EP3844338A1

EP3844338A1 - Use of silicon copolymers to provide fiber substrates with a wash-resistant finish

Info

Publication number: EP3844338A1
Application number: EP19725104.4A
Authority: EP
Inventors: Jens-Peter Moldenhauer; Walter Eichberger; Inge Seeger-Feichtinger
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 2019-05-15
Filing date: 2019-05-15
Publication date: 2021-07-07
Also published as: KR20210045492A; CN112840078A; US20220251306A1; WO2020228952A1; JP2022533954A

Abstract

Described is the use of compositions to provide fibrous substrates with a wash-resistant finish, said compositions containing silicone copolymers (A) of formula (I), wherein Y is the same or different and represents a divalent hydrocarbon radical having 1 to 20 carbon atoms, Z is the same or different and represents a divalent polyoxyalkylene-containing organic radical, preferably a radical of formula -(R⁶O)_w-R⁷-, R¹ is the same or different and represents a radical of formula -N(R⁴)-R⁵ or -O-R⁵, R² is the same or different and represents a monovalent hydrocarbon radical having 1 to 18 carbon atoms which may contain one or more halogen or oxygen atoms, R³ is the same or different and represents a hydrogen atom or a monovalent hydrocarbon radical having 1 to 18 carbon atoms, R⁴ represents a hydrogen atom, a C_1-18 alkyl radical or a hydrocarbon radical having 4 to 18 carbon atoms which contains one or more O or N atoms, R⁵ represents a C_1-18 alkyl radical or a hydrocarbon radical having 4 to 18 carbon atoms which contains one or more O or N atoms, R⁶ is the same or different and represents a C₁-C₁₀ alkylene radical, preferably a C₂-C₃ alkylene radical, R7 represents a C1-C10 alkylene radical, preferably a C₂-C₃ alkylene radical, n is an integer from 10 to 2000, p is an integer from 1 to 5, preferably 1 to 2, and w is on average 2.5 to 80.

Description

Use of silicone copolymers to make fibrous substrates washable

The invention relates to the use of silicone copolymers for making fibrous substrates wash-permanent.

Modern, silicone-containing softeners for making fibers water repellent consist mainly of functional silicone oils, which, for example, have hydrophilic or quaternary groups

Ammonium groups, such as. B. from DE 19652524 Al known,

contain. The quaternary products are mostly not

water-soluble and must be brought into an aqueous, applicable form by additional emulsification, while the hydrophilically modified siloxanes are partly water-dispersible. However, the latter are compared to classic

amino-functional siloxanes have poorer softness properties.

Siloxane copolymers, as described in US Pat. No. 5,001,210 A, US 2003/0032726 A1 and US 2008/0075683 A1, in which the amino groups are combined with hydrophilic groups, have the disadvantage that they have to be prepared in multistage synthesis steps. In some cases, toxic intermediate products, such as isocyanates and their derivatives, have to be used or are obtained as intermediate products, or complex hydrosilylation steps are necessary. The hydrophilic products are also not wash-resistant and, to that extent, are also not suitable

economically modifiable. Furthermore, some of them show a disturbing inherent color.

In US 7,501,184 copolymers are described by

Implementation of linear organopolysiloxanes with

Oxamidoester groups are terminated, can be obtained with organic diamines. Highly viscous to solid copolymers are obtained which are used in adhesives, in particular as hot melt glue. These highly viscous products cannot be emulsified in a stable manner and therefore cannot be integrated into the textile application chain. The object was to provide silicone copolymers and their emulsions for use in treating fibrous substrates, in particular textiles, which do not have the disadvantages mentioned above and which do not contain toxic substances such as

Isocyanates, can be produced to give the treated substrates improved wash resistance

equip.

The object is achieved by the invention.

The invention relates to the use of

Compositions for the permanent wash finish of fibrous substrates containing silicone copolymers (A) of the formula (I)

in which

Y is the same or different and is divalent

Hydrocarbon radical with 1 to 20 carbon atoms, which can contain one or more heteroatoms, preferably oxygen or nitrogen atoms, means,

Z is the same or different and is a divalent one

An organic radical containing a polyoxyalkylene group, preferably a radical of the formula - (R ⁶ O) _w -R ⁷ -,

R ^{1 is} identical or different and is a radical of the formula

-N (R ⁴ ) -R ⁵ (IV ') or -OR ⁵ (V'), preferably a radical of the formula -N (R ⁴ ) -R ⁵ (IV '),

R ^{2 is the} same or different and is monovalent

Hydrocarbon radical with 1 to 18 carbon atoms, which can contain halogen or oxygen atoms, means R ^{3 is} identical or different and is a hydrogen atom or a monovalent hydrocarbon radical with 1 to 20

Carbon atoms means

R ^{4 represents} a hydrogen atom, a C _1-18 -alkyl radical or a

Hydrocarbon radical with 4 to 18 carbon atoms, which contains one or more oxygen or nitrogen atoms, and

R ^{5 is} a C _1-18 -alkyl radical or a hydrocarbon radical with 4 to 18 carbon atoms which contains one or more oxygen or nitrogen atoms,

or R ⁴ and R ⁵ in formula (IV ') together represent a divalent hydrocarbon radical which can contain one or more oxygen or nitrogen atoms,

R ^{6 is} identical or different and is a Ci-Cio-alkylene radical, preferably a C ₂ -C ₃ -alkylene radical, preferably one

Means ethylene or iso-propylene radical, and

R ^{7 is} a C ₁ -C ₁₀ alkylene radical, preferably a C ₂ -C ₃ alkylene radical, preferably an ethylene or iso-propylene radical,

n is an integer from 10 to 2000, preferably 10 to 300,

p is an integer from 1 to 5, preferably 1 to 2, preferably 1, and

w is an average of 2.5 to 80, preferably 10 to 30.

The silicone copolymers according to the invention for the permanent washing finish of fibrous substrates are produced by (1) organopolysiloxanes of the formula (II) terminated with oxamidoester groups

where R ² , Y and n have the meaning given above and

R * is a monovalent hydrocarbon radical with 1 to 18 carbon atoms or a radical R ⁵ , where R ^{5 has} the meaning given above,

With

(2) Polyetheramines of the formula R ³ HN-Z-NHR ³ (III), where R ³ and Z have the meanings given above and

(3) primary or secondary amines of the formula

HN (R ⁴ ) -R ⁵ (IV) or alcohols of the formula HOR ⁵ (V), where R ⁴ and R ^{5 have} the meanings given above for them, are converted.

In contrast to the high molecular weight copolymers described in US Pat. No. 7,501,184, the silicone copolymers according to the invention for the permanent wash finish of fibrous substrates have a significantly lower molecular weight. The silicone copolymers preferably have a molecular weight Mn

(Number average) from 4000 - 30000 g / mol. In the context of the present invention, the number average molecular weight Mn is preferably determined by means of size exclusion chromatography (SEC). The number average is preferred

Molecular weight Mn using size exclusion chromatography (SEC) against polystyrene standard, in THF, at 60 ° C, flow rate 1.2 ml / min and detection with RI (refractive index detector) on a Styragel HR3-HR4-HR5-HR5 column set by Waters Corp. USA determined with an injection volume of 100 mΐ. Examples of the radical Y are divalent hydrocarbon radicals such as the methylene group, the 1,2-ethylene group, the 1,3-propylene group, the 1,3-butylene group, the 1,4-butylene group, the 1,5-pentylene group and the 1 , 6-hexylene group.

Further examples of the radical Y are alkylene radicals which contain one or more heteroatoms, e.g. the

-C ₂ H ₄ -NH-C ₃ H ₆ - group.

A preferred example is the 1,3-propylene group. Examples of the radical Z are divalent hydrocarbonoxy radicals, such as the polyethylene glycol radicals or polypropylene glycol radicals or mixtures of polyethylene glycol and

Polypropylene glycol residues. The radical Z preferably has a

Molecular weight from 120 g / mol to 4,500 g / mol, very particularly preferably a molecular weight from 500 g / mol to 1,800 g / mol.

Examples of radicals R ² are alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. -Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso- Octyl radicals such as the 2,2,4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical, and octadecyl radicals such as the n-octadecyl radical; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl,

Cycloheptyl and methylcyclohexyl radicals; Alkenyl radicals, such as vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl,

3-butenyl and 4-pentenyl radical; Alkynyl radicals, such as the ethynyl, propargyl and 1-propynyl radical; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; Alkaryl radicals such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

A preferred example of the R ² radical is the methyl radical. The above-mentioned radicals R ² can also be one or more

Contain halogen atoms or oxygen atoms.

Examples of hydrocarbon radicals R ^{2 also} apply to

Hydrocarbon radicals R ³ . Preferably R ^{3 is} a

Hydrogen atom or a C ₁ -C ₆ -alkyl radical, preferably one

Hydrogen atom.

The radical R ^{1 of} the formula -N (R ⁴ ) -R ⁵ (IV ') comes from a primary or secondary amine of the formula HN (R ⁴ ) -R ⁵ (IV) minus the hydrogen atom bonded to the nitrogen atom.

The radical R ^{1 of} the formula -OR ⁵ (V ') comes from an alcohol of the formula HOR ⁵ (V) minus the H atom bonded to the oxygen atom. The radicals R ⁴ and R ⁵ in the radical R ¹ can be identical or different C ₁ -C ₁₈ -alkyl radicals. The examples of Ci-Ci ₈ -alkyl radicals R ^{2 also} apply to C ₁ -C ₁₈ -alkyl radicals R ⁴ and R ⁵ . R ⁴ and R ⁵ in formula (IV ') can simultaneously be part of a cyclic radical.

The radicals R ⁴ and R ⁵ in the radical R ¹ can also be a hydrocarbon radical having 4 to 18 carbon atoms, which preferably contains at least one heteroatom nitrogen or oxygen. R ⁴ and R ⁵ in formula (IV ') can at the same time be part of a heterocyclic radical.

Examples of such radicals R ⁴ and R ⁵ are radicals of the formula - (CH ₂ ) ₃ -N (CH ₃ ) ₂ , - (CH ₂ ) ₃ -OCH ₂ CH ₃ and - (CH ₂ ) ₂ -OCH ₂ CH ₃ .

Preferred examples of amines of the formula HN (R ⁴ ) -R ⁵ (IV) are primary amines, such as H_NH- (CH ₂ ) 3-N (CH ₃ ) 2

(N ¹ , N ¹ -dimethylpropane-1, 3-diamine) and secondary amines, such as

HN- [(CH _{2) 3} -N (CH _{3) 2} ] 2 (N ¹ - (3- (Dimethylamino) propyl) -N ³ , N ³ -dimethylpropane-1,3-diamine) primary polyetheramines such as

H-NH- (CH ₂ ) 3-OCH ₂ CH3, H_NH- (CH ₂ ) 2-OCH ₂ CH3, secondary polyetheramines such as

NH- [(CH ₂ ) ₃ -OCH ₂ CH ₃ ] 2, NH- [(CH ₂ ) ₂ -OCH ₂ CH ₃ ] ₂ ,

The preferred radicals R ¹ correspond to the above-mentioned amines minus an H atom bonded to the nitrogen atom N, or the above-mentioned alcohols minus an O atom bonded to the oxygen atom 0,

thus preferred radicals R ^{1 are} those of the formula -NH- (CH ₂ ) 3-N (CH ₃₎ 2 and NH- (CH ₂ ) ₃ -OCH ₂ CH ₃

-N- [(CH ₂ ) ₃ -N (CH ₃ ) ₂ ] ₂ and -N- [(CH _{2) 3} -OCH ₂ CH ₃ ] ₂ .

The compositions according to the invention for making fibrous substrates permanent to wash can be solutions of silicone copolymers (Ά) according to the invention in organic solvents.

The compositions according to the invention are preferably used for the wash-permanent finishing of fibrous substrates

Containing aqueous emulsions

inventive silicone copolymers (A)

Emulsifiers (B) and / or coemulsifiers (B ') and

Water (C).

As emulsifiers (B) it is possible to use nonionic, anionic or cationic emulsifiers or also mixtures thereof. The aqueous emulsions according to the invention for the permanent washing finish of fibrous substrates contain emulsifiers known per se and mixtures thereof.

Particularly suitable anionic emulsifiers are:

1. Alkyl sulfates, especially those with a chain length of 8 to 18 carbon atoms, alkyl and alkaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic radical and 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units.

2. sulfonates, especially alkyl sulfonates with 8 to 18 carbon atoms, alkylarylsulfonates with 8 to 18 carbon atoms, taurides, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms; if appropriate, these alcohols or alkylphenols can also be ethoxylated with 1 to 40 EO units. 3. Alkali and ammonium salts of carboxylic acids with 8 to 20 C-

Atoms in the alkyl, aryl, alkaryl or aralkyl radical.

4. Phosphoric acid partial esters and their alkali and ammonium salts, especially alkyl and alkaryl phosphates with 8 to 20 carbon atoms in the organic radical, alkyl ether or alkaryl ether phosphates with 8 to 20 carbon atoms in the alkyl or alkaryl radical and 1 to 40 EO Units .

Particularly suitable non-ionic emulsifiers are:

5. Polyvinyl alcohol, which still has 5 to 50%, preferably 8 to 20% vinyl acetate units, with a degree of polymerization of 500 to 3000. 6. Alkyl polyglycol ethers, preferably those with 8 to

40 EO units and alkyl radicals of 8 to 20 carbon atoms.

7. Alkylaryl polyglycol ethers, preferably those with 8 to 40 EO units and 8 to 20 carbon atoms in the alkyl and

Aryl residues.

8. Ethylene oxide / propylene oxide (EO / PO) block copolymers,

preferably those with 8 to 40 E0 or PO units.

9. Addition products of alkylamines having alkyl radicals of 8 to 22 carbon atoms with ethylene oxide or propylene oxide.

10. Fatty acids with 6 to 24 carbon atoms.

11. Alkyl polyglycosides of the general formula R * -OZ _o , wherein R * is a linear or branched, saturated or unsaturated alkyl radical with an average of 8-24 carbon atoms and Z _{o is} one

Oligoglycoside residue with an average o = 1 - 10 hexose or

Mean pentose units or mixtures thereof.

12. Natural substances and their derivatives, such as lecithin, lanolin, saponins, cellulose; Cellulose alkyl ethers and

Carboxyalkyl celluloses, the alkyl groups of which each have up to 4 carbon atoms.

13. Linear organo (poly) siloxanes containing polar groups, in particular those with alkoxy groups with up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

The following are particularly suitable as cationic emulsifiers: 14. Salts of primary, secondary and tertiary fatty amines with 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acids. 15. Alkyl and alkyl benzene quaternary ammonium salts,

especially those whose alkyl groups have 6 to 24 carbon atoms, especially the halides, sulfates, phosphates and acetates. 16. Alkylpyridinium, alkylimidazolinium and

Alkyloxazolinium salts, especially those whose alkyl chain has up to 18 carbon atoms, especially the halides, sulfates, phosphates and acetates. The following are particularly suitable as ampholytic emulsifiers:

17. Long-chain substituted amino acids, such as N-alkyl-di (aminoethyl) glycine or N-alkyl-2-aminopropionic acid salts. 18. Betaines, such as N- (3-acylamidopropyl) -N, N-dimethylammonium salts with a Cg-C _] _g-acyl radical and alkylimidazolium betaines.

Preferred emulsifiers are nonionic emulsifiers, in particular those listed under 6 above

Alkyl polyglycol ethers listed under 9

Addition products of alkylamines with ethylene oxide or

Propylene oxide, the alkyl polyglycosides listed under 11. and the polyvinyl alcohols listed under 5.. Emulsifiers are used in amounts of 1% by weight to 70% by weight, based on the total weight of the aqueous emulsions

used. The aqueous emulsions for the permanent wash finish of fibrous substrates contain copolymers (A) according to the invention preferably in amounts of 0.5% by weight to 80% by weight, based on the total weight of the aqueous emulsions.

The aqueous emulsions according to the invention for the permanent washing finish of fibrous substrates can also contain further substances, such as polyethylene glycols, polypropylene glycols and polyethylene-polypropylene glycols and mixtures thereof, as well as acids. Examples of acids are carboxylic acids, such as

Acetic acid, formic acid, citric acid, and malic acid

Lactic acid.

The aqueous emulsions according to the invention for the permanent washing finish of fibrous substrates can contain solvents or co-emulsifiers (B ') as further substances.

Examples of non-aqueous solvents or co-emulsifiers are 1-pentanol, 1-hexanol, 1-octanol, propanediol,

1,3-butanediol, 1,2-hexanediol, 2-ethylhexane-1,3-diol,

1,2-octanediol, glycerine, diethylene glycol methyl ether,

Diethylene glycol ethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol methyl ether.

Used in the manufacture of silicone copolymers

wash-resistant finishing of fibrous substrates

Organopolysiloxanes (1) of the formula (II) terminated by oxamido ester groups can be prepared according to the method described in US Pat

(incorporated by reference), in particular column 13, lines 14 to 48, methods described are prepared. Dem

Other methods are also known to those skilled in the art.

Examples of the polyetheramines (2) used in the production of silicone copolymers to make fibrous substrates permanent to wash are Jeffamine® diamines of the D and ED series, commercially available from Huntsman, such as Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000,

Jeffamine® HK 511, Jeffamine® ED-600, Jeffamine® ED-900, and Jeffamine® ED-2003. In the production of silicone copolymers for

Polyetheramines (2) in amounts of preferably 0.3 to 0.8 mol, preferably 0.4 to 0.6, particularly preferably 0.5 mol, amino group in (2) per mole of oxamidoester group in organopolysiloxane ( 1) used.

Primary or secondary amines of the formula (IV) are preferably used as component (3). In the production of silicone copolymers for

Wash-permanent finishing of fibrous substrates are primary or secondary amines (3) in amounts of preferably 0.2 to 0.7 mol, more preferably 0.4 to 0.6 mol, particularly preferably 0.5 mol, amino group in (3) per mol Oxamidoester group in

Organopolysiloxane (1) used.

Preferably at least 80%, preferably at least 90%, very particularly preferably at least 95% of the oxamido ester groups contained in organopolysiloxane (1) are reacted with the amino groups contained in (2) and (3).

In the production of silicone copolymers for

The organopolysiloxanes (1) terminated with oxamidoester groups are preferably initially introduced for the wash-permanent finishing of fibrous substrates and the polyetheramines (2) and the amines (3) can be added together or the amines (3) can be added first and then the polyetheramines (2) or the polyether amines (2) can be added first and then the amines (3). The amines (3) and then the polyetheramines (2) are preferably added first. The alcohol formed in the reaction is preferably removed, preferably by distillation. The production of the silicone copolymers (A) for the permanent washing finish of fibrous substrates is preferably carried out at temperatures from 0.degree. C. to 100.degree. C., preferably from 15.degree. The process according to the invention is preferably carried out at the pressure of the surrounding atmosphere, such as about 1020 hPa, but it can also be carried out at higher or lower pressures.

The production of the silicone copolymers (A) for the permanent washing finish of fibrous substrates can be carried out batchwise, semicontinuously or continuously.

Examples of fibrous substrates which are treated with the compositions containing the silicone copolymers (A) according to the invention are natural or synthetically produced fibers, yarns, strands, ropes, and flat textile structures such as

Nonwovens, mats, woven, knotted, knitted or knitted textiles, leather and imitation leather, and hair. Preferred fibrous substrates are textiles. For the order of

In the composition according to the invention, the textiles can be in the form of individual fibers, fiber bundles, filler fibers, yarns, carpets, webs of fabric or pieces of clothing or parts of clothing.

The textiles can be made of cotton, wool, copolymers of vinyl acetate, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, aramid,

Polyimide, polyacrylate, polyacrylonitrile, polylactide, polyvinyl chloride, glass fibers, ceramic fibers, cellulose or their

Mixtures exist. The application to the fibrous substrates to be treated, preferably textiles, can be carried out in any manner which is widely known and suitable for the treatment of fibrous substrates, such as textiles, for example by dipping, brushing, pouring,

Spraying, rolling, padding, printing or foam application take place.

In use, the composition according to the invention can be used with customary textile auxiliaries, such as

Binders made from melamine or methylol resins, polyethylenes, polyurethanes, polyacrylates, polyvinyl alcohols,

Polyvinyl acetates, optical brighteners, matting agents, electrolytes, wetting agents, plastics, bleaching agents, antistatic agents, dispersions of metal oxides, silicates,

Perfume oils, dyes and preservatives, defoamers or other hydrophobic and oleophobic auxiliaries, such as perfluorinated hydrocarbons, can be combined.

Furthermore, the products according to the invention can with

Textile softeners based on polysiloxanes and organic softeners such as anionic, cationic and nonionic softeners and mixtures thereof can be used.

These include functional and non-functional silicones,

Salts of metal soaps, alkyl polysulfonates, sulfosuccinates and their derivatives, esterquats, 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

Paraffins, waxes, polyethylenes and polyesters. The treated fibrous substrates, preferably textiles, are preferably left to dry at temperatures from 20 ° C to 200 ° C, preferably 100 ° C to 180 ° C.

Wash-permanent finishing of the fibers means that

Properties that the treated fibers, such as textiles, can be awarded, even after washing.

Such properties are in particular hydrophilicity and

Soft feel, but also deepening of color, elasticity,

Abrasion resistance, abrasion resistance, shrinkage resistance, crease recovery and resilience.

The silicone copolymers (A) according to the invention or the

Compositions containing the silicone copolymers (A) according to the invention have the advantage that they can be easily emulsified and the fibrous substrates, such as textiles, treated with them are hydrophilic and have a soft feel which, in contrast to the prior art, is repeated

Washing remains, so the silicone copolymers (A) according to the invention give the treated fibrous substrates a wash-permanent finish.

In the examples described below, all parts and percentages are based on weight, unless stated otherwise. Furthermore, all viscosity specifications refer to a temperature of 25 ° C. Unless otherwise stated, the following examples are carried out at a pressure of the surrounding atmosphere, i.e. about 1010 hPa, and at room temperature, i.e. at about 20 ° C., or at a temperature that is achieved when the reactants are combined at room temperature without additional heating or Cooling set, carried out.

The following is:

Me for methyl radical and

Et for ethyl radical.

TA 187 = N ¹ - (3- (dimethylamino) propyl) -N ³ , N ³ -dimethylpropane-l, 3- diamine (available from SIGMA-ALDRICH, MERCK, Darmstadt, Germany)

DA 102 = N ¹ , N ^x -dimethylpropane-l, 3-diamine (available from SIGMA-ALDRICH, MERCK, Darmstadt, Germany) Example 1 (preparation of copolymer PI)

In a 1000 ml 3-neck flask with thermocouple, KPG stirrer and reflux condenser, 474 g (60 mmol) of dimethylpolysiloxane terminated with oxamidoester groups (7,923 g / mol), hereinafter referred to as oxamidoester-terminated silicone oil,

submitted. At 22 ° C with stirring within 10

Minutes 11.22 g (60 mmol) TA 187 and then 19.8 g (30 mmol) JEFFAMINE® ED-600 (available from Huntsman Performance Products, Everslaan 45, B-3078 Everberg, Belgium). The mixture was then stirred for a further 30 minutes. The reaction product was then freed from the alcohol formed at 40 ° C. and a pressure of 20 hPa. 502 g of an opaque, oligomeric product P1 with a value determined by SEC were obtained

Molecular weight of 20,050 g / mol.

Example 2 (preparation of copolymer P2)

109 g (10 mmol) of oxamidoester-terminated silicone oil (10,900 g / mol) were placed in a 200 ml 3-neck flask with thermocouple, KPG stirrer and reflux condenser. At 22 ° C., 1.87 g (10 mmol) were added within 10 minutes with stirring

TA 187 and then 3.3 g (5 mmol) JEFFAMINE® ED-600

(available from Huntsman Performance Products, Everslaan 45, B-3078 Everberg, Belgium). The mixture was then stirred for a further 30 minutes. The reaction product was then freed from the alcohol formed at 40 ° C. and a pressure of 20 hPa.

113 g of an opaque, oligomeric product P2 with a molecular weight determined by SEC of 23,378 g / mol were obtained. Example 3 (preparation of copolymer P3)

109 g (10 mmol) of oxamidoester-terminated silicone oil (10,900 g / mol) were placed in a 200 ml 3-neck flask with thermocouple, KPG stirrer and reflux condenser. At 22 ° C, while stirring, 1.02 g (10 mmol) DA 102 and then 3.3 g (5 mmol) JEFFAMINE® ED-600

112 g of an opaque, oligomeric product P3 with a molecular weight of 24,111 g / mol determined by means of SEC were obtained.

Example 4 (preparation of copolymer P4)

TA 187 and then 4.8 g (5 mmol) JEFFAMINE® ED-900

(available from Huntsman Performance Products, Everslaan 45,

B-3078 Everberg, Belgium) was added. The mixture was then stirred for a further 30 minutes. The reaction product was then freed from the alcohol formed at 40 ° C. and a pressure of 20 hPa.

115 g of an opaque, oligomeric product P4 with a molecular weight of 19,366 g / mol determined by means of SEC were obtained.

Example 5 (preparation of copolymer P5)

109 g (10 mmol) of oxamidoester-terminated silicone oil (10,900 g / mol) were placed in a 200 ml 3-neck flask with thermocouple, KPG stirrer and reflux condenser. At 22 ° C, while stirring, 1.02 g (10 mmol)

DA 102 and then 4.8 g (5 mmol) JEFFAMINE® ED-900

114 g of an opaque, oligomeric product P5 with a molecular weight determined by SEC of 21,042 g / mol were obtained. Example 6 (production of copolymer P6 analogously to example 4 in US 2008/0075683 A1 for comparative experiment)

635 g of an α, ω-dihydrogenpolydimethylsiloxane with 0.052% by weight of Si-bonded hydrogen are mixed with 205 g of a polyether of the formula H ₂ C = CH-CH ₂ - (OCH ₂ CH ₂ ) 9 _, 5-OH. The mixture is heated to 100 ° C. and 0.28 g of a 2.7 wt. -% (based on elemental platinum) solution of a platinum-1,3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex in an a, ω - divinyldimethylpolysiloxane with a viscosity of 1000 mPa -s at 25 ° C, a solution of the so-called Karstedt catalyst (the production of which is described in US Pat. No. 3,775,452),

metered in, whereupon the temperature of the reaction mixture rises by 19 ° C and a clear product is formed. After one hour at 100 to 110 ° C., complete conversion of the Si-bonded hydrogen is achieved. The polyether-polysiloxane

Intermediate product has an OH concentration of 0.512 mequ./g and contains 177 ppm water.

200 g of this intermediate product are 10.3 g

Bis (dimethylaminopropyl) amine mixed and heated to 84 ° C; 13.2 g of hexamethylene diisocyanate are metered in.

The ratio of the NCO groups to the sum of the organic functions reacting with them is 0.998, and 0.97 when water is included.

Without further catalysis, a complete conversion of the is achieved in one hour at about 90 ° C in a slightly exothermic reaction

Isocyanate groups reached. The polymer mixture contains 0.49 mequ. basic nitrogen per gram.

32 g of this polymer are mixed with a solution of 1.04 g

Acetic acid neutralized in 8 g of diethylene glycol monobutyl ether.

The molar ratios of the starting materials used in the production of the silicone copolymers ^{according to} the invention and the molecular weight Mn of the silicone copolymers P1 to P5 and their appearance is summarized in Table 1 for Examples 1 to 5.

Table 1 :

Example 7 (comparative experiment):

25.0 g of the comparative copolymer P6 were 5.0 g

Tridecyl alcohol ethoxylate mixed with 10 EO (80% solution in water, available as LUTENSOL® TO 108 from BASF SE, Ludwigshafen) and then slowly diluted with 70.0 g of water and adjusted to pH 4.5 with 80% acetic acid.

The amount given in Table 3 was prepared by diluting with water and using a padder on a

Cotton knitted fabric and a cotton-polyester blend fabric according to the specifications from Table 2 are applied.

Example 8:

20.5 g of Copolymer P1 were dissolved in 4.5 g of diethylene glycol monobutyl ether (available from Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany) and 4.0 g of tridecyl alcohol ethoxylate with 5 EO (available as LUTENSOL® TO 5 from BASF SE,

Ludwigshafen) and then mixed with 71.0 g of water slowly diluted and with acetic acid, 80% to pH 4.5

set.

Example 9: 20.5 g of copolymer P2 were mixed in 4.5 g of diethylene glycol monobutyl ether and 4.0 g of tridecyl alcohol ethoxylate with 5 EO and then slowly diluted with 71.0 g of water and with 80% acetic acid to pH 4.5 set.

Example 10:

20.5 g of copolymer P3 were mixed in 4.5 g of diethylene glycol monobutyl ether and 4.0 g of tridecyl alcohol ethoxylate with 5 EO and then slowly diluted with 71.0 g of water and adjusted to pH 4.5 with 80% acetic acid.

Cotton knitted fabric and a cotton-polyester blend fabric according to the specifications from Table 2 are applied. Example 11:

20.5 g of P4 were mixed in 4.5 g of diethylene glycol monobutyl ether and 4.0 g of tridecyl alcohol ethoxylate with 5 EO and then slowly diluted with 71.0 g of water and adjusted to pH 4.5 with 80% acetic acid. The amount given in Table 3 was prepared by diluting with water and using a padder on a

Example 12:

20.5 g of copolymer P5 were mixed in 4.5 g of diethylene glycol monobutyl ether and 4.0 g of tridecyl alcohol ethoxylate with 5 EO and then slowly diluted with 71.0 g of water and adjusted to pH 4.5 with 80% acetic acid.

Application technical tests:

A bleached, unfinished woven fabric PES / CO 65/35 Twill with a weight per unit area of 215 g / m ² , an unfinished terry toweling 100% CO with a

Basis weight of 460 g / m ² as well as an unequipped one

Knitwear 100% CO interlock with a weight per unit area of 190 g / m ^{2 is} used. A product padded with water and dried (= blank value) served as reference.

The fabric was soaked with the respective liquor, squeezed off with a two-roll foulard, stretched and the

Terry toweling was dried in a MATHIS laboratory stenter at 150 ° C for five minutes, the knitted fabric and the twill were dried for three minutes (see Table 2). The goods were then air-conditioned for at least 12 hours in an air-conditioned room at 23 ° C. and 62% humidity.

Table 2:

Determination methods for the results of the application examples: Determination of the soft handle (handle evaluation:

Since the soft feel of textiles is subject to the subjective perception of the test persons, only a standardization of the boundary conditions can be achieved, but not the evaluation. In order to still guarantee reproducibility, the finished samples were assessed with regard to their soft feel and ranked. For this purpose, points were awarded by four people depending on the number of samples tested, with the number of points correlating with the soft handle. The softest pattern receives the maximum number of points, while the least soft pattern receives 0 points. The grip rating of a sample is thus calculated as

Average of the points allotted to this sample.

Determination of the drop penetration time:

The finished sample was after the application of the silicone product eight hours for acclimatization in a climatic room at a temperature of 23 ° C and a humidity of

62% stored, then a drop of deionized water from a height of 1 cm was placed on the stretched fabric surface and the time after which the water droplet was absorbed by the fabric was determined, but no longer than three minutes (180 seconds). Five determinations were carried out and the mean value was formed.

Determination of wash resistance:

For the investigation of the wash fastness all

The finished textiles are washed together with approx. 3 kg of fiber in a household washing machine of the SIWAMAT 6143 brand from Siemens with the colored laundry program at 60 ° C and spun at 1400 rpm. 36 g of one were used as a washing surfactant

Liquid detergent of the brand "Spee Feincolor" from the company Henkel. A total of 2 washing cycles of each were carried out 90 minutes duration without intermediate drying.

The goods were then dried and conditioned for at least 12 hours in a climatic room at 23 ° C. and 62% humidity. The samples were then subjected to a soft hand comparison again.

In table 3, the results of the fabric finished using the padding process are compiled for some application examples:

The textiles finished according to the invention with oxamidoester-based silicone copolymers surprisingly show significantly improved wash permanence compared to the comparative product (silicone copolymer produced via hydrosilylation and isocyanate bridging), as evidenced by the still very good soft handle after washing, are comparable to hydrophilic and have a comparably soft feel even before washing.

Table 3:

Claims

1. Use of compositions for permanent washing

Finishing of fibrous substrates containing

Silicone copolymers (A) of the formula (I)

in which

Y is the same or different and is divalent

Hydrocarbon radical with 1 to 20 carbon atoms containing one or more heteroatoms, preferably

Oxygen or nitrogen atoms, means,

Z is identical or different and denotes a divalent organic radical containing a polyoxyalkylene group, preferably a radical of the formula - (R ⁶ 0) "- R ⁷ -,

R ^{1 is} identical or different and is a radical of the formula

-N (R ⁴ ) -R ⁵ (IV ') or -OR ⁵ (V'),

R ^{2 is the} same or different and is monovalent

Hydrocarbon radical with 1 to 18 carbon atoms, which can contain halogen or oxygen atoms, means

R ^{3 is} identical or different and denotes a hydrogen atom or a monovalent hydrocarbon radical having 1 to 20 carbon atoms,

R ^{4 represents} a hydrogen atom, a C _1-18 -alkyl radical or a

Hydrocarbon radical with 4 to 18 carbon atoms, which contains one or more oxygen or nitrogen atoms, and R ^{5 is} a C _1-18 -alkyl radical or a hydrocarbon radical having 4 to 18 carbon atoms which contains one or more

Contains oxygen or nitrogen atoms, or R ⁴ and R ⁵ in formula (IV ') together form one

divalent hydrocarbon radical, which may contain one or more oxygen or nitrogen atoms, mean

R ^{6 is} identical or different and denotes a Ci-Cio-alkylene radical, preferably a C2-C3-alkylene radical, preferably an ethylene or iso-propylene radical, and

R ^{7 is} a Ci-Cio-alkylene radical, preferably a C2-C3-

Alkylene radical, preferably an ethylene or iso-propylene radical,

n is an integer from 10 to 2000, preferably 10 to

300, is,

p is an integer from 1 to 5, preferably 1 to 2,

preferably 1, is and

w on average 2.5 to 80, preferably 10 to 30,

is.

2. Use according to claim 1, characterized in that Y is a 1,3-propylene radical.

3. Use according to claim 1 or 2, characterized in that R ^{1 is} a radical of the formula -N (R ⁴ ) -R ⁵ (IV '), where R ⁴ and R ^{5 have} the meaning given in claim 1 for this.

4. Use according to claim 1, 2 or 3, characterized

labeled that as compositions

Containing aqueous emulsions

Silicone copolymers (A) according to Claim 1, 2 or 3, Emulsifiers (B) and / or co-emulsifiers (B ') and water (C)

can be used.

5. Use according to one of claims 1 to 4, characterized

characterized in that the fibrous substrates are textiles.

6. A process for the wash-permanent finishing of fibrous substrates by applying the compositions according to one of claims 1 to 4 to the fibrous substrates and allowing the fibrous substrates treated in this way to dry at temperatures of preferably 20 to 200 ° C.

7. The method according to claim 6, characterized in that the fibrous substrates are textiles.