DE1803087A1 - Case 6298 / E New condensation products, processes for their manufacture and their use - Google Patents

Description

CIBA At. TIENGESELLSCHAFT, BASEL (SC HW EI Z)

Case 6298 / E

Germany

New condensation products, processes for their manufacture

and their application.

to It has been found that one can become valuable new Kono

^ atlons products that are capable of

cn armoring of cellulosic textile materials with amino

"^ occurring deterioration of the mechanical Elco

co properties largely fix if one

in aqueous medium at temperatures from -10 to

+30 C with a molecular ratio of 1: 2 to 1: 0.5. » preferably 1: 1.5 to 0.5

a colorless heterocyclic compound which has at least 2 nitrogen atoms in the heterocyclic ring and at least 2 halogen atoms bonded to carbon atoms of the heterocyclic ring, with Λ) a thiourea compound which contains at least 1 hydrogen atom bonded to the nitrogen, preferably thiourea itself, or an alkali or ammonium hydrogen sulfide and B) a mono- or dialkanolamine with a maximum of h carbon atoms, preferably mono- or diethanolamine, is reacted,

then at temperatures between 30 and 100 ° C, preferably 45 to 70 C, the reaction leads to the end and if necessary removed from the resulting mixture water by distillation .

The heterocyclic compound to be used here as a starting material must be practically colorless and at least have one, preferably a single, heterocyclic ring, which is the only ring of the compound at all be or e.g. another aromatic six-membered ring.,., _, ankondensier, t may contain. There are mainly connections with six-membered hetero rings into consideration, ins-. special ones with 2 to 3 nitrogen atoms = and if · to 3 Carbon atoms in the ring, such as ^ pyridazine, pyrimidine,. ......

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Quinazoline and especially 1,3 * 5-triamine compounds. These compounds contain at least 2 halogen atoms bonded to carbon atoms of the hetero ring, e.g. bromine atoms or preferably chlorine atoms. As examples selenium trichloropyrimidine, tetrachloropyrimidine, 2,4-diehlorquinazol ± n, 2,4,6-tribromo-1,315-triazine and especially 2,4,6-trichloro-1,315-triazine (Cyanuric chloride) mentioned, as further starting materials are a thiourea compound, the at least one hydrogen atom is bound to the nitrogen holds, but preferably thiourea itself or alkali and ammonium hydrogen sulfide, also mono- or dialkanolamines with a maximum of 4 carbon atoms, preferably Mono- or diethanolamine.

The reaction takes place in an aqueous medium which, in addition to water, also contains organic solvents, especially those which are miscible with water 'may contain. Lower alcohols and acetone may be mentioned.

A certain sequence of the individual reaction " steps is not required, i.e. the heterocyclic compound know first with the sulfur-containing compound or be reacted first with öem Älkanalamin.

3? Üt * the implementation of a "Je ^ eri MölS" of the components B) with der-iietei? Oöf <J2ischen VeMiiiMüiis wl-räl · £ Möl · fi

s- · in Föä ^t ^ ί ^^^ ^

BATH ORIGINAL

given, either all at once or in portions.

The reactions are carried out at temperatures between -10 and +30 C carried out, in the presence of organic solvents can be carried out below 0 ° C, while in the presence of purely aqueous reaction media with advantage the temperatures increased to 0 C or slightly above.

It is advisable not to start the second reaction stage until the first reaction has largely been completed. This is the case, for example, when, after adding the amount of alkali or its last portion in the reaction medium, a p n value of about 7 is established. The reaction is then brought to completion at temperatures between 30 and 100 ° C., preferably between 40 and 70 ° C., and can be completed after 2 to 3 hours. The p "value of the reaction mixture should be in the neutral or weakly alkaline range during this time. A decrease in the ρ value worsens the solubility properties of the reaction product considerably and can be avoided by adding further amounts of alkali. The condensation products can also be prepared in such a way that a colorless heterocyclic compound is obtained in an aqueous medium at temperatures from -10 to + 25 ° C. and at p "values from 6 to 9 in a molecular ratio of 11.5 to 1.5. which has at least 2 nitrogen atoms in the hetero ring and at least 2 halogen atoms bonded to carbon atoms of the hetero ring, allows a thiourea compound to act and after this has ended

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0.5 to 1.5 of a monoalkanolamino is added to the first reaction stage without intermediate separation per mole of heterocyclic halogen compound used, while maintaining p _TT values of

6 to 10, the temperature of the reaction medium first holding for at least 8 hours at 30 to 50 ° C and then for at least 5 hours at 60 to 65 ⁰ C, and optionally from the resulting mixture, water removed by distillation.

Using cyanuric chloride as a starting material, advertising i the generally per mole of halogen compound total

about 4 moles of mono-acid base, e.g. 3 moles of alkali metal hydroxide and 1 mole of alkanolamine consumed. The amount of water used as the reaction medium can be freely selected within wide limits are, expediently so that on the one hand the reaction mixture is easy to stir right from the start and the risk of a Heating above the prescribed temperature limits is avoided, but on the other hand not through unnecessary dilution the practical feasibility is called into question. Since the (heterocyclic halogen compounds are usually in the as The water used in the reaction medium is sparingly soluble, it is advisable to convert them into a finely divided state beforehand

Q, which can be done in a known manner by solving in

<x> an organic, water-miscible solvent such as ro

, ^ Acetone and pouring the solution on ice can be done. As mentioned earlier on, "to the heterocyclic Molekulärverhältnis ^W halogen compound to the sulfur-containing compound in the range of 1: 0.5: 2 to 1" preferably. 1; 1.5 ''to; , 1>, Ö, 5 '' and aas' molecular

ratio of heterocyclic halogen compound to alkanolamine likewise in the range from 1: 2 to 1: 0.5, preferably 1: 1.5 to 1: 0.5. Especially with cyanuric chloride Particularly good results are achieved if equimolecular amounts or amounts of the three reactants which differ only slightly are used.

After the reaction has ended, the product obtained can readily be used for the purpose indicated at the outset

ψ will be. In view of the generally not very high concentration of the mixture at the end of the reaction, however, it is advisable to distill off some or all of the water under reduced pressure. In this way, stable products are generally obtained which are at most slightly colored and easily and completely soluble in water.

As already mentioned, the products obtained by the process specified at the outset are suitable for use in Combination with aminoplasts for finishing textile materials

w lien, especially to increase dimensional stability. Textile materials made of cellulose, optionally in combination with other fibers, for example polyester fibers, come into consideration here. Accordingly, the preferred use of the products according to the invention is characterized in that an aqueous preparation is applied to textile materials,

-. ■ - · - ■ · ■ ■■■ - ■ ■ ■ - ■ · ■■ .- ■ -.; .-- .; . : ... ..-... ■■■■ .-S -., '=; ^ Which is a hardenable aminoplast precondensate, a hardening

90 9 825/1503

catalyst and. a condensation product of the specified composition contains, and the dried textile material cures by treatment at an elevated temperature.

Aminoplast precondensates are taken to mean addition products of formaldehyde with methylatable nitrogen compounds. Mentioned in this context amino-1, J>, 5-triazines are as at the nitrogen-substituted melamines such as A _mm elin, guanamines such as Benzoguanamln, acetoguanamine. Next are: Symmetrical Alkyltriazone, biuret, g thiourea, Alkyicarbamate, guanidine, alkyl or Ary ureas and thioureas, alkyleneureas or -diharnstoffe, for example ethyleneurea, propylene urea, acetylene diurea;! 4,5-Dihydroxy-imidazolidone-2 and its derivatives, for example 4,5-dihydroxyimidazolidone- -2 substituted in the 4-position on the hydroxyl group by the radical -CHg-CHp-CO-NH-CHp-OH. The methylol compounds of urea and melamine are preferred, it being possible, in particular in the case of melamine, to use lower or higher methylolated compounds. It is also possible to use compounds whose methylol groups are more or less completely etherified, for example with methyl groups.

The usual acidic or potentially acidic compounds such as ammonium chloride, magnesium chloride, zinc fluoroborate can be used as curing catalysts.

Particularly valuable results can also be

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aim, if in addition to finishing the textile materials the aminoplast precondensate, the hardener and the inventive An emulsion polymer is added to the condensation product; that from an N-methylolamide an α: ß-ethylenically unsaturated carboxylic acid or a Ether of such a methylolamide and an alkaline earth metal salt of an α: ß-ethylenically unsaturated Mor .carboxylic acid produced has been. In particular, the copolymers obtainable in aqueous emulsion

a) Oj25 to 10 percent by weight of an alkaline earth metal salt of an α: ß-ethylenically unsaturated monocarboxylic acid (e.g. calcium acrylate) ,

b) 0.25 to 30 percent by weight of an N-methylolamide or N-methylolamide ethers of an α: ß-unsaturated one Mono- or dicarboxylic acid (e.g. acrylic acid methylolamide, Methacrylic acid methylolamide or the methyl ethers of these methylolamides),

c) 99 * 5 to 60 percent by weight of at least one other copolymerizable compound (e.g. an ester of acrylic or methacrylic acid and an alkanol such as Methanol, ethanol, n-butanol, acrylic acid tertiary butylamide, vinylidene chloride, vinyl acetate, acrylonitrile, Styrene).

Depending on the purpose of the finish, the aqueous preparations can also contain other components, e.g. water repellants, suitable optical lighters, mesh and

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Dispersants or flame retardants, especially phosphorus compounds such as Dlalkylphosphono-propionäuremethylolamides. In very many cases, it is also advisable to add a non-ionic softening agent, e.g. a aqueous emulsion of a methylol melamine alkyl ether modified by stearic acid alkylolamide residues.

The Mengenverhältnisε 3 of the individual substances in the aqueous formulations can vary widely, and * the particular purpose to be adjusted. In general, it is advisable to use 1 to 4 parts of condensation product of heterocyclic halogen compound, thiourea and alkanolamine per 10 parts of aminoplast precondensate. Otherwise, the textile material can be treated in a conventional manner known per se. One can for example undyed or dyed fabric or knitted fabric at Foulard with the formulations impregnate and, practical after an intermediate drying at temperatures up to 100 ° C, subjected to a dry heat treatment at tem- i temperatures of l40 to l80 ° C for 2 to 20 minutes, the level of the temperature and the duration of the treatment are selected according to the purpose of the treatment, which can consist, for example, of an improvement in wet fastness for direct dyes, a crease-proof finish or permanent shaping (permanent press). The finishing can also be combined with a dyeing process, for example in such a way that the padding liquor still contains a dye, which, as a result of special substituents compared to the fiber or in particular

. 909825/1503

Is reactive towards the aminoplast precondensate and due to this property during the heat treatment or already is previously fixed on the substrate.

It is known that the mechanical properties of the cellulose-containing resins are increased by equipping them with aminoplast resins Fiber materials, especially the tear and abrasion resistance, adversely affected, namely the loss is generally greater, the higher the aminoplast content and the more vigorous the hardening. As mentioned at the beginning, these serious disadvantages can be avoided with the help of the new condensation products are largely eliminated or reduced to an acceptable level. As an additional effect These condensation products showed an improved soil release from the fiber will.

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example 1

190 g (1 mol) of cyanuric chloride are dissolved in 1 liter of acetone, the solution is poured onto 1 liter of water and 1 kg of ice and the precipitated cyanuric chloride is filtered off. The paste is then added to a solution which has been prepared at 45 ° C. from 76 g (1 mol) of thiourea and 500 ml of water and then cooled by adding 50 g of ice. In this first condensation stage, the p _T7 value is kept at 6.7 to 6.9 by adding dropwise 5N sodium hydroxide solution and the temperature is kept at 8 to 10 ° C. by indirect cooling. After about 5 hours and a consumption of about 3 * 5 moles of sodium hydroxide, the p., - value remains constant, and in the reaction

mixed practically everything is solved. 6l g (l mol) of monoethanolamine are then added all at once, and the now clear solution is kept in a further condensation stage for 15 hours at 35 to 40.degree. C. and then in a third stage for 8 hours at 55 to 60.degree. During this time, further sodium hydroxide solution is added as required, so that the p _TT value is always J ₉ O , for which about 0.5 mol of sodium hydroxide is required. Finally, the solution is evaporated to dryness in vacuo at 90 to 100 ° C. and the residue is ground in a ball mill. 410 g of a pale yellow, easily soluble in water, hygroscopic powder are obtained: 'Condensation product A.

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In addition to this product A, further condensation products obtainable by this procedure are listed in the table below with the associated data for the preparation .

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ε 0 SL / 928606 Amount in moles Thiourine
material Ethanol
ann τι TABLE I. Time
Hours. % - ■ 2nd stage ■ Time
Hours. % 3rd stage Time
Hours. ^p H Reconditioning • I.
'VH
I.
OO Cyanur
chloride 1 1 5 6.7-6.9 Temp. 15th 7th Temp.
C. 8th 7th E: Evaporation
in a vacuum
at: ⁰ C O
CjO
O
OO 1 1 1 1st stage 8th 6P-65 35-40 14th 7th 55-60 9 7th E 90-100 A. 1 1 1 Temp.
⁰ C 2 8-9 35-40 15th 7th 55-60 8th 7th E 90-100 B. 1 1 1 8-10 4 η 7th 35-40 15th 7th 55-60 8th 7th E 90-100 C. 1 1 1 0-10 5 ■ 7th 35-40 14th 7th 55-60 9 7th E 90-100 D. 1 1.5 0.5 0-12 8th 7th 35-40 13th 7th 55-60 7th 7th E 90-100 E. 1 0.5 1.5 0-10 22nd 7th 35-40 22nd 7th 55-60 8th 7th E "90-100 Ρ 1 2 2 0-8 14th 7th 35-40 18th 7th 55-60 8th 7th From unsolvable
Back off
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Example 2

18 > 5 g (0.1 mol) of cyanuric chloride are dissolved in 100 ecm of acetone, the solution is poured onto 0.1 liter of water and 0.1 kg of ice and the precipitated cyanuric chloride is filtered off. The paste is then added to a solution which has been prepared from 7 * 6 g (0.1 mol) of thiourea and 50 ml of water at 45 ° C. and then cooled by adding 50 g of ice. Ρ By adding 5 η dropwise Sodium hydroxide solution is used in this

first condensation stage the p _TT value to 6.7 to 6.Q and

rl

the temperature was kept at 8 to 10 ° C by indirect cooling. After about 5 hours and a consumption of approximately 3.5 moles of sodium hydroxide of p_ _T value remains constant, and

ri

Practically everything is dissolved in the reaction mixture. Now 10.5 S (0.1 mol) of diethanolamine were added at once and the reaction mixture is heated for a further addition of 10 ml 5 N sodium hydroxide (0.05 mol) at 55 to 60 ° C and 5 hours with stirring at Ψ leave this temperature.

The solution is then evaporated to dryness at 60 ° C. in vacuo. 46 g of a pale yellow in water are obtained readily soluble powder: condensation product J

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Example 3

18.5 g (0.1 mol) of cyanuric chloride are dissolved in 100 ml Suspended alcohol and the suspension is then cooled to a temperature between 5 and 10 ° C. Then there 6.1 g (0.1 mol) of monoethanolamine are added all at once, and 20 ml of 5N sodium hydroxide solution are then added dropwise over a period of 15 minutes (0.1 mol) and stir the reaction mixture for about 1 hour at the same temperature, until * a constant p "value of about 2.7 has set.

By adding 7.6 g (0.1 mol) of thiourea and 30 ml of 5N sodium hydroxide solution (0.15 mol), each in one portion, the reaction mixture temporarily reaches a p "value of 11, which after a further 30 minutes of reaction time, wherein the temperature is increased to 30 to 40 C, to about 7 going back. A further 20 ml of 5N sodium hydroxide solution are then added and the reaction is ended after stirring for 2 1/2 hours .

The colorless suspension thus obtained is evaporated to dryness at 40 ° C. in vacuo. 40 g of one are obtained light yellow product, easily soluble in water. Condensation product: K.

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Example 4

18.5 S (0.1 "mol) of cyanuric chloride are suspended in 200 ml of a mixture of 100 ml of water and 100 ml of acetone. 6.1 g (0.1 mol) of monoethanolamine are then added all at once at 0 ° C. by dropwise addition of anhydrous 5> S 3 (0.05 mol) of sodium carbonate in 15 ml of water for one hour maintaining the _pH value of the Reaktion'sgemisches at about ¹ J.

7.6 g (0.1 mol) of thiourea and 20 ml (0.1 mol) of 5η sodium hydroxide solution are now added. After the p "value has decreased to 7, the temperature is increased to 50C and the reaction was then brought to an end over 90 minutes with stirring, a further 40 ml (0.2 mol) of 5N sodium hydroxide solution to be added gradually. The reaction mixture obtained is evaporated to dryness in vacuo. 40 g of one are obtained ^ condensation product which is easily soluble in water. Condensation product: L.

Example 5

18.5 g (0.1 mol) of cyanuric chloride are suspended in 150 ml of water and at 0 ° C. for 60 minutes with 14.35 ml (0.1 mol) of a 39% solution of sodium hydrosulphide offset.

6.1 g (0.1 mol of monoethanolamine) are added to the resulting yellow suspension at room temperature, followed by 20 ml (0.1 mol) of 5 η sodium hydroxide solution in one portion; the mixture is then heated to 50 ° C. for about 2 hours left with stirring at this temperature The p _o value of the reaction mixture

xl

after this time it adjusts to about 7.

After a further addition of 20 ml (0.1 mol) of 5N sodium hydroxide solution and a reaction time of 3 hours at the same temperature, the reaction is ended. The p _o value is established at

Xl

10 a. The reaction mixture is first filtered in order to separate off the insoluble constituents (5 * 5 g · yellowish substance). The piltrate is then evaporated to dryness at 6o C in vacuo. 26.5 g of a white powder are obtained.
Condensation product: M.

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Example 6

Aqueous poulard liquors are prepared using the substances listed below
a) aminoplast precondensate

aqueous solution of a mixture of Dimethyloläthylenurea and methyl ether of a highly methylolated Melamine.

b) Softener

aqueous dispersion of a stearic acid alkanolamide modified methyl ether of a highly methylolated melamine.

c) copolymer

aqueous emulsion of a copolymer of 80 parts of n-butyl acrylate, 13 parts of vinylidene chloride, 6 parts of acrylic acid ethylolamide and 1 part of calcium acrylate.

d) condensation product

from cyanuric chloride, thiourea and monoethanolamine, produced according to example 1: condensation product A.

Poulard liquors, the composition of which can be seen from Table II, are used to impregnate mercerized and bleached cotton poplin with a plot absorption of 60 % (based on the weight of the fabric). After drying at βθ to 80 ° C, the fabric is subjected to a heat treatment for 4 1/2 minutes at 155 ° C, then washed at the boiling point with O2% sodium carbonate solution for 5 minutes,

cold sprayed and dried. _t; . <'-'QQQ- $ 2S / T 5 G 3 ~ -

TABLE II

l

ι

a) Aminoplate precondensate grams / liter

b) means of control
Grams / liter

c) copolymer emulsion Grams / liter

d) Condensation product A grams / liter

MgGIp.6H _? O grams / Liier

CH ₃ CQOH, grams / liter

150

30th

150 S150

30th

30th

40

19th

0.5

40

19th

0.5 »0.5 150

30th

40

40

19th

0.5

100

30th

13th

0.5

30th

100

30th

40

40

40

13th

0.5

13th

0.5

I 13 0.5 j

the padding liquor

Tear resistance Abrasion resistance '' "

Crease resistance

Xniti
wet <fc

D 2) 3)

Xnitterwinkel ■ ο ₄₎

100-

100

50

59

5.6 43

18th

130 113 5137

6.2 5.6 61 j 65!

128

111

137 6.2

5.6

55

43

119

119

6.2

65

S9

100

5.6 6.2

54

69

j

I!

125

54 1ü5 j

UttW &'lb / T

1) Determination of the tear strength on samples of 25 cm. 50 cm by increasing stress until they tear (SNV 98461). The weight load required for this is assumed to be 100% for the untreated fabric. The numbers in columns 1 to 8 indicate what percentage of this load is required before the treated tissue samples tear.

2) To determine the abrasion resistance, a loaded abrasive element (brush with nylon bristles) carries out a uniform

^ moderate rotary motion on the test material, which is also rotating uniformly. The number of rubbing turns (n) up to the formation of holes in the test material is determined after this number (m) has been determined for the untreated material. The abrasion resistance (S) of the treated fabric samples is calculated from this: S = - - ~

3), 4) To determine the crease angle, dry, or evenly wetted, rectangular pieces of fabric of 16 mm, cut diagonally to the threads. 44 mm parallel to the folded on the shorter side and loaded with 2 kg weights between glass plates. After 5 minutes of exercise and an hour To recover, the samples are placed in an angle measuring device of the usual type and the crease angles are measured.

909825/1503

t oar \ as

Example 7

According to the information in Table III, poulard liquors are prepared using additives b), c), d) and e). The composition of substances b), c), and d) is in example 2 described. The aminoplast precondensate used here is methylolated glyoxalmonourein instead of the melamine compound a) e) used. The baths of this composition are used to impregnate mercerized cotton poplin. Then at βθ to 80 ° C. and then treated at 170 ° C. for 13 minutes. Then the tissue is at the boiling point washed with 0.2 $ sodium carbonate solution for 5 minutes, rinsed cold and dried.

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0 1ononoT 1 CM 3 4th I Il I I r 140
30th
13th 140
30th
40
13th 140
30th
40
13th 140
30th
40
40
13th - 22 -
· "! TABLE III 100
100
47
64 4.5
25th
6th
143
124 5.1
51
40
126
112 4.6
28
5
149
131 5.1
52
48
132
119 1), 2), 3), 4): Find information on how to determine these quantities
then refer to Table II.
at Qfi2 ^ / 1503 a) Aminoplast precondensate grams / liter
b) Softener grams / liter
c) copolymer grams / liter
d) Condensation product A grams / liter
Zn (NO-) ₂ • 6H ₂ O grams / liter p _H - the foulard plot
Tear strength $> 1)
Abrasion resistance % 2)
Wrinkle angle dry ^ f- 3)
Crease angle wet Jf- ° 4)

Example 8

Prepare using the ones listed below Substances of aqueous padding liquors:

a) aminoplast precondensate

50/6 aqueous solution of a mixture of dimethylolethylene urea and methyl ether is a highly methylolated melamine.

b) Softener

30 # aqueous ^ dispersion of a with stearic acid alkanolamides modified methyl ether of a highly methylolated melamine.

c). Copolymer ........

27 $ aqueous emulsion of a copolymer Bo parts of acrylic acid n-butyl ester, 13 parts of vinylidene ■! ' ohlorid, 6 parts of acrylic acid methylolamide and 1 part Calcium acrylate. .

d) wetting agents.

25 # aqueous solution of the addition product p-NonylphenoO. and. 9 moles of ethylene oxide.

e) Remedy of the formula

HN - CH ₀ -CH _o S0 "Na I 2 2 3

C.
//

-N

C-HN- <L3-CH = CI SO ₃ Na

HN-CH ₂ CH ₂ SO ₃ Na

SO ₃ Na

OCH ^

ORIGINAL INSPECTED

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f) one of the following condensation products:

1.) Condensation product from cyanuric chloride, thiourea and monoethanolamine, prepared according to Example 1; Condensation product i.A.

2.) Condensation product of cyanuric chloride, monoethanolamine and thiourea, prepared according to Example 3; Condensation product: K.

3 «) condensation product from cyanuric chloride, sodium

sulfide and monoethanolamine, prepared according to Example 5j condensation product: M.

g) Magnesium chloride hexahydrate (M C1 _o * 6H _o 0)

q 2 2

Mercerized and bleached cotton poplin with a liquor pick-up of 60% based on the weight of the fabric) is impregnated with poulard liquors, the composition of which can be seen in Tables IV, V and VI. After drying at 60 to 80 ° C., the fabric is subjected to a heat treatment for 4 1/2 minutes at 155 ° C., then washed at boiling temperature with 0.2% sodium carbonate solution for 5 minutes, rinsed with cold water and dried.

9 0 9 8 2 5/1503

B. - 25th - E. IV 1 803087 E. I I A.

0 1 3 - 2 3 3 - 4th • - 150 3 15th 150 3 150 15th .150 a) Aminoplast precondensate grams / liter - 30th 5.9 30th 10 30th 5.9 30th b) Softener grams / liter - - 63 - 15th 40 63 40 c) Gram / liter copolymer emulsion - 19th 5.9 3 39 3 d) sedative gram / liter - 69 3 3 e) Lightening agent grams / liter - 133 59 130 10 f) Condensation product A grams / liter 116 124 15th g) M Cl ₂ .6H ₂ O 'grams / liter _ 122 5.9 Pjr value of the Foulard Elotte 100 121 69 Tear strength (#) ■ 1) 100 103 Abrasion resistance (#) 2) Knitterwinkel: "£ 53 127 a) dry 3) 65 126 b) wet 4)

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- 26 - B V 1 3 - 1 2 3 803087 - 4th T A B E L L: 150 3 15th 150 3 15th 150 0 30th 5.9 30th 5 3 5.9 30th _ - 63 - 15th .150 63 40 a) Aminoplast precondensate grams / liter - 19th 5.9 30th 39 3 b) Softener grams / liter - 69 40 3 c) Copolymerization gram / liter - 133 55 3 130 5 d) wetting agent grams / liter - 116 3 124 15th e) Lightening agent grams / liter - 123 5.9 f) condensation product K grams / liter 120 72 g) M Cl ₉ .6H ₉ O grams / liter 88 PxT value of the Eoulard plot.
η 100 Tear strength (#) 1) 100 120 Abrasion resistance (#) 2) 117 Wrinkle angle: £ ° 53 a) dry. 3) 65 b) wet 4) 90 9 825/1503

TABEL • VI 1 3 - 2 3 3 4th 150 3 15th 150 3 150 150 a) Aminoplast precondensate grams / liter 0 30th 5.9 30th 10 30th 30th b) Softener grams / liter - - 63 - 15th 40 40 o) copolymer emulsion grams / liter - 19th 5.9 3 3 d) wetting agent grams / liter - 69 3 3 e) Lightening agent '' grams / liter - 133 48 - 10 f) Condensation product M grams / liter - 116 15th 15th g) M Cl ₂ .6H ₂ Q grams / liter - 119 5.9 5.9 Pjj value of the padding fleet 119 63 '71' Tear strength (£) 1) warn 39 94 Abrasion resistance (#) 2) 100 Wrinkle angle: ^ ° 100 130 127 a) dry 3) 124 126 b) wet 4) 53 ; of these sizes Find 65 1), 2), 3) ι 4) -: ■ · Information about the determination then refer to Table II. 9 0 9825/1503

Claims (10)

Claims 1. Process for the preparation of condensation products, characterized in that in an aqueous medium at Temperatures from -10 to + 30 ° C in a molecular ratio of 1: 2 to 1: 0.5 * a colorless heterocyclic compound, the at least 2 nitrogen atoms in the hetero ring and at least 2 halogen atoms bonded to carbon atoms of the hetero ring W ·. ■ having, with A) a thiourea compound containing at least • a hydrogen atom bound to nitrogen contains, or an alkali or ammonium hydrogen sulfide, and B) a mono- or dialkanolamine with a maximum of 4 carbon atoms converts, then the reaction at temperatures between 30 and 100 ° C leads to the end and water is removed from the resulting mixture by distillation. 2. The method according to claim 1, characterized in that cyanuric chloride is used as the halogen-containing heterocyclic compound. 3 · Method according to one of claims 1 and 2, characterized characterized in that thiourea itself is used as the thiourea compound. 909825/1503 Annex 3 to the submission to the Deuteehe Patent Office dated Dec. 2 τ368 File number: P 18 03 087.0 - Applicant: GIBA-AG, Baeal Gases: 6298 / E - us. Sign: 21 382-BR / ro 4. The method according to any one of claims 1 to 3> characterized in that the alkanolamine used is mono- or diethanolamine. 5. The method according to claim 1, characterized in that the molecular ratio of the heterocyclic compound for components A) and B) is in each case 1: 1.5 to 1: 0.5. 6. The method according to claim 1, characterized in that one in an aqueous medium at temperatures of -10 to +25 C and with p "values from 6 to Q in the molecular Jl ratio of 1: 1.5 to 1: 0.5 a colorless heterocyclic compound that has at least 2 nitrogen atoms in the hetero ring and has at least 2 halogen atoms bonded to carbon atoms of the hetero ring, on a thiourea compound lets act and then without intermediate separation per mole of heterocyclic halogen compound used 0.5 up to 1.5 mol of a monoalkanolamine is added, while maintaining Ptj values of 6 to 10, the temperature of the reaction medium first for at least 8 hours at 30 to 50 C and then holds for at least 5 hours at 60 to 65 ° C and optionally from the resulting (remisch water by distillation removed" 7 »Use of the according to one of claims 1 to 6 available condensation products in combination with aaiino 903825/1503 Plastics for finishing textile materials, especially for increasing dimensional stability. 8. A method for finishing textile materials, characterized in that this is an aqueous Applies preparation, which precondensate a curable aminoplast, a curing catalyst and one after of claims 1 to 6 contains obtainable condensation product, and the dried textile material by treatment hardens at elevated temperature. 9. The method according to claim 8, characterized in that that urea and / or melamine derivatives are used as aminoplast precondensate. 10. The method according to any one of claims 8 and 9, characterized in that the aqueous preparation additionally in emulsified state a copolymer of a minor amount of an alkaline earth salt of an α, ß-ethylenically unsaturated monocarboxylic acid of an N-methylolamide or N-methylolamide ether of an α, β -unsaturated mono- or dicarboxylic acid and at least one other copolymerizable compound. 909825/1503