DE1113677B - Process for improving the mechanical properties of textiles made from natural and / or artificial cellulose-containing fibers - Google Patents

Description

It is known when finishing textiles such. As for the purpose of anti-wrinkling, or for dimensional stabilization of text lien fabrics made from native or regenerated cellulose, the same with the solu- tion of a condensable resin in the presence of impregnating a catalyst of extracting, optionally pre-dry and a short time above 100 ° C to heat for the purpose of condensation of the resin.

Further, a method for modifying the properties of fibers and films is made from natural or regenerated natural polymers such as wool or cellulose or their derivatives known, according to which the material to be treated is in close contact with an organic modifier is subjected to ionizing radiation. This modifier is essentially about unsaturated compounds which lead to the formation of addition polymers Vinyl polymerization are suitable, e.g. B. acrylates or methacrylates. These connections help Textiles made from cellulosic fibers have superficial coatings, but do not penetrate the fibers.

It is also a process for the chemical bonding of coatings made of inorganic metal salts or Oxides without the aid of any binders on surfaces of molded structures organic polymers known, according to which the structure provided with the coating of action is subjected to ionizing radiation. The formed structures are fibers, Fabrics, films and the like made primarily of synthetic polymers such as polyamides or polyesters among others, but also from natural and regenerated cellulose as well as from condensation resins such as phenol or urea-formaldehyde resins.

It has been found that the mechanical properties of textiles made from natural or artificial cellulose-containing fibers are improved, in particular which increases the crease, scuff and tear resistance as well as the permanence of embossing and calender effects can be treated by treating such textiles with condensable substances and then the effect of ionizing radiation, in particular gamma radiation or X-ray radiation are subjected, the condensable substances being condensed. The precondensates These substances penetrate the textile fiber and can be exposed to ionizing radiation lead to cross-linking inside the fiber.

It is further known the mechanical

the mechanical properties

of textiles made of natural and / or

artificial cellulosic fibers

Applicant:

Heberlein & Co. A. G., Wattwil (Switzerland)

Representative: Dr.-Ing. P. K. Holzhäuser, patent attorney,

Offenbach / M., Herrnstr. 37

Claimed priority:
Switzerland from April 1 and September 12, 1959

Dr. Georg Heberlein and Dr. Fritz Münzel,

Wattwil (Switzerland),
have been named as inventors

Properties of fine fabrics made of cotton and regenerated cellulose through treatment with concentrated To improve sulfuric acid in terms of stiffening and transparency of the tissue. It is also known to have similar effects by treating the tissue with a copper oxide-ammonia solution or a sodium zincate cellulose solution. Besides, it is It has been proposed to use these methods to make transparent fabrics by treating them with synthetic resin precondensates and subsequent heating to over 100 ° C to make it crease-proof. This method however, leads to the tissues that have already become somewhat brittle as a result of the transparency treatment a commercially unacceptable decrease in fiber strength.

It has now been shown that in the case of transparent fabrics, good crease resistance without any appreciable A reduction in fiber strength can be achieved if it is subjected to the treatment according to the invention will.

The method according to the invention is surprising, because the skilled person was not expected to that by irradiating the condensable substances a condensation thereof is brought about can be. In contrast, the radiation dose to be used according to the method according to the invention is as follows to be kept low so that the decrease in strength due to the irradiation is negligible. While at the usual textile finishing processes the condensation of the condensable substances on the fiber by heating to temperatures above 100 ° C

109 688/201

follows, thereby causing a great decrease in fiber strength, the present method has the essential advantage that no such heating is necessary, so that practically no reduction the tear and tear resistance occurs compared to the untreated textile material.

Another advantage of the present process is that, under suitable conditions, the The condensable substances can be applied without adding a catalyst, so that the tissue does not need to be washed out after irradiation.

The textiles treated according to the invention have good crease and rub resistance and have a pleasantly soft grip.

The ionizing radiation is primarily gamma radiation or x-ray radiation; B. ⁶⁰ Co, cleavage products of ²³⁵ U or ¹³⁷ Cs. The textiles are preferably exposed to a radiation dose between 0.5 · 10 ⁶ and 3 · 10 ⁶ X-rays at 15 to 25 ° C. The condensable substances can, depending on their nature, be used in the form of aqueous solutions, as dispersions or dissolved in organic solvents. There are z. B. aqueous solutions or aqueous dispersions of resin-forming substances usually used in the wrinkle-proof finishing, such as. B. methylolureas, methylolmelamines, dimethylolethylene urea, 2,6-dimethyloltriazinon-4, diglycidyl ether, etc. Mixtures of the condensable substances mentioned can also be used. The condensable substances mentioned can with or without the addition of the usual catalysts, such as. B. boron trifluoride, zinc nitrate, light and heavy metal halides, etc., can be used.

The method according to the invention can be applied primarily to woven or knitted fabrics made from native cellulose like cotton, but also on woven or knitted fabrics made from regenerated cellulose or those which contain fibers made from natural and regenerated cellulose. The procedure is suitable in primarily for anti-crease finishing and dimensional stabilization; it can be according to this Method but also permanent embossing effects such as gauze, corrugation, carpenter or moire effects, also produce calender effects with or without friction. The procedure can also be based on Use textile yarns, threads or threads.

The invention is explained in more detail with reference to the following examples.

example 1

A desized, mercerized and bleached cotton poplin fabric is given a 10% strength impregnated with an aqueous solution of a triazone derivative of the following constitution:

HIGH ₉ -N

H ₉ C

N-CH ₂ OH
CH ₂

The solution does not contain any catalysts. The tissue treated in this way is dried for 10 minutes at 60 to 70.degree. C. and then exposed to the action of gamma radiation in a total dose of 2-106 X-rays at 20.degree. ^{Fission products of 235} U serve as the radiation source. Washing out is not necessary after irradiation. The fabric shows practically no decrease in tear resistance and has good abrasion and tear resistance values ίο as well as good crease resistance.

Example 2

An imitation cotton poplin with 36/19 threads per ¹ Ai French inch and the English thread numbers 40/30 in warp and weft is singed, desized and bleached and then with a solution of 110 g of dimethylolethyleneurea dissolved in 11 g of water, which also contains 11 g of zinc nitrate as Catalyst was added, impregnated, pressed off and dried at 60 to 70 ° C for 20 minutes. The tissue treated in this way is then subjected to the action of gamma radiation in a total dose of 1 · 10 ⁶ X-rays at 20 ° C. ⁸⁰ Co. serves as the radiation source. After irradiation

he fabric is washed out and dried. The treated fabric shows a tear strength which is practically unchanged compared to the tear strength of the starting material. The tear strength in the weft direction, measured with a Schopper pendulum apparatus, is 22 kg per 2.5 cm. In addition, the fabric shows very good abrasion and tear resistance values. The crease angle is 111 ° in the warp and 112 ° in the weft. The crease recovery angle were determined by the following method: strips of 3 X 5 cm of the treated fabric were for 24 hours at 21 ⁰ C and 65% relative humidity conditioned, then folded in the warp or weft direction and kg loaded during one hour at 1. After removing the weight, the fabrics were left unloaded for 15 minutes and the crease angles were then measured. The fabric has a pleasantly soft feel.

Example 3

A conventionally pretreated cotton force is mixed with a 15% aqueous solution impregnated with aziridinyl phosphonium oxide of the following constitution:

CH ₂ -CH ₂

CH ₅

/ N-P =

CH /

CH ₉ -CH ₂

C ₅ H,

The solution also contains 15% boron trifluoride dihydrate, 65% (calculated on the aziridinyl compound), as a catalyst and 7.5% octadecylethylene urea emulsion as a plasticizer, 10% (calculated on the aziridinyl compound). The fabric treated in this way is dried for 10 minutes at 60 to 70.degree. C. and then subjected to the action of gamma radiation in a total dose of 1 · 10 ⁶ X-rays at 20.degree. ^{Fission products of 235} U serve as the radiation source.

strength of the fabric treated in this way is practically unchanged compared to that of the starting material, and the fabric exhibits good abrasion and tear resistance values. It also has good crease resistance on, is largely flame-retardant, and the handle is pleasantly soft.

Example 4

For the preparation of an aqueous dispersion of a diepoxy compound which is only partially soluble in water from glycerol monochlorohydrin and epichlorohydrin 100 g of this compound, 100 g of a 5% strength Polyvinyl alcohol solution and 20 g of a 20% dispersion of a polyethylene plasticizer with addition of 12.5 g of a 40% aqueous solution of zinc borofluoride with vigorous stirring in as much Entered water so that the volume of the dispersion obtained in this way is 11.

Cotton poplin is impregnated with this dispersion and exposed to gamma radiation in a total dose of 10 ^e X-rays at 23 ° C. without further pre-drying. ¹³⁷ Cs is used as the radiation source. It is then washed and dried. With very interesting crease resistance values, the fabric shows only insignificantly reduced tear and tear resistance values compared to the untreated fabric and is absolutely resistant to chlorine washing. The amount of resin on the fabric is not affected by repeated washing at the boil.

Example 5

100 g of a 5% polyvinyl alcohol solution, 25 g of a non-ionic plasticizer, 75 g of the diepoxide mentioned in Example 4, 60 g of a 50% solution of dimethylolethyleneurea and 13 g of a 40% zinc boron fluoride solution are dispersed with 750 g of water and an in Usually pretreated and mercerized fabric impregnated with it, the warp and weft yarns of which consist of 70% cotton and 30% rayon. The squeezing effect is 85%. The fabric is then dried for 30 minutes at 50 ° C. and a gamma radiation dose of 1.3 · 10 ^e X- ^{rays is applied by means of a 60 Co source at 18 ° C.} In addition to good wet and dry creasing properties, the fabric shows only insignificantly reduced mechanical values compared to the untreated fabric. It practically does not change its dimensions when washed in a washing machine with 5 g of soap per liter at 60 ° C.

Example 6

Cell wool gabardine is impregnated in the usual way with the aqueous solution of a urea-formaldehyde precondensate with the addition of 10% of the precondensate weight of magnesium chloride (MgCl _{2 · 6Η?} Ο) and 10% of the precondensate weight of a silicone emulsion and squeezed off with a squeezing effect of 90%. Without further drying, the tissue is subjected to gamma radiation in a total dose of 0.8 × 10 10 ^e X-rays; ¹³⁷ Cs is used as the radiation source. It shows similar properties to the fabric treated according to Example 5.

Example 7 ^6s

A bleached, mercerised cotton Mako twisting the English yarn count 60/2, is treated with an aqueous solution containing 70 g Dimethyloläthylenharnstoff and 10 g of zinc nitrate per liter, dried at 6O ⁰ C and exposure to gamma radiation for a total dose of 1 x Subjected to 10 ^G X-rays at 20 ° C. ⁶⁰ Co. serves as the radiation source. The yarn obtained has lost its tendency to shrink and is very suitable for embroidery purposes.

Example 8

According to known methods, mercerized and bleached cotton mousseline of the thread count per French customs of 24/19 and the English thread number 80/120 was treated with sulfuric acid from Treated 50.7 ° Be at room temperature for 7 seconds, washed, then with sodium hydroxide solution of 30 ° Be post-mercerized for 15 seconds, washed neutral and dried under tension. The goods pretreated in this way were, according to the corresponding information in Example 2, with the mentioned Dimethyloläthylenurea treated and irradiated. Subsequent to the irradiation, the tissue was washed and dried under tension. Through this treatment there will be a considerable increase in Achieved crease resistance. The crease angles of the transparent, but not resin-treated and Non-irradiated fabric is 39 ° in the warp and 20 ° in the weft. Due to the synthetic resin treatment and Irradiation increased the crease angles to 66 ° in the warp and 62 ° in the weft. The tear resistance as well the abrasion resistance are only slightly affected; in any case, there is practically no damage a.

Example 9

Mercerized and bleached cotton mousseline, as used for Example 8, was made with sulfuric acid parchment of 52.5 ° Be at 15 ° C for 16 seconds, then with sodium hydroxide solution of 30 ° Be post-mercerized for 15 seconds. The goods were under tension after neutral washing dried and then according to the corresponding information in Example 1 with the triazon mentioned treated and irradiated, which significantly increases the crease resistance of the goods; the crease angles increase in the warp direction from 14 to 62 °, in the weft direction from 11 to 71 °. Tear resistance and abrasion resistance remain practically unchanged.

Example 10

Mercerized and bleached cotton mousseline, as used for example 8, was immersed for 10 seconds in a cuoxam solution containing 18 g of copper, 150 g of ammonia OSTH ₃ ) and 10 g of caustic soda per liter, then introduced directly into dilute sulfuric acid, left in it until the copper is removed, then rinsed thoroughly, mercerized with sodium hydroxide solution at 30 ° Be for 15 seconds, washed neutral and dried under tension. The tissue was then treated with the aziridymylphosphonium oxide mentioned in Example 3 and irradiated. A substantial increase in the fastness to crease was achieved; the crease angle of about 10 ° in the mean of the warp and weft of the not treated with the aziridinyl compound and not irradiated

th tissue are increased to over 90 ° when treated and irradiated tissue.

Example 11

Mercerized and bleached cotton mousseline, as used for Example 8, was impregnated with a sodium zincate cellulose solution containing 50 g of cellulose, 20 g of zinc oxide and 75 g of NaOH per liter, then poured into dilute sulfuric acid (10 cm ³ conc . Sulfuric acid per liter) out, washed, ^{after-mercerized with sodium hydroxide solution of 30 0} Be and dried under tension. The fabric was then treated with the urea-formaldehyde precondensate mentioned in Example 6 and irradiated and finally dried under tension. The fabric shows a noticeable increase in crease resistance; the crease angles are before the resin impregnation and irradiation in the warp 24 °, in the weft 20 °, after the resin treatment and irradiation in both directions 45 °. Tear resistance and abrasion resistance are practically unchanged.

Example 12

Rayon muslin the thread count per ¹ 23/21 inches Zi French and English yarn count 60/70 was steamed by the conventional methods, and dried under tension, then treated with sulfuric acid by 47 ° Be at 10 ⁰ C for 10 seconds, washed, then After-mercerized with potassium hydroxide solution of 30 ° Be for 5 seconds, leached hot, neutralized and dried under tension. The fabric was then impregnated with a urea-formaldehyde precondensate solution according to Example 6, pressed, dried under tension and then subjected to gamma radiation in a total dose of about 1 · 10 ⁶ X-rays. This treatment significantly increases the crease resistance; Tear resistance and abrasion resistance are not significantly affected.

Claims (6)

PATENT CLAIMS: 1. A method for improving the mechanical properties of textiles made of natural and or or artificial cellulose-containing fibers by treatment with condensable substances, characterized in that the substances which are resin-forming with solutions or dispersions of precondensates, with themselves and or or with the fiber condensing substances Treated textiles are exposed to ionizing radiation, in particular to gamma radiation or X-rays provided ^{by radioactive isotopes such as 60} Co and ^{137 Cs.} 2. The method according to claim 1, characterized in that the textiles of the action of radiation in a total dose between 0.5 · ΙΟ «and 3,106 X-rays at 15 to 25 ° C be subjected. 3. The method according to claim 1, characterized in that with the condensable Textiles containing substances are irradiated in a moist or dry state. 4. The method according to claim 1, characterized in that the condensable substances be applied to the textiles in the presence or absence of catalysts. 5. The method according to claim 1, characterized in that with the condensable substance provided textiles before irradiation of a shaping mechanical treatment, z. B. embossing or calendering, are subjected. 6. The method according to claim 1, characterized in that the textiles to be treated transparent fine tissue can be used. Considered publications:
German Auslegeschrift No. 1042521;
British Patent No. 802 620. © 109 688/201 9.61