DE1619185A1 - Method for treating a cellulosic textile fabric - Google Patents

Description

PATENT LAWYERS 1 Rl QI QR

dr. w. Schalk dipl-ing. Peter Wirth

DIPL-ING. G. E. M. DANNENBERG, DR. V. SCHMIED-KOWARZIK

Dr. R WeinKoIl

6 FRANKFURT AM MAIN

OR. ESCHENHEIMER STR. 39

SK / SK C-64-02

Union Garbide Corporation

270 Park Avenue

New York, Ν.Ϊ. 10 017 ⁿ / USA

Method for treating a cellulosic textile fabric

The present invention relates to the manufacture of Textile fabrics with improved crease and shrinkage resistance and other improved properties. It relates in particular to a method for treating cellulosic textile fabrics with methylolated alkoxyalkyl carbamates and on the so manufactured, treated fabrics ·.

One of the most important, recent developments in finishing (treating, '! Finishing · ¹ ; of cellulosic textile fabrics was the

of ■.

Introduction / finishing products made by reacting aliphatic monocarbamates with formaldehyde. These products have proven to be very effective in imparting wrinkle resistance and "wash; w ^ r" properties to fabrics, having significant advantages over conventional nitrogen-containing sizing agents such as improved resistance to chlorine damage and the like Shelf life under conditions that accelerate acid hydrolysis, show, previously such finishing agents were made from alkyl carbamates, such as methyl, ethyl, propyl or butyl alcohol, or from hydroxyalkyl carbamates . ■ ■, '- '"■'■■ ^: ■' - ■. .'- ■ ■■. '■.' ■ · - - 2 -

109828/1763

amates such as hydroxyethyl or hydroxypropyl carbamate; it was found that these suffered from certain inadequacies, such as with regard to abrasion resistance, piss resistance and the handle, which prevents their optimal large-scale development to have. Although these sizing agents compared to conventional, nitrogen-containing sizing agents, v / ie dimethylolethylene urea or methylated methylolmelamine for damage due to chlorine and the resistance to acid hydrolysis are essentially superior, in some cases they still allow something w ^ ij-ow ^ n left. The present invention is now directed overcoming these shortcomings and creating treated fabrics with improved properties.

The present invention is based on the discovery that sizing agents for the treatment of cellulosic textile fabrics, which according to the reaction of formaldehyde described below with an alkoxyalkyl carbamate, the preparation of Allow fabrics with superior properties to the sizing agents prepared according to known methods of alkyl or HydroxyalLylcarbamaten are derived. It was not to be expected that the methylolated alkoxyalkyl carbamates described herein are superior finishing agents to both methylolated ■ Alkyl carbamates as well as methylolated hydroxyalkyl carbamates are. Without wishing to be bound by any theory, the present invention believes that this superior behavior is in part is based on the superior lubricating properties of the methylolated alkoxyalkyl carbamate, since the fiber lubricity is a is an important factor in determining many tissue properties.

109828/1763

1819185

Those used in the production of the textile treatment agents according to the invention Alkoxyalky! carbamates used are compounds of the general formula:

; ο ... ■■ .- ■■■■ - ", ■ '.-.

; RO- (E'-O) _n -O-IJH ₂ :

in which R stands for an alkyl group having 1-8 carbon atoms, preferably 1-4 carbon atoms; E ¹ denotes an alkyl group with 2-3 carbon atoms, and η is an integer with a value of 1 to 10, preferably 1 to 3 * öie can according to any. one of the known processes. It is particularly useful to prepare it by reacting urine with a glycol ether of the formula: ■ - "-_ ■

EO- (R'-O) _n -H ... '■

in y / elcher E, E ^ and η have the above meaning * for the formation of the Alkoxyalkyleybamates and release of ammonia * glycol ethers According to the definition above, the methyl, Athjtr * B'utyl-f isO-butyl, Hexyi- and 2'-ethylhexyl ether from Ithylehglyköiι propylene

glycol, diethylene glycol »DiprGpyiehglykoi, IDriäthylehglyköl, Tripföpyienglykölι Pölyäthylenglykolj Polypropylehglyköl and mixed polyethylene / polypropylene glycol *

The alkoxyalky! Carbamates described above are made with formaldehyde to form the methylolated Alköxyalkylcarbamate implemented j the according to the invention are used as textile finishing agents * The exact structure of the reaction product of i'ormaldehyde / with the Alkoxyalkyl carbamate was not fixed, but it is assumed that it is a mixture of monomethylol and dimethyloid derivatives acts, d * h * a mixture of one

1-0182071763

N-methylolalkoxyalkylearbamate of the formula

0 H

RO- (R'-O) _n -GN S ■ ·

and a Ν, Ν-iimethylolalkoxyalkylcarbainate of the formula:

OH ₂ OH

0 R-0- (R'-O) -G-N ^

where R, R ¹ and η have the above meaning. In addition to the combined formaldehyde represented in the reaction product by the methylol radicals, it is assumed that some formaldehyde is also present as free formaldehyde and some as combined formaldehyde in a form that has not yet been determined.

Although the conditions for carrying out the methylolation the Significantly influence the behavior of the reaction product, the reaction conditions are not very critical. A suitable one Method is to add the alkoxyalkylicarbamate in water Dissolve, add the formaldehyde to the aqueous solution, the pü value . set to the desired value and then heated the mixture for the time necessary to carry out the methylolation. After cooling, neutralizing, diluting with water and filtering, the product is a clear, colorless solution of the methylolated Alkoxyalkyicarbamates obtained.

109828/1763

The Eeaktion of formaldehyde and the Alkoxyalkyloarbaiiib "can at temperatures of about ⁰ SO G., preferably about 50 ^Q C, somewhat over 100 0., durchgefürt to Rüokflußtemperatur the Reaktiönsmisohungid.h. It may reaction times of about 10 minutes to about. Can be used for 24 hours, preferably for about 1-5 hours "The original pH value of the reaction mixture should be between about 4-10, preferably between about 8-10"

The most important factor in determining the behavior of the Finishing agent is the applied ratio of formaldehyde to alkoxyalkyl carbamate. Particularly suitable reaction products according to the invention are prepared by adding formaldehyde to the: alkoxyalkyl carbamate in a molar ratio of about 1.5 to about 3 moles of formaldehyde per mole of alkoxyalkyl carbamate, preferably in a molar ratio of about 2 to about 2.5.

The textile fabrics which can be treated with the sizing agents according to the invention are cellulosic textile fabrics. As used in the present application , the term "cellulosic textile fabrics" includes woven or knitted fabrics and clothing and other materials made from such fabrics, and further refers to cellulosic fabrics including regenerated cellulose and cellulosic fabrics. The oil-free textile fabrics thus include cotton fabrics, linen fabrics, rayon fabrics, fabrics made from mixtures of cotton, linen or rayon fibers, and fabrics made from mixtures of cellulose fibers and non-oil-based fibers. Faoe Islands.

100020/1763

"■." ■ - - 6 ■ - ■

The finish can be applied to the cellulosic textile fabric in any known in a suitable manner, e.g. by dipping or padding will. Usually the finishing agent (this term used herein refers to the reaction product also formaldehyde and the alkoxyalkyl carbamate) the fabric from a aqueous solution · applied. Such aqueous treatment solutions If necessary, in addition to the finishing agent, other materials used in textile finishing, such as plasticizers, Means for softening, grip improvement agents or weighting agents etc., included

The amount of finishing agent to be applied to the fabric will depend largely on the type of fabric and its intended use, and the present invention thus relates to the use of any effective amount. Usually, amounts of about 1 * 30 wt ■ -. $ _ Appretierungsmittel, based on the weight of the textile fabric ", ie an increase or inclusion of about 1-30 ft used * is preferably used an amount of at least about 4 $> In every particular finishing process, the uptake depends on the concentration of deai, the finishing agent in the treatment solution and the weight of acid that the textile fabric ssurüokhälif d »h # the liquid uptake». A liquid uptake of about 50-120 % can easily be achieved during normal processes, whereby the treatment solution applied to the textile fabric according to the invention can contain only about 2 $ or less to about 25 $ or more of finishing agent therefore no difficulties arise.

1 09 82 8/1? β 3

1819185

After der.Aufbringung to the textile fabric, the erf indungsgemäßen, methylQlierten Alkoxvalkylcärbamate require, such as the known nitrogen-containing TextiIfinischmittel, curing to accelerate the Eeaktion with the lasers desvGewebes, whereby the desired properties such as crease resistance and ¹¹ ViT ^ i-wear "properties Suitable catalysts for the hardening are metal salts of strong mineral acids, especially zinc fluoborate, "and the hydrates of magnesium chloride and nitrate. Usually the catalyst is added to the aqueous treatment solution; it should be used at a concentration sufficient to give a catalyst retention of about 0.5-5% by weight based on the weight of the fabric. * The optimum amount of catalyst will vary according to the particular catalyst used. With magnesium chloride, a weight ratio of fabric retained catalyst to sizing agent of about 0.2-0.6 is preferably used, while the preferred ratio for zinc nitrate or zinc fluoroborate is between about 0.05-0.2.

After the application of the aqueous treatment solution, the fabric is treated with heat to remove water; The hardening then takes place through the application of further heat. It is preferable to dry the fabric at temperatures that are below -denjenigen that werdai applied during curing Thus, the drying is usually conducted at temperatures up to about 150 ⁰ C., while in the curing temperatures of typically about 150-200 ° CU can be applied. The time required to achieve <1% curing varies from only about a minute or less to / Larger amounts of catalyst within the specified range are preferably used by the hWaevm. Absorption values of finishing agents used. 1 0 9 8 2 8/17 6 3 ^r

to about 5 minutes or more. If necessary, the usual hardening, i.e. curing immediately after drying, or delayed curing, i.e. curing after the Fabrics that have already been processed into a garment can be used.

Important aspects in the finishing technology of cellulosic Textile fabrics are resistance to chlorine damage caused by hypochlorite bleach and resistance to conditions that require acid hydrolysis

"Accelerate, such as cleaning Iw. scrubbing with acid. The invention treated textile fabrics have in many cases a superior resistance to damage by chlorine and / or improved resistance to acid hydrolysis compared to tissues made with known methylolated alkyl and hydroxyalkyl carbamates. In particular it was found that the methylolated alkoxyalkyl carbamates are usually are equivalent to the methylolated alkyl carbamates in resistance to damage by chlorine, while they

^ are superior in resistance to acid hydrolysis. on the other hand The methylolated alkoxyalkyl carbamates are usually the methylolated in resistance to acid hydrolysis Hydroxyalkyl carbamates are equivalent, but predominate in resistance to chlorine damage, in particular by being a show excellent resistance to chlorine damage even under the treatment and curing conditions of the fabric be varied greatly; in the case of the methylolated hydroxyalkyl carbamates, on the other hand, very specific treatment requirements must be adhered to The curing conditions of the substance are of decisive importance.

109828/176 3

speed. These are important and unexpected differences that are partly to distinguish the • present invention from known ones Process serve. ._., .- '■

In addition to the excellent resistance to acid hydrolysis, the associated wakefulness and its jj'ähiigkelt to achieve a fabric that is not damaged by / hypochlorite ^ bleaching solutions the finishing agents according to the invention from methylolated alkoxy / alkyl carbamates result in improved abrasion resistance “Nd in certain cases a more comfortable grip than: compared to the methylolated alkyl and hydroxyalkyl arbamates. On molar They are still more effective and just as effective on a weight basis as the known finishing agents.

The evaluation of the inventively treated fabric "according to ASTM or AATOC test procedures or by the methods described in the foliowing method» The following tests were ^conducted:. :; - y "Wash-wear" rating: determined in accordance with AATOG Tentative Test Method 88A-1964T. The rating, which is a sign of the smooth appearance of the fabric, is between 1 and 5, with intermediate values being given as + and f · ν ^; : -. \ '^; .. \' ^: " _: ': Wrinkle recovery? determined according to AATOC Tentative Test Method 66-1959T. ^>:;

Tensile strength: determined ingeniously by ASTM method D39-49 (Grab Test). Tear strength: determined according to ASTM method D H24-56 (Elmendorf), Abrasion resistance; determined according to ASTM procedure Dl175-51T-B. Damage from retained chlorine: determined according to AATOC Standard procedure 92-1962 * /

109828/1703

■ - ίο -

Resistance to Acid Hydrolysis: Samples of the treated tissue were made. Hydrolyzed for 30 minutes at 60-65 ⁰ in G. Clark and Lubs buffer solution at a controlled pH, then washed in cold water, dry ironed, conditioned and tested on dry crease recovery.

The following examples illustrate the present invention without limiting it.
B 'eis ρ ie 1 1

119 g of methoxy / ethyl carbamate F (prepared by reacting urea with ethylene glycol monomethyl ether), 66 g of paraformaldehyde and 120 g of water were placed in a reaction flask; the molar ratio of formaldehyde to methoxyethyl carbamate was 2.2: 1. The pH of the slurry was adjusted to 10 by adding 10 $ -i &NaOH; then for 2 hours to form the methylolated Methoxyäthylcarbamates was heated to RücMLuß, whereupon neutralized, diluted with water to 50 i * active material and was filtered.

Samples of desized, cleaned, bleached and mercerized, white cotton printing material with a thread count of 80 χ were padded with a treatment bath containing the methylolated methoxyethyl carbamate * in each pail the treatment bath consisted of methylcarbated methoxyethyl , MgCl ₂ . 6H ₂ O, "Farbritone PE" (commercial softening agent of an emulsified polyethylene wax with 30 Festatoffgehalt fo) and "Tergitol TMN" (trade name for a nonionic surfactant, trimethyl-nonylather of Polyathylenglykol)

109828/1763

where der'Rest consisted of water. Hach the treatment of the wet material was applied to a pin frame, 1.5 minutes at 150 ⁰ C. cured dried, and 1.25 minutes at 175 ⁰ C..

For comparison purposes, identical samples of the cotton print fabric were treated as above, but instead of the methylolated methoxyethyl carbamates, methylolated ethyl carbamate was used. The methylolated ethyl carbamate had been prepared under the same reaction conditions with a molar ratio of formaldehyde to ethyl carbamate of 2.2: 1 (the reaction mixture consisted of 89 g of ethyl carbamate, 66 g of paraformaldehyde and 90 g of water, and the treated tissue samples were as above in Case of the methylolated methoxyethyl carbamate dried and cured. The composition of the treatment bath and the absorption values, which were the same in each particular experiment for the methylolated methoxyethyl carbamate and the methylolated ethyl carbamate, are listed in Table 1 below; the properties of the treated substance are given in Table 2 , "are treated _w χ liiertem Methoxyäthylcarbamat samples -B referred to.." wherein said treated with methylolated Athylcarbamat tissue samples with A and with me i / ^':

1 0B828 / 17 63

Table 1

Treatment bath; Sew. -jo

Attempt. At> pret »MgCl ₉ .6H ₉ O" Pabritone "lergi-Ir. ' medium ■ '* * . . PE " toi TMN"

3 "

5.0

7.5

10.0

12.5
15.0

17.5
20.0

1.0
, 5

2.0
2.5
3.0
3.5
4.0

1.8
1.8

1.8

1.8
1.8
1.8
1.8

0.1 0.1 0.1 0.1 0.1 0.1 0.1 uptake; Gew * - ^ of the substance or tissue Appret. MgGl ₉ -6H _p 0 "Pabritone PE" medium.

0.8 i, 2 1.6

2.0 2.4 2.8 3.2

0.4 0.4

0.4 0.4 0.4 0.4 0.4

CD CO CX)

labile 2

Tissue-
sample dry putty
recreation
Warp + weft
(Degree) Eeälfestigk.
Warp + weft.
Cg) Tensile strength
Shot Wash-wear Rating Abrasion
*. ** strength
(Cycles ,,
until, to
Fracture) ¹ 2 '
2 691
Θ94 _i dry creases
recovery after hydro
lysis, at pH 2 1 -A. ■■
tB ". 233
232 ■. . ■■. ,. ■,,
1270
1300 8.6
9.5 2+
2 ·> 3
2 388
466 204
214 ρ "ft
2 B , · 268
256 1140
1120 "lall 3+
3 .. ' ..3 +. 313
400 217
223 3-A ■
3-1 278
277 970
1070 8.2
w - ■ '■': ■ 4-
4- 4th 207
281 237
243. 4-A '
4-B, ' 291
287 '■ / ^: 910 ■■; ■.: ■' : 8.6 ν ·· '■: ■; ■
7.7 4+
.4 + 1 ■■ 4th
3+ 170
206 ■■ ... '. ■■■ / '243 ■' '"■:
, 2 ^ 58 /. ■ ■■ ...., -. 5-A · '.
5-B: ■ ;. ■ '■ 285''"' ■. · '■■'
288 ': 870
930 8.6
8.6 : 4+ ■
■ 5r; ' 4 ·
4+ 163
174 V U6 \ ■. ■ '. ■
O CT i * ^ ^: 6-A
6-B .290
297 770
900 8.2
7.7 4+
4+ 116 265
261 7-B '- ■ 297
289 750
850 7.7
8.6 5- Γ ■ '
5 ~ ' 261
274 V

α. dried by tumbling, ■ _:
= kneaded by centrifugation

109828/1763

CD CD OO

cn

As can be seen from the data in Tables 1 and 2, the methylolated methoxyethyl carbamate according to the invention used with the tissue samples designated as B results in improved bite resistance, abrasion resistance and resistance to acid hydrolysis compared to the methylolated ethyl carbamate used with the tissue samples designated as A, while a at least equivalent behavior with regard to the other fabric properties is obtained. Furthermore, it has been found that the methylolated methoxyethyl carbamate gives a treated fabric with a more pleasant feel than the fabric treated with methylolated ethyl carbamate.
Example 2 *

Various methylolated alkoxyalkyl carbamates have been prepared and evaluated as finishing agents for cotton fabrics; methylolated hydroxyethylearbamate was prepared for comparison and evaluated in a similar manner. The methylolated alkoxyalkyl carbamates were prepared by dissolving paraformaldehyde in an aqueous solution of the corresponding alkoxyalkyl carbamate (prepared by reacting urea with the corresponding glycol ether in the presence of zinc acetate as a catalyst) in an amount of 2 moles of paraformaldehyde per mole of alkoxyalkyl carbamate solution of paraformaldehyde heated to about 8O ⁰ G. and the mixture is then allowed to stand at room temperature for several hours. The methylolated Hydroxyethylcarbamä was prepared by i-araformaldehyde with Hydroxyäthylcarbamat (prepared by reacting equimolar amounts of Ethylencarbou «^ and ammonium hydroxide in aqueous solution at 0-1Ö ° G. For a period of 2 hours) in a ratio of 2 mol paraformaldehyde

10 9 8 2 8/1763

-15. "- ■ converted per mole of hydroxyethyl carbamate.

The carbamate sizing agents were applied to samples of descaled, cleaned, bleached and mercerized white cotton print fabric with a thread count of 80-80 at different levels of sizing agent and catalyst pick-up using a Butterworth laboratory padding device. In each case the catalyst used was MgOIr, .6H ₂ O, and the treatment bath contained 0.1% by weight of "Tergitöl TMN". After treatment, the wet fabric was stretched on a Hadelrahmen, dried 1.5 minutes at 150 ⁰ O. and 1.25 minutes at 175 ° C. hardened. The uptake values and properties of the treated fabric are shown in Table 5.

109828/1763

Finishing center recording

of

methylolated.
Hydroxyethyl

Carbamate

methylolated.
Methoxyethyl carbamate

methylolated.

Ethoxyethyl

carbamate

methylolated.

Butoxyethyl

carbamate

methylolated.
Is obut oxyethylxbamate

4 3

8 1

8 2

8 3

8 4

. 3

4 3

8 1

8 2

8 3

8 4

3

4 "■ 3

8 1

8 2

8 3

8 4

3

⁴ ?

8 1

8 2

8 3

8 4

12 3

⁴ ? 8 1

8th ·

8th

8th

12th

Table 3
.Crease-

Shot

chain

^(Degree )

⁺ nb = not determined

251 790 256 900. 264 86.0.

269 680, 276 810, 260 690

255 660

237 850

. 266 710

263 640

273 550

267 660

247 610 '

252 660.

253 590

270 570, 263 580 272 580.

235 620

229 720.

237 660.

256 600.

263 560.

246 640.

247 600

207 770

226 640.

259 620

258 580.

247 640

109828/1763

10.4

.12.7

12.7

8.6

11.3

10.0

10.9
10.9

10.9

10.9

10.4

9.5

8.2
10.9

9.5

9.1
10.0

10.4

8.6

13.2

11.8

9.1

10.0
10.0

10.0
13.6
11.8
9.5
11.8
10.0

3+

5-

4-

nb *
5-

4- 5+.

n.b- nüb »

5- 4-

2+

2+

'4-4
5-

3+

3+

5-

4-

4th
4th
4th

4-

2-

3+

5-

4-

2-

4-

4-

3-

2+

4-

4-

2+

reason v. back content of chlorine

not determined not determined not determined

74

not determined not determined

10.5

not determined not determined

13 not determined

not determined not determined not determined

10

not determined not determined

not determined not determined not determined

not determined not determined

not determined not determined not <5 determined

not

not ^ firmly immt

cn 5fe

The data in Table 3 show that the loss of strength of the tissue due to chlorine damage with the methylolated alkoxyalkyl carbamates according to the invention is significantly lower than with the known methylolated hydroxyethyl carbamate. For example, when 8% was taken up, there was a finishing agent. and io the catalyst lestigkeitsverlust aufgrundvon retained chlorine evaluated 3 with methylolated Hydroxyäthylcarbamat 74 $ 13 $ in comparison with höchsteng for the four, methylolated Alkoxyaikylcarbamäte. The data also show that the methylolated alkoxyalkyl carbamates generally give at least comparable behavior in terms of environmental recovery, wash-wear properties and tissue strength to the methylolated hydroxyethyl carbamate. ^: ; \ -

Example 5 ':

This example shows the effect of the methylolation conditions on the behavior of the methylolated Methoxyäthylearbamatea as a finishing agent for cellulosic textile fabrics A strength (warp + weft) of 1180 g and a tensile strength (weft) of 16.8 kg were used. The catalyst was MgCl _{2 .6H 2} O, the uptake was 4% of methylolated methoxyethyl carbamate and T, 2 catalyst and that treated fabric was dried for 1.5 minutes at 150 ⁰ C. and cured 1.25 minutes bei175 ^0C. In the second series of tests, the same cotton printing material was used. The catalyst was Zn (NQ ₅ ) ₂ .6H ₂ O; the uptake was 4 $ to methyloliertemMethoxyäthylcarbamat and 0.2 io of catalyst; and the treated material was: 1.5 minutes dried at 1 50 ⁰ C, and 1.25 minutes at 165 ⁰ G, cured.

109828/1723

In the third series of tests, the fabric used was a cotton fabric with a thread count of 136 × 64, a dry crease recovery of 155 (degrees), a hot strength (warp + shoe) of 1520 g and a tensile strength (weft) of 27.7 kg MgCl ₂ .6H ₂ catalyst was Oj recording was 4 $> at methylolated Methoxyäthylcarbamat and 1.6 fi of catalyst; and the treated fabric was dried for 1.5 minutes at 15O ⁰ G. and 1.25 minutes at 175 ° C. hardened; The reaction conditions when carrying out the methylolation of the methoxyethyl carbamate and the properties of the fabric samples which had been treated with the finishing agents produced under different reaction conditions are listed in Tables 41 5 and 6 for test series 1, 2 and 3.

109 828/1763

initial Reaction temp.
C. Tabel 4th 5 ' 1170
1120 Tensile strength Loss of tensile strength molar ratio PH value Time
hours 103
103 dry crease Tear strength 1040 Shot due to returned
holding chlorine
'■■ *:. · '. ■■■. ■ of formaldehyde too
Carbamate 10
■ ίο 2
2 103 recreation
Chain shot
(Degree) Warp + weft
S. 960 12.7
10.4 not determined
not determined ^1: 1 st
I.
1.5: 1 |. . 10 ': 2. 103 199
237 • 1260
1130 930 \ 10.0 not determined * 2: 1> 10 2 103 257 1060 10.0 9 · '' ■ '; '■ 2.5: f 10 2 '268 1010 10.0 103
103 274 ^: 930 10
10 2. '
■■ '2: 103 Tabel 12.2 .-
10.9 not determined
not determined 1: 1
1.5: 1 10 2 103 197
231 10.6 ■ ■ ■■ ' 1 ''' / '':. . · 2: 1 10 ; ■ 2 103 267 10.0 , ■ .. ■■■■ "V ⁵ ■" ■. ' ■ '■■■■.'. '. 2.5: 1 10 2 ', 273
■ 8j6 ¹ '■ ■ ■ . ■■■ '3: 1' ■■, ■ '/ ■ 283 /■.■■: '

10982871763

f OO CXl

Tabel

molar ratio. .tteaktxons- track.Knitter- tear strength. Zugfeatigk.

v. .Formaldehyde to pH. zext, temp. ' er.o: lung chain + ■ .; Λπιβ shot

Carbamate std GC *. Chain. + Weight,: g kg

Terluat bxl tensile strength due to: 7: 021 holding CtLLor

TQ 2 103 2S8; TQ9Q T T, 8 12th 8 ^: 2 TÜ3 254 ΐΌτσ TQ-, 4th ..: 23> ' 6th Z 103 264 .1020 10.9 ^ TQ 4th 2 ■: TQ3 257 1070 TT. 3 21st TO Q, 25 TQ3 265, 1040 1T, 8 10 TQ 0.5 103 263 T040: 10.9 5 ' 10 " 1 103 259 1060 12.2 4th 10 ■ 5- 55 26Q 1120 10.0 12th 1Q 2 85 253 ' T020 9, T. 23 TQ 2 257 T07Q T2.7 25th

109828/1763

■ · - ■ '■. - ²¹ - ■ ■ ■ ■ ■: - - ''"From .the data in Tables 4, 5 and 6 shows» daßvdie invention methylolated Alkoxyalkyleärbamat-Appretierungsmittel can be made over a relatively wide area Methylolierungabedingungen and show up yet effective * the molar ratio of formaldehyde to Alkoxyalkylcarbamat is the most important variable, check the crease recovery and increased tear strength and tensile strength ATake, when the iOrmaldehyd / increased Alkoxyalkylcarbamat ratios. ^'v

Be is ρ i e 1 4

Methylolated methoxyethyl carbamate and methylolated hydroxyethyl carbamate were evaluated from sizing agents for cotton fabrics using various methylolation conditions and different fabric treatment and curing conditions. The methylolation and fabric treatment conditions are summarized in the following table for convenience, while the properties of the treated fabric are given in Table 8. In / that case MgOIp.6HpO was used as a catalyst and the treatment bath contained 0.1% "Tertigol TMN". The fabric used was stripped, cleaned, bleached and mercerized white cotton print material with a thread count of 80 80; in each case was padded with a Butterworth laboratory-block device in a nasaen pickup of 80 fo T and then, dried for 5 minutes on a pin frame at 150 ⁰ O.. · ^:

100828/1763

Test Sr.

Finishing agents

Table 7

MethylolierungsbediiLgunffen 'molar RATIOS. pH time v. Formaldehyde. Value std to carbamate

Temp,

B-2 B-3 B-4

B-6 B-7

methyloliert .Methoxyäthylcarbamat i

methylolated.Hydrpxyät hylcarbamat

Il

It

η it η η 2.2 *

2.2 * 2.2 * 3.3 *

2.5 * 2.5 ⁺ 2.2 *

2.2 * 2.2 *

10 **

10 ** 10 ** 10 **

10-11 -11 10 **

«Methylolation with paraformaldehyde (95 1 ·>)

= adequate pH value

= Methylolation with formalin. (37.5 ° F) ■ «constant pH value during methylolation

2 2

2 2 2 2 2 2

Reflux

H Il

Il

50 50

Reflux 50 50

109828/1763

- 23 ^

CD
Φ
a?
φ

eft

Pi Φ

fciJ

-d

■ Η 0} ta

: cö

όΐ

f ^

I R

rl

+ • Η

pi

<a αϊ

US tiS lh

t \ j O N C \ j

Lh th lh lh ih ipj cy csl e \ j Oj

ρ c ~ - t ~ -

i t

vö

O. (o

O in in O -O ir \ α

t- 't -Φ h->> * t- KO

OO whether ö

CVl (Oi r "OJ (O ¹ ^

ι ρ ι ii ι

s ^ jv <4 "pqr- pcj .GQ pq

pci pq

Finishing agents dry-crease'- 253 r Table 8 WantL we ar evaluation ** Vexj.u.Kiii a tensile strength I.
ro test recreation 260 Tear strength . Tensile strength due to returned! Fr. Warp + weft 244 Warp + weft Shot Chlorine; <$> (Degree) 245 G kg 3- methylolated. 255 239 4th 2,, A-1 oxyäthy1garbamate 243 450/210 10.4 certainly π 263 = dried by tumbling not 3+ 3 A-2 Il 260 460/200 9.1 4 * 3 6th A-3 methylolated.Hydroxy-2 57 460/170 ■ 8.6 4+ O B-1 ethyl carbamate 500/210 10.4 certainly π not certainly 26th B-2 η 460/200 10.4 not 3+ 45 η 530/220 10.4 4th 3- 60 B-4 500/220 10.4 4th 3+ 87 B-5 " 530/210 10.4 4th certainly 87 π 530/220 10.4 not 87 B-7 530/260 9, T.

109828/1763

From the data in Tables 7 and 8 it can be seen that methylolated Hydroxyäthyloarbamat a, good resistance to damage only supplies by chlorine if a very high formaldehyde / carbamate ratio is used in the methylolation, causing the fabric an unpleasant, very strong formaldehyde odor receives. Changes in the pH value also affect it in the treatment bath or changes in the curing conditions the resistance to chlorine damage to one with methylolated Hydroxyäthylcarbamat treated tissue essential, however with a methylolated methoxyethyl carbamate little effect on the resistance to chlorine damage. Therefore, one is significantly less in the case of methylolated methoxyethyl carbamate precise control of the tissue treatment conditions possible. This distinguishes the methylolated alkoxyalkyl carbamate sizing agents of the present invention substantially different from the known methylolated hydroxyalkyl carbamate sizing agents.

109828 Al 763 V ί IX

Claims (1)

! .-. A method for treating a cellulosic textile fabric. characterized in that one, effective on the textile fabric Amount of the product from the reaction of formaldehyde with. an alkoxyalkyl carbamate of the general formula: 0. RO- (R'-Q) _n -C-NH ₂ in which R stands for an alkylene group with 1-8 carbon atoms, R ^{1 stands} for an alkylene radical with 2-3 carbon atoms and η is an integer with a value from T to 10, applies. 2. Process according to claim 1, characterized in that a compound is used in which R is an alkyl group with 1-4 carbon atoms and η is an integer with a value of 1 to 3. 1 and
3. Process according to Claim 2, characterized in that the formaldehyde and the alkoxyalkyl carbamate are reacted in a ratio of about 1.5 to about 3 mol, preferably about 2 to about 2.5 mol, of formaldehyde per mole of alkoxyalkyl carbamate. 4.- Method according to claim 1 to 3, characterized in that the reaction of formaldehyde and the Alkoxyalkylcarbamat at a temperature of about 5O ⁰ C. to about the reflux temperature of the reaction mixture is performed. 5.- The method according to claim 1 to 4, characterized in that the reaction of formaldehyde and alkoxyalkyl carbamate via a Duration of about 1 to about 5 hours is carried out. 6.- The method according to claim 1 to 5, characterized in that the initial pH of the reaction mixture to about 4 to about 109828/1763 10, preferably about 8 "to about 10 *. 7. - Verfaüaren according to: Claims 1 to 6, characterized in that the reaction product is applied to the textile fabric in an amount of at least about 4% by weight, based on the weight of the textile fabric "; - ': -_-'. 8.- The method according to claim 1 "to 7, characterized in that as alkoxy alkyl carbamate methoxyathyicariDamat is used. 9. Cellulosic textile fabric, characterized in that .that it with the reaction product of I'ormaldehyde with an alkoxyalkylcartamate the general Bormel in which B stands for an alkyl group with '1-8 carbon atoms and B' for an alkylene radical with 2-3 carbon atoms and η stands for an integer with a value of 1 "to 10, in a ratio of about 1, i? up to about 3 moles of formaldehyde per mole of alkoxyalkyl carbamate has been treated, the treated fabric containing about 1-30% by weight of this reaction product, based on the weight of the untreated fabric. The iatentanwalt: 109828/1763