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Publication numberUS3793419 A
Publication typeGrant
Publication dateFeb 19, 1974
Filing dateJan 31, 1972
Priority dateOct 1, 1968
Also published asDE1948487A1
Publication numberUS 3793419 A, US 3793419A, US-A-3793419, US3793419 A, US3793419A
InventorsH Nobs, F Steinlin
Original AssigneeCiba Geigy Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the manufacture of viscose fibres with novel dyeing properties
US 3793419 A
Abstract  available in
Previous page
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,793,419 PROCESS FOR THE MANUFACTURE OF VISCOSE FIBRES WITH NOVEL DYEING PROPERTIES Felix Steinlin, Dornach, Soleure, and Horst Nobs, Magden, Aargou, Switzerland, assignors to Ciba-Geigy AG, Basel, Switzerland No Drawing. Continuation of abandoned application Ser. No. 858,138, Sept. 15, 1969. This application Jan. 31, 1972, Ser. No. 222,319 Claims priority, application Switzerland, Oct. 1, 1968, 14,660/ 68 Int. Cl. D011 3/12 US. Cl. 264-78 8' Claims ABSTRACT OF THE DISCLOSURE A process is provided for the manufacture of viscose fibres with improved dyeing properties. -In this process a polyamine-amide from (a) a higher unsaturated fatty acid or its dimer or polymer and (b) a polyalkylene-polyamine and a further reaction product of (c) a polyepoxide compound and (d) a stoichiometric excess of a polyalkylenepolyamine are incorporated into the viscose spinning solution in a finely divided form from which spinning solution the viscose being thereafter precipitated and shaped.

The fibres obtained show a good receptivity for dyestuffs suitable for dyeing cellulose materials and also for acid wool dyestuffs and dispersion dyestuffs.

This is a continuation of application Ser. No. 858,138 filed on Sept. 15, 1969' and now abandoned.

The present invention relates to a process for the manufacture of viscose fibres having novel dyeing properties. According to the present invention there is provided a process for the manufacture of viscose fibres which comprises adding to the viscose spinning solution before precipitation of a polyamide-amide derived from (a) an unsaturated fatty acid with at least 12 carbon atoms or a dimer or polymer thereof and, (b) a polyalkylene-polyamine, and a further reaction product of (c) a polyepoxide compound and (d) a stoichiometric excess of a polyalkylene-polyamine, the additives being in finely divided form and added in an amount totalling 1 to 20%, preferably 1 to 12% by weight relative to the cellulose content in the spinning solution.

The nitrogen-containing additives employed in the process of this invention are known compounds, which can be incorporated into the viscose spinning solution in an aqueous medium, appropriately, with the aid of emulsifiers; they have good compatibility with the viscose.

To manufacture the amides containing amino groups;

aliphatic, unsaturated monocarboxylic acids with at least are also suitable. The unsaturated fatty acids can also be used mixed with their dimerized, or polymerized deriva tvies, or the dimers or polymers may be used instead of the monomers. The polymerization of the acids probably takes place by a Diels-Alder mechanism, in that conjugated and, therefore, reactive carbon-carbon double bonds are produced in the unsaturated fatty acids by a partial or complete isomerization, these double bonds then completing the reaction to give a mixture of dimeric and higher polymeric fatty acids. Of course such a reaction can only take place if a starting material contains at least two conjugated carbon-carbon double bonds. With oleic acid, for example, it can only react if another compound having at least two conjugated double bonds is present.

Aliphatic polyamines with at least two primary or secondary amine groups, such as ethylenediamine, diethylenetiamine and triethylenetetramine, serve as component In addition to adding the pol'yamine-amide derived from components (a) and (b), it is required to add it to the viscose spinning composition with a further reaction product of a polyepoxide (c) and a stoichiometric excess of a polyalkylene-polyamine (d).

Suitable polyepoxides which may be used include the polyglycidyl ethers such as those accessible by etherification of a dihydric alcohol or diphenol with epichlorohydrin in the presence of alkali. The epoxides which are obtained by reaction of bis(p-hydroxyphenyl)-dimethylmethane Bisphenol A) with epichlorohydrin should be particularly mentioned. Reaction of these products with the polyamines (d) then yields the second additive.

The polyamines (d) may be the same or similar to the amines which have been mentioned for component (b). The adduct of (c) and (d) contains no further free epoxide groups since a stoichiometric excess of amine is always used.

The amounts of the components (a) to (d) which are reacted can vary within wide limits. Thus the amides containing amine groups may, for example, contain 40 to 80% by weight of fatty acid or dimerized or polymerized fatty acid and '60 to 20% by weight of polyamine whilst the epoxide-amine compound is suitably derived from 25 to 40% by weight of an epoxide compound and 75 to 60% by weight of polyamine.

The additives (a) are added 90 to 10% by weight being a polyamine-amide derived from (a) and (b) and 10 to 90% by weight being a reaction product of (c) and (d).

In addition to the essential additions described above, the reaction products may contain furthed additives, such as solvents and additional reagents such as epoxides and phenols.

The product of (a) and (b), mixed with a. product of (c) and (d), are suitably introduced in an aqueous medium into the viscose spinning solution. If the products are not water-soluble or only show limited solubility in water, an aqueous medium can be used which contains emulsifiers and/or organic solvents. The emulsifiers used can be anionic or cationic, but are preferably non-ionic. Suitable non-ionic emulsifiers include the addition products of 4 to 12 mols of ethylene oxide to long chain amines or alcohols with 12 to 24 carbon atoms or to alkylphenols with 10 to 18 carbon atoms. The emulsifiers are generally employed in amounts of between 1 and 20%, preferably between 1 and 5% by weight relative to the cellulose. The compounds and preparations intended for the manufacture of the viscose with novel dyeing properties can now be stirred directly in finely dividedform into the spinning solution. The filtratability of the viscose is generally not adversely affected by the presence of the additives, so that during the spinning process blocking of sieven mounted in front of the spinning nozzle arising from the presence of such additives, does not occur and a homogeneous filament material can be manufactured without fluctuations in gauge. The shaping of the viscose may be carried out in known maner, e.g. through spinnerets into a precipitation bath (e.g. a Muller bath) with optional post-treatment in further baths.

I .,ing nitrogen-containing fibres or polyester material, may

also be used.

Thus many useful dyestuffs can be used for dyeing cellulose material as a result of the process of this invention. These dyestuffsgenerally yield uniform and nonstripy dyeings with good fastness properties on the cellulosic material manufactured according to, the invention.

Amongst the many known acid wool dyestuffs which can be used here, there may especially be mentioned the metal-containing dyestuffs such as 1:2-chromium or cobalt complex dyestuffs, the dyestulf molecule of which can contain free acid groups conferring solubility in water, or 1:1 metal complex dyestuffs. Of the dispersion'dyestuffs, azo and anthraquinone dyestuffs should particularly be mentioned.

The cellulose material manufactured according to this invention behaves particularly well in a mixture with, for example, untreated cellulosic fibres. 'Here it is possible to achieve, with a dyestuff mixture of a direct dyestuff and wool dyestuff, applied from a single dyebath, dyeing effects and color patterns which are determined by the fibre distribution (for example strips of any desired width and any desired spacing) in the mixed fabric. The direct dyestuff dyes the entire fabric whilst the wool dyestutf only dyes the fibres in the fabric which has been manufactured according to the invention (differential dying).

Tone-in-tone dyeings of fibre mixtures of the fibre material according to the invention and wool/polyamides or polyester fibre material can be obtained using wool or dispersion dyestutf.

The dyeing of the material may be carried out in the usual manner for these dyestuffs, for example, according to the padding process or the exhaustion process at an elevated temperature. I

The essential advantage of the cellulose material manufactured according to this invention resides in the fact it remains cellulose like and, nevertheless, possesses the novel dyeing properties described. It thus differs from the so-called animalized cellulosic fibres which are obtained from viscose spinning composition into which large amounts of nitrogen-containing substances are incorporated. These animalized cellulosic fibres have partially lost the dyeing properties of cellulose and in this respect behave more like wool. a g

The following examples further illustrate the present invention. Unless otherwise stated, the parts quoted in the example are parts by weight.

EXAMPLE I 5 g. of the preparation A described below are emulsified with 5 g. of an addition product of 8 mols of ethylene oxide to 1 mol of p-tert.octylphenol, filtered and stirred into 983 g. of viscos g. of cellulose). The viscose is spun in the usual manner with the aid of a precipitation bath containing sulphuric acid to give long fibres. The fibres are subsequently washed in after-treatment baths (for example water desulphurized (for example with dilute aqueous solutions of sodium sulphide. and sodium hydroxide) washed and brightened.

Preparation A consists of 28.6 parts of a Component I and 71.4 parts of'a Component II. Component I is manufactured as follows: A reaction mixture of 48.2 parts of diethylenetriamine, 34.6 parts of bisphenol A and 17.2 parts of a bisphenol A-epichlorohydrin resin with 182 to 191 epoxide equivalents per kg. of resin is reacted for about 5 hours at 200 C., with the'volatile constituents being distilled ofi towards the end of the reaction by -applying a water pump vacuum.

Component II is manufactured as follows: A mixture of 40 parts oftall oil fatty acid and 13.8 parts of dimerised fatty acids is heated to C. whilst stirring and is mixed with 34 parts of triethylenetetramine at this temperature. The temperature is then raised to 200 C. and is kept for 3 hours at this value, with a water pump vacuum being applied in the last hour.

The resulting polyamine-amide is then further mixed with 17.2 parts of xylene.

The cellulose material manufactured with this preparation can be well dyed with acid wool dyestutf and dispersion dyestuffs according to the methods known for dyeing .with these dyestuffs. Suitable dyestuffs are, amongst others:

1:2-ehromlum complex (1) HO OH H0 Reddish brown:

, l c=N I Hg N0 I 8 0d! 1 g v v 1:2-cobalt complex (2 .1321: HO Yellow.

CH; N=NC I C= H]- OQNHCHI 1:2-chromium complex 3 HO Oran B; Ho 8 N=NC\ I I OzNHz 1:2-chrom1um complex TABLEContlnued 1 Z-chromium complex ZL'O T N=NC S 02C H 1:2-eobalt complex OZNH(CH:)3O CH1 1 :2cobalt complex OH HO 0 zN l (7) O NH:

YN Omzoocmcr 1:1-chromlum complex (9).....'...' O NH1 OCH;

i) NH-S 00cm a NE Red.







7.5 g. of the Preparation B described below are filtered in the form of a strength aqueous solution and stirred into 983 g. of viscose (75 g. of cellulose).

The viscose is spun as described in Example 1 and the fiber material is appropriately after-treated. Preparation B is manufactured as follows:

A solution of 49.4 g. of 'a condensation product of polymerized linoleic acid and diethylenetriamine having an amine equivalent of 247, and 49.4 g. of methanol, are

added over the course of 24 minutes, with good stirring, into a solution, warmed to 51 C., of 38.4 g. of an epoxide formed from 4,4'-dihydroxydiphenyl-Z,2'-propane and epichlorhydrin, having an epoxide equivalent of 191, and 38.4 g. of methanol, the reaction temperature being 51 to 53 C. 3 g. of glacial acetic acid are added after 8 minutes and again after 18 minutes from the start of the dropwise addition, and after 24 minutes a further 2 g. of glacial acetic acid are added. The reaction is continued for a further 2 hours and minutes at 55 to C. The reaction product is then soluble in water to form an opalescent solution. Thereafter 4 g. of glacial acetic acid and 273.4 g. of water are added whilst stirring. A yellowish viscous cloudy 20% solution having a pH-value of 5.2 is obtained.

A mixed cellulosic fabric of viscose fibres and fibres manufactured according to the invention with Preparation B, the latter having been woven in as stripes, is dyed by 7 the exhaustion process, in a known manner, with the following dyestufls:

A fast blue dyeing with violet stripes is obtained.

We claim:

1. A process for the manufacture of viscose fibers with novel dyeing properties, which comprises adding to the viscose spinning solution before precipitation from 1 to 20% by weight, based on the weight of cellulose content in said spinning solution, of a mixture comprising:

(A) from 90 to by weight of a polyamine-amide obtained by reacting (a) from 40 to 80% by weight of an unsaturated fatty acid with at least 12 carbon atoms or a dimer or polymer thereof and, (b) from to 60% by weight of a polyalkylene-polyamine; and

(B) from 10 to 90% by weight of a polyepoxide-polyamine product obtained by reacting (c) from to 40% by weight of a polyepoxide and (d) a stoichiometric excess of a polyal-kylene-polyamine, said polyalkylene-polyamine being present in an amount of from 75 to 60% by weight.

2. A process according to claim 1 wherein (a) is an --unsaturated fatty acid With"'l 2 to"l8 carbon atoms'or a' dimeror polymer thereof. 1 1.

3. A process according to claim 1 wherein (c) i s a;

reaction product of Bi'sphenol A andepichlorohydrin.

4. A" process "according to claimil wherein (b) and (d) is ethylenediarnine, diethylenetr'iarnine or triethylenetetramine. ,1 f v 5. A process according to claim 1 wherein the additives derived from (a) and"'(b) and from (c) and (d) are added to the spinning solution asan aqueous or organic solution or a dispersion. 6; t 1

6. A process according to claim 5 wherein the additives are added to the spinning-"solution inthepiesence of a non-ionic emulsifier. 1

7. A process according to claiml whereinthej additives are added to 10% by weight being a polyaniine-amide derived from (a) and (b) and 90%;;byweight being a reaction product of (c) and (d), W

8. A process according to clairn 1 hereln the additives are added in an amount totalling 1 to 512% by wei ght based on the celluloseconte'nt in the spinning solution. Reference Cited r UNITED STATES RATENTS 2,767,089 10/1956 Renfrew 61111. Gil -2i 2,852,334 9/1958 Hollihauet 211,1" 064444 2,971,816 2/1961 Hollihan et a1. 3 264-193 3,016,305 1/1962 Vosfers 106-165 3,046,085 7/1962 Burroughs et al.- 264-194 3,066,032. l1/.1 962. Fukushima et al 106165 3,106,444' -10/196'3 Mueller; 264-194 3,278,560 10/1966 Garbner .-s 116.2

FOREIGN PATENTS H 37-17771 10/1962 Japan 264-188 .TAY H. WOO, Primary Examiner "Us, c1. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4767807 *Aug 18, 1986Aug 30, 1988Nippon Shokubai Kagaku Kogyo Co. Ltd.Coloring agent for dope-dyeing viscose rayon
US5529585 *Jun 7, 1995Jun 25, 1996Hoechst AgRayon modified with polymeric amine compounds
US5542955 *Sep 29, 1995Aug 6, 1996Hoechst AktiengesellschaftDyeing modified viscose fibers with acid or direct dyes
US5565007 *May 15, 1995Oct 15, 1996Hoechst AktiengesellschaftAmination of rayon
US5684141 *Jan 26, 1995Nov 4, 1997Hoechst AktiengesellschaftAminated cellulosic synthetic fibers
US5865858 *Oct 31, 1997Feb 2, 1999Hoechst AktiengesellschaftAminated cellulosic synthetic fibers
U.S. Classification264/78, 524/35, 264/191, 264/194, 524/168, 524/242, 524/159, 106/166.43, 524/106, 106/166.42
International ClassificationD01F2/10
Cooperative ClassificationD01F2/10
European ClassificationD01F2/10