EP0016907B1 - Preparation for making wool shrink-proof - Google Patents

Description

The invention relates to a preparation for shrink-proofing wool.

It is known that wool in the untreated state shrinks and mattes when washed in an aqueous liquor. In order to counteract this shrinkage and matting, chemical treatments have been recommended in which the structure of the wool is changed or equipment is used which contains resin which is deposited on the surface of the wool fiber and envelops it. However, both processes result in products whose so-called grip is perceived by the consumer as unpleasant.

It has also been recommended to reduce wool shrinkage during washing by treating with organosilicon compounds. Such methods are described in GB-A-594 901, GB-A-613267 and GB-A-629329. According to these processes, the wool is treated with certain silanes.

GB-A-746 307 describes a method for preventing the shrinkage of the wool, the wool fibers being provided with certain organopolysiloxanes. A certain degree of shrink resistance is achieved in this way, but this effect is not washable.

In a number of other publications, e.g. For example, DE-A-2 242 297, DE-A-2 335 751 and DE-A-2 523 270 disclose processes for shrink-proofing keratin fibers by applying organopolysiloxane, an essential feature being that these compounds contain amino groups.

verwendet, worin bedeuten:

• n einen Durchschnittswert von 1,9 bis 2,1 und
• R einen über eine Silicium-Kohlenstoff-Bindung an Silicium gebundenen organischen Rest, wobei 0,25 bis 50% der Substituenten R einwertige Reste mit weniger als 30 Kohlenstoffatome sind, die im Abstand von wenigstens 3 Kohlenstoffatomen von dem Siliciumatom wenigstens eine Iminogruppe und wenigstens eine primäre oder sekundäre Arrinogruppe -NX2 enthalten, worin X ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 30 Kohlenstoffatomen oder eine Arylgruppe ist, und wobei die übrigen Substituenten R einwertige Kohlenwasserstoffreste, halogenierte Kohlenwasserstoffreste, Carboxyalkylreste oder Cyanalkylreste mit 1 bis 30 Kohlenstoffatomen sind, von denen mindestens 70% aus einwertigen Kohlenwasserstoffresten mit 1 bis 18 Kohlenstoffatomen bestehen.

For example, the process according to DE-A-2 242 297 is characterized in that organopolysiloxanes are those having units of the general formula

used, in which mean:

• n an average value of 1.9 to 2.1 and
• R is an organic radical bonded to silicon via a silicon-carbon bond, where 0.25 to 50% of the substituents R are monovalent radicals having less than 30 carbon atoms, which are at least 3 carbon atoms from the silicon atom and at least one imino group and at least one contain primary or secondary arrino group -NX2, wherein X is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group, and wherein the other substituents R are monovalent hydrocarbon radicals, halogenated hydrocarbon radicals, carboxyalkyl radicals or cyanalkyl radicals having 1 to 30 carbon atoms, of which at least 70% consist of monovalent hydrocarbon radicals with 1 to 18 carbon atoms.

• A) ein Polydiorganosiloxan mit endständigen, an Siliciumatome gebundenen Hydroxygruppen und einem Molekulargewicht von mindestens 750, wobei mindestens 50% der organischen Substituenten des Polydiorganosiloxans Methylgruppen sind und wobei die weiteren Substituenten einwertige Kohlenwasserstoffgruppen mit 2 bis 30 Kohlenstoffatomen darstellen, ist und
• B) ein Organosilan der allgemeinen Fcrmel
  
  in der R eine einwertige, aus Kohlenstoff, Wasserstoff, Stickstoff und ggf. Sauerstoff aufgebaute Gruppe, die mindestens 2 Aminogruppen enthält und über eine Silicium-Kohlenstoff-Bindung an Silicium gebunden ist, R' eine Alkylgruppe oder eine Arylgruppe, X Alkoxygruppen mit 1 bis 4 Kohlenstoffatomen einschließlich und n Null oder 1 bedeuten, und/oder ein Teilhydrolysat und Kondensat des Organosilans ist.

From DE-A-2 335 751 a process for the treatment of keratin phase is known, which is characterized in that the organopolysiloxane composition contains the product obtained by mixing A) and B), whereby

• A) a polydiorganosiloxane with terminal hydroxyl groups bonded to silicon atoms and a molecular weight of at least 750, at least 50% of the organic substituents of the polydiorganosiloxane being methyl groups and the further substituents being monovalent hydrocarbon groups having 2 to 30 carbon atoms, and
• B) an organosilane of the general formula
  
  in which R is a monovalent group composed of carbon, hydrogen, nitrogen and optionally oxygen, which contains at least 2 amino groups and is bonded to silicon via a silicon-carbon bond, R 'is an alkyl group or an aryl group, X alkoxy groups with 1 to 4 carbon atoms including and n are zero or 1, and / or is a partial hydrolyzate and condensate of the organosilane.

In this DE-A-S it is stated that the two mixing partners should be reacted when application from an aqueous medium is desired. However, as practical experiments have shown, it is not possible to produce stable aqueous emulsions from such reaction products. Gel-like reaction products are formed which cannot be converted into emulsion form. They are therefore unsuitable for shrink-proofing wool.

If these reaction products are used in the form of organic solutions, it can be seen that the effect which can be achieved is too small for successful use in practice. In addition, from the solvent-containing liquors, siloxane separates out after some time due to the action of atmospheric moisture, which clogs the devices for treating the wool.

In the journal "Journal of the Textile Institute", 68 (1977), 163 ff., Preparations for Described shrink resistant equipment of wool, which contain polysiloxanes, in which polyether chains are bound to the molecule. However, the observed effect is insufficient. In addition, the temperatures of 120 ° C. and exposure times of 60 min required for fixing these compounds on the wool fiber are so great that considerable damage and discoloration of the wool can already be caused.

From DE-A-1 769 249 a method for the treatment of fiber material, for. B. wool, known, in which organosiloxanes are used in emulsion form, which contain mercaptopropyl groups. With these connections, however, it is only possible to reduce the dirtiness. The connections are not suitable for making wool shrink-resistant.

With the preparations of the prior art, it was therefore not possible to carry out a perfect and fully satisfactory shrink-proof treatment of wool.

The invention is therefore based on the object of finding a preparation for making wool shrink-proof, which contains both in emulsion form and in the form of an organic solution compounds which are suitable for making wool shrink-proof, these properties even after repeated washing of the wool in the customary manner Washing machines should be preserved. It is in particular an object of the invention to find a preparation which can be used optionally in the various stages of wool processing by means of different types of application. The aim is to ensure that the wool can also be treated after the wool has been dyed and that the known treatment methods, such as the pull-out method and the block method, can be used. The active ingredient contained in the preparation must not adversely affect the so-called feel of the wool or the knitted fabrics and fabrics made from the wool.

• a) 1 bis 50 Gew.-% Organopolysiloxanen, welche aus
  • ai) 90 bis 99,8 Mol-% Einheiten der Formel
    
    und
  • a₂) 0,2 bis 10 Mol-% Einheiten der Formel
    
    aufgebaut sind,
  • wobei R¹ und R² einerseits aus
  • 0,1 bis 10 Mol-% Polyoxyalkylenresten
  • und andererseits aus
  • 0,03 bis 3 Mol-% Mercaptoalkyl- oder Mercaptoarylresten und/oder
  • 0,06 bis 6 Mol-% Aminoalkylresten und/oder
  • 0,1 bis 10 Mol-% über C-Atome an Si-Atome gebundene anionische Gruppen gebildet sind,
  • und der verbleibende Anteil an R¹- und R^2-Gruppen Methylgruppen sind, von denen jedoch bis zu 10 Mol-% durch längerkettige Alkyl-, Aryl- oder Wasserstoffreste ersetzt sein können und bis zu 5 Mol-% der an Si gebundenen Sauerstoffatome durch jeweils zwei niedere Alkoxy- oder Hydroxygruppen ersetzt sein können, und
• b) 50 bis 99 Gew.-% Wasser, gegebenenfalls Emulgatoren und/oder organischen Lösungsmitteln und gegebenenfalls üblichen Zusatzstoffen,

besteht.These properties can be found in the preparation according to the invention which consists of

• a) 1 to 50 wt .-% organopolysiloxanes, which from
  • ai) 90 to 99.8 mol% of units of the formula
    
    and
  • a ₂ ) 0.2 to 10 mol% of units of the formula
    
    are set up
  • where R ¹ and R ² on the one hand
  • 0.1 to 10 mol% of polyoxyalkylene radicals
  • and on the other hand
  • 0.03 to 3 mol% of mercaptoalkyl or mercaptoaryl residues and / or
  • 0.06 to 6 mol% of aminoalkyl residues and / or
  • 0.1 to 10 mol% of anionic groups bonded to Si atoms via carbon atoms,
  • and the remaining proportion of R ¹ and R ² groups are methyl groups, of which, however, up to 10 mol% can be replaced by longer-chain alkyl, aryl or hydrogen radicals and up to 5 mol% of the oxygen atoms bound to Si by each two lower alkoxy or hydroxy groups can be replaced, and
• b) 50 to 99% by weight of water, optionally emulsifiers and / or organic solvents and, if appropriate, customary additives,

consists.

Common additives are e.g. B. Flame retardants.

The organopolysiloxane skeleton, which is formed from the units a ₁ ) and a ₂ ), is a slightly to moderately branched siloxane. The units a ₁ ) and a ₂ ) are preferably statistically distributed in the siloxane molecule.

It is essential to the invention that these organopolysiloxanes can have 0.1 to 10 mol% of polyoxyalkylene radicals. In addition, wool-affine groups are bound to the organopolysiloxane skeleton. These wool-affine groups are mercaptoalkyl or mercaptoaryl residues, aminoalkyl residues or anionic groups bonded to Si atoms via C atoms. It is sufficient if, in addition to the polyoxyalkylene radicals, only one of the three types of wool-affinity groups shown, e.g. B. 0.03 to 3 mol% of mercaptoalkyl or mercaptoaryl radicals are included.

It is therefore also sufficient if, in addition to the polyoxyalkylene radicals, aminoalkyl radicals are present in the molecule in amounts of 0.06 to 6 mol%. Another possibility is that in addition to the polyoxyalkylene radicals, 0.1 to 10 mol% of anionic groups bonded to Si atoms via carbon atoms are present. However, these three different groupings can also exist side by side, e.g. B. mercaptoalkyl radicals together with aminoalkyl radicals or mercaptoalkyl radicals with anionic groups. You can also use all three different groupings be built into the molecule at the same time.

The remaining R ¹ and R ² groups are methyl groups, of which, however, up to 10 mol% can be replaced by longer-chain alkyl or aryl radicals. Examples of such alkyl or aryl radicals are the ethyl, propyl, dodecyl or phenyl radical.

The combination of the polyoxyalkylene residues bound to the polysiloxane skeleton with one or more of the wool-affine groups enables the preparation requirements to be met.

welche direkt durch eine SiOC-Brücke oder über einen zweiwertigen Kohlenwasserstoffrest durch eine SiC-Brücke an das Polysiloxan gebunden sind und wobei

• Z ein Wasserstoffrest, ein einwertiger Alkyl- oder Arylrest, ein Acylrest oder ein Trimethylsilylrest ist,
• n einen Wert von 2 bis 3 und
• x einen Wert von 2 bis 80 hat.

The polyoxyalkylene radicals preferably correspond to the formula

which are bonded directly to the polysiloxane via an SiOC bridge or via a divalent hydrocarbon radical through an SiC bridge, and wherein

• Z is a hydrogen radical, a monovalent alkyl or aryl radical, an acyl radical or a trimethylsilyl radical,
• n has a value from 2 to 3 and
• x has a value from 2 to 80.

wobei

oder der Trimethylsilylrest ist und y einen Wert von 4 bis 20 hat.The polyoxyalkylene radical preferably corresponds to the formula

in which

or the trimethylsilyl radical and y has a value from 4 to 20.

If the polyoxyalkylene block contains oxypropylene units in addition to oxyethylene units, polyoxyalkylene radicals with at least 40 mol% of polyoxyethylene units are preferred.

Within the stated range that R ¹ and R ² should consist of 0.1 to 10 mol% of polyoxyalkylene radicals, a range of 0.3 to 5 mol% is particularly preferred.

Examples of mercaptoalkyl or mercaptoaryl residues attached to the polysiloxane skeleton are the mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, 3-mercaptoisobutyl or mercaptophenyl residue. The 3-mercaptopropyl radical is particularly preferred.

0.03 to 3 mol% of these mercaptoalkyl or mercaptoaryl residues are bound to the organopolysiloxane molecule, preferably 0.1 to 1 mol%.

Examples of suitable aminoalkyl radicals, which are also preferably used, are the 3- (2-aminoethyl) aminopropyl or the 3-aminopropyl radical.

Further examples of suitable aminoalkyl radicals are the 4- (2-aminoethyl) aminobutyl radical or the 3- (2-aminoethyl) aminoisobutyl radical.

These aminoalkyl radicals form 0.06 to 6 mol% of the radicals R ¹ and R ² . The preferred range is 0.2 to 2 mol%.

wobei m 0 oder 1 ist und X ein -O- Rest oder die Gruppe -OR⁴ ist. R⁴ ist dabei ein Wasserstoffrest oder ein Alkylrest mit 1 bis 4 C-Atomen. Diese anionischen Reste können in Form der freien Säure vorliegen oder ganz oder teilweise neutralisiert sein.Anionic groups can also be bound to the organopolysiloxane molecule. These anionic groups are bound to the silicon atom by a divalent hydrocarbon radical. The carbon chain R ^{3 of} the divalent hydrocarbon radical can be interrupted by oxygen, nitrogen or sulfur atoms. The groups are particularly suitable as anionic groups

where m is 0 or 1 and X is an -O- radical or the group -OR ⁴ . R ⁴ is a hydrogen radical or an alkyl radical with 1 to 4 carbon atoms. These anionic radicals can be in the form of the free acid or can be completely or partially neutralized.

0,1 bis 10 Mol-% der Gruppen R^T und R² sind durch derartige anionische Gruppen gebildet, vorzugsweise jedoch 0,3 bis 6 Mol-%.Examples of such groups are

0.1 to 10 mol% of the groups R ^T and R ² are formed by such anionic groups, but preferably 0.3 to 6 mol%.

In principle, the preparations according to the invention can be produced in two different ways. On the one hand, there is the possibility of producing the organopolysiloxane by emulsion copolymerization of the individual reactants in the aqueous phase; on the other hand, the reaction can also be carried out in the form of cocondensation in an anhydrous medium.

in Gegenwart anionischer oder kationischer Polymerisationslcatalysatoren die entsprechenden organomodifizierten α,ω-Polydimethylsiloxandiole hergestellt werden. Diese Siloxandiole lassen sich dann weiter mit Polyalkylenglykoläther-modifizierten oder -SH oder Aminogruppen enthaltenden Trialkoxysilanen umsetzen und auch mit Silanen beispielsweise der Formel

über welche eine anionische Gruppe in das Organopolysiloxan eingeführt werden kann. Die Synthese der organomodifizierten Alkoxysilane ist dem Fachmann bekannt.If one chooses the route of the emulsion polymerization, cyclic siloxanes can be used in a known manner (US Pat. No. 2,891,920), optionally from their mixture with organomodified di (tri) alkoxysilanes, such as, for. B. 3-mercaptopropyl-methyl-diethoxysilane, 3-aminopropyl-methyl-diethoxysilane or silanes of the formula

the corresponding organomodified α, ω-polydimethylsiloxane diols are prepared in the presence of anionic or cationic polymerization catalysts. These siloxane diols can then be reacted further with trialkoxysilanes modified or modified with polyalkylene glycol ether or with SH or amino groups and also with silanes, for example of the formula

via which an anionic group can be introduced into the organopolysiloxane. The synthesis of the organomodified alkoxysilanes is known to the person skilled in the art.

aus.In the preparation of the organopolysiloxanes in the non-aqueous phase, it is expedient to start from a sulfuric acid ester of an organosilicon alcohol of the formula

out.

(p = ganze Zahl > 1)
umgesetzt werden.This starting product, which also has a potential anionic group, can in the presence of an acid acceptor, such as. B. an amine, with α, ω-polydimethylsiloxane diols, e.g. B. the formula

(p = integer> 1)
be implemented.

In addition to the anionic groups, the reaction product also contains terminally reactive SiOH groups which are capable of cocondensation with the alkoxy groups of the silanes modified with polyalkylene glycol ether, optionally also with mercaptoalkyl. After the cocondensation, which is preferably carried out at higher temperature in the presence of tertiary amines, removed the solvents by simple distillation.

• Man mischt α,ω-Polydimethylsiloxandioi mit Di-(Tri)alkoxysilanen, welche die anspruchsgemäßen funktionellen Gruppen enthalten und kondensiert in üblicher Weise z. B. durch Hitzeeinwirkung unter Stickstoffatmosphäre, gegebenenfalls nach Zusatz üblicher Katalysatoren wie Wasser, Organozinnverbindungen und/oder starke Säuren. Ersetzt man einen Teil der organofunktionellen Di-(Tri)alkoxysilane durch Di-(Tri)chlorsilane, erübrigt sich im allgemeinen ein Katalysatorzusatz ebenso wie bei Verwendung des zuerst beschriebenen sauren Schwefelsäureesters.

In addition to this process, which is based on the reaction of the sulfuric acid ester described with siloxane diols, the following can also be carried out:

• Mixing α, ω-polydimethylsiloxane dii with di- (tri) alkoxysilanes, which contain the functional groups as claimed, and condensed in a conventional manner, for. B. by the action of heat under a nitrogen atmosphere, if appropriate after adding conventional catalysts such as water, organotin compounds and / or strong acids. If part of the organofunctional di- (tri) alkoxysilanes are replaced by di- (tri) chlorosilanes, there is generally no need to add a catalyst, as is the case when using the acidic sulfuric acid ester described first.

The organopolysiloxanes prepared in this way can also be converted into aqueous preparations according to the invention by incorporating water, possibly in the presence of suitable emulsifiers.

R⁵ = Mercaptoalkylrest und/oder Aminoalkylrest und Polyoxyalkylenrest

R⁶= Mercaptoalkylrest und/oder Aminoalkylrest und/oder über C-Atome an Si-Atome gebundene anionische Gruppe

R2 = Mercaptoalkylrest und/oder Aminoalkylrest und/oder über C-Atome an Si-Atome gebundene animonische Gruppe und ein Rest der Formel

R^{7 =} Polyoxyalkylenrest, gegebenenfalls über C-Atome an Si-Atome gebundene anionische Gruppe

• p ist eine ganze Zahl von 5-1000
• q ist eine ganze Zahl von 1- 20
• r ist eine ganze Zahl von 1- 15

Examples of organopolysiloxanes contained in the preparations according to the invention are compounds of the following structure

R ⁵ = mercaptoalkyl radical and / or aminoalkyl radical and polyoxyalkylene radical

R ⁶ = mercaptoalkyl radical and / or aminoalkyl radical and / or anionic group bonded to Si atoms via C atoms

R2 = mercaptoalkyl radical and / or aminoalkyl radical and / or animonic group bonded to Si atoms via C atoms and a radical of the formula

R ^{7 =} polyoxyalkylene radical, optionally an anionic group bonded to Si atoms via carbon atoms

• p is an integer from 5-1000
• q is an integer from 1-20
• r is an integer from 1-15

example 1

und eine Mischung aus 370,8 g (0,27 Mol) α,ω-Polydimethylsiloxandicl (p = 18,1) und 30,45 g (0,3 Mol) Triäthylamin bei Raumtemperatur zu. Zur besseren Steuerung der Umsetzung verdünnt man die Reaktionspartner mit Methylenchlorid auf ein Volumen von 500 ml.In 200 ml of a suitable solvent, such as methylene chloride, which are placed in a reaction vessel, 29.2 g (0.135 mol) of a sulfuric acid ester of an organosilicon alcohol of the formula are simultaneously added dropwise from two dropping funnels with stirring

and a mixture of 370.8 g (0.27 mol) of α, ω-polydimethylsiloxane dicl (p = 18.1) and 30.45 g (0.3 mol) of triethylamine at room temperature. To better control the reaction, the reactants are diluted with methylene chloride to a volume of 500 ml.

und 7,97 g (0,033 Mol HS-) eines gering kondensierten partiellen Hydrolysats von 3-Mercaptopropyltriäthoxysilan mit 15 Gew.-% OH versetzt, auf 60° C erhitzt und weitere 2 h gerührt.After a two-hour stirring phase, the reaction product with 64.8 g (0.071 mol) of a silane of the formula

and 7.97 g (0.033 mol HS-) of a slightly condensed partial hydrolyzate of 3-mercaptopropyltriethoxysilane with 15% by weight OH, heated to 60 ° C. and stirred for a further 2 hours.

The partially condensed partial hydrolyzate was obtained by the reaction of 3-mercaptopropyltriethoxysilane with 2% hydrochloric acid in methylene chloride.

• 1.35 Mol-% durch
  
  Reste,
• 0,71 Mol% durch
  
  Reste
• und 0,32 Mol-% durch
  
  Reste ersetzt sind. Durch einfaches Einrühren von Wasser lassen sich aus dem Organopolysiloxan wäßrige Zubereitungen mit Wirkstoffgehalten von 1 bis 50 Gew.-% herstellen.

The solvent is then removed by simple distillation. The reaction product, which is freed from the triethylammonium chloride by pressure filtration, is a low-viscosity, slightly yellowish organopolysiloxane, the residues R ¹ and R ² of which are methyl residues, of which, however

• 1.35 mol% through
  
  Leftovers,
• 0.71 mol% through
  
  Leftovers
• and 0.32 mol%
  
  Leftovers are replaced. By simply stirring in water, aqueous preparations with active substance contents of 1 to 50% by weight can be produced from the organopolysiloxane.

Example 2

versetzt, welche in 200 ml Methylenchlorid gelöst wurden. Anschließend rührt man 2 h bei Raumtemperatur nach, fügt 39,7 g (0,075 Mol) eines Silans der Formel

hinzu und erhitzt auf 60°C. Nach einer weiteren zweistündigen Nachrührphase werden 4,12 g (0,021 Mol) 3-Mercaptopropyltrimethoxysilan zugetropft und wiederum 60 min bei 60° C gerührt.400 ml of methylene chloride, 223.3 g (0.3 mol) of α, ω-polydimethylsiloxane diol (p = 9.6) and 61.1 g (0.6 mol) of triethylamine are placed in a suitable reaction vessel and stirred with a dropping funnel with 43.3 g (0.2 mol) of a sulfuric acid ester of an organosilicon alcohol of the formula

added, which were dissolved in 200 ml of methylene chloride. The mixture is then stirred for 2 h at room temperature, 39.7 g (0.075 mol) of a silane of the formula are added

added and heated to 60 ° C. After a further two-hour stirring phase, 4.12 g (0.021 mol) of 3-mercaptopropyltrimethoxysilane are added dropwise and the mixture is again stirred at 60 ° C. for 60 min.

• 3,13 Mol-% aus
  
  Resten,
• zu 1,17 Mol-% aus
  
  Resten
• und zu 0,32 Mol-% aus
  
  bestehen - die verbleibenden Reste sind Methylreste -, lassen sich durch einfaches Einrühren von Wasser stabile Zubereitungen mit Siloxangehalten von 1,0 bis 50% herstellen.

Now the solvent is carefully distilled off and the reaction product is freed from triethylammonium chloride by pressure filtration. From the organopolysiloxane, its residues R ¹ and R ² too

• 3.13 mol%
  
  Leftovers,
• to 1.17 mol%
  
  Leftovers
• and 0.32 mol%
  
  consist - the remaining residues are methyl residues -, stable preparations with siloxane contents of 1.0 to 50% can be prepared by simply stirring in water.

Example 3

und 10 g einer 1 molaren Kalilauge vorgelegt und unter Rühren auf 95° C erwärmt.480 g of water, 3.3 g of didecyldimethylammonium chloride, 1.7 g of dioctadecyldimethylammonium chloride and 3.5 g of a betaine of the formula are placed in a reaction vessel

and 10 g of a 1 molar potassium hydroxide solution and heated to 95 ° C. with stirring.

hinzu und läßt 1 h lang kräftig nachrühren. Anschließend tropft man der Emulsion 2,4 g (0,0122 Mol) 3-Mercaptopropyltrimethoxysilan zu und rührt weitere 30 min nach. Danach kühlt man die Emulsion auf 40° C ab und neutralisiert die erhaltene Lauge durch Zusatz von 12,0 g einer 10%igen Essigsäure. Die so hergestellte feinteilige Zubereitung enthält ein Organopolysiloxan, bei welchem die Reste R¹ und R² zu 1,29 Mol-% aus

und zu 0,322 Mol-% aus -(CH₂)₃-SH-Resten bestehen; die verbleibenden Reste sind Methylreste.136 g (0.459 mol) of octamethylcyclotetrasiloxane and 34.4 g (0.0488 mol) are added over a dropping funnel in the course of 45 min.

add and let stir vigorously for 1 h. Then 2.4 g (0.0122 mol) of 3-mercaptopropyltrimethoxysilane are added dropwise to the emulsion and the mixture is stirred for a further 30 min. The emulsion is then cooled to 40 ° C. and the resulting alkali is neutralized by adding 12.0 g of a 10% acetic acid. The fine-particle preparation thus prepared contains an organopolysiloxane in which the radicals R ¹ and R ² are 1.29 mol%

and 0.322 mol% consist of - (CH ₂ ) ₃ -SH residues; the remaining residues are methyl residues.

Example 4

und 2,95 g (0,015 Mol) 3-Mercaptopropyltrimethoxysilan tropfenweise hinzu und rührt weitere 30 min kräftig nach.167 g (0.56 mol) of octamethylcyclotetrasiloxane are added dropwise to a 95 ° C. hot emulsifier solution corresponding to example 3. After a one-hour stirring phase, add 14.0 g (0.015 mol) with an interruption of 30 minutes.

and 2.95 g (0.015 mol) of 3-mercaptopropyltrimethoxysilane are added dropwise and the mixture is stirred vigorously for a further 30 min.

After cooling to 40 ° C., the potassium hydroxide solution contained in the emulsion is neutralized by adding 12 g of a 10% acetic acid.

• 0,33 Mol-% durch
  
  -Reste
  
  Reste ersetzt sind.

The finely divided aqueous preparation contains an organopolysiloxane, the residues R ¹ and R ² of which are methyl residues, of which, however

• 0.33 mol% through
  
  Remains
  
  Leftovers are replaced.

Example 5

versetzt. Nach dem Zutropfen rührt man 1 h nach und fügt 6,05 g (0,027 Mol) 3-(Aminoäthyl-)aminopro- pyltrimethoxysilan hinzu. Im Anschluß an eine weitere 30minütige Nachrührphase kühlt man auf 40°C ab und neutralisiert die Emulsion durch die Zugabe von 16 g 10%iger Essigsäure.A 95 ° C. hot emulsifier solution corresponding to Example 3 is added dropwise with vigorous stirring with 167 g (0.56 mol) of octamethylcyclotetrasiloxane and 15.95 g (0.03 mol)

transferred. After the dropwise addition, stirring is continued for 1 h and 6.05 g (0.027 mol) of 3- (aminoethyl) aminopropyltrimethoxysilane are added. Following a further 30 minute stirring phase, the mixture is cooled to 40 ° C. and the emulsion is neutralized by adding 16 g of 10% acetic acid.

• 0,65 Mol-% aus
  
  -Resten
• und zu 0,59 Mol-% aus
  
  -Resten bestehen; die verbleibenden Reste sind Methylreste.

The finely divided aqueous preparation contains an organopolysiloxane in which the radicals R ¹ and R ² are added

• 0.65 mol%
  
  -Remains
• and 0.59 mol%
  
  -Remains exist; the remaining residues are methyl residues.

Example 6 (not according to the invention)

zu und rührt wiederum 30 min nach. Danach wird die Emulsion auf 40° C abgekühlt und durch die Zugabe von 12 g 10%iger Essigsäure neutralisiert.Analogously to Example 3, an emulsifier solution is prepared, which, after heating to 95 ° C. with vigorous stirring, is added via a dropping funnel to 167 g (0.56 mol) of octamethylcyclotetrasiloxane added. After stirring for a further 60 min, 27.98 g (0.03 mol) are added dropwise

and stir again for 30 min. The emulsion is then cooled to 40 ° C. and neutralized by adding 12 g of 10% acetic acid.

ersetzt sind.The finely divided aqueous preparation contains an organopolysiloxane, the radicals R 'and R ² of which are methyl radicals, of which, however, 0.66 mol%

are replaced.

Example 7

380 g of water and 3 g of dodecylbenzenesulfonic acid are placed in a reaction vessel and heated to 95 ° C. with stirring.

• 167,00 g (0,56 Mol)

Octamethylcyclotetrasiloxan,

• 5,61 g (0,015 Mol)
  
• 27,98 g (0,03 Mol)
  
  und
• 2,95 g (0,015 Mol) 3-Mercaptopropyltrimethoxysilan

über einen Tropftrichter der Emulgatorlösung zugefünt. Nach erfolgter Zugabe der verschiedenen Komponenten wird jeweils 60 min lang kräftig gerührt. Danach kühlt man die Emulsion auf 40° C ab und neutralisiert die erhaltene Säure durch den Zusatz von 11 g einer 1molaren Kalilauge.For the preparation of the organopolysiloxanes a) consisting of the units a ₁ ) and a ₂ )

• 167.00 g (0.56 mol)

Octamethylcyclotetrasiloxane,

• 5.61 g (0.015 mol)
  
• 27.98 g (0.03 mol)
  
  and
• 2.95 g (0.015 mol) of 3-mercaptopropyltrimethoxysilane

added to the emulsifier solution via a dropping funnel. After the various components have been added, the mixture is stirred vigorously for 60 minutes. The emulsion is then cooled to 40 ° C. and the acid obtained is neutralized by adding 11 g of a 1 molar potassium hydroxide solution.

• 3,33 Mol-% aus
  
  -Resten,
• zu 0,66 Mol-% aus
  
  Resten
• und zu 0,33 Mol-% aus
  
  Resten bestehen; die verbleibenden Reste sind Methylreste.

The finely divided aqueous preparation contains an organopolysiloxane in which the radicals R ¹ and R ² are added

• 3.33 mol%
  
  -Residues,
• to 0.66 mol%
  
  Leftovers
• and 0.33 mol%
  
  Remains exist; the remaining residues are methyl residues.

Example 8 (Comparative example according to DE-OS 2 365 977)

The following compounds were mixed:

For the preparation of the impregnation solution, the required amount of this mixture is dissolved in toluene and diluted to the desired application concentration.

Application example

• % L = prozentualer Längenschrumpf
• % B = prozentualer Breitenschrumpf

Knitted fine wool material is treated with the preparations mentioned in Examples 1 to 8 in such a way that after simple drying of the impregnated fabric at 90 ° C., a solids coating of 1% results. In Examples 1 to 5 and 7 according to the invention, however, drying can also take place at room temperature, since the preparations described in these examples contain organopolysiloxanes which cure completely even at this temperature. After storage for 24 hours at 20 ° C., the finished and untreated material was washed in a household washing machine at 40 ° C. with the addition of 5 g / l perox needle soap and 2 g / l soda and dried in the tumbler between the washes. The surface felt shrinkage was determined after twenty washes of 20 minutes each. The surface felt shrinkage was calculated according to the following formula

• % L = percentage length shrinkage
• % B = percentage width shrinkage

The following values were determined:

In contrast to the treated materials, the unfinished sample showed a heavily matted surface. The handle of the treated samples was also significantly softer after washing than the handle of the untreated material after washing and corresponded to the handle before washing.

Claims (7)

1. Preparation for shrinkproofing wool, which comprises

a) 1 to 50% by weight of organopolysiloxanes which are built up from

a₁) 90 to 99.8 mol % of units of the formula

and

a₂) 0.2 to 10 mol % of units of the formula

wherein R¹ and R² are formed from, on the one hand, 0.1 to 10 mol % of polyoxyalkylene radicals and, on the other hand, 0.03 to 3 mol % of mercaptoalkyl radicals or mercaptoaryl radicals and/or 0.06 to 6 mol % of aminoalkyl radicals and/or 0.1 to 10 mol % of anionic groups which are bonded to Si atoms via C atoms, and the remaining proportion of R¹ groups and R² groups are methyl groups, of which up to 10 mol % can, however, be replaced by longchain alkyl radicals, aryl radicals or hydrogen radicals, and up to 5 mol % of the oxygen atoms bonded to Si can be replaced by two lower alkoxy groups or two hydroxyl groups, and

b) 50 to 99% by weight of water and, if appropriate, emulsifiers and/or organic solvents and, if appropriate, customary additives.

2. Preparation according to Claim 1, characterised in that the polyoxyalkylene radicals correspond to the formula

and are bonded to the polysiloxane either directly by a SiOC bridge or by a SiC bridge via a divalent hydrocarbon radical, and Z is a hydrogen radical, a monovalent alkyl radical, a monovalent aryl radical, an acyl radical or a trimethylsilyl radical, n has a value of 2 to 3 and x has a value of 2 to 80.

3. Preparation according to Claim 2, characterised in that the polyoxyalkylene radicals correspond to the formula

wherein

radical or the trimethylsilyl radical and y has a value of 4 to 20.

4. Preparation according to one or more of the preceding claims, characterised in that the mercaptoalkyl radicals contain a straight-chain or branched alkylene radical having 1 to 4 C atoms.

5. Preparation according to one or more of the preceding claims, characterised in that the aminoalkyl radicals are 3-(2-aminoethyl)-aminopropyl radicals or 3-aminopropyl radicals.

6. Preparation according to one or more of the preceding claims, characterised in that the anionic groups correspond to the formulae

and are present in the form of the acid or are completely or partially neutralised and R³ is a bivalent hydrocarbon radical which can be interrupted by oxygen atoms, nitrogen atoms or sulphur atoms, X is the -O- radical or the group -OR⁴, wherein R⁴ is a hydrogen radical or an alkyl radical having 1 to 4 carbon atoms, and m is 0 or 1.

7. Preparation according to one or more of the preceding claims, characterised in that R¹ and R² are formed from. on the one hand, 0.3 to 5 mol % of polyoxyalkylene radicals and, on the other hand, 0.1 to 1 mol % of mercaptoalkyl radicals or mercaptoaryl radicals and/or 0.2 to 2 mol % of aminoalkyl radicals and/or 0.3 to 6 mol % of anionic groups which are bonded to Si atoms via C atoms. and the remaining proportion of R' groups and R² groups are methyl groups, of which up to 10 mol % can, however, be replaced by long-chain alkyl radicals or aryl radicals.