DE19852621A1 - Permanent means of finishing fibers or fiber products - Google Patents

Abstract

The invention relates to permanent agents for finishing fibres or fibre-based products, to the production of said agents and to their use in preparations for the surface treatment of fibres or fibre-based products.

Description

The invention relates to permanent means for finishing fibers or fibers existing products, the production of these agents and their application in Preparations for the surface treatment of fibers or of fibers existing products.

DE 44 30 165 A1 relates to the use of hydrophilically modified Polyisocyanates for the production of textile materials with permanent washing Shine.

DE 196 28 018 A1 relates to organosilicon compounds containing oxyalkylene groups with units of the formula

where R is identical or different, denotes a monovalent halogenated or non-halogenated hydrocarbon radical, X is identical or different, is a chlorine atom or a radical of the formula -OR ¹ , where R ¹ denotes an alkyl radical which can be substituted by an ether oxygen atom,
a is 0 or 1,
b 0, 1, 2 or 3,
c is 0, 1, 2 or 3, and the sum a + b + c ≦ 4 is and
A is a residue of the formula

R ^{2 is} a linear or branched, substituted or unsubstituted divalent hydrocarbon radical which may or may not contain ether, amine, sulfide, ester, amide, carbonate, urea and urethane groups,
B is the same or different, X, -NR ₂ ¹ , -OC (= O) -R ¹ , -SR ¹ or a radical of the formula

NR ³ R ² [O-CH (CH ₃ ) -CH ₂ ) _d ] [OCH ₂ CH ₂ ] _e [O (CH ₂ ) ₄ ] _f OR ⁴ (III)

means, where X, R ¹ and R ^{2 have} the meaning given above, R ^{3 is the} same or different, has a hydrogen atom or the meaning of R, R ^{4 has} the meaning of R ³ or a radical of the formula

-C (= O) -R, -R ² NR ₂ ³ , -NR ³ R ² -, -R ² NR ₂ ³ H ⁺ X ^-

represents, d, e and f is an integer of 0-200, provided that the Sum d + e + f ≧ 1 and B per polymer molecule is at least one residue of Contains formula (III).

US-A-5,158,575 relates to permanent hydrophilic silicone textile treatment agents which on textiles containing cellulose are made to last to impart hydrophilic softness and permanent ironing properties. The Silicon finish is made from an aqueous solution of glyoxal, a reactive organically modified silicone copolymer, a glycol and one Acid catalyst. The treatment solution is applied to the textiles and crosslinked by heating at elevated temperature to adhere the silicone to the cellulose tie.  

US-A-4,401,698 relates to silylated organic polymers based on textile materials can be applied to give them hydrophilic properties. These are produced by reacting a polymeric organic acid with silylated amino functional polyethers. The resulting composition can then be crosslinked to make the textile materials treated with it permanent to impart hydrophilic properties.

The aim of the invention is to provide a means that the surface properties permanently influenced by fibrous products in that the Combination of handle components, optionally hydrophilizing Components and suitable crosslinking products are obtained with regard to the soft grip and wettability to a wide variety of requirements are sufficient to use products according to the state of the art that either soft, hydrophobic and partially wash-resistant or soft and are hydrophilic with insufficient permanence.

The present invention in a first embodiment relates to permanent agents of the general formula (I)

The permanent agents according to the invention are composed of the following components, which are reacted with one another in a manner known per se in the presence of a catalyst system, where
R ¹ for a residue of a polyisocyanate-functional compound whose NCO content after the reaction with R ² and / or R ^{3 is} up to 3% by weight, based on the weight of the formula,
R ² for a residue of a conventional soft-grip agent with at least one acidic H atom,
R ^{3 represents} a residue of a conventional hydrophilizing agent with at least one acidic H atom,
x for an integer equal to or greater than 1 and
y represents an integer equal to or greater than 0,
where y is chosen so that at y = 0 permanently hydrophobic surface properties and at y <0 permanently hydrophilic surface properties are achieved.

For example, tertiary amines, in particular, can be used as the catalyst system Triethylamine, N-methylpiperidine, N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N- Dimethylcyclohexylamine, 1,4-diazabicyclo- (2.2.2) octane, 1,2-dimethylimidazole and organotin compounds, in particular tetra-n-butyltin, tri-n-butyltin acetate, Di-n-butyltin diacetate, di-n-butyltin dilaurate, di-n-butyltin dichloride, dimethyltin dichloride and mixtures thereof are used.

According to the invention, R ¹ represents a residue of one or more customary polyisocyanates, which are based on customary diisocyanates and / or customary higher-functionality polyisocyanates with an average NCO functionality of 2.0 to 4.4. These components can be present alone or in a mixture.

Examples of conventional diisocyanates are aliphatic diisocyanates such as Tetramethyl diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octa methylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, Tetradecamethylene diisocyanate, trimethylhexane diisocyanate or trimethyl hexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, or 1,3- or 1,2-diiso cyanatocyclohexane, 4,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-tri methyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate) or 2,4- or 2,6- Diisocyanato-1-methylcyclohexane and aromatic diisocyanates such as 2,4- or 2,6- Toluene diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 1,3- or 1,4-phenylene diisocyanate, 1-chloro-2,4- phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'- Diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4-diisocyanate or  Diphenyl ether 4,4'-diisocyanate. Mixtures of the above can also be used Diisocyanates are present.

Of these, aliphatic diisocyanates, in particular hexa, are preferred methylene diisocyanate and isophorone diisocyanate.

Triiso, for example, are suitable as customary higher-functional polyisocyanates cyanatotoluene or 2,4,4'-triisocyanatodiphenyl ether or mixtures of di-, tri- and higher polyisocyanates.

Due to their lower tendency to yellowing, customary aliphatic, higher-functional polyisocyanates of the following groups are of particular interest:

• a) polyisocyanates containing isocyanurate groups of aliphatic and / or cycloaliphatic diisocyanates. The corresponding ones are particularly important Isocyanato isocyanurates based on hexamethylene diisocyanate and Isophorone diisocyanate. The present isocyanurates are especially simple tris-isocyanatoalkyl or trisisocyanatocycloalkyl Isocyanurates, which are cyclic trimers of the diisocyanates, or um Mixtures with their higher, more than one isocyanurate ring Homologues. The isocyanato isocyanurates generally have an NCO Content of 8 to 30 wt .-%, in particular 15 to 25 wt .-%, and an average NCO functionality from 2.2 to 4.5.
• b) uretdione diisocyanates with aliphatic and / or cycloaliphatic bound Isocyanate groups, preferably of hexamethylene diisocyanate or iso derived from phorone diisocyanates. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
• c) Biuret groups containing polyisocyanates with aliphatic bound Isocyanate groups, in particular. Tris (6-isocyanatohexyl) biuret or its Mixtures with its higher homologues. These biuret groups Polyisocyanates generally have an NCO content of 18 to 25 wt .-% and average NCO functionality from 3 to 4.5.
• d) polyisocyanates containing urethane and / or allophanate groups aliphatic or cycloaliphatic isocyanate groups, as in  for example by converting excess amounts of hexa methylene diisocyanate or isophorone diisocyanate with simple polyvalent Alcohols such as trimethylolpropane, glycerin, 1,2-dihydroxypropane or their Mixtures can be obtained. The urethane and / or allophanate groups containing polyisocyanates generally have an NCO content of 12 up to 20% by weight and an average NCO functionality of 2.5 to 3.
• e) polyisocyanates containing oxadiazinetrione groups, preferably from Hexamethylene diisocyanate or isophorone diisocyanate derived.

Of particular interest are aliphatic polyisocyanates whose NCO content up to is blocked to 90%. Customary blocking agents are known to the person skilled in the art.

Blocking agents which are particularly preferred are those which are desired Split the temperature range from 70 to 180 ° C again and the desired Respond. Examples of such blocking agents are acetone oxime, Butanone oxime, caprolactam, phenol, malonic ester, isononylphenol, bisulfite.

Partially blocked aliphatic is used for the agents according to the invention Diisocyanates and partially blocked aliphatic higher polyisocyanates particularly preferred.

The described diisocyanates and / or higher functionalized polyisocyanates are used for conversion into modified polyisocyanates, which are essential for the invention are particularly preferred, reacted with NCO-reactive compounds.

According to the invention, R ² stands for a residue of a conventional softening agent with at least one acidic H atom,

• A) on the basis of a silicone-free softening agent to additionally achieve a lower flammability of synthetic fibers such. B. polyester filler fibers in the application of the permanent agent according to the invention.
  These are, in particular, reaction products of fatty acids with amines, polyamines, alkanolamines as are usually used for soft-grip finishing. Conversion products of coconut fatty acid, palmitic acid, tallow fatty acids, stearic acid, hydroxystearic acid, behenic acid and oleic acid with ethanolamine, diethanolamine, triethanolamine, diethylene triamine, diisopropylmethylamine, triethylene tetramine and tetraethylene pentamine are particularly preferred. The reaction products can optionally be quaternized with conventional alkylating agents. For this purpose, dimethyl sulfate, benzyl chloride, methyl tosylate are usually used.
  To improve the dispersibility and / or wettability, the reaction products can also contain polyoxyalkylene radicals. The residues can also be bound by the condensation of polyoxyalkylenes or by alkoxylation of the reaction products.
• B) In order to achieve a particularly flowing, soft feel of high-quality articles of clothing and good wrinkling properties of the goods finished with the permanent agent according to the invention, customary silicone-containing soft handle agents with the general formula (II)
  used, where
  n = a number from 0 to 300,
  m = a number from 0 to 20,
  n + m <= 30,
  X ¹ , X ² and X ³ are selected so that at least one radical has an H-acidic group,
  where the radicals X ¹ , X ² and X ³ independently of one another are aliphatic or aromatic hydrocarbon radicals having 1 to 18 carbon atoms, alkoxy or hydroxyl radicals or alkylglycol radicals having 1 to 12 carbon atoms and / or a group MZ, where Z is the radical
  is
  R ⁴ , R ⁵ , R ⁶ , R ⁷ each represent a hydrogen atom, an alkyl radical having 1 to 22 carbon atoms or an alkenyl radical having 2 to 22 carbon atoms, where the alkyl or alkylene radicals can have hydroxyl groups;
  R ⁸ , R ⁹ each represent a hydrogen atom and / or an alkyl radical having 1 to 22 carbon atoms or an alkylene radical having 2 to 22 carbon atoms, it being possible for the alkyl or alkylene radicals to have hydroxyl groups or optionally fluorine, chlorine or bromine-substituted C ₁ - up to G ₁₀ alkyl residues,
  R ¹⁰ for an -O or NR ¹¹ radical, R ¹¹ for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms or hydrogen radical,
  o = 1 to 4,
  A ^⊖ for an inorganic or organic anion which derives from a customary physiologically acceptable acid, in particular acetic acid, L-hydroxycarboxylic acids and aromatic carboxylic acids,
  R ^{19 represents} a hydrogen atom or C ₁ - to C ₂₀ -alkyl, in particular C ₁ - to C ₄ -alkyl, or C ₂ - to C ₂₀ -alkenyl, cyclopentyl, cyclohexyl, glycidyl, oxethyl, phenyl, trialkylphenyl, tolyl, benzyl , Furfuryl or tetrahydrofurfuryl,
  A for propylene or in particular ethylene, where mixed ethoxylated and propoxylated compounds can also occur in blocks,
  p = 3 to 50, in particular 8 to 25,
  K ^⊕ for an inorganic or organic cation, in particular alkali metal cations and ammonium compounds,
  M for a divalent residue selected from the group
  the quaternary N atom of the Z radical being connected to the M radical via the carbon atom adjacent to the C-OH group in the M radical, while the electrically neutral Z radicals can be linked to a M radical from the following group
  - (CH ₂ ) _q -NR ¹² - (CH ₂ ) _r - - (CH ₂ ) _s -
  in which,
  q, s = 1 to 18,
  r = 2, 3 or 4,
  R ^{12 represents} a hydrogen atom or an optionally fluorine, chlorine or bromine substituted C ₁ to C ₁₀ alkyl radical.

For the use according to the invention to achieve permanent hydrophobic Surface properties are preferably electrically neutral amino functional Polydimethylsiloxane used. In contrast, to achieve permanent hydrophilic surface properties with polydimethylsiloxanes ionic groups or polyalkoxy groups are preferably used.

According to the invention, R ³ stands for a residue of a hydrophilic compound having at least one acidic H atom, the ionicity of the hydrophilic compound being dependent on the compatibility of the agent according to the invention with other textile auxiliaries. The permanent agent can thus be adapted to the desired requirements with the aid of an anionic, cationic or nonionic radical R ³ .

R ³ preferably represents the rest of a compound which

• A) non-ionic of the formula
  R ¹³ -Q- (AO) _t -H
  corresponds, where R ^{13 is} C ₁ - to C ₂₀ -alkyl, in particular C ₁ - to C ₄ -alkyl, or C ₂ - to C ₂₀ -alkenyl, cyclopentyl, cyclohexyl, glycidyl, oxethyl, phenyl, trialkylphenyl, tolyl, benzyl , Furfuryl or tetrahydrofurfuryl,
  Q for sulfur or oxygen, especially oxygen,
  A for propylene or in particular ethylene, where mixed ethoxylated and propoxylated compounds can also occur in blocks,
  t stands for 3 to 120, in particular 8 to 50.
  Compounds of the formula
  in which
  R ¹³ , Q, A, t have the meanings given above and M can be either a hydrogen atom or a methyl group.
  There are also polyalkylene glycols of the formula
  HO- (AO) _t -H
  can be used, where A and t have the meanings given above;
• B) can be anionic, the anionic compounds in particular Acid groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups included. The acid groups can partially or completely a base should be neutralized. As a hydrophilic compound with at least one acidic H atoms come hydroxycarboxylic acids such as 2-hydroxyacetic acid, 3- Hydroxypropionic acid, 4-hydroxybutyric acid or hydroxypivalic acid and 2,2- Bis- and 2,2,2-tris (hydroxymethyl) alkanoic acids, for example 2,2-bis (hydroxy methyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) - butyric acid or 2,2,2-tris (hydroxymethyl) acetic acid and hydroxysulfonic acids such as 2-hydroxypropane-1-sulfonic acid, 3-hydroxypropane sulfonic acid, 4- Hydroxybutanesulfonic acid, 5-hydroxypentanesulfonic acid, N-tris (hydroxymethyl) - methyl-2-aminoethanesulfonic acid, N-tris (hydroxymethyl) methyl-3-aminopropane  sulfonic acid into consideration. The acids can also by propoxylation and / or Modified ethoxylation;
• C) may contain an alkylatable or protonatable function with the formation of a cationic center. In particular, those functions are aminic in nature which can be easily quaternized or protonated. As such connec tions come preferably amino alcohols of the formula
  being considered,
  R ¹⁴ , R ¹⁵ , R ¹⁷ independently of one another represent a hydrogen atom or a linear or branched C ₁ to C ₂₀ alkyl, in particular C ₁ to C ₅ alkyl, or together with the N atom a five- or six-membered ring form, which may also contain an O atom or a tertiary N atom, in particular a piperidine, morpholine, piperazine, pyrrolidine, oxazoline or dihydrooxazine ring, the radicals R ¹⁴ and R ¹⁵ additionally containing hydroxyl groups, in particular can each carry a hydroxyl group, and
  R ^{16 is} a C ₂ to C ₁₀ alkylene group, in particular a C ₂ to C ₆ alkylene group, which can be linear or branched.

Particularly suitable amino alcohols are propanolamine, N-methylpropanolamine, Ethanolamine, N-methylethanolamine, N-methyldietlhanolamine, N-methyldi (iso) pro panolamine, N-butyldiethanolamine, N-butyldi (iso) proppanolamine, N-stearyldi ethanolamine, N-stearyldi (iso) propanolamine, N'N-dimethylethanolamine, N, N- Dimethyl (iso) propanolamine, N, N-diethylethanolamine, N, N-dietyl (iso) propanolamine, N, N-dibutylethanolamine, N, N-dibutyl (iso) propanolamine, tri (iso) propanolamine, - (2- Hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N- (2-hydroxy ethyl) piperidine, N- (2-hydroxypropyl) piperidine, N-methyl-N '- (2-hydroxy ethyl) piperazine, N-methyl-N '- (2-hydroxypropyl) piperazine, N-methyl-N' - (4-hydroxy butyl) piperazine, 2-hydroxyethyl oxazoline, 2-hydroxypropyl oxazoline, 2-hydroxy ethyldihydrooxazin, 2-hydroxypropyldihydroxazin or 3-hydroxypropyl-dihydro oxazin.  

Furthermore, such compounds with nitrogen atoms are preferably diamines of the general formulas A and B

in which R ¹⁴ to R ^{16 have} the meanings given above and R ¹⁸ denotes C ₁ - to C ₅ -alkyl or forms a five- or six-membered ring, in particular a piperazine ring, with R ¹⁴ .

Particularly suitable as diamines A are N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-diamione-2,2-dimethylpropane, N, N-1,3-propylene diamine , N- (3-aminopropyl) morpholine, N- (2-aminopropyl) morpholine, N- (3-aminopropyl) piperidine, N- (2-aminopropyl) piperindine, 4-amino-1- (N, N-diethylamino ) pen tan, 2-amino-1- (N, N-dimethylamino) propane, 2-amino-1- (N, N-diethylamino) propane or 2-amino-1- (N, N-diethylamino) -2- methyl propane.

Particularly suitable as diamines B are N, N, N'-trimethylethylenediamine, N, N, N'-triethylethylenediamine, N-methylpiperazine or N-ethylpiperazine.

Furthermore, as compounds with at least one acidic H atom Polyether (poly) ole with built-in nitrogen atoms by propoxylation and / or ethoxylation of starter molecules having amine nitrogen can be produced, used.

The preparation of the agents according to the invention is advantageous in aprotic aliphatic or aprotic aromatic solvent, wherein as Solvent toluene, xylene, acetone or ethyl acetate can be used can.

In addition, it is advantageous to use the reaction product in a to convert aqueous emulsion, being one of those mentioned  Solvent dissolved permanent agent, a suitable emulsifier and a organic or inorganic acid can be added.

The solvent can be removed under reduced pressure; who are there Forming highly viscous preparation with water to the desired Concentration diluted. Depending on the composition of the components mentioned Milky white to water-clear emulsions are formed.

Suitable fatty alcohol ethoxylates in customary amounts are suitable as emulsifiers from 5 to 60% by weight based on the permanent agent used. The addition the organic or inorganic acid, such as hydrochloric acid or acetic acid depends on the basicity of the reaction product, usually sufficient 0.01 to 5 wt .-% to adjust the usual pH values from about 4 to 6. Die The concentration of the permanent agent can vary from 2 to 80% by weight based on the train preparation.

Other constituents of the permanent means can be conventional adjusting means such as for example butyl diglycol, propylene glycol, ethylene diglycol and wetting agents such as for example, dialkyl sulfosuccinates and fatty alcohol ethoxylates.

The above agents may preferably be used in the equipment of Fibers or products made of fibers in aqueous baths and Application fleets for permanent influencing, if necessary hydrophilizing surface properties.

a) Examples Example 1/2: (synthesis)

0.2 mol of dimethylaminopropylamine, 50 ml of 2-propanol were placed in a 2 l three-necked flask equipped with a stirrer, intensive cooler, thermometer and dropping funnel, and 0.2 mol of acetic acid were added at 20 ° C. The mixture was allowed to react at 25 ° C. for 30 min and then 0.1 mol of epoxy siloxane of the general formula was added dropwise

Example 1: n = 28
Example 2: n = 80
to. The reaction mixture was first stirred at 25 ° C. for 0.5 h and then heated to 90 ° C. The solvent was then distilled off at 90 ° C. and 0.2 bar. The polysiloxane was obtained as a colorless to light yellow colored, oily product. The product was filtered after cooling to room temperature.

Example 3: (Synthesis)

0.1 mol of dimethylaminopropylamine, 50 ml of 2-propanol were placed in a 2 liter three-necked flask equipped with a stirrer, intensive cooler, thermometer and dropping funnel, and 0.1 mol of acetic acid was added at 20 ° C. The mixture was allowed to react at 25 ° C. for 30 min and then 0.1 mol of epoxy siloxane of the general formula was added dropwise

Example 3: n = 80; m = 12
to. The reaction mixture was first stirred at 25 ° C. for 0.5 h and then heated to 90 ° C. The solvent was then distilled off at 90 ° C. and 0.2 bar. The polysiloxane was obtained as a colorless to light yellow colored, oily product. The product was filtered after cooling to room temperature.

Example 4: (Medium)

A mixture of 10.4 g of a polyhexamethylene diisocyanate with an NCO content of 12.5% and 0.314 g (0.003114 mol) of triethylamine were dissolved in 20 ml of ethyl acetate. At room temperature, 2.17 g (0.025 mol) of butanone oxime, dissolved in 10 ml of ethyl acetate, were metered in and then heated to 60 ° C. for 60 minutes. The cooled, clear reaction solution was then slowly added to a solution of 16 g of K 4737 (amine content, N = 1.09%) in 25 ml of ethyl acetate. The slightly cloudy solution was heated to 60 ° C. for 60 minutes. Thereafter, 12.8 g of C ₁₀ oxo alcohol with 8 EO and 0.64 g of 60% acetic acid were added to the reaction mixture and all volatile constituents were removed at 70 ° C. and a vacuum of about 25 mbar. The clear to slightly cloudy, yellowish mixture was then added in portions with vigorous stirring with 88.7 g of water. A stable emulsion with a solids content of 33% by weight was obtained.

Example 5: (Medium)

A mixture of 2.6 g of a polyhexamethylene diisocyanate with an NCO content of 12.5% and 0.1 g (0.000158 mol) of dibutyltin didodecanate and 5.78 g of tributylphenol polyglycol ether with 50 ethylene oxide units (OH content = 0.67 %) were dissolved in 20 ml of toluene and heated to 35 ° C for 1.5 hours. Then 0.34 g (0.0039 mol) of butanone oxime, dissolved in 5 ml of toluene, was added and the mixture was stirred at 35 ° C. for a further 1.5 hours. The reaction mixture was then cooled to room temperature and metered into a solution of 8.95 g of K 5035 (amine content, N = 0.48%) in 10 ml of toluene. After the addition was complete, the reaction mixture was heated to 50 ° C for one hour. Then 7.88 g of C ₁₃ oxo alcohol with 6 EO and 0.39 g of 60% acetic acid were added to the reaction mixture and all volatile constituents were removed at 70 ° C. and a vacuum of about 25 mbar. The cloudy, slightly yellowish mixture was then mixed with 52.8 g of water in portions with vigorous stirring. A stable emulsion with a solids content of 33% by weight was obtained.

Example 6: (Medium)

A mixture of 2.6 g of a polyhexamethylene diisocyanate with an NCO content of 12.5% and 0.1 g (0.000158 mol) of dibutyltin didodecanate was dissolved in 20 ml of toluene and with a solution consisting of 0.98 g of G10- Oxo alcohol with 11 ethylene oxide units (OH content = 2.65%), 0.4 g (0.00467 mol) butanone oxime and 5 ml of toluene. The mixture was then stirred at 35 ° C. for 1.5 hours. The reaction mixture was then cooled to room temperature and metered into a solution of 10.4 g of K 5073 (amine content, N = 0.21%) in 10 ml of toluene. After the addition was complete, the reaction mixture was heated to 50 ° C for one hour. Then 3.22 g of C ₁₃ oxo alcohol with 5 EO; 3.22 g of C ₁₃ oxo alcohol with 8 EO and 0.32 g of 60% acetic acid were added and all volatile constituents were removed at 70 ° C. and a vacuum of approx. 25 mbar. The cloudy, slightly yellowish mixture was then mixed with 43.12 g of water in portions with vigorous stirring. A clear, stable emulsion with a solids content of 33% by weight was obtained.

Example 7: (Medium)

A mixture of 2.1 g of a polyisophorone diisocyanate with an NCO content of 16.5% and 0.1 g (0.000158 mol) of dibutyltin didodecanate was dissolved in 20 ml of toluene and with a solution consisting of 1.05 g of C ₁₀ Oxo alcohol with 11 ethylene oxide units (OH content = 2.65%), 0.42 g (0.00492 mol) of butanone oxime and 5 ml of toluene. The mixture was then stirred at 35 ° C. for 1.5 hours. The reaction mixture was then cooled to room temperature and metered into a solution of 10.96 g of K 5073 (amine content, N = 0.21%) in 10 ml of toluene. After the addition was complete, the reaction mixture was heated to 50 ° C for one hour. Then 3.37 g of C ₁₃ oxo alcohol with 5 EG; 3.37 g of C ₁₃ oxo alcohol with 8 EO and 0.34 g of 60% acetic acid were added and old volatile constituents were removed at 70 ° C. and under a vacuum of about 25 mbar. The cloudy, slightly yellowish mixture was then mixed with 45.11 g of water in portions with vigorous stirring. A clear to slightly cloudy, stable emulsion with a solids content of 33% by weight was obtained.

Example 8: (Medium)

A mixture of 10.5 g of a polyisophorone diisocyanate with an NCO content of 16.5% and 0.5 g (0.00079 mol) of dibutyltin didodecanate was dissolved in 60 ml of toluene and with a solution consisting of 3.94 g of C ₁₀ Oxo alcohol with 11 ethylene oxide units (OH content = 2.65%), 1.6 g (0.0184 mol) of butanone oxime and 15 ml of toluene. The mixture was then stirred at 35 ° C. for 1.5 hours. The reaction mixture was then cooled to room temperature and metered into a solution of 8.84 g of di (palmitamidoethyl) amine (NH content = 2.78%) in 10 ml of toluene. After the addition was complete, the reaction mixture was heated to 50 ° C for one hour. 5.64 g of C ₁₃ oxo alcohol with 5 EO; 5.64 g of C ₁₃ oxo alcohol with 8 EO and 0.56 g of 60% acetic acid were added and all volatile constituents were removed at 70 ° C. and a vacuum of approx. 25 mbar. The cloudy, slightly yellowish mixture was then mixed in portions with vigorous stirring with 75.58 g of water. A clear to slightly cloudy, stable emulsion with a solids content of 33% by weight was obtained.

Example 9: (Medium)

A mixture of 10.5 g of a polyisophorone diisocyanate with an NCO content of 16.5% and 0.5 g (0.00079 mol) of dibutyltin didodecanate were dissolved in 60 ml of toluene and with a solution consisting of 2.14 g (0 , 0264 mol) butanone oxime and 10 ml of toluene were added. The mixture was then stirred at 35 ° C. for 1.5 hours. The reaction mixture was then cooled to room temperature and metered into a solution of 8.84 g of di (palmitamidoethyl) amine (NH content = 2.78%) in 10 ml of toluene. After the addition was complete, the reaction mixture was heated to 50 ° C. for one hour: 4.77 g of C ₁₃ oxo alcohol with 5 EO; 4.77 g of C ₁₃ oxo alcohol with 8 EO and 0.48 g of 60% acetic acid were added and all volatile constituents were removed at 70 ° C. and a vacuum of approx. 25 mbar. The cloudy, slightly yellowish mixture was then mixed with 63.96 g of water in portions with vigorous stirring. A clear to slightly cloudy, stable emulsion with a solids content of 33% by weight was obtained.

Example 10: (Medium)

A mixture of 10.5 g of a polyisophorone diisocyanate with an NCO content of 16.5% and 0.5 g (0.00079 mol) of dibutyltin didodecanate was dissolved in 60 ml of toluene and with a solution consisting of 3.94 g of C ₁₀ Oxo alcohol with 11 ethylene oxide units (OH content = 2.65%), 1.6 g (0.0184 mol) of butanone oxime and 15 ml of toluene. The mixture was then stirred at 35 ° C. for 1.5 hours. The reaction mixture was then cooled to room temperature and a solution of 11.1 g of di (palmcarboxyethyl) hydroxyethyl methylammonium methosulfate. (OH content = 2.51%) in 10 ml of toluene. After the addition was complete, the reaction mixture was heated to 50 ° C for one hour. Then 6.14 g of C ₁₃ oxo alcohol with 5 EO; 6.14 g of C ₁₃ oxo alcohol with 8 EO and 0.61 g of 60% acetic acid were added and all volatile constituents were removed at 70 ° C. and a vacuum of approx. 25 mbar. The cloudy, slightly yellowish mixture was then mixed in portions with vigorous stirring with 82.34 g of water. A clear to slightly cloudy, stable emulsion with a solids content of 33% by weight was obtained.

Example 11: (Medium)

A mixture of 2.6 g of a polyhexamethylene diisocyanate with an NCO content of 12.5%, 0.1 g (0.000158 mol) of dibutyltin didodecanate and 4.8 g of tributylphenol polyglycol ether with 50 ethylene oxide units (OH gel content = 0.67 %) were dissolved in 20 ml of toluene and heated to 65 ° C for 1.5 hours. Then 0.37 g (0.0043 mol) of butanone oxime, dissolved in 5 ml of toluene, was added and the mixture was stirred at 35 ° C. for a further 1.5 hours. The reaction mixture was then cooled to room temperature and metered into a solution of 8.4 g of an a, wN- (aminoethyl) aminopropyl-functionalized aminosiloxane (amine content, N = 1.03%) in 10 ml of toluene. After the addition was complete, the reaction mixture was heated to 50 ° C for one hour. Then 3.62 g of C ₁₃ oxo alcohol with 5 EO; 3.62 g of C ₁₃ oxo alcohol with 8 EO and 0.36 g of 60% acetic acid were added and all volatile constituents were removed at 70 ° C. and a vacuum of approx. 25 mbar. The cloudy, slightly yellowish mixture was then mixed in portions with 48.45 g of water with vigorous stirring. A clear to slightly cloudy, stable emulsion with a solids content of 33% by weight was obtained.

Example 12: (Medium)

A mixture of 2.6 g of a polyhexamethylene diisocyanate with an NCO content of 12.5% and 0.1 g (0.000158 mol) of dibutyltin didodecanate was dissolved in 20 ml of toluene and with a solution consisting of 0.94 g of a polyoxyalkylene amine with a PO / EO ratio of 9 / l (amine content, N = 2.31%), 0.4 g (0.00467 mol) butanone oxime and 5 ml toluene. The mixture was then stirred at 35 ° C. for 1.5 hours. The reaction mixture was then cooled to room temperature and metered into a solution of 10.4 g of K 5073 (amine content, N = 0.21%) in 10 ml of toluene. After the addition was complete, the reaction mixture was heated to 50 ° C for one hour. Then 3.21 g of C ₁₃ oxo alcohol with 5 EO, 3.21 g of C ₁₃ oxo alcohol with 8 EO and 0.32 g of 60% acetic acid were added to the reaction mixture and all volatile constituents at 70 ° C. and a vacuum about 25 mbar away. The cloudy, slightly yellowish mixture was then mixed with 43.00 g of water in portions with vigorous stirring. A clear, stable emulsion with a solids content of 33% by weight was obtained.

Comparative Example 1

A commercial microemulsion functionalized with ammonium groups Siloxane with a solids content of 30% by weight.

Comparative Example 2

A commercially available microemulsion of an aminosiloxane with a solids content of 30% by weight.

Comparative Example 3

A commercially available emulsion of an organic plasticizer with a Solids content of 20% by weight.

Application examples

To check the grip and the hydrophilicity of the present invention were native or synthetic fibers or fiber products equipped with the following procedure:

Padding process

To test the soft hand and the hydrophilicity of emulsions A) to L), a cotton fabric (125 g / m ² ) and a polyester microfiber fabric (140 g / m ² ) with a liquor containing 35 g / l of the corresponding emulsion were used, padded and squeezed to 70% liquor absorption. Then dried at 120 ° C for 3 minutes and fixed at 150 ° C for 3 minutes. The result was a very soft, pleasant, silky and elegant handle on the finished textile substrate. In addition, the goods equipped in this way had high elasticity and improved wrinkling properties. The test results with regard to the soft hand are shown in Tables 1a) and 2a) and with regard to the hydrophilicity in Tables 1b) and 2b).

Test methods Grip assessment

An experienced team was put together to assess the grip anonymized grip pattern, the one equipped with emulsions A) to L) Tissue, assessed using the hand test. As a comparative sample, a untreated tissue added to the test series.

Testing hydrophilicity

The TEGEWA drop test was used to check the hydrophilicity (Melliand 68, 1987, 581-583). The equipment was equipped to carry out the test Tissue stretched horizontally on a suitable tensioning device so that it does not come into contact with the pad. From a drop height of 40 mm a water drop of 0.050 ml +/- 10% was dropped onto the tissue. Once the Drops hit the test material, the time measurement was started. The Timekeeping was stopped when the drop was completely in the tissue penetrated and the shine has disappeared or longer than 300 seconds required to penetrate the test material. In this case the measurement canceled and the value "<300 sec" and the current spread specified. The spread was in the warp and weft directions in millimeters certainly. In the results table, the spread of the drop was first in warp then indicated in the weft direction.

Washing process

The washing operations were carried out in a commercial washing machine, Zanker Classic 8082, with the wash cycle for colored laundry at 40 ° C. with a commercial heavy-duty detergent, Persil phosphate-free. In addition, the machine was equipped with a kilogram of polyester fabric as the filling material. The test subjects were then dried at room temperature overnight.

Claims (17)

1. Permanent means of the general formula
in which
R ¹ for a residue of a polyisocyanate-functional compound whose NCO content after the reaction with R ² and / or R ^{3 is} up to 3% by weight, based on the weight of the formula,
R ² for a residue of a conventional soft-grip agent with at least one acidic H atom,
R ^{3 represents} a residue of a conventional hydrophilizing agent with at least one acidic H atom,
x for an integer equal to or greater than 1 and
y represents an integer equal to or greater than 0. 2. Permanent agent according to claim 1, characterized in that
R ¹ for a residue of one or more polyisocyanates with a base of a diisocyanate and / or higher functional polyisocyanates with an average NCO functionality of 2.0 to 4.4. 3. Permanent agent according to claim 1 or 2, characterized in that
R ^{1 represents} a residue of an aliphatic and / or cycloaliphatic higher functional polyisocyanate with an NCO content of 8 to 30% by weight and an average NCO functionality of 2.2 to 4.5. 4. Permanent means one of claims 1 to 3, characterized in that up to 90% of the NCO groups of the polyisocyanates are blocked. 5. Permanent agent according to claims 1 to 4, characterized in that the radical R ^{2 is} a radical based on a silicone-free soft handle with at least one acidic H atom. 6. Permanent agent according to one of claims 1 to 5, characterized in that R ² for a residue of a reaction product of fatty acids with amines, polyamines, alkanolamines, in particular reaction products of coconut fatty acid, palmitic acid, tallow fatty acids, stearic acid, hydroxystearic acid, behenic acid and / or Oleic acid with ethanolamine, triethanolamine, diethanolamine, diethylenetriamine, diisopropylmethylamine, triethylene tetramine and / or tetraethylene pentamine. 7. Permanent means according to claim 6, characterized in that the reaction products with an alkylating agent are quaternized, especially dimethyl sulfate, benzyl chloride and / or methyl tosylate. 8. Permanent agent according to claim 5 or 6, characterized in that the reaction products by condensing of polyoxyalkylenes or by alkoxylation of the reaction products. 9. Permanent agent according to claims 1 to 5, characterized in that the radical R ² for a radical of a silicone-containing soft handle with at least one acidic H atom with the general formula (II)
stands,
in which
n = a number from 0 to 300,
m = a number from 0 to 20,
n + m <= 30,
X ¹ , X ² and X ³ are selected so that at least one radical has an H-acidic group,
where the radicals X ¹ , X ² and X ³ independently of one another are aliphatic or aromatic hydrocarbon radicals having 1 to 18 carbon atoms, alkoxy or hydroxyl radicals or alkylglycol radicals having 1 to 12 carbon atoms and / or a group MZ
mean, where Z is the rest
is
R ⁴ , R ⁵ , R ⁶ , R ⁷ each represent a hydrogen atom, an alkyl radical having 1 to 22 carbon atoms or an alkenyl radical having 2 to 22 carbon atoms, where the alkyl or alkylene radicals can have hydroxyl groups,
R ⁸ , R ⁹ each represent a hydrogen atom and / or an alkyl radical having 1 to 22 carbon atoms or an alkylene radical having 2 to 22 carbon atoms, it being possible for the alkyl or alkylene radicals to have hydroxyl groups or optionally fluorine, chlorine or bromine-substituted C, to C ₁₀ alkyl residues,
R ^{10 represents} an -O- or NR ¹¹ radical, R ^{11 represents} an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms or a hydrogen atom,
o = 1 to 4,
A ^⊖ for an inorganic or organic anion, a physiologically acceptable acid, in particular acetic acid, L-hydroxycarboxylic acids and aromatic carboxylic acid,
R ^{19 represents} a hydrogen atom or C ₁ to C ₂₀ alkyl, in particular C ₁ to C ₄ alkyl, or C ₂ to C ₂₀ alkenyl, cyclopentyl, cyclohexyl, glycidyl, oxethyl, phenyl, trialkylphenyl, tolyl, benzyl, Furfuryl or tetrahydrofurfuryl,
A represents propylene or ethylene, in particular mixed ethoxylated and propoxylated compounds in blocks,
p = 3 to 50, in particular 8 to 25,
K ^⊕ for an inorganic or organic cation, in particular alkali metal cations and ammonium compounds,
M stands for a divalent residue selected from the group
wherein the quaternary N atom of the Z radical is connected to the M radical via the carbon atom adjacent to the C-OH group in the M radical, the electrically neutral Z radicals can optionally be selected from the group with a M radical
(CH ₂ ) _q -NR ¹² - (CH ₂ ) _r - - (CH ₂ ) _s -
is linked
in which,
q, s = 1 to 18,
r = 2, 3 or 4,
R ^{12 represents} a hydrogen atom or an optionally fluorine, chlorine or bromine substituted C ₁ to C ₁₀ alkyl radical. 10. Permanent agent according to one of claims 1 to 5 and 9, containing electrically neutral amino-functional polydimethylsiloxane residues. 11. Permanent means according to claim 10, characterized in that polydimethylsiloxane residues ionic groups and / or Contain polyalkoxy groups. 12. Permanent agent according to one of claims 1 to 5, characterized in that the radical R ^{3 is} a radical of a hydrophilic compound having at least one acidic H atom which has anionic, cationic, zwitterionic or nonionic properties. 13. Permanent agent according to one of claims 1 to 5 and 12, characterized in that the radical R ³ for the nonionic radical
R ¹³ -Q- (AO) _t -H
stands, where
R ^{13 is} C ₁ to C ₂₀ alkyl, in particular C ₁ to C ₄ alkyl, or C ₂ to C ₂₀ alkenyl, cyclopentyl, cyclohexyl, glycidyl, oxethyl, phenyl, trialkylphenyl, tolyl, benzyl, furfuryl or Tetrahydrofurfuryl,
Q for sulfur or oxygen, especially oxygen,
A represents propylene or ethylene, in particular ethoxylated and propoxylated compounds mixed in blocks,
t = 3 to 120, in particular 8 to 50,
Compounds of the formula

in which
R ¹³ , Q, A, t have the meanings given above and M can either be a hydrogen atom or a methyl group. 14. Permanent agent according to one of claims 1 to 5 and 12, characterized in that the radical R ^{3 stands} for the anionic radical containing acid groups, in particular carboxyl groups, sulfonic acid groups or phosphoric acid groups. 15. Permanent means according to claim 14, characterized in that acid groups partially or completely by a Base are neutralized. 16. Permanent means according to claim 14, characterized in that the hydrophilic compound with at least one acidic H atom, especially hydroxycarboxylic acids, especially 2- Hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid or hydroxypi valic acid, 2,2-bis- and 2,2,2-tris (hydroxymethyl) alkanoic acids, for example 2,2- Bis (hydroxymethyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hy droxymethyl) butyric acid or 2,2,2-tris (hydroxymethyl) acetic acid, hydroxysulfone acids, especially 2-hydroxypropane-1-sulfonic acid, 3-hydroxypropane sulfonic acid, 4-hydroxybutanesulfonic acid, 5-hydroxypentanesulfonic acid, N-tris (hydroxy methyl) methyl-2-aminoethanesulfonic acid, N-tris (hydroxymethyl) methyl-3-aminopro pansulfonic acid, optionally by propoxylation and / or Ethoxylation are modified. 17. Use of the permanent agent according to one of claims 1 to 16 when finishing fibers or fiber products in aqueous Baths and application fleets for the permanent influencing of Surface properties.