DE1469473A1 - Process for improving the absorption capacity of cellulose fibers - Google Patents

Description

Description of the patent application

SHELI INTERNATIONAL RESEARCH MAATSCHAPPIJ N.V. 30 Oarel van Bylandtlaan, The Hague / Netherlands

concerning

Process for improving the absorption capacity of cellulose fibers

It is well known that many textile fabrics, such as cotton fabrics, insufficient elasticity and therefore mostly show permanent Creases or wrinkles when creased or otherwise subjected to localized pressure .. In addition, the dimensional stability of these materials is poor, which is reflected in their low shrinkage strength. TJm this To overcome shortcomings, it is common to use a resin, e.g. a urea or Sielamin-formaldehyde resin, to cover the goods to treat. While this method was not unsuccessful, it had drawbacks in that the merchandise in most In some cases does not have the ability to be absorbed by the crosslinking agent, so that strong catalysts and

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Significant amounts of crosslinking agent are necessary to also to achieve only a small degree of heat ability with the material. In addition, block baths with urea resins have one limited stability and must be consumed within a relatively short time. It therefore seemed extremely desirable to develop a way of working with which, using a bath of unlimited stability, one can achieve a higher level Reactivity of the cellulose fiber with the crosslinking agents achieved.

The invention relates to such a method, namely a method for improving the absorption capacity for anti-crease finishing, Dyes, impregnating agents and the like in the case of cellulose fibers and the structures containing them, in particular Textile products, which is characterized in that one the material pretreated with aqueous alkali in a manner known per se is subjected to the action of a solution while still moist, which a Hydrocarbon sultone, preferably 1,3-propane sultone, contains.

The method according to the invention can be used for the treatment of cellulose-containing material of any kind may be applied, including Paper, wood and fabrics. The fabrics can be woven and nonwoven goods, threads, cheesecloth, yarn, corduroy, twine, netting and the like. That Procedure also includes the treatment of textile

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Certificates that have already been pretreated, e.g. mercerized. "Cellulose-containing" here means products which contain any desired, preferably at least 50 percent, proportion of cellulose substances, such as natural cellulose, for example cotton or linen, or other cellulose substances, such as viscose or copper ammonia eeyon, regenerated cellulose or cellulose acetate; If necessary, the cellulose fibers are mixed with wool and synthetic fibers, for example with fibers made of acrylonitrile (Orion, a 100 # A _C rylnitrilpolymer) or of vinylideneoyanide polymers or polyamides (nylon, a super polyamide), of polyester polyamides, of polymers of corn protein and Formaldehyde, or from copolymers of the above monomers, such as acrilan (85 $ acrylonitrile and 15 $ vinyl acetate), Dynel (60 $ vinyl chloride and 40 $ acrylonitrile), saran (85 $ vinylidene chloride and 15 $ vinyl chloride). Other synthetic materials or fibers, made from polyallylenes, such as polyethylene or polypropylene, polyurethanes, mineral fibers (fiberglass) or alginic acid materials, such as alginate grayon, are added to the cellulose materials in embossing.

Preferred for use in the method according to the invention are, inter alia, fabrics with at least one 60 percent cellulose, especially made of cotton, Eeyon and cellulose acetate can be made up.

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It has been found that using the method according to the invention, the cellulose-containing fiber material can be modified in such a way that there is a greatly increased ability to react to other substances, such as wetting agents or basic dyes. So it was found, for example, that textile fabrics treated according to the invention are extremely reactive towards agents such as formaldehyde, urea-formaldehyde resins, dirnethylolethylene urea, Acrolein-formaldehyde resins, dicyandiamide-formaldehyde resins, melamine-formaldehyde resins and polyepoxides are and thus quickly convert to a material that has a very high recovery capacity against Has wrinkles when wet and dry · It was further found that the modified cellulose-containing Material without the use of the usual acidic catalysts with the crosslinking agents and other reactants reacted. This material and the resulting dyes also react readily with basic dyes The colors are deeper and more resistant to fading during exposure and washing. Another advantage resulted from the fact that the fibrous materials treated according to the invention have an increased stiffness and therefore for many important uses in the textile industry can be used. In addition, the modified cellulose-containing products have a lasting effect strong acidity, due to which they are further implemented or can be modified.

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When carrying out the method according to the invention , the fiber material to be treated is brought into contact with an aqueous alkali solution, preferably with a sodium hydroxide solution, which, however, can also be replaced by a potassium hydroxide or another alkali or alkaline earth metal hydroxide solution. The strength of the alkali solution can vary widely; concentrations between 1 and 30, in particular from 5 to 20 percent by weight, are preferred. In the usual Keroerisierungsverfahren alkali solutions are used in a concentration of 16-18 i ", which are in an ideal manner for the method according to the invention. In practice, the process can follow immediately after the mercerization stage and is therefore part of the normal wet treatment of textiles «

Impregnating or soaking with the aqueous alkali can be done in any way, e.g. by dipping, spraying or padding. Preferably you can see how at the well-known padding technique, the material through the aqueous solution. The amount of wet absorbed varies according to the case in question; it is preferably 20 to 100 parts of solution per 100 parts of dry material.

The temperature of the alkali solution and. that of the material to be soaked can be different; preference as both approximately correspond to the tree temperature · Mercerisierungstemperaturen between 10 and 40 ⁰ C are in general

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my preferred.

The material soaked with the alkali solution is then treated with a solution of a sultone.

The sultones to be used according to the invention are intermolecular oyolic esters of hydroxysulfonic acids and can be of aliphatic, oycloaliphatic or be derived from aromatic acids. Examples of sultones which can be used according to the invention are the 1,3-propane sultones, the 1,4-butanesultones, the 1,3-Hezansultones and the benzyl- and tolu (> y! sultone as well as mixtures drraus. The ones to be used Sultones can be the gamma sultones, preferably Hydrocarbon sultones, such as 1,3 — propane— 8ulton. The sultones can be produced in a customary manner, which is not claimed, e.g. by sulfo-chlorination of chlorinated hydrocarbons, whereby the resulting chlorosulfonic acid is then used for the formation of the sultones used · The Sulton solutions can be used in any way be prepared, e.g. by mixing the sultone with Water, acetone or alcohol or mixtures thereof. In general, an aqueous one is preferably used Solution. The concentration of the sulfone solutions can be within one big thing. J are preferred 'is the use of solutions containing 1 to 25 percent by weight sultone.

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If necessary, it can be part of the goal to add wetting agents, including a larger number of different compounds of canonical, anionic or nonionic character are available · Are preferred the ionic agents, and especially those with a polar structure, in which a hydrophilic (predominantly Hydrocarbon) radical is a charged ionic group is bound. Such anionic surface-active compounds include the higher alkali and ammonium soaps Fatty acids, such as potassium or sodium myristate or laurate, palraitate, oleate or stearate or ammonium stearate; also the salts of long-chain aliphatic amines and quaternary Ammonium bases such as laurylamine hydr ο chloride and stearylamine hydrochloride are suitable · Examples of nonionic agents include the partial esters of polyvalent Alcohols and fatty acids, such as the hexitanes and hexitide esters, e.g. sorbitan monolaurate, the hydroxypolyoxyalkylene ethers of the above-mentioned partial esters e.g. the polyethylene glycol ethers of the sorbitan monolaurate, or the hydroxy polyoxyalkylene ethers of phenols, such as the reaction product of ethylene oxide and bisphenol-A or mixtures of the above Substances The wetting agents are preferably used in amounts of 0.1 to 5 wt Wt .- ^ added.

The soaking of the alkali-pretreated fiber material can be done in any way, e.g. by Dipping, spraying or padding. In general it is

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expediently, the fiber material through the SuIton solution pull through it, as happens when padding .. The amount of solution absorbed can vary depending on the circumstances ▼ be different, but is preferably between 10 and 100 jC.

The temperature of the sulton solution as well as that of the alkaline pretreated fiber material to be soaked, »

can vary within wide limits, for example between 15 and 90 ⁰ O j

and is preferably between 20 and 70 ° 0!

The time necessary to react with the Sulton '

depends on the temperature and the concentration of the solution j away. At an elevated temperature, the reaction is complete in most cases within one or two hours.

After the impregnated material has been removed from the Suiton solution, it is washed, dried and immediately put to commercial use in order to remove any remaining reaction components. Washing is preferably done with water to which cleaning agents (detergents) can optionally be added, drying at temperatures between room temperature and 125 ^° C.

The material obtained as above, while having the same appearance as before, generally has a stiff feel and can be used as stiffener in a wide variety of textiles

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be turned. The material treated according to the invention is also characterized by a greater 'tenderness (elongation at break) excellent. It has essentially the same strength as before the treatment and is the same as the untreated one Material also with regard to the absence of chlorine

The textile material obtainable according to the invention has many active sulfonic acid groups and, as already noted, is particularly reactive towards many crosslinking agents. Any known method can be used to apply these agents to the textile material pretreated according to the invention. Preferably, an aqueous pad solution is prepared which contains these agents and optionally other additives such as softening agents and then the fiber material treated according to the invention is introduced into the solutions or through them, whereupon the excess solution is removed and the treated textile material hardens. The concentration of the padding solutions can be between 5 and 25, preferably between 5 and 15 percent by weight. They treatment is carried out at 20 to 100 ° C and curing is preferably performed at 70-175 ⁰ O.

You can then use products treated in this way are put to the intended use. Textiles can e.g. for the production of clothes, suits, Furniture covers, cloth shoes, carpets, trestles, shirts, uniforms, ropes and the like or also as textile fabrics

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used in the construction industry.

The examples explain the implementation of the invention Procedure closer

The post-wrinkle recovery values (denoted MCRA.) Were determined by the ASQf Desig. D 1295-53T described test method (referred to in the regulation as "Tentative Method of Test for Recovery of Textile Fabrics from Creasing, Using the Vertical Strip Apparatus"), values for the average warp and weft measurements are given together. The tensile strength values were determined with the aid of an arrangement called "Instron Tensile Testing Machine, Method 5100" in Federal Specifications CCC-T-Ii) 1.6. · All tests were carried out at 65 + 2 # relative humidity and 20 - 22 ⁰ C carried out.

example 1

The example shows the treatment of cotton fabrics with a solution of propane sultones.

A cotton product of 0.11 kg / m (fineness number 80 ζ 80) was placed in a 20 # strength sodium hydroxide solution at room temperature for 15 minutes in order to suck in. The goods were then taken out and the excess

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Solution removed by squeezing between rubber coated rollers. The still moist goods were then placed in an impregnation solution of 25 g propane sultone, 75 g water and 3 g urodium myristyl sulfate, where they ^{remained at 49 0} C for 1 1/2 hours.After removal, the excess solution was squeezed off between rollers and the goods washed carefully and ^{dried at 121 0} O for 12 minutes. The product, which contained 0.49 $ sulfur as sulfonic acid after this treatment, was then pulled through a solution containing 5 ^e fo an acrolein Pormaldehyd condensate contained, after which the material thus treated by heating at 163 for 5-10 minutes ⁰ O has been hardened. The dried fabric was then examined to determine the wrinkle resistance and the tensile strength. The determinations gave the following results:

Textile material

HCRA wet Tensile strength in kg dry 133 Chain shot 140 145 27/15 166 29/19

Untreated goods

after treatment with propane sultone

after treatment with propane sultone plus

Aerolein formaldehyde

resin 272 242 9/5

untreated goods plus acrolein formaldehyde

without a catalyst no change compared to un-

traded goods.

From the above results it can be seen that calibrated the goods pretreated with propane sultone with the crease-proof

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afterwards. Hars in the absence of any catalyst to one Product that had excellent crease recovery values would have.

Example 2

The procedure was as in Example 1, except that the pre-treated with propane goods instead of acrolein Pormaldehydharz with Dime ^J was treated uhyloläthylenharnstoff wrinkle-resistant to make them · The results can be seen from the table hervort

Textile material MCEl tensile strength in kg

dry wet warp / weft

Untreated goods HO 133 27/15 after pretreatment

with propane sultone and

aftercare with

Dimethylolethylene

urea 282 194 11/6

Untreated goods plus
Dimethylolethylene urea without acid

, Catalyst no change compared to un-

traded goods

Example 3

It was worked according to Example 1, but the Conditions for the alkali treatment, the amount of propane sultone and the conditions for curing according to the table were varied. The amount of sulfur was in each case

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true, as it is a measure of the conversion with the cellulose gives. The following results were obtained!

1st stage
NaOH 2nd stage
Propane sultone Min / ° 0 Sulfur ¹ * 'in weight ji
on the goods Ji Mln / ° 0 75/80 20 75/80 25th 70/58
5/51 2.12 20 5/24 10 100/24 1.32 20 5/24 10 30/49 0.64 20 15/24 5 90/24 0.22 20 60/49 25th 30/49 1.35 20 60 / 49- 25th 30/49 0.87 20 15/24 10 60/49 0.55
0.53 20 15/24 10 15 / Π 0.91 20 15/24 10 30/49 1.00 20 15 / room temperature 25th - 0.49
0.40 20 60/49 0 - <0.02 20 15/24 P. ^ 0.02 Untreated goods B.)
'Treated goods, washed thoroughly
to remove unreacted substances 0.01 Example 4 •
•

The example shows the improved dye uptake of the products modified according to the invention.

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! A cotton fabric was analogous to Example 1 for 15 minutes at 24 ⁰ G 20 £ Lger hydroxide solution and then 60 minutes at 49 ⁰ C with a 1Obigen Propansultonlösung treated · fabric pattern of 7 | 5 x 7 _t 5 cm were then inked by half-hour cooking 0 , 1 » methylene blue and 0.196 acetic acid. The reflection in 96 was determined; it is given in the table in comparison with that of the untreated goods and the goods treated only with alkali. The following results were obtainedχ

Commodity color reflection in

untreated royal blue 44

only with 20 # darker blue

STaOH treated as above 43

treated with 20 # very dark

NaOH, post-treated blue 1.5

with 1 above Propanaulton - *

Example 5

In further experiments, the improved ink acceptance of the new products has been shown with a less concentrated dye bath and various amounts used on propane. · The swatches were 30 Hinuten in 0.01 mooch methylene blue with 0.01 i> acetic. acid cookedThe results are shown in the table:

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H69473 Treatment, min / ° C Light Blue Reflection in i » Untreated Light Blue 69 20 # NaOH, 60/49 dark blue 69 20 # NaOH, 60/49
25 # propane sultone, 90/24 dark blue 20th 20 # NaOH, 15/24
10--6 propanaulton, 80/38 dark blue 19th 20 # NaOH, 15/24
10 # propane sultone, 30/49 dark blue 22nd 20 # NaOH, T5 / 24
IO96 propane sultone, 60/49 dark blue 23.5 2096 NaOH, 15/24
IO96 propane sultone, 15/71 dark blue 21 20 # NaOH, 15/49
£ 5 propane sultone, 30/49 dark blue 25.5 20 # NaOH, 15/24
25 # Propanaulton, 30/49 24 Example 6

The procedure was as in Example 1 except that the concentration of the Natriumhydroxyds 17.6 #, the concentration of the PropaneultonlöBung $ 10, and the temperature was 71 ⁰ C of the latter in the treatment. After treatment, the product was post-treated yet with an aqueous solution 1Obigen vpn Crlyzeringlycidyläther and at 150 ⁰ G, cured. The fabric thus obtained had good crease resistance.

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Example 7

The procedure was as in Example 1, except that the cotton fabric was replaced by one made of 35 $> cotton and 65 ^ synthetic fibers (Daoron). The results corresponded to the above.

Claims

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Claims (1)

DR. ING. F. WUKSTIIOFF β Μ0ΝΟΠΚΝ 0O 1 A 6 9 4 7 3 TOFU ING. G. Pulse acMw * ia * MTÄ4ee »» DR.BTPBCHMANN τηΐΜφ * · * ·· Μ SR. ING. D. BKHRBNS iiuouhim IU wmmwT 1A-28 881 February 25, 1969 Claims 1. Processes to improve the capacity for Anti-crease finishing, dyes, impregnating agents and the like in the case of cellulose fibers and sebaceous substances containing them, in particular textile products, characterized in that one in a known manner with Aqueous alkali pretreated material still wet subjected to the action of a solution, which is a carbon hydrogen sulton, preferably 1,3-propane sultone, contains « 2. The method according to claim 1, characterized in that the temperature of the aqueous, preferably 1 to 25 weight percent Sultonlösung and the wet material to be treated 20 to 70 ⁰ C. · 3. The method according to claim 1 or 2, characterized in that the solution is a wetting agent, preferably in an amount of 0.1 to 5.5 of the weight of the solution added. 8647 _M. BATH ORIGINAL 009812/1528