DE1224699B - Process for the crease-proof finishing of textiles - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

D 06 m

German class: 8 k- 1/20

Number: 1224 699

File number: G 36058 IV c / 8 k

Filing date: October 2, 1962

Opening day: September 15, 1966

The invention relates to a method for the crease-proof finishing of textiles, i. H. an improvement (i.e. increase, increased durability, etc.) in dimensional and form strength properties of fiber materials; such properties are e.g. B. the dimensional stability in wet and or in the dry state, the durability of creases and (desired) other creases, the so-called hanging of (undesired) creases and creases, dimensional stability, »wash-and-wear properties, Swell resistance, shrinkage resistance, tensile strength, the retention of in usual Shaped surfaces or surface appearances produced by embossing, pleating, etc., such as gloss appearances, etc., as well as the improvement in resistance to Moth damage and mildew, washing, bleaching agents and acids, chlorine retention, industrial gases and other environmental influences, the development of undesirable odors, yellowing or discoloration, Hydrolysis, heat and / or abrasion and the like.

Means for improving the crease resistance of fibrous materials, especially cellulose materials, such as B. Cotton, have come very much to the fore lately, and many The fabrics now available on the market are designed to achieve the so-called “wash-and-wear” properties and the like have been treated with such agents. Most of these funds are made from resins, and this leads to various ones Disadvantages such as B. unnecessarily high costs, stiffening or otherwise changing the properties of the fiber material and the like further fiber properties can still be significantly improved.

In U.S. Patent 2,524,399 there is one method to improve the shrinkage and crease resistance of fabrics, in which cellulose fibers be reacted with divinyl sulfone in an aqueous alkaline medium. Although at resin is not used in this process and therefore some of the disadvantages mentioned above are avoided there are several other objections to this process that affect its commercial exploitation prevented. Divinyl sulfone causes severe skin and eye irritation, and its use is therefore extremely dangerous, even with expensive special devices. Another The disadvantage of this process is that the crease resistance of the cellulose material in dry Condition is not improved significantly.

Process for the crease-proof finishing of
textiles

Applicant:

General Aniline & Film Corporation,

New York, N.Y. (V. St. A.)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Named as inventor:

Harlan Benjamin Freyermuth, Eastern, Pa .;

David Irwin Randall,

New Vernon, N.J. (V. St. A.)

Claimed priority:
V. St. v. America 6 October 1961
(143 303, 143 304)

Another recently developed method to improve shrinkage and wrinkle resistance, which is more successful and used economically is the treatment of fiber materials with 2,2'-sulfonyl diethanol in the presence of an aqueous alkaline medium, whereupon the treated Fibers are dried and cured at elevated temperature. With this procedure, that is not the case is dangerous and fiber materials with surprisingly good crease resistance in both dry and dry supplies in the wet state takes place during the treatment of the fiber material in the aqueous alkaline Medium no reaction takes place, but the crosslinking of the fiber material with the 2,2'-sulfonyl diethanol occurs during the final cure. This procedure is true for most Purposes very satisfactory, but has the disadvantage that the crosslinked fibers obtained have none Assume colors and can no longer be mechanically deformed. It is therefore very difficult to provide permanent wrinkles or color to the crosslinked product.

The invention relates to a method for the crease-proof finishing of cellulose textiles, which thereby characterized, is that the material in an aqueous alkaline medium with 2-vinylsulfonylethanol im-

609 660/391

impregnated, the product obtained at least one mechanical shaping or chemical treatment and then the material is fixed at a temperature of at least 105 ° C.

During the treatment of the fiber material with the impregnation agent, at any temperature between can be carried out around room temperature and the boiling point of the medium, this reacts 2-Vinylsulfonyläthanol monofunctional by the Vinyl group with a reactive site on the fiber material, such as. B. the hydroxy group in the Cellulose fiber. This fiber material, which contains a Hydroxäthylsulfonyläthylgruppe, can by the following formula can be represented:

Cellulose - O - CH ₂ CH ₂ - SO ₂ - CH ₂ CH ₂ - OH

This "monofunctional" reaction product made from fibers and 2-vinylsulfonylethanol is not crosslinked and has practically no better dry wrinkle resistance than the original fiber, though its Crinkle resistance when wet is already significantly improved. Also its resilience to wet treatments or treatments with various non-functional agents, such as. B.

Dyes, brighteners, antistatic agents, plasticizers, etc., has not been increased significantly. This initial reaction product can now be any desired chemical and / or mechanical Be subjected to intermediate treatment,

ίο what the fiber or fabric in any desired Shape can be fixed and dimensionally stabilized by placing it at increased Temperature cures in the presence of an alkaline catalyst. During this final

is hardening, the fibers are caused by reaction between the free Hydroxyäthylsulfonyläthylgruppe in the first product of the above formula and a reactive one Networked point of an adjacent fiber. The cross-linked fiber material can then through the can be represented in the following forms:

Cellulose - O - CH ₂ CH ₂ - SO ₂ - CH ₂ CH ₂ - O - Cellulose

The possibility of subjecting the converted fiber material to such an intermediate treatment, is obviously of the greatest benefit. The fiber, fabric, or object can be after it first reacted with the 2-vinylsulfonylethanol in the presence of an aqueous alkaline medium is treated with dyes, other chemicals and agents, processed in the usual way, sewn, cut to size, creased, etc., whereupon the dyes, chemicals or other added this treatment means used as well as the mechanical deformations, such as. B. hems, folds and the like, by the final heat treatment described above to crosslink the fibers be permanently fixed in the material.

If appropriate, the process can of course also be carried out continuously and without intermediate treatments be carried out in order to only increase the dimensional and form strength of the material to enhance; for this purpose, the fibers are used immediately after the initial reaction with 2-vinylsulfonylethanol dried and cured in the presence of an aqueous alkaline medium. In this embodiment it is recommended not to wash the fiber material with it after the first reaction also the 2-vinylsulfonylethanol, which is not yet with in the presence of the aqueous alkaline medium the fiber has been converted or has formed a homopolymer or a ring, fully effective comes. In this way, the unreacted 2-vinylsulfonylethanol and the cleavage products also carry from homopolymers and cyclized products during the final curing for the implementation and crosslinking of the fibers.

It should be noted that the term "mechanical deformation" also includes the Smoothing, stretching, pressing or tensioning the fiber material, which is used to remove any wrinkles in the Fiber material may be required to be understood; the final hardening can thus a permanently crease-resistant product can also be obtained.

The preferred alkaline medium is alkali (sodium, Potassium, lithium, etc.) hydroxide, carbonate, bicarbonate, phosphate, silicate, borate, acetate Od. Like., Or an organic base, such as. B. triethanolamine or the like., Used in such an amount, that a pH of about 7.5 to 10.5 or more is obtained. This amount can be between be less than 0.5% and 10% or more. The alkali hydroxides are preferred, in particular Sodium hydroxide, as this compound initiates the initial reaction between 2-vinylsulfonylethanol and the fiber material is promoted particularly well. However, others can also be alkaline reactive compounds, such as. Sodium sulfide, dipotassium tartrate, disodium phthalate and the like are used will.

The alkaline compound can, if desired, simultaneously with the solution of 2-vinylsulfonylethanol applied to the fabric; but it is also possible to use the alkaline solution or after treatment with the solution of 2-vinyl sulfonylethanol.

The concentration of 2-vinylsulfonylethanol in the treatment solution is not critical and can be between 0.5 and 60% or more, depending according to the type of application to the fiber material, the type of fiber material used, the desired one Properties and the like The aqueous medium containing 2-vinylsulfonylethanol can by dipping, spraying, padding, printing or the like. Continuously or batchwise onto the Fiber material are applied. The aqueous alkaline 2-vinylsulfonyl ethanol is preferred containing medium applied in excess, followed by squeezing the tissue; as a result, the fiber material takes about 30 percent by weight or less to 100 percent by weight or more liquid. Can be used for printing or other decorative purposes the aqueous solution of 2-vinylsulfonylethanol can be thickened in a known manner. In general The best dimensional and form strengths are achieved when about 1 to 12 percent by weight in the fiber material combined (bound) 2-vinylsulfonylethanol, based on the weight of the fiber material, to be introduced. Therefore, the initial concentration and / or the amount must of 2-vinylsulfonylethanol, which affects the fiber

5 6

material is applied to be controlled so that a reactive group included in the the aqueous alkaline medium described above by homopolymerization, cyclization or the like lost amounts of 2-vinylsulfonylethanol and / or in the subsequent fixation stage be balanced; in some cases it can react with the treated fiber. Such Loss of up to 50% or more of the treatment 5 reactive dyes are z. B. Nitro dyes, dye solution added 2-vinylsulfonylethanol compounds from the azo, anthroquinone and phthalocyanine series do. or the like, including inorganic dyes, the

After the 2-vinylsulfonylethane has been applied, it can be free of metals or it can contain metal complexes on the fiber material in the presence of the aqueous (cf. British patents for the alkaline medium). 733 471, material pressed out and immediately dried and cured 740 533, 775 308, 772 030, 774 925, 780591, or any chemical or mechanical Papers 901187 and 907103, Belgian patent act; if desired, steps 497 065, 543 214, 543 215, 543 216 and the material between steps can be washed to 15 U.S. Patents 1935929, 2151857, 2424493. Preferably the treated and pressed fiber material is left 2434150.2 657 205.2670265.2728762.2743267 for 5 minutes (2,766,231, 2,784,204 and 2,895,785).
are left without treatment for up to 2 hours or longer, the fiber material should be dyed at the same time so that the initial reaction is terminated. This can be done in a suitable amount of the reactive by adding the impregnated fiber material 20 dyestuff to the aqueous medium described above, a waterproof blanket or cover or the like, which contains the 2-vinylsulfonylethanol and the alkali compound ; the procedure

The restraint to achieve the desired remains unchanged. The crosslinking concentration must be carried out in the presence of an alkaline reactive dye, which is the aqueous catalyst. If the medium is added, the fiber material released by a person skilled in the art can be washed and / or selected and varies between 0.05 and 2 other wet treatments, so that the up to 3%, depending on the dye used, of the alkaline, together with the 2-vinylsulfonyl desired color nuance, etc. The reactive ethanol applied compounds no longer dye can of course also be present after the present, so the material must be renewed with a quick reaction of the fiber material with the similar alkaline compound in 2-vinylsulfonylethanol and before the alkaline similar amounts are treated before the Ma- hardening are applied to the fiber material, material can be hardened. For this second loading the process according to the invention is particularly treatment with alkaline compounds are those to improve the properties of natural alkali carbonates, especially sodium carbonate, loading 35 or synthetic cellulose fibers such. B. Tree particularly suitable because it makes the crosslinking very woolly, linen, paper, regenerated cellulose and the like, well promoted and the damage to the fiber material suitable. The fiber material can be woven, knitted or matted processed in natural rials due to the required high hardening temperature. The fixation will be at such. B. in the form of staple fibers or a temperature of at least about 105 ⁰ C and 4 ° continuous filaments in bulk form, as rope, rope, preferably at least about 115 ° C. Yarn, roving, warps, fabric, felt and the like, the duration of the fixation varies depending on both the wound bundles, the temperature and the type of fiber. Generally speaking, as a fibrous material, the fixation takes 10 minutes or mass form etc. Mixed fabrics and mixed fibers more at 105 ° C, up to 15 seconds or less 45 can also be treated according to the invention, at 245 to 260 ° C. If the fixation is too long, the fiber according to the invention is particularly advantageously damaged. drive for the treatment of white felt and fabric

After fixing, the treated fiber can be used for fabrics, especially cotton shirt fabrics, material simply washed and / or bleached bed linen, clothes and the like. where the usual oxidizing agents, such as 50 rial colored at the same time, so are lighter, color z. B. sodium hypochlorite, hydrogen peroxide u. Even Find application. In the case of white materials, this becomes fiber material if already with dyes or pigments expediently immediately or against. acted materials according to the invention bleached after a washing stage. One driving is that improvement The lightfastness of dyed fiber materials 55 can also be determined by bleaching.

It should be noted that in the case of the inven-

level darker, duller or discolored, all other substances have been used in accordance with the procedure,

can. Care should be taken to ensure that the B. optical brighteners, stabilizers,

the mentioned intermediate treatments used plasticizers, surface-active agents, reactive

Dyes against an alkaline fixation at 60 capable bacterostatic agents, antistatic agents

the above temperatures and in relation to the and other finishing agents can also be used

Bleach are resistant. can.

The method according to the invention can also be used with functional agents if they are used in that the fiber material, which contains 2-vinylsulfonylethanol, is dyed with a reactive dye at the same time. As a solution, at the same time a monofunctional dye, all types, including organic, can react with the impregnation agent.
but mainly inorganic dyes, the agent is therefore also used in this, which has a reactive atom or catch stage through hydroxyethylsulfonylethyl groups

substituted. During the final fixation, the functional components that have already been implemented react Means in a similar manner as described above for the crosslinking with the fibers, whereby the functional means is firmly permanently attached to the fiber. It can e.g. B. Materials, such as polyvinyl alcohol, Starch and other finishing agents or other functional agents that are reactive Hydroxy, amino, thiol groups or the like. Contain the first, the 2-vinylsulfonylethanol containing Treatment solution are added in such quantities that - depending on the desired effect - z. B. about 0.5 to 20 percent by weight of the agent, based on the weight of the fibers, on the fiber material are deposited, whereby the above-mentioned permanent effect is achieved. It's clear, that in these cases higher amounts of 2-vinylsulfonylethanol are present in the treatment solution have to compensate for the amounts lost through reaction with the functional agent will. The reaction between the functional agent and the 2-vinylsulfonylethanol occurs in general before. the reaction between fibers and 2-vinylsulfonylethanol, since the functional Means is already added to the treatment solution and / or moreover greater reactivity with the 2-vinylsulfonylethanol. For these reasons, equivalent results can be obtained can also be achieved if you first mix the 2-vinylsulfonylethanol with the functional Means such as B. polyvinyl alcohol, starch or the like., Implemented in a separate preliminary stage to the process and then the monovalent reacted product as the final wet treatment before curing to the Applying fiber material. This last-mentioned embodiment is particularly preferable when the Once reacted fiber material can be subjected to further wet treatments before curing should, as this removes the monovalent converted functional agents from the fiber material before they are fixed on the fiber.

The 2-vinylsulfonylethanol used according to the invention is water-soluble at room temperature Oil that does not irritate the skin, eyes or other toxic properties and is therefore easy to use technical use and leads to the above improvements and advantages.

The production of 2-vinylsulfonylethanol can in an analogous manner to those mentioned in U.S. Patents 3,006,962, 3,005,962 and 3,005,852 Procedure.

The invention is illustrated in the following examples. Unless otherwise stated, all parts stand for parts by weight.

example 1

A piece of cotton fabric was padded in the following solution until the fabric was 80% fluid had recorded:

26.0 parts (34% active) 2-vinylsulfonylethanol,
2.0 parts sodium carbonate,

72.0 parts of water.

The treated fabric was then dried and set at 182 ° C for 1.5 minutes, whereupon the fabric washed, rinsed and dried. It had excellent dry wrinkle resistance and wet condition (ASTM method D-1295-53T).

Example 2

A piece of cotton fabric was padded with a 25% aqueous 2-vinylsulfonylethanol solution, until it had absorbed 60% of the liquid, then - if necessary after intermediate drying - taken up in a 2% aqueous NaOH solution padded until the liquid uptake 100%, wound on a stainless steel roller, covered with a polyethylene film

ίο prevent evaporation and 1 hour or left standing less. Then the fabric was unwound from the roller with a 1% aqueous Acetic acid solution rinsed to neutralize the excess alkali, washed, rinsed and dried. The fabric thus obtained showed better wrinkle resistance in a wet state than that untreated tissue. It showed a sulfur content of 0.98% which was evidence that the 2-vinylsulfonylethanol reacts with the tissue

ao had.

The addition of a salt, e.g., 10-20% sodium sulfate, to the above aqueous NaOH solution has often been found to be particularly effective in the stripping of the 2-vinylsulfonylethanol from the Prevent tissue.

A portion of the fabric treated according to Example 2 became a garment with folds, hems etc. processed. This garment was then treated with a 2% aqueous sodium carbonate solution treated until fluid absorption was 100%, ironed with a warm iron to remove the Remove wrinkles, dry and set in an oven for 1.5 to 2 minutes at 182 to 188 ° C. That so treated garment showed significantly better crease resistance in the dry state than the untreated, and the folds, hems and other mechanical deformations could through Washing, ironing, cleaning, pressing or the like cannot be removed.

Another part of the fabric produced according to Example 2 was dyed with an aqueous medium, about 1.25 to 1.5 percent by weight, based on the weight of the fiber, one against alkali and peroxide Resistant direct dye or another type of dye contained. The dyed fabric was then treated with a 2% aqueous solution of sodium carbonate until liquid was absorbed 100% padded, dried and fixed at about 182 ° C for 1.5 minutes. The fabric was then using Peroxide bleached, rinsed and dried. It showed compared to a stained but otherwise untreated one Fabric, excellent crease resistance both in wet and dry Shape, and the color was washable.

The preparation of the 2-vinylsulfonylethanol, which was used in the above examples, took place in the following way:

A 50% solution of sodium hydroxide was added dropwise, with stirring, to a mixture of 0.33 g of tungstic _{acid (WO 3} · H ₂ O) and 38 ecm of water until a pH of 12.0 was achieved. After stirring for 10 minutes and all of the tungstic acid dissolved, the pH was lowered to 6.0 by adding acetic acid dropwise. The sodium tungstate solution and 52.0 grams of 2-vinylthioethanol (0.5 moles) were then placed in a 300 cc three-necked flask fitted with a stirrer, thermometer and dropping funnel

was provided, given. 98 ecm of 31% hydrogen peroxide (34 g 100% H ₂ O ₂ ) were placed in the dropping funnel and the mixture in the flask was heated to 60 to 65 ° C. The first half of the hydrogen peroxide was added at 60 to 65 ° C, while the temperature was increased to 65 to 70 ° C with the addition of the second half. The oxidation was exothermic. After 3 hours at 65 to 70 ° C an examination for hydrogen peroxide with starch-iodide paper and with a titanyl sulfate solution gave a negative result. The solution contained 34%> 2-vinylsulfonylethanol. The product was isolated from the reaction mixture by distilling off the water in vacuo.

Claims (3)

Patent claims: 1. A method for the crease-proof finishing of cellulose textiles, characterized in that that the material in an aqueous alkaline medium 10 impregnated with 2-vinylsulfonylethanol, the material obtained is at least one mechanical molding or chemical treatment and then subjected to a Temperature of at least 105 ° C is fixed. 2. The method according to claim 1, characterized in that the cellulose textiles are impregnated in an aqueous alkaline medium with 2-vinylsulfonylethanol, the material obtained is dyed and then the dyed textile material is cured ^{at a temperature of at least 105 ° C.} 3. The method according to claim 1 and 2, characterized in that the aqueous alkaline medium Contains sodium hydroxide or sodium carbonate. Considered publications:
French patent specification No. 1227 817.