DE1094225B - Process for crease and shrink-proof finishing of cellulose textiles - Google Patents

Description

GERMAN

The invention relates to the use of a resin precondensate for the treatment of cellulosic fabrics.

It is known to impregnate textile goods with an aqueous solution of a resin precondensate towards this dry and heat to make the resin insoluble. It is common to use a catalyst in the impregnation solution to be added to promote the formation of the insoluble resin upon heating. The presence of the Catalyst in the impregnation solution can cause premature precipitation of the insoluble resin and cause the formation of insoluble resin on the surface of the textiles.

Such methods are described in U.S. Patent 2,730,427 and British Patent Specification, among others 732 573. The processes specified there are other resin-like products than used in the present process. In the U.S. patent, a resinous product is formula

H ₂ C; CH-CH ₂ -ORO-CH ₂ -CH CH ₂

Method of creasing

and anti-shrink equipment

of cellulose textiles

Applicant:

Courtaulds Inc.,

New York, N.Y. (V. St. A.)

Representative: Dr. A. Marck, patent attorney,
Frankfurt / M., Roseggerstr. 3

Claimed priority:
Great Britain 22 February 1955

George Cecil Daul, Mobile, Ala. (V. St. A.),
has been named as the inventor

indicated, where R is an alkylene group and correspondingly in the British patent a polyepoxy compound. Citric acid is used as the catalyst according to these patents; these procedures can not be carried out with the desired effect, so that both of these methods premature precipitation of the insoluble resin can occur.

The subject of the claimed method consists in the use of a resin precondensate, which in Cellulose textiles can be used without a catalyst and the textile goods have good physical properties granted.

The method according to the invention for the crease and shrinkage resistance of cellulose textiles with resinous Fabrics is characterized by the use of a permanent, water-soluble, resinous precondensate as an impregnation agent, which by implementation

NH ₂ -C -NH ₂ + CH ₂ -CH-CH ₂ Cl

II

as a resin-forming amino compound that has at least two amino groups in the molecule and the remainder of the molecule

I!

> N - C - N <

contains and where X is oxygen or trivalent nitrogen, with an epihalohydrin and a compound, which can form Methylolgrappen with the amino compound is obtained, whereupon the impregnated textile material is dried and heated.

Suitable resin-forming amino compounds are urea, melamine, guanidine or dicyandiamide or a Mix of these.

Some of the possible reactions that occur during formation e.g. B. the urea-epichlorohydrin-formaldehyde precondensate occur are as follows:

11

-> NH ₂ -C-NH-CH ₂ -CH-CH ₂ CI

OH
III

This reaction occurs when the mixture has a p _H of 7 or less; in the presence of alkali the batch reacts according to:

009 677/432

NH ₂ -C -NH ₂ + CH ₂ -CH-CH ₂ Cl + NaOH

I II

NH ₂ -C -NH-CH ₂ -CH-CH ₂ + NaCl

IV

The reactions of III and IV with formaldehyde give: O

NH ₂ -C-NHCH ₂ -CH-CH ₂ Ci + HCHO OH

HIGH, - NH - C - NH - CH ₉ - CH - CHXl

ι
OH

III
O

VI

NH ₂ -C -NH-CH ₈ -CH-CH ₈ + HCHO IV V

HIGH ₂ - NH - C - NH - CH ₂ - CH - CH ₈
VII

As further reactions of III and IV with urea or formaldehyde, the following are possible: O O O OH

NH ₂ -C _{-NH-CH 2} -CH-CH ₂ + NH ₂ -C-NH ₈ > NH ₂ -C-JNH-CH ₂ -CH-CH ₂ -NH-C-Nh ₂

^x o ^x

I OH

IV
O

VIII
OH

NH ₂ -C-NH-CH ₂ -CH-CH ₂ -NH-C-Nh ₂ + HCHO> HOCH ₂ NH-C-NH-CH ₂ -CH-CH ₂ -NH-C-Nh ₂

VIII V IX

The resin precondensate used probably consists of a mixture of compounds VI and VII or from a reaction product of compounds VI and VII with the methylol compounds involved. Compound VI is believed to act as a catalyst in insolubilizing the resin acts and that the glycol groups formed by opening the epoxy ring as a softening agent for serve the resin.

In a resin precondensate that is preferably used, urea is reacted with epichlorohydrin in aqueous solution under reflux, some of the water is removed in vacuo, the urea-epichlorohydrin intermediate is cooled and reacted with neutral aqueous formaldehyde, with sufficient sodium hydroxide being added to the solution to make the solution at to hold p _H about 8; the mixture is heated to 40 to 70 ^° C. in order to complete the reaction with the formaldehyde, and the product is left to stand at room temperature for several hours. The resin precondensate is soluble in water. A solution that contains 40 to 60 percent by weight of the precondensate may form crystals on standing, which easily dissolve when heated. Solutions of the Harzvorkondensats retain during standing a p _H of 7 for a long time, without any further condensation takes place of Harzvorkondensats. The urea-epichlorohydrin intermediate can therefore be produced in larger quantities and stored for reaction with formaldehyde for later use.

The molar amounts of the three reagents can be varied widely. The precondensates however, they are preferably prepared from 1 mole of urea, 0.5 to 1 mole of epichlorohydrin and 1.5 to 2 moles of formaldehyde.

The precondensate containing the impregnating solution for the treatment of cellulosic textiles may also have a content of 0.15 ° / ₀ sodium oleate and 0.15 ° / ₀ oleic acid or a water repellent agent, for. B. stearamidomethylpyridinium chloride or a silicone.

The cellulose textiles to be treated can be made of cotton or viscose silk and as Threads, yarns or staple fibers are present as knitted or woven fabrics. The method is particularly suitable for those Treatment of viscose rayon, as the wet strength is increased and the water absorption is reduced.

The crease resistance, the abrasion resistance and the shrinkage resistance of the treated with the resin precondensate Good things are improved. Washing of the treated goods is not necessary as no odor remains. The treated goods do not become stiff or yellow as a result of the process. The treatment with the resin precondensate is usually carried out without the addition of a catalyst; if desired, one can latent acid-forming catalyst are added.

In the following examples, the percentages are percentages by weight. For the production of the Protection of the condensation product is not sought here.

example 1

60 g of urea (1 mole), 25 cc water and 120 g of a neutral 40 ° / ₀ solution of formaldehyde (1.6 moles) are dissolved under stirring, 30.9 cc epichlorohydrin (0,4MoI) was added dropwise and the mixture: 1 hour heated at 7O ^{0 C.} The mixture is neutralized with 20 ° / ₀ sodium hydroxide solution and filtered. The next

5 6

Some crystals will be noticed for days. A paste formed on cooling 60 g of urea (1 mol) with 40 ecm of epichlorohydrin (0.5 mol) with ice. Part of this paste is refluxed in the presence of 50 ecm of water. When dissolved in alcohol, nitrated and recrystallized, then 108 ⁰ C, the heating is interrupted and 126 g of melamine dried under vacuum. This product melts at (1 mole) with stirring and heating again about 116 ° C and contains 29.3 ⁰ I ₀ and l nitrogen, 02 ° / ₀ 5 added. There are then 80 ecm of epichlorohydrin chlorine. (1 mol) added dropwise, the reflux

The resin precondensate is used to maintain aqueous conditions. After completion of solution with a content of 0.15 ° / ₀ sodium oleate and the addition of epichlorohydrin 15 minutes further 0.15% oleic acid. So much solution is added that it is heated.

the resin 10 ° / ₀ is the rayon, and it is io In a vacuum 22 cc of water and 3 not ecm 1 hour at 110 ⁰ C dried. The rayon obtained removes converted epichlorohydrin. Be at 25 ° C has a soft feel, is white in color and shows ecm 20 25 _^0/0 sodium hydroxide solution was added and a water absorption of 35%. well mixed. To be 155 g 38 ° / ₀ sodium formaldehyde

The aqueous solution of the resin precondensate is mixed into 10 ecm of 20% sodium hydroxide solution and a viscose silk fabric is applied so that the fabric is added to the above conversion. 62.7 g Paraformmit 10 ° / ₀ is loaded resin. It is centrifuged, aldehyde is then added and the mixture is dried and heated to make the resin insoluble. heated to 74 ° C. with stirring. The clear precondensate - the treated fabric has a soft feel, a solution is filtered and left to stand for 24 hours,
Reduced water absorption and anti-wrinkling and it contains 75% solid components. When viscose

Shrink resistant. ao rayon with a 14 ° / _o solution of the precondensate

treated, squeezed off the excess and it for 1 hour

Example 2 ₁₁₅ ° _{C, it} hi _tz t, is the water absorption capacity

60 g of urea (1 mol) are in 65.3 ecm of water on the artificial silk 35 ° / ₀ .

and treated with 30.9 cc of epichlorohydrin (0.4 mol) drop- When a Viskoseseidegewebe with a 14 ° / ₀ solution

wisely offset. The mixture is treated under reflux with 25% of the precondensate and centrifuged, heated with stirring and so much sodium hydroxide is added to dry and, in order to make the resin insoluble, bep _H setting to 7 is added. At 110 ° C after about, it gets improved swelling properties and one hour the heat source is removed and under improved wrinkle and shrink resistance.
40 ecm of water is distilled off in a vacuum. The product will. .

cooled to 20 ⁰ C and with 120g40 ° / formaldehyde ₀ 30 Example 5

(1.6MoI) (neutralized with dilute sodium hydroxide) 84.1 g dicyandiamide, 100 ecm water and 40 ecm epi-

offset. In order to maintain p _H at 7, 17 cc of chlorohydrin as a whole are added to a 12.5 ° / ₀ sodium hydroxide solution under reflux for 45 minutes at 104 ° C. treated. 23 ecm of water are removed in vacuo; The mixture is stirred for 1 hour and filtered. This the product is cooled to 28 ° C, at which point product does not crystallize on standing. 35 it crystallizes. There are 14 cc of 20 ° / ₀ strength sodium

The resin solution contains approximately 54 ° / ₀ solid constituents hydroxide solution and 237 g of a 38 ° / o formaldehyde parts. The resin precondensate is added to an aqueous solution with stirring and then ^{heated to 50 °} C. for 30 minutes with a content of 0.15% sodium oleate and 0.15%. (The weights used are added oleic acid. It is used in the same way as in Example 1 40 and 3 mol formaldehyde.) One with 12% solutions is used with a continuous equivalent to 1 mol of dicyandiamide, 0.5 mol of epichlorohydrin, rayon yarn in the same way as in Example 1. The water absorption of the untreated the precondensate at _pH from 7 to 8.5 -wide treated rayon is 89%; the synthetic rayon fiber treated with the resin has a water absorption capacity of silk has a water absorption of 50, 45 and 40% at 45 to 50%.

5, 10 and 15% applied resin condensate. BeWenn with a 12% solution of the resin precondensate the aqueous solution of the resin precondensate in 45 is, centrifuged, dried and after-treated the same Way as in Example 1 on a viscose silk deltes viscose fabric has a pattern of fabric is applied, so the treated untreated fabric gets improved crease resistance and Fabric improved water swelling properties and shrink resistance.

good crease and rub resistance. _,. . ,.

^ö _ ₀ Example 6

Example ό Guanidine is mixed with epichlorohydrin and formaldehyde in a resin precondensate solution with a content of molar ratios of 1: 0.5: 2, 1: 0.5: 3 and 1: 1: 2 of 1 mol of urea, 0.3 mol of epichlorohydrin, 1 , 7 moles implemented according to the previous example. The liquid formaldehyde and 0.15 mol of sodium hydroxide after the product thickened when dehydrated to a game 2 produced. The resin precondensate solution has a syrup and solidifies on cooling. When spinning moisture content of solids of 55.3%. If it is applied to a viscose silk with resin solutions in concentrations of viscose rayon in an aqueous solution of 15% of 10, 12 and 14% concentration treated with a catalyst, then the finished silk has an acid dye even after rayon has a water absorption capacity of 52, 5%, hot washing, whereupon a reaction between the non-finished goods a water-based rayon and the resin suggests,
has an absorption capacity of 118.5%. Those obtained from guanidine, epichlorohydrin and formaldehyde, when an aqueous solution of 15% concentration, of the resin precondensate is applied to a viscose silk fabric, are also used to impregnate samples of viscose-dried and further treated fabric against fabric. After centrifugation, drying a sample of an untreated tissue and post-treatment, the resin-treated wrinkle and shrink resistance are improved. Fabric pattern resistant to creasing.

Example 4 Example 7

It is a melamine-urea-epichlorohydrin form- 30 g urea, 63 g melamine, 75 ecm water and

aldehyde precondensate produced by reacting 70 40 ecm epichlorohydrin are 2 hours at a temperature

temperature up to 104 ° C implemented under reflux. 23 ecm of water are distilled off in vacuo and the product is cooled to 20 ° C. 7 cc of a 20 ⁰ / "sodium hydroxide solution and 197 g of a 38 ° /" formaldehyde solution are added to the above product under stirring the mixture at 64 ° C. and held for 30 minutes at this temperature. This gives a clear solution with 51.6 ° / ₀ solid components. Artificial silk fibers treated with 10 to 14% of this precondensate have a water absorption capacity of 35 to 39%. The molar ratio of the reagents in this precondensate is: 1 melamine: 1 urea: 1 epichlorohydrin: 5 formaldehyde.

The treated with a 10% aqueous solution of this resin precondensate, centrifuged, dried and post-treated viscose fabric shows reduced water absorption and is crease and shrink-proof.

Example 8

This example shows the application of the invention according to the precondensate with plasticizers, the resin being stabilized by the addition of alkali.

60 g of urea (1 mol), 126 g of melamine (1 mol) and 50 ecm of water are heated to 80 ° C. and 80 ecm of epichlorohydrin (just over 1 mol) are added dropwise over the course of one hour. After 15 minutes, the heat source is removed and 16 ecm of water and an excess of epichlorohydrin are distilled off in vacuo. At 35 ° C., 20 cm of cold (5 ° C.) 20% sodium hydroxide solution are added with stirring. 10 cm of cold 20% sodium hydroxide solution is added to 406 g of 37% formaldehyde (5 mol), mixed and added to the above addition with stirring. A clear solution forms at 65 ° C. Stirring is continued without supply of heat until 25 ^° C. is reached. 12.5 g of solid sodium hydroxide beads are added with stirring and the solution is allowed to stand for 16 to 24 hours before use.

The resin precondensate lasts for several months. When a latent acid generating catalyst is added to the Resin precondensate is added, no condensation can be observed even after standing for 2 weeks.

6, 8 and 10% concentrations of this resin precondensate in a 0.2% solution of a cationic softener with 5% (based on the resin content) of a latent acid-forming catalyst are applied to spun-damp staple viscose, the excess squeezed off and the material 40 minutes at 8O ⁰ C dried and ^{aftertreated at 150 0} C for 15 minutes. Water absorption values of 45, 39 and 39% are obtained.

The treated fibers are carded, spun into yarn and woven. Part of the tissue is in heated in an oven at 110 ° C for 1 hour. The water absorption capacity is 42%. After ten washes in a washing machine - like cotton goods usual - the water absorbency is 47%. The fabric shows only 4% shrinkage. Part of the fabric is ironed with a hot iron and then has a water absorption capacity of 50%.

Claims (6)

Patent claims: 1. A method for the crease-proof finishing of cellulose textiles, characterized by the use of a stable, water-soluble resinous precondensate as an impregnating agent, which is produced by reacting a resin-binding amino compound, the at least two amino groups in the molecule and a molecular residue .11 "N-C-N" and wherein X is oxygen or trivalent nitrogen, with one epihalohydrin and one Compound that can form methylol groups with the amino compound is obtained, whereupon the impregnated textile material is dried and heated. 2. The method according to claim 1, characterized by the use of a precondensate, which by Implementation of urea, melamine, guanidine or dicyandiamide or a mixture of these with one Epihalohydrin and subsequent reaction with formaldehyde or a formaldehyde-forming compound is preserved. 3. The method according to claim 1 and 2, characterized by the use of a precondensate, which consists of 1 mole of urea, 0.5 to 0.1 mole of epichlorohydrin and 1.5 to 2 moles of formaldehyde is obtained. 4. The method according to claim 1, characterized by the use of precondensates, in which the urea and, if necessary, melamine only with epichlorohydrin and then reacted with formaldehyde. 5. The method according to claim 1 to 4, characterized by the additional use of a water-repellent Means. 6. The method according to claim 1 to 5, characterized in that a spinning-moist viscose rayon is treated. Considered publications:
British Patent No. 732,573;
U.S. Patent No. 2,730,427. ι 009 6π / 432 11.60