DE1469507B - Process for the aldehyde treatment (For malisierung) of cellulose, cellulose esters or starch - Google Patents

Description

For textile finishing and especially for crease-proof finishing and to reduce the swellability and increase the wet tensile strength and For shrinkage resistance, it is known to treat cellulose with aldehydes, in particular formaldehyde. At 5 When the cellulose is formalized, some of the aldehyde on the fiber is converted into polyoxymethylene over; In addition, an ether-infecting crosslinking occurs in the presence of acidic catalysts via methylene bridges and to an acetal ring formation with two adjacent hydroxyl groups. In general, these reactions only take place on the fiber surface.

Often the formalization does not involve aldehydes alone, but urea-aldehyde precondensates, e.g. B. as 15 to 30% aqueous solutions, applied to the tissues to be treated with the addition of organic acids or acidic salts. To squeezing off the excess liquor is first pre-dried at low temperature and then reheated. The precondensates condense to form crosslinked water- and alkali-insoluble ones Resins. In addition to the resin formation, there is also a certain formalization of the fibers, so that too there is a reduction in the swelling capacity. Lately attempts have been made in so-called "tamed" Formalization processes through the use of formaldehyde-releasing products instead of formaldehyde solutions carry out non-iron equipment yourself.

In all of these processes, however, it is difficult to determine the amount of formaldehyde that has accumulated in advance or to regulate these reproducibly. In many cases, concentrated formaldehyde solutions are used used with large amounts of acid, which decompose the material to be treated. At a Normal formalization will only actually produce relatively small amounts of formaldehyde the cellulose is absorbed while the rest is lost.

When using the already known precondensates of formaldehyde with alkyl carbamates, z. B. formaldehyde methyl carbamate, the nitrogen of the precondensate is bound to the Cellulose instead, which is opposed by the high nitrogen content of the cellulose treated in this way shows the relatively lower nitrogen content of the untreated cellulose. A nitrogen fixation therefore leads to great difficulties because it tends to bind chlorine Washing of the products finished in this way occurs. The one bound via the fixed nitrogen When heated, for example when ironing the fabric, chlorine is decomposed, decomposing the nitrogen-chlorine bonds released and leads to discoloration and damage. The chlorine is bound in primarily through a substitution of hydrogen atoms bound to nitrogen by chlorine, the however, also observed with organically substituted nitrogen atoms bound to the tissue will.

In contrast, the present invention now relates to a process for treating aldehyde (Formalization) of cellulose, cellulose esters or starch in the presence of a catalyst and a carbamate, which is characterized in that the treatment with an aqueous Carries out mixture that an aldehyde and a carbamate of the general formula

NCOOR ₂
R ₁

contains in a ratio of 3 to 60 moles of aldehyde per mole of carbamate, where R ₁ and R ₃ denotes a hydrogen atom, an alkyl radical or a carbocyclic aryl radical and R ₂ denotes an alkyl radical or a carbocyclic aryl radical, and is then heated to temperatures of up to 205.degree .

The essence of the present invention is to be seen in the fact that it was carried out under such conditions is that although the aldehyde is bound in the desired sufficient and always controllable amount, without nitrogen addition takes place. This is surprisingly made possible by the fact that instead of a precondensate, a mixture of Aldehyde and carbamate are used, the temperature being considerably increased during subsequent treatment can increase. The carbamate apparently only serves as a carrier for the formaldehyde, so that more Aldehyde can combine with the cellulose ester.

The products treated with the method according to the invention have excellent ironing resistance, Color fastness, dirt repellency, resistance to rotting and the like the content of the added aldehyde by simply setting the aldehyde concentration uniformly set ^ whereby there is no binding of nitrogen.

Cellulose, such as cotton, α-cellulose, can be regenerated with the method according to the invention Cellulose or rayon, copper ammonium rayon or viscose rayon or paper or cellulose esters, such as cellulose acetate, Cellulose acetate butyrate and cellulose acetate propionate.

The cellulosic material to be treated can also be made with synthetic fibers, e.g. B. polyester fibers, such as Polyethylene terephthalate, acrylic acid fibers, e.g. B. made of polyacrylonitrile or acrylonitrile vinyl chloride, polyhexamethylene adipamide fibers, Polypropylene, propylene-ethylene mixed polymer and vinyl chloride-vinyl acetate fibers may be mixed.

The main aldehydes are formaldehyde, but also glyoxal, methylglyoxal, glutaraldehyde, Acetaldehyde, propionaldehyde, butyraldehyde and hydroxyadipaldehyde can be considered; this is glyoxal preferred to increase strength. Instead of formaldehyde, other formaldehyde suppliers can also be used such as paraformaldehyde, trioxane and hexamethylenetetramine can be used. However, these extend the duration of treatment due to the elimination of formaldehyde.

If alkyl carbamates of the general formula H ₂ NCOOR are used as the carbamate, the alkyl radical can be methyl, ethyl, propyl, isopropyl, butyl, "amyl, hexyl, octyl, decyl, dodecyl, cyclohexyl" Mixtures of the most varied of carbamates can of course also be used, such as, for example, a eutectic mixture of 52% ethyl carbamate and 48% methyl carbamate.

As aryl carbamates, phenyl, the various ortho-, meta- and para-tolyl, p-butyl-

phenyl, the α- or / 3-naphthyl or the 2,4-xylyl carbamate be used.

As N-hydrocarbyl-substituted carbamates the general formula

R ₁ NHCOOR ₂

in which R ₁ and R _{2 are} alkyl or aryl radicals, N-phenyl-isopropyl, N - phenyl - phenyl, N - ρ - tolylethyl, N - phenyl - methyl, N-phenylethyl, N-methyl -phenyl-, N-ethyl-phenyl-, N-methyl-methyl-, N-methyl-ethyl-, N-methyldecyl-, N-ethyl-methyl-, N-ethyl-ethyl-, N-dodecylmethyl -, N-butyl-cyclohexyl-, Ν, Ν-diethyl-ethyl-, Ν, Ν-dimethyl-ethyl-, Ν, Ν-diethyl-methyl- or the Ν, Ν-diphenyl-methyl-carbamate can be used.

In general, higher temperatures are required to produce acrylic carbamates and N-hydrocarbyl carbamates to activate, while in contrast the lower alkyl carbamates, such as methyl carbamate and ethyl carbamate, require lower temperatures, so that the latter are generally preferred ^ the. It is useful if the carbamate "^ is used in 0.1 to 5% solution.

If you use an aqueous mixture of an aldehyde and a carbamate according to the invention, you can work at up to 205 ° C * .Dias is based on the fact that the formation of the methylol carbamate is relatively slow and the addition ^; ties formaldehyde to the cellulose. At these temperatures, the carbamate surprisingly acts only as a carrier and supports the attachment of the formaldehyde to the cellulose without binding itself to the cellulose. The temperature data relate to the actual temperature to which the treated product has been heated and which can be determined pyrometrically by determining the surface temperature or according to the infrared method. This temperature corresponds to a slightly higher furnace temperature or the temperature of the radiation source.

In order to anneal the aldehyde better to the cellulose, are at least 0.1 and preferably min- xj least 0.3 weight percent methyl carbamate, z. B. in aqueous solution or dispersion, or the corresponding amounts in mole percent and percent by weight of other carbamates can be used. If less carbamate is used, the amount of formaldehyde deposited is more difficult to control, while with amounts of at least 0.5% a very excellent, reproducible formalization is achieved. Higher amounts beyond the 1 to 5% range give no benefit.

The aldehyde is usually used in amounts of 1 to 8 percent by weight in the aqueous system used, and with a stronger formalization even 10 to 15% can be used. Lower Aldehyde concentrations are preferred, which makes the process according to the invention over the known Process highlights because the annoying formaldehyde odor is also reduced.

For example, in the treatment of cotton, α-cellulose, starch and paper in general use aqueous solutions with a formaldehyde content of 1.25 to 4 percent by weight, to add 0.25 to 1.25% formaldehyde to the material; in treating rayon and Cellulose esters can use aqueous formaldehyde solutions with a content of 2.5 to 8% to add 0.50 to 2.5% formaldehyde.

The mixture of aldehyde and alkyl carbamate can be used in a wide variety of mixing ratios and packaged as a relatively concentrated aqueous solution to be used with Water to be diluted to the desired content. For reasons of stability, the mixture preferably packaged neutrally, but can also be alkaline or acidic.

The cotton or the material to be treated is generally passed through a bath, which contains a preferably acidic or latently acidic catalyst, e.g. B. formic acid, hydrochloric acid, ammonium chloride, Magnesium chloride, calcium chloride, zinc nitrate, zinc chloride, zinc fluoborate or mixtures these substances. Since only a little catalyst is required, this can also be made available by residual acid salts on the goods to be treated, such as. B. ammonium chloride.

The formalization invention is also possible in alkaline baths, in which case alkali metal carbonates, bicarbonates or hydroxides _ver: applies to. Here, too, the alkaline catalysts can be added to the bath on the goods to be treated, usually in amounts of 0.1 to 2%.

The alkyl carbamate is preferably present in the bath in amounts of at least about 0.5%. The molar ratio of formaldehyde to alkyl carbamate is preferably about 12.5: 1. The baths you can also use the usual additives, such as wetting agents, plasticizers, Contains lubricants, optical brighteners and other protective substances.

A major advantage of the method according to the invention is that the in the usual textile finishing process' occurring loss of strength in the present case very much is less. So far you had to reckon with a strength decrease of about 40 to 50%, which you only have could compensate for this with additional treatments or solid material. In the inventive Process, the loss of strength is usually only 15 to 25%, which is essentially due to this * is based on the fact that for aldehyde addition - in contrast to the hardening of resins at high temperatures - only a relatively low temperature is required and that also a low one Sufficient catalyst concentration; It also plays a role that you can't get up to the full Dryness of the fabric must dry. The method of the present invention gives excellent results Results if you dry to a residual moisture level of 2 to 4%, usually with an resistance moisture meter is measured. However, the very best results are achieved with very dry material. Furthermore, with the invention Method of resistance to yellowing and resistance to swelling in cellulose fabrics and in particular improved for viscose rayon or non-woven viscose rayon, which also increases the shrinkage resistance will.

example 1

In order to eliminate the larger shrinkage of the edge thread in towels, those for the edges are used used cotton yarn with an aqueous solution

surig treated, which 1% methyl carbamate, 0.5% B =

Mägriesium chloride hexahydrate, 0.5% formic acid, 1.2% sodium chloride and 0.17% of a dimethyl- C =

polysiloxane) Is contains as a plasticizer. the Baths are mixed with various amounts of formaldehyde, as can be seen from the following table 1 results. After the treatment, the cotton E =

Yarns dried at 93 ° C. and then woven into the edge areas of the cotton towels, where F = the results listed in Table 1 below are achieved; The individual columns in this table have the following meanings:
A = molar ratio of formaldehyde to methyl carbamate;

Percentage of formaldehyde in the yarn in the finished towel;

Percentage of formaldehyde in the yarn in a towel washed 30 times;
Percentage of nitrogen in the yarn
finished towel;

Percentage of nitrogen in the yarn in a towel washed 30 times;
Percent shrinkage after thirty washes, calculated from the different shrinkage, ie the ratio of the difference between the width of the towel and the width of the edge of the towel to the width of the towel, multiplied by 100.

table

attempt A. B. C. D. E. F. 1 5.0: 1
7.5: 1
10.0: 1
12.5: 1
2.5: 1 0.28
0.56
0.77
1.13
0.16 0.30
0.56
0.72
0.95
0.16 0.05
0.07
0.08
0.07
0.04
0.03
0.058 0.05
0.07
0.04
0.07
0.03
0.07
0.052 -0.2
-0.8
-1.9
-1.2
1.6
6.3 2 6 (untreated control sample) .......
Average of the treated
Yarn 3 4th 5

If the methyl carbamate had attached to the yarn, the nitrogen content would, for example be at least 0.26 for a sample with 1.13% formaldehyde in the yarn (sample 4).

The tenacity retention of the yarns is excellent and does not depend on the amount of the formaldehyde absorbed by the yarn, as shown in Table 2 below, in which the individual columns have the following meanings:

A = tensile strength of the yarn layers (in kg);
B = retention of strength (in%);
C = tensile strength of the single thread (in kg).

Table 2

attempt . A. B. C. B. 1 135.0
138.5
143.5 .. 72
74 ·
77 2.41
2.54
2.72 71
71
72 2 143.5
119.0
186.5 77
64 2.67
2.59
3.72 75
68 3 4 .. 5 6 (control sample)

The values given under B are in comparison to bleached, mercerized yarn treatment with methyl carbamate and formaldehyde. When keeping the strength on untreated, i.e. unbleached, mercerized yarn (3.18 kg tear strength of the single thread) If what corresponds to the usual determination of the yarn strength is obtained, then the values are of the yarns at 80 to 88%.

Example 2

Cotton yarn is in the liquor with an aqueous mixture with a content of 0.5% magnesium chloride hexahydrate, 0.5% formic acid, 0.3% methyl carbamate and the amounts of formaldehyde given below treated, whereupon the yarns under vacuum at 82 ° C to a residual moisture content of 2 to 3% to be dried. The following Table 3 shows that the amount of formaldehyde added in the Yarn is usually about 20 to 25% of the formaldehyde content in the aqueous mixture. In this Table means

45

% Formaldehyde in the mixture;
% Formaldehyde on the treated yarn; Molar ratio of formaldehyde to methyl carbamate.

Table 3

attempt A. B. C. 55 1
2
3
4th 1.5
1.5
2.5
2.7 0.37
0.40
0.52
0.52 12.5: 1
12.5: 1
20.8: 1
22.5: 1

60 B e 1 s ρ i e 1 3

An aqueous mixture containing 5% formaldehyde, 1% methyl carbamate and 1% magnesium chloride hexahydrate is on bleached canvas with a moisture absorption of 55 to 60% applied, dried at 82 ° C to about 10% moisture content and then for different lengths of time heated to different temperatures. The A-

individual values are given in the following table 4, whose columns have the following meaning:

A = temperature (in ⁰ C);

B = duration of treatment (in minutes);

C =% formaldehyde attached to the substance after the substance! Was washed for hour at 93 ⁰ C in an alkali containing 0.25% soap and 0.50% soda and then rinsed thoroughly;

D =% nitrogen on the fabric;

E =

F =

Appearance of the fabric, which was determined after five _{washes (E 1} ) or after twenty washes (E ₂ ) according to a standard scale (AATCC) from 5 (best value) to 1 (worst value) -kg washing machine ^{washed at 40 0} C and then dried in an automatic drying system;

Shrinkage of the warp thread, also after five (F ₁ ) or twenty (F ₂ ) washes.

Table 4

A. 220 B. C. D. egg 3.5 F ₁ F ₂ 260 5 0.52 0.07 4.0 4.0 ' 4.3 4.1 300 3 0.47 0.08 3.0 4.0 2.8 2.5 340 2 0.50 0.08 3.5 4.0 2.4 2.1 300 1 0.57 0.09 4.0 3.0 1.9 2.0 Control 15th 0.58 0.09 3.5 3.3 3.5 sample - 0.04 - 8.3 -

B e i s ρ i e 1 4

A mercerized and bleached cotton cloth is treated with an aqueous solution which contains 2.5% formaldehyde, 1.0% methyl carbamate and a catalyst. The moisture absorption is 60%. The fabric is ^{dried at 82 °} C. to a residual moisture content of about 10% and then heated ^{to 127 ° C. for 3 minutes.} The following Table 5 shows that again only traces of nitrogen can be found in the treated fabric and that the carbamate is not present on the cloth immediately after heating. This is presumably an indication of the reaction mechanism, since

the carbamate is apparently decomposed by the heating, which is also shown by other investigations can be confirmed. In the following table 5 means

A = added formaldehyde after 1 hour

_ Wash at 93 ° C in a 0.25% soap

and washing liquor containing 0.50% soda

and subsequent thorough rinsing;

B = percentage nitrogen before (B _t ) or after (B ₂ ) washing;

C = crease resistance, measured as the crease angle (W + F) in the dry (C ₁ ) and wet (C ₂ ) state.

catalyst Table 5 A. B ₁ B ₂ Q C ₂ sample , 1% MgCl ₂ -6H ₂ O
+ 1% HCOOH
1% MgCl ₂ -OH ₂ O.
1% HCOOH
0.1% NH ₄ Cl 0.72
0.70
0.70
0.70 0.08
0.05
0.02
0.08
0.02 0.07
0.08
0.02
0.10
0.04 252.
259
245
257
127 212
246
234
242
159 1 2 3 4th Control
sample ...

In sample 4, the NH ₄ Cl content is estimated. The bathroom is neutral; the NH ₄ C1 residues come from the previous treatment of the substance. .

B ei s ρ ie I 5

Bleached, mercerized cotton yarn is treated with an aqueous solution containing 2.5% formaldehyde, 1.36% sodium chloride, 0.5% magnesium chloride hexahydrate, 0.5% formic acid, 0.1% dimethylpolysiloxane and contains the specified amounts of methyl carbamate. The material is then dried at 82 ° C. In the following table 6 the individual columns mean:

A = molar ratio of formaldehyde to methyl

carbamate;

B = percentage methyl carbamate;

C = percentage of accumulated formaldehyde.

1 table A. 6th B. C. sample 2 62.5: 1
20.8: 1
8.9: 1
6.25: 1
12.5: 1 0.1
0.3
0.7
1.0
0.5 0.30
0.52
0.76
0.20
0.33 ⁶⁵ 3 4th 5

109 513/357

9 10

Example 6 When placed in the oven at 52 ° C

_.,. , '.' ■ · ·. T> η · ■ j ■ -. After 25 minutes 77 ° C

Bleached, mercensed cotton yarn is marked with _XT , ,,, _Λί ·. ₈ ™ _r

. .. ". ' _T ..,, ... ILi τη / XT After 45 minutes 85 C

treated with an aqueous solution, which contains 1.3% Na- _{Naeh 93} ° C for 9Q minutes

trium chloride, 0.5% magnesium chloride hexahydrate,

0.5% formic acid and 0.1% dimethylpolysiloxane, the strength of this cloth is before and after

0.3% methyl carbamate and the specified amounts of treatment measured with a micrometer and

Contains formaldehyde. Then the yarn is also soaked in water after it has been wetted.

dried at 82 ° C. In the following table 7 are true. In the following table 8 the individual

the individual columns have the following meaning: 10 individual columns have the following meaning:

A = molar ratio of formaldehyde to carbamate; A = percentage of the formaldehyde

B = percentage of formaldehyde in solution; hyds;

C = percentage of accumulated formaldehyde. B = thickness when dry (in mm);

C = starch when saturated with water

Table 7 ^I5 (in mm).

Table 8.

sample A. B. C. 1 2.5: 1
7.5: 1
'12.5: 1
17.5: 1
22.5: 1 0.3
0.9
1.5
2.1
2.7 0.05
0.24
0.40
0.34
0.52 2 3 4th 5

B eisρ ie I 7

Mercerized cotton yarn is treated in a bath with an aqueous solution containing 0.5% Ethyl carbamate, 2.1% formaldehyde (molar ratio of formaldehyde to carbamate 12.5: 1) and 0.5% Contains magnesium chloride and 0.5% formic acid. The yarn is then dried at 93 ° C, to attach the formaldehyde to the yarn. The carbamate-formaldehyde process according to the invention reduces the swelling capacity of the substances, as can be seen from the following experiments on the treatment of Rayon needle felt fabric yields.

The following substances have been used:

a) a 230 g viscose rayon needle felt, which with a 46 g polypropylene gauze material was processed;

b) a fabric consisting of 60% polypropylene and 40% viscose rayon of 230 g each, the processed with a 28g polypropylene gauze material was;

c) a 92.4 g material made of 60% polypropylene and 40% viscose rayon, with a 28 g cotton gauze material was used.

The fabrics a), b) and c) were calendered and smoothed needle felts. An aqueous one is applied to these substances Mixture (mixture A) applied, which 1% methyl carbamate, 4% formaldehyde, 0.83% magnesium chloride, 0.83% formic acid and 0.2% nonylphenyl-ethylene oxide adduction product contains as a wetting agent.

This mixture A is applied at 50.degree. C. with a laboratory applicator, after which substances a) and b) are dried in a continuous oven at 121.degree. C. and substances) at 105.degree. The fabrics are then rolled up and left in a circulating oven _{at 105 ° C for 1/2} hour to mimic the conditions encountered in hot web rolling in conventional manufacturing processes. The temperature can be determined as follows using thermocouples in the fabric rolls:

20th Untreated substance a) A. B. C. Treated substance a) ... 0 1.02 1.73 Untreated substance b) 0.66 1.14 .1.50 ²⁵ treated substance b) . 0 1.02 1.04 Untreated fabrics) 0.51 0.86 0.91 Treated substances) 0 0.56 0.74 0.56 0.58 0.63

The treated sample has in each case a considerably lower strength in the moist state and results

, even with the already slightly swellable substance b) one

"further reduction in thickness or less swelling.

The formaldehyde addition in this and in the following examples is based on the total weight of the Of the substance.

Examples
The following substances are used:

40

a) a 230 g viscose rayon web, which is processed with a 46 g polypropylene gauze material, is calendered and smoothed;

b) a 230g of 60% viscose rayon and 40% polypropylene consisting of a web, which with a 46g polypropylene gauze material is processed;

c) a web according to b), but which is calendered and smoothed.

Mixture A from Example 7, a mixture B and a mixture are used as treatment solutions; the latter two differ from mixture A in that they contain 8% formaldehyde, while mixture C has a content of 2% methyl carbamate and 8% formaldehyde. The mixtures are all applied to the fabric with a laboratory applicator at room temperature and then extracted under vacuum. The material is dried at 127 ^° C. in a continuously operating drying system. The fabric treated with mixture A has a surface temperature of 111.degree. C., that treated with mixture B has a surface temperature of 101.degree. C. and that treated with mixture C has a surface temperature of 99.degree. This temperature difference also influences the amount of formaldehyde deposited.

After drying, the fabrics are treated with sodium bisulfite solution treated to remove the formaldehyde odor; the fabrics are then with a

Treated aqueous mixture containing 0.83% MgCl ₂ and 0.83% formic acid. The fabrics are dried after washing in a 150 ° C oven, on a twin-roll mill at 12O ⁰ C hot calendered, and then in two passes at 127 ° C on a drum of a .Two-roll compression shrinking device smoothed.

The swelling effect is determined as in Example 7 by adding the fabric in the dry state with water saturated or saturated with NaOH solution, is examined. The source properties are displayed before or

after calendering and after calendering and smoothing, the values being listed in Table 9 below, in which the individual columns have the following meaning:
■

A = added formaldehyde (in%);

B = thickness when dry (in mm);

C = strength of the substance saturated with water

(in mm);

D = thickness of the substance saturated with 20% NaOH (in mm).

Table 9

material Treated with mixture A. 0 B. C. D. a) untreated 0.72 1.07 1.37 1.78 ^: a) • A before calendering - 1.19 1.22 1.47 a) A calendered 0.77 0.91 1.19 1.37 a) A calendered and smoothed 0.60 0.91 1.14 1.37 a) B before calendering - ■ 1.14 1.19 1.47 a) B calendered 0.47 0.91 1.19 1.35. a) B calendered and smoothed 0.56. 0.81 1.12 1.42 a) C before calendering - 1.14 .1,19 1.45 a) C calendered 0.45 1.14 1.19 1.37 ^a ) C calendered and smoothed 0 0.86 1.19 1.57 b) untreated 0.44 1.57 1.47 1.73 b) A before calendering . ■■■ - , 1.35 1.40 1.37 b) A calendered 0.46 1.02 1.09 1.14 b) A calendered and smoothed 0 1.02 1.02 1.19 c) untreated 0.53 0.71 '0.81 1.07 c) A before calendering .. ■ - 0.76 0.76 0.91 c) A calendered 0.46 0.71 0.74 0.86 c) A calendered and smoothed 0.64 0.66 0.89

The values clearly show that the tendency to swell is considerable both in water and in 20% strength NaOH has been reduced. The untreated fluffy fabric b) shows an extremely high value for the strength in dry condition. If it were pressed like the other fabrics, it would have a strength of very much less than 1.47mm. There is always a significant reduction in the swellability of the substances if this contains significant amounts of cellulosic fibers, e.g. B. 10 or usually at least 20% as lower Limit, included.

Example 10

Three samples of a light white fabric containing 65% polyester fibers and 35% cotton fibers are treated with an aqueous mixture containing 1.0% methyl carbamate, 6.0% formaldehyde, 0.83% magnesium chloride and 0.83% formic acid and 0.5% acrylic polymer, namely ethyl acrylate, Methyl methacrylate, acrylic acid and acrylamide as well as 0.25% polyvinyl alcohol and 0.2% nonylphenol-ethylene oxide condensation product contains as a wetting agent. The material is then dried. The three different types of fabric are

a) a 125 χ 72 count fine cloth weighing 3 _{> 5} 3O m / 450 g;

b) a 96 χ 84 count batiste weighing 3.80 m / 450 g;

c) a 94 χ 80 count batiste with a weight ■ of 3.90 m / 450 g. > ■ · ■■. ■ ■ - ·

The moisture absorption of these substances is in the range of 35 to 40%. Is dried with a Air dryer set at 166 ° C. The working speed is 100 m / min., and the dwell time of the fabric in the dryer is 14 seconds. The substance temperatures measured with an infrared pyrometer are in a range from 118 to 124 ° C.

After drying, the fabric is passed through a sodium bisulfite solution to remove the unreacted To remove formaldehyde. The material is then washed and dried with an on Fatty acid built up plasticizer is treated, dried, and then passed through a compression shrink device guided.

The substances have a fixed formaldehyde content, which essentially also after numerous Washes remains constant. This results from the following table, in which the percentage of Formaldehyde, based on the total weight of the substance, is shown; the individual columns have the following meaning:

A = a material which is treated with a boiling 1% soda solution for 1 hour is;

B = a material which has been washed 5 times in a household washing machine, and according to the AATCC test method 88-1964T;

C = the material is sanforized 5 times for 1 hour starting at the boiling point subjected;

D = the material is subjected to 5 times for 37 minutes washed in the usual manner at 71 ⁰ C, a chlorine bleach and treated with zinc silicofluoride.

Table 10

IO

Swatch

A. B. C. 0.62 0.56 0.50 0.59 0.56. 0.56 0.62 0.61 0.62

0.53
0.52
0.61

These fabrics have excellent ironing resistance and have remained unchanged even after numerous washes Handle and unchanged color. No decrease in the degree of whiteness is found. At the When washing with colored laundry, untreated laundry items show discoloration, while the treated items Material discolored only slightly under these conditions.

Example I 11 · "" "

A heavy, previously mercerized and dyed cotton body (250 g / 0.84 m ² ) is passed through a bath containing 1.0% methyl carbamate, 4.0% formaldehyde, 0.83% MgCl ₂ , 0.83% HCOOH, Contains 1.0% acrylic acid polymer, 0.5% polyvinyl alcohol and 0.2% nonylphenol-ethylene oxide condensation product. The fabric is dried in a forced air oven at 166 ° C; the residence time is 21 seconds, and the spell temperature is measured at 110 ⁰ C. The substance is then passed through an aqueous, buffered catalyst mixture which contains 0.83% MgCl ₂ , 0.83% HCOOH, 0.50% Na ₂ S ₂ O ₅ and 2.5% emulsified tallow softening agent. Thereafter, the sheet is again dried in a convection oven of 121 ⁰ C at a web temperature of 88 ⁰ C.

Creases are ironed into these fabric sections using a steam ironing machine, with an ironing time of 15 seconds and a steam pressure of 7 kg / cm ² . The samples are then placed in an oven at 135 to 165 ° C for 6 minutes. After repeated washing, the fabric sections show the same appearance as the creases. It is advisable to add more catalyst to maintain the ironing strength in order to compensate for catalyst losses that occur in the first heating period when the material treated with formaldehyde is dried. The crease resistance is already achieved after the first hardening.

been: 300 g (3.37 mol) of ethyl carbamate are dissolved in 812 g of water. 558 g (6.7 moles) of a 36% Formaldehyde solution, the pH of which has been adjusted to 8 with sodium hydroxide beforehand added and the solution allowed to stand overnight at room temperature (about 24 ° C). the The ethyl carbamate / formaldehyde content is thus 30% and the molar ratio is 1: 2.

Starting from this solution, an application solution containing 13.5% ethyl carbamate / formaldehyde and 4% MgCl ₂ -OH ₂ O is prepared. Using this coating solution, a sample of cotton is treated strip 7 minutes heated dried at 6O ⁰ C and then for 3 minutes at 16O ⁰ C.

The solution prepared according to the invention contains 1.0% methyl carbamate, 4.0% formaldehyde, 1.0% magnesium chloride, 1.0% formic acid and 0.2% of an alkylphenol poly (ethylene oxide) condensation product as a wetting agent. The molar ratio of formaldehyde to methyl carbamate is thus 10: 1. This solution is applied also to a, cotton sample strips, after which a sample for 1 minute, and another sample 2 minutes, dried at 126 ⁰ C.

The following table shows the sample treated according to US Pat. No. 3,144,299 with "carbamate resin" denotes, while for the samples treated according to the invention the designations "303-1" and »303-2«, depending on the different drying times, are used.

The test strips are rinsed in a nonionic detergent at 60 ° C (samples A), others Samples are subjected to a washing test at 60 ° C. with the same detergent, with the treatment corresponds to about five washes in a household washing machine (sample B). In the end samples are prepared in the same way using a commercially available one containing builders Washed with detergent (samples C).

The formaldehyde analyzes are carried out according to the chromomotropic acid method, the samples being treated beforehand _{with 12n H 2} SO _{4 at room temperature overnight.} The nitrogen determinations are carried out according to the Kjeldahl method. The values given below are each average values obtained on two different areas of the test strips.

Table 11

For s ρ ie 1 12
(Comparison tests)

The following treatment solution is prepared on the basis of Example 1 of US Pat. No. 3,144,299

65 sample

A. Carbamate resin.

303-1

303-2

Comparative sample

B. Carbamate resin.

303-1

303-2 .. _T

Comparative sample

C. Carbamate resin.

303-1

303-2

Comparative sample

% N % CH ₂ O 0.36 1.15 0.10 0.51 0.11 0.75 0.05 - 0.28 1.09 0.05 0.33 0.03 0.58 0.01 - 0.37 1.09 0.08 0.38 0.04 0.64 0.05 -

Molar ratio CH ₂ O: N

1.7
4.8

5.8

1.9

3.8

10.0

1.6
6.0

QO

1469 §07

15 16

The molar ratio of formaldehyde to nitrogen has been calculated using the following formula:

% Formaldehyde / 30

Molar ratio =

(% N of the sample -% N of the comparison sample) /! 4th

The nitrogen content of the comparison sample is thus in each case dependent on the nitrogen content of the examined. A sample is withdrawn to determine the amount of nitrogen bound to the fiber by the treatment.

It is noteworthy that the samples treated according to the invention were dried for 2 minutes an average of 0.25% higher formaldelyde content than those dried for only 1 minute without affecting the nitrogen content increases, so that the ratio of formaldehyde to nitrogen for the longer dried samples is considerable increases. Under the conditions used, drying lasts 1 minute still sufficient, but not optimal.

It is essential that the ratio of formaldehyde to nitrogen in the samples according to the prior art is always below 2, while this value is always, mostly even, in the method according to the invention very substantially, exceeds.

Claims (4)

Patent claims: 1. Process for the aldehyde treatment (formalization) of cellulose, cellulose esters or starch in the presence of a catalyst and a carbamate, characterized in that the treatment is carried out with an aqueous mixture containing an aldehyde and a carbamate the general formula NCOOR, in a ratio -from 3 to 60 moles of aldehyde per mole of carbamate, where R ₁ and R ₃ is a hydrogen atom, an alkyl group or a carbocyclic aryl group and R ₂ represents an alkyl group or a carbocyclic aryl radical, and then to temperatures up to 205 ⁰ C. warmed up. 2. The method according to claim !, characterized in that a lower alkyl carbamate, especially methyl carbamate is used. 3. The method according to claim 1 or 2, characterized in that the carbamate in 0.1 to 5% solution is used. 4. Method according to claim! to 3, characterized in that the aldehyde is formaldehyde used. 109513/357