A substrate, in particular a textile substrate, treated with a polysiloxane according to any one of claims 1 to 6, wherein the textile substrate preferably comprises 0.04 to 2.4 wt. %, particularly preferably 0.08 to 1.2 wt. %, of polysiloxane, based on its total mass.

15. (i) providing a substrate; (ii) applying to the substrate a polysiloxane according to any one of claims 1 to 6 or a composition according to claim 10 or 11; (iii) optionally treating the substrate obtained after step (ii) at elevated temperature, in particular at a temperature of 110°C to 150°C, preferably to remove water; Including, A process in which step (ii) is preferably carried out by foularding, spraying, brushing, dipping, padding and / or exhaustion of the substrate.

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