Aqueous dispersions of amino-functionalized organopolysiloxanes pre-crosslinked with oxalate polyether

Abstract

An aqueous dispersion comprising (1) a pre-crosslinked organopolysiloxane comprising the formula R2SiO 2 / 2 (I) unit, and average at least one SiR 1 O 2 / 2 -Y-SiR 1 O 2 / 2 (III) structural unit, where Y represents -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 - a divalent group, where Z represents a divalent organic group containing a polyoxyethylene group, preferably represented by the formula –(R 5 O) m -R 6 - group, R represents a monovalent, optionally substituted C1-C group. 18 hydrocarbon group, R 1 Indicates group R or group -O-R 7 R 2 This represents the divalent linear or branched C3-C bonds in SiC bonding. 18 hydrocarbon group, R 3 Represents hydrogen atom, C1-C 10 Alkyl or acyl, R 4 R represents a divalent C1-C6 hydrocarbon group. 5 Are they the same or different and represent C3-C 18 Alkylene, R 6 Indicates C1-C 10 Alkylene, R 7 Indicates hydrogen or monovalent C3-C 18 The hydrocarbon group may be interspersed with one or more independent oxygen atoms, n is 0, 1, 2, 3 or 4, and m is on average 1 to 80, (2) emulsifier, and (3) water.

Description

[0001] This invention relates to aqueous dispersions of pre-crosslinked organopolysiloxanes, their preparation, and their use in compositions for treating substrates (preferably fibrous substrates).

[0002] Organopolysiloxanes are used in a variety of consumer products to achieve specific beneficial effects. Examples include specific softness or smoothness, improved tactile quality, reduced wrinkles, improved gloss properties, improved perceived color, color protection properties, reduced static charge, or protective properties for hair or fibers under heat load.

[0003] The use of organopolysiloxanes (especially amino-functionalized organopolysiloxanes) in textile finishing is a long-established existing technology, as reported, for example, in HJ Lautenschlager, Textil Praxis International, Vol. 47, 5, 1992, pp. 460-461.

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

[0005] According to US 2008 / 0064813 A1, an aqueous dispersion of a pre-crosslinked organopolysiloxane is obtained by reacting an amino-functionalized organopolysiloxane containing alkoxy or hydroxyl groups with a reactive alkoxysilane, without the use of a metal-containing catalyst. After the dispersion is applied to a substrate and the water is evaporated, an elastomeric film is obtained. This elastic effect can also be used to reduce wrinkles in textiles.

[0006] The drawback of these amino-functionalized pre-crosslinked organopolysiloxanes alone is their hydrophobic effect on textiles.

[0007] Hydrophilically modified siloxanes are known. According to WO 2019 / 114953 A1, they are linear copolymers of oxalamid-terminated organopolysiloxanes and amino-terminated polyethers. They exhibit significantly enhanced hydrophilicity compared to amino-functionalized organopolysiloxanes alone. However, due to their linear structure, they do not exhibit any elasticity effect.

[0008] US 7,501,184 describes copolymers obtained by reacting oxalamide-terminated linear organopolysiloxanes with organodiamines. High-viscosity to solid copolymers were obtained, which are used in adhesives, more specifically as hot melt adhesives. These high-viscosity products cannot be stably emulsified and are therefore unsuitable for treating fibrous substrates such as textiles. Furthermore, due to their linear structure, they do not exhibit elasticity.

[0009] The objective is to provide pre-crosslinked organopolysiloxanes, more specifically, aqueous dispersions of pre-crosslinked organopolysiloxanes—which do not have the disadvantages stated above, can be prepared inexpensively, preferably form an elastomeric film after water removal, and can be used in compositions for treating substrates, preferably fibrous substrates, and more particularly for textiles. Furthermore, the objective is to provide compositions for treating substrates, preferably fibrous substrates, and more particularly for textiles, in order to, for example, clean and care for them, and impart improved properties to them, such as good hydrophilicity. This objective is achieved through the present invention.

[0010] One subject of the present invention is an aqueous dispersion, preferably an aqueous emulsion, comprising:

[0011] (1) A pre-crosslinked organopolysiloxane comprising units of formula (I) and at least one structural unit of formula (III), preferably at least two structural units of formula (III):

[0012] R2SiO 2 / 2 (I),

[0013] SiR 1 O 2 / 2 -Y-SiR 1 O 2 / 2 (III)

[0014] in

[0015] Y is a divalent group in the following formula:

[0016] -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 -,

[0017] Z can be the same or different, and is a divalent organic group containing a polyoxyethylene group, preferably Z is of the formula –(R 5 O) m -R 6 - group,

[0018] R can be the same or different, and is a monovalent, unsubstituted or substituted, saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms.

[0019] R 1 They can be the same or different, and are either group R or group -OR. 7 ,

[0020] R 2 It is a SiC-bonded divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms, preferably an alkylene group having 3 to 10 carbon atoms.

[0021] R 3 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group, such as an acetyl group, preferably a hydrogen atom.

[0022] R 4 It is a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms.

[0023] R 5 They are the same or different, and are C1-C. 10 Alkylene, preferably C2-C3 alkylene, more preferably ethylene or isopropylene radical, and

[0024] R 6 It is C1-C 10 Alkylene, preferably C2-C3 alkylene, more preferably ethylene or isopropylene,

[0025] R 7 They can be the same or different, and are either hydrogen or a monovalent hydrocarbon group having 1 to 18 carbon atoms and possibly interspersed with one or more independent oxygen atoms.

[0026] n can be 0, 1, 2, 3, or 4, preferably 0 or 1.

[0027] m is an integer with an average value of 1 to 80, preferably 2 to 50.

[0028] (2) Emulsifiers, and

[0029] (3) Water.

[0030] The dispersion of the present invention comprises 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, and very preferably at most 35% by weight of a crosslinked organopolysiloxane (1).

[0031] The dispersion of the present invention contains preferably 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 an emulsifier (2).

[0032] The dispersion of the present invention contains preferably at least 1% by weight, more preferably at least 5% by weight, more particularly at least 10% by weight, and preferably at most 94.5% by weight, more preferably at most 85% by weight, more particularly at most 80% by weight of water (3).

[0033] Another subject of the present invention is a pre-crosslinked organopolysiloxane comprising a unit of formula (I) and an average of at least one structural unit of formula (III), preferably at least two structural units of formula (III):

[0034] R2SiO 2 / 2 (I),

[0035] SiR 1 O 2 / 2 -Y-SiR 1 O 2 / 2 (III)

[0036] in

[0037] Y is a divalent group in the following formula:

[0038] -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 -,

[0039] R, R 1 R 2 R 3 R 4 Z and n have the meanings indicated by the above.

[0040] The pre-crosslinked organopolysiloxane (1) may additionally include structural units of the following formula:

[0041] R 1 ASiO 2 / 2 (II)

[0042] in

[0043] A can be the same or different, and is a group of the following formula:

[0044] -R 2 -[NR 3 -R 4 -]n NR 3 2,

[0045] R 2 It is a SiC-bonded divalent linear or branched hydrocarbon group having 1 to 18 carbon atoms, preferably an alkylene group having 3 to 10 carbon atoms.

[0046] R 3 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group, such as an acetyl group, preferably a hydrogen atom.

[0047] R 4 It is a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and

[0048] n can be 0, 1, 2, 3 or 4, preferably 0 or 1.

[0049] It has been surprisingly found that side-chain amino-functionalized organopolysiloxanes with oxalamid ester-terminated polyether bridges, as well as aqueous dispersions of such organopolysiloxanes, can be used as active ingredients in compositions for caring for and cleaning fiber substrates (more particularly textiles), wherein the fiber substrates (more particularly textiles) treated with them exhibit significantly improved properties, especially good hydrophilic properties.

[0050] The pre-crosslinked organopolysiloxane aqueous dispersion of the present invention preferably forms an elastomeric film after water removal.

[0051] The pre-crosslinked organopolysiloxane of the present invention is preferably hydrophilic.

[0052] The pre-crosslinked organopolysiloxane (1) of the present invention is more particularly selected from those of the following formula:

[0053] [ARSiO 2 / 2 ] j [RSiO 2 / 2 ] k [R2SiO 2 / 2 ] l [R 3-e (OR 7 ) e SiO 1 / 2 ]2

[0054]

[0055] [ARSiO 2 / 2 ] j [RSiO 2 / 2 ] k [R2SiO 2 / 2 ] l [R 3-e (OR7 ) e SiO 1 / 2 ]2,

[0056] [A(OR 7 SiO 2 / 2 ] j [(OR 7 SiO 2 / 2 ] k [R2SiO 2 / 2 ] l [R 3-e (OR 7 ) e SiO 1 / 2 ]2

[0057]

[0058] [A(OR 7 SiO 2 / 2 ] j [(OR 7 SiO 2 / 2 ] k [R2SiO 2 / 2 ] l [R 3-e (OR 7 ) e SiO 1 / 2 ]2

[0059] and their mixtures, in which

[0060] R, R 7 A and Y have the meanings indicated by the above.

[0061] e is 0 or 1.

[0062] j is 0 or an integer from 1 to 15.

[0063] k is at least 1, preferably at least 2 and at most 15, preferably at most 10, more preferably at most 7, and

[0064] l is at least 40, preferably at least 65, more preferably at least 110, and at most 1000, preferably at most 800, and more preferably at most 500.

[0065] The pre-crosslinked organopolysiloxane (1) of the present invention may optionally contain a small amount of the structural unit T(RSiO) 3 / 2 ) or Q(SiO 4 / 2 ).

[0066] In the context of this invention, formula (IVa) or (IVb) should be understood to refer to 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 [R2SiO 2 / 2 They can be distributed in any desired manner—for example, in block form or randomly—within organopolysiloxane molecules.

[0067] One cross-linked organopolysiloxane (1) of the present invention, or a mixture of two or more, may be used.

[0068] Another subject of the present invention is a method for preparing an aqueous dispersion of a pre-crosslinked organopolysiloxane (1), characterized in that an organopolysiloxane (4) is reacted with an oxalamid-terminated polyether (5) in the presence of an emulsifier (2) and water (3), the organopolysiloxane (4) comprising a unit of formula (I) and an average of at least one structural unit of formula (II):

[0069] R2SiO 2 / 2 (I),

[0070] R 1 ASiO 2 / 2 (II)

[0071] in

[0072] R, R 1 A and B have the meanings indicated by the above.

[0073] The oxaloylamino ester-terminated polyether (5) is of formula (V):

[0074]

[0075] in

[0076] Z and R 3 Having the meanings indicated by them above, and

[0077] R 8 They may be the same or different, and are monovalent hydrocarbon groups having 1 to 18 carbon atoms and may be interspersed with one or more independent oxygen atoms.

[0078] The properties and amounts of the organopolysiloxane (4) and the oxaloylamino ester-terminated polyether (5) are selected here to crosslink the organopolysiloxane (1) in the obtained dispersion.

[0079] Therefore, the dispersion of the present invention preferably does not contain a catalyst.

[0080] Therefore, the dispersion of the present invention contains a pre-crosslinked, preferably hydrophilic, organopolysiloxane, which is further crosslinked after water removal and preferably forms an elastomeric membrane, wherein the crosslinked, preferably hydrophilic organopolysiloxane has a high molecular weight branched structure.

[0081] The dispersion of the present invention is preferably an aqueous suspension or aqueous emulsion of a pre-crosslinked organopolysiloxane.

[0082] During drying, without adding a catalyst or changing the pH, the dispersion of the present invention develops into an organosilicon network, preferably an elastic organosilicon network.

[0083] In addition to the pre-crosslinked organopolysiloxane (1), emulsifier (2), and water (3), the aqueous dispersion of the present invention may optionally contain other components that do not directly participate in the reaction, such as:

[0084] (6) Non-aqueous solvents or co-emulsifiers, and

[0085] (7) Additives, examples of which are pH adjusters, salts, foam inhibitors, thickeners and / or protective colloids, preservatives, disinfectants, wetting agents, corrosion inhibitors, dyes, fragrances or mixtures thereof.

[0086] Examples of hydrocarbon group R are:

[0087] Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl (e.g., n-hexyl), heptyl (e.g., n-heptyl), octyl (e.g., n-octyl and isooctyl, such as 2,2,4-trimethylpentyl), nonyl (e.g., n-nonyl), decyl (e.g., n-decyl), dodecyl (e.g., n-dodecyl), and octadecyl (e.g., n-octadecyl).

[0088] Cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl.

[0089] Alkenyl groups, such as vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl, and 4-pentenyl.

[0090] Aryl groups, such as phenyl, naphthyl, anthraceneyl, and phenanthrene,

[0091] Alkyl groups, such as ortho-, meta-, and p-tolyl; xylyl and ethylphenyl, and

[0092] Aryl groups, such as benzyl, α- and β-phenylethyl, or 2-phenylpropyl.

[0093] The preferred radical R is methyl, ethyl, octyl, or phenyl; methyl and ethyl are particularly preferred.

[0094] Examples of substituted groups R are haloalkyl groups, such as 3,3,3-trifluoro-n-propyl, 2,2,2,2',2',2'-hexafluoroisopropyl, heptafluoroisopropyl, and haloaryl groups, such as ortho-, meta-, and para-chlorophenyl.

[0095] Group R 1 Examples include the alkyl groups listed above for R, as well as hydroxyl, methoxy, ethoxy, and hexoxyethyl groups, wherein the group R... 1 Preferably, it contains methyl, ethyl, hydroxy, methoxy, and ethoxy groups.

[0096] Group A is of formula -R 2 -[NR 3 -R 4 -] n NR 3 The 2 has a monovalent group containing at least one basic amino group.

[0097] R 2 Examples are divalent groups, such as methylene, 1,2-ethylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, and 1,6-hexylene.

[0098] Particularly preferred examples are 1,3-propylidene and 1,3-butylidene.

[0099] R 4 Examples are divalent groups, such as 1,2-ethylidene, 1,3-propylidene, 1,3-butylidene, 1,4-butylidene, 1,5-pentylidene, and 1,6-hexylidene.

[0100] A particularly preferred example is 1,2-ethylene.

[0101] Preferably, R 3 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acetyl group.

[0102] Alkyl R 3 Examples include methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, and hexyl, such as n-hexyl and isohexyl. Group R 3 Preferred examples are hydrogen atoms or methyl groups; hydrogen atoms are particularly preferred.

[0103] Examples of group A are:

[0104] -(CH2)3NH2

[0105] -(CH2)3-NH-(CH2)2-NH2

[0106] -CH2CH(CH3)CH2-NH-(CH2)2-NH2

[0107] -(CH2)3-NH (cyclohexyl)

[0108] -(CH2)3-NHCH3

[0109] -(CH2)3-NHCH2CH3

[0110] -(CH2)4-NH2

[0111] -CH2CH(CH3)CH2-NH2

[0112] -(CH2)3-NH-(CH2)2-NHCH3

[0113] -(CH2)3-NH-(CH2)2-NHCH2CH3

[0114] -(CH2)3[-NH-CH2CH2]2-NH2.

[0115] Examples of group Y are:

[0116] -(CH2)3-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-(CH2)3-

[0117] -(CH2)3-NH-(CH2)2-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-(CH2)2-NH-(CH2)3-

[0118] -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-

[0119] -(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-

[0120] -(CH2)3-N(CH2CH3)-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-N(CH2CH3)-(CH2)3-

[0121] -(CH2)4-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-(CH2)4-

[0122] -CH2CH(CH3)CH2-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-CH2CH(CH3)CH2-

[0123] -(CH2)3-NH-(CH2)2-NCH3-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NCH3-(CH2)2-NH-(CH2)3-

[0124] -(CH2)3-NH-(CH2)2-N(CH2CH3)-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-N(CH2CH3)-NH-(CH2)3-

[0125] -(CH2)3[-NH-CH2CH2]2-NH-C(O)-C(O)-NH-Z-NH-C(O)-C(O)-NH-[CH2CH2-NH-]2(CH2)3-,

[0126] Z has the meaning indicated by the above.

[0127] Examples of group Z are divalent hydroxyl groups, such as polyethylene glycol groups or polypropylene glycol groups, or mixtures of polyethylene glycol and polypropylene glycol groups. 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.

[0128] Examples of group Z are:

[0129] -(CH2-CH2-O) m -CH2-CH2-

[0130] -(CH(CH3)-CH2-O) m -CH2-CH(CH3)-

[0131] -(CH(CH3)-CH2-O) x -(CH2-CH2-O) y -(CH(CH3)-CH2-O) z -CH2-CH(CH3)-

[0132] The average value of m is 1 to 80, with a preferred value of 2 to 50.

[0133] Furthermore, x, y, and z are each 0 or an integer, provided that the sum of x + y + z averages between 2 and 80, preferably between 3 and 50.

[0134] Preferred examples of group z are:

[0135] -(CH2-CH2-O)2-CH2-CH2-

[0136] -(CH(CH3)-CH2-O) 约2.5 -CH2-CH(CH3)-

[0137] -(CH(CH3)-CH2-O) 约6.1 -CH2-CH(CH3)-

[0138] -(CH(CH3)-CH2-O) 约33 -CH2-CH(CH3)-

[0139] -(CH(CH3)-CH2-O) 约0.6 -(CH2-CH2-O)2-(CH(CH3)-CH2-O) 约0.6 -CH2-CH(CH3)-

[0140] -(CH(CH3)-CH2-O) 约1.8 -(CH2-CH2-O)9-(CH(CH3)-CH2-O) 约1.8 -CH2-CH(CH3)-

[0141] -(CH(CH3)-CH2-O) 约3 -(CH2-CH2-O) 约12.6 -(CH(CH3)-CH2-O) 约3 -CH2-CH(CH3)-

[0142] -(CH(CH3)-CH2-O) 约3 -(CH2-CH2-O) 约39 -(CH(CH3)-CH2-O) 约3 -CH2-CH(CH3)-

[0143] The emulsifier (2) used in the dispersion of the present invention may be any emulsifier known to those skilled in the art for preparing organosilicon emulsions, such as nonionic, anionic, cationic or amphoteric emulsifiers; the emulsifier (2) may be used alone or as a mixture of different emulsifiers.

[0144] The following are (non-limiting) examples of nonionic emulsifiers used:

[0145] 1. Alkyl polyethylene glycol ethers, preferably those having 3 to 40 EO units and 8 to 20 carbon atoms of alkyl groups.

[0146] 2. Carboxylic acid polyethylene glycol esters, more particularly fatty acid polyethylene glycol esters, preferably those having more than 6 EO units and carboxylic acid groups with 8 to 20 carbon atoms.

[0147] 3. Ethoxylated or non-ethoxylated sorbitol fatty acid esters.

[0148] 4. Ethoxylated castor oil or hydrogenated variants.

[0149] 5. Polyglycerol carboxylate.

[0150] 6. Formula R*-OG o Alkyl polysaccharide glycosides, wherein R* is a linear or branched, saturated or unsaturated alkyl group having an average of 8-24 carbon atoms, and G o It is an oligoglycoside group having an average of 1-10 hexose or pentose units or mixtures thereof.

[0151] 7. Alkyl aryl polyethylene glycol ethers, preferably those having 5 to 30 EO units and having 8 to 20 carbon atoms in the alkyl and aryl groups.

[0152] 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 40 EO and PO units.

[0153] 9. Polyvinyl alcohol, which also contains 5 to 50 mol%, preferably 8 to 20 mol%, vinyl acetate units, with a degree of polymerization of 500 to 3000.

[0154] 10. An adduct of an alkylamine having an alkyl group having 8 to 22 carbon atoms with ethylene oxide or propylene oxide.

[0155] 11. Natural substances and their derivatives, such as lecithin, lanolin, saponins, cellulose; cellulose alkyl ethers and carboxyalkyl cellulose, wherein each alkyl group has at most four carbon atoms.

[0156] 12. Linear organo(poly)siloxanes containing polar groups, particularly those containing elements O, N, C, S, P, Si, and even more particularly those organo(poly)siloxanes having alkoxy groups containing up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

[0157] 13. Fatty acids having up to 6 to 24 carbon atoms.

[0158] Preferred nonionic emulsifiers are:

[0159] 1. Alkyl polyethylene glycol ethers, preferably those having 3 to 30 EO units and 8 to 20 carbon atoms of alkyl groups, such as cetearyl alcohol polyether-20, oleyl alcohol polyether-10, oleyl alcohol polyether-20, lauryl alcohol polyether-3, lauryl alcohol polyether-4, lauryl alcohol polyether-20, lauryl alcohol polyether-23, tridecyl alcohol polyether-5, tridecyl alcohol polyether-6, tridecyl alcohol polyether-8, tridecyl alcohol polyether-10, tridecyl alcohol polyether-12, tridecyl alcohol polyether-16, tridecyl alcohol polyether-20, stearyl alcohol polyether-20 or stearyl alcohol polyether-21 (as named according to INCI).

[0160] 2. Carboxylic acid polyethylene glycol esters, more particularly fatty acid polyethylene glycol esters, preferably those having more than 6 EO units and carboxylic acid groups with 8 to 20 carbon atoms, such as PEG-20 laurate, PEG-7 olive oil ester, PEG-8 oleate, PEG-8 laurate, PEG-4 stearate, PEG-6 stearate, PEG-20 stearate or PEG-100 stearate (as named according to INCI).

[0161] 3. Ethoxylated or non-ethoxylated sorbitol fatty acid esters, such as sorbitol laurate, polysorbate 20, polysorbate 60, polysorbate 80 or polysorbate 85 (as named according to INCI).

[0162] 4. Ethoxylated castor oil or hydrogenated variants, such as (as specified in INCI nomenclature) PEG 200 castor oil or PEG-60 hydrogenated castor oil.

[0163] 5. Polyglycerol carboxylate, such as polyglycerol-10 oleate, polyglycerol-10 laurate, or polyglycerol-10 stearate.

[0164] 6. Formula R*-OG o Alkyl polysaccharide glycosides, wherein R* is a linear or branched, saturated or unsaturated alkyl group having an average of 8-24 carbon atoms, and G o It is an oligoglycoside group having an average of 1-10 hexose or pentose units or mixtures thereof, such as Glucopon 215, Glucopon 225, Glucopon 600 (named according to trade name).

[0165] Non-limiting examples of anionic emulsifiers are as follows:

[0166] 1. Alkyl sulfates, particularly those with a chain length of 8 to 18 carbon atoms, alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in a hydrophobic group and 1 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units.

[0167] 2. Sulfonates, particularly alkyl sulfonates having 8 to 18 carbon atoms, alkyl aryl sulfonates having 8 to 18 carbon atoms, taurides, sulfosuccinic acid, and esters and monoesters of monohydric alcohols or alkylphenols having 4 to 15 carbon atoms; these alcohols or alkylphenols may also optionally be ethoxylated with 1 to 40 EO units.

[0168] 3. Alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in alkyl, aryl, alkylaryl or aralkyl groups, more particularly alkali metal and ammonium salts of fatty acids, preferably those carboxylic acid groups having 8 to 20 carbon atoms.

[0169] 4. Phosphate metaesters and their alkali metal and ammonium salts, particularly alkyl and alkylaryl phosphates having 8 to 20 carbon atoms in the organic group, and alkyl ether phosphates and alkylaryl ether phosphates having 8 to 20 carbon atoms in the alkyl or alkylaryl group and 1 to 40 EO units.

[0170] Preferred anionic emulsifiers are:

[0171] 1. Alkyl sulfates, such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium alkyl sulfonate of secondary C13-C18 alkane, sodium lauryl sulfate of C12-C18 fatty alcohol, alkyl ether sulfates, such as ammonium alkyl ether sulfate of C12-C14 fatty alcohol, ammonium alkyl ether sulfate of C12-C14 fatty alcohol, and alkyl aryl ether sulfates, such as sodium alkylbenzene sulfonate of secondary C10-C13.

[0172] 2. Alkyl sulfonates, such as disodium 2-sulfolanoate.

[0173] 3. Alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in alkyl, aryl, alkylaryl, or aralkyl groups; particularly preferred anionic emulsifiers are alkali metal and ammonium salts of fatty acids, preferably those with carboxylic acid groups having 8 to 20 carbon atoms, such as sodium, potassium, or triethanolamine salts of lauric acid, myristic acid, palmitic acid, stearic acid, or oleic acid.

[0174] 4. Phosphate esters, such as sodium salt of C8 / C10 fatty alcohol phosphate ester (Crodaphos 810A) or monoethanolamine salt.

[0175] Non-limiting examples of cationic emulsifiers are as follows:

[0176] 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.

[0177] 2. Alkylpyridine, alkylimidazoline and alkyloxazoline salts, especially those whose alkyl chains have up to 18 carbon atoms, particularly halides, sulfates, phosphates and acetates.

[0178] 3. Quaternary alkylammonium and alkylphenylammonium salts, especially those whose alkyl groups have 6 to 24 carbon atoms, and even more particularly halides, sulfates, phosphates and acetates.

[0179] Non-limiting examples of amphoteric emulsifiers are as follows:

[0180] 1. Amino acids with long-chain substitutions, such as N-alkyl-di(aminoethyl)glycine or N-alkyl-2-aminopropionate.

[0181] 2. Betaines, such as N-(3-acylaminopropyl)-N,N-dimethylammonium salts having C8-C18 acyl groups, and quaternized or substituted alkyl derivatives of alkylimidazolium betaine or N,N-dimethylglycine.

[0182] Preferred emulsifiers for preparing aqueous dispersions of pre-crosslinked hydrophilic organopolysiloxanes are nonionic emulsifiers, and more particularly the alkyl polyethylene glycol ethers listed above.

[0183] Component (2) may consist of one or a mixture of two or more of the emulsifiers described above; it may be used in pure form or as a solution of one or more emulsifiers in water or an organic solvent.

[0184] Non-aqueous solvents or co-emulsifiers (6) may optionally be used as other components in the dispersions of the present invention.

[0185] The dispersion of the present invention contains a non-aqueous solvent or co-emulsifier (6) in an amount preferably at least 0.1% by weight, more preferably at least 0.4% by weight, more particularly at least 0.8% by weight, and preferably at most 20% by weight, more preferably at most 15% by weight, and more particularly at most 10% by weight.

[0186] The non-aqueous solvent (6) that can be used in the aqueous dispersion of the present invention is derived from, for example, monohydric or polyhydric alcohols, alkanolamines or diol ethers.

[0187] 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, glycols, propylene glycol, and 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, diethylene glycol, propyl or butyl diethylene glycol, 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-β-butyl ether, propylene glycol tert-butyl ether, methoxytriethylene glycol, ethoxytriethylene glycol, butoxytriethylene glycol, 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 Acrylates, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl and hexyl acetates; methyl, ethyl and tert-butyl propionates; methyl, ethyl, propyl and butyl butyrates; 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.

[0188] Examples of preferred non-aqueous solvents or co-emulsifiers (6) are 1-alkanols having C5 to C8 chains listed above, alkanediols having C4 to C8 chains listed above, glycerol, propyl, butyl and pentyl acetates, 2-pentanone, and ethylene glycol, propylene glycol, dipropylene glycol or diethylene glycol monoalkyl ethers listed above.

[0189] Particularly preferred non-aqueous solvents or co-emulsifiers (6) are 1-pentanol, 1-hexanol, 1-octanol, propylene glycol, 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 monobutyl ether, and propylene glycol methyl ether.

[0190] Another possibility is to use polyalkylene glycols, such as polyethylene glycol (e.g., PEG600, PEG1000, or PEG6000) or polypropylene glycol (e.g., PPG2000), polyalkylene block polymers, such as so-called poloxamers (block copolymers of ethylene oxide and propylene oxide units), such as PEG-PPG-PEG block polymers. L-31, PEG-PPG-PEG block polymer L-61, PPG-PEG-PPG block polymer 17R4, PPG-PEG-PPG Block polymer 31R1 (available from Sigma-Aldrich), or poloxamine (a copolymer of ethylene oxide and propylene oxide units bridged via ethylenediamine cores), such as Tetronic 701 or Tetronic 90R4 (available from Sigma-Aldrich), are used as co-emulsifiers.

[0191] As other components in the dispersion of the present invention, (7) additives such as pH adjusters, salts, foam inhibitors, thickeners and / or protective colloids, preservatives, disinfectants, wetting agents, corrosion inhibitors, dyes, fragrances or mixtures thereof may be optionally used.

[0192] All known acids and bases can be used as pH adjusters, provided that they are not prohibited from use for performance or environmental reasons or for consumer protection reasons.

[0193] The acid used here is used to establish the desired pH, or it can form an acid addition salt with the amino-containing groups (A) or (Y) of the pre-crosslinked organopolysiloxane (1).

[0194] Examples of inorganic acids that can react with amino-containing groups (A) or (Y) mentioned above include 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 include formic acid, acetic acid, propionic acid, butyric 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.

[0195] Acetic acid, lactic acid, and formic acid are particularly preferred.

[0196] Examples of salts (electrolytes) are more particularly those from the group of inorganic salts, of which any of a wide variety can be widely used. Preferred cations are alkali metals and alkaline earth metals; preferred anions are halide ions and sulfate ions. From a preparation point of view, it is preferred to use sodium acetate or sodium chloride in the aqueous emulsion of the present invention.

[0197] Examples of foam inhibitors are soap, paraffin, or silicone oil.

[0198] Examples of preservatives include 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.

[0199] In the method of the present invention for preparing pre-crosslinked organopolysiloxanes (1) and their aqueous dispersions, those selected from the following formulas are preferably used as organopolysiloxanes (4):

[0200] [ARSiO 2 / 2 ] j [R2SiO 2 / 2 ] l [R 3-e (OR 7 ) e SiO 1 / 2 ]2 (VIa),

[0201] [A(OR 1 SiO 2 / 2 ] j [R2SiO 2 / 2 ] l [R 3-e (OR 7 ) e SiO 1 / 2 ]2 (VIb),

[0202] and their mixtures,

[0203] Among them, A, R, R 1 and R 7 And j, l, and e have the meanings indicated above for them.

[0204] In the preparation of the dispersion of the present invention, an oxaloylamino ester-terminated polyether (5) of formula (V) can be used.

[0205]

[0206] Or different types of oxalamid-terminated polyethers of formula (V) (5),

[0207] Where R 3 R 8 Z has the meaning indicated above.

[0208] Examples of oxalamidoester-terminated polyethers (5) are as follows:

[0209]

[0210] The average value of m is 1 to 80, with a preferred value of 2 to 50.

[0211] Furthermore, x, y, and z are each 0 or an integer, provided that the sum of x + y + z averages between 2 and 80, preferably between 3 and 50.

[0212] Preferred examples of oxalamido ester-terminated polyethers (5) are:

[0213]

[0214]

[0215] In the method of the present invention for preparing pre-crosslinked organopolysiloxanes (1) and aqueous dispersions thereof, the amount of oxalamido ester-terminated polyether (5) is preferably at least 0.1 moles, more preferably at least 0.15 moles, and more preferably at most 1 mole, more preferably at most 0.75 moles per mole of amino group in the organopolysiloxane (4).

[0216] Oxaloamino ester-terminated polyethers (5) are known and described, for example, in N. Fukada, Bull. Chem. Soc. Jpn., 69, 1397-1401 (1996). Oxaloamino ester-terminated polyethers (5) are separated as trace products as byproducts after chromatographic separation.

[0217] The oxalamido ester-terminated polyether (5) can specifically be prepared from an amino-terminated polyether using a diester of oxalate (such as diethyl oxalate), for example, if the diester of oxalate is used in stoichiometric excess and the excess is subsequently removed by distillation. In this case, the diester of oxalate is preferably used in a 2-20 molar excess, more preferably in a 2-10 molar excess.

[0218] Therefore, the oxalamid-terminated polyether (5) is preferably prepared by reacting the amino-terminated polyether with an oxalate diester of the following formula:

[0219] R 8 -OC(=O)-C(=O)-OR 8

[0220] Where R 3 R 8 Z and Z have the meanings indicated above, provided that the amount of oxalate diester is preferably 2 to 20 moles, more preferably 2 to 10 moles of oxalate diester per mole of amino-terminated polyether.

[0221] The dispersion of the pre-crosslinked organopolysiloxane (1) of the present invention is produced by vigorously mixing the organopolysiloxane (4) with the following substances:

[0222] Oxaloylamino ester-terminated polyether (5),

[0223] Water (3),

[0224] Emulsifier (2),

[0225] Optional non-aqueous solvents or co-emulsifiers (6), and

[0226] Optional adjuvants (7).

[0227] In each case, based on the total weight of the dispersion, the dispersion of the present invention is prepared using the following amounts of organopolysiloxane (4): 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, and very preferably at most 35% by weight.

[0228] The mixing properties of the components required to prepare the dispersion of the present invention are not particularly critical and can be carried out in various orders. However, depending on components (2), (3), (4), (5), optional (6) and optional (7), there may be preferred steps, which should be examined as appropriate.

[0229] For example, components (4) and (5) can be premixed together before adding one or more emulsifiers (2) and optionally the component (6), and then water (3) and optionally the component (7) can be added. Components (2) through (7) can also be metered into the emulsification apparatus in sequence. In certain cases, due to the viscosity or reactivity of the siloxane, it may be advantageous, for example, to mix the oxalamid-terminated polyether (5) with the organopolysiloxane (4) and then introduce a different organopolysiloxane (4), or vice versa, depending on how to produce more favorable rheological properties for component treatment.

[0230] In addition, oxalamido ester-terminated polyether (5) can be added to the complete emulsion of organopolysiloxane (4) to achieve the desired reaction and crosslinking of organopolysiloxane (4) in the emulsion and to form a dispersion of crosslinked organopolysiloxane (1) of the present invention.

[0231] When preparing dispersions, alcohol R is obtained as a byproduct of condensation. 8 OH (where R) 8 (with the meanings indicated above) may be retained in the product or removed, for example, by vacuum distillation, membrane technology, or extraction.

[0232] The emulsification step for preparing the aqueous emulsion of the crosslinked organopolysiloxane (1) of the present invention is preferably carried out at a temperature of at least 10°C, more preferably at least 15°C, and more preferably at most 80°C, more preferably at most 70°C.

[0233] Preferably, the temperature is increased by introducing the mechanical shear energy required for the emulsification process. The temperature increase is not intended to accelerate the chemical process (more specifically, crosslinking). Furthermore, the method of the present invention is preferably carried out at ambient atmospheric pressure, but can also be carried out at higher or lower pressures.

[0234] Preparation can be carried out in batches or continuously.

[0235] Techniques for preparing organopolysiloxane emulsions are known. Therefore, vigorous mixing and dispersion can be carried out in rotor-stator mixers, colloid mills, high-pressure homogenizers, microchannels, membranes, nozzles, etc., or by means of ultrasound. Homogenization apparatus and techniques are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, CD-ROM edition 2011, Wiley-VCH Verlag, under the title "Emulsions".

[0236] The average particle size of the dispersion of the present invention, as measured by light scattering, is preferably 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 3 to 9, and more preferably 4 to 8.

[0237] The pre-crosslinked organopolysiloxane (1) or its aqueous dispersion of the present invention is used as an active ingredient in products for treating substrates, preferably fiber substrates, more preferably textiles, especially in compositions for caring for and cleaning substrates, preferably fiber substrates, more preferably textiles.

[0238] One subject of the present invention is a composition for treating a substrate, preferably a fibrous substrate, and more particularly for textiles, the composition comprising an aqueous dispersion of the pre-crosslinked organopolysiloxane (1) of the present invention, or the pre-crosslinked organopolysiloxane (1) of the present invention.

[0239] Therefore, another subject of the present invention is the use of the pre-crosslinked organopolysiloxane (1) or its aqueous dispersion thereof in the treatment of compositions for use with substrates, preferably fibrous substrates, more preferably textiles, especially for use with care and cleaning substrates, preferably fibrous substrates, more preferably textiles.

[0240] The term "active ingredient" here refers to a substance that serves the following purpose:

[0241] (a) Provide care for the article, in other words, maintain the article in its original form, reduce or prevent the effects of external influences (e.g., time, light, temperature, pressure, contamination, chemical reactions with other reactive compounds in contact with the article), such as aging, contamination, material fatigue, discoloration, or even improve the desired positive properties of the article.

[0242] Examples of improvements in the softness of textile fibers and fabrics include: significantly improved softness after washing; reduced wrinkling during rinsing and drying; reduced wrinkling or crease formation before ironing; reduced force required to iron fabrics; prevention of wrinkling during use; maintenance of the shape of textile fabrics during washing, care, and use; improved wettability of fibers / fabrics; reduced pilling (i.e., the formation of fuzz or fluff) in textile fabrics; suppression of the drying stiffness effect that occurs in dried clothes; greater elasticity in fibers / fabrics; improved luster in fibers; or reduced color fading in fibers / fabrics.

[0243] The term "active ingredient" should be further understood to refer to substances that fulfill the following purposes:

[0244] (b) Cleaning products, in other words, removing or supporting the removal of impurities generated by the use of the products.

[0245] In this context, products (more specifically compositions) used for care and cleaning should be understood to include the following formulations or compositions:

[0246] Preparations used in homes and industries for the care and cleaning of surfaces such as fibers, leather, fabrics, wood, glass, ceramics, tiles, linoleum, and plastics.

[0247] Examples of products used for cleaning and caring for such surfaces include laundry detergents (heavy-duty laundry detergents, color-safe laundry detergents, fabric softeners, etc.), dishwashing detergents, machine-washable dishwashing detergents, rinsing aids, neutral detergents, window cleaning products, multi-purpose cleaners, glass cleaners, sanitary cleaners, toilet cleaners, carpet cleaners, and car care products.

[0248] In each case, based on the total weight of the composition, the amount of the aqueous dispersion of the present invention in these compositions is preferably 0.1 to 40% by weight, more preferably 0.2 to 30% by weight, and very preferably 0.4 to 20% by weight.

[0249] The compositions using the aqueous dispersions of the present invention can be in the form of W / O emulsions (water-in-oil emulsions), O / W emulsions (oil-in-water emulsions), or complex emulsions.

[0250] Water is the preferred medium in the composition.

[0251] These preferred compositions typically comprise an emulsion in which one phase of finely dispersed droplets surrounded by an emulsifier shell exists in a second phase (water droplets in a W / O emulsion or lipid vesicles in an O / W emulsion).

[0252] The droplet diameter of a “microemulsion” is approximately 0.01 μm to approximately 0.1 μm. In the case of “macroemulsions”, the droplet diameter is approximately 0.1 μm to approximately 50 μm.

[0253] Such a "coarse emulsion" is milky white and opaque in color without further coloring additives. Similarly, a finer "coarse emulsion" with droplet diameters of approximately 0.1 μm to approximately 1 μm is bluish-white and opaque in color without coloring additives.

[0254] "Microemulsion" is a transparent or translucent emulsion.

[0255] The clear and transparent appearance is due to the retention of micelles and molecular solutions with particle sizes smaller than about 0.01 μm.

[0256] In the following embodiments, unless otherwise specified, all statements of portions and percentages are based on weight.

[0257] Unless otherwise indicated, the following examples were carried out at ambient atmospheric pressure (in other words, at about 1000 hPa) and room temperature (in other words, about 20°C), or at temperatures reached when the reactants are combined at room temperature without additional heating or cooling.

[0258] For HLB values, the HLB values ​​reported by the respective manufacturers are used. This is because emulsifiers (such as polyethers) are primarily oligomers / polymers with a specific molecular weight distribution, which may vary from manufacturer to manufacturer. Therefore, different manufacturers may make different statements regarding the corresponding HLB values, and this may differ from the theoretical HLB for a specific chemical name.

[0259] Dynamic viscosity was measured on an “MCR 302” rheometer (obtained from Anton Paar) using a cone-plate system (CP50-2 cone) with an opening angle of 2°, according to DIN EN ISO 3219:1994 and DIN 53019. The instrument was calibrated using 10000 standard oil obtained from Physikalisch-Technische Bundesanstalt [German National Metrology Institute]. The measurement temperature was 25.00℃ ± 0.05℃, and the measurement time was 3 minutes. The viscosity plot (recorded in mPa·s) represents the arithmetic mean of three independently performed measurements. The measurement uncertainty of dynamic viscosity was 1.5%. The shear rate gradient was selected according to the viscosity and determined individually for each viscosity plot.

[0260] According to DIN 51562-Part 1 or ISO / DIS 3105 (including their calibration), use Schott The AVS 350 viscosity measurement system uses a Ubbelohde viscometer tube with a constant (e.g., from Windaus or VWR) to determine kinematic viscosity. Measurements are performed at 25.0°C (±0.1°C). Viscosity graph (in mm) 2 (Reported by / s) represents the arithmetic mean of three independently performed measurements: the measurement uncertainty for kinematic viscosity is 1.05%. Depending on the measurement range, different viscometer tubes with corresponding orientation constants are used.

[0261] Measurement range Capillary tube No. Orientation constant <![CDATA[0.5-3mm 2 / s]]> 0c 0.003K <![CDATA[0.8-5mm 2 / s]]> 0a 0.005K <![CDATA[1.2-10mm 2 / s]]> I 0.01K <![CDATA[3-30mm 2 / s]]> Ic 0.03K <![CDATA[10-100mm 2 / s]]> II 0.10K <![CDATA[30-300mm 2 / s]]> IIc 0.30K <![CDATA[100-1000mm 2 / s]]> III 1K <![CDATA[300-3000mm 2 / s]]> IIIc 3K <![CDATA[1000-10 000mm 2 / s]]> IV 10K

[0262] According to VWR-Laborkatalog, 2011-2013, page 645.8, the measurement range, corresponding capillary number, and constant are reported.

[0263] The amine value is equivalent to the number of mmol of KOH per gram of the analyte. The amine value is determined according to DIN 16945 – Version 1989-03.

[0264] 1 H-NMR spectroscopy was performed at a measurement frequency of 500.13 MHz on a Bruker Avance 500 NMR spectrometer (5mm selective). 1 The data was recorded using a solution in CDCl3 on the H-NMR sample head.

[0265] The evaluation was conducted in a manner known to those skilled in the art and is described in the following references: die 1 H-, 13 C-and 29 Si-NMR chemischen Verschiebungen einiger linearer,verzweigter undcyclischer Methyl-Siloxan-Verbindungen" [On the 1 H-, 13 C-and 29Si NMR chemical shifts of certain linear, branched and cyclic methyl-siloxane compounds], G.Engelhardt, H.Jancke; J.Organometal.Chem.28 (1971), 293-300; "Chapter 8-NMRspectroscopy of organosilicon compounds", Elizabeth A.Williams, The Chemistryof Organic Silicon Compounds, 1989John Wiley and Sons Ltd,511-533.

[0266] Particle size was determined using dynamic light scattering (Mie measurement method) on a Zetasizer Nano-S particle size analyzer (from Malvern, software version 6.01). For this purpose, the dispersion was diluted to 0.5% by weight with filtered and degassed water. The reported values ​​always refer to the D(50) value. D(50) is understood as the volume average particle size of 50% of all measured particles having a volume average diameter less than the determined D(50) value. Measurements were performed at 25°C with the following settings established: water refractive index (Dispersant RI) of 1.330; viscosity (cP) of 0.8872; dispersed phase refractive index (Material Ri) of 1.39; material absorption at 0.010; measurement duration (Duration Used) of 50 seconds; and measurement position of 0.65 mm. The photon count rates reported in the dispersion examples were obtained from the corresponding dilutions of the samples and are therefore different. Importantly, the measurement procedure publishes the results with the notation "Result Quality: Good".

[0267] Example 1: Oxaloylamino ester-terminated polyether A

[0268] On a rotary evaporator, using a hot oil bath under reduced pressure of 0.1 mbar and a hot bath temperature of 100°C, 200 g of α,ω-diamino-terminated polyether (trade name can be used) was evaporated in a 1 L round-bottom flask. ED-600 (purchased from Huntsman Corporation) dehydrates for 2 hours to remove trace amounts of water and volatile components. ED-600 has an amine value of 3.3 milliequivalents / g (MG = 606 g / mol).

[0269] Under a protective nitrogen atmosphere and with vigorous stirring, 243 g of diethyl oxalate (1.66 mol) (obtained from Sigma-Aldrich (St. Louis, Missouri / USA)) was slowly and dropwise mixed with 100 g of dehydrated Jeffamine ED-600 (0.33 mol of NH2) so that the reaction mixture temperature did not rise above 50 °C. The mixture was then stirred further at room temperature for 1 hour. The excess diethyl oxalate was subsequently distilled off using a rotary evaporator under reduced pressure (1 mbar) and a bath temperature of 90 °C. This yielded 222.3 g of a clear, pale yellow liquid.

[0270] Example 2: Oxaloylamino ester-terminated polyether B

[0271] Under a protective nitrogen atmosphere and vigorous stirring, 883 g of diethyl oxalate (6.04 mol) (obtained from Sigma-Aldrich (St. Louis, Missouri / USA)) was slowly and dropwise mixed with 100 g (1.14 mol) of 3,3'-ethylenedioxybis(propylamine) (MW = 176 g / mol) (trade name available) EDR-176 (purchased from Huntsman Corporation) was mixed so that the reaction mixture did not rise above 50°C. The mixture was then stirred further at room temperature for 1 hour. The excess diethyl oxalate was subsequently distilled off using a rotary evaporator under reduced pressure (1 mbar) and a bath temperature of 90°C. This produced a clear, light brown liquid.

[0272] Example 3: Oxaloylamino ester-terminated polyether C

[0273] On a rotary evaporator, using an oil-heated bath under reduced pressure of 0.1 mbar and a bath temperature of 100°C, 250 g of α,ω-diamino-terminated polyether (trade name can be used) was evaporated in a 1 L round-bottom flask. D-2000 (purchased from Huntsman Corporation) dehydrates for 2 hours to remove trace amounts of water and volatile components. D-2000 has an amine value of 1.015 milliequivalents / g (MG = 1970 g / mol).

[0274] Under a protective nitrogen atmosphere and with vigorous stirring, 296.66 g of diethyl oxalate (2.03 mol) (obtained from Sigma-Aldrich (St. Louis, Missouri / USA)) was slowly and dropwise mixed with 200 g (0.20 mol) of dehydrated NH2. The D-2000 mixture was stirred until the reaction mixture was not heated above 50°C. The mixture was then stirred further at room temperature for 1 hour. The excess diethyl oxalate was subsequently distilled off using a rotary evaporator under reduced pressure (1 mbar) and a bath temperature of 90°C. This produced a clear, light brown liquid.

[0275] (Comparative) Example 4: Emulsion of amino-functionalized polydimethylsiloxane CE1 (Not an invention)

[0276] Premix 1.6 g of 80% isotrimethylene decaethoxylate aqueous solution (available from BASF under the trade name Lutensol TO 10), 5.8 g of isotrimethylene pentaethoxylate (available from BASF under the trade name Lutensol TO 5), 2.5 g of completely softened water, and 0.3 g of 80% acetic acid at 5000 rpm using Ultra-Turrax T 50 emulsifier (available from Janke & Kunkel / IKA).

[0277] The premix was mixed in four batches with 14.8 g of a hydroxyl / methoxy-terminated copolymer conditioned at 40 °C. This copolymer consisted of 3-(2-aminoethylamino)propylmethylsiloxy units and dimethylsiloxy units, and had an amine value of 0.30 mequ / g and a molecular weight ratio of 800-1800 mmHg. 2 The viscosity was set at 25.0 °C; capillary number IIIc, with each batch introduced at 5000 rpm shear and homogenized within 2 minutes. Slow dilution was performed in batches at 4000 rpm with 70.0 g of completely softened water to produce the desired emulsion. 0.9 g of 2-phenoxyethanol (available under the trade name S&M Phenoxyethanol (Schülke and Mayr GmbH and CO KG)) and 4.0 g of 86% glycerol were added, followed by homogenization at 4000 rpm for another 2 minutes.

[0278] This produces a transparent to milky white, colorless, low-viscosity microemulsion with a solids content of 27% and a pH of 5.5. The emulsion remains stable and homogeneous even during storage.

[0279] (Comparative) Example 5: Emulsion of amino-functionalized polydimethylsiloxane CE2 (Not an invention)

[0280] Emulsion CE2 with a particle size D(50) of 28 nm (at a photon count rate of 286 kcps) was prepared using an LDV 1 dissolver (from PC Laborsystem) as follows: 6.5 g of isotridecylpentaethoxylate (available from BASF under the trade name TO 5), 20.0 g of a copolymer of 3-(2-aminoethylamino)propylmethylsiloxy units and dimethylsiloxy units (with an amine value of 0.13 mequ / g and a particle size of 3900 nm). 2 The emulsion contained 2.9 g of glycerol, 0.12 g of 80% acetic acid, 0.19 g of N-morpholinomethyltriethoxysilane, and 70 g of water. 0.13 g of 2-phenoxyethanol (available under the trade name S&M Phenoxyethanol (Schülke and Mayr GmbH and CO KG)) was introduced into the emulsion by mixing.

[0281] (Comparative) Example 6: Emulsion of amino-functionalized polydimethylsiloxane CE3 (Not an invention)

[0282] At 5000 rpm, premix 6.0 g of C11-15 alkanol polyether-7 (ethoxylated secondary alcohol, 7 ethylene oxide units) (available from Dow under the trade name Tergitol 15-S-7) and 1.9 g of hot, completely softened water using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA). Weigh 1.0 g of lauryl ethoxylate-9 (ethoxylated primary alcohol, 9 ethylene oxide units) (available from KLK Kolb under the trade name Sympatens AL / 090), 3.0 g of molten isotrimethylene dodecyl ethoxylate (available from BASF under the trade name Lutensol TO 12), and 1.9 g more hot, completely softened water into the premix, and homogenize the mixture at 5000 rpm for 2 minutes. Subsequently, 2.3 g of 86% glycerol was metered in and the mixture was homogenized at 5000 rpm for 2 minutes. Then, 20.0 g of a hydroxyl / methoxy-terminated copolymer of 3-(2-aminoethylamino)propylmethylsiloxy and dimethylsiloxy units was added to the mixture in three batches. This copolymer had an amine value of 0.25 mequ / g and a molecular weight of 1500-2100 mmHg. 2The viscosity was [value] / s (25.0 °C; capillary no. IIIc), and homogenized for 2 minutes in each case, sheared at 5000 rpm. 0.9 g of 2-phenoxyethanol (available under the trade name S&M Phenoxyethanol (Schülke and Mayr GmbH and CO KG)) and 0.4 g of 80% acetic acid were added, followed by homogenization at 5000 rpm for another 2 minutes. Slow dilution was performed in batches at 4000 rpm with 62.6 g of completely softened water to produce the desired emulsion.

[0283] This produces a transparent to milky white, colorless, low-viscosity microemulsion with a solids content of 33% and a pH of 5.0.

[0284] Example 7: Emulsion of amino-functionalized polydimethylsiloxane crosslinked with oxalamido ester-terminated polyether E4

[0285] At 5000 rpm, using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA), 99.26 g of emulsion CE1 was homogenized with 0.74 g of oxalamidoester-terminated polyether A (approximately 5% by weight, based on amino-functionalized polydimethylsiloxane) for one minute. This produced a low-viscosity, transparent to slightly cloudy, colorless to slightly yellow emulsion with a solids content of 28% and a pH of 5.0. E4 .

[0286] After drying at 25°C for 1-3 days, the evaporation of the emulsion produces a significantly white, elastic, and soft film that adheres well to the aluminum and is not sticky on the surface.

[0287] Example 8: Emulsion of amino-functionalized polydimethylsiloxane crosslinked with oxalamido ester-terminated polyether E5

[0288] At 5000 rpm, using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA), 99.70 g of emulsion CE1 was homogenized with 0.30 g of oxalamidoester-terminated polyether B (approximately 2 wt%, based on amino-functionalized polydimethylsiloxane) for one minute. This produced a low-viscosity, transparent to slightly cloudy, colorless to slightly yellow emulsion with a solids content of 27% and a pH of 5.0. E5 .

[0289] After drying at 25°C for 1-3 days, the evaporation of the emulsion produces a significantly white, elastic, and soft film that adheres well to the aluminum and is not sticky on the surface.

[0290] Example 9: Emulsion of amino-functionalized polydimethylsiloxane crosslinked with oxalamido ester-terminated polyether E6

[0291] At 5000 rpm, using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA), 98.52 g of emulsion CE1 was homogenized with 1.48 g of oxalamidoester-terminated polyether C (approximately 10% by weight, based on amino-functionalized polydimethylsiloxane) for one minute. This produced a low-viscosity, turbid, colorless to slightly yellow emulsion with 28% solids content and a pH of 5.0. E6 .

[0292] After drying at 25°C for 1-3 days, the evaporation of the emulsion produces a white, elastic, and soft film that adheres well to the aluminum and is not sticky on the surface.

[0293] Example 10: Emulsion of amino-functionalized polydimethylsiloxane crosslinked with oxalamido ester-terminated polyether E7

[0294] At 5000 rpm, using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA), 97.00 g of emulsion was... CE3 With 3.00g of oxalamidoester-terminated polyether A (Approximately 15% by weight, based on amino-functionalized polydimethylsiloxane) was homogenized within one minute. This produced a low-viscosity, slightly turbid, pale yellow emulsion E7 with a solids content of 35% and a pH of 4.5.

[0295] After drying at 25°C for 1-3 days, the evaporation of the emulsion produces a white, elastic, and soft film that adheres well to the aluminum and is not sticky on the surface.

[0296] Example 11: Emulsion of amino-functionalized polydimethylsiloxane crosslinked with oxalamido ester-terminated polyether E8

[0297] At 5000 rpm, using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA), 99.20 g of emulsion was... CE3 With 0.80g of oxalamidoester-terminated polyether B (Approximately 4% by weight, based on amino-functionalized polydimethylsiloxane) was homogenized within one minute. This produced a low-viscosity, transparent, slightly yellow emulsion with a solids content of 34% and a pH of 4.5. E8 .

[0298] After drying at 25°C for 1-3 days, the evaporation of the emulsion produces a significantly white, elastic, and soft film that adheres well to the aluminum and is not sticky on the surface.

[0299] Example 12: Emulsion of amino-functionalized polydimethylsiloxane crosslinked with oxalamido ester-terminated polyether E9

[0300] At 5000 rpm, using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA), 96.00 g of emulsion CE3 was homogenized with 4.00 g of oxalamidoester-terminated polyether C (approximately 20% by weight, based on amino-functionalized polydimethylsiloxane) for one minute. This produced a low-viscosity, cloudy, slightly yellow emulsion with 36% solids content and a pH of 4.5. E9 .

[0301] After drying at 25°C for 1-3 days, the evaporation of the emulsion produces a white, elastic, and very soft film that adheres well to the aluminum and is not sticky on the surface.

[0302] (Comparative) Example 13: Emulsion of linear oxaloylamino ester polyether-bridged polydimethylsiloxane CE10

[0303] lotion CE10 Prepared in accordance with Example 1, similar to WO 2019 / 114953 A1:

[0304] 100 g (20 mmol) of linear oxalamidoester-terminated silicone oil (5065 g / mol) was added to a 500 ml three-necked flask equipped with a thermocouple, a KPG stirrer, and a reflux condenser. 3.74 g (20 mmol) of TA 187 (=N) was added with stirring over 10 minutes at 22 °C. 1 -(3-(dimethylamino)propyl)-N 3 N 3 -Dimethylpropane-1,3-diamine, available at SIGMA-ALDRICH, MERCK, Darmstadt, Germany, was subsequently added at a concentration of 6.6 g (10 mmol). ED-600 (available from Huntsman Performance Products, Everslaan 45, B-3078, Everberg, Belgium). Then stir for another 30 minutes. Afterward, release the reaction product from the resulting alcohol at 40°C and 20 hPa. This yields 107 g of opaque oligomer. 21.2 g of the obtained product was mixed with 4.7 g of diethylene glycol monobutyl ether (purchased from Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany) and 4.1 g of tridecyl alcohol ethoxylate (as...). Mix the ingredients (TO purchased from BASF SE, Ludwigshafen) and then slowly dilute with 70.0g of water and adjust the pH to 4.5 with 80% acetic acid.

[0305] Example 14:

[0306] The degree of crosslinking was determined using the emulsions described in Table 1. The emulsions were poured into aluminum trays, and their appearance was evaluated after water was removed.

[0307] Table 1: Crosslinking Experiment C1 to C9

[0308]

[0309] Symbol explanation: pc = partially crosslinked; e = elastic; g = gel-like; o = oily; P = pasty; s = soft.

[0310] *) Not this invention; **) This invention

[0311] Example 15: Determination of wrinkle recovery angle:

[0312] Performance tests related to the determination of wrinkle recovery angle were performed using the following aqueous formulations described in Table 2. The amount of emulsion containing polyoxysiloxane was selected such that the polyoxysiloxane content (blank value) was... F1 Except for the ones mentioned above, they are always the same.

[0313] Table 2: Aqueous Formulations F1 to F8

[0314]

[0315] *) Not a present invention

[0316] **) This invention

[0317] The formulation (both of the present invention and non-the present invention) is prepared by simply mixing the components (using the IKAEurostar Power basic stirrer mechanism with a paddle stirrer).

[0318] To evaluate the expected effect in terms of wrinkle recovery angle:

[0319] 2×5cm textile strips were taken from WFK 10A cotton test fabric (100% cotton, with approximately 170g / m²). 2 Basis weight (from wfk-Testgewebe), the fabric has been washed twice with a commercial heavy-duty powder detergent at 90°C.

[0320] Use a trigger sprayer to apply the aqueous formulation. F1 to F8 (See Table 2) Sprayed onto textile strips. Formulations applied by spraying. F1 to F8 The quality was selected to be the same as that of the textile strip. The textile strip was dried online overnight, conditioned for 24 hours in a conditioning room at 23°C / 60% humidity, and then ironed on a "cotton" soleplate.

[0321] The wrinkle recovery angle was determined according to the method of DIN 53 890 / 1972.

[0322] Each textile strip is folded laterally so that the length of the sample side to be covered is 10 mm. A 0.15 mm thick aluminum foil is placed under the sample side to prevent fiber adhesion. The sample is covered with a microscope slide and weighted with a 1000 g weight, ensuring the weight rests only on the covered sample side. The weighting time is 30 minutes.

[0323] After removing the weights from the microscope slide, the gradually increasing wrinkle recovery angle was measured on both sides of the lateral bend at 5 and 30 minutes using a protractor.

[0324] For each type of textile, at least ten samples should be prepared and measured. The reported measurement results are the average of the corresponding determinations.

[0325] Table 3: Determination of wrinkle recovery angle of WFK 10A cotton test fabric

[0326]

[0327]

[0328] *) Non-inventory emulsions containing uncrosslinked amino-functionalized polydiorganosiloxanes

[0329] **) The emulsion of the present invention comprising a crosslinked hydrophilic polydiorganosiloxane.

[0330] Compared to textiles sprayed only with water (blank value) F1 Regarding the use of emulsions containing the present invention E4 to E9 formulations F3 to F8 Modification of textiles resulted in a significant increase in the wrinkle recovery angle.

[0331] With non-inventory emulsions containing uncrosslinked amino-functionalized polydimethylsiloxane CE2 formulations F2 The comparison also shows that the formulation of the present invention F3 to F8 Especially formulations F3 and F8 It exhibits an increased wrinkle recovery angle.

[0332] Therefore, when the emulsion of the present invention is used in textiles, a significantly reduced tendency to wrinkle is achieved compared to that provided by the prior art. The function of the emulsion of the present invention is to reduce or inhibit wrinkling in textiles (such as clothing).

[0333] Example 16: Droplet Absorption Time

[0334] The performance tests related to the determination of droplet absorption time used the aqueous formulations described in Table 2. F2 to F5 (Example 15) was performed.

[0335] The wfk 10A cotton test fabric (obtained from wfk-Testgewebe) was modified according to the method described in Example 15.

[0336] After drying, a drop of deionized water was placed from a height of 4 cm onto the stretched surface of the modified textile, and the time it took for the water droplet to be absorbed by the fabric was measured. Five measurements were performed, and an average value was calculated.

[0337] Table 4: Determination of droplet absorption time on WFK 10A cotton test fabric

[0338]

[0339] Compared to non-inventive emulsions containing uncrosslinked amino-functionalized polydimethylsiloxanes. CE2 formulations F2 In terms of modification, using an emulsion containing the present invention E4 to E6 formulations F3 to F5Modification of the cotton test fabric resulted in a significant reduction in the droplet absorption time on the fabric. As a result, the textile achieved significantly better water absorption compared to existing technologies.

[0340] Example 17: Soft hand feel in application as a fabric softener component

[0341] Performance tests related to the determination of softness were performed using the following aqueous formulations described in Table 5.

[0342] Table 5: Aqueous Formulations F9 to F13

[0343]

[0344] *) Not a present invention

[0345] **) This invention

[0346] ***) N,N-bis[ethyl(tallow ester)]-N-(2-hydroxyethyl)-N-methylammonium methyl sulfate (90% ethanol solution), can be traded under the name VK90 purchased from Stepan

[0347] To evaluate the expected effect on softness, six terryhand towels made of cotton fabric were washed with approximately 2 kg of ballast fabric in a MIELE Softronic W 1935WPS EcoLine household washing machine using a hot (boil) / 40°C color wash program at 1200 rpm. The detergent surfactant added here was 65 g of ECE-2 test laundry detergent powder (obtained from WFK). The formulation was added via the detergent drawer after the wash cycle. F9 to F13 (Pre-dilute in 1 liter of tap water at 16°dH [German hardness]). Finally, dry the material online in a conditioning chamber at 23°C and 60% atmospheric humidity for at least 12 hours.

[0348] Measurement of softness (hand feel assessment):

[0349] Because the softness of textiles is highly dependent on the tester's subjective feeling, only boundary conditions can be standardized, not the evaluation. However, to ensure reproducibility, the softness of modified specimens is evaluated and graded. For this purpose, 10 testers assign scores from 1 to n, depending on the number of specimens n tested, where score n is assigned to the softest specimen and score 1 is assigned to the modified specimen with the lowest softness. Unmodified reference specimens receive a score of 0. The softness evaluation of each specimen is calculated accordingly as the average of the scores assigned to that specimen.

[0350] Table 6: Evaluation of the softness and feel of terry cloth

[0351]

[0352] Compared to existing technology formulations with a lower softness, F13 (Emulsions containing uncrosslinked amino-functionalized diorganopolysiloxanes) CE1 Regarding the formulation of the present invention, F10 to F12 Modification of textiles resulted in a significantly improved soft hand feel.

[0353] preparation F12 The combination of cationic surfactants, particularly in the emulsions of this invention, further contributes to a soft hand feel that can only be achieved by significantly increasing the content of cationic surfactants, such as in formulations. F9 This leads to a reduction in the use of raw materials, representing a significant environmental and economic improvement from existing technologies.

Claims

1. An aqueous dispersion comprising: (1) A pre-crosslinked organopolysiloxane comprising a unit of formula (I) and an average of at least one structural unit of formula (III): R2SiO 2 / 2 (I) SiR 1 Oh 2 / 2 -Y-SiR 1 Oh 2 / 2 (III), in Y is a divalent group in 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 can be the same or different, and is a divalent organic group containing a polyoxyethylene group. R can be the same or different, and is an unsubstituted or substituted, saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms. R 1 They can be the same or different, and are either group R or group -OR. 7 , R 2 It is a linear or branched divalent hydrocarbon group with 1 to 18 carbon atoms bonded to SiC. R 3 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group. R 4 It is a divalent hydrocarbon group with 1 to 6 carbon atoms. R 7 They can be the same or different, and are either hydrogen or a monovalent hydrocarbon group having 1 to 18 carbon atoms and may be interspersed with one or more independent oxygen atoms. n is 0, 1, 2, 3 or 4, and (2) Emulsifiers, and (3) Water.

2. The aqueous dispersion according to claim 1, characterized in that... Z is the formula – (R) 5 O) m -R 6 - groups, in which Z can be the same or different, and is a divalent organic group containing a polyoxyethylene group. R 5 They are the same or different, and are C1-C. 10 Alkylene R 6 It is C1-C 10 Alkylene m is an integer and its average value is between 1 and 80.

3. The aqueous dispersion according to claim 1, characterized in that... The pre-crosslinked organopolysiloxane (1) comprises structural units of the following formula: R 1 ASiO 2 / 2 (II) in A can be the same or different and is a group of the following formula: -R 2 -[NO 3 -R 4 -] n NR 3 2 in R 1 It has the meaning indicated by claim 1. R 2 It is a linear or branched divalent hydrocarbon group with 1 to 18 carbon atoms bonded to SiC. R 3 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group. R 4 It is a divalent hydrocarbon group having 1 to 6 carbon atoms, and n can be 0, 1, 2, 3, or 4.

4. The aqueous dispersion according to claim 1, 2 or 3, characterized in that... The pre-crosslinked organopolysiloxane (1) is selected from the following formulas and mixtures thereof: in R, R 7 Y has the meaning indicated by them in claim 1. A has the meaning indicated for it in claim 3. e is 0 or 1. j is 0 or an integer from 1 to 15. k is at least 1 and at most 15, and l is at least 40 and at most 1000.

5. The aqueous dispersion according to claim 1, 2 or 3, characterized in that... After water removal, the pre-crosslinked organopolysiloxane forms an elastomer film.

6. A pre-crosslinked organopolysiloxane (1) comprising units of formula (I) and at least one structural unit of formula (III): R2SiO 2 / 2 (I) SiR 1 Oh 2 / 2 -Y-SiR 1 Oh 2 / 2 (III), in Y is a divalent group in 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 can be the same or different, and is a divalent organic group containing a polyoxyethylene group. R can be the same or different, and is an unsubstituted or substituted, saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms. R 1 They can be the same or different, and are either group R or group -OR. 7 , R 2 It is a linear or branched divalent hydrocarbon group with 3 to 18 carbon atoms bonded to SiC. R 3 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group. R 4 It is a divalent hydrocarbon group with 1 to 6 carbon atoms. R 7 They can be the same or different, and are either hydrogen or a monovalent hydrocarbon group having 1 to 18 carbon atoms and may be interspersed with one or more independent oxygen atoms. n can be 0, 1, 2, 3, or 4.

7. The pre-crosslinked organopolysiloxane according to claim 6, characterized in that... Z is the formula – (R) 5 O) m -R 6 - groups, in which Z can be the same or different, and is a divalent organic group containing a polyoxyethylene group. R 5 They are the same or different, and are C1-C. 10 Alkylene R 6 It is C1-C 10 alkylene, and m is an integer and its average value is between 1 and 80.

8. A method for preparing an aqueous dispersion of a pre-crosslinked organopolysiloxane (1), characterized in that... In the presence of emulsifier (2) and water (3), an organopolysiloxane (4) is reacted with an oxaloylamino ester-terminated polyether (5), wherein the organopolysiloxane (4) comprises a unit of formula (I) and an average of at least one structural unit of formula (II): R2SiO 2 / 2 (I) R 1 ASiO 2 / 2 (II), in R and R 1 They have the meaning indicated by them in claim 1, and A has the meaning indicated for it in claim 3. The oxalamido ester-terminated polyether (5) is of formula (V): in Z and R 3 They have the meaning indicated by them in claim 1, and R 8 They may be the same or different, and are monovalent hydrocarbon groups having 1 to 18 carbon atoms and may be interspersed with one or more independent oxygen atoms.

9. The method according to claim 8, characterized in that... The organopolysiloxanes (4) used comprise those selected from the following formulas and mixtures thereof: [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), Among them, R, R 1 and R 7 They have the meaning indicated by them in claim 1. A has the meaning indicated for it in claim 3, and j, l, and e have the meanings indicated by them in claim 4.

10. A composition for treating a substrate comprising an aqueous dispersion of a pre-crosslinked organopolysiloxane (1) according to claim 1, 2 or 3, or an aqueous dispersion of a pre-crosslinked organopolysiloxane (1) prepared according to claim 8 or 9, or a pre-crosslinked organopolysiloxane (1) according to claim 7.

11. The composition according to claim 10, characterized in that... The fiber substrate is a fiber substrate.

12. The composition according to claim 10, characterized in that... The fiber substrate is a textile.

13. Use of the composition according to claim 10 or 12 for treating a substrate.

14. The use according to claim 13, characterized in that... The substrate is a fiber substrate.

15. The use according to claim 13, characterized in that... The composition is used for cleaning and caring for substrates.

16. The use according to claim 15, characterized in that... The substrate is a fiber substrate.

17. The use according to claim 14 or 16, characterized in that... The fiber substrate is a textile.

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