DE1419369A1 - Process for the treatment of material consisting entirely or partially of cellulose or a cellulose derivative - Google Patents

Description

PATENT LAWYERS

DR. MOLLER-BORg · DIPL-ING. GRALFS

DR. MANiTZ ■ DR. DEUFEL

8 MUNICH 22, ROBERT-KOCH-STR. 1

TELEPHONE 225 110

ίΟ. July 1968 P 14 19 369 2 B 362 - D / Sch / zb

The Bradford Dyers * Association Limited 39 Well Street »Bradford t, Yorkshire / England

Process for the treatment of material consisting wholly or partly of cellulose or a cellulose derivative

Priority Great Britain from October 8th, 1959 and May 27th * 1960

The invention relates to a method for treating whole or partially consisting of cellulose or a cellulose derivative material which is still reactive or replaceable water contains material atoms.

The inventive method is particularly applicable to cellulose and Cellulose derivatives can be used in the fibrous state. In such an application, the process does not change the actual one fibrous character of the material.

As will be explained in more detail below, however, the invention is also applicable to cellulose in any conventional form

IfaHft documents! Art 7 & I ads. U No. ι sentence 3 dep change. v,

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bar, ζ.Β «in the form of Bred * fibers, yarns, woven or knotted Woven, foil, nonwoven ©, paper and regenerated Cellulose film. .

The process has the general effect of solubility of the material in solvents that normally make the material solve, is decreased. However, if at all, it reduces does not significantly reduce the swellability of the material in water and does not unduly weaken the material or make it brittle Processes that can be generated are increased wet crease recovery, increased dimensional stability, increased resistance to microbiological attack or the like. Worth mentioning, the effect of dyeing and finishing treatments is not affected.

The inventive method for treating material which consists wholly or partially of cellulose or a cellulose derivative which still contains reactive or replaceable hydrogen atoms, by impregnating the material with an aqueous liquid which methylolates a nitrogen compound and an acid with a concentration of not more than 12 * 5 η and preferably in the range from 4 η to 6 η, the material being swollen, whereupon it is ^{kept in the moist state for a time at a temperature between 0} ° C. and 80 ° C. and

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anscM.leßsnd rinsed before TroGlsnen and optionally removal of excess sur Re & gesitlen is neutralized, is characterized in that one carries out the treatment with a nitrogen compound, b © i aer it is a methylolier "

Γ ι

tea urea derivative - in which the grouping «N - CO - small Forms part of a ring, or around © insn ther of such Derivative »and the one crosslinking of the cellulose molecules without resin separation causes, while the, material in the wet, swollen State is

It can be seen that this procedure differs significantly from previous procedures differs when carrying out cellulose or a Cellulose derivative with an aqueous solution of an aldehyde compound or a resin-forming aldehyde or a methylolated condensation product together with an acid or a potentially acidic substance treated and then dried and heated to produce a reaction cause"

Xn the Austrian patent I85 7 ^ 3 describes a process in which a cellulose-containing fiber material is impregnated with an acidified solution or emulsion of a curable aminoplast resin, such as a condensation product of formaldehyde with urea or melamine, or their alkyl «or acyl derivatives, and that treated material kept in the foamed state for a long time at fine temperatures between room temperature and 80 ⁰ C and then the

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MateriaX is rinsed with water and usual snacks and then dried. Until the acid has the Zweek to act as HErtungsbesehleuniger so TLM the SEizFekonzentra- 'ti not on a Konsentration 12.5 π exceeds and low in the practice of betrMehtlieii is · According to the known method, the JkuM & ltehm & ohmn of the resin achieved without a subsequent hardening step. is required · The insoluble resin is formed on the fiber without any chemical change in the

The process according to the invention is fundamentally different from these known processes, namely because of the different types of methoxide nitrogen veneers that are used, which means that in the process according to the invention there is no resin deposition, but only a cross-linking of the cellulose molecules to be attributed to the fact that, contrary to the present invention, new and overlooked results _{9 are achieved,} in particular with regard to a valuable wet smoothness of the treated materials.

In the practical implementation of the method according to the invention the heating fluid can move onto the o ^ ilulosetiimaterial A variety of conventional methods can be applied, which may depend on the shape of the cellulose material * Example » The material can wisely be put in a bath of the heating liquid

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be immersed for an appropriate period of time until the reaction has taken place «Alternatively, the reaction liquid can be circulated using mechanical devices through a mass of pulp» fibers or oarn. However, if the cellulose material is in the form of fabrics or foils or silk, then the process can be carried out in an expedient manner by immersing the material in a reaction bath for a longer period of time. It is more expedient to simply soak up the material in the bath let it "after removal roll up into a roll and to leave the erforderliehe time" wherein However care taken to ensure herds miB that you came for this purpose, during this tent range not dry kaim "the rolled material advantageously catfish in an impervious material be enveloped, b @ i @ piolswei @ © in © iner PolySthylenfolle "If the heating times are relatively short" then the treatment can be expanded to a continuous process "for example by" that the treated material is hung outside after drinking · One can also proceed in such a way that the material is subjected to a series of before caulking and before washing Rolling runs »An essential feature of the present invention is to keep the material in the wet, swollen state at all times during its reaction time with the reaction liquid.

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The term "cellulose material" also includes, of course Mixtures with other materials, see below, for example mixed yarns or mixed fabrics, the other fibers, such as Wool, regenerated protein, nylon, polythylene terephthalate, Cellulose triacetate or aeryl resin derivatives contain. The cellulose " material does not necessarily have to predominate in such mixtures.

The methylol compounds which can be used in the process of the invention are normally applied in solution in the aqueous acid *

Ethylol groups also include etherified methylol groups understand, especially methylated methylol groups. Corresponding the term "methylolate" should also be understood.

Mixtures of methylol compounds can also be used. Furthermore, reaction solutions can be used which drive on the production of methylol compounds accumulate "" rich have partially or initially reacted «without the essential Methylol compound or the essential methylol compounds isolated have been.

Methylol compounds which are particularly suitable for achieving the effects intended in the present invention are heterocyclic ones Compounds in which, in the hanging, at least two nitrogen atoms

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1 T I S

sit with which methylol groups are directly linked can. Example © for methylol derivatives of nitrogenous compounds « which are used in the method according to the invention can »are;

Polymethylol compounds, which are of ethylene urea and related Derive connections. For example, is dimethylolurea the formula

C% -CHL

T I

HIGH ₂ -K. K-CHgOH.

CO

effective.

The dimethylol derivative of dihydroxyethylene urea is of particular importance the formula

CH CH

HIGH-N.

Elective catfish are applicable terms for this connection 1,3 »bis (Hydroxyineth3rl) - ^, 5 * dihydro3qr« iHiida2solidon and Dimethylol-

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Instead of using the specified connections as solohe, Mixtures can also be used which are partially oösr initial reaction from the compounds glyoxal, urea and Formaldehyde * This is how glyoxal can initially be mixed with urine * substance can be reacted under such conditions - that yield essentially glyoxal monourea, but none Isolation takes place, whereupon ethylolated by adding formaldehyde can · The reaction bond formed in this way leaves then use for the method according to the invention. Optional can also use the three components glyoxal «urea and formaldehyde are mixed together * whereupon they are allowed to "ground" a reaction Such a mixture can be either siethylolated glyoxal monourea as well as methylolated urea derivatives are unacceptable the nature of the reaction mixture may affect the invention Procedure to be used «Another alternative is« first urea with formaldehyde to form ssethylolated To let derivatives react «what then these derivatives with Glyoxal are implemented. Furthermore, it can sometimes be practical and It is advisable to add the components separately to the acidic solution that is used to treat the cellulose material becomes * ^

Instead of glyoxal, methylglyozal and α-hydroxyadipaldehyde can also be used to carry out the reactions described will"

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-Another valuable product stemming from ethylene urea is aetylenäiharastoff '. Do the methylolation of this product, which has the formula given below «when applied in connection with an acid achieves technical effects, which are similar to those »described under" Using Dimethylol · dihydroxyethylene urea can be obtained "

CHgOH CH ₂ OH H

CO I CO

Could result in different eubßtituierte Xthylenharnstoff®, the appropriate Msthyloivarbindungen "are alky! Derivatβ _s like SB" methyl "äthylQnharnstoff

CH

or alkoxy derivatives, for example

CELO

CE —.CH

I I

CO-

Instead of iron ^ ethylene urea the propylea urea derivatives can be used * from aamn the simplest diethylolpropylene urea is it

r r

K-CI ^ OH

Another class of compounds which are valuable polyethylol « Derivate derives, based on the triazon ~ (Triazlnon ~) ~ rings these Compounds are made through the methyl, ethyl and hydroxyethyl triazone which each represents the formula

ClL CH ₉ CH ₅ CH ₀

ι ι ι ι ² r

HH HN ^^ NH. HN ^ NH

co ^"co: - _M ■" co

own *., - = ■

Polymethylol derivatives of other ring compounds which contain nitrogen, aB the compounds based on iydantoin or substituted hydantoins, such as efondmethyl ~ or & η, are also of value.

These Bing connections each have the formula »

Π Q Q 1 O i t ο / η

CO · - CH “CO ———— CH GO

Polyethylol derivatives of ureas and substituted ureas are also suitable. _;

Heat position of acidic reactant solutions like those used in boers " The method according to the invention should be used mineral acids, for example / Sohwefeleäursj, Nitric acid, GhlorifassersfeoffsSure οά @ ^ PüosphorsSure, use, äa when using such acids relatively high water " Material ion concentrations achieved and relatively low working temperatures to be adhered to know · strong; organic acids, such as e.g. Triohlor@ssigsg.ure, can be used in a similar way will. In addition, weaker acidic organisms can be married Use acids, but in this case an elevated temperature is normally required for the treatment. Examples for suitable weaker acids are formic acid? Acetic acid* Tartaric acid, citric acid, and oxalic acid,

e 'when working at Ziianerteniperatur, ie ". in ungef§hr ^ 2NC ^e C, preferred acid is sulfuric acid. At such a temperature, the acid concentration is preferably between 1 and η η η 10 and in particular between 4 and 6 N * where the material

BADOiHGlNAl.

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the reaction medium is exposed to the reaction medium for a period of icy hours * normally for two or cirei hours *. A suitable change in the material exposed to the treatment can be observed after 30 minutes of your time *. span of 24 hours. In most cases it is advisable to work at room temperature. However, in order to shorten * the treatment tent ZVL , the temperature can be increased. However, if this causes the cellulose-containing material to be destroyed * then it may be necessary * to reduce the acid normality of the reaction * ie to set the normality to less than, for example, 0.1 η or even O ₀ OOi η.

A guide that can be used to find suitable B @ action times using solutions with different concentrations can be determined on sulfuric acid »is in the following table compiled:

Abnormality treatment set at SO ⁰ O

1 24 hours

5 2 = r ■ '■

to; 1/2 - 1 "■

The addition also falls within the scope of the present invention from salts to the acidic solution to reduce the degree of swelling of the cellulose

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or to modify the catalytic activity of the acid.

The invention is special in that it provides a simple and vjirks & Biss process for the treatment of cellulose-containing B3at © riali © n, with a number of improved technical effects is achieved. When applied to textiles an® exceptionally good wet crease »recovery ability and improved dimensional stability. It is known that fabrics are produced in this way "which" if they are made into garments, are washed and hung up to dry "whereupon they are immediately ready to be worn again" without the need to hang them. In order to obtain such smoothly drying fabrics, measures must be taken to ensure that the fabric is free of wrinkles when the reaction takes place; because the ßew @ b® tends to “maintain” the state in which © s you are during the reaction time. In some cases, however, the reaction can be combined with mechanical treatment * e * B. with © inör Satinier- oder Pllssierhehandlung »Basinleren can be carried out before a chemical reaction * On the other hand, pleating is preferably done in the moist state» after the fabric has been impregnated with the reaction solution «If a modified cellulose is used» the reactive one or replaceable Masserstoffatome includes, for example Cellnlosediacstafe "can bastehexi d & e technical result in a higher SweiehiiBgsfcempsratur" then

it is useful if the fabric is ironed hot.

M & n, has found that with regard to the biinsession stability in tissues which consist entirely or mainly of normal regenerated cellulose, only a moderate © dimensional stability is achieved by regeneration of cellulose fibers from a solution of cellulose xanthate or the like.

However, it has been found that when such a regenerated C & Zlttlosemat.erial is subjected to a pretreatment, the
a & zu is able to give it a certain degree of dimensional stability su, the subsequent treatment with acid and
a methylolated nitrogen compound gives a very much improved diffusional capability of the material, and is dimensionally stable. is greater than most people as a result of S \ m ~ ralerung the effects can be expected that each individual in the pretreatment and the subsequent. Are obtained Heaktionsbehandlung "In fact, it would seem ά & Β the combined treatment besitst a synerglstisohen character.

The pretreatment can, for example, consist of a treatment with

»
Steam or superheated steam or from a treatment

with a swelling agent, preferably an alkaline substance, such as

ft η α ft 1 7/1 7 /. 7th

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for example sodium hydraagrdi exist · Bin © weiter® pretreatment, which provides for the addition of resin and the material, can also be used «

The technical effects obtained by the refinemental measures are not removed by repeated washing because they are based on a chemical modification of the cellulose structure. An important feature of the present invention is that the fibers remain swellable in water and such treatments which then enable the application of coloring or finishing agents, in particular customary resin treatment using condensation resins of the amine ormal & ehyd-Tfps according to known methods.

VersteifungsmltteX "EnseiehungssBitt © !," esseratatofiend making © means Fiuores25 © nzaufheller or other customary Auarüstungsmittel know are applied "Cellulosehaltig® SSE ^ © b @ _a the erflndutigsgeffiSß ^ treated" acquainted with directly applied Tree "wollferbstof £ s, Vat Dyes * Solubilized vat dyes «dye combinations based on azo or with active dye». fan-colored · dl® fabrics or materials can be printed on Mimliche Welse using conventional methods *

It should be pointed out that the initial procedure is followed Celluios®gew9he and other Cellulos © materiali © n that previously

BAO ORIGINAL

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certain customary Ausrttstuagsb © hanö3Aiiige3 & im & have been given, for example a Harssung with A ^ n / Forraal ^ sSipl-Koiidessatesi, is applicable " know new effects thereby © ralelt were." that first of all the tissue in © iner aqueous dispersion of a cellulose »athers impregnated and dried" whereupon the impregnated fabric to the action of the wt indungsgemäßen Beaktionsl is subjected ^ solution · The Heaktionsmittel ύιοη Celluloseäfcher a chemical modification of the substrate appears sugätzlich su au fix or modify ·

It should also be pointed out that the reaction liquid gels Equipment can be added. That way you can cellulose, which is dispersible in acid, can be fixed »

Optionally, a cellulose material which can be used according to the invention has been modified, an aftertreatment with a swelling agent or swelling agents can be subjected · For example, a treatment in sodium hydroxide as professional mercerization if necessary be performed*

Particularly suitable preparations for the preparation of cellulose materials according to the present invention contain between 5 and 25 parts by weight of Bimethyloldihydro ^ Sthyleiiaarnstoff and between 95 and 75 de "." file with an aqueous sulfuric acid a normality between 4 η and 12.5 n »

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The following examples illustrate the present invention * Me Partial data refer to the part of the wind «

Example t

6.4 Qom concentrated sulfuric acid are added to 100 ecm of water, whereupon the solution is allowed to cool. 20 g of pear ethylethylene urine are added to the mixture, whereupon the mixture is made up to 50 cubic centimeters with water will. 2 samples of mercerized Baunsrollgewebes be wrapped at 60 ⁰ C in the Misehung a dipped "into a FoXyäthjrXexirolIe to a vmü to vernin ^ i ^ e vsnä ürnm m & oh ä <& m rolling each case 1 for 3 hours in an oven with eimmr temperature τοη 60 ⁰ O held "The treated samples Kerdxn Sann in a HatriuiaoarlsonatldBung new" f well in Waee @ s * rinsed out unä aiisehlioBmid Getrcoknat *

the treated (3 @ K @ b @ ii removed fibers are in cuprammonium *

unl $ sliQh * Sfaels. ü®m washing sseigen beiö © sample "Compared to a niehtbehandelt @ n öewebeprobe improved NaS knitterbeetMndigkeit"

Example 2

20 g of Din & t ^ lel & thyi-s-tri & zinon are dissolved in 50 & ®m water. 56 com-centered sulfuric acid are added separately for 7500m, whereupon the whole thing is allowed to cool. The two

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Solutions are then mixed gründlieh _# whereupon water to adjust a total volume of 200 cc is added. The acid orisality of the solution is about 6n .

A simply woven cotton clothing material is soaked in the solution prepared in this way, squeezed out, rolled up free of folds and frizz and wrapped in a polyethylene film. To avoid evaporation.This holl is then left to stand for ^{4 hours at 20 0 O *} The treated sample is then neutralized in a sodium carbonate solution and rinsed well in water, whereupon it is dried.

Example ~ *>

S Dimethylolethylene urea are dissolved in a mixture of 100 cc in concentrated hydrochloric acid and 100 ecm of water, whereupon the goose is made up to 250 ecm.

A mercerized cotton fabric sample is soaked with this solution, "printed out" and rolled up free of wrinkles and frills

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Polyathylenfolle wrapped and left about 4 feet & the long 20 ^e C st © h @ n. Then this © Prob® la © än © r H & triumo & rbön & t solution is neutralized and rinsed well with water, whereupon the oils are allowed to dry »

A washing test of the treated sample results in comparison to an untreated sample ^ s gl @ ioh @ n fabric a very strong improved Na £ knitt @ rb @ stgndigkelt *

Example 4.

18 ecm of a concentrated "Sefewefels acid are added to 5'0 oom water" whereupon the liquid is allowed to cool. Then 10 g DimethyloldilH5iär # 3syätbyl © nbarnstoff are added, whereupon the goose is filled with water to 100 e @ m. The acid normality is about 7.8 n.

A sample of a mercerized cotton poplin is drunk, squeezed and rolled in the manner described in the previous examples. NaOH a reaction time of 20 hours at ⁰ C ty good salt cold water is neutralized by means of a dilute Hatriumoarbonatluäung »rinsed and dried using a Stlftratasens ·

After washing, the sample has a noticeably improved dimension crease-resistant

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A sample of a bleached and mercerized double cotton yarn is soaked with the same liquid, wound around a glass tube and ^{left to stand at SO 0} C for 4 hours, the sample being protected against evaporation. After neutralization using a sodium carbonate solution and rinsing in Water and drying, the yarn shows good knitting conditions.

Example 5

A sample of a mercerized cotton poplin is impregnated with a liquid prepared according to Example 4, with 8.5 g of tetramethylolacetylenediurea being used instead of the dircethyloldlhydroxyethyleneurea. The sample is then expressed “rolled up and ^{left to stand for 2 hours at SO 0} C”. After neutralization, it is rinsed well in water and dried on a pen frame.

When washed, the sample shows good wet crease resistance. Example 6

Samples from a viscose Rayonstapelfaesr shirting be placed on a Stiftrehmen and 20 seconds at 20 ⁰ C in an aqueous solution of sodium hydroxide © (5 £ lg) dipped · They are then rinsed in cold water "neutralized and overall

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trooknet · While ele retain their original dimensions on the frame, ele are then in solutions of sulfuric acid (5 * 5 n) immersed * with the solutions each 1) 10 parts DimethyloldihydroxyKthylenuratoff (DM-OH-EU), 2) 8.6 parts Dimethyloltetrahydro-5-ethyl-e-triazinon (DM?) And 3) to parts Dirnetbyloläthylenurea (DMEU) contain «on each 100 parts of solution, they are then rinsed out with a 1 $ oil aqueous. Sodium carbtraate solution neutralized »again in water rinsed out * so that essentially all acid is removed «and dried on a frame.

For comparison purposes, other samples are treated in a similar way, whereby the treatment with the aqueous K & trlumhy & rojqrd solution is omitted.

Another sample is treated in a similar way * with the Treatment with a din »thylol compound and bohwee rock lture under« remain.

After a 5 ml full wash in a 0 * 2% weaker cloth. Filling solution and hanging up to dry show dl · samples « based on their initial dimensions «the following shrinkage values.

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chain Sohuss untreated 15.0 5.25 treats BHOHEU 5.5 ^ O DMT. 9.5 4, ο DMEU 9.5 4.0 sodium hydroxide only 11.5 4 * 75 Hatriurahydroxyd, then
ßend DHOHBU 5.25 1.5 Sodium hydroxide * then
ßend WH! 6.25 6.25 Sodium hydroxide, then
ßend OMEU 7 * 0 4.0

The tissue samples treated with the methylol compounds also show improved resistance to media. _#

Example 7

Viekowe-Rayonstapelfßser-Heraden & toff is treated with steam under a pressure of 5.52 kg / cm for 5 minutes. Treated and untreated samples of this fabric are then attached to a pin frame and stored for Z hours at 20 ⁹ C in sulfuric acid (5 * 5 η), which contains 10 parts of dimethylol-ethylene urea per 100 parts of aeration So shrinkage values determined:

shrinkage (%) ftft shot

untreated 15.0 5.25 treated with DMEU 10.5 3 * 0

Treated only with steam 11.0 1.75

m. Waaeerdaiapf and DBfEU he-

^ is 6.0 2.0

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Rehearsals in miniballs? Weis ©> -Hours laaag in one X / 5sung treats »In which» 3rd, 6 ropes i) irÄetb ^ loia.i.liyilrö2? yätiiylönhan% -stoff be used instead of the difflsfchylolathylenharnstGffs, then the following © results are achieved 3

Chain Sohuss

. treated with DMOHEU 5.5 4.0

treated with steam and DMOHEU 2.75 S, 5

Example 8

Samples from a fabric treated with water vapor and not with water vapor are made according to that described in Example 7
Method that samples in Kettrlchtung during treatment with Dimethjrlolverbindungen by 5 $ stretched the gutted _© Λ DSS and then are dried to their original dimensions "

The dimensional changes in the subsequent washing are like follows *

not treated

treated with DMOHEU

treated with DMEU

Treated only with steam treated with Waßaerdampf and DMOHEU Treated with steam and Di-IEU

The negative Seichen means a stretch,

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chain Shot 15 * 0 5 »S5 1 * 0 4 * 75 11 * 0 ) l £? 5.25 2.5

With the ffethylolbludungen treated tissue samples, an® improved NaßiraiitterbastMnäigkoit ·; '

Example 9

Two 20 gs «servings» of a solution of
Urea (00 ^) are diluted to 100 com * whereupon the pH of the Kiöiang is adjusted to 3.1 or Öjö by adding small amounts of sulfuric acid.

Samples on a simply woven niohtra © r2 © risi © rfcen
Fabrics are soaked with the respective solution at SO ⁰ C, wound on a llohr , with oiwar PoXyäthylenfoli © "mwiokelt." ma a vaporizing au vertiinöern »and for 24 hours at 80 * in
kept in an oven. After unwinding, the samples are still "moistened by the solution * they are then neutralized in a sodium carbonate solution", rinsed well in water, then dried *

In comparison with non-treated samples from the same variety, the treated samples have improved resistance to wet creasing.

Fibers of the treated tissue samples are unlüßXiöh in cuprammoniiiaihydrcxyd.

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Example 10

A reaction product from urea, -formaldehyde and glyoxal with etaera Holv © rhUlfcöis of 1 t S j 1 is made by adding Ί56 ecräeiner * GlyoÄallößtsng (57 # Gewicht / Veluraan) sra 1-500cm of a form · »aMshydlöfcung (40 Ja Gawioht / Voluiaen) · The solution is made by Zygafoe oinex »Na'cri ^ irabyilroxyölösims (adjusted to a pH of 8 © in» Then 60 g of urea suctionQgobQn are added Hollowing mixtures are then diluted with water and added to 40 o cm of a 12 η sulfuric acid solution, whereupon the total volume is adjusted to 100 ecm with the use of water - with a poly "SthylenXolie wrapped" around a Verdampfon prevent> Stun "long at 20 ⁰ C allowed to stand, then rinsed well in © ne of sodium carbonate" solution Äöutralisiertj in water and dried..

The tissue protosn treated in this way populated in comparison

an improved Haßknltterbeatändlgkalt compared to untreated samples

and are insoluble in cupraramoniurahydroiqyd.

Samples of the tissue treated in this way »become with untreated fabric samples in a soil eh © contains rotten plants, and for 2 months left dug in * When digging up one finds feat that the

BATH

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Treated samples are essentially unavailable. " while see the niehtfoehan & elfceii Profoisn sersetat habszw

A Roakfcionsprodulst is in the manner described above prepared, with the 60 g Urnscofi 'through. 78 g of thiourea are to be replaced besoteleben wsrdenj, there is also an improvement here Wet crease resistance of the Gswobss as well as an insolubility in

Example 11

60 g Hasinatoff herds, (150 com sin © i 'formaldehyde solution weight / volume), 6 ccra Animoniusaihydroxyd, specific gravity 0.188 °, added, whereupon the mixture is stirred. After 4 hours, 168 ecm of a glyoxal solution (36 # weight / volume), which has previously been neutralized to a pH of 7 using sodium hydroxide solution, is augmented, whereupon the solution is left to stand for a further 16 hours Forßialöehyö is found to be 2 % in the solution.

20 g Oer Heakticnsraischung 4 · 0 Oora added a 12 η lOaung, whereupon the volume using van water to 100 coin © Inga tollt * is Frohen a "BaumwoXlpopelinegewebes are then eingstaueht in Lösiutig represents and NaOH in the Bsisplsl 10

t »<: - _Vi ..- * ■ ....,. BAD Of »© iNAL

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Treated white,

iM treated Profcött get on © good \ mü αΐτιύ. insoluble in QuiYPmwmniw & iirüvoxfäWQwa & Qn.

(AGfS treated tissue. Leave © low in mi ' ri <Weis © ttdft aq. Directly to be drawn
Brilliant Pine 2B (C, X * Diffeot Kad
(Caledon Jade Green XK (D 'I. Vat Green I)), a solubiliaierten vat dye (Sol "3 <lon Jade Green X (CX, Sulubilieed Vat Qraen 1)) _{f f} öixiera A?, Ofarbstoff of from Brenthol FR (CX . Asoic Coupling Coiapo «· n @ at 20) trnd Brentamin © Fast Scarlet GCr Salt (c * X * Aaoic Diazo CornpQund 5) consists and olnem nealctivfarbatoff öibßoron Turquolee Blue α (CX. Reacti ν © Bye 7) (Giba Ltd.) to dye.

ta

iüO -s Binsa.ta ^ leldihyäroaEyafcliyleoteanietoff (50 $ ig) been au 75 ecm © in © j? 7 * 5 'Ci- Chlon-iaGiBsrstofiBaur® tanned'. Vorauf (iao Yolumen filled to 100 'cm wiM * samples from a cellulose diacetate' - a are immersed for 3 hours at 20 ^C C in εϋ © IÄ5ß \ sng © * © Ine heat treatment with a matrix carbonate solution he «.t'olst

ln.at a ■ temperature yon 110 »116 ⁰ C ₅ while unbß ·« eXt® tissue proto®n and such a tissue sample, the xxav iBit © inei »

. '■ *' * ■■■.

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have been treated without the addition of diraetbylolglyojcalinonourea, already reweld or weld ^{when ironing at a temperature of 99 Mg 104 9 C.}

In the treated fabric samples it is also found that si © are insoluble in acetone, while the non-agile. dissolve samples in acetone.

Example 13.

20 s of a solution of DiiBethyloldihydroxyMthylenhansstofi · (50 % fleht / volume) are added to a dilute solution of acetic acid, whereupon the mixture is made up to 100 μm with water. The solution has an acid normality of n / 10.

Samples from a mercerized cotton pop © llne fabric are in immersed the solution and then in that described under Example 12 Working method treated * The treated tissue samples have good Nafi wrinkle properties. Fibers from then treated tissue samples are insoluble in cuprammonium hydroxide solutions, similar Properties are retained »if the n / 10 acetic acid is replaced by n / 10» Solutions of oxalic acid, tartaric acid, citric acid, lactic acid or formic acid are replaced ·.

Example 1-4

A reaction mixture of thiourea, formaldehyde and glyoxal

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rait Qlmm MolverhiiltnXs of 1} 1.5 ί 1 is made; * ixxöeia first 116 ecm © inej? Formaldehyde is added © hydl8ßung (# 40 w / v) to 76 & thiourea "ground ,, whereupon the set pEMiert using Jtooniurahydroxyd to 8.5 * The mixture is left at 25 ⁰ G erwSrmt, wherein the exothermic Rüalrision progressive to is "After t hour herds 191 com a aiyoxallöaung (30% öewicht / Voliiniön), which has been previously neutralized using Hatriumhydi'oxyd ₃ added with stirring. The solution is left to stand for 2k hours. 20 g of the reaction substance are diluted with water and 40 ecm of a 12 η sulfuric acid are added, whereupon the volume is adjusted to 100 ecm using Was * 8 © r * samples are made from a mercerized building block poplin fabric immersed in the solution and then further treated in the procedure described in Example 14. The treated samples show improved wet wrinkle properties, compared to the untreated fabric, and are insoluble in a cupraramonium hydroxide solution *

Example 15

Samples from a linen-bound * bleached and mercerized Tissues are treated according to the procedure described in Example 4

The treated fabric has improved anti-crease properties' and let you see in satisfactory catfish with Soledon jade Green X

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(CI. Solubllised Vat "ffyeen 1) and IMigosol Bins IBCS (CI. Sulibllissd Vat Blue.6} stain *.

Example 16

A reaction product of urea, formaldehyde and glyoxal in a molar ratio of 1 s 1: 1 is according to that in Example 10 described Arbeitsxveise produced. The reaction product will on samples of Bauaiwollpapeline fabric according to or in Example 10 described working method applied

The treated fabric has improved wet wrinkle properties, and a was on an untreated fabric by comparison, and is insoluble in a cuprammoniutnaydroxjdlösung,

Example 17

Its reaction mixture is prepared by adding 40 ecm of a 15 η sulfuric acid 8.5 ecm of a formaldehyde solution (40 # weight / volume 8.7 ecm of a glyoxal solution (> 7 % weight / volume) and 3.4 g of urea The mixture is made up to 100 cums using water and stirred until the urea has dissolved. The healing mixture is left to stand for 24 hours at room temperature treated according to the procedure described in Example 10 * The treated fabric has good wet kneading properties, the fibers being insoluble in cupric hydroxide.

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Example 18

Samples from a cotton pop-up made from milk in * sgewet> 8 are treated with an acidic drink from Biisetli ^ loldihsrarosyafchylenhaimstofi 'according to the procedure described in example k . The samples vj & väen it einsr Haohverharzungsbeiiandliins by immersion in a Lösimg imterzogen, holds the following components ent:

10 g Diraethylolt €) trahydro «5" * ethyl-s-fcriazinon 1 s 2inknitrathexahydrat und
0.05 ε acetic acid »namely the 100

Drying country curing is carried out during a period of 5 minutes bsi 15O ⁰ C. The samples are washed for 2 minutes at 6O ⁰ C in a solution of 0.1% sodium carbonate, and 0% * 2 * Natriuinperborat and then dried

The treated samples have good wet and dry wrinkle resistance.

Example 19

A reaction mixture of urethane, formaldehyde and glyoxal in a molar ratio of 1 s 2 s 1 is hsrge in the following way » represents:

BATH

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- 52 »

52 com of a glyoxal solution 07 Ji weight / volume) are converted into-50: -pan of a foraldehyde solution (40 % weight / volume) sugetsetst * whereupon the pH is adjusted to 8

27 seconds of urethane are added and the mixture is refluxed at Bo ⁹ C over a period of 90 minutes.

50 g of the product are added to 40 ocra of 1J η sulfuric acid, whereupon the volume is increased to 100 ecm using water is set. Samples from a mercerized cotton poplin fabric are immersed in this solution and treated further according to the procedure described in Example 10

The treated fabric has improved creasing properties and is insoluble in a cupramnioniura hydroxide solution.

Example 20

A simply woven Bauomoll lining is soaked in a polyvinyl alcohol solution (1%) and dried. The dry tissue is then immersed in an acidic solution of dimethyloldihydroxyethylene urea and. further treated according to the procedure described in example 4 · The treated fabric has a frizzy feel »which is retained after washing in a boiling soap solution«

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The fabric is pretreated in a starch solution (1 % i &) instead of in the polyvinyl alcohol solution.

Example St

A non-woven product made from a web of viscose rayonatapal fibers, which are connected using a regenerated viscose, is in a Läeung of Dimethyloldihydroxyäthylenharnetoff immersed in sulfuric acid and following the procedure in Example 4 described working method further treated »

After vialing, the treated web shows excellent performance Wrinkle recovery in the wet state »in comparison to the untreated web

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Claims (1)

Claim 1. Process for the treatment of material «which consists wholly or partially of cellulose or a cellulose derivative» which still contains reactive or replaceable hydrogen atoms «by impregnating the material with an aqueous liquid« the methylolated nitrogen! »Compound and an acid with a concentration of not more than 12.5 η and preferably in the range of 4 η to 6 η «which causes the material to swell * whereupon it is kept in a ^{moist state for a period of time at a temperature between 0} ° C. and 80 ° C. and then before drying rinsed and neutralized if necessary to remove excess reagents "characterized in that the treatment is carried out with a methylolated nitrogen compound" which is a methylolated urea derivative "in which the group -N-CO-K- forms part of a ring" or a compound of such a derivative, and which crosslinking of the cellulose molecules without Resin coating works while the material is in the wet, swollen state. 2 * Method according to claim 1 «characterized« that one as the methylolated nitrogen compound, the dimethylol derivative of » K iW. / * ι now. ± «r. ι aau 3 des Anderiingsses. v. *. 809812/1247 1418369 Dl ^ droxy & thylenhams toff or a compound containing this compound Reafctionsgemiseh used, which by Urasatsung of urea, Glyoxal and formaldehyde was produced * 5. The method according to any one of the preceding claims, characterized characterized that wan for the treatment of the material a combination used, the between 5 and 25 parts by weight of dimethylol « dihydroxyethylene urea and between 95 and 75 parts by weight aqueous sulfuric acid with a concentration of 4 η and 12.5 a contains. 4 »Cellulose material according to one of the preceding claims was treated" ORlGfNAL «09812 / 12A7