DE1126353B - Process for sizing and starching cellulose fabrics - Google Patents

Description

The invention relates to a new method for sizing and starching cellulosic fabrics Starch, and rind special application in the textile industry. According to the invention, these substances brought together in an aqueous medium with a size or sizing agent, which by a special treatment was given a positive charge.

Starch, either raw or modified, has long been used to sizing textiles in various Stages of their manufacture, as well as for starching clothes and linen in the household and in the commercial sector Laundries have been used. It is customary to use the starch in gelatinized or paste form apply. A paste is made by cooking either raw or modified starch in Water or by dispersing a pregelatinized starch in cold or warm water. Then it will be the material to be treated is immersed in the paste or passed through it or added something to it leaves a film of starch paste on the material. Subsequent drying stiffens the film the material.

Cold water starch of clothing consists of immersing the clothing in a cold water slurry ungelatinized starch and hot ironing to gelatinize the starch.

Various problems arise with these applications. For example, there is not only that Problem, a uniform film or uniform distribution of starch on the treated Good to receive, but also the problem of applying the right amount of the agent or the to achieve the correct efficiency. These difficulties are likely due to the following reasons: Cellulose-like substances have an anionic charge. Used in treatment baths cooked starches or uncooked starches used in dipping baths were previously of a nonionic type or in the same way as the cellulose well loaded. Natural starches in the unmodified state carry essentially no charge. Oxidized Starches and most starch ethers are anionic in behavior.

Because of the charge conditions, introducing cellulose material into a solution or cooked paste or suspension of starch could only lead to non-substantive moistening of the fiber or tissue, for example, or to physical entrainment of starch granules; both results may be non-uniform due to the non-homogeneity of the pastes, wrinkles in clothing, etc. The through the process of finishing and starching
of cellulosic fabrics

Applicant:

Corn Products Company,
New York, NY (V. St. A.)

Representative: Dr.-Ing. A. van der Werth, patent attorney, Hamburg-Harburg 1, Wilstorfer Str. 32

Claimed priority:
V. St. v. America of November 16, 1956 (No. 622 545)

Harry Meisel, Englewood, NJ (V. St. A.),
has been named as the inventor

Solution or liquid passing through material or that remaining in the treatment vessel is in the essentially of the same composition as that absorbed by the cellulosic material. Fiber or Tissue e.g. B. should basically remove the same ratio of solid starch particles to water as in the original starch and water combination, leaving a lower one Amount of total liquid but unchanged water-to-starch composition.

As a result of the properties of cellulose and starch just described, it is not a quantitative one Exploitation of strength is possible, and much of it can therefore be found in technical processes in the Sewage. This means an economic loss and also creates a serious sewage problem.

It has now been found that the above difficulties have been overcome while providing additional advantages when treating cellulose goods with various carbohydrates with special properties can be obtained. These carbohydrates include starches and non-ionic ones in hot water soluble cellulose derivatives which have been treated to give them a positive charge. Through the Use of carbohydrate, which is cationic in nature and thus opposite to cellulose is, these ratios between negatively charged fibers, the positive carbohydrate and the aqueous medium changed. The strength is in ali-

209 557/412

quota sharing was added to the aqueous medium.

Accordingly, the method of the present invention for sizing and starching cellulosic fabrics is thereby characterized in that the Cellülosestoffe in one aqueous medium are brought together with a cationic nitrogen-containing starch derivative, said treating agent being either a cationic starch of the formula

NH

(Starch residue) - O — C — N

ίο

R ₂

represents, wherein R ₁ and R _{2 can be} alkyl, substituted alkyl, alkene, aryl and aralkyl, or is a cationic starch which can be prepared in a conventional manner by reacting starch in the presence of an alkaline catalyst with either an amine compound of the formula

wherein R _{3 is} 2,3-epoxypropyl and 3-halo-2-hydroxypropyl and R ₁ and R _{2 are} H, alkyl, substituted alkyl, alkene, aryl, aralkyl, heterocyclic group, 2,3-epoxypropyl and 3-halo Can be -2-hydroxypropyl, or with quaternary ammonium salts of the formula

35

R ₁ -N-

R ₂
R ₃

wherein R _{4 is} 2,3-epoxypropyl or 3-halo-2-hydroxypropyl and R ₁ , R ₂ and R _{3 are} alkyl, substituted alkyl, alkene, aryl, aralkyl, 2,3-epoxypropyl, 3-halo-2 -hydroxypropyl, but when R ₁ , R ₂ and R _{3 are the} same they should not contain more than 4 carbon atoms.

Cationic amino starches are preferably used to carry out the process according to the invention a degree of substitution of about 0.03 to 0.04 and iminodiallyl carbamate starch or a cationic one Quaternary ammonium starch derivative, produced by reacting starch in the presence of an alkaline one Catalyst with

H ₂ C

C -CH,

-NR _a

55

wherein R is - CH ₃ or C ₂ H ₅ , and a cationic starch derivative prepared by reacting starch in the presence of an alkaline catalyst with a morpholine-pichlorohydrin addition product or a cyclohexylamine addition product is used.

When carrying out the process, the cellulose substances are cationic with an aqueous slurry nitrogenous starch derivative brought together in unswollen granular form.

The surprising discovery regarding cationic starch as a treating agent is that it for it can be used without pasting and that they are uniformly removed from the treatment Can be distributed well.

The simplest method to carry out the invention is to paste the cationic starch in granular form in cold water and the to be treated To pass well through the pulp or to add the pulp to the item to be treated. the Starch granules stick firmly to the cellulose fibers because of their opposite charges, and the subsequent Gelatinization and drying in situ creates the adhesive bonds between the Cellulose fibers. Certain synthetic fibers, e.g. B. acetate, rayon, can be sized in the same way will.

example 1

25 g of cationic starch with a degree of substitution of 0.04, produced by reacting starch with the addition product of triethylamine and epichlorohydrin, were made into a paste in cold water and added to a standard household washing machine half full of warm water. 1.58 kg Cotton laundry was added, the stirrer turned on for 4 minutes, and then the laundry was spun. While stirring, the milky appearance of the water disappeared in an unimaginable manner, indicating that no starch remained in the pulp that could be thrown away. After spinning Very few build-ups of starch were seen on the walls of the washing machine, and none Spots could be observed on the estate. An examination apron was made from this charge immediately ironed without drying and found to contain a little more starch than if 340 g of a normal laundry starch were used under the same conditions. Under use under the same conditions, it was found that 50 g of cationic starch was a medium-weight and 75 g resulted in a medium strengthening.

Example 2

The procedure of Example 1 was repeated except that 75 grams of the same cationic Starch to which 6% borax had been added was added to the washing machine. the Strengthening was found to be moderate, heavier than when no borax was used (Example 1).

Example 3

For comparison, the procedure of Example 2 was repeated except that 100 g raw corn starch with 6% borax content was used. It was observed that the water of was milky in appearance at the end of the stirring and that there were no starch stains on the laundry. However there were starch deposits on the laundry and on the walls of the machine after spinning found.

Example 4

The same cationic starch as in Example 1 was used in this example. When 0.454 kg

Cotton laundry were immersed in an aqueous slurry which contained 7 g of this cationic starch, a slight strengthening was achieved. 15 g of this strength produced a medium and 20 g a heavy Strengthening. In each of these examples, the amount of water used to paste the starch was not essential as all starch suspended in the water is attracted to and retained on the property even while wringing it out. The distribution of the starch was even and uniform over the surface, and when the starch was gelatinized under the iron, the bond that formed in situ was perfect because the uptake of starch was quantitative and uniform. Because the amount of water is not essential, cationic starch is ideally suited for automatic washers because the Starch is not thrown out during spinning because once it adheres to the fabric, it remains on it.

20 Example 5

Cationic starch, produced by reacting starch with the addition product of trimethylamine and epichlorohydrin, was used to size rayon, acetate and dacron cotton blend. 30 g of the starch containing 12% borax were used for 1.81 kg of mixture used from the above types of laundry.

The cationic starch was attracted to acetate and rayon, but the starch was used as a more beneficial on acetate crepe and shirt cloth more than on woven rayon shirt cloth and rayongabardin considered. The cationic starch was only negligibly, if at all, attracted to one piece of dacron cotton blend laundry.

Example 6

A number of cationic quaternary ammonium starches with degrees of substitution from 0.023 to 0.11 of the type used in Example 5 were tested for their laundry starch ability. The strength method was the following: 1.35 g, dry basis, of cationic starch was stirred into water at 1 1.1361 26.67 ⁰ C for 15 seconds. Two swatches of linen measuring 304.80 x 444.50 mm and weighing 30 g were added to the slurry and stirred therein for 30 seconds. They were then removed, squeezed out by hand, and ironed.

The results are given in Table I.

Table I.

Cationic starch
Degree of substitution

% Laundry moisture ^a )

Dry matter

of strength

in the wash W

grams per 2.9 feet of dry matter

of strength

in the laundry <0

g per 2.9 feet

% Dry matter

strength
in the laundry ^d )

control

No. 3402 ^e >

"Cato" starch β)
0.03

50
52
52
52
53
53
51
52
50
51

0.05
0.47
0.66
0.70
0.73
0.83

0.38

0.71

0.72

1.0

1.0

1.04

0.81

0.70

0.78

28
53
53
74
74
77
60
52
58

Ό Hand squeezed.

^b ) Estimated from filtration measurements.

<=) Estimated from the increase in laundry weight.

^d ) Based on the increase in laundry weight, that is the fraction of starch removed from the aqueous suspension by the laundry.

^e ) Commercially available thick-boiling corn starch.

^f ) Allowed to hydrate 30 minutes before use, β) One amino starch.

The results in Table I show that when the degree of substitution is increased to about 0.06, so too the percentage of starch obtained by a given weight of laundry from an aqueous suspension to the same starch weight, removed, increase.

Example 7

This example shows the use of different types of cationic starches as laundry starches. That The procedure of Example 8 was used in carrying out the tests except that the amounts of cationic starches were different. The results are shown in Table II.

Table II

Starch derivatives
produced by implementing with Degree of substitution % Starch product
removed from the
Dispersion
through the laundry a) General
Ironing behavior Proportional
stiffness
(estimated*") Morpholine pichlorohydrin
Diallyl cyanamide
Cyclohexylaminepichlorohydrin .......
Triethylaminepichlorohydrin 0.09
0.03
0.09
0.04 28
58
31
51 Well
bad
Well
satisfactory 8th
13th
5 ±
13th

a) Based on the use of 91 g starch product in about 571 water and about 2 kg cotton laundry.

^b ) For commercial liquid starch in 1: 1 solution, a value of

Claims (5)

PATENT CLAIMS: 1. A method for sizing and starching cellulosic fabrics, characterized in that the cellulosic fabrics are brought together in an aqueous medium with a cationic nitrogen-containing starch derivative, this treatment agent either being a cationic starch of the formula NH (Starch residue) - O — C — N: R ₁ represents, wherein R ₁ and R _{2 can be} alkyl, substituted alkyl, alkene, aryl and aralkyl, or is a cationic starch which can be prepared in a conventional manner by reacting starch in the presence of an alkaline catalyst with either an amine compound of the formula R, - N ^ wherein R _{3 is} 2,3-epoxypropyl and 3-halo-2-hydroxypropyl and R ₁ and R _{2 are} H, alkyl, substituted alkyl, alkene, aryl, aralkyl, heterocyclic group, 2,3-epoxypropyl and 3-halo Can be -2-hydroxypropyl, or with quaternary ammonium salts of the formula R ₄ -N; R ₂ 3-halo-2-hydroxypropyl and R ₁ , R ₂ and R ₃ alkyl can be substituted alkyl, alkene, aryl, aralkyl, 2,3-epoxypropyl, 3-halo-2-hydroxypropyl, but when R ₁ , R ₂ and R _{3 are the} same, they should not contain more than 4 carbon atoms. 2. The method according to claim 1, characterized in that the agent is cationic amino starch with a degree of substitution of about 0.03 to 0.04. 3. The method according to claim 1 or 2, characterized in that the agent used is iminodiallyl carbamate starch or is a cationic quaternary ammonium starch derivative prepared by reacting starch in the presence of an alkaline one Catalyst with H ₂ C - C - CH ₂ - NR ₃
wherein R - CH ₃ or C ₂ H ₅ JSt. 4. Process according to the preceding claims, characterized in that the cellulosic substances with an aqueous slurry of the cationic nitrogen-containing starch derivative in unswollen granular form are brought together. 5. The method according to claim 1, characterized in that the agent used is a cationic Starch derivative is produced by reacting starch in the presence of an alkaline one Catalyst with a morpholinepichlorohydrin addition product or a cyclohexylamine addition product. is prepared, wherein R ₄ 2,3-epoxypropyl or contemplated publications:
U.S. Patent No. 2,131,120. © 209 557/412 3.62