Silicone copolymers, their preparation and their use for the treatment of fibrous substrates

Abstract

The present invention relates to modified oxamide-terminated organosilicon copolymers, which are suitable in the field of fibrous substrate treatment, and more particularly in the field of textile treatment.

Description

[Technical Field]

[0001] The present invention relates to the technical field of organic silicone copolymers, which are suitable for the field of fiber substrate processing and more preferable for the field of textile processing. [Background technology]

[0002] US7501184B2 or CN101346414B describes copolymers obtained by the reaction of linear organopolysiloxanes terminated with oxamide ester groups with organic diamines. The resulting copolymers have high viscosity or are solid and are used as adhesives, particularly as hot-melt adhesives. These high-viscosity products cannot be stably emulsified and therefore cannot be incorporated into textile chains.

[0003] WO2019114953A1 discloses oxamide-containing silicone copolymers, which are obtained from organopolysiloxanes, polyetheramines, and monofunctional primary or secondary amines terminated with oxamide ester groups under mixing and stirring conditions. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Patent No. 7,501,184 [Patent Document 2] Specification of Chinese Patent No. 101346414 [Patent Document 3] International Publication No. 2019 / 114953 [Overview of the project]

[0005] This invention discloses a novel type of organosilicon copolymer used for treating fibrous substrates, the treated fibrous substrate having better hydrophilicity and tactile feel, and at the same time, additional antibacterial effects.

[0006] The silicone copolymer of the present invention contains a structural unit represented by the general formula (I-a).

[0007] [Chemical formula] M is N(R 1 )4, and R 1 are the same or different and represent a monovalent hydrocarbon group having 1 to 18 carbon atoms, benzyl or adamantyl. Preferably, R 1 is methyl, ethyl, propyl, butyl, benzyl, dodecyl, octadecyl, and more preferably R 1 is methyl. Y is a divalent hydrocarbon group which may be substituted with one or more heteroatoms, preferably methylene, 1,2-ethylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, -C2H4-NH-C3H6, and more preferably 1,3-propylene. R 2 are the same or different and represent a monovalent hydrocarbon group having 1 to 18 carbon atoms and may contain a halogen or oxygen atom. n is an integer from 10 to 2000, preferably an integer from 10 to 300. [Embodiments for Carrying Out the Invention]

[0008] Preferably, R 2 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkylaryl, aralkyl. R 2It is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethylpentyl, nonyl such as n-nonyl, decyl such as n-decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl, cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl, vinyl, 5-hexenyl, cyclohexenylphenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl, ethynyl, propargyl and 1-propynyl, phenyl, naphthyl, anthryl and phenanthryl, O-tolyl, m-tolyl and p-tolyl, xylyl and ethylphenyl, benzyl, α- and β-phenethyl.

[0009] More preferably, R 2 is methyl.

[0010] The silicone copolymer of the present invention has a much smaller molecular weight and contains different types of hydrophilic groups, which is different from the high molecular weight copolymers described in US7,501,184. The difference from the copolymer described in WO2019114953A1 is that the end groups of the present invention are more hydrophilic and can simultaneously provide an antibacterial function.

[0011] The silicone copolymer preferably has a number average molecular weight Mn of 4000 to 30000 g / mol, preferably 4000 to 20000 g / mol, more preferably 4000 to 15000 g / mol. This number average molecular weight Mn is preferably measured by size exclusion chromatography (SEC) for the purposes of the present invention.

[0012] The number-average molecular weight Mn is more preferably measured by size exclusion chromatography (SEC) with a detection by RI (refractive index detector) on a PLgel MiniMIX-C column set manufactured by Agilent at a flow rate of 0.3 ml / min in toluene at 45°C with an injection volume of 20 μl, against polystyrene standards.

[0013] The above copolymer contains a structural unit represented by the general formula (I-b).

[0014]

Chemical formula

[0015] The above copolymer contains a structural unit represented by the general formula (I-c).

[0016]

Chemical formula

[0017] The above copolymer contains a structural unit represented by the general formula (I-d) and / or (I-d’).

[0018]

Chemical formula

[0019] The method for preparing the above copolymer is: (1) Organopolysiloxanes containing structural units represented by general formula (II)

[0020] [ka] [In the formula, R 2 Y and n have the above definitions with respect to their representation. R * This is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably methyl or ethyl, more preferably ethyl. This is obtained by reacting with the following component (3) and any component (2). The quaternary amine base component (3) is represented by the compound of general formula (III-3), N(R 1 )4 + X - (III-3) [In the formula, R 1 [The same definition as above applies, and X is OH.] (2) is R 3 HN-Z-NHR 3 (III-2)[R 3 And Z has the definition shown above. It is a polyetheramine of ].

[0021] In this invention, it is R 4 R represents a hydrocarbon group having 4 to 18 carbon atoms, which has a hydrogen atom or a C1-18 alkyl group or one or more oxygen atoms or nitrogen atoms. 5 HN(R) represents a hydrocarbon group having 4 to 18 carbon atoms, which is a C1-18 alkyl group or has one or more oxygen or nitrogen atoms. 4)-R 5 (IV) may also contain a small amount of (33) primary or secondary amine, provided that the amount of (33) is 200 mol% or less, preferably 120 mol% or less, and component (1) is calculated as 100 mol%.

[0022] Formula HN(R 4 )-R 5 Preferred examples of amines in (IV) are as follows: Primary amines, for example, H-NH-(CH2)3-N(CH3)2(N 1 ,N 1 -Dimethylpropane-1,3-diamine) Secondary amines, for example, HN-[(CH2)3-N(CH3)2]2(N 1 -(3-(dimethylamino)propyl)-N 3 ,N 3 -Dimethylpropane-1,3-diamine) Primary polyetheramines, for example, H-NH-(CH2)3-OCH2CH3, H-NH-(CH2)2-OCH2CH3, Secondary polyetheramines, for example, NH-[(CH2)3-OCH2CH3]2, NH-[(CH2)2-OCH2CH3]2

[0023] In the above method, the amount of the quaternary amine base component (3) is 10 moles or more, preferably 20 moles or more, preferably 30 moles or more, per 100 moles of polymer in the organopolysiloxane (1), for example, 35, 45, 55, 65, 70, 100, 150 millimoles, more preferably between 40 and 400 moles, more preferably between 50 and 300 moles, and more preferably between 60 and 200 moles.

[0024] In the above method, the reaction is carried out at 70-120°C under a vacuum of 30-70 mbar, preferably 40-60 mbar.

[0025] In the above method, the reaction time is between 0.5 and 5 hours, preferably between 1 and 3 hours.

[0026] In the above method, the water content of the reactants is less than 1% by weight, preferably less than 0.1% by weight, and component (1) is calculated to be 100% by weight.

[0027] In the above method, the reaction is carried out by alcohol R 1 It is performed in the presence of OH, R 1 The definition is the same as above, and preferably methanol or ethanol.

[0028] In the above method, the quaternary amine base component (3) is mixed with a solvent beforehand to obtain a solution of the quaternary amine base component (3) or a dispersion of the quaternary amine base component (3).

[0029] In the above method, the preferred solvent satisfies the following conditions: Under conditions of 20°C and 1 atm, 100g of the solvent can dissolve 1g or more of the quaternary amine base component (3).

[0030] In the above method, the water content of the quaternary amine base component (3) solution or quaternary amine base component (3) dispersion is 10% by weight or less, preferably 8% by weight or less.

[0031] In the above method, the quaternary amine base component (3) is not premixed with the solvent; that is, it is mixed with the organopolysiloxane of component (1).

[0032] In the above method, the quaternary amine base component (3) may coexist with some of the water in the crystal, and the water content of the crystal is preferably 100% by weight or less, preferably 80% by weight or less, and more preferably 60% by weight or less, based on 100% by weight of the quaternary amine base component (3).

[0033] In the above method, the polyetheramine (2) can optionally be used in an amount of 0.3 to 2 moles, or 0.5, 0.8, 1.2, 1.4, 1.6, or 1.8 moles, preferably 0.4 to 0.6 moles, and more preferably 0.5 moles, of amino groups in (2) per mole of polymer in organopolysiloxane (1).

[0034] The composition obtained by the above method.

[0035] A composition comprising the above copolymer, wherein the copolymer comprises a structural unit represented by general formula (Ia).

[0036] A composition comprising the above copolymer, wherein the copolymer comprises a structural unit represented by general formula (Ib).

[0037] A composition comprising the above copolymer, wherein the copolymer comprises a structural unit represented by general formula (Ic).

[0038] A composition comprising the above copolymer, wherein the copolymer comprises structural units represented by the general formula (Id) and / or (I-d').

[0039] The aqueous emulsion contains the following: Composition (A) contains the above-described silicone copolymer, Emulsifier (B) and / or co-emulsifier (B'), and Water (C).

[0040] In the aqueous emulsion described above, the amount of component (A) used, which is between 10 and 50% by weight, preferably between 15 and 40% by weight, is calculated as 100% by weight based on the total amount of the aqueous emulsion.

[0041] Use of the above copolymers, compositions, or emulsions in the textile field, preferably for improving the hydrophilicity and / or feel of textiles.

[0042] The above uses are preferably those that simultaneously improve the hydrophilicity and antibacterial properties of the fabric.

[0043] In one method, the composition is applied to a fibrous substrate, and the fibrous substrate thus treated is dried at a temperature preferably of 20 to 200°C.

[0044] In the above method, the fibrous base material is a woven fabric.

[0045] The emulsifier (B) used may be a nonionic, anionic, or cationic emulsifier, or a mixture thereof.

[0046] The aqueous emulsion of the present invention comprises emulsifiers known on their own, and mixtures thereof.

[0047] Particularly suitable anionic emulsifiers include the following:

[0048] 1. Alkyl sulfates, particularly those having a chain length of 8 to 18 carbon atoms, alkyl and alkali ether sulfates having 8 to 18 carbon atoms in the hydrophobic group and 1 to 40 ethylene oxide (EO) units and / or propylene oxide (PO) units.

[0049] 2. Sulfonates, particularly alkyl sulfonates having 8 to 18 carbon atoms, alkylaryl sulfonates having 8 to 18 carbon atoms, taurids, esters and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms, these alcohols or alkylphenols may optionally be ethoxylated with 1 to 40 EO units.

[0050] 3. Alkali metal salts and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in an alkyl group, aryl group, alkaryl group, or aralkyl group.

[0051] 4. Phosphate partial esters and alkali metal and ammonium salts thereof, in particular alkyl and alkali phosphates having 8 to 20 carbon atoms in the organic group, and alkyl ethers and alkali ether phosphates having 8 to 20 carbon atoms and 1 to 40 EO units, respectively, in the alkyl or alkali group.

[0052] Particularly suitable nonionic monomers include the following:

[0053] 5. A polyvinyl alcohol further having 5-50%, preferably 8-20%, of vinyl acetate units and a degree of polymerization of 500-3000.

[0054] 6. Alkyl polyglycol ethers, preferably those having 8 to 40 EO units and 8 to 20 alkyl groups of carbon atoms.

[0055] 7. Alkylaryl polyglycol ethers, preferably 8 to 40 EO units, and having 8 to 20 carbon atoms in the alkyl and aryl groups.

[0056] 8. Ethylene oxide / propylene oxide (EO / PO) block copolymer, preferably having 8 to 40 EO and PO units.

[0057] 9. An adduct of an alkylamine having an alkyl group of 8 to 22 carbon atoms with ethylene oxide or propylene oxide.

[0058] 10. Fatty acids having 6 to 24 carbon atoms.

[0059] 11. General formula R ** -O-Zo alkyl polyglycoside, in the formula R ** represents a linear or branched saturated or unsaturated alkyl group having an average of 8 to 24 carbon atoms, and Zo represents an oligoglycoside group having an average of 1 to 10 hexose units or pentose units or combinations thereof.

[0060] 12. Natural substances such as lecithin, lanolin, saponin, and cellulose, and their derivatives, cellulose alkyl ethers, and carboxyalkyl cellulose, each having up to four carbon atoms in its alkyl group.

[0061] 13. Linear organo(poly)siloxanes containing polar groups, particularly those having up to 24 carbon atoms and / or up to 40 EO groups and / or PO groups (alkoxy groups).

[0062] Particularly suitable cationic emulsifiers include the following:

[0063] 14. Salts of primary, secondary, and tertiary aliphatic amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid, and phosphoric acid.

[0064] 15. Quaternary alkylammonium salts and alkylbenzeneammonium salts, more specifically those in which the alkyl group has 6 to 24 carbon atoms, particularly halides, sulfates, phosphates, and acetates.

[0065] 16. Alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts, more specifically those in which the alkyl chain has up to 18 carbon atoms, in particular halides, sulfates, phosphates and acetates.

[0066] Particularly suitable amphoteric emulsifiers include the following:

[0067] 17. Long-chain substituted amino acids such as N-alkyl-di(aminoethyl)glycine or salts of N-alkyl-2-aminopropionic acid.

[0068] 18. Betaines such as N-(3-acylamidopropyl)-N,N-dimethylammonium salts having C8-C18 acyl groups, and alkylimidazolium betaine.

[0069] Preferred emulsifiers are nonionic emulsifiers, particularly alkyl polyglycol ethers listed in 6., adducts of alkylamines with ethylene oxide or propylene oxide listed in 9., alkyl polyglycosides listed in 11., and polyvinyl alcohols listed in 5.

[0070] The emulsifier is used here in an amount of 1% to 70% by weight based on the total weight of the aqueous emulsion.

[0071] The aqueous emulsion contains the copolymer of the present invention in an amount of preferably 0.5% to 80% by weight, based on the total weight of the aqueous emulsion.

[0072] The aqueous emulsion of the present invention may also contain polyethylene glycol, polypropylene glycol, polyethylene-polypropylene glycol and mixtures thereof, as well as further substances such as acids. Examples of acids are carboxylic acids such as acetic acid, formic acid, citric acid, malic acid, and lactic acid.

[0073] Further substances that may be present in the aqueous emulsion of the present invention include a solvent or a coemulsifier (B').

[0074] Examples of non-aqueous solvents or emulsifiers include 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, and propylene glycol methyl ether.

[0075] The organopolysiloxane (1) of formula (II) used in the process of the present invention can be prepared by the process described in US7,501,184B2 (as incorporated by reference), particularly column 13, lines 14-48. Those skilled in the art also know other methods.

[0076] Examples of polyetheramines (2) used in the process of the present invention are Jeffamine(R) diamines of series D and ED, such as Jeffamine(R) D-230, Jeffamine(R) D-400, Jeffamine(R) D-2000, Jeffamine(R) HK 511, Jeffamine(R) ED-600, Jeffamine(R) ED-900, and Jeffamine(R) ED-2003, which are commercially available from Huntsman.

[0077] In the method of the present invention, it is preferable to first introduce an organopolysiloxane (1), a quaternary amine base (3), and an optional polyetheramine (2), and either an optional primary or secondary amine (33) may be added together, or the polyetheramine (2) may be added first, followed by the quaternary amine base (3), or the quaternary amine base (3) may be added first, followed by the polyetheramine (2). It is preferable to add the polyetheramine (2) first, then the quaternary amine base (3), and finally the optional primary or secondary amine (33).

[0078] The alcohol formed in this reaction is preferably removed, and more preferably by distillation.

[0079] The method for preparing the silicone copolymer of the present invention can be carried out in batch, semi-batch, or continuous manner.

[0080] Examples of fibrous substrates treated with composition (A) containing the silicone copolymer of the present invention include naturally or synthetically produced fibers, yarns, skeins, cables, nonwovens, mats, woven, knotted or knitted fabrics, sheet-like woven structures such as leather and leatherette, and hair. A preferred fibrous substrate is a woven fabric. For application of the composition of the present invention, the woven fabric may take the form of individual fibers, fiber bundles, fiber-filler fibers, yarns, carpets, fabric webs, or garments or parts of garments.

[0081] Textiles may consist of cotton, wool, vinyl acetate copolymer, rayon, linen, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, aramid, polyimide, polyacrylate, polyacrylonitrile, polylactide, polyvinyl chloride, glass fiber, ceramic fiber, cellulose, or mixtures thereof.

[0082] The coating of the fibrous substrate to be treated, preferably a textile, can be carried out by any desired method widely known and suitable for treating fibrous substrates, such as textiles, for example, by dipping, coating, casting, spraying, rolling, padding, printing, or foam coating.

[0083] In application, the compositions of the present invention can be combined with, for example, binders containing melamine resin or methylol resin, polyethylene, polyurethane, polyacrylate, polyvinyl alcohol, or polyvinyl acetate, optical gloss agents, matting agents, electrolytes, wetting aids, plastic resins, bleaching agents, antistatic agents, dispersions of metal oxides, silicates, fragrance oils, dyes and preservatives, defoaming agents, or general textile additives such as further hydrophobic and oleophobic aids, for example, perfluorinated hydrocarbons.

[0084] Furthermore, the products of the present invention can be used in conjunction with fabric softeners based on polysiloxanes and organic softeners such as anionic, cationic, and nonionic softeners, as well as mixtures thereof.

[0085] These include functional and non-functional silicones, salts of metal soaps, alkyl polysulfonates, sulfosuccinates and their derivatives, ester quats, sulfoalkylene fatty acid amides, alkylammonium sulfates, triethanolamine fatty acid esters, fatty acid polyglycol esters, fatty amine polyalkylene adducts, fatty acid amide polyalkylene adducts, and dispersions of paraffin, wax, polyethylene and polyester.

[0086] The treated fibrous substrate, preferably a woven fabric, is dried at a temperature of preferably 20°C to 200°C, more preferably 100°C to 180°C.

[0087] The silicone copolymer of the present invention and composition (A) containing the silicone copolymer of the present invention have the advantage that fibrous substrates treated with them, such as textiles, are hydrophilic, have a soft feel, and are easily emulsifiable.

[0088] In the examples below, unless otherwise specified, all references to parts and percentages are by weight. Furthermore, all viscosity standards are based on a temperature of 25°C.

[0089] Unless otherwise specified, the examples and comparative examples in Table 1 were carried out at the temperature reached during mixing at 50 mbar and approximately 85°C. The reaction time was between 0.5 and 5 hours, preferably between 1 and 3 hours.

[0090] In this invention, Me represents methyl and Et represents ethyl. [Examples]

[0091] Oxamide ester-terminated silicone oil (Mw=11000g / mol, Mn=7000g / mol), bifunctional, provided by Wacker Chemie AG. The TMAH content is 25% by weight of the tetramethylammonium hydroxide methanol solution based on the total solution (100% by weight). A 25% by weight dodecyltrimethylammonium chloride ethanol solution based on the total solution (100% by weight), JEFFAMINE(R) ED-900, a polyetheramine manufactured by Huntsman Performan Products (Belgium B3078 Everberg Everlaan 45), DA102, N 1 ,N 1-Dimethylpropane-1,3-diamine (commercially available from SIGMA-ALDRICH, MERCK, Darmstadt, Germany).

[0092] <Preparation> Oxamide ester-terminated organopolysiloxane (1) was charged into a 1000 ml four-neck flask equipped with a thermocouple, KPG stirrer, and reflux condenser, while stirring internally at 70-100°C for 15 minutes. An arbitrary polyetheramine (2) was added and stirred for 30-60 minutes. Next, a quaternary amine base (3) solution was added and stirred for a further 10 minutes. Subsequently, the resulting small molecules were removed at 70-120°C and under a vacuum of 50 mbar for 2-4 hours. Next, DA102 was added as needed, and the resulting small molecules were removed at 70-120°C and under a vacuum of 50 mbar for 1-2 hours to obtain the copolymer. Its molecular weight was measured by SEC.

[0093] [Table 1]

[0094] [Table 2]

[0095] Table 2-1 shows nuclear magnetic NMR Si 29 H 1 and C 13 The relative molar percentage ratios of each functional group and structural unit are calculated through testing. Among these, the -Si-Y-NH structural unit possesses the properties it has in the sense of general formula (Ia).

[0096] The inventors of this case discovered that copolymers having the (Ia) structural unit can be obtained by using a quaternary amine base material. Compared with C.Ex.7, which does not have the (Ia) structural unit, the novel copolymer of the present invention (Ex.1) has a better feel and hydrophilicity (shorter droplet absorption time). Furthermore, the novel copolymer of the present invention can simultaneously achieve good hydrophilicity and antibacterial properties. Moreover, this novel copolymer has a longer antibacterial effect, is safer, and is more environmentally friendly.

[0097] [Table 3]

[0098] [Table 4]

[0099] [Table 5]

[0100] <Measurement of flexibility (evaluation of touch)> Since the flexibility of a fabric is highly dependent on the subjective perception of the tester, only boundary conditions can be standardized, rather than the evaluation itself. Nevertheless, to ensure reproducibility, the completed test specimens were evaluated and ranked according to their flexibility. For this purpose, points were assigned according to the number of test specimens tested by four testers, and the level of the score correlated with flexibility. The softest test specimen received the highest score, and the least soft test specimen received a score of 0. Therefore, the evaluation of the feel of a test specimen is calculated as the average of the scores given by that particular test specimen.

[0101] <Measurement of droplet absorption time> After coating with the silicone product, the finished test specimens were stored for 8 hours in a controlled chamber at 23°C and 62% atmospheric humidity for acclimatization. Then, a droplet of deionized water was placed from a height of 1 cm onto a taut cloth surface, and the time required for the cloth to absorb the droplet was measured, provided that the time was within 3 minutes (180 seconds).

[0102] Five measurements were taken, and the results were averaged.

[0103] The hydrophilicity score is 5 points for 40 seconds or less, 4 points for 50 seconds or less, and 3 points for 60 seconds or less.

[0104] <Measurement of yellowing> The degree of yellowing was determined using a spectro-guide sphere gloss(R) colorimeter (BYK GARDNER, Germany, Gerreed). In this case, the fabric sample was measured at three different points, and the average was found. This "average yellowing b+" was compared to the untreated sample.

[0105] A smaller b+ value indicates a decrease in yellowing.

Claims

1. A silicone polymer containing a structural unit represented by general formula (Ia): 【Chemistry 1】 [M is N(R １ ) ４ and R １ are the same or different and represent a monovalent hydrocarbon group having 1 to 18 carbon atoms, benzyl or adamantyl, preferably R １ is methyl, ethyl, propyl, butyl, benzyl, dodecyl, octadecyl, more preferably R １ is methyl; Y is a divalent hydrocarbon group optionally substituted with one or more heteroatoms, and is preferably methylene, 1,2-ethylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, -C ２ H ４ -NH-C ３ H ６ and more preferably 1,3-propylene. R ２ are the same or different and represent monovalent hydrocarbon groups having 1 to 18 carbon atoms and which may contain halogen or oxygen atoms; n is an integer of 10 to 2000, preferably an integer of 10 to 300.

2. The copolymer according to claim 1, comprising a structural unit represented by general formula (Ib): 【Chemistry 2】 wherein the group M is as defined above, the group Z is a divalent hydrocarbyloxy group, preferably a polyethylene glycol group or a polypropylene glycol group or a mixture of polyethylene glycol groups and polypropylene glycol groups, the group Z preferably has a molecular weight of 120 to 4500 g / mol, more preferably 500 to 1800 g / mol; R ３ are the same or different and are selected from hydrogen atoms or monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably hydrogen atoms, methyl, ethyl, and propyl. p is an integer of 1 to 5, preferably an integer of 1 or 2, and more preferably 1.

3. The copolymer according to claim 1 or 2, comprising a structural unit represented by general formula (Ic): 【Transformation 3】 [Groups M, R ２ , and R ３ is as defined above, q is 0 or an integer of 1 to 5, preferably 0 or an integer of 1 to 2, and more preferably 0 or 1.

4. 2. The copolymer according to claim 1, comprising structural units represented by general formula (I-d) and / or (I-d'). 【Chemistry 4】 [Group M and Group R ２ is as defined above, R ＊ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably methyl or ethyl, more preferably ethyl.

5. A process for preparing the copolymer according to any one of claims 1 to 4, comprising the steps of: (1) An organopolysiloxane containing a structural unit represented by general formula (II): 【Transformation 5】 [In the formula, R ２ , Y, and n have the above definitions for their designations; R ＊ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably methyl or ethyl, more preferably ethyl. reacting with the following component (3) and optional component (2): The quaternary amine base component (3) is represented by a compound of general formula (III-3): () １ ) ４ ＋ ︸ － (_.). [In the formula, R １ has the same definition as above, and X is OH. Component (2) is R ３ HN-Z-NHR ３ (III-2) [R ３ and Z has the definition given above.

6. 6. The method of claim 5, wherein the quaternary amine base (3) is used in the following amount: for each 100 moles of polymer in the organopolysiloxane (1), the amount of component (3) is 10 moles or more, preferably 20 moles or more, preferably 30 moles or more, and more preferably between 40 and 400 moles, more preferably between 50 and 300 moles, more preferably between 60 and 200 moles.

7. A copolymer prepared by the method of claim 5 or 6.

8. Use of the copolymers according to any one of claims 1 to 4 or 7 in the textile field, preferably for improving the hydrophilicity and / or hand of textiles.

9. Use of a copolymer according to any one of claims 1 to 4 or 7, preferably for simultaneously improving the hydrophilic and antibacterial properties of textiles.