Aqueous dispersion of an amino-functionalized organopolysiloxane prepolymerized with oxalate polyether

Abstract

(1) Formula R2SiO 2 / 2 (I) units, and the formula SiR 1 O 2 / 2 -Y-SiR 1 O 2 / 2 (III) a pre-crosslinked organopolysiloxane containing, on average, at least one structural unit of the formula -R 2 -[NR 3 -R 4 -] n NR 3 -C(O)-C(O)-NR 3 -Z-NR 3 -C(O)-C(O)-NR 3 -[R 4 -NR 3 -] n R 2 -, Z represents a divalent organic group containing a polyoxyalkylene group, preferably a group of the formula -(R 5 O) m -R6-, where R is a monovalent optionally substituted C i ~C is represents a hydrocarbon group, and R 1 is residue R or residue -OR 7 represents R 2 is a divalent, linear or branched, C3-C bonded SiC 18 represents a hydrocarbon residue, and R 3 are hydrogen atoms, C1 to C 10 represents an alkyl residue or an acyl residue, and R 4 is a divalent C1-C6 hydrocarbon residue, and R 5 are the same or different, C3 to C 18 represents an alkylene residue, and R 6 is C1~C 10 represents an alkylene residue, and R 7 is a monovalent C3-C group optionally interrupted by hydrogen or one or more other oxygen atoms 18 represents a hydrocarbon residue, n is equal to 0, 1, 2, 3, or 4, and m is an average of 1 to 80.], (2) an emulsifier, and (3) water.

Description

Technical Field

[0001] The present invention relates to aqueous dispersions of pre-crosslinked organopolysiloxanes, their production, and their use in compositions for treating substrates, preferably fibrous substrates.

Background Art

[0002] Organopolysiloxanes are used in a number of consumer products to achieve certain benefits. Examples are a certain softness or smoothness, improvement of tactile properties, reduction of wrinkles, influence on gloss properties, improvement of the perceived color, color protection properties, reduction of electrostatic charges, or protection properties of hair or fibers under thermal load.

[0003] The use of organopolysiloxanes, especially amino-functionalized organopolysiloxanes, in fiber finishing has long been established prior art, as reported, for example, by H.J. Lautenschlager, Textil Praxis International, Vol. 47, No. 5, 1992, pp. 460 - 461.

[0004] The use of organopolysiloxanes, especially amino-functionalized organopolysiloxanes, in textile care products has been reported by R. Becker in SOFW-Journal, Vol. 139, No. 9, pp. 36 - 38. These amino-functionalized organopolysiloxanes are non-crosslinked products.

[0005] According to US2008 / 0064813A1, an aqueous dispersion of pre-crosslinked organopolysiloxanes is obtained by the reaction of an amino-functional organopolysiloxane containing an alkoxy group or a hydroxyl group with a reactive alkoxysilane without the use of a metal-containing catalyst. When this dispersion is applied to a substrate and the water is evaporated, an elastomeric film is obtained. This elastic effect can also be utilized to reduce wrinkles in textiles.

[0006] The drawback of such exclusively amino-functionalized and pre-crosslinked organopolysiloxanes is their hydrophobic effect on fabrics.

[0007] Siloxanes that have undergone hydrophilic modification are known. According to WO2019 / 114953A1, these are linear copolymers of oxalamide ester-terminated organopolysiloxanes and amino-terminated polyethers. They exhibit significantly enhanced hydrophilicity compared to exclusively amino-functionalized organopolysiloxanes. However, due to their linear structure, they do not show any elastic effect.

[0008] US 7,501,184 describes copolymers obtained by the reaction of linear organopolysiloxanes terminated with oxalamide ester groups and organic diamines. High viscosities are obtained for the solid copolymers used as adhesives, more specifically hot melt adhesives. These high-viscosity products cannot be stably emulsified and as a result, cannot be used for treating fibrous substrates such as fabrics. Furthermore, due to their linear structure, they do not show an elastic effect.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0010]

Patent Document 1

Patent Document 2

[0011] The object was to provide a pre-crosslinked organopolysiloxane, more specifically an aqueous dispersion of a pre-crosslinked organopolysiloxane, which does not have the above-mentioned drawbacks, can be prepared inexpensively, preferably forms an elastomeric film after water removal, and can be used in a composition for treating a substrate, preferably a fibrous substrate, more specifically a textile. The object was further to provide a composition for treating a substrate, preferably a fibrous substrate, more specifically a textile, for cleaning the substrate, caring for them, and imparting improved properties to them, such as good hydrophilic properties. This object is achieved by the present invention. MEANS FOR SOLVING THE PROBLEM

[0012] The subject of the present invention is an aqueous dispersion, preferably an aqueous emulsion, comprising: (1) units of the following formula R2SiO 2 / 2 (I) and a pre-crosslinked organopolysiloxane containing, on average, at least one structural unit, preferably at least two structural units, of the following formula SiR 1 O 2 / 2 -Y-SiR 1 O 2 / 2 (III) [wherein Y is a divalent group of the following formula -R 2 -[NR 3 -R 4 -] n NR 3 -C(O)-C(O)-NR 3 -Z-NR 3 -C(O)-C(O)-NR 3 -[R 4 -NR 3-[[]] n R 2 - Z is the same or different and is a divalent organic group containing a polyoxyalkylene group. Z is preferably a group of the formula -(R 5 O) m -R 6 -. R may be the same or different and is a monovalent unsubstituted or substituted saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms. R 1 may be the same or different and is a group R or a group -O-R 7 . R 2 is a divalent linear or branched hydrocarbon group having a SiC bond and having 1 to 18 carbon atoms, preferably an alkylene group having 3 to 10 carbon atoms. R 3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an acyl group, such as an acetyl group, and is preferably a hydrogen atom. R 4 is a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms. R 5 may be the same or different and is a C1-C 10 alkylene group, preferably a C2-C3 alkylene group, more preferably an ethylene group or an isopropylene group. R 6 is a C1-C 10 alkylene group, preferably a C2-C3 alkylene group, more preferably an ethylene group or an isopropylene group. R 7 may be the same or different and is hydrogen or a monovalent hydrocarbon group having 1 to 18 carbon atoms and may be interrupted by one or more other oxygen atoms. n is 0, 1, 2, 3 or 4, preferably 0 or 1. m is an integer and on average is from 1 to 80, preferably from 2 to 50.]] (2) An emulsifier, and (3) Water.

[0013] The dispersion of the present invention preferably contains at least 5% by weight, more preferably at least 10% by weight, and preferably at most 60.0% by weight, more preferably at most 45% by weight, and very preferably at most 35% by weight of the crosslinked organopolysiloxane (1).

[0014] The dispersion of the present invention preferably contains at least 0.5% by weight, more preferably at least 0.8% by weight, very preferably at least 1.2% by weight, and preferably at most 20% by weight, more preferably at most 15% by weight, and very preferably at most 10% by weight of the emulsifier (2).

[0015] The dispersion of the present invention preferably contains at least 1% by weight, more preferably at least 5% by weight, more specifically at least 10% by weight, and preferably at most 94.5% by weight, more preferably at most 85% by weight, more specifically at most 80% by weight of water (3).

[0016] A further subject of the present invention is a pre-crosslinked organopolysiloxane having units of the following formula R2SiO 2 / 2 (I), and a pre-crosslinked organopolysiloxane containing, on average, at least one structural unit, preferably at least two structural units, of the following formula SiR 1 O 2 / 2 -Y-SiR 1 O 2 / 2 (III) [wherein Y is a divalent group of the following formula -R 2 -[NR 3 -R 4 -] n -NR 3 -C(O)-C(O)NR 3 -Z-NR 3 -C(O)-C(O)-NR 3 -[R 4 -NR 3 n -R 2 -​ R, R 1 , R 2 , R 3 , R 4 , Z and n have the meanings indicated for them above.]

[0017] The pre-crosslinked organopolysiloxane (1) may further contain a structural unit of the following formula. R 1 ASiO 2 / 2 (II) [wherein, A may be the same or different and is a group of the following formula, -R 2 -[NR 3 -R 4 -] n NR 3 2, R 2 is a divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms and SiC bonds, preferably an alkylene group having 3 to 10 carbon atoms, R 3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an acyl group, for example, an acetyl group, preferably a hydrogen atom, R 4 is a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, n is 0, 1, 2, 3 or 4, preferably 0 or 1.]

[0018] Surprisingly, organopolysiloxanes having amino-functionalized side chains crosslinked with oxalyl amide ester-terminated polyethers, and aqueous dispersions of such organopolysiloxanes, can be used as active ingredients in compositions for the care and washing of fibrous substrates, more specifically textiles (the fibrous substrates, more specifically textiles, treated with the organopolysiloxane exhibit significantly improved properties, particularly good hydrophilic properties).

[0019] The aqueous dispersion of the pre-crosslinked organopolysiloxane of the present invention preferably forms an elastomeric film after removing water.

[0020] The pre-crosslinked organopolysiloxane of the present invention is preferably hydrophilic.

[0021] The pre-crosslinked organopolysiloxane (1) of the present invention is more specifically selected from the group of the following formulas and mixtures thereof.

[0022] [Chemical formula] [In the formula, R, R 7 , A and Y have the meanings shown for them above, e is 0 or 1, j is 0 or an integer between 1 and 15, k is at least 1, preferably at least 2, and at most 15, preferably at most 10, more preferably at most 7, l is at least 40, more preferably at least 65, more preferably at least 110, and at most 1000, preferably at most 800, more preferably at most 500.]

[0023] The pre-crosslinked organopolysiloxane (1) of the present invention may also optionally contain a small amount of structural units T(RSiO 3 / 2 ) or Q(SiO 4 / 2 ).

[0024] In the context of the present invention, formula (IVa) or (IVb) is respectively j units [ARSiO 2 / 2 or j units [A(OR 7 )SiO 2 / 2 and k units [RSiO 2 / 2 -Y-[RSiO 2 / 2 or k units [(OR 7 )SiO 2 / 2 -Y-[(OR 7 )SiO 2 / 2 and l units [R2SiO2 / 2 It should be understood that ] can be distributed in the organopolysiloxane molecules in any desired manner, for example, in block form or randomly.

[0025] It is possible to use one crosslinked organopolysiloxane (1) of the present invention, or a mixture of two or more.

[0026] A further subject of the present invention is a method for producing an aqueous dispersion of a pre-crosslinked organopolysiloxane (1), which comprises units of the following formula R2SiO 2 / 2 (I), and on average at least one structural unit of the following formula R 1 ASiO 2 / 2 (II) [wherein, R, R 1 and A have the meanings shown for them above. ] The organopolysiloxane (4) containing is reacted in the presence of an oxalamide ester-terminated polyether (5) of the following formula (V), an emulsifier (2) and water (3).

[0027]

Chemical formula

[0028] Here, the properties and amounts of the organopolysiloxane (4) and the oxalamide ester-terminated polyether (5) are selected such that the organopolysiloxane (1) in the resulting dispersion is crosslinked.

[0029] Therefore, it is preferred that the dispersion of the present invention does not contain a catalyst.

[0030] Accordingly, the dispersion of the present invention contains a pre-crosslinked, preferably hydrophilic organopolysiloxane, which further crosslinks after water removal, preferably forming an elastomeric film, and the crosslinked, preferably hydrophilic organopolysiloxane has a high molecular weight branched structure.

[0031] The dispersion of the present invention is preferably an aqueous suspension or an aqueous emulsion of a pre-crosslinked organopolysiloxane.

[0032] When dried, the dispersion of the present invention develops a silicone network, preferably an elastic silicone network, without the addition of a catalyst or modification of the pH.

Embodiments for Carrying Out the Invention

[0033] Similar to the pre-crosslinked organopolysiloxane (1), the emulsifier (2) and water (3), the aqueous dispersion of the present invention may optionally contain further components that do not directly participate in the reaction, such as the following may optionally be included. (6) a non-aqueous solvent or co-emulsifier, and (7) auxiliaries, examples of which include pH regulators, salts, foam suppressants, thickeners and / or protective colloids, preservatives, disinfectants, wetting agents, corrosion inhibitors, pigments, fragrances or mixtures thereof.

[0034] Examples of the hydrocarbon group R include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl groups, hexyl groups such as n-hexyl group, heptyl groups such as n-heptyl group, octyl groups such as n-octyl group and isooctyl groups such as 2,2,4-trimethylpentyl group, nonyl groups such as n-nonyl group, decyl groups such as n-decyl group, dodecyl groups such as n-dodecyl group, octadecyl groups such as n-octadecyl decyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and methylcyclohexyl group, alkenyl groups such as vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl groups, aryl groups such as phenyl, naphthyl, anthryl group, phenanthryl group, alkaryl groups such as o-, m-, p-tolyl group, xylyl group and ethylphenyl group, and aralkyl groups such as benzyl group, alpha- and beta-phenylethyl group or 2-phenylpropyl group.

[0035] As the group R, methyl, ethyl, octyl and phenyl groups are preferable, and methyl and ethyl groups are particularly preferable.

[0036] Examples of the substituted group R include haloalkyl groups such as 3,3,3-trifluoro-n-propyl group, 2,2,2,2’,2’,2’-hexafluoroisopropyl group, heptafluoroisopropyl group, and haloaryl groups such as o-, m- and p-chlorophenyl groups.

[0037] Group R 1 Examples are the alkyl groups enumerated above for R, and hydroxyl, methoxy, ethoxy and hexyloxyethyl groups, and the group R 1 preferably contains methyl, ethyl, and hydroxyl, methoxy and ethoxy groups.

[0038] Group A contains at least one basic amino group of the formula -R 2 -[NR3 -R 4 -] n NR 3 is a monovalent group of 2.

[0039] R 2 Examples of are divalent groups such as a methylene group, a 1,2-ethylene group, a 1,3-propylene group, a 1,3-butylene group, a 1,4-butylene group, a 1,5-pentylene group, and a 1,6-hexylene group.

[0040] Particularly preferred examples are a 1,3-propylene group and a 1,3-butylene group.

[0041] R 4 Examples of are divalent groups such as a 1,2-ethylene group, a 1,3-propylene group, a 1,3-butylene group, a 1,4-butylene group, a 1,5-pentylene group, and a 1,6-hexylene group.

[0042] Particularly preferred example is a 1,2-ethylene group.

[0043] Preferably, R 3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acetyl group.

[0044] Alkyl group R 3 Examples of are hexyl groups such as methyl, ethyl, n-propyl-, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl group, n-hexyl and isohexyl groups. Group R 3 Preferred examples of are a hydrogen atom or a methyl group, and particularly preferred is a hydrogen atom.

[0045] Examples of group A are as follows. -(CH2)3NH2 -(CH2)3-NH-(CH2)2-NH2 -CH2CH(CH3)CH2-NH-(CH2)2-NH2 -(CH2)3-NH(cyclohexyl) -(CH2)3-NHCH3 -(CH2)3-NHCH2CH3 -(CH2)4-NH2 -CH2CH(CH3)CH2-NH2 -(CH2)3-NH-(CH2)2-NHCH3 -(CH2)3-NH-(CH2)2-NHCH2CH3 -(CH2)3[-NH-CH2CH2]2-NH2

[0046] Examples of group Y are as follows. -(CH2)3-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-(CH2)3- -(CH2)3-NH-(CH2)2-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-(CH2)2-NH-(CH2)3- -CH2CH(CH3)CH2-NH-(CH2)2-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-(CH2)2-NH-CH2CH(CH3)CH2- -(CH2)3-N(cyclohexyl)-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-N(cyclohexyl)(CH2)3- -(CH2)3-NCH3-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NCH3-(CH2)3- -(CH2)3-N(CH2CH3)-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-N(CH2CH3)-(CH2)3- -(CH2)4-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-(CH2)4- -CH2CH(CH3)CH2-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-CH2CH(CH3)CH2- -(CH2)3-NH-(CH2)2-NCH3-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NCH3-(CH2)2-NH-(CH2)3- -(CH2)3-NH-(CH2)2-N(CH2CH3)-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-N(CH2CH3)-NH-(CH2)3- -(CH2)3[-NH-CH2CH2]2-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-[CH2CH2-NH-]2(CH2)3- In the formula, Z has the meaning shown above for it.

[0047] Examples of the group Z are divalent hydrocarbon groups such as polyethylene glycol groups or polypropylene glycol groups, or combinations of polyethylene glycol groups and polypropylene glycol groups. The group Z preferably has a molecular weight (Mn, number average) of 50 g / mol to 4500 g / mol, and very preferably a molecular weight of 75 g / mol to 2500 g / mol.

[0048] Examples of the group Z are as follows. -(CH2-CH2-O) m -CH2-CH2- -(CH(CH3)-CH2-O) m -CH2-CH(CH3)- -(CH(CH3)-CH2-O) x -(CH2-CH2-O)y-(CH(CH3)-CH2-O) z -CH2-CH(CH3)- In the formula, m is on average 1 to 80, preferably 2 to 50, and x, y and z are each 0 or an integer, provided that the sum of x + y + z is on average 2 to 80, preferably 3 to 50.

[0049] Preferred examples of the group z are as follows. -(CH2-CH2-O)2-CH2-CH2- -(CH(CH3)-CH2-O) 約2.5 -CH2-CH(CH3)- -(CH(CH3)-CH2-O) 約6.1 -CH2-CH(CH3)- -(CH(CH3)-CH2-O) 約33-CH2-CH(CH3)- -(CH(CH3)-CH2-O) 約0.6 -(CH2-CH2-O)2-(CH(CH3)-CH2-O) 約0.6 -CH2-CH(CH3)- -(CH(CH3)-CH2-O) 約1.8 -(CH2-CH2-O)9-(CH(CH3)-CH2-O) 約1.8 -CH2-CH(CH3)- -(CH(CH3)-CH2-O) 約3 -(CH2-CH2-O) 約12.6 -(CH(CH3)-CH2-O) 約3 -CH2-CH(CH3)- -(CH(CH3)-CH2-O) 約3 -(CH2-CH2-O) 約39 -(CH(CH3)-CH2-O) 約3 -CH2-CH(CH3)-

[0050] The emulsifier (2) used in the dispersion of the present invention can be any emulsifier known to those skilled in the art for producing silicone emulsions, such as nonionic, anionic, cationic or amphoteric emulsifiers, and the emulsifier (2) can be used individually and as a mixture of different emulsifiers.

[0051] Non-limiting examples of nonionic emulsifiers used are as follows.

[0052] 1. Alkyl polyglycol ethers, preferably those having 3 to 40 EO units and an alkyl group of 8 to 20 carbon atoms

[0053] 2. Poly glycol esters of carboxylic acids, more specifically poly glycol esters of fatty acids, preferably those having more than 6 EO units and a carboxylic acid group of 8 to 20 carbon atoms

[0054] 3. Ethoxylated or non-ethoxylated sorbitan fatty acid esters

[0055] 4. Ethoxylated castor oil or hydrogenated variant

[0056] 5. Polyglycerol carboxylic acid esters

[0057] 6. Alkyl polyglycosides of the formula R*-O-G o wherein R* is a linear or branched saturated or unsaturated alkyl group having on average 8 to 24 carbon atoms, and G o is an oligoglycoside group having on average o = 1 to 10 hexose or pentose units, or a combination thereof

[0058] 7. Alkylaryl polyglycol ethers, preferably those having 5 to 30 EO units and 8 to 20 carbon atoms in the alkyl and aryl groups

[0059] 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 40 EO and PO units

[0060] 9. Polyvinyl alcohol having 5 to 50 mol%, preferably 8 to 20 mol% of vinyl acetate units and a degree of polymerization of 500 to 3000

[0061] 10. Adducts of alkylamines having an alkyl group of 8 to 22 carbon atoms with ethylene oxide or propylene oxide

[0062] 11. Natural substances and their derivatives, such as lecithin, lanolin, saponin, cellulose, cellulose alkyl ethers and carboxyalkyl cellulose each having an alkyl group with a maximum of 4 carbon atoms

[0063] 12. Linear organo(poly)siloxanes containing polar groups, especially those containing the elements O, N, C, S, P, Si, in particular organo(poly)siloxanes having an alkoxy group with a maximum of 24 carbon atoms and / or an EO group and / or a PO group with a maximum of 40 carbon atoms

[0064] 13. Fatty acids having 6 to 24 carbon atoms at most

[0065] Preferred non-ionic emulsifiers are as follows.

[0066] 1. Alkyl polyglycol ethers, preferably those having 3 to 30 EO units and 8 to 20 carbon atoms, such as Ceteareth-20, Oleth-10, Oleth-20, Laureth-3, Laureth-4, Laureth-20, Laureth-23, Trideceth-5, Tridecethe-6, Trideceth-8, Trideceth-10, Trideceth-12, Trideceth-16, Trideceth-20, Steareth-20 or Steareth-21 (according to INCI names)

[0067] 2. Poly glycol esters of carboxylic acids, more specifically fatty acid poly glycol esters, preferably those having more than 6 EO units and carboxylic acid groups of 8 to 20 carbon atoms, such as PEG-20 laurate, PEG-7 olive oil fatty acid salt, PEG-8 oleate, PEG-8 laurate, PEG-4 stearate, PEG-6 stearate, PEG-20-stearate or PEG-100 stearate (according to INCI names)

[0068] 3. Ethoxylated or non-ethoxylated sorbitan fatty acid esters, such as sorbitan laurate, polysorbate 20, polysorbate 60, polysorbate 80 or polysorbate 85 (according to INCI names)

[0069] 4. Ethoxylated castor oil or hydrogenated variants, such as PEG200 castor oil or PEG-60 hydrogenated castor oil (designated according to INCI nomenclature)

[0070] 5. Polyglycerol carboxylic acid esters, such as polyglycerol-10 oleate, polyglycerol-10 laurate or polyglycerol 10 stearate

[0071] 6. Alkyl polyglycoside of the formula R*-O-G o wherein R* is a linear or branched saturated or unsaturated alkyl group having on average 8 to 24 carbon atoms, and G o is an oligoglycoside group which is on average o = 1 to 10 hexose units or pentose units or a combination thereof, such as alkyl polyglycosides, for example, Glucopon 215, Glucopon 225, Glucopon 600 (names by trade names)

[0072] (Non-limiting) examples of anionic emulsifiers are as follows.

[0073] 1. Alkyl sulfates, especially those having a chain length of 8 to 18 carbon atoms, alkyl and alkyl ether sulfates having 8 to 18 carbon atoms in the hydrophobic group and having 1 to 40 ethylene oxide (EO) units and / or propylene oxide (PO) units

[0074] 2. Sulfonates, especially alkyl sulfonates having 8 to 18 carbon atoms, alkyl aryl sulfonates having 8 to 18 carbon atoms, taurides, esters and monoesters of sulfosuccinic acid with a monohydric alcohol or alkylphenol having 4 to 15 carbon atoms (these alcohols or alkylphenols can optionally also be ethoxylated with 1 to 40 EO units).

[0075] 3. Alkali metal salts and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl group, aryl group, alkyl group or aralkyl group, especially alkali metal salts and ammonium salts of fatty acids, preferably those having a carboxylic acid group of 8 to 20 carbon atoms

[0076] 4. Partial esters of phosphoric acid and their alkali metal salts and ammonium salts, in particular alkyl phosphates and alkyl phosphates having 8 to 20 carbon atoms in the organic group, alkyl ether phosphates and alkyl ether phosphates having 8 to 20 carbon atoms and 1 to 40 EO units in the alkyl or alkyl group

[0077] Preferred anionic emulsifiers are as follows.

[0078] 1. Alkyl sulfates, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium secondary C13-C18 alkane sulfonate, sodium C12-C18 fatty alcohol sulfate, alkyl ether sulfates, for example, ammonium C12-C14 fatty alcohol 2EO-ether sulfate, ammonium C12-C14 fatty alcohol 2EO-ether sulfate, alkyl aryl ether sulfates, for example, sodium secondary C10-C13-n-alkyl benzene sulfonate

[0079] 2. Alkyl sulfonates, for example, disodium 2-sulfolaurate

[0080] 3. Alkali metal salts and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl group, aryl group, alkyl group or aralkyl group, particularly preferred anionic emulsifiers are alkali salts and ammonium salts of fatty acids, preferably those having a carboxylic acid group of 8 to 20 carbon atoms, for example, sodium salts, potassium salts, triethanolammonium salts of lauric acid, myristic acid, palmitic acid, stearic acid or oleic acid

[0081] 4. Partial esters of phosphoric acid, for example, sodium salt of C8 / C10 fatty alcohol phosphoric acid partial ester (Crodaphos 810A) or monoethanolamine salt

[0082] Examples of (non-limiting) cationic emulsifiers are as follows.

[0083] 1. Salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acid

[0084] 2. Alkylpyridinium salts, alkylimidazolinium salts and alkyloxazolinium salts, especially those having an alkyl chain with a maximum of 18 carbon atoms, especially halides, sulfates, phosphates and acetates

[0085] 3. Quaternary alkylammonium salts and alkylbenzeneammonium salts, more specifically those having an alkyl group with 6 to 24 carbon atoms, more specifically halides, sulfates, phosphates and acetates

[0086] Examples (non-limiting) of amphoteric emulsifiers are as follows.

[0087] 1. Amino acids having long-chain substitution, for example, N-alkyl-di(aminoethyl)glycine or N-alkyl-2-aminopropionate

[0088] 2. Betaines, for example, N-(3-acylamidopropyl)-N,N-dimethylammonium salts with C8-C18 acyl groups, and quaternized alkyl or substituted alkyl derivatives of alkylimidazolium betaine or N,N-dimethylglycine

[0089] Preferred as an emulsifier for the production of an aqueous dispersion of a pre-crosslinked hydrophilic organopolysiloxane is a nonionic emulsifier, more specifically the above-mentioned alkyl polyglycol ether.

[0090] Component (2) can consist of one of the above-mentioned emulsifiers, or a mixture of two or more of the above-mentioned emulsifiers, which can be used in pure form or as a solution of one or more emulsifiers in water or an organic solvent.

[0091] The non-aqueous solvent or co-emulsifier (6) can optionally be used as a further component in the dispersion of the present invention.

[0092] The dispersion of the present invention contains a non-aqueous solvent or co-emulsifier (6) in an amount preferably of at least 0.1% by weight, more preferably at least 0.4% by weight, more specifically at least 0.8% by weight, and preferably at most 20% by weight, more preferably at most 15% by weight, more specifically especially at most 10% by weight.

[0093] The non-aqueous solvent (6) that can be used in the aqueous dispersion of the present invention is derived from, for example, the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.

[0094] Examples of solvents include ethanol, n- or isopropanol, butanol, such as 1-butanol, 2-butanol or 2-methyl-2-propanol, pentanol, such as 1-pentanol, 2-pentanol or 3-pentanol, hexanol, such as 1-hexanol, 2-hexanol or 3-hexanol, heptanol, such as 1-heptanol, 2-heptanol, 3-heptanol or 4-heptanol, octanol, such as 1-octanol, 2-octanol, 3-octanol or 4-octanol, glycol, propanediol, butanediol, such as 1,2-butanediol or 1,3-butanediol, hexanediol, such as 1,2-hexanediol or 2-methylpentane-2,4-diol, octanediol, such as 2-ethylhexane-1,3-diol or 1,2-octanediol, glycerol, diglycol, propyl- or butyldiglycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol-b-butyl ether, propylene glycol t-butyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 1-butoxyethoxy-2-propanol or 3-methyl-3-methoxybutanol, 1-aminobutane, 2-aminobutane, 2-amino-2-methylpropane, 1-aminopentane, 2-aminopentane, 1-aminohexane, 1-aminoheptane and 1-aminooctane, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate and hexyl acetate, methyl propionate, ethyl propionate, propyl propionate and tert-butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate and butyl butyrate, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 5-methyl-3-heptanone, 2-octanone and 3-octanone, and mixtures of these co-surfactants.,

[0095] Examples of preferred non-aqueous solvents or co-emulsifiers (6) are the above-mentioned 1-alkanols having a C5-C8 chain, the above-mentioned alkanediols having a C4-C8 chain, glycerol, propyl acetate, butyl acetate and pentyl acetate, 2-pentanone, and the above-mentioned ethylene glycol, propylene glycol, dipropylene glycol or diethylene glycol monoalkyl ethers.,

[0096] Particularly preferred as the non-aqueous solvent or co-emulsifier (6) are 1-pentanol, 1-hexanol, 1-octanol, propanediol, 1,3-butanediol, 1,2-hexanediol, 2-ethylhexane-1,3-diol, 1,2-octanediol, glycerol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol methyl ether.

[0097] A further possibility is to use, as co-emulsifier, a polyalkylene glycol, for example polyethylene glycol (for example PEG600, PEG1000 or PEG6000) or polypropylene glycol (for example PPG2000), a polyalkylene block polymer, for example a so-called poloxamer (for example a block copolymer of ethylene oxide units and propylene oxide units), for example a PEG-PPG-PEG block polymer Pluronic(R) L-31, a PEG-PPG block polymer Pluronic(R) L-61, a PPG-PEG-PPG block polymer Pluronic(R) 17R4, a PPG-PEG-PPG Pluronic(R) block polymer 31R1 (available from Sigma-Aldrich) or other poloxamines (copolymers of ethylene oxide units and propylene oxide units linked via an ethylenediamine core), for example Tetronic 701 or Tetronic 90R4 (available from Sigma-Aldrich).

[0098] As further components in the dispersion of the present invention, it is optionally possible to use (7) auxiliaries, for example pH regulators, salts, foam suppressants, thickeners and / or protective colloids, preservatives, disinfectants, wetting agents, corrosion inhibitors, dyes, fragrances or mixtures thereof.

[0099] In the present specification, all known acids and alkalis can be employed as pH regulators, provided that their use is not prohibited for performance or environmental reasons, or for reasons of consumer protection.

[0100] The acids used in this specification can help establish the desired pH or can form acid addition salts with the amino acid-containing group (A) or other group (Y) of the pre-crosslinked organopolysiloxane (1).

[0101] Examples of mineral acids that can react with the above amino-containing group (A) or other group (Y) are hydrochloric acid, perchloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, hydrofluoric acid, phosphoric acid, diphosphoric acid, and polyphosphoric acid. Examples of suitable carboxylic acids are formic acid, acetic acid, propionic acid, butanoic acid, citric acid, trichloro-, dichloro-, and chloroacetic acid, trifluoroacetic acid, cyanoacetic acid, phenylacetic acid, benzoic acid, m- and p-nitrobenzoic acid, oxalic acid, malonic acid, and lactic acid.

[0102] Particularly preferred are acetic acid, lactic acid, and formic acid.

[0103] Examples of salts (electrolytes) are, more specifically, those from the group of inorganic salts, and any of a very wide variety of salts may be used extensively. Preferred cations are alkali metals and alkaline earth metals, and preferred anions are halides and sulfates. From the viewpoint of production, it is preferable to use sodium acetate or sodium chloride in the aqueous emulsion of the present invention.

[0104] Examples of foam suppressants are soap, paraffin, or silicone oil.

[0105] Examples of preservatives are methylisothiazolinone, chloromethylisothiazolinone, benzylisothiazolinone, phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben, isobutylparaben, alkali metal benzoates, alkali metal sorbates, iodopropynyl butylcarbamate, benzyl alcohol, and 2-bromo-2-nitropropane-1,3-diol.

[0106] In the process according to the invention for preparing the pre-crosslinked organopolysiloxane (1) and its aqueous dispersion as organopolysiloxane (4), it is preferred to use those selected from the group of the following formulas and their mixtures. [ARSiO 2 / 2 j [R2SiO 2 / 2 l [R 3-e (OR 7 ) e SiO 1 / 2 2(VIa), [A(OR 1 )SiO 2 / 2 j [R2SiO 2 / 2 l [R 3-e (OR 7 ) e SiO 1 / 2 2(VIb) wherein A, R, R 1 and R 7 and j, l and e have the meanings given for them above.

[0107] In the production of the dispersion according to the invention, it is possible to use one kind of oxalamide ester-terminated polyether (5) of formula (V) or different kinds of oxalamide ester-terminated polyethers (5) of formula (V).

[0108]

Chemical formula

[0109] Examples of the oxalamide ester-terminated polyether (5) are as follows.

[0110]

Chemical formula

[0111] Preferred examples of the oxalamide ester-terminated polyether (5) are as follows.

[0112] [Chemical formula] TIFF0007700226000006.tif125162

[0113] In the method of the present invention for preparing the prepolymerized organopolysiloxane (1) and producing its aqueous dispersion, the oxalamide ester-terminated polyether (5) is preferably used in an amount of at least 0.1 mol, more preferably at least 0.15 mol, and preferably at most 1 mol, more preferably at most 0.75 mol, per mole of the amine group in the organopolysiloxane (4).

[0114] The oxalamide ester-terminated polyether (5) is known and is described, for example, in N. Fukada, Bull. Chem. Soc. Jpn., 69, 1397 - 1401 (1996). The oxalamide ester-terminated polyether (5) was isolated in trace amounts as a by-product after separation by chromatography.

[0115] The oxalamide ester-terminated polyether (5) can be specifically prepared from the amino-terminated polyether, for example, by using a diester oxalate in a stoichiometric excess and then removing the excess by distillation. In this case, the diester oxalate is preferably used in a 2 - 20-fold molar excess, more preferably a 2 - 10-fold molar excess.

[0116] Therefore, the oxalamide ester-terminated polyether (5) is preferably prepared by reacting the amino-terminated polyether with a diester oxalate of the following formula. R 8 -O-C(=O)-C(=O)-O-R 8 In the formula, R 3 , R 8 and Z have the meanings shown for them above, provided that the oxalic acid diester is used in an amount of preferably 2 to 20 moles, more preferably 2 to 10 moles of oxalic acid diester per mole of amino-terminated polyether.

[0117] The dispersion of the present invention of the pre-crosslinked organopolysiloxane (1) is produced by mixing the organopolysiloxane (4) strongly with the following. Oxalamide ester-terminated polyether (5), Water (3), Emulsifier (2), Optionally a non-aqueous solvent or co-emulsifier (6), and Optionally an auxiliary agent (7)

[0118] The dispersion of the present invention is produced using, in any case, based on the total weight of the dispersion, preferably at least 5% by weight, more preferably at least 10% by weight, and preferably at most 60.0% by weight, more preferably at most 45% by weight, very preferably at most 35% by weight of the organopolysiloxane (4).

[0119] The essence of mixing the components necessary to produce the dispersion of the present invention is not very important and can be carried out in various orders. However, depending on the components (2), (3), (4), (5), optionally (6) and optionally (7), there may be a preferred procedure, which should be considered individually.

[0120] For example, it is possible to premix components (4) and (5) with each other before adding emulsifier(s) (2) and optionally component (6), and then compounding water (3) and optionally component (7). It is also possible to meteringly supply components (2) to (7) correctly in sequence into the emulsifying device. In special cases, for example due to the siloxane viscosity or the reactivity of the siloxane, it may be advantageous to mix, for example, oxalamide ester-terminated polyether (5) with organopolysiloxane (4) and then incorporate a different organopolysiloxane (4), and vice versa depending on how more advantageous rheological properties are generated for the treatment of the components.

[0121] Furthermore, it is also possible to add oxalamide ester-terminated polyether (5) to the finished emulsion of organopolysiloxane (4) to achieve the desired reaction and crosslinking of the organopolysiloxane (4) in the emulsion and form the dispersion of the crosslinked organopolysiloxane (1) according to the invention.

[0122] R 8 has the meaning indicated above therefor, and the alcohol R 8 OH obtained when generating the dispersion as a by-product of the condensation may remain in the product or may be removed, for example, by vacuum distillation, membrane technology, or extraction.

[0123] The emulsification procedure for producing the aqueous emulsion of the crosslinked organopolysiloxane (1) according to the invention is preferably carried out at a temperature of at least 10°C, more preferably at least 15°C, and preferably at most 80°C, more preferably at most 70°C.

[0124] The temperature increase preferably occurs by introducing the mechanical shear energy required for the emulsification operation. This temperature increase is not necessary for the purpose of promoting chemical processes, especially crosslinking. Furthermore, the method according to the invention is preferably carried out under the pressure of the ambient atmosphere, but it can also be carried out at higher or lower pressures.

[0125] Manufacturing can be carried out batchwise or continuously.

[0126] Manufacturing techniques for emulsions of organopolysiloxanes are known. Thus, strong mixing and dispersion can be carried out in a rotor - stator stirrer, colloid mill, high - pressure homogenizer, microchannel, membrane, jet nozzle, etc., or by ultrasound. Homogenizing devices and techniques are described, for example, in Ullmann’s Encyclopedia of Industrial Chemistry, CD - ROM Edition 2011, under the entry “Emulsions” by Wiley - VCH Verlag.

[0127] The average particle size measured by light scattering in the dispersion of the present invention is preferably in the range of 0.001 to 50 μm, more preferably 0.005 to 10 μm, and very preferably 0.01 to 5 μm. The pH value can vary from 1 to 14, preferably from 3 to 9, and more preferably from 4 to 8.

[0128] For the pre - crosslinked organopolysiloxane (1) of the present invention or its aqueous dispersion, use is found as an active ingredient in products for treating substrates, preferably fibrous substrates, more preferably textiles, in particular in compositions for the care and cleaning of substrates, preferably fibrous substrates, more preferably textiles.

[0129] The subject matter of the present invention is an aqueous dispersion of the present invention of the pre - crosslinked organopolysiloxane (1) or a composition for treating substrates, preferably fibrous substrates, more specifically textiles, comprising the pre - crosslinked organopolysiloxane (1) of the present invention.

[0130] Accordingly, a further subject matter of the present invention is the use of the pre - crosslinked organopolysiloxane (1) of the present invention or its aqueous dispersion in a composition for treating substrates, preferably fibrous substrates, more preferably textiles, in particular in a composition for the care and cleaning of substrates, preferably fibrous substrates, more preferably textiles.

[0131] As used herein, the term "active ingredient" refers to a substance that (a) provides care for an article, i.e., maintains the article in its original form, e.g., reduces or prevents the effects of external influences such as aging, dirt, material fatigue, bleaching, or improves the desirable beneficial properties of the article, such as those caused by time, light, temperature, pressure, dirt, chemical reactions with other reactive compounds in contact with the article).

[0132] Examples in the case of textile fibers and fabrics include achieving a significant improvement in the softness of the fibers / fabric after washing, reducing the wrinkles in the fabric during the rinsing and drying stages, reducing the formation of creases or wrinkles before ironing, reducing the force required for ironing the fabric, preventing wrinkles during use, maintaining the shape of the fabric during washing, care and use, improving the wettability of the fibers / fabric, reducing the pilling effect (i.e., the formation of pills or fuzz) in the fabric, suppressing the effect of drying stiffness caused by dry cleaning, achieving greater elasticity in the fibers / fabric, achieving improved luster in the fibers, or reducing the fading of color in the fibers / fabric.

[0133] The term "active ingredient" is further understood to refer to a substance that (b) cleans an article, i.e., removes or aids in the removal of impurities resulting from the use of the article.

[0134] In this context, products for care and cleaning, particularly compositions, are understood to include the following formulations or compositions.

[0135] Formulations used in the home and industry for the care and cleaning of surfaces such as fibers, leather, fabrics, wood, glass, ceramics, tiles, linoleum, and plastics.

[0136] Examples of products for the cleaning and care of such surfaces include laundry detergents (heavy-duty laundry detergents, color laundry detergents, fabric softeners, etc.), dishwashing detergents, dishwasher detergents, rinse aids, neutral cleaners, window cleaners, multi-purpose cleaners, glass cleaners, sanitary cleaners, toilet cleaners, carpet cleaners, and automotive care products.

[0137] In these compositions, the aqueous dispersion of the present invention is preferably used in an amount of 0.1 to 40% by weight, more preferably 0.2 to 30% by weight, and very preferably 0.4 to 20% by weight, based on the total weight of the composition.

[0138] The compositions in which the aqueous dispersion of the present invention is used can take the form of a W / O emulsion (water-in-oil emulsion), an O / W emulsion (oil-in-water emulsion), or a multiple emulsion.

[0139] The preferred medium in the composition is water.

[0140] These preferred compositions generally contain an emulsion (water droplets in a W / O emulsion or lipid vesicles in an O / W emulsion) in which one phase of finely dispersed droplets, surrounded by a shell of an emulsifier, is present in a second phase.

[0141] A "microemulsion" has a droplet diameter in the range of about 0.01 μm to about 0.1 μm. In the case of a "macroemulsion", the diameter of the droplets is in the range of about 0.1 μm to about 50 μm.

[0142] Such a "macroemulsion" is milky white and opaque without the addition of further coloring. A finer "macroemulsion" with a droplet diameter in the range of 0.1 μm to 1 μm is bluish-white and not transparent without the addition of further coloring.

[0143] A "microemulsion" is a transparent or translucent emulsion.

[0144] A clear and transparent appearance is in the region of micellar solutions and molecular solutions with a particle size of less than about 0.01 μm.

Examples

[0145] In the following examples, unless otherwise specified, all descriptions of parts and percentages are based on weight.

[0146] The following examples are carried out at ambient atmospheric pressure, i.e. about 1000 hPa, and at room temperature, i.e. about 20 °C, unless otherwise stated, or at the temperature that results when the reactants are combined at room temperature without additional heating or cooling.

[0147] For the description of the HLB values, the HLB values reported by the respective manufacturers were adopted. For example, assuming that most emulsifiers such as polyethers are oligomers / polymers having a molecular weight distribution, this distribution can vary from manufacturer to manufacturer. Therefore, it is also possible to make different descriptions for the corresponding HLB for each manufacturer, which may also differ from the theoretical HLB for a specific chemical name.

[0148] The dynamic viscosity was measured with a cone-plate system (CP50-2 cone) with an opening angle of 2° using an Anton Paar "MCR 302" rheometer in accordance with DIN EN ISO 3219:1994 and DIN 53019. This instrument was calibrated with 10000 standard oils from the Physikalisch-Technische Bundesanstalt [German National Metrology Institute]. The measurement temperature was 25.00 °C ± 0.05 °C and the measurement time was 3 minutes. The viscosity graph (recorded in mPa·s) represents the arithmetic mean of three individual measurements carried out independently. The measurement uncertainty of the dynamic viscosity is 1.5%. The shear rate gradient was selected according to the viscosity and specified separately for each viscosity graph.

[0149] The kinematic viscosity is determined using a Schott ViscoSystem(R) AVS 350 viscosity measurement system with a constant (e.g. from Windaus or VWR) Ubbelohde viscometer tube in accordance with DIN 51562-Part 1 or ISO / DIS 3105 (including calibration). The measurement is carried out in the temperature range of 25.0 °C (± 0.1 °C). The viscosity graph (reported in mm 2 / s) represents the arithmetic mean of three individual measurements carried out independently. The measurement uncertainty of the kinematic viscosity is 1.05%. Depending on the measurement range, different viscometer tubes with corresponding direction constants are used.

[0150]

Table 1

[0151] Report of the measurement range, corresponding capillary number and constant according to VWR-Laborkatalog, 2011 - 2013, p. 645.8.

[0152] The amine value indicates the number of millimoles of KOH equivalent to 1 g of the substance during measurement. The amine value is determined according to DIN 16945 - 1989 - 03 edition.

[0153] 1 The 1H-NMR spectrum was recorded as a solution in CDCl3 on a Bruker Avance 500 NMR spectrometer (5 mm selective 1 1H-NMR sample head) using a measurement frequency of 500.13 MHz Te mark recorded.

[0154] The evaluation was based on the following references known to those skilled in the art, namely, "Ueber die 1 1H-, 13 13C- and 29 Si-NMR Chemical Shifts of Some Linear, Branched and Cyclic Methyl-Siloxane Compounds" (1H-, 1 13C- and 13 Si-NMR chemical shifts of certain linear, branched and cyclic methyl-siloxane compounds 29Regarding the Si-NMR chemical shift, it is carried out in the manner described in G. Engelhardt, H. Jancke, J. Organometal. Chem. 28 (1971), 293 - 300, "Chapter 8 - NMR spectroscopy of organosilicon compounds", Elizabeth A. Williams, The Chemistry of Organic Silicon Compounds, 1989 John Wiley and Sons Ltd, 511 - 533.

[0155] The particle size is determined by the dynamic light scattering method (Mie measurement method) using a Zetasizer Nano - S particle size analyzer manufactured by Malvern (Software Version 6.01). For this purpose, the dispersion is diluted to 0.5 wt% with filtered and degassed water. The reported value always refers to the D(50) value. D(50) is understood to be the volume - average particle size in which 50% of the total measured particles have a volume - average diameter smaller than a specific value of D(50). The measurement is carried out at 25 °C with the following established settings: refractive index of water (dispersant RI) 1.330, viscosity (cP) 0.8872, refractive index of the dispersed phase (material RI) 1.39, substance absorption 0.010, measurement time (duration used) 50 s, and measurement position 0.65 mm. The photon counting rates reported in the dispersion examples are different because they are obtained from the respective dilutions of the sample. It is important that the measurement program publishes the results with the annotation "Quality of results: Good".

[0156] [Example 1: Oxalamide - ester - terminated polyether A] Into a 1 L round - bottom flask, 200 g of α,ω - diamino - terminated polyether available for purchase under the trademark Jeffamine(R) ED - 600 (manufactured by Huntsman Corporation) is liquefied for 2 hours using a rotary evaporator with an oil heating bath at a heating bath temperature of 100 °C under a reduced pressure of 0.1 mbar for the removal of trace amounts of water and volatile components. The dehydrated Jeffamine(R) ED - 600 has an amine value of 3.3 eq / g (MG = 606 g / mol).

[0157] Under a nitrogen protective gas, 243 g (1.66 mol) of diethyl oxalate from Sigma-Aldrich (St. Louis, Missouri, USA) is strongly stirred and slowly added dropwise and mixed with 100 g of dehydrated Jeffamine ED-600 (0.33 mol as NH₂) so that the reaction mixture does not become too hot above 50 °C. Subsequently, it is stirred at room temperature for another 1 hour. Subsequently, the excess diethyl oxalate is distilled off using a rotary evaporator at a bath temperature of 90 °C under reduced pressure (1 mbar). Thereby, 222.3 g of a clear yellowish liquid is obtained.

[0158] [Example 2: Oxalamide Ester-Terminated Polyether B] Under a nitrogen protective gas, 883 g (6.04 mol) of diethyl oxalate from Sigma-Aldrich (St. Louis, Missouri, USA) is strongly stirred and slowly added dropwise and mixed with 100 g (1.14 mol of NH₂) of 3,3’-ethylenedioxybis(propylamine) (MW = 176 g / mol) available for purchase under the trade name Jeffamine(R) EDR-176 (manufactured by Huntsman Corporation) so that the reaction mixture does not become too hot above 50 °C. Subsequently, it is stirred at room temperature for another 1 hour. Subsequently, the excess diethyl oxalate is distilled off using a rotary evaporator at a bath temperature of 90 °C under reduced pressure (1 mbar). Thereby, a clear light brown liquid is obtained.

[0159] [Example 3: Oxalamide Ester-Terminated Polyether C] In a 1 L round-bottom flask, 250 g of α,ω-diamino-terminated polyether available for purchase under the trademark Jeffamine(R) D-2000 (manufactured by Huntsman Corporation) is liquefied using a rotary evaporator with an oil heating bath at a heating bath temperature of 100 °C under a reduced pressure of 0.1 mbar for 2 hours for the removal of trace amounts of water and volatile components. The dehydrated Jeffamine(R) D-2000 has an amine value of 1.015 eq / g (MG = 1970 g / mol).

[0160] 296.66 g (2.03 mol) of diethyl oxalate from Sigma-Aldrich (St. Louis, Missouri, USA) is slowly added dropwise and mixed with 20 g of dehydrated Jeffamine D-2000 (0.20 mol of NH₂) with strong stirring under N₂ protective gas, such that the reaction mixture does not become too hot and exceed 50 °C. Subsequently, stirring is continued for an additional 1 hour at room temperature. Subsequently, the excess diethyl oxalate is distilled off using a rotary evaporator at a bath temperature of 90 °C under reduced pressure (1 mbar). This gives a clear light brown liquid.

[0161] [(Comparative) Example 4: Emulsion CE1 of Amino-Functionalized Polydimethylsiloxane (Non-Invention)] Using an Ultra-Turrax T 50 emulsifier (manufactured by Janke & Kunkel / IKA) at 5000 rpm, 1.6 g of an 80% aqueous solution of isotridecyl decaethoxylate (available from Lutensol TO 10, BASF), 5.8 g of isotridecyl pentaethoxylate (available from Lutensol TO 5, BASF), 2.5 g of completely demineralized water, and 0.3 g of 80% acetic acid are premixed.

[0162] This premix is mixed in 4 portions with 14.8 g of a hydroxy / methoxy-terminated copolymer composed of 3-(2-aminoethylamino)propylmethylsiloxy units and dimethylsiloxy units, having an amine value of 0.30 eq / g and a viscosity of 800 - 1800 mm 2 / s (at 25.0 °C, capillary number IIIc), with each portion being incorporated and homogenized at 5000 rpm shear for 2 minutes. It is slowly diluted in several portions with 70.0 g of completely demineralized water at 4000 rpm to obtain the desired emulsion. 0.9 g of 2-phenoxyethanol (available from trademark S&M phenoxyethanol, Schuelke and Mayr GmbH and CO KG) and 4.0 g of 86% glycerol are added and homogenized at 4000 rpm for an additional 2 minutes.

[0163] This results in a colorless microemulsion with a solids content of 27% and a low viscosity of pH 5.5 that emits a transparent to opalescent light. The emulsion remains stable and uniform during storage.

[0164] [(Comparative) Example 5: Emulsion CE2 of Amino-Functionalized Polydimethylsiloxane (Non-Invention)] Using an LDV 1 dissolver from PC Laborsystem, 6.5 g of isotridecyl pentaethoxylate, available under the trademark Lutensol TO 5 (manufactured by BASF), with an amine value of 0.13 eq / g and a viscosity of 3900 mm 2 / s (at 25.0 °C, capillary number IV), 20.0 g of a copolymer of 3-(2-aminoethylamino)propylmethylsiloxy units and dimethylsiloxy units, 2.9 g of glycerol, 0.12 g of 80% acetic acid, 0.19 g of N-morpholinomethyltriethoxysilane, and 70 g of water to prepare Emulsion CE2, which has a particle size D(50) of 28 nm (photon counting rate 286 kcps). To this emulsion, 0.13 g of 2-phenoxyethanol, available under the trademark S&M Phenoxyethanol (Schuelke and Mayr GmbH and CO KG), is incorporated by mixing.

[0165] [(Comparative) Example 6: Emulsion CE3 of Amino-Functionalized Polydimethylsiloxane (Non-Invention)] Using an Ultra-Turrax T 50 emulsifying device (manufactured by Janke & Kunkel / IKA) at 5000 rpm, premix 6.0 g of C11-15 Pareth-7 (ethoxylated secondary alcohol, 7 ethylene oxide units) purchasable under the trademark Tergitol 15-S-7 (manufactured by Dow) and 1.9 g of hot, completely demineralized water. To this premix, weigh in 1.0 g of lauryl ethoxylate-9 (ethoxylated primary alcohol, 9 ethylene oxide units) purchasable under the trademark Sympatens AL / 090 (manufactured by KLK Kolb), 3.0 g of molten isotridecyl dodecaethoxylate purchasable under the trademark Lutensol TO 12 (manufactured by BASF), and more than 1.9 g of hot, completely demineralized water, and homogenize the mixture at 5000 rpm for 2 minutes. Subsequently, meter in 2.3 g of 86% glycerol and homogenize the mixture at 5000 rpm for an additional 2 minutes. To this mixture, add 20.0 g of a copolymer of 3-(2-aminoethylamino)propylmethylsiloxy units and dimethylsiloxy units having an amine value of 0.25 eq / g and a viscosity of 1500 - 2100 mm 2 / s (25.0 °C, capillary number IIIc) in three portions and homogenize each portion at 5000 rpm shear for 2 minutes. Add 0.9 g of 2-phenoxyethanol purchasable under the trademark S&M phenoxyethanol (Schuelke and Mayr GmbH and CO KG) and 0.4 g of 80% acetic acid, and homogenize at 5000 rpm for an additional 2 minutes. Slowly dilute 62.6 g of completely demineralized water in several portions at 4000 rpm to obtain the desired emulsion.

[0166] Thereby, a colorless microemulsion with a solids content of 33% and a pH of 5.0, which is low-viscosity, transparent to opalescent, is obtained.

[0167] [Example 7: Emulsion E4 of Amino-Functionalized Polydimethylsiloxane Crosslinked with Oxalamide Ester-Terminated Polyether] Using an Ultra-Turrax T 50 emulsifying device (manufactured by Janke & Kunkel / IKA) at 5000 rpm, 99.26 g of emulsion CE1 is homogenized with 0.74 g of oxalamide ester-terminated polyether A (about 5% by weight based on the amino-functionalized polydimethylsiloxane) for 1 minute. Thereby, a low-viscosity, transparent to slightly turbid, colorless to slightly yellowish emulsion E4 with a solids content of 28% and a pH of 5.0 is obtained.

[0168] After drying at 25 °C for 1 to 3 days and then evaporating the emulsion, a significantly white, elastic, soft film that adheres well to aluminum and does not stick to the surface is formed.

[0169] [Example 8: Emulsion E5 of amino-functionalized polydimethylsiloxane crosslinked with oxalamide ester-terminated polyether] Using an Ultra-Turrax T 50 emulsifying device (manufactured by Janke & Kunkel / IKA) at 5000 rpm, 99.70 g of emulsion CE1 is homogenized with 0.30 g of oxalamide ester-terminated polyether B (about 2% by weight based on the amino-functionalized polydimethylsiloxane) for 1 minute. Thereby, a low-viscosity, transparent to slightly turbid, colorless to slightly yellowish emulsion E5 with a solids content of 27% and a pH of 5.0 is obtained.

[0170] After drying at 25 °C for 1 to 3 days and then evaporating the emulsion, a significantly white, elastic, soft film that adheres well to aluminum and does not stick to the surface is formed.

[0171] [Example 9: Emulsion E6 of amino-functionalized polydimethylsiloxane crosslinked with oxalamide ester-terminated polyether] Using an Ultra-Turrax T 50 emulsifying device (manufactured by Janke & Kunkel / IKA) at 5000 rpm, 98.52 g of emulsion CE1 is homogenized with 1.48 g of oxalamide ester-terminated polyether C (about 10% by weight based on amino-functionalized polydimethylsiloxane) for 1 minute. Thereby, a low-viscosity, turbid, colorless to slightly yellowish emulsion E6 with a solids content of 28% and a pH of 5.0 is obtained.

[0172] After drying at 25 °C for 1 to 3 days and then evaporating the emulsion, a white, elastic, soft film that adheres well to aluminum and does not stick to the surface is formed.

[0173] [Example 10: Emulsion E7 of amino-functionalized polydimethylsiloxane crosslinked with oxalamide ester-terminated polyether] Using an Ultra-Turrax T 50 emulsifying device (manufactured by Janke & Kunkel / IKA) at 5000 rpm, 97.00 g of emulsion CE3 is homogenized with 3.00 g of oxalamide ester-terminated polyether A (about 15% by weight based on amino-functionalized polydimethylsiloxane) for 1 minute. Thereby, a low-viscosity, slightly turbid, slightly yellowish emulsion E7 with a solids content of 35% and a pH of 4.5 is obtained.

[0174] After drying at 25 °C for 1 to 3 days and then evaporating the emulsion, a white, elastic, soft film that adheres well to aluminum and does not stick to the surface is formed.

[0175] [Example 11: Emulsion E8 of amino-functionalized polydimethylsiloxane crosslinked with oxalamide ester-terminated polyether] Using an Ultra-Turrax T 50 emulsifying device (manufactured by Janke & Kunkel / IKA) at 5000 rpm, 99.20 g of emulsion CE3 is homogenized with 0.80 g of oxalamide ester-terminated polyether B (about 4% by weight based on amino-functionalized polydimethylsiloxane) for 1 minute. As a result, a low-viscosity, transparent, slightly yellowish emulsion E8 with a solids content of 34% and a pH of 4.5 is obtained.

[0176] After drying at 25 °C for 1 to 3 days and then evaporating the emulsion, a significantly white, elastic, soft film that adheres well to aluminum and does not stick to the surface is formed.

[0177] [Example 12: Emulsion E9 of amino-functionalized polydimethylsiloxane crosslinked with oxalamide ester-terminated polyether] Using an Ultra-Turrax T 50 emulsifying device (manufactured by Janke & Kunkel / IKA) at 5000 rpm, 96.00 g of emulsion CE3 is homogenized with 4.00 g of oxalamide ester-terminated polyether C (about 20% by weight based on amino-functionalized polydimethylsiloxane) for 1 minute. As a result, a low-viscosity, turbid, slightly yellowish emulsion E9 with a solids content of 36% and a pH of 4.5 is obtained.

[0178] After drying at 25 °C for 1 to 3 days and then evaporating the emulsion, a white, elastic, very soft film that adheres well to aluminum and does not stick to the surface is formed.

[0179] [(Comparative) Example 13: Emulsion CE10 of linear oxalamide ester-polyether-bonded polydimethylsiloxane] Emulsion CE10 is produced in a manner similar to Example 1 of WO2019 / 114953A1.

[0180] A 500 ml three-necked flask equipped with a thermocouple, a KPG stirrer and a reflux condenser was charged with 100 g (20 mmol) of a linear oxamide ester-terminated silicone oil (5065 g / mol). While stirring, 3.74 g (20 mmol) of TA 187 (=N 1 -(3-(dimethylamino)propyl)-N 3 ,N 3 -dimethylpropane-1,3-diamine, available from SIGMA-ALDRICH, MERCK, Darmstadt, Germany), followed by 6.6 g (10 mmol) of JEFFAMINE(R) ED-600 (available from Huntsman Performance Products, Everberg, Everslaan 45, B-3078, Belgium) were added. Subsequently, stirring was continued for an additional 30 minutes. Thereafter, the alcohol formed at 40 °C under a pressure of 20 hPa was removed from the reaction product. This gave 107 g of an opaque oligomer product. 21.2 g of the resulting product were mixed with 4.7 g of diethylene glycol monobutyl ether (Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany) and 4.1 g of tridecyl alcohol ethoxylate (available as LUTENSOL(R) TO from BASF SE, Ludwigshafen), then slowly diluted with 70.0 g of water and adjusted to pH 4.5 with 80% acetic acid.

[0181] [Example 14] The degree of crosslinking was determined using the following emulsions listed in Table 1. Here, this emulsion was poured into an aluminum tray and the appearance of the emulsion was evaluated after removal of the water.

[0182]

Table 2

[0183] [Example 15: Determination of wrinkle recovery angle] The performance test regarding the determination of the wrinkle recovery angle was carried out using the following aqueous formulations described in Table 2. The amount of the polyoxyalkylene siloxane-containing emulsion is selected so that the polysiloxane content (excluding the blank value F1) is always the same.

[0184]

Table 3

[0185] The formulations (both of the present invention and non-invention) are produced by simple mixing of the components (with the help of an IKA Eurostar Power basic stirring mechanism equipped with a paddle stirrer).

[0186] <Evaluation of the Desirable Effect from the Perspective of the Wrinkle Recovery Angle> A 2×5 cm fabric strip is taken from a wfk 10 A cotton test fabric (100% cotton, with a basis weight of about 170 g / m 2 produced by wfk-Testgewebe), and this fabric is washed twice with a commercially available heavy-duty powder detergent at 90°C.

[0187] The aqueous formulations F1 to F8 (see Table 2) are sprayed onto the said fabric strip using a trigger spray. The mass of the formulations F1 to F8 applied by spraying is selected to be the same as the mass of the said fabric strip. The fabric strip is dried overnight on a line and conditioned for 24 hours in a conditioning chamber at 23°C / 60% humidity, and then ironed with an iron set to the "cotton" setting.

[0188] The wrinkle recovery angle is determined by the method of DIN 53 890 / 1972.

[0189] Each fabric strip is folded transversely so that the length of the stacked sample side is 10 mm. An aluminum foil with a thickness of 0.15 mm is placed under the sample side to prevent fiber adhesion. The sample is covered with a microscope slide, and a weight of 1000 g is lowered so that the weight is applied only to the stacked sample side. The weighting time is 30 minutes.

[0190] After removing the weights on the microscope slide, the gradually increasing wrinkle recovery angles are determined using a protractor on both sides of the angular profile at 5 and 30 minutes.

[0191] At least 10 samples should be prepared and measured for each fabric. The reported measurement results are the average values from each measurement.

[0192] [Table 4]

[0193] The modification of the fabric by formulations F3 - F8 containing the emulsions E4 - E9 of the present invention results in a significant increase in the wrinkle recovery angle compared to the fabric sprayed with only water (blank test value F1).

[0194] Similarly, the comparison with formulation F2 containing the non - inventive emulsion CE2 of non - crosslinked amino - functionalized polydimethylsiloxane shows that the formulations F3 - F8 of the present invention, particularly formulations F3 and F8, exhibit an increased wrinkle recovery angle.

[0195] Therefore, when using the emulsion of the present invention in fabric products having the function of reducing or suppressing wrinkles in fabrics such as clothing, the tendency to increase wrinkles is significantly reduced compared to that provided by the prior art.

[0196] [Example 16: Droplet Absorption Time] The performance test regarding the determination of the droplet absorption time was carried out using the aqueous formulations F2 - F5 described in Table 2 (Example 15).

[0197] The wfk 10 cotton test fabric made by wfk - Testgewebe is modified according to the method described in Example 15.

[0198] After drying, a drop of deionized water is placed on the stretched fabric surface of the thus - modified fabric from a height of 4 cm, and the time taken for the water droplet to be absorbed by the fabric is determined. Five determinations are made and averaged.

[0199] [Table 5]

[0200] The modification of the cotton test cloth with the formulations F3 to F5 containing the emulsions E4 to E6 of the present invention significantly shortens the droplet absorption time on the cotton test cloth compared to the modification with the formulation F2 containing the non-inventive emulsion CE2 of non-crosslinked amino-functionalized polydimethylsiloxane. As a result, significantly better water absorption is achieved for the fabric than in the prior art.

[0201] [Example 17 Soft touch in the use as a fabric softener component] Soft touch The performance test regarding the determination of was carried out using the following aqueous formulations described in Table 5.

[0202] [Table 6]

[0203] To evaluate the desirable effects from the perspective of a soft touch, six terry woven hand towels made of cotton cloth were washed together with about 2 kg of ballast cloth in a MIELE Softronic W 1935 WPS EcoLine household washing machine rotated at 1200 rpm using a boiling / color washing program at 40°C. The washing surfactant metered and supplied here was 65 g of the ECE-2 test washing detergent powder manufactured by WFK. After the washing cycle, the formulations F9 to F13 (pre-diluted with 1 liter of tap water at 16°dH [German hardness]) were added via the detergent drawer. Finally, the material was dried in a conditioning chamber at 23°C and an atmospheric humidity of 60% on the line for at least 12 hours.

[0204] [Determination of soft touch (evaluation of touch)] Since the soft feel of a fabric depends greatly on the subjective perception of the tester, only the boundary conditions can be standardized, not the evaluation. Nevertheless, in order to ensure reproducibility, the modified test specimens were evaluated and ranked for their soft feel. For this purpose, depending on the number n of test specimens tested, 10 testers gave points from 1 to n. Here, n points were given to the softest test specimen, and 1 point was given to the modified test specimen that was not the softest. A reference test specimen that was not modified was given 0 points. As a result, the evaluation of the feel of the test specimen was calculated as the average of the points assigned to each test specimen.

[0205]

Table 7

[0206] When the fabric is modified with the formulations F10 - F12 of the present invention, a significantly improved soft feel is obtained compared to the prior art formulation F13 (containing the emulsion CE1 of a non-crosslinked amino-functionalized diorganopolysiloxane), which has a less soft feel.

[0207] The combination of a cationic surfactant, and in particular the emulsion of the present invention in formulation F12, further provides a soft feel that, as in the case of formulation F9, can only be achieved with a significantly increased cationic surfactant content otherwise. This results in a reduction in the cost of raw material use, which represents a clear improvement over the prior art both environmentally and economically.

Claims

1. An aqueous dispersion comprising the following: (1) Units of the following formula (I) R ２ SiO ２／２ (I) and a pre-crosslinked organopolysiloxane containing, on average, at least one structural unit of the following formula (III) SiR １ O ２／２ -Y-SiR １ O ２／２ (III) [wherein, Y is a divalent group of the following formula (VII), -R ２ -[NR ３ -R ４ -] ｎ NR ３ -C(O)-C(O)-NR ３ -Z-NR ３ -C(O)-C(O)-NR ３ -[R ４ -NR ３ -] ｎ R ２ -(VII) Z is the same or different and is a divalent organic group containing a polyoxyalkylene group, R may be the same or different and is a monovalent unsubstituted or substituted saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, R １ may be the same or different and is a group R or a group -O-R ７ and R ２ is a divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms and bonded to SiC, R ３ is a hydrogen atom, an alkyl group or an acyl group having 1 to 8 carbon atoms, R ４ is a divalent hydrocarbon group having 1 to 6 carbon atoms, R ７ may be the same or different and is a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be interrupted by one or more additional oxygen atoms, n is 0, 1, 2, 3 or 4.] (2) An emulsifier, and (3) Water.

2. The aqueous dispersion according to claim 1, wherein the pre-crosslinked organopolysiloxane (1) contains a structural unit of the following formula (II). R １ ASiO ２／２ (II) [wherein, A may be the same or different and is a group of the following formula (VIII), -R ２ -[NR ３ -R ４ -] ｎ NR ３ ２ (VIII), R １ may be the same or different and is a monovalent unsubstituted or substituted saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, or the group -O-R ７ wherein R ７ may be the same or different and is a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be interrupted by one or more additional oxygen atoms, R ２ is a divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms and bonded to SiC, R ３ is a hydrogen atom, an alkyl group or an acyl group having 1 to 8 carbon atoms, R ４ is a divalent hydrocarbon group having 1 to 6 carbon atoms, n is 0, 1, 2, 3 or 4.]

3. The aqueous dispersion according to claim 1 or 2, wherein the pre-crosslinked organopolysiloxane (1) is selected from the group consisting of the following formulas (IVa and IVb) and mixtures thereof. 【Chemical 1】 [wherein, R may be the same or different and is a monovalent unsubstituted or substituted saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, R ７ may be the same or different and is hydrogen or a monovalent hydrocarbon group having 1 to 18 carbon atoms which may be interrupted by one or more additional oxygen atoms, Y is a divalent group of the following formula (VII), -R ２ -[NR ３ -R ４ -] ｎ NR ３ -C(O)-C(O)-NR ３ -Z-NR ３ -C(O)-C(O)-NR ３ -[R ４ -NR ３ -] ｎ R ２ -(VII) A may be the same or different and is a group of the following formula (VIII), -R ２ -[NR ３ -R ４ -] ｎ NR ３ ２ (VIII), R ２ is a divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms and bonded to SiC, R ３ is a hydrogen atom, an alkyl group or an acyl group having 1 to 8 carbon atoms, R ４ is a divalent hydrocarbon group having 1 to 6 carbon atoms, n is 0, 1, 2, 3 or 4, e is 0 or 1, j is 0 or an integer between 1 and 15, k is at least 1 and at most 15, l is at least 40 and at most 1000.]

4. The aqueous dispersion according to claim 1, 2 or 3, wherein the pre-crosslinked organopolysiloxane forms an elastomeric film after removal of water.

5. A pre-crosslinked organopolysiloxane (1) comprising units of the following formula (I) R ２ SiO ２／２ (I) and a pre-crosslinked organopolysiloxane containing, on average, at least one structural unit of the following formula (III). SiR １ O ２／２ -Y-SiR １ O ２／２ (III) [wherein, Y is a divalent group of the following formula (VII), -R ２ -[NR ３ -R ４ -] ｎ NR ３ -C(O)-C(O)-NR ３ -Z-NR ３ -C(O)-C(O)-NR ３ -[R ４ -NR ３ -] ｎ R ２ -(VII) Z is the same or different and is a divalent organic group containing a polyoxyalkylene group, R may be the same or different and is a monovalent unsubstituted or substituted saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, R １ may be the same or different and is a group R or a group -O-R ７ and R ２ is a divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms and bonded to SiC, R ３ is a hydrogen atom, an alkyl group or an acyl group having 1 to 8 carbon atoms, R ４ is a divalent hydrocarbon group having 1 to 6 carbon atoms, R ７ may be the same or different and is a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be interrupted by one or more additional oxygen atoms, n is 0, 1, 2, 3 or 4.]

6. A method for producing an aqueous dispersion of a pre-crosslinked organopolysiloxane (1), which comprises units of the following formula (I) R ２ SiO ２／２ (I), and an organopolysiloxane (4) containing on average at least one structural unit of the following formula (II), R １ ASiO ２／２ (II) [wherein, R may be the same or different and is a monovalent unsubstituted or substituted saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, R １ may be the same or different and is a group R or a group -O-R ７ and R ７ may be the same or different and is a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be interrupted by one or more additional oxygen atoms, A may be the same or different and is a group of the following formula (VIII), -R ２ -[NR ３ -R ４ -] ｎ NR ３ ２ (VIII), R ２ is a divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms and bonded to SiC, R ３ is a hydrogen atom, an alkyl group or an acyl group having 1 to 8 carbon atoms, R ４ is a divalent hydrocarbon group having 1 to 6 carbon atoms, n is 0, 1, 2, 3 or 4. ] The method is characterized in that it is reacted in the presence of an oxalamide ester-terminated polyether (5) of the following formula (V), an emulsifier (2) and water (3). 【Chemical 2】 [wherein, Z is the same or different and is a divalent organic group containing a polyoxyalkylene group, R ３ is a hydrogen atom, an alkyl group or an acyl group having 1 to 8 carbon atoms, R ８ are the same or different and are monovalent hydrocarbon groups having 1 to 18 carbon atoms, which may be interrupted by one or more additional oxygen atoms.

7. The method according to claim 6, characterized in that the organopolysiloxane (4) used comprises those selected from the group of the following formulas (VIa and VIb) and mixtures thereof. [ARSiO ２／２ ｊ [R ２ SiO ２／２ ｌ [R ３－ｅ [(OR ７ ) ｅ SiO １／２ ２ (Via),​​​ [A(OR １ )SiO ２／２ ｊ [R ２ SiO ２／２ ｌ [R ３－ｅ (OR ７ ) ｅ SiO １／２ ２ (Vib)​​​ [wherein, R may be the same or different and is a monovalent unsubstituted or substituted saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, R １ may be the same or different and is a group R or a group -O-R ７ and R ７ may be the same or different and is a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be interrupted by one or more additional oxygen atoms, A may be the same or different and is a group of the following formula (VIII), -R ２ -[NR ３ -R ４ -] ｎ NR ３ ２ (VIII), R ２ is a divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms and bonded to SiC, R ３ is a hydrogen atom, an alkyl group or an acyl group having 1 to 8 carbon atoms, R ４ is a divalent hydrocarbon group having 1 to 6 carbon atoms, n is 0, 1, 2, 3 or 4, e is 0 or 1, j is 0 or an integer between 1 and 15, l is at least 40 and at most 1000. ]

8. An aqueous dispersion of the pre-crosslinked organopolysiloxane (1) according to the present invention described in claim 1, 2 or 3, or a composition for treating a substrate, comprising the pre-crosslinked organopolysiloxane (1) of the present invention described in claim 5.

9. The composition according to claim 8, characterized in that the substrate is a fabric.

10. Use of the composition according to claim 8 or 9 for treating a substrate.

11. The use according to claim 10, characterized in that the composition is used for cleaning and caring for the substrate.

12. The use according to claim 10 or 11, characterized in that the substrate is a fabric.

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