DE1961843A1 - Process for the production of preparations for treating textiles - Google Patents

Description

CtBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case ARL l47 / E

Germany

Process for the manufacture of preparations for treatment

of textiles.

The present invention relates to a method for the production of preparations for the treatment of
Textiles are suitable, the received in this way

0D9830 / 19A0

preparations and their use for treating textiles.

Ν, Ν ¹ -Bis- (hydroxymethyl) -uron, also known as 3 * 5-dimethylol-tetrahydro-oxadiazin-4-one, is usually made by reacting 1 mole of urea with at least 4 moles of aqueous formaldehyde under alkaline conditions. The uncleaned product can be used to give textiles a "wash-wear" finish and has the advantage over the cyclic N, N'-bis (hydroxymethyl) alkylene ureas also used for this purpose of being considerably cheaper. However, it is because of ^; not entirely suitable due to its chlorine retention capacity. It is known that on a substance which has been treated first with a substance containing free amide hydrogen atoms and then with a chlorine-containing bleaching agent such as hypochlorite, N-chlorine compounds are formed which can decompose, releasing hydrochloric acid which attacks the tissue, if the tissue, such as when ironing, for example, is very hot.

The reaction by means of which N, N'-bis- (hydroxymethyl) -uron is formed is not complete and the yield is not complete on uron seldom exceeds 8o #; one assumes that a considerable amount of non-cyclic N-hydroxymethylated Urea, especially dimethylolurea, is formed. These non-cyclic ureas, which are probably a

Give "wash-wear" equipment also require the ability to retain chlorine. Often more than 4 moles of formaldehyde per mole of urea are used to promote the formation of uron. The product is then uncomfortable to handle because of its high formaldehyde content, so that it is sometimes subjected to a post-reaction with urea, which, however, further increases the proportion of non-cyclic N-hydroxymethylurea. Because it is difficult to extract noncyclic hydroxymethylated urea from the N, N ^! To separate -bis- (hydroxymethyl) -uron, the methylated product, e.g. N, N ¹ -bis- (methoxymethyl) -uron, has been used because it is separated from methoxymethylated non-cyclic urea by means of fractional distillation under reduced pressure can be separated. This method is costly because the methylated acyclic urea fractions are lost. Another disadvantage is that Ν, Ν ¹ -bis- (methoxymethyl) -uron only hardens under conditions in which the tissue is weakened and discolored.

These difficulties can largely be overcome by using formulations which are prepared by reacting the crude N, N ¹ -bis- (hydroxymethyl) -uron with certain primary amines and formaldehyde. In such preparations, the by-products, namely the non-cyclic methylolureas, have been converted into cyclic Triazc-ne, which are also used for the

009830/1940

"Wash-wear" equipment is useful, but what less tend to cause chlorine retention damage. However, it was found that the reaction between the non-cyclic methylolureas and the amine not • Works well when in the presence of a large amount of formaldehyde -Excess is carried out. On the other hand, it is desirable to use the triazones as textile reagents to be converted into N-hydroxymethyl derivatives.

The present invention accordingly relates to a method for producing preparations for the treatment of textiles, characterized in that 'one

a) a mixture of N, N'-bis (hydroxymethyl) uron and a non-cyclic methylolurea in the absence substantial amounts of free formaldehyde with an aliphatic, cycloaliphatic ^ araliphatic or heterocyclic primary amine and then

b) reacts with formaldehyde.

The present invention also relates to a method for treating textiles, characterized in that that the textiles are impregnated with a preparation produced according to the invention and then the equipment hardens.

The mixture of the N-hydroxymethyl urea ^{derivative and the N, N 1} -bis- (hydroxymethyl) -uron is on.

QQ883Q / 194G

• usually by reaction in an aqueous solution of one mole of urea with not more than 10, preferably 7.5, moles, Formaldehyde with a p "value between 9 and 14 and one

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Temperature of 25 to 110 ° C, preferably 50 to 100 ° C,: obtained. The urea is for 30 minutes to 2 hours

• Treated with formaldehyde for hours or more, the duration of the treatment depending on the temperature used, if necessary it is cooled and then neutralized. The mixture preferably contains, based on the molar ratio, more Ν, Ν ¹ -bis- (hydroxymethyl) -uron than N-hydroxymethylated non-cyclic urea, a mixture which is at least 60 percent by weight, based on the urea-formaldehyde, is particularly advantageous Reaction product, N, N ^! Contains bis (hydroxymethyl) uron.

The mixture often contains free formaldehyde because it is generally used to promote the formation of uron one mole of urea two or even more moles of formaldehyde can be obtained.

As already mentioned, this mixture should be reacted with the amine in the absence of large amounts of formaldehyde be performed? the mixture expediently contains less than 0.2 mol of free formaldehyde per amine hydrogen equivalent of the amine to be used. To reduce the free formaldehyde content, the mixture can

009830/1040

before the reaction .with the amine with urea, a cyclic Alkylene urea or a carbamate; in the process, N-methylol derivatives are used in a known manner of urea, cyclic urea or carbamate.

Examples of suitable cyclic ureas are ethylene urea (imidazolidin-2-one), dihydroxyethylene urea (^, S-dihydroxyimidazolidin ^ -one) ', hydantoin, 1,2-propylene urea (4-methylimidazolidin-2-one), 1,3-propylene urea (hexahydro-2H-pyrimid-2-one), hydroxypropylene urea (5-Hydroxyhexahydro-2H-pyrimid-2-one), dimethylpropyleneurea (5> 5-Dimethylhexahydro-2H-pyrimid -2-one), and dimethylhydroxypropyleneurea or dimethylmethoxypropyleneurea (4-Hydroxy- or 4-methoxy-5,5-dimethylhexahydro -2H -pyrimid -2-one.).

Suitable carbamates are methyl carbamate, ethyl carbamate, Isopropyl carbamate, 2-hydroxyethyl carbamate, 241ethoxyäthylcarbamat and 2-hydroxy-n-propyl and 3-hydroxy-n-propyl carbamate and ethylene glycol dicarbamate.

It is advisable to take as much urea, cyclic urea or carbamate that there are 1 to 1.5 mols present free formaldehyde 1 amide hydrogen equivalent comes, the reaction between 0 and 110 ° C, in particular from 35 to 75 C, and under neutral or alkaline conditions, preferably at a p "value of 7 to 12

is carried out.

As mentioned, the yield of Ν, Ν ¹ -bis- (hydroxymethyl) -uron rarely exceeds 8o; H of the theoretical value, so that 20% or even more of the urea used can be converted into non-cyclic methylolureas. In general, 0.75 to 1.25 moles per mole of urea not converted into the desired urone. Amine added. Based on the total amount of urea used, 0.1 to 0.8, preferably 0.2 mol of amine are added per mole of urea. The reaction with the amine is preferably at a temperature of 0 to 110 ° C, especially at least 70 ° C, at a.

'ρ -, - value from 7 to 12 and throughout 1 to 24 hours

led., For best results, the The reaction mixture is heated to reflux temperature for at least one hour.

It is best to use amines that contain no more than two primary amino groups. Connections with only primary amino groups are preferred. Araliphatic amines such as benzylamine, heterocyclic Amines such as pururfuryiamine or cycloaliphatic amines such as cyclohexylamine can be used. Are preferred but aliphatic, in particular mono- or diprimary amines, "which contain up to 18 carbon atoms and optionally may be substituted with hydroxyl groups. Examples include methylamine, ethylamine, n-propylamine, 3so-

003833/1940

propylamine allylamine, n-butylamine, isobutylamine, afethylenediamine, Propylenediamine, propane-1,2-diamine, hexamethylenediamine, Ethanolamine, propanolamine or isopropanolamine. Methylamine, ethylamine, n-propylamine and ethanolamine are particularly preferred. Purely aromatic amines such as aniline are not suitable.

For the reaction with the formaldehyde, 1.5 to 2.5 moles of formaldehyde are generally used per mole of amine; the temperature of the mixture is set to 0 to 110 ° C., preferably between 50 and 75 ° C., and the "p" value is increased 7 to 11, preferably 8 to 10, held. The hand, The duration of the lungs can vary between 20 minutes and 8 or more hours, in general, depending on the conditions but they are between 30 minutes and 2 hours. if When the reaction has ended, it is advisable to remove unchanged formaldehyde in order to remove the formaldehyde that would otherwise be obtained when heating prevent unpleasant formaldehyde development on impregnated textiles. This formaldehyde can like previously removed by distillation or reaction with urea a cyclic alkylene urea or a carbamate will.

The formaldehyde is best added in an aqueous solution.

The preparations produced according to the invention are usually used to produce the impregnation baths

009330/1940

Water dilutes, and a curing catalyst will either added to the bath or applied to the impregnated fabric, after this has been taken from the bath.

Organic acids, potentially acidic compounds or metal salts or mixtures thereof can be used as catalysts. Suitable organic acids are citric acid, maleic acid and tartaric acid. Suitable ammonium salts, which develop as a potentially acidic compounds in the mixture acid are ammonium chloride, ammonium dihydrogen phosphate, ammonium sulfate and ammonium thiocyanate ,, amine salts, such as 2-amino-2-methylpropanolhydrochlorid, likewise ¹ can optionally be used. Suitable metal salts include zinc nitrate, zinc fluoroborate, zinc chloride, zirconium oxychloride, magnesium chloride, magnesium fluoroborate or magnesium dihydrogen orthophosphate. A particularly effective catalyst is a mixture of magnesium chloride and citric acid. These catalysts are generally most effective when used in concentrations of $ 0.3 to $ 5. It is also possible to use stronger acids such as hydrochloric or sulfuric acid, in which case they are used in aqueous solution (preferably 4 to 8 normal solution) or in a mixture of water and a solvent which is immiscible or only partially miscible with water or as acid gases.

009830/1943

- ίο -

Textile auxiliaries such as plasticizers, optical Brighteners or flame retardants can also be added to the impregnation solution and if so desired can use other textile treatment resins such as melamine-formaldehyde condensation products, especially Hexamethylolmelamine or its methyl esters are also used.

The preparations can advantageously not only be applied to cellulose-containing textiles of all types, such as Yarns, fibers, threads, woven, unwoven and knitted fabrics, or textiles made entirely or in part natural or regenerated cellulose, but also on textiles made from synthetic materials, such as polyamides, polyesters or polyacrylonitrile. When finishing fabrics that contain cellulose fibers, the preparations are particularly suitable for imparting crease resistance, shrinkage resistance, ironing fastness, permanent embossing effects such as corrugation, carpenter or moiré effects and calender effects. Also have in many cases they have no adverse effect on the lightfastness of dyes. You can also go for the wash-resistant fixation of starch finishes, in Printing and dyeing operations to achieve washable color effects and washable stiffening effects on poly-

000330/1940

amide fibers are used.

The preparations are applied by spraying, dipping, or padding, the latter method is generally the most appropriate. The impregnated material is pulled through nip rollers or other devices, to remove the excess mixture and the desired liquor uptake depending on the fabric and required effect to achieve. For cotton fabrics, the preferred range of the liquor uptake of the product extends of the method of the present invention from about 5 # to about 40 #, for viscose rayon from about 5 $ to about 60 #, calculated on the weight of the completely dry textile goods.

The products of the preparations according to the invention can be cured after the impregnated fabric has been dried, or under damp or "wet" conditions Conditions, if necessary with heating or by irradiation. The dried impregnated fabric can be pleated or pimped and / or made into garments before the finish is cured; should the tissue ironing, curing can be carried out after or during the formation of the wrinkles. After hardening the equipment, unconsumed catalyst can be washed out of the fabric or garment.

The term "non-volatile matter content" used in the following refers to the weight fraction in #, the

0Q983O / 194O

after heating 3 S sample of the preparation during Remains at 110 ° G for 90 minutes.

Unless otherwise noted, percentages, parts and ratios are by weight.

009830/19 * 0

example 1

A mixture of N, N ¹ -bis- (hydroxymethyl) -uron and N-methylolurea, hereinafter referred to as "Dimethyloluron A", is prepared as follows:

0.5 kg of urea are added with stirring to 4 kg of a yfile aqueous solution of formaldehyde (molar ratio of formaldehyde to urea 5.94). The mixture is heated and 137 * 2 ml of a 20 # strength sodium hydroxide solution are added. The mixture is kept at 60 ° C. and after 15 minutes 27.2 ml of a 20% aqueous sodium hydroxide solution are added. Six further additions of 27.2 ml each of 20% aqueous sodium hydroxide solution are then made at 15 minute intervals. After the mixture has been heated to 60 ° C. for a total of 2 hours, it is cooled and treated with 6ö ml hydrochloric acid (34%) to a p "value of 7 (bromothymol blue)

xl

brought. The yield is 4.95 kg. This product, dimethyloluron A, contains free formaldehyde and is first treated with urea.

270 g of dimethyloluron A (made from 0.452 mol Urea), 25.9 S (0.431 mol) urea and 1.4 ml 2G # ige aqueous sodium hydroxide solution are heated together for one hour to 60 C and then with 0.9 ml of hydrochloric acid (34 # ig) neutralized.

Then this mixture with 36.4 g of a

70 # »igen aqueous solution of ethylamine (0.567 mol) during,

009830/1940!

ORIGINAL INSPECTED

Heated to 50 ° C. for 8 hours and neutralized again with 5.8 ml of hydrochloric acid (34%). So. 9.2 g of a 37 # strength aqueous formaldehyde solution (1.13 mol) are added, the p "value of the mixture is increased with 10.2 ml of a 20 # strength

Sodium hydroxide solution brought to 9 and the mixture during heated to 60 ° C for one hour. Finally, the mix neutralized with 2.2 ml of hydrochloric acid (34/6) and cooled to room temperature.

Example 2

Dimethyloluron A is treated with urea as described in Example 1; however, the reaction temperature is 40 ° C. After the neutralization, the product is cooled to 20 ° C. and 42.7 g (0.56 mol) of isopropanolamine are added. The reaction is allowed to continue for 5 hours at 50 ° C., then 92.5% of a 37% aqueous formaldehyde solution (1.14 mol) is added, and the p "value of the mixture is adjusted to 9 with 1 ml of a 20% aqueous sodium hydroxide solution heated to 60 ° C. for one hour. The product is neutralized with 4 ml of hydrochloric acid (34%) and cooled.

008130/1940

Example 3

A mixture of 400 g of dimethyloluron A (prepared with 0.68 mol of urea) and 64 g (0.64 mol) of propylene urea is brought to a p ^ value of 9 with 0.4 ml of a 20 # strength sodium hydroxide solution and selected Heated to 60 C for one hour. After neutralization with 0.2 ml of hydrochloric acid (34 # Lg), the mixture is cooled and treated with 12.9 g of a 70 # aqueous solution of ethylamine (0.2 mol), which is added dropwise.

^ The temperature of the mixture is kept below 10 ° C. The mixture is then left to react for one hour at 15 ° C., heated to 25 ° C. for one hour, 50 ° C. for one hour , 75 ° C. for one hour and finally to reflux temperature for one hour. The resulting solution is cooled to 60 ° C., treated with 32.4 g of a 37% aqueous formaldehyde solution (0.4 mol) and 1 ml of a 20% aqueous sodium hydroxide solution and heated to 60 ° C. for one hour. Finally, the solution is neutralized with 1.6 ml of hydrochloric acid (34%) and then cooled.

009830/1940

Example 4

400 g of dimethyloluron A; 67 g (0.64 mol) of 2-Hydroxyäthylcarbamat and 3 ml of a 20 # ^r aqueous sodium hydroxide are heated together for 2 hours at 6o ° C, whereupon the solution .neutralisiert (ig ^ 3) with hydrochloric acid and cooled to 10 ° C will. Over a period of 15 minutes, 12.9% of a 70 # strength aqueous solution of ethylamine (0.2 mol) are added dropwise. The mixture is allowed to react and then heated, the temperature being increased every hour. It is treated with 37 * 4 g of a 37 # strength aqueous formaldehyde solution, heated, neutralized and cooled as described in Example 3.

Example 5

600 g of dimethyloluron A (made with 1.02 moles of urea), 20 g (0.33 moles) of urea and 5 ml of one 20 # aqueous sodium hydroxide solution is heated to 60 ° C. for one hour. This is where the mix is neutralized with hydrochloric acid (34 # ig), cooled and treated dropwise with 39 g (0.64 mol) of ethanolamine, whereby

009830/1940

the temperature of the mixture is kept below 10 ° C. Now allowed to react, heated, and treated with aqueous formaldehyde s'ie as described in.Beispiel 3, except that the 104 37 # g ^r Pormaldehydlö strength solution (1.28 mol) are used, the mixture. After neutralizing with hydrochloric acid (3 ^ # ig) the solution is for 2 hours. heated to 96 to 105 ° C to remove the excess formaldehyde. Finally, enough water is added to make the nonvolatile content $ 50.

Example 6

Example 5 is repeated, instead of the aetna However, nolamins are 63.1 g (0.6 mol) of cyclohexylamine used.

009830/1940

Example 7

Example 5 is repeated using kl g of a 70 # strength aqueous solution of ethylamine (0.64 mol) instead of ethanolamine.

Example 8

Example 7 is repeated, but the product is heated to 96 to 105 C until the portion of non-volatile substances is 50 #.

Example 9

In this example, the free formaldehyde content of the dimethyloluron-methylolurea mixture reduced by reaction with urea and cyclic alkylene urea.

600 g of dimethyloluron A and 20 g of urea are used with 5 ml of 20 # aqueous sodium hydroxide solution during one hour; heated to 60 ° C, whereupon 33 g (0.33 mol) Propylene urea added and during another

009830/1940

Is heated to 60 ° C for an hour. The mixture is neutralized and cooled to 41, ² g of I-70 # aq Aethylamlnlösung (0.64 mol), and cooled (1.28 mol) is treated with 104 g 37 # aq formaldehyde solution. »By adding 20 # Lger aqueous sodium hydroxide solution

the p "value is brought to Q. Last will be like in leg

game 3 described neutralized.

Example 10

The procedure is as in Example 9, with the order in which the urea and propylene urea are added in reverse .

Example 11

Example 3 is repeated with the exception that 600 g of dimethyloluron A (made from 1.02 mol Urea), 33 g (0.33 mol) propylene urea and 20 g (0.33 mol) urea with 5 ml of 20 # aqueous sodium "hydroxide solution, then 27 g of the 70 # aqueous ethyl

009830/1940

amine solution (0.42 mol) and 50.4 g of 37 # aqueous formaldehyde solution (0.62 mol) are used, wherein the hydroxymethylation is carried out at a p ~ value of _H. 9

Example 12

Dimethyloluron A is prepared as described in Example 1, but not neutralized. Then 270 g of this substance are heated with 20 g (0.33 WoI) of urea for one hour at 60 ° C. and neutralized with hydrochloric acid (34 ^{%), which results in "Dimethyloluron B 1} '". 40.5 g of 70% are now obtained aqueous ethylamine solution (0.63 mol) is added to the cooled dimethyloluron B. The mixture is left for one hour at 10 ° C., one hour at 25 ° C., one hour at 50 ° C., one hour at 75 ° C. and "one" react for a further hour at reflux temperature. 103 S 37% formaldehyde solution (1.26 mol) are then added; the reaction is allowed to continue for a further hour at 60 ° C. and a p "value of 9. Finally, the mixture is neutralized with hydrochloric acid (34 # ig) and then cooled.

009830/1940

Example 13

Dimethyloluron A is described as in Example 1 manufactured but not neutralized. To remove the free formaldehyde, the product is kept at 96 to Heated 105 ° C until the non-volatile content is $ 85.

594 g of this dirnethyloluron mixture ("Dimethyloluron C ") are diluted with 59 ^ g of water and then with 59 g Treated 70 # ethylamine solution (0.92 mol), the reaction being carried out as described in Example 12. The neutralized product is kept at 96 to 105 C ' heated until the non-volatile content is 50 #.

example

Example 13 is repeated, using 39 g 70 # aqueous ethylamine solution are needed.

009830/1940

Example 15

Samples of bleached cotton poplin (108 g / m)

be with a solution containing 18 g of magnesium chloride per liter hexahydrate and the products of Examples 1 to 4 in the concentrations given in Table I, padded up to a plot of $ 70. The shares of the products of the present invention change according to their non-volatile content (see below defined above) so that the solutions are of comparable strength. The samples are heated to 80 ° C. for 10 minutes dried to their original dimensions on stenter frames. The equipment is then heated to 160 ° C. for 3 minutes hardened, i.e. under normal conditions that are customary for conventional crease-free removal. To those in delayed Curing process to achieve more stringent conditions will cured for 8 minutes at 165.degree. For comparison purposes other samples are treated in the same way with dimethyloluron A or with N, N'-dimethylol-1,3-propyleneurea. The latter compound gives an excellent "wash-wear finish" and causes only negligible small chlorine retention damage, but is very expensive.

The dry wrinkle angles of the treated samples are measured by the Monsanto method, in each of which

008030/1940

Test 12 samples (6 folded in the warp direction and 6 in the weft direction) are used; the samples are folded for 3 minutes under a weight of 2 kg and hung over a wire for 3 minutes before the crease angle is measured. The value given in Table I is in each case the average value from the 12 values. Tear strengths are determined by the Elmendorf method according to TAPPI / Standard T 414 n-49. Three samples, each 63 mm by 63 mm in size, are used, and the tear strengths are measured in the direction of the chain. The method laid down in ASTM Specification D-1682 is followed to measure the tensile strength: The values given, average values from 3 results, are measured on samples from 15 cm by 2.5 cm in the direction of the chain.

Chlorine retention damage v / earth according to A.A.T.C.C. (American Association of Textile Chemists and Colorists) Specification 92-1967. The ones overlaid with A, B and C. Columns show in sequence the tensile strength before the chlorination, after the chlorination and after chlorination and scorching.

009830/1940

Table II shows those obtained with the products of Examples 5 to 9 * 13 and 14 in the same manner Results, as well as some comparative data. The equipments are kept at 160 ° C for 3 1/2 minutes or cured for 8 minutes at 170 ° C. "Catalyst I indicates that the poulard liquor as at the beginning -this example mentioned, l8 g of magnesium chloride hexahydrate per liter contains, while "catalyst II" indicates that the padding liquor per liter 9 g of citric acid and Contains 9 g of magnesium chloride hexahydrate.

009830/1940

Table I. Reaction
nittel not-
volatile
ger share
<*) use
te concentrations
tration
g / l Property
3 minutes at 160 ° C i / pus
tear
solidifying
lceit (g) tensile strength B.
(kg) C.
(kg) ten after hardening during
8 minutes at 165 ° C Further-
tear
solidifying
ability (g) Resistance to cracking B.
(kg) C.
kg) j - 25 - . "
O no SSnTETer-
angle
(O) A.
(kg) Crease
angle
(O) A.
(kg) O
a) Dimethylol
uron A 33.0 182 43 352 > 7.5 14th 43 272 23.5 19.5 Dimethylol
propylene
urea -48.5 124 94 464 27.5 50.5 27 97 400 28 27 24 Product of
example 1 36.7 164 ■ 97 576 27 106 480 26th Product of
Example 2 34.8 172 560 • 50 25th 100 432 25.5 24.5 Product of
Example 3 39.6 152 .94 560 30.5 30th 25th 96 432 27.5 25.5 24.5 Product of
Example 4 36.6 164 89 464 30.5 99 400 27.5 97 106

good-
cursed
tiger
proportion of use
dete
Conc
tration 3 1/2 Table II properties
at 160 ° C ' B.
(kg) G '
(kg) after hardening during
8 minutes at L. . 170 ° B.
(kg) G
(kg) Kata
lysa
gate ff Reaction
middle (g / l) Cnitter
angle
(O) Minutes Tear resistance 33.5
21 7th
11.8 ttn'i-b-fcer-
angle
(O) 28
17.8 • 8.5
18.2 • 85 70.5 87
92 tear
festign
ability (g) A.
(kg) 26.5
15th 14.1
15th 94
99 18.5
15th 18th
10.9 I.
II Dimethylol
uron C 50.0 120 101
105 496
336 23.5
25.5 36.3
32.7 25.1
29.6 109
88 Tear resistance 31.9
28.2 30.6
29.0 I.
II CO
cn Dimethylol
dihydroxy
ethylene-
urea 50.0 120 74.
62 336
160 25th
15th 30.4
19.1 26, E
14.5 6.2
60 A.
(kg) 29.2
21.8 14.0
19.1 I.
II CD
CJ Dimethylol
j-ethyl-
1,3,5 -
fcriazin-2-one * 50.0 120 90
101 656
608 29.2
31 29
30.5 25.2
27, € '87
82 22.5
19.2 29.5
24.5 27, d
22, Tj I.
II Dimethylol
aron G **
and Dimethy Id-
, -ethyl-1,3,5-
fcriazin-2-one 49.0 121 92
91 496
472 30.4
19.1 88.5
84 20th
10.5 product of
Example 3 440
384 30.7
34.2 Cloth treated with this reactant will turn yellow
2 moles of dimethyloluron C: 1 mole of dimethylol-5-ethyl-1,3,5-triazine-2-OE
- 26 - 26, E
19.1 Veiter
tear
solidifying
ability (g) 25, '
22 / 288
224 29
25th 192
96 468
304 420
272 320
■ ^ 256.

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009830 / 19A0

BATH ORIGINAL

Claims (1)

Claims 2. 'The method according to claim 1, characterized in that said mixture is obtained by reacting 1 mole of urea with 4 to 10 moles of formaldehyde in aqueous solution. 3- The method according to claim 2, characterized., that said mixture by reaction of 1 mol of urea with 4.3. tls 7.5 mol of formaldehyde is obtained. - A method according to any one of claims 1 to 3 * dadureii in that the said mixture by Reaktio ... ^"Cr:; i - ::,:;> / t :. fY with formaldehyde at a p" ert -V / "on BATHROOM ORIGINAL Ö09830 / 134Ö • '"19618Λ3 5. The method according to any one of claims 1 to 4, characterized in that said mixture by
Treatment of urea with formaldehyde at a temperature of 25 to 110 ° C. 6. The method according to claim 5 *, characterized in that that said mixture is obtained by heating urea with formaldehyde to 50 to 100 ° C. 7. The method according to any one of claims 1 to 6, characterized in that said mixture, based on the molecular ratio, contains more N, N ^f -Bis- (hydroxymethyl) - 'uron than N-hydroxymethylated non-cyclic urea . 8. The method according to claim 7, characterized in that at least 60 percent by weight of the urea-formaldehyde reaction product in said mixture
Is N, N'-bis (hydroxymethyl) uron. \ 9 · The method according to any one of claims 1 to 8, characterized in that said mixture contains a substantial amount of free formaldehyde and before
Reaction with the amine with urea, a cyclic one
A-alkylene urea or a carbamate is treated. 10. The method according to claim 9 *, characterized in that said mixture with as much urea,
cyclic! Alkylene urea or carbaraate is treated, 0OSI3Ö / 1940 that for every 0.5 to 1.5 moles of free formaldehyde present there is 1 amide hydrogen equivalent. 11. The method according to any one of claims 9 and 10, characterized in that said mixture is treated at a temperature of 0 to 110 ° C. 12. The method according to claim 11, characterized in that that said mixture at a temperature of 35 to 75 ° C is treated. 13. The method according to any one of claims 9 to 12, characterized in that said mixture at _; a p "value from 7 to 12 is processed. n. 14. ^ experience according to one of claims 1 to 8, characterized in that said mixture is a Has substantial amount of free formaldehyde, which largely before the reaction with the amine by means of distillation Will get removed. 15. The method according to any one of claims 9 to 14, \ characterized in that the content of said mixture of free formaldehyde to less than 0.2 mol per mole-equivalent of Amlnwasserstoff is lowered to be _used} amine. 16. The method according to any one of claims 1 to 15, characterized in that per mole of urea-formaldehyde reaction products in the mixture mentioned 0.1 up to 0.8 mol of the amine can be used. 009830/1940 ORIGINAL INSPECTED • - 31 - 17. The method according to claim 16, characterized in that per mole of urea-formaldehyde reaction products 0.2 to 0.8 mol of amine can be used. 18. The method according to any one of claims 1 to IJ, characterized in that the amine is treated with said mixture at a temperature of 0 to 110 ° C. 19. The method according to claim 18, characterized in that the amine is heated to at least 70 ° C with said mixture. ^; 20. The method according to any one of claims 1 to 19, characterized in that the amine and the mixture mentioned are allowed to react with one another at a p n value of 7 to 12. 21. The method according to any one of claims 1 to 20, characterized in that the amine and said mixture are allowed to react with one another for 1 to 24 hours . 22. The method according to any one of claims 1 to 21, characterized in that the amine and the said mixture is heated to the temperature of the flow of water for at least one hour. 23 · Method according to one of Claims 1 to 22, r-iv ' ¹ . -r; marked that the amine is no more than 009830/1940 contains two primary amino groups. 24. The method according to any one of claims 1 to 23, characterized in that the amine is only primary Contains amino groups. 25. The method according to claim 24, characterized in that the amine is an aliphatic mono- or is a diprimary amine which contains up to 18 carbon atoms and is optionally substituted with hydroxyl groups. 26. The method according to claim 25, characterized in that the amine is methylamine, ethylamine or is n-propylamine. 27. The method according to claim 25 *, characterized in that the amine is ethanolamine. 28. The method according to any one of claims 1 to 27, characterized in that the reaction product of said mixture and the amine is treated with formaldehyde, 1.5 to 2.5 moles of formaldehyde being used per mole of amine. 29. The method according to claim 28, characterized in that the treatment with formaldehyde at a Temperature before. 0 to 110 ° C is carried out. 009830/1940 30. The method according to claim 29, characterized in that the treatment is carried out at a temperature of 50 to 75 ^σ C. 31. The method according to any one of claims 1 to 30, characterized in that the reaction product of mentioned mixture and the amine at a p "value of "7 to 11 is treated with formaldehyde. 32. The method according to claim 31 * characterized by that the reaction product is at a Pjj value from 8 to 10 is treated with formaldehyde. 33 · Method according to one of Claims 1 to 32, characterized in that the reaction product is treated with formaldehyde for 30 minutes to 2 hours. 34. The method according to any one of claims 1 to 33 * characterized in that the formaldehyde is added in aqueous solution. ' 35 · 'Preparations made according to the process one of claims 1 to 36. A method for treating textiles, characterized in that the textiles with one of the in claim 35 claimed preparations are impregnated and the equipment is hardened. 37 · The method according to claim 36 * characterized in that that the textiles are made of cellulose. 009830/1940 originally inspected 38. Textiles made according to the method of claims 36 and 37 have been treated. 009830/1940