US2307973A - Dyeings - Google Patents

Description

UNITED STATES PATENT OFFICE l.

nmmds Wilhelm Tischbein and Otto Bayer, Leverkusen I. G.-Werk, Johannes Nelles, Leverkusen- Schlebusch, and Fritz Ruf, Dormagen, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware I No Drawing. Application May 12, 1938, Serial No. 207,502. In Germany May 20, 1937 10 Claims. (01. 18-54) The present invention relates to a process of By all these methods it is possible to more or pmvi dyeings with wool dyestuffs, which are less increase the affinity of the cellulosic mateof insufficient fastness to wet treatment, on aniri l W00 y t malized cellulosic material. However, it has been a serious practical dis- It is known that the aiiinity of all kinds of 5 advantage f these pro ss s that the e ss cellulosic material, for instance fibers, bands and produced on the material'th'us animalized were films of natural or regenerated cellulose or cellu- Often not sufiiciently fast towards wet t ea lose derivatives, to wool dyestuiiscan be increased for i s e owa Wa W flllling, p by incorporating. with the material a basic subting, p spi atio et This was sp y t stance. Since thereby the material, in its becase with the best known anim'alizing agents haviour towards dy t is rendered more or which themselves do not sufliciently take on the less similar to animal fibers, this m th d of i fiber, i. e. which are not sufiiciently substantive. creasing the afiinity to wool dyestuffs i com- Generally, therefore, dyeings produced on animonly called animalizing and the basic submalized cellulosic material, lacked the good faststances incorporated with the cellulose material Hess to wet treatments Possessed by dyeings wit to produce the said effect are called animalizing the a dyestuffs 011 1- agents. It is an object of our invention to avoid these Animalizing maybe performed, for instance, by disadvantages and to furnish a method which incorporating with the material a compound will allow to produce dyeings on animalized celtainlng basi nit phosphorus or ulf r lulosic material which are of similar fastness This may be done i any suibabm stage of the towards wet treatments as the dyeings produced production or treatment of the material. \Among 011 wool even when animalizing agents of the compounds which may and have been used cient substantivity have been used. This and for this purpose there may be mentioned, for i other objects of our invention will be apparen stance, polyalkylenepclyamlnes, p01ya1ky1ene from the following description thereof. imines, derivatives of urea and guanidlne, basic Broadly speaking, our invention consists in condensation products from P1191101, frm.a1de plying to the cellulosic materiaLbesides the said hyde and aliphatic monoor diamines, reaction animalizing agent agents, a Practically products of halogenated aliphatic or aromatic less non-basic Organic Substance being of the hydrocarbons, esters, ketones, po1y1neri ate t :50 character of a mordanting agent. By the term with primary, secondary or t t mines f mordanting agen as used in the description of polyamines. Moreover, high mOIecular ammo our invention and the claims annexed'thereto, as I nium, phos honi and sulfoniu compounds customary in the art, such agents are meant and also reaction P s cf esters of polyal which are capable of forming insoluble comhols with m or polybasic aliphaticor arm :15 pounds with basic dyestuffs and which are suitmatic acids, fQI i t toluene sulf ni acid able, therefore, in the art of dyeing as mordants ester of star h t nitrogen containing for applying basic dyestuffs to the cellulosic fiber. pounds come int ti 1 As such compounds there may be specifically Sometimes it is preferable not to incorporate mentioned for instance, n, gallnut extract, the animalizi agents in t ready made state 40 other natural or synthetic tanning agents, tamiin with the material, t; t produce the animaliz substitutes like phenol/sulfur condensation proding'asent from suitable reactive components in p and the metal compounds thereof condensa" and on the material itself, for instance by req products of phenols with phenol sulfonic acting suitable reactive compounds with nitroof phenols or hydroxyarylsulfones with gen phosphoms or sulfubcontahfing :5 aldehydes like formaldehyde, of phenols with poumh For instance, there may be added to the acetylene, and many more like compounds.

DiHmn' a solution of celluloseor cellulose deriva- 3 mordagtlpg agentstaccoidmg to our Hifive halogenated Substances like halogenated ven 1011 may e mcorpora ed w1th he cellulosic material at any stage of the manufacture thereparaflln, halogenated polymensates, or esters like of, before, together with or after the incorporathe toluene sulfonic ester of starch, and the filat of th animalizing agent. The mordanting m n fi e bands, films or the like precipiagents may be applied in any suitable way from tated from these solutions may be treated with neutral, alkaline or acid solution or emulsion. bas1c substances like pyridine, ethylenediamine, They may also be incorporated with spinning sopolyalkylenepolyamines etc. so lutions of cellulose or cellulose derivatives. The

treatment of the material with the mordanting agents may be performed at room temperature or preferably at higher temperatures, up to boiling temperature. In many cases it is advantageous to use, besides the mordanting agent, other compounds which are known to promote its going on the fiber, for instance, organic or inorganic salts.

The amounts of animalizing and mordanting agents to be used may vary over a relatively large range. agents depend on the kind of material to be treated and of the kind of dyeing one wants to produce. In case the mordanting agent does not possess sufiicient substantivity, like for instance 'in the case of tannin, it is advantageous to treat the material in the usual way with 'a fixing agent for the mordanting compound, for instance, in the case of tannin with tartar emetic.

The dyeings produced on the material thus treated with wool dyestufis are of improved fastness towards water, perspiration, fulling, potting, steaming, washing, etc., in comparison with dyeings on material which has not been treated according to the present invention with a substance of mordanting character.

In some cases the afiinity of the animalized material to dyestuffs is slightly changed by the treatment with the mordanting agent; it may be increased orlessened. This is especially apparent when simultaneously dyeing the animalized material and wool, for instance, in mixed yarns or mixed fabrics, and may be used in order to obtain more level dyeings. It .was also observed that on dyeing such mixed material with dyestuff mixtures a much better tone-in-tone coloration was obtained on the material treated according to the present invention.

Of course, the exact amounts of both Tables, Vol. II, 1932, page 203), Supramine Violet R (Schultz, Dyestufif Tables, vol. II, 1932, page The invention is further illustrated by the following examples without being restricted thereto, the parts being by weight:

Example 1 3.5% of a condensation product of chlorinated paramn and ethylenediamine according to British specification No. 359-,001 are added to a spinning solution of cuprammonium cellulose. 100 parts of the resulting cellulose are impregnated at 80 to 90- C. for 2 minutes in a bath containing 5 to 10 parts of a phenol-sulfur compound prepared according to British specification No. 173,313 and 2 to 5% sodium carbonate. The rinsed and dried fiber is dyed as usual with Wool Fast Blue -BL' 204), Anthralan Violet 3B (Schultz, Dyestufi Tables, 1st sup. vol., 1934, page 68), Anthralan ,Blue, G (Schultz, Dyestuff Tables, 1st sup. vc1.,

1934, page 68), Alizarine Light Grey BBLW (Schultz, Dyestuff Tables, vol. II, 1932, page 12), Diamond Black P2B (Schultz, Dyestuff Tables, vol. I, 1931, No. 234) Example 2 If, instead of cuprammonium cellulose, viscose cellulose or viscose artificial silk is employed, the fastness properties of the dyeings with acid wool dyestuffs are considerably improved by the treatment according to Example 1.

Example 3 When dyeing cellulose or cuprammonium cellulose together in the same dyeing bath or as mixed yarn, mixed fabrics or mixed tissues with wool according to Example 1 or 2, for instance, in the proportion 50:50, the dyeing is also improved in comparison with the non-treated material.

Example 4 When using a condensation product of polyethyleneimine and alkylhalogenides, for instance octadecylbromide, instead of the animalizing agent of Example 1, on dyeing, for instance with Anthralan Red BBT (Schultz, Dyestufi Tables, 1st sup. vol., 1934, page 68) a considerable improvement of the fastness properties is obtained.

Example 5 A spun viscose fiber is animalized with 3% octadecylbiguanide in the usual manner and subsequently treated with a phenol sulfur compound as described in Example 1. The fiber dyed together with wool, for instance with the dyestui-f of Example 1 shows an improved fastness to water, washing and perspiration.

Example 6 Cuprammonium cellulose is animalized with 5% of a condensation product of ethylenediamine with a higher fatty acid chloride. On aftertreating the same with tannin or a tannin substitute the dyeings are further improved.

Example 7 a certain reserving of the animalized fiber is ef- Similar results are obtained when dyeing with 7 other acid wool dyestuffs; as for instance Anthralan Yellow G (Schultz, Dyestuff Tables, 1st sup. vol., 1934, page 68), Supra Light yellow GL (Schultz, Dyestufi Tables, vol. I, 1931. No. 736),

Anthralan Red B (Schultz, Dyestuff Tables, 1st

sup. vol., 1934, page 68) Supranol Brilliant Red B, (Schultz, Dyestuff Tables, vol. II, 1932, page 204). Supramine Bordo B (Schultz, Dyestufi fected.

Example 8 Example 9 Animalized staple fiber prepared as described in Example 1 from a cuprammonium cellulose solution is treated at about 90? C. for .3 minutes in a bath containing 5 to. parts methylenedisalicylic acid of the formula:

i l C0011 C0011 Example 10 The staple fiber animalized as described in the foregoing example is treated similarly as above described with a condensation product'from dihydroxydiphenylsulfone and formaldehyde (obtainable according to German Patent 464,088). Dyeings with wool dyestuffs on this material, besides showing better fastness to Wet treatment, are also of better fastness to light in comparison with dyeings on material which has not been treated with the mordanting agent.

Example 11 To a cuprammonium cellulose solution with which an animalizing agent has been incorporated ficial fibers there are added 5% of a product obtainable by precipitating the animalizing agent of Example 1 (chlorinated parafiin+c amine) from its acid aqueous solution by adding a phenol-sulfur condensation product (compare British Specification 173,313). Dyeings with acid dyestuifs on such material are of improved fastness to wet treatments.

Example 15 Staple fiber from viscose prepared similarly as described in Example 1 with addition of an animalizing agent to th spinning solution is dyed with Anthralan Violet 3B (see. Example 1) and aftertreated with a soda-solution of the phenolsulfur condensation product of Example 1. The

fastness of the dyeing to wet treatments is increased thereby.

Example 16 Staple fiber is spun from a cuprammonium cellulose solution containing 3% of a phenol-sulfur as described in Example 1 there are added 1 to 3% of a phenol-sulfur compound (see British Specification No. 173,313), and the mass is well kneaded. Staple fiber prepared from this solution is dyed with excellent fastness to wet treatments by wool dyestufis.

Example 1 A viscose spinning solution is prepared, similarly as described in the foregoing example, by first adding the animalizing agent and thereupon the mordant. Fibers producedfrom this solution are dyed by wool dyetuifs with excellent fastness, ex-

ceedlng the fastness of dyeings on material containing no mordant.

Example 13 Animalized staple fiber prepared as described in Example 9 from a cuprammonium spinning solution is treated as described in Example 1 with a mordanting compound of the formula:

Dyeings with wool dyestuffs on this material are of improved fastness when compared with dyeings which have been produced in the absence of a mordant.

Example 14 To a spinning solution for cuprammonium articondensation product. The material is then treated with an aqueous emulsion of the animalizing agent mentioned in Example 1. and dyed with Anthralan Blue G (see Example 1). The dyeing is of improved fastness when compared with the dyeing on material containing no mordant.

Example 1 7 Staple fiber animalized and mordanted as described in Example 1 is dyed in thepresence of an equal quantity of wool with the following wool dyestuffs:

Rhodamine B extra (Schultz, Dyestufi Tables, vol.

1, 1931, N0. 864), Turkise Blue BB (Schultz, Dyestuff Tables, vol. 1,

1931, No. 757) Victoria Blue B (Schultz, Dyestuif Tables, VO1.'1,

A good tone-intone coloration is obtained. Animalized staple fiber which has not been treated with the mordanting agent is' not or only slightly dyed with insufficient fastness by the said dyestuffs.

Example 18 50 parts of staple fiber from cuprammonium cellulose animalized as described in Example 1 are treated for 5 minutes at to C. in an aqueous bath containing per liter 7.5 gs. of a alkali-soluble phenolformaldehyde resin (prepared by condensing the components in an acid medium) and 5 ccms. of caustic soda lye of 32% strength. The material is then squeezed, treated for a short time in a bath containing.5 ccms.

glacial acetic acid per liter, rinsed and dried;

The material is then dyed in the usual manner alone or in the presence of wool with acid wool dyestuffs like 2% Supra Light Yellow GGL (Schultz, Dyestuff Tables, vol. 1, 1931, No. Z36) 8% Diamond Black P2B (Schultz, Dyestufl! Tables, vol. 1, 1931, No. 234),

2% Palatine Fast Blue BN (Schultz, Dyestufi' Tables, 1st sup. vol., 1934, page 117).

Instead of the above-mentioned condensation product from phenol, also similar condensation products from the homologues of phenol, for instance from cresols, may be employed.

The treatment of the staple fiber with the mordanting agent may be performed during any stage of its manufacture, before or after the final drying of the fibers.

Example 19 If instead of the phenolaldehyde condensation product of the foregoing example an equal quantity of an alkali soluble reaction product from phenol and acetylene (compare the German Patent 642,886, Example 1) is used, the fibers are dyed by wool dyestuffs with better fastness to wet treatments than if the fibers were not treated with the phenol-acetylene condensation product.

We claim: 7

1. A process of improving the fastness to wet treatment of dyeings wtih wool dyestuffs on shaped animalized cellulosic material which comprises treating said material at any stage of its manufacture with an organic mordanting agent for basic dyestuffs and dyeing the mordanted material with an acid dyestufi.

2. A process of improving the fastness to Wet treatment of dyeings with wool dyestuffs on animalized cellulosic material which comprises treating the material after precipitation from a spinning solution containing an animalizing agent with an organic mordanting agent for basic dyestuffs and dyeing the mordanted material with an acid dyestuff.

3. A process for improving the fastness to Wet treatment of dyeings with wool dyestuffs on animalized cellulosic material which comprises incorporating an animalizing agent and an organic mordanting agent for basic dyestuffs with a spinning solution of the cellulosic material, precipitating and dyeing the precipitated material with an acid dyestufi.

4. A process of improving the fastness to wet treatment of dyeings with wool dyestufis on animalized cellulosic material which comprises treating said material after precipitation from a spinning solution having incorporated therein an animalizing agent, at temperatures from 50- 100 C. with an aqueous alkaline solution of about i 10 to of an organic mordanting agent for basic dyestuffs and dyeing the mordanted material with an acid dyestufi.

5. A process of improving the fastness to wet treatment of dyeings with wool dyestuffs on animalized cellulosic material which comprises treating said material after precipitation from a spinning solution having incorporated therein a condensation product from chlorparafiin and ethylenediamine, at temperatures of from C. with an aqueous alkaline solution of about 10 to 15% of a phenolformaldehyde mordanting agent for basic dyestuffs and dyeing the mordanted material with an acid dyestuff.

6. A process of improving the fastness to wet treatment of dyeings with wool dyestufis on animalized cellulosic material which comprises treating the material after precipitation from a spinning solution having incorporated therein a condensation product from chlorparaffin and ethylenediamine, at temperatures 'of from 50- 100 C. with an aqueous alkaline solution of about 10 to 15% of a phenolsulfur mordanting agent for basic dyestuffs and dyeing the mordanted material with an acid dyestuif.

7. Cellulosic fibers having incorporated therewith an animalizing agent and an organic mordanting agent for basic dyestuffs, said fibers being dyed with an acid dyestufi".

8. Fibers from regenerated cellulose having incorporated therewith an animalizing agent and an organic mordanting agent for basic dyestufis, said fibers being dyed with an acid dyestufi.

9. Fibers from regenerated cellulose having in corporated therewith a condensation produc'. from chlorparafline and ethylenediamine and a phenol-formaldehyde mordanting agent for basic dyestufi's, said fibers being dyed with an acid dyestuff. 1

10. Fibers from regenerated cellulose having incorporated therewith a condensation product from chlorparaffine and ethylenediamine and a phenol-sulfur-mordanting agent for basic dyestuffs, said fibers. being dyed with an acid dyestuff.

WILHELM TISCHBEIN. OTTO BAYER. JOHANNES NELLES. FRITZ RUF.