Organosilicon copolymers, their preparation methods and their applications in fiber substrate treatment

Abstract

This invention relates to a modified oxalamide-terminated organosilicon copolymer; suitable for the field of fiber substrate treatment; and even more suitable for the field of textile treatment.

Description

Technical Field

[0001] This invention relates to the field of organosilicon copolymer technology; it is applicable to the field of fiber substrate treatment; and even more applicable to the field of textile treatment. Background Technology

[0002] US7501184B2 or CN101346414B describes copolymers obtained by reacting linear organopolysiloxanes terminated with oxalamido ester groups with organodiamines. The resulting copolymers, which are high-viscosity or solid, are used in adhesives, particularly as hot-melt adhesives. These high-viscosity products cannot be stably emulsified and therefore cannot be integrated into textile applications.

[0003] WO2019114953A1 discloses an organosilicon copolymer containing oxalamide, which is obtained by mixing and stirring an organopolysiloxane with oxalamide ester group-terminated, a polyetheramine, and a monofunctional primary or secondary amine. Summary of the Invention

[0004] This invention discloses a novel organosilicon copolymer, which is used to treat fiber substrates, resulting in better hydrophilicity and hand feel, and also provides additional antibacterial effects.

[0005] The invented organosilicon copolymer contains structural units represented by the general formula (Ia).

[0006]

[0007] M is N(R) 1 )4, R 1 The same or different, and indicating a monovalent hydrocarbon group, benzyl or adamantyl group having 1 to 18 carbon atoms, preferably R. 1 The compounds are methyl, ethyl, propyl, butyl, benzyl, dodecyl, octadecyl, and more preferably R. 1 It is methyl.

[0008] Group Y is a divalent hydrocarbon group, optionally substituted with one or more heteroatoms, preferably methylene, 1,2-ethylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 1,5-pentene, 1,6-hexene, -C2H4-NH-C3H6-; more preferably 1,3-propylene;

[0009] Group R 2 Same or different, and indicates a monovalent hydrocarbon group having 1 to 18 carbon atoms and may include halogen or oxygen atoms.

[0010] n is an integer from 10 to 2000, preferably an integer from 10 to 300.

[0011] Preferred, R 2 It can be alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkylaryl, or aralkyl. R 2 Selected from methyl, ethyl, n-propyl, isopropyl, 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 (e.g., 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); cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl; vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl, and 4-pentenyl; ethynyl, propynyl, and 1-propynyl; phenyl, naphthyl, anthraceneyl, and phenanthrene; o-, m-, and p-tolyl, xylyl, and ethylphenyl; benzyl, α-, and β-phenylethyl.

[0012] More preferably, R 2 It is a methyl group.

[0013] The organosilicon copolymer of the present invention differs from the high molecular weight copolymer described in US7501184 in that it has a much lower molecular weight and contains a different type of hydrophilic groups. It also differs from the copolymer described in WO2019114953A1 in that its end groups are different; the end groups of the present invention are more hydrophilic and can simultaneously provide antibacterial function.

[0014] The organosilicon copolymer of the present invention preferably has a molecular weight Mn (number average) of 4,000-30,000 g / mol; more preferably between 4,000-20,000, and even more preferably between 4,000-15,000. For the purposes of the present invention, the number average molecular weight Mn is preferably determined by size exclusion chromatography (SEC). More preferably, the number average molecular weight Mn is determined by size exclusion chromatography (SEC) of a polystyrene standard in toluene at 45°C and a flow rate of 0.3 ml / min, and detected by an RI (refractive index detector) using a 20 μl injection volume on an Agilent PLgel MiniMIX-C column.

[0015] The copolymers described above contain structural units represented by the general formula (Ib):

[0016]

[0017] Group M is defined as described above.

[0018] Group Z is a divalent hydroxyl group, preferably polyethylene glycol-based, polypropylene glycol-based, or a mixture of polyethylene glycol-based and polypropylene glycol-based; preferably, the molecular weight of group Z is 120-4500 g / mol, more preferably 500-1800 g / mol.

[0019] Where R 3 Whether the groups are the same or different, they are selected from hydrogen atoms or monovalent hydrocarbon groups having 1 to 20 carbon atoms.

[0020] p is an integer from 1 to 5, preferably an integer from 1 to 2, and more preferably 1.

[0021] The copolymers described above contain structural units represented by the general formula (Ic):

[0022]

[0023] Groups M, R 2 R 3 As defined above,

[0024] q is an integer from 0 to 5, preferably an integer from 0 to 2, and more preferably 0 or 1.

[0025] The copolymers described above contain structural units represented by the general formula (Id) and / or (I-d'):

[0026]

[0027] Groups M, R 2 As defined above,

[0028] R * It is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably methyl or ethyl, and more preferably ethyl.

[0029] The method for preparing the copolymer as described above is by

[0030] (1) An organopolysiloxane containing a structural unit represented by general formula (II):

[0031]

[0032] Among them, R 2 Y and n have the definitions described above that indicate them, and

[0033] R* is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably methyl or ethyl, more preferably ethyl.

[0034] Reaction with the following component (3), and optional component (2):

[0035] Quaternary ammonium base component (3) is a compound represented by the general formula (III-3).

[0036] N(R 1 )4 + X - (III-3)

[0037] Where R 1 As defined above, X is OH.

[0038] Where (2) is R 3 HN-Z-NHR 3 (III-2) polyetheramine, R 3 Z has the definition indicated by the above.

[0039] This invention may also contain a small amount of (33) HN(R) 4 )-R 5 (IV) Primary or secondary amines, wherein R 4 R represents a hydrogen atom or a C1-18 alkyl group or a hydrocarbon group having 4 to 18 carbon atoms and including one or more oxygen or nitrogen atoms. 5 It means a C1-18 alkyl group or a hydrocarbon group having 4 to 18 carbon atoms and including one or more oxygen or nitrogen atoms. However, the amount of (33) should be less than or equal to 200 mol%, preferably less than or equal to 120 mol%, calculated with component (1) being 100 mol%.

[0040] General formula HN(R) 4 )-R 5 Preferred examples of (IV) amines are:

[0041] Primary amines, such as H-NH–(CH2)3-N(CH3)2(N 1 N 1 -dimethylpropane-1,3-diamine), and

[0042] Secondary amines, such as HN-[(CH2)3-N(CH3)2]2(N 1 -(3-(dimethylamino)propyl)-N 3 N 3 -dimethylpropane-1,3-diamine),

[0043] Primary polyetheramines, such as H-NH–(CH2)3-OCH2CH3 and H-NH–(CH2)2-OCH2CH3,

[0044] Secondary polyetheramines, such as NH–[(CH2)3-OCH2CH3]2 and NH–[(CH2)2-OCH2CH3]2.

[0045] As described above, the quaternary ammonium base (3) is used in the following amounts: relative to 100 moles of polymer in the organopolysiloxane (1), the amount of component (3) is greater than or equal to 10 mol, preferably greater than or equal to 20 mol, more preferably greater than or equal to 30 mol, for example, 35, 45, 55, 65, 70, 100, 150 mmol, more preferably between 40 and 400 mol, more preferably between 50 and 300 mol, and more preferably between 60 and 200 mol.

[0046] The method described above is wherein the reaction is carried out at 70-120°C and a vacuum of 30-70 mbar, preferably 40-60 mbar.

[0047] The method described above, wherein the reaction time is between 0.5 and 5 hours, preferably between 1 and 3 hours.

[0048] As described above, the water content of the reactants is less than 1 wt%, preferably less than 0.1 wt%, calculated with component (1) being 100 wt%.

[0049] The method described above, wherein the reaction occurs in alcohol R 1 The process takes place in the presence of OH, where R 1 The definition is the same as above, with methanol and ethanol being preferred.

[0050] As described above, the quaternary ammonium base component (3) is premixed with a solvent to obtain a solution of the quaternary ammonium base component (3) or a dispersion of the quaternary ammonium base component (3).

[0051] As described above, the preferred solvent satisfies the following condition: at 20°C and 1 atm, 100g of solvent can dissolve greater than or equal to 1g of the quaternary ammonium base component (3).

[0052] As described above, the water content of the quaternary ammonium base component (3) solution or the quaternary ammonium base component (3) dispersion is less than or equal to 10 wt%, preferably less than or equal to 8 wt%.

[0053] As described above, the quaternary ammonium base component (3) is not premixed with the solvent, but is mixed with the organopolysiloxane component (1).

[0054] In the above method, the quaternary ammonium base component (3) can coexist with a portion of the water of crystallization, preferably with a water of crystallization content of less than or equal to 100 wt%, more preferably less than or equal to 80 wt%, and more preferably less than or equal to 60 wt%, based on 100 wt% quaternary ammonium base component (3).

[0055] As described above, the polyetheramine (2) may optionally be used in the following amounts: 0.3 to 2 mol, or 0.5, 0.8, 1.2, 1.4, 1.6, 1.8 mol, preferably 0.4 to 0.6 mol, more preferably 0.5 mol, of amino groups per mole of polymer in the organopolysiloxane (1).

[0056] A composition obtained by the above method.

[0057] A composition comprising a copolymer as described above, the copolymer containing structural units represented by general formula (Ia).

[0058] A composition comprising a copolymer as described above, the copolymer containing structural units represented by general formula (Ib).

[0059] A composition comprising a copolymer as described above, the copolymer containing structural units represented by general formula (Ic).

[0060] A composition comprising a copolymer as described above, the copolymer containing structural units represented by general formula (Id) and / or (I-d').

[0061] An aqueous emulsion includes:

[0062] Composition (A) contains the organosilicon copolymer as described above.

[0063] Emulsifier (B) and / or co-emulsifier (B'), and

[0064] Water (C).

[0065] The aqueous emulsion described above, wherein the amount of component (A) is between 10-50 wt%, preferably between 15-40 wt%, calculated based on a total aqueous emulsion amount of 100 wt%.

[0066] Uses of the copolymers, compositions, or emulsions described above in the textile field; preferably, uses that improve the hydrophilicity and / or hand feel of textiles.

[0067] The uses described above; preferably, uses that simultaneously improve the hydrophilicity and antibacterial properties of textiles.

[0068] One method involves applying the composition to the fiber substrate and drying the treated fiber substrate at a temperature preferably between 20 and 200°C.

[0069] In the method described above, the fiber substrate is a textile.

[0070] The emulsifier (B) used can be a nonionic emulsifier, anionic emulsifier, or cationic emulsifier, or a mixture thereof.

[0071] The aqueous emulsions of the present invention include emulsifiers and mixtures thereof that are known per se.

[0072] Particularly suitable anionic emulsifiers include:

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

[0074] 2. Sulfonates, particularly alkyl sulfonates having 8 to 18 carbon atoms, alkyl aryl sulfonates having 8 to 18 carbon atoms, taurines, sulfosuccinic acids, and esters and monoesters of monohydric alcohols or alkylphenols having 4 to 15 carbon atoms; these alcohols or alkylphenols may optionally be ethoxylated by 1 to 40 EO units.

[0075] 3. Alkali metal salts and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in alkyl, aryl, alkylaryl, or aralkyl groups.

[0076] 4. Phosphate esters and their alkali metal and ammonium salts, especially alkyl and alkylaryl phosphate salts having 8 to 20 carbon atoms in the organic group, and alkyl ether and alkylaryl ether phosphate salts having 8 to 20 carbon atoms in the alkyl or alkylaryl group and having 1 to 40 EO units.

[0077] Particularly suitable nonionic monomers include:

[0078] 5. Polyvinyl alcohol having an additional 5 to 50%, preferably 8 to 20%, of vinyl acetate units, having a degree of polymerization of 500 to 3000.

[0079] 6. Alkyl polyethylene glycol ethers, preferably those having 8 to 40 EO units and 8 to 20 carbon atoms.

[0080] 7. Alkyl aryl polyethylene glycol ethers, preferably those having 8 to 40 EO units and having 8 to 20 carbon atoms in the alkyl and aryl groups.

[0081] 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 40 EO and PO units.

[0082] 9. Alkylamines having 8 to 22 carbon atoms and adducts with ethylene oxide or propylene oxide.

[0083] 10. Fatty acids with 6 to 24 carbon atoms.

[0084] 11. Alkyl polysaccharides of the general formula R**-O-Zo, wherein R** represents a straight-chain or branched, saturated or unsaturated alkyl group having an average of 8-24 carbon atoms, and Zo represents an oligoglycoside group having an average of o = 1-10 hexose or pentose units or mixtures thereof.

[0085] 12. Natural substances and their derivatives, such as lecithin, lanolin, saponins, cellulose; cellulose alkyl ethers and carboxyalkyl cellulose, wherein each alkyl group has up to 4 carbon atoms.

[0086] 13. Linear organo(poly)siloxanes containing polar groups, especially those with alkoxy groups having up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

[0087] Particularly suitable cationic emulsifiers include:

[0088] 14. Salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acid.

[0089] 15. Alkyl quaternary ammonium salts and alkylbenzene quaternary ammonium salts, especially those whose alkyl groups have 6 to 24 carbon atoms, particularly halides, sulfates, phosphates and acetates.

[0090] 16. Alkylpyridinium salts, alkylimidazoline salts and alkyloxazoline salts, especially those whose alkyl chains have up to 18 carbon atoms, particularly halides, sulfates, phosphates and acetates.

[0091] Particularly suitable amphoteric emulsifiers include:

[0092] 17. Amino acids with long-chain substituents, such as N-alkyl-di(aminoethyl)glycine or N-alkyl-2-aminopropionate.

[0093] 18. Betaines, for example, N-(3-acylaminopropyl)-N,N-dimethylammonium salts having C8-C18 acyl groups, and alkylimidazolium betaines.

[0094] Preferred emulsifiers are nonionic emulsifiers, particularly alkyl polyethylene glycol ethers listed in item 6 above, adducts of alkylamines with ethylene oxide or propylene oxide listed in item 9, alkyl polysaccharides listed in item 11, and polyvinyl alcohol listed in item 5.

[0095] The amount of emulsifier used here is from 1% to 70% by weight, based on the total weight of the aqueous emulsion. The aqueous emulsion comprises preferably 0.5% to 80% by weight of the copolymer of the present invention, based on the total weight of the aqueous emulsion.

[0096] The aqueous emulsion of the present invention may also include other substances, such as polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol mixtures thereof, as well as acids. Examples of acids are carboxylic acids, such as acetic acid, formic acid, citric acid, malic acid, and lactic acid.

[0097] Other substances that may be present in the aqueous emulsions of the present invention include solvents or co-emulsifiers (B').

[0098] Examples of non-aqueous solvents or co-emulsifiers are 1-pentanol, 1-hexanol, 1-octanol, propylene glycol, 1,3-butanediol, 1,2-hexanediol, 2-ethylhexyl-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.

[0099] The organopolysiloxane (1) of formula (II) used in the method of the present invention can be prepared by the process described in US 7501184B2 (incorporated by reference), particularly in column 13, lines 14 through 48. Other processes are also known to those skilled in the art.

[0100] Examples of polyetheramines (2) used in the method of the present invention are the D-series and ED-series, which are commercially available from Huntsman. Diamines, for example, D-230 D-400 D-2000 HK 511 ED-600 ED-900 and ED-2003.

[0101] In the method of the present invention, it is preferable to first introduce an organopolysiloxane (1), and the quaternary ammonium base (3) and optionally a polyetheramine (2) and optionally a primary or secondary amine (33) may be added together, or the polyetheramine (2) may be added first and then the quaternary ammonium base (3), or the quaternary ammonium base (3) may be added first and then the polyetheramine (2). Preferably, the polyetheramine (2) is added first, followed by the quaternary ammonium base (3), and finally the optional primary or secondary amine (33).

[0102] The alcohol formed in the reaction is preferably removed, more preferably by distillation.

[0103] The method of the present invention for preparing organosilicon copolymers can be carried out in batches, semi-batches, or continuously.

[0104] Examples of fibrous substrates treated with the composition (A) including the organosilicon copolymer of the present invention are naturally or synthetically produced fibers, yarns, strands, cables, sheet textile structures, such as nonwovens, mats, woven fabrics, knotted or knitted textiles, leather and artificial leather, and hair. Preferred fibrous substrates are textiles. For application of the compositions of the present invention, textiles may take the form of individual fibers, fiber bundles, fiberfill fibers, yarns, carpets, fabric webs, or garments or portions thereof.

[0105] Textiles may consist of the following: cotton, wool, copolymers of vinyl acetate, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, aramid, polyimide, polyacrylate, polyacrylonitrile, polylactide, polyvinyl chloride, glass fiber, ceramic fiber, cellulose, or mixtures thereof.

[0106] It can be applied to the fiber substrate to be treated, preferably textiles, in any desired manner. These methods are suitable for and well-known for treating fiber substrates, such as textiles, for example, by dip coating, spreading, casting, spraying, roller coating, filling, printing, or foaming.

[0107] In application, the compositions of the present invention can be combined with common textile auxiliaries, such as binders comprising melamine resins or hydroxymethyl resins, polyethylene, polyurethane, polyacrylates, polyvinyl alcohol, polyvinyl acetate, fluorescent whitening agents, matting agents, electrolytes, wetting agents, plastic resins, bleaching agents, antistatic agents, dispersions of metal oxides, silicates, fragrance oils, dyes and preservatives, defoamers or other hydrophobic and oleophobic auxiliaries, such as perfluorinated hydrocarbons.

[0108] Furthermore, the products of this invention can be used with polysiloxane-based fabric softeners and organic softeners, such as anionic, cationic, and nonionic softeners and mixtures thereof.

[0109] These include functional and non-functional organosilicones, salts of metal soaps, alkyl polysulfonates, sulfosuccinates and their derivatives, ester quaternary ammonium salts, sulfonyl alkylene fatty acid amides, alkyl ammonium sulfates, triethanolamine fatty acid esters, fatty acid polyethylene glycol esters, fatty amine polyalkylene adducts, fatty acid amide polyalkylene adducts, and dispersions of alkanes, waxes, polyethylene, and polyesters.

[0110] The treated fiber substrate, preferably textile, is dried at a temperature of 20°C to 200°C, more preferably 100°C to 180°C.

[0111] The organosilicon copolymers of the present invention and compositions (A) including the organosilicon copolymers of the present invention have the following advantages: the fiber substrates (e.g., textiles) treated therewith are particularly hydrophilic, have a soft hand feel, and are easily emulsified.

[0112] In the embodiments described below, unless otherwise stated, all parts and percentages mentioned are by weight. Furthermore, all viscosity references are based on a temperature of 25°C.

[0113] Unless otherwise stated, the examples and comparative examples in Table 1 were carried out at temperatures reached when mixed at 50 mbar and approximately 85°C. The reaction time was between 0.5 and 5 h, preferably between 1 and 3 h.

[0114] In this invention, Me represents methyl and Et represents ethyl. Detailed Implementation

[0115] Oxamidoester-terminated silicone oil (Mw = 11,000 g / mol, Mn = 7,000 g / mol), bifunctional, supplied by Wacker Chemie.

[0116] Tetramethylammonium hydroxide methanol solution, wherein the content of tetramethylammonium hydroxide is 25 wt%, calculated based on a total solution volume of 100 wt%.

[0117] A dodecyltrimethylammonium chloride ethanol solution, wherein the content of dodecyltrimethylammonium chloride is 25 wt%, calculated based on a total solution volume of 100 wt%.

[0118] ED-900, polyetheramine, is available from Huntsman Performance Products, Everslaan 45, B3078, Everberg, Belgium.

[0119] DA102, N 1 N 1 -Dimethylpropane-1,3-diamine (available commercially from SIGMA-ALDRICH, MERCK, Darmstadt, Germany).

[0120] Preparation method:

[0121] Oxalamyl ester-terminated organopolysiloxane (1) was loaded into a 1000 ml four-necked flask equipped with a thermocouple, a KPG stirrer, and a reflux condenser. Under stirring at 70-100°C for 15 minutes, an optional polyetheramine (2) was added, and the mixture was stirred for 30-60 minutes. Then, a solution of a quaternary ammonium base (3) was added, and the mixture was stirred for another 10 minutes. Subsequently, small molecules were removed under vacuum of 50 mbar at 70-120°C for 2-4 hours. DA102 was then optionally added, and small molecules were removed under vacuum of 50 mbar at 70-120°C for 1-2 hours to obtain the copolymer. Its molecular weight was determined by SEC.

[0122] Table 1

[0123]

[0124] The raw materials in Table 1 are pure substances, and the amount used is in mmol.

[0125] Table 2-1

[0126]

[0127] Table 2-1 shows the relative mol% proportions of each functional group and structural unit as determined by NMR Si. 29 H 1 and C 13 Test calculations show that the -Si-Y-NH- structural unit has the same meaning as in the general formula (Ia).

[0128] The inventors of this invention discovered that copolymers containing general formula (Ia) structural units can be obtained using quaternary ammonium base raw materials. Compared to C.Ex.7, which does not contain (Ia) structural units, the novel copolymer (Ex.1) of this invention has better hand feel and hydrophilicity (shorter droplet absorption time). Furthermore, the novel copolymer of this invention can simultaneously achieve good hydrophilicity and antibacterial properties. Moreover, the antibacterial effect of this novel copolymer is longer-lasting, safer, and more environmentally friendly.

[0129] Table 2-2

[0130] Ex1 Ex4 C.Ex7 Weight-average molecular weight Mw 24840 25080 21960 Number average molecular weight Mn 6661 4906 6667

[0131] Table 3

[0132] Ex1 Ex4 C.Ex7 feel 5 3 4 yellowish 5 4 5 Droplet absorption time 5 5 3

[0133] Table 4

[0134] Dosage Examples or comparative samples 41.00 MULTISO 13 / 50 was provided by Sasol. 10.25 water 150.00 acetic acid 0.41 total 201.66

[0135] The raw materials in Table 4 are pure substances, and the amount used is in g.

[0136] Softness measurement (hand feel assessment):

[0137] Since the softness of textiles largely depends on the subjective feeling of the testers, only the boundary conditions can be standardized, not the evaluation itself. However, to ensure reproducibility, the finished samples were evaluated and ranked according to their softness. For this purpose, four testers assigned scores based on the number of samples tested, with the score level correlated with softness. The softest sample received the highest score, while the least soft sample received 0 points. Therefore, the hand feel evaluation of a sample was calculated as the average of the scores obtained for that particular sample.

[0138] Determination of droplet absorption time:

[0139] After applying the silicone product, the treated sample was stored in a conditioning room for eight hours to acclimatize at 23°C and 62% atmospheric humidity. Then, deionized water droplets were dropped from a height of 1 cm onto the surface of the taut fabric, and the time it took for the fabric to absorb the water droplets was measured—but not exceeding three minutes (180 seconds).

[0140] Five measurements were performed, and the average of the results was taken. The hydrophilicity scores were as follows: 5 points for less than 40 seconds, 4 points for less than 50 seconds, and 3 points for less than 60 seconds.

[0141] Determining the yellowing:

[0142] using spectro guide sphere A colorimeter (BYK GARDNER, Geretsried, Germany) is used to determine the degree of yellowing. In this case, the textile sample is measured at three different points, and the average value is calculated. This "average yellowing b+" is then compared to an untreated sample.

[0143] A smaller b+ value indicates a reduced yellowing.

Claims

1. An organosilicon copolymer containing structural units represented by general formula (Ia), M is N(R) 1 )4, R 1 Same or different, and indicates a monovalent hydrocarbon group having 1 to 18 carbon atoms. Group Y is a divalent hydrocarbon group, which may optionally be substituted by one or more heteroatoms; Group R 2 Same or different, and indicates a monovalent hydrocarbon group having 1 to 18 carbon atoms and may include halogen or oxygen atoms. n is an integer from 10 to 2000.

2. The copolymer of claim 1, wherein, R 1 Methyl, ethyl Group Y is methylene, 1,2-ethylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, -C2H4-NH-C3H6-, n is an integer from 10 to 300.

3. The copolymer of claim 1, comprising structural units represented by general formula (Ib): Group M is defined as described above. Group Z is polyethylene glycol-based, polypropylene glycol-based, or a mixture of polyethylene glycol-based and polypropylene glycol-based; the molecular weight of group Z is 120-4500 g / mol. Where R 3 Same or different, selected from hydrogen atoms or monovalent hydrocarbon groups having 1 to 20 carbon atoms, where p is an integer from 1 to 5. Y,R 2 and n as defined in claim 1.

4. The copolymer of claim 3, wherein R 3 Selected from hydrogen atom, methyl, ethyl, propyl, p is an integer from 1 to 2.

5. The copolymer of claim 3, comprising structural units represented by general formula (Ic): Groups M, R 2 R 3 As defined in claim 3, q is 0 or an integer from 1 to 5. Y, Z and n are as defined in claim 3.

6. The copolymer of claim 3, wherein q is 0 or an integer from 1 to 2.

7. The copolymer of claim 1, comprising structural units represented by general formula (Id) and / or (I-d'): Groups M, R 2 As defined above, R * It is a monovalent hydrocarbon group with 1 to 18 carbon atoms. Y and n are as defined in claim 1.

8. The copolymer of claim 7, R * It is methyl or ethyl.

9. A method for preparing the copolymer as described in any one of claims 1-8, comprising: (1) An organopolysiloxane containing a structural unit represented by general formula (II): in, R 2 Y and n have the definitions described above that indicate them, and R* is a monovalent hydrocarbon group having 1 to 18 carbon atoms. Reaction with the following component (3), and optional component (2): Quaternary ammonium base component (3) is a compound represented by the general formula (III-3). N(R 1 )4 + X - (III-3) Where R 1 As defined in claim 1, X is OH. Component (2) is R 3 HN-Z-NHR 3 (III-2) polyetheramine, R 3 Z has the definition indicated in claim 3.

10. The method of claim 9, wherein, R * It is methyl or ethyl.

11. The method of claim 9, wherein the quaternary ammonium base (3) is used in an amount of 10 mol or more relative to 100 mol of polymer in the organopolysiloxane (1).

12. The method of claim 11, wherein the quaternary ammonium base (3) is used in an amount of 40-400 mol relative to 100 mol of polymer in the organopolysiloxane (1).

13. The copolymer prepared by the method according to any one of claims 9-12.

14. Use of the copolymer as described in any one of claims 1-8 or 13 in the textile field for improving the hydrophilicity and / or hand feel of textiles.

15. Use of the copolymer as described in any one of claims 1-8 or 13 in the textile field for simultaneously improving the hydrophilicity and antibacterial properties of textiles.

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