DE1237976B - Means for textile finishing - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int.Cl .:

D 06 m

German class: 8 k - 1/20

Number: 1237 976

File number: B 81036IV c / 8 k.

Filing date: March 18, 1965

Opened on: April 6, 1967

It is known to use methylol compounds of urea as agents for textile finishing, especially for the wrinkle and shrink-free finishing of textiles that contain cellulose or made from it exist.

So far one has produced such means for the trade mostly as water-containing pastes, which from Urea and formaldehyde have been prepared in a molar ratio between approximately 1: 1.4 and .1: 2.2. Such pastes have the disadvantage that they have little storage ίο are stable as they gradually condense to form higher molecular weight products. Try such pastes Dry to solid finishing agents have so far only led to success when they are out Urea and formaldehyde had been produced in a molar ratio of 1: 1.9 to 1: 2.2. It is still known to produce dimethylolurea in solid form. These solid substances have the disadvantage that they are rather sparingly soluble in water and also show a low rate of dissolution, which is what makes the preparation ready-to-use baths difficult. In addition, they are not sufficiently stable in storage either, but also change relatively quickly to partially insoluble or poorly soluble higher molecular ones Products, which is noticeable in textile finishing. Also monomethylolurea can be made in solid form. However, like dimethylolurea, it also shows a deficiency Shelf life. So far it has not yet been possible to find a solid, methylol compound of the urine substance Produce containing agent that combines easy water solubility and good durability.

It has been found that the above-mentioned requirements to an extent not previously achieved by a Means for textile finishing are met as a solid, no more than 0.3 percent by weight of free formaldehyde Mixture containing urea and / or monomethylolurea and dimethylolurea in such amounts that the molar ratio of free and bound urea to bound Formaldehyde 1: 1.4 to 1: 1.85, preferably 1: 1.55 up to 1: 1.8.

The urea content of the new agent can be up to 17.6 percent by weight, that of monomethylol urea to 53 percent by weight and that of dimethylolurea 47 to 96.1 percent by weight, wherein but only those mixing ratios come into consideration that are shown in the graphic illustration lie within the hatched field. That in the graph within the hatched The dotted field lying on the side encloses the preferred mixing ratios. In this dar-. Means for textile finishing

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Hans-Joachim Grasshoff, Bad Dürkheim;

Dr. Rolf Fikentscher,

Dr. Wilhelm Rüttiger, Ludwigshafen / Rhine

position means H urea, MMH monomethylol urea and DMH dimethylolurea. The fields of the graphic representation result from the fact that the points corresponding to the following mixing ratios are connected by straight lines:

Molar ratio
Urea too
formaldehyde Dimethylol
urea
Weight Monomethylol
urea
ight percent urine
material 1: 1.85 88.3
96.1 11.7
0 0
3.9 1: 1.8 84.2
95 15.8
0 0
5 1: 1.55 61.9
87.3 38.1
0 0
12.7 1: 1.4 47
82.4 53
0 0
17.6

The free, chemically unbound formaldehyde content of the agent should be 0.3 percent by weight, based on the weight of the solid mixture.

An addition of other well-known products, such as glycols or oils as dust binders, melamine as a buffer substance or grip-giving means can be advantageous in individual cases.

The textile finishing agent according to the invention can can be made in different ways. So you can, for example, solid pure dimethylolurea Mix thoroughly with solid pure monomethylol urea and / or solid pure urea. Particularly However, the following procedure is advantageous and therefore preferred:

Urea and formaldehyde are used in a molar ratio 1: 1.4 to 1: 1.85, preferably 1: 1.55 to 1: 1.8, in aqueous solution at a pH of

709 548/362

6.5 to 8.5, preferably 7.0 to 8.0, and at a temperature of 30 to 4O ⁰ C 0 to 5, preferably 0.5 to 2 hours, to each other, the reaction mixture is cooled to 15 to 28 ° C, it is stirred for at least 24 hours, preferably 30 to 70 hours, at this temperature and the resulting crystal slurry is spray-dried.

Basically reacting substances are used to adjust the pH of the reaction solution; Medium-strength organic bases are particularly suitable for this purpose, since they are particularly storage-stable when they are used End products are created. Examples are: low molecular weight alkanolamines, such as triethanolamine, Diethanolamine, N-methylethanolamine and N-dimethylethanolamine.

It is particularly advantageous if the crystal slurry intended for spray drying has a dry residue of at least 30 percent by weight. Products that are particularly stable in storage are obtained from Crystal pastes that have 40 to 50 percent by weight dry residue; such pastes can also be used well convey and atomize. The production of the crystal pastes can be discontinuous or continuous, e.g. B. in a stirred tank cascade.

The drying of the crystal pulp to the end product can be carried out in nozzle or disk atomizers. Particularly good results can be achieved by using high-speed running of the atomizer disks. Furthermore, it has proven itself for the spray-drying particularly, the dryer inlet temperature between 135 and 17O ⁰ C, to choose preferably between 140 and 16O ⁰ C and the dryer outlet temperature between 50 and 8O ⁰ C, preferably between 60 and 75 ° C. It may be necessary to take measures to prevent the end product from overheating on the dryer wall. This can be done, for example, by cooling the door locker walls to a temperature below 55 ° C or by blowing in a veil of cool air to shield the walls. Such measures are generally unnecessary if the drying is carried out in cocurrent and if both the drying air and the material to be dried are supplied in the center of the cross section at the upper end of the drying unit. It is expedient to rapidly cool the material discharged from the dryer good as possible, for example by means of a cooling trough, to a temperature of 40 ⁰ C or less.

Furthermore, it has proven to be very useful for separating entrained fractions of the process product from the To use exhaust air cyclones, which are provided with an elastic wall covering, for example rubber. '■

The agent according to the invention is characterized by a remarkably long shelf life combined with a high rate of dissolution, low Dissolving temperatures and the possibility of producing concentrated stock solutions. While the known Reaction products of urea and formaldehyde have an intense formaldehyde odor when they dissolve develop, the agent according to the invention can be solved with practically no odor nuisance. Opposite to the known solid and less stable urea-formaldehyde reaction products it also has the advantage that when the padded textiles do not tend to recrystallize on the surface. It therefore does not cause graying dark colored fibers and is particularly suitable for velvet finishing. Das.Mitte} shows the Another advantage is that on soft textile material with a crease-free finish, disruptive stiffeners can avoid. In contrast to finishing with known products, the textile goods retain their properties its soft, elegant handle.

Surprisingly, the agent achieves a molar ratio of urea to formaldehyde for example 1: 1.75 higher crease angles than

ίο with equal amounts of known solid products with a molar ratio of 1: 1.9 to 1: 2.0 in contrast to the well-known phenomenon that with decreasing formaldehyde content the "yield" in the crease angle decreases (see Marsh, Selfsmoothing fabrics, London, 1962, p. 220).

example 1

A textile finishing agent according to the invention consists of a solid mixture which contains 75.7 percent by weight of dimethylolurea and 24.3 percent by weight of monomethylolurea. 100 g of this agent dissolve ^{in 740 g of water at 23 °} C., while 100 g of pure dimethylolurea require 900 g of water to dissolve under the same conditions.

After a storage time of 4 weeks at 40 ° C., the agent according to the invention contains only 0.2% insoluble condensation products. Pure dimethylolurea, on the other hand, contains 0.6 ^O / _O o after the same storage time, i.e. three times the amount of insoluble secondary products.

At game 2

18 parts of a 60 ° / _o aqueous solution of urea of a 33 ° / _o aqueous solution of formaldehyde are mixed with 26.2 parts. The pH of the mixture is / ₀ aqueous solution adjusted by adding Triäthänölamih in 50 ° to 7.2 to 7.3, and the whole mixture heated to 40 ⁰ C and 30 minutes allowed to react. After this time it is cooled to 20 to 25 ° C and stirred for 60 hours at this temperature; in the process, a crystal pulp is formed; which has 44.1% solids content / The crystal slurry is dried to powder in a spray dryer; The spray dryer is set so that the dryer inlet temperature is .15G ⁰ C, the dryer ^{outlet temperature is 68 0} C. A powder is obtained which consists of a mixture of monomethylolurea and dimethylolurea and in which the molar ratio of urea to formaldehyde 1: 1.60.

After 6 weeks long storage at 20 ° C dissolve this powder of 100 g in 680 g water of 23 ° C. After 4 weeks long storage at 40 * C, the powder contains 0.2 ° / ₀₀ insolubles.

Is used to adjust the pH instead destriethanolamine diethanolamine, N-methylethanolamine or N-dimethylethanolamine, one obtains

same result. . '■■,. "...'

Instead of allowing the reaction mixture 30 minutes Läng at 4O ⁰ C react, they can with equal success for 2 hours to react at 30 ⁰ C.

^{: For} S ρ i el 3 ^:

The procedure given in Example 2 is used Conditions, but instead of the 20.2 parts of 33% formaldehyde solution used the following amounts of same solution: A = 27.8, B = 29.4, C = 31.1 parts. Powder is obtained which also consists of mixtures Represent monomethylol and dimethylol urea,

but in which the molar ratio of urea to formaldehyde is A = I: 1.67, B = 1: 1.75 and C = 1: 1.79. After 6 weeks of storage at 20 ^° C., 100 g of these powders dissolve in the following amounts of water at 23 ^° C.: A = 740 g, B = 820 g, C = 850 g. After 4 weeks of long-term storage at 40 ⁰ C, the powders contain the following amounts of insoluble constituents: A = 0.2 ° / _00, B = 0.4 ° / _00, C = 0.2 "Z _00th

D. For comparison, a powder that is almost pure dimethylolurea was produced according to the same procedure. For this purpose, the amount of the 33 ° / ₀ igerFormaldehydlösung was increased to 36 parts and worked is otherwise as described in Example 2. FIG. In the powder thus obtained, urea and formaldehyde had reacted in a molar ratio of 1: 2.02. After 6 weeks of storage at 20 ^° C., 100 g of this powder required 1000 g of water to dissolve; after 4 weeks long storage at 40 ⁰ C, the powder contained l, 2 ° / ₀₀ insolubles.

Example 4

Comparative tests were carried out with the following products:

A dimethylolurea.

B Mixture of 88.3 percent by weight dimethylol urea and 11.7 percent by weight monomethylol urea (Molar ratio of urea to formaldehyde 1: 1.85).

C Mixture of 80 percent by weight dimethylolurea and 20 percent by weight monomethylolurea (Molar ratio of urea to formaldehyde 1: 1.75).

D Mixture of 93.3 percent by weight dimethylolurea and 6.7 percent by weight urea (Molar ratio of urea to formaldehyde 1: 1.75).

E mixture of 85.55 percent by weight dimethylolurea, 11.34 percent by weight monomethylolurea and 3.11 percent by weight urea (molar ratio of urea to formaldehyde 1: 1.75).

F Mixture of 47 percent by weight dimethylol urea and 53 percent by weight monomethylol urea (Molar ratio of urea to formaldehyde 1: 1.4).

G monomethylolurea

5 °

Products B, C and F according to the invention as well as one component of the mixture of E have been carried out Spray drying of the corresponding crystal mashes prepared according to Example 3.

Products D and E according to the invention were prepared by intimately mixing urea and dimethylolurea prepared according to Example 3, D or a mixture of dimethylolurea and monomethylolurea prepared as indicated in the previous paragraph, the mixture components being in extremely fine powder form. The products to be compared were stored in closed vessels for 3 months at room temperature. Aqueous solutions with a content of 200 g / l were then prepared from them by placing 200 g of one of the products in each case, topping up with water at 25 ° C. to a volume of 11 and the mixture to 50 by introducing steam within 6 minutes ⁰ C was heated. It was found that dimethylolurea (product A) and monomethylolurea (product G) gave very cloudy solutions, the solution of the monomethylolurea more than 5% insoluble constituents in the form. contained by flakes. The solutions of the products B to F according to the invention showed neither cloudiness nor undissolved residues. After cooling the solution to room temperature and a residence time of 8 hours, precipitates separated out from the solution of the Dimethylolharnstoffs, the more 5 ° / ₀ accounted as the total solids content. In contrast, the solutions of the products according to the invention remained unchanged and clear.

Equipment trials

The solutions of products A and G were filtered, those of the products according to the invention without further used. To each solution, 5 g of ammonium nitrate was added as a catalyst.

These solutions were used to impregnate samples of a black-dyed imitation cotton poplin fabric of 130 ^{g / m 2;} the tissue samples were squeezed to a liquor pick-up of 75 ° / ₀ in the case of the solutions of the products according to the invention, of 80 ° / ₀ in the case of the solutions of products A and G (to compensate for the filtration losses), dried at 80 ° C. for 10 minutes and 3 minutes at 140 ⁰ C condensed.

The sample finished with product A had taken on a gray color. She had a dry wrinkle recovery angle from 140 ° after finishing and from 120 ° after three boil washes.

The sample finished with product G was not gray; but it was very stiffened and had the very low dry wrinkle recovery angle of 125 ° after finishing and 95 ° after three boil washes.

The samples finished with products B to F according to the invention were neither gray nor gray stiffened. They had dry wrinkle recovery angles of 145 to 150 degrees after finishing and 130 to 140 ° after three boil washes.

Claims (1)

Claim: Agent for textile finishing containing methylol compounds of urea, thereby characterized in that it is a solid formaldehyde containing no more than 0.3 percent by weight of free formaldehyde Mixture of urea and / or monomethylolurea and dimethylolurea in such Amounts that contain the molar ratio of free and bound urea to bound Formaldehyde is 1: 1.4 to 1: 1.85. 1 sheet of drawings 709 548/362 3. 67 Buiidesdruckerei Berlin