EP0013388A2 - Textile finishing agent and process for its preparation and use - Google Patents

Abstract

Process for the production of textile finishing agents based on a mixture of methylolated polyethylene glycol carbamates and methylolated oligo- or monoethylene glycol carbamates, the textile finishing agents themselves and their use for the easy care of cellulose-containing or consisting of textiles.

Description

From DE-OS 24 59 765 and 26 20 010 processes for the production of carbamates and carbamate mixtures by reacting alcohols and polyethylene glycols with urea in the presence of ion exchangers containing nickel ions are known. The products available in this way are excellent textile finishing agents, but are brownish to brown in color, which is usually perceived as annoying.

The present invention was therefore based on the object of developing a process based on technically easily accessible starting materials for producing such textile finishing agents which are as colorless as possible and which, at the same time, are still further improved in the entirety of their application properties.

The solution to this problem was found in the method according to claim 2. The finishing agents obtainable in this way are not only colorless or almost colorless, but also have the following very important properties: storage stability of the neutral solution and bath stability in acid solution with good reactivity at the same time; high chlorine and hydrolysis resistance on the finished textile; good abrasion resistance; pleasant textile grip even without plasticizer; low soiling; low release of formaldehyde. After all, the finished textiles can be printed very well. The combination of colorlessness with all of these excellent properties, which have practically no disadvantages, makes the finishing agent obtainable according to the invention extremely valuable.

For the implementation in the first stage, approximately equimolar amounts (any excess of one or the other component can be compensated for in the second stage) are urea and polyethylene glycol III (one end of which may be etherified with methyl, ethyl, propyl or butyl alcohol; However, preference is given to the free, that is to say unetherified at both chain ends, polyethylene glycols) of degree of polymerization 9 to 100, preferably 9 to 20, expediently in an inert gas stream in order to exclude air and to remove the ammonia formed, some without catalyst, with stirring (about 2 to 7, preferably 3 to 6) Heated to 130 to 160, preferably 145 to 155 ° C. The reaction can be carried out under pressure or under pressure continuously or batchwise with or preferably without a solvent. Higher-boiling organic liquids, e.g. aromatic or araliphatic hydrocarbons, for example toluene, xylene, ethylbenzene, isopropylbenzene and mixtures thereof. The solvent is distilled off after the reaction.

The implementation follows the equation

If R1 = H, the reaction does not of course proceed entirely according to the idealized scheme above, but dicarbamates also result from the reaction of both hydroxyl end groups of the polyethylene glycol, while part of the latter does not react at all. For the purposes of However, this does not matter to the present invention and is therefore not considered in the following, ie "monocarbamate" is used, although the reaction mixture actually present is meant.

If at least 50, preferably at least 65, in particular more than 80% of this reaction has taken place (where in the case of R ¹ = H than 100% the conversion of on average one of the two hydroxyl groups of the polyethylene glycol is to be regarded; the degree of conversion can, for example, on Residual urea content can be recognized) you can start with the second stage, in which the analogous implementation takes place and the first is completed if necessary.

For this purpose, further urea, the alkyl glycol or glycol IV, preferably methyl glycol, and optionally the catalyst are added to the reaction mixture with stirring, and heating is advantageously continued for 2 to 40, preferably 5 to 20, hours, preferably in a vacuum, while the inert gas stream is passed through or in vacuo with catalyst to 130 to 165, in particular 145 to 155 ° C, or without catalyst to 150 to 200, in particular 160 to 190 ° C, with a lower temperature of course corresponding to a longer reaction time and vice versa. The reaction temperature is only of importance insofar as discoloration is to be expected if the temperature is too high and the reaction time is excessively increased if the temperature is too low. The molar ratio of alkyl glycol or glycol IV to the urea used for the second stage should be 1: (0.5 to 1), preferably about 1: 1. At a ratio of 1: (1), the excess of IV is then distilled off. The molar ratio of carbamate I to carbamate II is in the range from 12: 1 to 1:20, preferably from 1: 1 to 1:15, , in particular from 1: 2.5 to 1:12, the range from 12: 1 to about 1: 1 only being considered for polyester-cotton mixed goods.

The catalyst which is expediently used in the second stage consists of nickel ion-containing, generally acidic ion exchangers, preferably acidic synthetic resin exchangers. Such exchangers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 1/1, page 528, Table 3. Strongly and moderately strong acid exchangers, for example phenolic or polystyrene sulfonic acid resins, or exchangers containing corresponding acid resins, for example bifunctional condensation resins, are preferably used. It is also possible to use styrene-phosphonic acid, styrene-phosphinic acid, resorcinol resins and aliphatic or aromatic carboxylic acid resins. The aforementioned cation exchangers are commercially available in numerous variants. Before the reaction, the exchanger is loaded with nickel using the customary methods, expediently by treatment with solutions, advantageously aqueous solutions, of nickel salts. Suitable nickel salts are suitably nickel chloride, acetate, bromide, nitrate or preferably nickel sulfate. The nickel compounds can also be present as corresponding hydrates, for example nickel chloride hexahydrate. However, it is also possible to use, for example, nickel phosphate, nickel carbonate, nickel bicarbonate, nickel borate, nickel oxalate, nickel propionate. The exchanger is expediently activated with acid, preferably with sulfuric acid or the acid corresponding to the anion of the nickel salt, before the treatment with the nickel salt. Advantageously, the exchanger is first left under or in water at a temperature of 15 to 40 ° C. for 10 to 30 minutes, then activated with acid for 10 to 60 minutes, advantageously in the form , a 2 to 15 weight percent aqueous solution, at a temperature of 15 to 40 ° C and washes the exchanger with water to the neutral point. The treatment with the nickel salt solution is expediently carried out at temperatures between 10 and 50 ° C., advantageously between 20 and 30 ° C. The reaction can be carried out under pressure or under pressure, batchwise, for example by a stirring or batch process, or preferably continuously, for example in exchange columns, in a fixed bed, fluidized bed, in the fluidized bed, in tray columns. It is expedient to use 5 to 50 percent by weight nickel salt solutions and treatment times of 10 to 60 minutes. Subsequently, it is advantageously rinsed with water until the washing liquid emerging from the exchange column has a neutral reaction, and then washing with one of the abovementioned inert solvents or an alcohol at 15 to 40 ° C. for 10 to 60 minutes is largely anhydrous. A loading of 0.01 to 0.2, preferably from 0.02 to 0.1, in particular 0.02 to 0.08 parts by weight of nickel per part by weight of exchanger and an amount of 0.01 to 0.25, preferably from 0, are expedient , 02 to 0.1 parts by weight of exchanger per part by weight of urea.

In principle, nickel salts are also suitable as catalysts instead of the ion exchangers containing nickel ions, but the ion exchangers are much easier to separate from the reaction product by filtration or sedimentation than the salts (which should be precipitated as hydroxide).

Technical purity is sufficient for the starting products.

After completion of the second stage, the reaction mixture can be cooled to about 70 ° C and the catalyst - advantageously L by filtration - to be separated. Excess methylglycol is then distilled off, if necessary under reduced pressure.

The carbamate mixture obtained in the manner described is then methylolated in the customary manner for conversion into the desired textile finishing agent. For this purpose, it is treated with excess aqueous formaldehyde solution at pH 7.5 to 11, preferably 8.5 to 10 for 1 to 10, preferably 2 to 5 hours at a temperature of 10 to 80, preferably 30 to 60 ° C. The solution is then neutralized with any water-soluble acid, for example sulfuric acid, and if necessary diluted with water to the desired concentration. If necessary, the solution can be filtered, possibly with the addition of filter aids such as activated carbon.

The completely or almost colorless, clear, aqueous solution thus obtained is the finished textile finishing agent. It comes in the form of concentrated (30 to 70% by weight) solutions with a pH in the range from 5 to 8, preferably 6 to 7, 5 on the market and can be diluted, acidified, mixed with catalysts and other auxiliary agents, other finishing agents, pigments, plasticizers etc. for use. It is used for shrink-proof and crease-resistant and thus easy care for textiles that contain or consist of cellulose in native or regenerated form.

The parts and percentages given in the examples relate to the weight, unless stated otherwise.

example 1 a) Preparation of the nickel-containing catalyst

A column is filled with 1000 parts of a commercially available cation exchanger made from sulfonated crosslinked polystyrene and left to stand for 15 minutes with the addition of 1000 parts of water. 500 parts of 10 percent hydrochloric acid are then added, the column is left to stand for 20 minutes and the column is washed neutral with distilled water. 3400 parts of a 10% solution of NiSO ₄ .7 H ₂ 0 are added to the exchanger thus activated. If there is no longer an acidic solution at the column outlet, the absorption of the nickel salt has ended. The exchanger filling is washed neutral with water and then washed water-free with methanol and dried. The exchanger is ready for use and contains 8 - 8.5 parts nickel per 100 parts exchanger.

b) Preparation of a co-carbamate from polyethylene ethylenediol (= polyethylene glycol) H (OCH ₂ CH ₂ ) ₁₈ OH, methyl glycol (= ethylene glycol monomethyl ether) and urea

In a stirring apparatus with reflux cooling and gas inlet tube, the mixture of 276 parts of polyethylene ethylenediol with a molecular weight of 810 (H (OCH ₂ ) ₁₈ 0H) and 21 parts of urea is heated to 145 ° C. for three hours while stirring and simultaneously passing a stream of nitrogen through it. The conversion is then 65% (measured by determining the residual urea content). Then 472 parts of methyl glycol, 373 parts of urea and 31 parts of a commercially available cation exchanger treated as above under 1a) are added. The re- Action mixture is heated to reflux temperature (maximum 150 ° C) for 15 hours while stirring and passing a stream of nitrogen. The reaction solution is then cooled to 120 ° C. and the exchanger is filtered off. 936 parts of a co-carbamate are obtained. This corresponds to a yield of 91% of theory. The residual urea content is 0.4%.

c) conversion to the methylolation mixture

785 parts of the co-carbamate obtained according to Example 1b) are heated in a stirrer with 634 parts of a 40% formaldehyde solution with the addition of 17 parts of a 50% sodium hydroxide solution at 50 ° C. for 3 hours. Then it is neutralized with dilute sulfuric acid. 1450 parts of a 63% solution are obtained. The free formaldehyde content is 2.2%. A 50% solution is obtained by adding 570 parts of water.

Example 2

300 parts of a polyethylene ether diol of molecular weight 600 are heated in a stirrer with 300 parts of urea to 150-155 ° C. for three hours while passing through a stream of nitrogen. The degree of implementation is 90%. 68.4 parts of methyl glycol, 54 parts of urea and 35 parts of a nickel-containing exchanger obtained according to Example 1a) are then added. The reaction mixture is heated to reflux temperature (maximum 155 ° C.) with stirring for 18 hours. After cooling to 110-120 ° C, the exchanger is filtered off. There are 401 parts of the co-carbamate a residual urea content of 0.3%. This corresponds to a yield of 94%.

The methylolation is carried out analogously to Example 1.

Example 3

600 parts of a polyethylene ether diol with a molecular weight of 4,000 and 9 parts of urea are heated at 150 to 155 ° C. for 3 hours in a stirring apparatus. A degree of implementation of 90% is achieved. Nickel-containing exchanger after the addition of 31.8 parts diethylene glycol, 18 parts of urea and 4.5 parts of a ..nach Example la) produced the reaction mixture is heated 15 hours to 155 ⁰ C while passing a stream of nitrogen. The mixture is then cooled to 110 ° C. and the exchanger is filtered off. 611 parts (94% of theory) of the co-carbamate are obtained. The residual urea content is 0.25%.

611 parts of the co-carbamate thus obtained are heated in a stirrer with 61 parts of a 40% formaldehyde solution after adding 3 parts of a 50% sodium hydroxide solution at 50 to 55 ° C. for 3 hours. After adding 400 parts of water and neutralization with dilute sulfuric acid, 1080 parts of a 58% solution of the methylol compound with a content of 1.7% free formaldehyde are obtained.

Example 4

810 parts of the polyethylene ether diol H (OCH ₂ ) ₁₈ OH and 60 parts of urea are mixed in a stirrer for 3 hours heated to 150 ° C while passing a stream of nitrogen. A degree of implementation of 85% is achieved. Then 2158 parts of methyl glycol, 1065 parts of urea and 94 parts of a nickel-containing ion exchanger prepared according to Example 1a) are added as a catalyst. The reaction mixture is heated to the reflux temperature while passing a stream of nitrogen through it. At 132 to 134 ⁰ C, the reflux temperature is reached, the increases in the course of 5 hours at 150 ° C. The mixture is then heated to 150 ° C. for a further 10 hours. After cooling to 90 ° C., the catalyst is separated off by filtration. At about 100 ° C, the excess methyl glycol is distilled off under reduced pressure. There are 2700 parts of a co-carbamate obtained from 30% Polyäthylenätherdiolmonocarbamat and 70% methoxyäthylcarbamat. This corresponds to a yield of 92% of theory The residual urea content is 0.2%.

2700 parts of the co-carbamates of a 40% formaldehyde solution with the addition of 30 parts of a 50% sodium hydroxide solution is heated in a stirred apparatus with _'2200 parts of 3 hours at 50 to 55 ° C. After neutralization with 25 parts of a dilute sulfuric acid, 1780 parts of water are added. 6735 parts of a 51% strength solution of the methylolation mixture (hereinafter referred to as "dimethylolcocarbamate") with a content of 1.8% free formaldehyde are obtained.

Example 5

8 ₁₀ parts of a polyethylene ether diol H (OCH ₂ CH ₂ ) ₁₈ 0H and 60 parts of urea are heated to 150 ° C. for 6 hours while passing a strong stream of nitrogen. There is a yield of 845 parts of the monocarbamate (or the reaction mixture referred to here as such) with a residual urea content of only 0.1%. This corresponds to a yield of 99% of theory 4240 parts of diethylene glycol (HOH ₂ CH ₂ OCH ₂ CH ₂ OH) and 2400 parts of urea are then mixed in and the whole is heated to 180 ° C. with stirring for 5 hours without a catalyst while passing through a strong stream of nitrogen. The yield is 5900 parts of diethylene glycol monocarbamate (= 99% of theory).

The two carbamates are heated together with 4800 parts of a 40% formaldehyde solution with the addition of 55 parts of 50% sodium hydroxide solution at 50 to 55 ° C. for 3 hours. After neutralization with dilute sulfuric acid, 5700 parts of water are added. 17330 parts of a 50% solution of the methylolation mixture containing 1.9% free formaldehyde are obtained.

Example 6

In a stirring apparatus, 590 parts of a polyethylene ether diol with a molecular weight of 590 (H (OCH ₂ CH ₂ ) ₁₃ 0H) and 60 parts of urea are heated at 150 ° C. for 4 hours while passing a stream of nitrogen through them. A degree of implementation of 91% is achieved. Then 1140 parts of methyl glycol, 900 parts of urea and 90 parts of the nickel-containing catalyst prepared according to Example la) are added. The reaction mixture is heated to the reflux temperature which is reached at about 134 to 135 ° C. The mixture is heated for 15 hours, the temperature should not exceed 155 ° C. After filtering off the catalyst, 2320 parts of a cocarbamate mixture consisting of 25% polyetherdiol monocarbamate H (OCH ₂ CH ₂ ) ₁₃ OCONH ₂ and 75% methoxyethyl carbamate are obtained. This mixture is with 2160 parts of a 40% formaldehyde solution with the addition of 35 parts of a 50% sodium hydroxide solution at 50 to 60 ° C hydroxymethylated and then neutralized with dilute sulfuric acid. 4550 parts of an approximately 65% solution of the methylolation mixture with a content of 2.6% free formaldehyde are obtained.

Example 7

In a stirred apparatus 810 are parts of a Polyäthy- _l enätherdiols (H (OCH ₂ CH _{2) 18} OH) and 60 parts of urea heated by the molecular weight of 810 for 5 hours at 150 ° C while passing a stream of nitrogen. After this time, the degree of implementation is 92%. Then 2680 parts of dipropylene glycol, 1200 parts of urea and 100 parts of the nickel-containing exchanger prepared according to Example 1a) are added. The reaction mixture is heated to 155 ° C. for 16 hours while passing a stream of nitrogen through it. After cooling to about 100 ° C, the catalyst is separated off by filtration. 4350 parts of the cocarbamate mixture are obtained, consisting of 24% of a polyethylene ether diol monocarbamate H (OCH ₂ CH ₂ ) ₁₈ OCONH ₂ and 76% dipropylene glycol monocarbamate.

The mixture of these cocarbamates is hydroxymethylated with 2800 parts of a 40% formaldehyde solution with the addition of 40 parts of a 50% sodium hydroxide solution at 50 ° C. and a reaction time of 3 hours and then neutralized with dilute sulfuric acid. 7250 parts of a 75% solution of the methylolated cocarbamates are obtained.

Example 8

428 parts of a monomethylpolyethylene ether diol with the Structure CH ₃ - (OCH ₂ CH ₂ ) ₉ OH are heated with 60 parts of urea at 145 to 150 ° C. for 3 hours in a stirrer while stirring and passing a stream of nitrogen through. This converts approximately 85% to carbamate. Then 2120 parts of diethylene glycol and 1200 parts of urea are added. The reaction mixture is heated to 190 ° C. for 6 hours without a catalyst while passing a stream of nitrogen through it. Here, the urea is converted to a residual content of 0.2%. 3420 parts of a cocarbamate are obtained. This corresponds to a yield of 99% of theory 2550 parts of a 40% formaldehyde solution and 40 parts of a 50% sodium hydroxide solution are added to this cocarbamate mixture and the mixture is stirred at 50 to 55 ° C. for 3 hours. After neutralization with dilute sulfuric acid, 6070 parts of a 73% solution of the methylolated cocarbamate mixture are obtained.

Examples of use

Application examples 9 to 13 are carried out with the product described in example 4.

Example 9

An aqueous solution is prepared which contains 7.5% of the dimethylolcocarbamate (100%) according to Example 4 and 0.18% basic aluminum chloride. A sample of a polyester / cotton blend (50:50; sheets) that has only been bleached is padded with this solution, with the liquor absorption being 65%. The samples are then heated to 205 ° C for 20 seconds.

• a) Diemthylolmethylcarbamat
• b) Dimethylolmethoxyäthylcarbamat
• c) Dimethylol-4,5-dihydroxyäthylenharnstoff behandelt worden ist.

A part of the sample treated in this way is compared with a sample, which is analogous to

• a) dimethyl methyl carbamate
• b) dimethylol methoxyethyl carbamate
• c) Dimethylol-4,5-dihydroxyethylene urea has been treated.

Methylolated polyethylene oxide monocarbamates alone, i.e. not in the form of the mixture according to the invention, are not used at all for comparison, since, as is well known, they give an insufficient finishing effect (due to their high molecular weight) because the crosslinking possibilities with the cellulosic hydroxyl groups are too low (durable press rating too low and shrinkage too high).

The formaldehyde odor of the finished fabric is determined in a sealed vessel according to test method 112 - 1975 from the Association of Textile Chemists an Colorists. With this method, the amount of formaldehyde released under conditions similar to those of practical storage can be determined analytically. The experiment is carried out twice; the average values are given below.

From these values it can be seen that finishing with the agent according to the invention leads to less formaldehyde odor development than with the other finishing agents mentioned above.

Example 10

A padding liquor is made from the following substances:

This liquor is padded onto polyester / cotton fabric (65:35; sheets), the liquor absorption being 50-55%. After drying, the fabric is heated in a stenter to 205 ° C for 20 seconds.

The rest in both cases is tap water at ambient temperature. The differences in the type and amount of the catalysts are due to the different requirements. Achieving optimal results conditionally.

If the fabrics are to be printed after finishing, their absorption capacity is important. The wettability or the absorbency of the tissue is determined according to the AATCC test method 79-1975. The shorter the average wetting time, the more absorbent the textile material is. A time of less than 10 seconds corresponds to a good pumping speed for textile printing. The cocarbamate formulation (a) gave a hydrophilic finish, as can be seen from the following table:

It is clearly evident from this that the fabrics treated with the finishing agent according to the invention show a favorable behavior compared to most resin finishes for subsequent printing.

Example 11

Recipes a), b) and c) from Example 10 are again used. These finishing agents are padded onto polyester / cotton fabric (50:50; sheets). The tissues are then heated to 205 ° C for 20 seconds.

The fabrics treated in this way, hereinafter referred to as A, B and C, are printed with various patterns using the film printing process, using the following printing paste:

Results

• 1) Appearance Sample A has a higher color yield and brilliance than Sample B, which looks somewhat "washed out". Sample C shows a similar color yield as Sample A.
• 2) Sharpness of the print sample The prints made on sample A are sharper than those obtained on samples B and C. Samples B and C appear slightly smeared in two colors (e.g. black and red). Sample A has little or no smear, so the lines of pressure are sharper.
• 3) Handle of the fabric after printing The handle of sample A is fuller and softer than that of sample B. Sample C has a handle that is as soft as sample A. The samples are assessed independently by three people.
• 4) Color fastness The rub fastness of the prints is determined according to the AATCC test procedure 8-1974. The following results are achieved:
  

Example 12

In this example, the tendency of the samples to redeposition of oily substances and contaminants which are dissolved or dispersed in the washing liquid is determined. The padding liquors described in Examples 10a, b and c are padded onto polyester-cotton fabric (50:50; sheets); the tissues are then heated to 205 ° C for 20 seconds. The samples obtained are designated A (recipe 10a), B (recipe 10b) and C (recipe 10c) and subjected to the Celanese re-soiling test explained at the end of the description. The soiling of the fabrics in the Launder-Ometer is determined using a Hunter reflectometer, type D-40, manufactured by Hunter Associates Laboratory, Inc., 5421 Briar Ridge Road, Fairfax, Va., U.S.A.

• W = Y + 4 (Z - Y) (%)
• W = % Weißgrad
• Y = Grün-Reflexionsgrad
• Z = Blau-Reflexionsgrad

The value of the whiteness (W) can be calculated from these values using the following formula:

• W = Y + 4 (Z - Y) (%)
• W =% whiteness
• Y = green reflectance
• Z = blue reflectance

The purpose of this experiment is to measure the whiteness retention of the polyester-cotton fabric after the washing process has been carried out. The values obtained are listed in the following table:

From the table it can be seen that fabrics B and C have lost some or most of their whiteness as a result of washing. This shows that much less dirt from the wash liquor is deposited on sample A.

Example 13

The dimethylolcocarbamate prepared according to Example 4 and prepared according to Example 9 is applied to polyester-cotton fabric (bedding) and fixed as in Example 9. Comparative samples of the same tissue will do in the same manner with a corresponding prepara- ^g of a 45% N-methylol-2-methoxyethyl-carbamate solution and b with the preparation described in Example 10 and treated c, in which dimethylol-4,5- dihydroxy-ethylene urine is used.

The samples are heated to 205 ° C for 20 seconds.

According to the abrasion resistance test (accelerotor method; 1 minute at 3000 rpm), they have the following abrasion values:

It is evident that the dimethylolcocarbamate of the invention has a relatively low tendency to form dust (important because of dust generation in sewing and fabric packaging plants).

Example 14

wird auf Polyester-Baumwoll-Gewebe (65/35) mit einem Gewicht von 120 g/m² aufgeklotzt, wobei die Flottenaufnahme 70 % beträgt. Nach dem Trocknen wird das Gewebe in einem Spannrahmen 20 Sekunden auf 205°C erhitzt.A block fleet

is padded onto polyester-cotton fabric (65/35) with a weight of 120 g / m ^{2, the} liquor absorption is 70%. After drying, the fabric is heated in a stenter to 205 ° C for 20 seconds.

For comparison, further samples are padded in a similar manner with the following fleet:

In both cases, the equipment optimal catalyst type and quantity selected.

The fabric is dried and heated as described above (20 seconds at 205 ° C).

The two samples are designated A (formulation a) and B (formulation b) and tested in essentially the same manner as described above. The following table summarizes the results:

The table shows the superiority of the equipment according to the invention over that of the closest prior art. Despite using an expensive plasticizer, Sample B's grip is less than that of Sample A, which did not use a plasticizer. Shrink and crease resistance properties and whiteness are approximately the same. These and various other results are therefore not listed in this table. The equipment according to the invention does not appear to be inferior to the known one.

The comparative tests of Examples 9 and 13 illustrate the superiority of the mixtures according to the invention, inter alia. compared to a single component. The other component, polyethylene oxide monocarbamate, is, as explained in more detail in Example 9, unusable on its own. It is surprising that a mixture of two substances, each of which gives unsatisfactory results, gives results which are at least satisfactory and in some respects even excellent. In addition, the comparative tests of Examples 9 to 14 show the superiority of the mixture according to the invention even over some of the best finishing agents currently customary.

Examples 15 and 16

Samples of a bleached polyester-cotton fabric (50:50; sheets, 108 g / m ² ) are padded with an aqueous solution containing the following substances:

The fleet intake is 65%. The fabric is heated to 205 ° C in a stenter for 20 seconds.

Finishing agent A consists of a 50% aqueous solution of a mixture of 9 parts of dimethylol-diethylene glycol monocarbamate and 1 part of dimethylol-polyethylene glycol (800) -monocarbamate (N, N-dimethylolmonocarbamate of a polyethylene glycol of molecular weight 800).

Finishing agent B consists of a 50% aqueous solution of the same components in a weight ratio of 19: 1 (95% dimethylol-diethylene glycol monocarbamate and 5% dimethylol-polyethylene glycol (800) monocarbamate, based on the weight of the carbamate mixture).

Celanese-Wiederanschmutzungstes:

• Apparatur: Launder-Ometer 60°C Celanese Standard-Schmutz (sollte einmal wöchentlich 60 Minuten lang gemischt werden).

Examination of the two samples, which is carried out essentially as described above, leads to the following results:

Celanese re-pollution test:

• Equipment: Launder-Ometer 60 ° C Celanese standard dirt (should be mixed once a week for 60 minutes).

Samples: 2 samples measuring 15 x 15 cm.

• 1. Alle Wolle enthaltenden Gewebe: 40°C
• 2. Trikotwaren, Rundwirkwaren und bedr_ugke Waren 50°C
• 3. Alle gewebten Textilien: 60°C

Before being tested, the fabrics are machine washed according to the normal program applicable to the type of fabric concerned.

• 1. All fabrics containing wool: 40 ° C
• 2. Tricot goods, circular knitwear _and printed goods 50 ° C
• 3. All woven textiles: 60 ° C

• 1. Schmutzlösung herstellen, 16 g/l.
• 2. 200 ml Schmutzlöser in den Behälter des Launder-Ometer einfüllen und 10 Stahlkugeln zugeben.
• 3. Proben in Behälter einführen; Behälter verschließen und 30 Minuten drehen.
• 4. Proben entnehmen und in kaltem Leitungswasser spülen.
• 5. Proben in der Maschine mit 50 ccm eines haushaltüblichen Waschmittels was chen, und zwar im Kaltwasch--Vorgang.
• 6. Im Wäschetrockner trocknen.

Method:

• 1. Prepare dirt solution, 16 g / l.
• 2. Pour 200 ml of dirt remover into the container of the Launder-Ometer and add 10 steel balls.
• 3. Insert samples into containers; Close the container and turn for 30 minutes.
• 4. Take samples and rinse in cold tap water.
• 5. Wash samples in the machine with 50 cc of a household detergent, in a cold wash process.
• 6. Tumble dry.

Claims (3)

1. Finishing agent for cellulose-containing or consisting of textiles, consisting of a 30 to 70 percent by weight aqueous solution of a mixture of carbamates I and II methylolated with formaldehyde in a manner known per se

in which R ^{1 is} hydrogen or an alkyl radical having 1 to 4 carbon atoms and R ² and R ^{3 are} hydrogen or one of both methyl, in a weight ratio I: II such as 12: 1 to 1:20. 2. Process for the preparation of textile finishing agents. According to claim 1 by reaction of glycols or alkyl glycols of the formulas III and IV

wherein R ¹ , R ² and R ^{3 have} the aforementioned meaning. ben, with urea with elimination of ammonia at temperatures above 100 ° C to carbamates and subsequent methylolation with formaldehyde by conventional methods, characterized in that firstly in a first stage glycol or alkyl glycol of formula III at 130 to 160 ° C without a catalyst to min- reacted at least 50% with urea to give the carbamate I and in a second stage either in the presence of ion exchangers containing nickel ions as a catalyst at 130 to 165 ° C. or without a catalyst at 150 to 200 ° C. with the addition of glycol or alkyl glycol of the formula IV and further urea the carbamate mixture in the weight ratio I to II as 12: 1 to 1:20. 3. Use of textile finishing agent according to claim 1 for easy care finishing of textiles containing or consisting of cellulose.