Aminofunctional polyorganosiloxanes, their preparation and use

The invention relates to new water-soluble or easily dispersible, amino-functional polyorganosiloxanes which are obtained by radical polymerization of vinyl compounds containing amino or ammonium groups onto polyorganosiloxanes containing at least one mercapto group and can be used as textile finishing agents.

Polyorganosiloxanes containing amino or ammonium groups have been known from the literature for a long time and various ways of producing them have been described. As an example, reference is made here to the synthesis of organopolysiloxanes containing tertiary amino groups described by EL Morehouse in DE-OS 14 93 327, in which the desired compounds are obtained by hydrosilylation of methylhydrogensiloxane.

Such as B. is known from US 4 098 701, amino group-bearing polysiloxanes are suitable for finishing fiber material to give these the desired properties such. B. to give a soft, flowing handle and crease resistance. Therefore, these compounds are commonly used as textile finishing agents.

No. 4,098,701 describes polyorganosiloxanes which, as an amino-functional group, have the grouping - (CH₂)₃NHCH₂CH₂NH₂ contain. This grouping, however, causes a strong tendency towards thermal yellowing, a discoloration that is intensified by elevated temperature. To solve this problem, e.g. B. proposed in EP-A 0 692 567 nitrogen-containing organopolysiloxanes with side chains that do not contain primary amino groups. Furthermore, EP-A 0 441 530 describes the replacement of the aminoethylaminopropyl group by the N-methylpiperazino group or EP-A 0 342 830 recommends the reaction of siloxanes containing aminoethylaminopropyl groups with butyrolactone.

The synthesis of modified siloxanes, for example by grafting ethylenically unsaturated compounds, such as. B. styrene or methyl methacrylate, on mercapto-containing polydimethylsiloxanes (including DE 17 95 389 and US 4 071 577) has long been known. WO 94/14875 describes the synthesis of graft polymers based on perfluoroalkyl acrylates and mercapto-siloxanes and their use as water and oil-repellent finishing for textiles.

Furthermore, US Pat. No. 4,985,155 describes a silicone-based textile finishing agent which is produced by polymerizing mercaptosiloxanes and alkyl acrylates or methacrylates, it being possible for up to thirty percent of the acrylates to be replaced by other acrylic acid derivatives such as acrylamides or else dimethylaminopropyl acrylate. These water-insoluble products, which have only a low cationogenicity, are suitable for particularly soft coatings of textiles that are supposed to be water and windproof, such as sports or ski clothing, raincoats, umbrellas, tents and car hoods. A proportion of at least 70% by weight of alkyl acrylates or methacrylates is, however, absolutely necessary to achieve a soft coating. A proportion below 70% by weight would impair the coating in such a way that the connection to the fiber surface is disturbed and satisfactory mechanical properties of the coating film are no longer obtained. In order to obtain an effective coating, a crosslinking compound (e.g. polyisocyanates) is added to the treatment. The proportion by weight of the coating in the total weight of the coated fabric is usually at least 20% by weight, but in some cases also considerably more.

In the case of the coating of textile fabrics mentioned, the substance to be coated is provided with a closed, preferably pore-free layer of a water-repellent organic coating in order to, for. B. for rainwear in addition to surface hydrophobization to achieve dielectric strength against rain and a water pressure resistance. The coating agent can either one side by devices such. B. a squeegee or on both sides z. B. applied by a foulard. The compounds used for coating can be present either as water-containing pastes or dissolved in an organic solvent. The coating compositions are bound to the surface of the textile by means of added organic crosslinking agents, such as. B. isocyanates, methylol group-containing or epoxy group-containing compounds. The aim of this process is to design the coating process in such a way that the mechanical strength of the film is as high as possible, without this leading to excessive stiffening of the coated textile. This is achieved by pre-hydrophobizing the textile to be coated, which prevents the coating composition from penetrating too deeply into the fabric and thus preventing the fibers from sticking together

In the finishing of textiles, significantly fewer quantities of finishing agents are used. Before being used in textile finishing, however, the siloxanes first have to be converted into aqueous emulsions, sometimes with considerable effort. The usual emulsion processes, such as shear emulsification or emulsification by phase inversion, for the production of usable emulsions are technically very complex and always compromise between the stability of the emulsions required for commercial use and the deterioration in the application properties, such as. B. soft hand or rub fastness of the treated textile substrate. This is caused by the addition of surfactants, cosurfactants or hydrotropics necessary for the emulsion preparation. Another disadvantage of this form of preparation is the fact that silicone emulsions can only be concentrated up to a certain upper limit without phase separations showing up or the emulsion solidifying into a paste which is difficult to process further. These disadvantages have led to the fact that the amino-functional siloxanes have hitherto been applied almost exclusively to the textile substrates by padding.

However, a large part of the plasticizer used in textile finishing for textile substrates is applied in the exhaust process. In order to be able to use a plasticizer here, in addition to high mechanical stability in the liquor, it must also have good stability with respect to fluctuations in pH, light or self-dispersing properties and good pull-out behavior and substantivity.

The object of the invention was to provide amino-functional polyorganosiloxanes which are water-soluble or easily emulsifiable or self-emulsifying and which can be produced economically, in particular using commercially available starting materials. The amino-functional polyorganosiloxanes are said to be usable in aqueous formulations, as textile finishing agents or surfactants.

Surprisingly, it has been found that graft copolymerization of ethylenically unsaturated monomers having amino groups onto mercaptosiloxanes gives very easily emulsifiable to self-emulsifying amino-functional polyorganosiloxanes which give textiles finished with them an excellent soft feel.

The invention relates to amino-functional polyorganosiloxanes of the general formula (I)<chemistry id="chem0001" num="0001"><img file="EP0930342A2_D0001.tif" /></chemistry> where R¹ independently of one another either alkyl, aryl, alkoxy or hydroxyl radicals, R independently of one another, identical or different, substituted or unsubstituted alkyl, aryl or alkylaryl radicals and R³ independently of one another denotes a linear or branched, substituted or unsubstituted alkylene radical having 2 to 10 carbon atoms which is interrupted or not interrupted by hetero groups, b values ​​from 50 to 1,000, preferably 90 and 800 and c values ​​from 1 to 100 and a and d each having values ​​of Assume 0 to 2, with the proviso that the sum of (a + d) is a maximum of 2 and k is either 1 or 2, and Z the structure of formula (II)         (M1) (M2) (M3) H (II) corresponds, where (M1) is a structural unit selected from<chemistry id="chem0002" num="0002"><img file="EP0930342A2_D0002.tif" /></chemistry> represents, where W is a NR²- or -O grouping, U is a linear or branched alkylene group having 2 to 10 carbon atoms, X^⊖ a negatively charged ion stable in aqueous solution, R² independently of one another alkyl radicals with 1 to 4 carbon atoms or hydrogen, R⁴ independently substituted or unsubstituted alkyl, aryl or alkylaryl radicals having 1 to 10 carbon atoms and R⁵ are independently substituted or unsubstituted, saturated or unsaturated alkyl, aryl or alkylaryl radicals having 1 to 10 carbon atoms or hydrogen, and h assume values ​​between 0 and 250, preferably up to 150, particularly preferably up to 100, (M2) a structural unit selected from<chemistry id="chem0003" num="0003"><img file="EP0930342A2_D0003.tif" /></chemistry> represents, where R⁵ has the meaning given above and i assumes values ​​between 0 and 400, preferably up to 300, particularly preferably up to 200, and (M3) a structural unit selected from<chemistry id="chem0004" num="0004"><img file="EP0930342A2_D0004.tif" /></chemistry> represents, where R⁶ a ―COOR⁷- or ―CONR²―R⁸-Groups represents in which R⁷ represents a linear or branched alkyl radical having 1 to 18 carbon atoms, hydroxyalkyl radicals having 2 to 5 carbon atoms, alkoxypolyethylene glycol radicals having a molecular weight of 73 to 1,000 g / mol or a hydroxy group and R⁸ is a hydroxymethylene or methylene ether residue, a 2-methylpropanesulfonic acid residue or hydrogen and R⁹ Represents hydrogen or chlorine and j assumes values ​​between 0 and 200, preferably up to 150, particularly preferably up to 100. with the proviso that the sum (h + i) is always larger (2 · j), preferably larger (2.3 · j).

In the compound of the general formula (I), the radicals R are methyl and / or ethyl radicals and the radical R¹ Methyl, ethyl, hydroxy, methoxy and / or ethoxy radicals are preferred. The rest R³ in the general formula (I) should have no readily hydrolyzable groups, such as, for example, ester groups, and also no unsaturated and / or no proton-releasing groups. For example, R³ with hydroxyl, halogen or alkoxy groups substituted alkylene radicals having 1 to 10 carbon atoms, such as propylene, 2-methylpropylene, butylene, decanylene groups. The rest R³ represent an alkylene radical having 1 to 10 carbon atoms, which can also be interrupted by one or two hetero groups selected from ether, thioether, amino, carboxyl, carbamide and / or sulfonamide groups, an example of which is<chemistry id="chem0005" num="0005"><img file="EP0930342A2_D0005.tif" /></chemistry> Grouping.

The amino-functional polyorganosiloxanes according to the invention can be prepared by reacting a compound of the general formula (I) which has at least one mercapto group, where Z is hydrogen, with the corresponding compounds which form the structural units (M1), (M2) and / or (M3) M1, M2 and M3 in the presence of an initiator. The reaction is usually carried out by radical graft polymerization onto the mercapto group.

Typical examples of the compound M1 are aminoalkyl acrylates and / or methacrylates, aminoalkyl acrylamides and / or aminoalkyl methacrylamides and / or their ammonium compounds, for the compound M2 can be diallylamines and diallylammonium compounds and for the compound M3 alkyl acrylates, alkyl methacrylates, methylolated acrylic and methacrylamides and their alkyl ethers , Acyl acids and methacrylic acids, maleic acid or its anhydride, fumaric acid. Itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinyl acetate, vinyl propionate, vinyl chloride and / or vinylidene chloride can be used.

The radical polymerization is usually carried out in the presence of an initiator. the initiation can take place both via a thermally cleavable compound, such as azo compounds and / or peroxides, or via photolytically cleavable compounds, such as benzoin. Furthermore, all compounds known for this reaction mechanism can be used. In particular, compounds or their mixtures are used, their photochemical excitation states and / or their secondary products are capable of H-abstraction or addition to double bonds and can thus trigger free-radical polymerization, such as, for example, benzoin ethers, bezilketals, dibenzoyl peroxides, benzophenones or hydrodroxyacetophenones.

The reaction can be carried out in solution or solvent-free. Alcohols such as 2-propanol, isopropanol, 1-butanol, 2-butanol, alomatics, esters or ketones can be used as solvents. The solvent is preferably present in the reaction mixture in up to 50% by weight.

Ranges between 40 and 150 ° C. can be selected as the reaction temperature if thermally cleavable initiators are used and between -10 and 150 ° C. in the case of photolytically cleavable compounds. The reaction is usually complete within 1 to 15 hours, preferably within 3 to 8 hours. The use of pressure or working under vacuum is possible, but not preferred.

A further variant for the preparation of the amino-functional polyorganosiloxanes according to the invention is the reaction of a compound of the general formula (I) which has at least one mercapto group, where Z is hydrogen, first with a compound selected from methyl acrylate, methyl methacrylate, ethyl acrylate and / or ethyl methacrylate and then with Compounds of the general formula H₂N ― U ― N (R⁴)₂ (IV), where R⁴ and U have the meaning given above. The reaction takes place in the first step by radical polymerization as described above and in the second by aminolysis. In relation to the general formula (I), the structural units (M2) and (M3) are not present in the amino-functional polyorganosiloxane obtained, ie i and j are 0.

Possible reactions of the monomers with one another or with one another are possible, but do not interfere with the preparation and the later use of the amino-functional polyorganosiloxanes according to the invention.

The mercaptosiloxanes of the general formula (I) used as starting materials for the preparation of the polyorganosiloxanes according to the invention<chemistry id="chem0006" num="0006"><img file="EP0930342A2_D0006.tif" /></chemistry> where all radicals and coefficients have the meaning given above, and their preparation are known. For example, it is possible to convert them to siloxanes containing mercaptropyldimethoxymethylsilane by reacting mercaptopropyldimethoxymethylsilane with a dihydroxyoligodimethylsiloxane or by coequilibrating mercaptopropyl-containing siloxane cycles with trimethylsiloxy-terminated polydimethylsiloxanes, or by converting commercially available amino or epoxy group-containing siloxanes to siloxanes.

Two reactions for the preparation of the mercapto-functional siloxanes are shown as examples:<chemistry id="chem0007" num="0007"><img file="EP0930342A2_D0007.tif" /></chemistry><chemistry id="chem0008" num="0008"><img file="EP0930342A2_D0008.tif" /></chemistry>

The compounds according to the invention can have, for example, the structures below:<chemistry id="chem0009" num="0009"><img file="EP0930342A2_D0009.tif" /></chemistry>

However, compounds according to the invention which contain both terminal and pendant amino-functional groupings Z can also be synthesized without any problems.

The amino-functional polyorganosiloxanes are preferably used in the form of aqueous preparations, for example as emulsions, which can be prepared by known processes.

Areas of application for the compounds according to the invention include use as textile finishing agents or as surfactants. Furthermore, they can also be used as building protection agents, as an additive for water-based paint systems and in personal care, for example as conditioners in shampoos.

Because of their cationogenicity, which is due to the number of amino groups in the molecule, the amino-functional polyorganosiloxanes according to the invention adhere very well to substrates such as textiles, for example to cotton, polyester or polyamide. The textiles finished with it are breathable, water-permeable and rub-fast and have a much softer feel than those compounds which have a high proportion of acrylate groups and a low cationogenicity. By copolymerizing monomers having other functionalities, specific properties, such as, for. B. the washing permanence can be positively influenced.

Embodiments

I. Production of the mercapto-functional siloxanes used:

Example S1

125 g mercptopropyldimethoxymethylsilane (DYNASYLAN 3403, Sivento Chemie GmbH) were mixed with 3,000 g of a hydroxy-terminated organopolysiloxane with the average composition HO (Si (CH3)₂O)₂₃H and 0.5 g of sulfuric acid (98%) are weighed into a 4 l three-necked flask, inertized with nitrogen and heated to 140 ° C. with stirring. After a reaction time of five hours, a Liebig cooler was put on and 100 g of equilibrium cycles were distilled off at a pressure of 780 mbar. The silicone oil thus obtained was slightly cloudy and had a viscosity of 4,000 mPas.

Example S2

85 g of a mixture of [O-Si (CH3) (CH2CH2CH2SH)] were placed in a 4 l three-necked flask._n with n = 3 to 5, 2500 g of a trimethylsilyl endblocked polydimethylsiloxane having a viscosity of 1,000 mPas and 30 g of Tonsil catalyst and kept at 90 ° C. for 20 hours under a nitrogen atmosphere. The product thus obtained was filtered and a clear oil with a viscosity of 500 mPas was obtained.

Example S3

In a 0.25 l three-necked flask equipped with a stirrer, gas inlet tube and gas outlet, a mixture of 0.1 g of diazabicyclooctane and 200 g of a trimethylsilyl-end-blocked, glycidether-modified polydimethylsiloxane (epoxy content: 0.31 mmol epoxy groups / g siloxane; viscosity at 25 ° C: 300 mPas) over a period of two hours at 20 ° C hydrogen sulfide. In the highly viscous reaction product were in¹³C-NMR spectrum the two signals at 50.4 ppm and 43.5 ppm disappeared and new signals emerged at 30.1 ppm and 76.2 ppm.

Example S4

A mixture of 100 g of m-xylene, 500 g of a polydimethylsiloxane modified with aminoethylaminopropyl groups (viscosity at 25 ° C.: 534 mPas; 0.68% by weight nitrogen) was placed in a 1 l three-necked flask equipped with a stirrer, thermometer and reflux condenser , trimethylsilylendblockiert) and 35 g of thioglycolic acid methyl ester boiled under reflux at 150 ° C for eight hours. The reaction mixture was then devolatilized for two hours at 150 ° C. and p = 50 mbar. No amino groups were detectable titrimetrically in the highly viscous and strongly yellow-colored siloxane thus obtained.

Example S5

76 g of compound HS (CH₂)₃Themselves₃)₂OSi (CH₃)₂(CH₂)₃SH, 2,350 g of a mixture of hexamethyltrisiloxane and octamethyltetrasiloxane and 25 g of Tonsil catalyst are added and the mixture is kept at 90 ° C. for 20 hours under a nitrogen atmosphere. The product thus obtained was filtered and devolatilized at 150 ° C. for two hours. A clear oil with a viscosity at 25 ° C. of 100 mPas was obtained.

Example S6

In a 4 liter three-necked flask, 15 g of the compound HS (CH₂)₃Themselves₃)₂OSi (CH₃)₂(CH₂)₃SH, 55 g of a mixture of (O-Si (CH3) (CH2CH2CH2SH))_n with n = 3 to 5, 2,300 g of a mixture of hexamethyltrisiloxane and octamethyltetrasiloxane and 25 g of Tonsil catalyst and kept at 90 ° C. for 20 hours under a nitrogen atmosphere. The product thus obtained was filtered and devolatilized at 150 ° C. for two hours. A clear oil with a viscosity at 25 ° C. of 1900 mPas was obtained.

II. Production of the amino-functional polyorganosiloxanes:

General process variants

Option A:

The mercapto-functional siloxane was mixed with the monomers, the solvent and the initiator in a 250 ml three-necked flask under a nitrogen atmosphere and was kept under stirring for eight hours at the stated temperature. 100 g of the product were mixed with 1,000 g of an aqueous acetic acid solution (3% by weight) and 100 g of volatiles were distilled off at 90 ° C. under reduced pressure.

Variant B

The non-ionic monomers, the solvent and the initiator were added to the mercapto-functional siloxane in a 250 ml three-necked flask under a nitrogen atmosphere and the mixture was kept at the indicated temperature with stirring for eight hours. After one hour the ionic monomer was added. 100 g of the product obtained were mixed with 1,000 g of an aqueous acetic acid solution (3% by weight) and 100 g of volatiles were distilled off at 90 ° C. under reduced pressure

Variant C

The mercapto-functional siloxane was mixed with the monomers, the solvent and the initiator in a 250 ml three-necked flask under a nitrogen atmosphere and was kept under stirring for eight hours at the stated temperature. 100 g of the product were mixed with 1,400 g of an aqueous acetic acid solution (3% by weight) and 400 g of volatiles were distilled off at 90 ° C. under reduced pressure.

Variant D

In a 250 ml three-necked flask, 10% by weight of the mercapto-functional siloxane, the monomers, the solvent and the initiator were mixed under a nitrogen atmosphere and the mixture was kept under stirring for a total of eight hours at the stated temperature. Starting after one hour's reaction time, the remaining 90% by weight of the mercapto-functional siloxane were added dropwise uniformly over the course of five hours. 100 g of the product were mixed with 1,000 g of an aqueous acetic acid solution (3% by weight) and 100 g of volatiles were distilled off at 90 ° C. under reduced pressure.

Process examples V1 to V21 and comparison examples Cf. 1 and Cf. 2

These examples were compiled in the form of a table (Table 1) which contains the substances used, the respective variant according to which the preparation was carried out, and the appearance of the product.

Process example V22

In a 1 liter three-necked flask equipped with a stirrer, reflux condenser and thermometer, 100 g of the product from Example S2 were mixed with 50 g of methyl acrylate, 0.3 g of azobis (isobutyronitrile) and 200 g of o-xylene and then at 70 ° C. with stirring warmed up. A few minutes after the reaction temperature has been reached, a clearly exothermic reaction is observed, which must be countered by cooling the batch. After a reaction time of seven hours, a clear, colorless product is obtained which, however, has become significantly more viscous than the starting mixture. 100 g of 3-dimethylamino-1-propylamine are added to this intermediate and the mixture is heated at the boiling point at 150 ° C. for twenty hours. A sample was then taken from the mixture and a titrable almin nitrogen content of 4.7% by weight was determined (corresponds to a degree of conversion of 74%). The reflux condenser is replaced by a distillation condenser and the xylene and excess amine are distilled off at 150 ° C. under reduced pressure. After the distillation had ended, a viscous, yellow paste was obtained. 100 g of this were mixed with 900 g of an aqueous acetic acid solution (3% by weight). After stirring for one hour, a translucent, translucent, yellowish emulsion was obtained.

Process example V23

30 g of dimethylaminopropyl acrylate, 100 g of mecaptosiloxane from example S2, 50 g of 2-propanol and 1.8 g of dibenzoyl peroxide were weighed into a reactor with a quartz glass immersion burner, mixed continuously by means of a stream of nitrogen and cooled to 5 ° C. with a thermostat. After 4 hours of irradiation with a 125 W medium pressure mercury lamp, a product was obtained which was clearly soluble in an aqueous acetic acid solution (3% by weight).

III. Production of emulsions

Emulsion E1

5 g of acetic acid (100% by weight) were added to 100 g of the polymerization product from process example V5 and 150 g of demineralized water were added with stirring. 150 g of water / solvent mixture were distilled off from this solution at 80 ° C. in vacuo. The emulsion thus obtained was clear and easily dilutable with water.

Comparative Example See 3

15 g of a siloxane with trimethylsilyl end groups and aminoethylaminopropyl side chains (0.65% by weight nitrogen viscosity at 25 ° C: 2,100 mPas) were mixed with 10 g of an isotridexcylpolyethylene glycol with an average of seven ethylene oxide units, 1 g of acetic acid (100% by weight) and 15 g of isopropanol are stirred until a clear mixture is obtained. A total of 69.5 g of water was then added to the mixture in small portions while stirring. A clear to slightly blue-tinted microemulsion was obtained.

IV. Finishing of textiles (application examples)

IV.a) Foulard process - Examples A1 to A10

Were used<ul id="ul0001" list-style="dash" compact="compact"><li>a bleached, unequipped cotton terry ware with 400 g / m² for the determination of soft grip and water sink time as well</li><li>a red cotton weave with 120 g / m² for the determination of rub fastness and dry crease recovery angle.</li></ul> The materials were impregnated with the respective liquor, squeezed to 80% liquor absorption with a two-roll pad and dried at 120 ° C. for 10 minutes. The finished goods were then left at room temperature for at least eight hours.

In Table 2, the products used and the results of the materials finished by means of padding processes are compiled for Examples A1 to A10.

IV.b) Exhaust method - Examples A11 to A13

A bleached, unequipped cotton tote ware with 400 g / m was used². This was immersed in the respective liquor (liquor ratio 120), left at 20 ° C. for 20 minutes, then removed and then dried at 120 ° C. for 10 minutes and laid out at room temperature for at least 8 hours.

The following results were obtained: <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Product from Ex.</entry><entry namest="col3" nameend="col3" align="center">Product quantity, based on the weight of the terry cloth in% by weight</entry><entry namest="col4" nameend="col4" align="center">Soft grip (grip evaluation)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Example A11</entry><entry namest="col2" nameend="col2" align="left">V1</entry><entry namest="col3" nameend="col3" align="char" char=",">7,0</entry><entry namest="col4" nameend="col4" align="right">3</entry></row><row><entry namest="col1" nameend="col1" align="left">Example A12</entry><entry namest="col2" nameend="col2" align="left">See 1</entry><entry namest="col3" nameend="col3" align="char" char=",">7,2</entry><entry namest="col4" nameend="col4" align="right">1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Example A13</entry><entry namest="col2" nameend="col2" align="left">See 3</entry><entry namest="col3" nameend="col3" align="char" char=",">2,0</entry><entry namest="col4" nameend="col4" align="right">2</entry></row></tbody></tgroup></table></tables>

V. Methods of determination for the results of the application examples

Determination of the soft grip (grip evaluation)

Since the softness of textiles is strongly subject to the subjective feeling of the test subjects, only a standardization of the boundary conditions, but not the evaluation, can be achieved. In order to ensure reproducibility despite this, the finished samples were assessed with regard to their softness and ranked. For this purpose, 1 to n points were awarded by 10 people depending on the number n of the tested patterns, with n points being awarded for the softest pattern and 1 point for the least soft pattern. The tables show the average values ​​of the points allocated to the individual samples.

Determination of the water sink time

The finished sample was left to acclimatize to atmospheric humidity for at least eight hours, then a drop of deionized water was added to it and the time until the water drop was absorbed by the fabric, but no longer than three minutes. Five determinations were carried out and the mean was formed.

Determination of rub fastness

The determinations were carried out in accordance with the standards EN ISO 105-X12 and 105-A03 with a red cotton woven fabric.

Determination of fleet stability

The following test was carried out to test the stability of organopolysiloxane emulsions against alkalis in finishing liquors: The liquors were prepared according to the recipe given in a 1000 ml beaker and adjusted to pH 10 with sodium hydroxide solution (10% by weight). The liquor was then stirred for twenty minutes with a paddle stirrer at two thousand revolutions per minute. At the end of this time, the stirrer was switched off, the resulting foam disintegrated and the liquid surface was assessed for deposits after a further fifteen minutes.<dl id="dl0001" compact="compact"><dt>Rating:</dt><dd>1 no deposits or cloudiness 2 Turbidity in the fleet has increased 3 Oil film is visible on the surface 4 drops of oil and deposits are visible</dd></dl>

In the case of emulsions which have deposits or an oil film, there is a risk in textile finishing practice that alkali is introduced into the finishing liquor and that the emulsion is destroyed and this leads to roller coverings and stains on the goods.<tables id="tabl0002" num="0002"><img file="EP0930342A2_D0010.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0930342A2_D0011.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0930342A2_D0012.tif" /></tables>