DE1963574C3 - Process for making textiles permanently water-repellent - Google Patents

Description

A-CO-NH-R-NH-CO-B

As is known, there are a number of methods for impregnating and hydrophobizing textiles Using different products. Mentioned are, for example, the paraffin waxes, the aluminum soaps, complex chromium compounds, N-methylolamides of fatty acids, pyridinium salts, condensation products of melamine and formaldehyde or of ureas (or phenols) and formaldehyde, perforated organic compounds, silicones and isocyanates.

However, these products generally do not result in permanent water repellency because over the course of the process They become the washing and degreasing processes to which the substances impregnated with them are subjected gradually more and more worn away; this disadvantage is even more noticeable when the one in question Coming agents have a structure due to which they do not interact with the cellulose of the tissue can react or or and if they are used for treating textile fabrics on which they cannot be fixed chemically.

in which R represents a toluene or hexamethylene radical, while A and B, which can be identical or different, represent the groups NHR ¹ or NHR ² , N (R ¹ J ₂ or N (R ² ) ₂ , OR ¹ or OR ² , R ¹ or R ² , where the radicals R ¹ and R ^{2 are} identical or different and are aliphatic hydrocarbon radicals of the formula

C _n H _{2n + 1}

in which η stands for a number between 12 and 22, and a polyisocyanate is applied in the usual way and the compound is crosslinked on the fiber with the polyisocyanate by means of heat treatment, removing the solvent.

The compounds to be used according to the invention are white crystalline solids which are present in the usual organic solvents such as aromatic hydrocarbons, for example benzene or toluene or in the chlorinated aromatic hydrocarbons, preferably the mono-, di- and trichlorobenzenes, which are readily soluble in heat. In the cold, the degree of their solubility is different and depends on the connection in question. In general, however, the solubility in solvents is sufficient such as 1,2-dichlorobenzene or 1,3,5-trichlorobenzene or in nitrobenzene for the intended use.

The compounds to be used according to the invention can with the help of the on the relevant Area classical procedures can be obtained. Some manufacturing processes that rely on toluene or Hexamethylene diisocyanate run out are described below. As tolylene diisocyanate, a Isomer mixtures are used; the commercial product is preferably used that consists of 20% of the 2,6 isomer and 80% of the 2,4 isomer consists. The symmetrical derivatives, i.e. H. those whose residues A and B are identical can, if it is bis-urea, by reacting the isocyanate in question with the amine in question in an organic solvent which is inert under the reaction conditions, in particular a chlorobenzene or acetone. The bis-carbamates can through Heating the isocyanate in question with the alcohol in question in an inert solvent be obtained in the presence of a tertiary amine as a catalyst. Finally, the bis-amides are in particular by reacting hexamethylene or toluene diisocyanates with an aliphatic Acid in the presence of a catalyst, which may be a tertiary amine, produced.

The asymmetric derivatives can either contain different hydrocarbon radicals R ¹ and R ² or different functional urea, carbamate and amide groups or at the same time each contain one of these different groupings.

In the former i-ail they are described by means of the above Methods obtained by making the isocyanate simultaneously with reactants of the two Types implements; the other Fa uses a two-step process.

Examples of compounds of the above formula are: hexamethylene-bis- {octadecyl-3-urea), Hexamethylene-bis-octadecanamide, hexamethylene-bis-tetradecyl-carbamate, the 2,4 and 2,6 isomers, alone or in a mixture of bis (dodecyl-3-ureido) -toluo! Bis- (tetradecyl-3-ureido) -toluene, bis- (hexadecyl-3-ureido) -toluene, Bis- (octadecyl-3-ureido) -toluene, bis- (di-octadecyl-S-ureidoJ-toluo ^ toluylene-bis-tetradecyl- or octadecyl or eicosyl carbamate, toluenebishexadecanamide, tolylenebis octadecanamide; (Dodecyl - 3 - ureido - octadecyl - 3 '- ureido) - toluene, N - (Octadecyl - 3 - ureido) - toluylene - octadecanamide and N - (octadecyl - 3 - ureido) toluylene octadecyl carbamate.

In practice, the preferred procedure is to use an organic solution of the invention to be used compounds and this already the polyisocyanate used for later crosslinking and optionally adding a catalyst of known type which accelerates this reaction; the solution is then applied to the woven or knitted fabric in a known manner, e.g. B. by spraying or in the impregnation device according to Foulard and subjects the fabric after the Solvent has been driven off, a heat treatment causing the crosslinking.

The concentration of the compounds to be used according to the invention in the organic solvent can vary within wide limits. In general, it is expediently between 20 and 100 g / l solution. The warm- or cold-dissolving solvents described above are used. Slightly viscous solutions with a translucent appearance are obtained within the concentration range mentioned. _;

Isocyanates suitable for crosslinking the compounds used according to the invention can be used all kinds of known di- or polyisocyanates can be used, e.g. B, hexamethylene diisocyanate or its reaction product with water; Toluene diisocyanate, in particular the mixture of isomers mentioned above; Diphenylmelhandiisocyanat or the gene

mix of this product and its higher homologues; a polyisocyanai with an isocyanurate structure or a condensation of trimethylolpropane and triisocyanate obtained from tolylene diisocyanate. The isocyanate must be at least in the theoretically

Networking the compounds of the formula given required amount can be used. However, the isocyanate is preferably used in excess for example 50 to 150%.

As already mentioned, you can still use the solution Add catalysts of known type, which the reaction between the compound and the polyisocyanate accelerate. Suitable catalysts are, above all, tertiary amines and organometallic compounds and metal salts of organic acids.

It is noteworthy that the mixtures prepared in this way, which contain the compound in solution, the polyisocyanate and optionally the catalyst, are stable in the cold and can be stored as such for several days. They are applied to the tissue at normal or elevated temperatures, e.g. B. at about 50 to 8O ⁰ C applied. As already mentioned, the textile fabric is impregnated using conventional methods, e.g. B. by spraying or padding and squeezing. the

The amount of the solution is adjusted in consideration of its concentration so as to be that intended Amount of dry matter (calculated as compound + polyisocyanate) on the fabric. This proportion is usually between 0.5 and 5%, preferably between 1 and 3%, based on the textile weight before the treatment.

After the solvent has been driven off, the crosslinking is effected in situ by cutting the piece subjected to a heat treatment. The temperatures used are in a range that is suitable for the treated textiles is not a disadvantage. In practice, you work at temperatures that depend on the The polyisocyanate used are generally between 100 and 150 "C. The reaction proceeds fairly well quickly; after a treatment time of 3 to 4 minutes, the crosslinking can be sufficient; in general, a complete reaction course can be achieved if the piece is used during a Period not exceeding 15 minutes and generally 5 to 7 minutes, those mentioned above Exposes to temperatures.

The method of waterproofing according to the specification can be applied to textiles of all types, It doesn't matter whether they are made from natural fibers such as viscose, rayon or cellulose acetate or from purely synthetic fibers Fibers such as polyacrylic, polyester or polyamide fibers or, whether they are mixed fabrics, such as polyester-cotton or polyester-viscose. Is particularly advantageous the method according to the invention for the treatment of purely synthetic textiles, such as polyamides, the is known to be the hardest to make hydrophobic. The water repellency or hydro-

In general, from the outset, phobing is superior to that obtained with the known products and is superior to washing and resp. or degreasing treatments quite resistant.

The following under A to E describes the preparation of compounds to be used according to the invention described. Examples 1 to 4 below illustrate the invention and relate to attempts to make various water repellants Textiles.

A. The experiment was carried out in a device equipped with a stirrer, thermometer, inlet opening for isocyanate and reflux condenser.

300 kg of monochlorobenzene and 50 kg of octadecylamine were placed in the device. After heating the mixture to 8O ⁰ C 16 kg toluene diisocyanate with 80% 2,4-isomer and 20% 2,6-isomer were introduced within 1 hour, with vigorous stirring, keeping the temperature between 85 and 95 ° C. After cooling, the reaction mixture was filtrieit and the solid colorless residue is washed with acetone, flat drying were 62.7 one kilogram obtained at 175 ^a C-melting product that is of as a mixture of the 2,4- and 2,6-isomers Bis- (octadecyl-3-ureido) -toluo! S proved.

Elemental analysis: Calculated ... C 75.78, H 11.87, N 7.85%;

found .... C 75.70, H 11.86, N 7.77%.

If the toluylene diisocyanate 80/20 was replaced by hexamethylene diisocyanate under otherwise identical working conditions, hexamethylene bis (octadecyl-3-urea) was obtained at 175 to 176 ° C melted.

B. In a device that corresponded to that used under A, 160 kg of acetone and 80 kg of dioctadecylanrine were applied at normal temperature. A solution of 13.4 kg of toluene diisocyanate 80/20 in 50 kg of acetone was then added over the course of 45 minutes with vigorous stirring, the temperature being kept at about 30 ^° C. After everything was added, the reaction mixture was refluxed for 1 hour. After cooling, a crystalline white solid was isolated by filtration, which after drying in air weighed 80 kg.

The product, melting at 53-55 ° C, was found as a mixture of bis- {di-octadecyl-3-ureido> -2 _; ⁴ - and 2,6-toluene identified (nitrogen content: calculated 4.60, found 4.65).

C. In a smaller device corresponding to the procedure under A, 1 kg of trichlorethylene, 320 g of 1-octadecanol and 1 g of triethylamine were added, for which 110 g of tolylene diisocyanate 80/20 were slowly added. The mixture was refluxed with stirring for 1 hour. After cooling to 20 ⁰ C, the reaction mixture was filtered and the colorless Röckstand washed with acetone. The product weighed 330 g and was identified as a mixture of toluene 2,4- and 2,6-biscarbamate of octadecyl. Mp 90 to 92 ° C; Nitrogen content: calculated 3.92; found 4.03.

D. 306 g of 80/20 tolylene diisocyanate were slowly added dropwise with stirring into a mixture of 1 kg of octadecanoic acid and 5 g of triethylamine, heated to 170 to 180 ^{° C.} After all was admitted the mixture was kept for 2 Z ¹ ₂ hours at 170 to 18O ⁰ C, cooled to 100 ⁰ C, peeled and crushed later. 1.14 kg of a colorless solid were obtained, which was identified as a mixture of toluene-2,4- and 2,6-bis-octadecanamide. After recrystallization from dimethylformamide, the product melted at from 133 to 135 ° C. (nitrogen content: calculated 4.27; found 4.20).

E. For the purpose of preparing the N- [Octadecyl-3-ureido) -toluylene] -carbaraates of octadecyl in two-stage In the process, tolylene diisocyanate is first used with 1-octadecanol (molar ratio 1: 1) in acetone around and then introduces 1 mole of octadecylamine per mole of isocyanate, whereupon the reaction mixture is added filtered to isolate the colorless precipitate formed. The product was immediately washed in acetone and dried.

example 1

A solution is prepared of 50 g of bis (stearyl-3-ureido) toluene in 1 I o-DichlorbenzuI forth by incorporating the substance with stirring, in the heated at 8O ⁰ C solvent. After cooling to 20 ^° C., two batches are prepared from this solution by adding the following substances:

in the first case:

Tolylene diisocyanate 80/20 25 g / l Zinc octanoate 0.2 g / l

in the 2nd case:

Mixture of diphenylmethane diisocyanate and its higher homologues 39 g / l

Zinc octanoate 0.2 g / l

Then were in a conventional design with a transport roller for the textile material at the bottom of the Drinking tub and two squeegee rollers at Um ambient temperature 2 pieces of fabric made of polyester-cotton soaked with one of the two approaches each and squeezed off by 60%, so that about 2.0% dry matter was deposited on each piece of fabric. The pieces were then ^{dried at 6O 0} C and Subjected to a heat treatment at 130 ^° C. for 5 minutes. Half of the two pieces of fabric were then washed and degreased several times, one after the other Ber- «test, which is generally known in the textile industry (AFNOR G 07-057 standard). The test consists in the fact that one measures the maxims en water pressure! At 20 ⁰ C, which is exerted on the fabric before it from the water by will penetrate. (The test also "was lung after treatmen performed prior to washing or degreasing.) The washing was carried out so that the piece at 6O ⁰ C for 30 minutes with an aqueous solution of 5 g / l soap and 2 g / l sodium

6s treated (ISO 3 standard). Degreasing took place at 20 ^° C. within 30 minutes with the aid of perchlorethylene.

The results are shown in Table I:

In general, from the outset, phobing is superior to that obtained with the known products and is superior to washing and resp. or degreasing treatments quite resistant.

The following under A to E describes the preparation of compounds to be used according to the invention described. Examples 1 to 4 below illustrate the invention and relate to attempts to make various water repellants Textiles.

A. The experiment was carried out in a device equipped with a stirrer, thermometer, inlet opening for isocyanate and reflux condenser.

300 kg of monochlorobenzene and 50 kg of octadecylamine were placed in the device. After heating the mixture to 8O ⁰ C 16 kg toluene diisocyanate with 80% 2,4-isomer and 20% 2,6-isomer were eingefiihrt over 1 hour with vigorous stirring, keeping the temperature between 85 and 95 ° C. After cooling, the reaction mixture was filtered and the solid, colorless residue was washed with acetone. After drying, 62.7 kg of a product which melted at 175 ° C. and was found to be a mixture of the 2,4- and 2,6-isomers of bis (octadecyl-3-ureido) toluene were obtained.

Elemental analysis: Calculated ... C 75.78, H 11.87, N 7.85%;

found .... C 75.70, H 11.86, N 7.77%.

If the toluylene diisocyanate 80/20 was replaced by hexamethylene diisocyanate under otherwise identical working conditions, hexamethylene bis (octadecyl-3-urea) was obtained at 175 to 176 ° C melted.

B. In a device which corresponded to that used under A, 160 kg of acetone and 80 kg of dioctadecylanrin were added at normal temperature. A solution of 13.4 kg of toluene diisocyanate 80/20 in 50 kg of acetone was then added over the course of 45 minutes with vigorous stirring, the temperature being kept at about 30 ^° C. After everything was added, the reaction mixture was refluxed for 1 hour. After cooling, a crystalline white solid was isolated by filtration, which after drying in air weighed 80 kg.

The product, which melts at 53 to 55 ° C, was as a mixture of bis (di-octadecyl-3-ureido) -2,4- and -2,6-tohiol identified (nitrogen content: calculated 4.60; found 4.65).

C. In a smaller device corresponding to the procedure under A, 1 kg of trichlorethylene, 320 g of 1-octadecanol and 1 g of triethylamine were added abandoned, for which 110 g of toluene diisocyanate 80/20 were slowly added. The mixture was under Stirring kept under reflux for 1 hour. After cooling to 20 ° C, the reaction mixture became filtered and the colorless residue washed with acetone. The product weighed 330 g and was identified as a mixture of toluene-2,4- and 2,6-biscarbamate of octadecyl. Mp 90 bfc 92 ° C; Nitrogen content: calculated 3.92; found 4.03.

D. In a mixture, heated to 170 to 180 ^° C., of 1 kg of octadecanoic acid and 5 g of triethylamine, 306 g of toluene diisocyanate 80/20 were slowly added dropwise with stirring. After all was admitted the mixture was held at 170 to 180 ^° C. for a _{further 2 1/2} ^{hours, cooled to 100 °} C., drawn off and later comminuted. 1.14 kg of a colorless solid were obtained, which was identified as a mixture of toluene-2,4- and -2,6-bis-octadecanamide. After recrystallization from dimethylformamide, the product melted at .133 to 135 ° C (nitrogen content: calculated 4.27; found 4.20).

E. For the purpose of preparing the N- [Octadecyl-3-ureido) -toluy! En] -carbamate of octadecyl in a two-stage process In the process, tolylene diisocyanate is first used with 1-octadecanol (molar ratio 1: 1) in acetone around and then introduces 1 mole of octadecylamine per mole of isocyanate, whereupon the reaction mixture is added filtered to isolate the colorless precipitate formed. The product was immediately washed in acetone and dried.

Example I.

A solution of 50 g of bis (stearyl-3-ureido) toluene in II o-dichlorobenzene is prepared by introducing the substance into the solvent heated to 80 ° C. with stirring. After Abkühien at 20 ⁰ C is prepared from this solution two Ansähe by adding thereto the following substances:

in the first case:

Tolylene diisocyanate 80/20 25 g / l Zinc octanoate 0.2 g I.

in the 2nd case:

Mixture of diphenylmethane diisocyanate and its higher homologues 39 g / l

Zinc octanoate 0.2 g / l

Then were in a conventional design with a transport roller for the textile material at the bottom of the Drinking tub and two squeegee rollers at Um ambient temperature 2 pieces of fabric made of polyester-cotton soaked with one of the two approaches each and squeezed off by 60%, so that about 2.0% dry matter was deposited on each piece of fabric. The pieces were then ^{dried at 6O 0} C and Subjected to heat treatment at 130 ° C for 5 minutes. Both pieces of fabric were then each one half washed and degreased several times in a row, each after the first and the fifth treatment the so-called "pain Ber- «test, which is generally known in the textile industry (AFNOR G 07-057 standard). The test consists in that the maximum water pressure is measured at 20 ⁰ C, which is exerted on the fabric before it from the water by will penetrate. (The test was also 'after the hand treatment, carried out before washing or degreasing.

The washing was carried out in such a way that: Piece at 6O ⁰ C for 30 minutes with an aqueous Solution of 5 g / l soap and 2 g / l sodium carbonate

treated (ISO 3 standard). The degreasing takes place «at 20 ⁰ C within 30 minutes with the help of per chlorethylene. The results are shown in Table I:

Measurement results

1. degreasing,

2. degreasing,

3. Degrease

4. degreasing,

5. Degrease

to L'rfindungsgemaß
Schmerber-Tesl I Spray-Tesi 4th
4th
4th
4th
3 mil Λ
Schmerber-Tesl isal / 1
Spray Tcsl 10 I.
I.
1
I.
1 Tissue treatment 137
132
137
120
106 50
38
50
50
34 I.
I.
1 1 963 574
continuation with sowing / Il
Schmerber-Tesl J SpravTes 57
36
50
24
22nd

As can be seen, is the degree of water repellency. which the fabrics by the invention Procedure awarded and determined by the Schmerber test, even after five washing and degreasing processes even higher than the specimens treated with known agents at the beginning. The wettability is also expressed in very satisfactory marks, while the with the test pieces treated with batches I and II, the results drop off very quickly.

Example 4

Of all the connections that have been made according to the procedures B to E, were by Dissolution of the solids in o-dichlorobenzene under Stirring at normal temperature produces solutions of 50 g / l. The basic solutions became through Adding the following substances prepares two series of approaches:

to the first series:

Toluylene diisocyanal 80/20 25 μ 1

Cobalt naphthenate 0.2 μ I

to the second series:

Diphenylmelane diisocyanate 39 g 1

Cobalt naphthenate 0.2 μ I.

The eight blends were used to foulard test pieces of polyamide-6,6 with a 2 to 3% dry solids deposition on the fabric. After drying at 100 ° C, the tissues were subjected to 5 minutes to a heat treatment at 130 ⁰ C.

The specimens then underwent multiple washing and degreasing treatments, as tested Schmerber and subjected to the spray test as described above.

The results are shown in Table IV.

Table IV

Sch. ¹ ) B. Spr. ² ) Sch. Spr. Sch. j Substance according to Spr. Sch. Way of working Sch. D. Spr. Sch. Spr. I. Sch. C. 125 i: 4th 120 5 140 5 130 Approach (series) 140 5 125 5 105 115 4th 120 4th 70 3 130 70 3 70 4th 80 90 3 105 3 80 3 80 90 4th 80 3 75 Testing Results Spr. After: treat 5. Laundry .... 5 5. Degreasing 3 4th

') Schmerber test - results expressed in mm of water.
² ) Test with the »spray tester«.

Spj.

5
3
3

J ^ L j- ^S PL

130

95

130

From the table it can be seen that the ability of the impregnated fabrics to repel the water, even after five washing or degreasing treatments are retained to a satisfactory degree.

Claims (3)

Patent claims: 1. Process for making textiles permanently water-repellent by applying reactive ones Compounds and isocyanates containing groups and reaction on the fiber by heat treatment, characterized in that that one on the textiles an organic solution of compounds of the general formula A-CO-NH-R-NH-CO-B in which R represents a toluene or hexamethylene radical, while A and B, which can be identical or different, represent the groups NHR ¹ or NHR ² , N (R ^l ) ₂ or N (R ² J ₂ , OR ¹ or OR ² , R ¹ or R ² , where R ¹ and R ^{2 are} identical or different and are aliphatic hydrocarbon radicals of the formula in which η stands for a number between 12 and 22, represent, and a polyisocyanate applies in the usual way and the compound on the fiber crosslinked with the polyisocyanate while removing the solvent by means of heat treatment. 2. The method according to claim 1, characterized in that the textiles with a solution treats which the compounds of the general formula according to claim 1 and the Contains polyisocyanate. 3. The method according to claim 1 or 2, characterized in that the textiles with a Treated solution, which is a known crosslinking catalyst, preferably a tertiary Amine, an organometallic compound or a metal salt of an organic acid has been added is. If these compounds are also applied to the textiles from aqueous dispersions, so emulsifiers must be added to them in order to improve the wettability of the textile. Such However, hydrophilic additives reduce the effect of the water-repellent agents. It is also already known to use compounds containing reactive groups such as amines, imines, Alcohols, diamines or glycols and isocyanates are applied to textiles and on the fiber Heat treatment to form urea or urethane compounds or linear polyamides, polyurethanes, To implement polyureas or polythioureas (cf. German patent specification of the branch Austria 157 696 and 159 796 as well as patent specification No. 4 705 of the Office for Inventions and Patents in East Berlin). With these uncomfortable means a moderately washable hydrophobic finish of the textiles is already achieved. There has now been a new method of rendering textiles water repellent by crosslinking developed from isocyanates with certain organic compounds on the fiber. The procedure can be applied to all types of textile fabrics, the water-repellent properties achieved are above all remarkable because they are really permanent and repeatedly sharpen Withstand washing or degreasing treatments than with the known equipment with uncrosslinked Connections can be applied. The method according to the invention for making textiles permanently water-repellent by application of reactive group-containing compounds and isocyanates and reaction on the fiber by heat treatment is characterized in that an organic Solution of compounds of the general formula