US2261294A

US2261294A - Process of increasing the affinity of fibers and films for acid and substantive dyestuffs

Info

Publication number: US2261294A
Application number: US152994A
Authority: US
Inventors: Schlack Paul
Original assignee: WALTHER H DUISBERG
Current assignee: WALTHER H DUISBERG
Priority date: 1936-07-24
Filing date: 1937-07-10
Publication date: 1941-11-04
Anticipated expiration: 1958-11-04
Also published as: BE422662A; FR826740A; NL50107C; GB484984A

Description

Patented Nov. 4, 1941- UNITED STA ES PATENT OFFICE um I I PROCESS OF INCREASING THE F "FIBERS AND FILMS FOB ACID AND I SUBSTANTIVE DYESTIJFFS I l'aui'schlack, Berlin-Trenton Germany, assignor, by mesne asalgnmen Duisberg, New York, N. Y. I I

Application Jub 10, 19:1. sen-n1 No. In Germany NoDrawing.

is, a Walther n.

sl-r 24, ms

5 Claims. 8-ll3) My present invention. relates to a process of improving thedyeing. properties of natural or artificial fibrous 'material'and foils and more particularly to a process in which fibrous materials or foils containing acid hydroxyl-groups are treated 'with alkylene imines or their salts. I

It is an object of-the invention to provide a process by which the afiinity of these products towards acid and substantive dyes is esentially increased. I

Further objects will be apparent from the-detailed specification following hereafter.

My invention is based on the observation that natural products or artificial structures such as fibers, sheets, leather, wood or paper which contain in a fixed form residues with hydroxyl groups united with carbon and of pronolmced acid char-- acter, cially carboiwl groups or mercapto alkyl groups but not when united to. protein residues, acquire an intense aihnity for dyestuffs of all kinds having acid groups if they are subjected, if desired during. or immediately following the shaping operation, to a treatment with an alkylene imine or a saltthereof. In this manner the original afiinity of the structulrefor basic I dyestufis decreases as the action of the alkylene imine increases and may finally completely disappear.- If thegoods under treatment are very rich in acid, groups at intermediate stages of the treatment the aflinity for acid or dyeshlfi's sufilce but in the case of basic dyestuffs it is advantageous to dye at comparatively low temma I The process based on the foregoing observation is especially important in casesin. which the dimculties of dyeing are greatest, namely in particular the dyeing of artificial structures-e pecially fibers or products made-therefrom, which consist or did consist originally essentially of organophil components, for example structures of organic cellulose derivatives such as acetyl cellulose or ethyl cellulose; also structures from vinyl polymerides, for instance polyvinyl esters. P vinyl acetals, polyvinlyacetal-acid esters and such mixed polymerizates as contain vinyl esters. acrylic acid esters, acrylic acidamides, acrylic acid nitriles as components. In so far .as the structures contain saponifiable m l they may be pretreated with a saponifying agent or denitrating agent before being subjected to the action of the alkylene'imine whereby thereactivity is increased. Such a saponification may be conducted in a manner in itself known, such that it follows a heterogeneous course, that is to say tively uniform, occurring also in the deeper layers, the action thus being quasi-homogeneous or permutoid. In general the last named type of reaction which is obtainable with ammonia or organic amines has the advantage. By such a saponification the acid groups necessary for the process, in particular the carboxyl groups, are first unblocked. Obviously also free phenolic hydroxyl groups may be produced in this manner, but generally speaking phenol esters are so freely capable of hydrolysis that their scission occurs already by the action of the imine in case they are used in the. form of the free base. It is therefore not unconditionally necessary in such cases that there should be a separate preliminary saponification treatment Reactive carboxyl groups can also be produced from suitable components by means of a pretreatment with an oxidizing agent correspondingly with the disclosure contained in U. S. pa nt application Ser. No. 57,524, filed January 4, 1936.

'For the process of this invention there are used acid components which are named in large numher in the aforesaid U. S. patent application Ser.

No. 57,524. Here, therefore, only the more important components will be named. po ymeric carboxylic acids, their anhydrides. and esters,=in particular mixed polymerizates obtained from unsaturated monoor di-ca'rboxylic acids and functional derivatives thereof as components, for example mixed polymerizates from vinyl alkyl ethers products from aromatic hydrocarbons with side chainscarrying hydrogen in aposition and c-B- unsaturated dicarboxylic acid anhydridesiU. S. patent application Ser. No. 733,126, now Patent No, 2,121,183) for instance a product of the reaction of. nlene and maleic acid anhydride, also phenol aldehyde resins and their acyl derivatives, especially acetyl derivatives, acetyl tannin, sulfur products from phenol of high-molecular weight, polyvalent mercapto compounds and acyl derivatives thereof, for instance the acylated reaction product of the chlorinated resin from xylene formaldehyde with potassium hydrosulfide.

It is to be noted'thatthe process is in no way limited to the above mentioned productsfrom organophil highly polymeric bodies. It is equally there is a stratified action or that it is compa'n- '5 appli able to structures of the more or less pronounced hydrophil substances, for example natural or artificial cellulose products like cotton, cellulose artificial fibers with which the acid components, for instance pectin substances, polyacrylic acids, mixed polymerizates from maleic acid and vinylalkyl ether, vinyl ester or vinyl halide, phenol aldehyde resins, phenol aldehyde resins which have been caused to react with chloracetic acid, tannin, sulfurized phenols have been incorporated before or during the spinning or casting process. The incorporated substance must, so as to be within the scope of the invention. be fixed in the structure and therefore must be with difiioulty or not at all removable by water. A simple impregnation with a watersoluble body of low molecular weight which has no aillnity for the fiber, that is to say which is not fixed o1- precipitated on the fiber, is not within the ambit of this invention.

A particularly strong action is produced when the acid groups, particularly carboxylic acid groups, have been saturated with organic bases before the reaction with alkylene imine, the organic bases carrying halogen alkyl groups, preferably several; such as three or more. Not only are nitrogen bases useful for this purpose, but also bases containing 5-valent phosphorus or 4- valent sulfur as a basic element. Suitable bases are, for instance, the chloroand bromo-alkylamines obtainable by halogenation of oxalkyl bases, for instance pV-dichlorodiethylamina pp'p"-trichlorethylamine, the products of the action of excess of allq'lene halide such as ethylene chloride, ethylene bromide, trimethylene bromide or 1:2:3-trichloropropane on monoand polyamines such as triethylamine, ethylene diamine or tetramethylethylene diamine. Espe-, cially suitbale for use are the poly-'y-chloro-fihydroxy-propylamines obtainable in completely colorless condition, which are accessible in good yield by the invention of U. S. patent application Serial No. 53,003, filed December 5, 1935, now Patent No. 2,143,383, from ammonium salts or amine salts.

A reinforcing effect is produced by a pretreatment with a polyvalent mercapto alkyiamine, for instance the reaction product of ethylene diamine and 4 mols propylene sulfide. The mercaptans are preferably applied to the structure in presence of a reducing agent, for instance a hydrosulfite, in order to prevent oxidation or premature oxidation.

As example of imines suitable for the invention the following may be named: ethylene imine, C-methyl-ethylene imine, N-methylethylene imine, N-butylethylene imine, N-cyclohexylethylene imine, the quaternary iminium salts from N'N'-dimethyl-N'N'-di-p-chloroethylethylene diamine and NN'-di-'y-chloro-p-hydroxypropyl piperazine. Quaternary iminium salts are advantageously used in the case of hydrophil structures, but in the case of hydrophobe fibers they generally give only comparatively. feeble effects.

In so far as imines are suiilclently volatile the solvent or emulsified with one of these. Liquid imines, for example N-butylethylene imine as well as the higher homologues thereof, may be used directly by spraying them on the goods to be treated, especially if by subsequent raising of the temperature in a closed vessel there is produced at least a partial evaporation and thereby a uniform distribution of the agent. Such a spraying operation is particularly suitable when cu't staple fibers are under treatment.

"The reaction may be combined with an aminetion of groups with alkylating function attached to residues of high molecular weight. (Loniponents suitable for this special case are for instance those resins having alkylating groups named in U. S. patent application Serial No. 41,500, filed September 20, 1935, now Patent No. 2,142,007. and also cellulose derivatives having reactive halogen. An alkylene imine, for instance ethylene imine may be the sole reactive agent. However, with a special advantage may be used besides alkylene imines another aminating agent or its equivalent, for instance pyridine, trimethylamine, isoquinoline, or triethylene phosphine. Mixtures may also be used which contain, for example besides a free tertiary base such as pyridine, an ethylene imine in the form of'a salt, for instance the acetate or paratoluene sulfonate. In this manner'control of the action Obviously such reactions may be conducted in stages which may be of advantage when one detreatment may preferably be conducted in a gassires first to satisfy the tendency of the acid groups to combine with the dymtuifs and only then to change the character of the amnity of the structure fo dyes, in order, for example, to

top dye with a certain basic dyestuflf another.

fibrous material present in the mixed fabric or in order to permit a further dyeing with an acid dyestufl. The combined action of the alkylene imine on the acid groups and the amination of the groups with alkylating function is especially of interest in a case of fibers and other structures of hydrophobe character.,. As such may be cited fibers from acetyl cellulose which contain in addition to a mixed polymerizate having free carboxyl groups or car-bowl groups which spontaneously become free, for instance the mixed polymerizate from vinylmethyl ether and maleic acidanhydridc, a highly polymeric substance with reactive halogen, bound in the manner of a hydrogen-halide-ester, for instance polyvinyl chloracetate.

The structures obtained or changed by the process of the invention may be dyed with very many acid and substantive dyestuffs of the various classes in various tints which have good properties of fastness. Structures which already exhibit ailinity for the dyestuffs in question acquire an increased dyeing capacity, and in most cases the fastness of the dyeings is not inconsiderably' increased. The fastness on cellulose, fibers and fibers of cellulose derivatives may dimethyl sulfate, para-toluene sulicnic acid methyl ester, epichlorhydrin, 3-chloro-L2- propylene'sulfide, chloracetic acid diethylamide, benzyl chloride, xyiylene-bromide. 1.4-dichlorbutene-2.3, .a-dichlordimethyl-ether, chloracetone, 1:3-dichloracetone, diethylethylene-iminiumchloride. In this connection reference may be made to my copending applications Ser. No. 53,004 filed December 5, 1935, now Patent No.

2,131,146; Serial No. 60,061 filed January 21,

application Ser. No. 123,867, filed February 3,.

1987). Both the primary treatment and the after-treatment may occur in the presence of swelling agents for the substratum.

The following examples illustrate the invention:

1. A fabric of acetate artificial silk consisting of 90 per cent acetyl cellulose with 54 per cent of bound acetic acid and 10 per cent 01' a mixed polymerizate from 1 mol vinyl-methyl ether and 1 moi maleic acid anhydride is thoroughly desized at 60-65 C. by means of a soap solution containing grams per liter, then acidified with a dilute acetic acid, rinsed and heated for 14 hours at 80 C. in a closed vessel of 50 parts by volume capacity containing 20 per cent of N-butyi-ethyiene imine absorbed in a.

clay plate, the relative moisture being 75 per cent of atmospheric moisture. Care is taken prescribed is treated with 20 per cent oi C- methyl-ethyiene imine in the absence of a conditioning agent for 8 hours at 75 0.; the imine disappears completely. The thoroughly acidified fiber may be dyed with many acid dyestufis, for example with Supranol Brilliant Red B (Schultz Farbstoiltabellen, 7th ed., vol. II, page 204), Azo Acid Black 3 BL (Schultz Farbstofitabellen, 7th ed., vol. II. P e 29), Alizarinecyanine Green G Extra; deep tints are produced.

4. Acetate artificial silk from acetyl cellulose containing 53 per cent of bound acetic acid and containing 12.5 per cent of theresinous anhydride made as described in U. S. patent application Ser. No. 733,126, now Patent No. 2,121,183, from xylene and maleic acid anhydride is heated with 15 per cent of ethylene imine in the vapor phase for four hours at 60 C. The fiber has now a distinct afilnity i'oracid dyestullfs, for instance Orange 11 or Alizarine Direct Blue A.

5. The acetate artificial silk obtained by'the I dry-spinning process from a solution in methyl ene chloride and alcohol and having 58 per cent that the atmosphere within the vessel is continually in motion, for example by rythmic variation of pressure as described in U. S. patent applicaflon Ser. No. 46,445, filed October 23, 1935. After, this treatment the goods are acidified with a solution of acetic acidvcontaining 2 grams per liter for 5' hour at 60 C. and are finally soaped for a short time. The fabric may now be dyed with many acid dyestuffs, for example Orange II (Schultz Farbstofltabelien, 7thv ed., vol. I, page 86). Aiizarine Direct Blue A (Schultz Farbstoiitabeiien, 7th ed., vol. II. page 9), Alizarlnecyanine Green G Extra (Schultz Farbstofltabelien, 7th ed., vol I, page 532), deep tones being; produced: for example a liquor containing 6 per cent oi Orange II, 10 per cent of Glauber salt and 4 per cent of acetic acid is exhausted at 60-75 C.

2. The same acetate artificial silk as is used-in Example 1 after having been acidified is treated in a liquor ratio of 1:20 with 20 per cent oifv tetrai' -chioro-p-hydroxypropyll ammonium chloride and the equivalent quantity of sodium acetate 161' 1 hour at 70 C. The silk remains pure white. It is then heatedat 70 C. for 4 to 8 hours with 10 per cent of ethylene imine in the vapor phase, the volume ratio being 1:40 calculated on the weight of the goods. Alter aciditying the treated silk exhibits a strong amnity tor substantive dyestuffs and quite especially for acid wool dyestufls oi the various classes. For example it can be dyed in very fast tints by aiter-chroming dyestuiis. Thus a 3 per cent dyeing with Acid Anthracene Brown KB (Schultz Farbstoiitabellen, 7th ed., vol. II. P e 187) becomes when after-chromed very fast to washing and iulling. The liquor and white material are only slightly tinted during alkaline iulling.

3. Acetate cellulose 01 the same constitution as given in Example 1 for the artificial silk there of bound acetic acid and 10 per cent 0! the acetyl tannin known in commerce underthe trade mark "Tannigeir is treated with 15 per cent of ethylene imine for 14 hours at 80 C. in'

the gaseous phase. The silk can now be dyed with many acid dyestufi's, for instance Alizarine Direct Blue A.

6. To a crude solution of cellulose triacetate in acetic acid there are added 10 per cent oi. the mixed polymerizate from 1 mol maleic acid anhydride and 1 mol vinyl-methyl ether. The films made from this solution are easily dyed with basic dyestuffs and acquire afiinity for acid dyestufifs when they are heated in a. closed vesselat 80 C. with 15 per cent of ethylene imine for 16 hours or over-night. The period of the reaction may be essentlally diminished by exposing the film to the action of the imine in a swollen condition. A suitable swelling agent is dioxane.

7. Acetate artificial silk having 54 per cent or bound acetic acid and containing 7.5 per cent of 'polyvinylchloracetate and 5 per cent oi the mixed polymerizate from 1 mol maleic acid anhydride and 1 mol vinylmethyl ether isheated for 8 hours at C. with the equivalent quantity oi N-methylethylene imine calculated on the reactive chlorine and the unblocked carboxyl groups. The aminated and subsequently scoured 'G (Schultz l'arbstofitabellen, 7th ed. V01- I, 9886- 295), Benzo Past Scarlet 4 BS (Schultz Farbstofltabellen, 7th ed., vol. 1, me 134), Diamine Pure Blue FF (Schultz Farbstofitabellen, 7th ed., vol. I, page 209), Sirius Light Blue 1'' 3 (3L (Schultz Farbstoiitabellen, 7th ed., Suppl. vol., page 131), the dye bath containing 9. per cent of calcined Glauber salt and 4 per cent of acetic acid may easily be exhausted. J

8. An acetate artificial silk made irom' an acetyl cellulose and in 54 per cent of bound acetic acid and containing 12 per cent of the mixed polymerizate from 1 mol maieic acid anlrvdride and 1 mol viuylmethyl ether is thoroughly soaped at 65 C. and soured with hydrochioric acid of 0.3 per cent strength; it is then calculated on the weight or thesilk. Aiter rinsing and souring with a solution of acetic acid containing 2 grams per liter for hali-an-hour at 60 0. the silk yields a good black when dyed with 8 per cent. of A20 Acid Black 3 BL in presence of 4 per cent of acetic acid at 40 to 80 C.

A silk which has not been aminated is only tinted light blue in the same bath. I

11 before the action otthe imine the same acetatesilk is treated in presence of the equivalent quantity of sodium acetate with a reaction product from N-butylamine chlorohydrate and 3.2 mols epichlorhydrin, the aiilnltyis further increased.

9. A solution of 20 per cent strength in glycolmethylene-ether (glycol formal) 01' 90 parts of acetyl cellulose having 58.2 per cent of bound acetic acid and containing parts. of mixed polymerizate'irom 1 mol malclc acid anhydride stuiis are improved considerably inv their fastness, particularly it the basic character oi the after-treatment with the alkylatingagent is reinforced by means of an isothio urea ether or cyanamide.

Also viscose artificial silk which has been mordanted with tannin and tartrametic alone and then treated with vapor of ethylene imine (15-20 per cent) at 70 C. exhibits an amnity to acid dyestufls such as Orange 11. The dyeing is comparatively fast to washing, but not so good as when an intermediate treatment with tetral- -chloro-p-hydroxypropyll ammonium chloride follows'the mordanting. r

13. Cellulose film which contains 8 percent 01 the polymeric carboxylic acid produced by splitting the mixed polymerizate from vinyl ethyl ether and maleic acid anhydride is suspended for 2 hours at 80 C. in vapor oi ethylene imine. The material cut into narrow bands may serve as an efiect material for the hat industry and may be dyed fast to light and water with acid 01' vinyl ethyl ether and maleic acid anhydride in the molecular ratio 1:1 is denitrated by means of a solution oi 12 per cent strength oi'ammoaqueous ethylene imine solution of 10 per cent strength at 40 C. and a short heating to 80 C. the silk becomes a strongly basic fibrous material which can easily be dyed with acid wool dyestufi's. The fastnessoi the dyeings, for instance that with 4 per cent of Alizarinecyanine Green G Extra is improved if theaminated fiber is treated before or after dyeing or simultaneously with the fixing of the dyestufif with an alkylating agent, for instance epichlorhydrin. Thus the silk impregnated with the dyestufi solution may be dried and the dyeing fixed by heating for 4 hours at 70 C. and 75 per cent relative moisture in presence of vapor of chlorhydrin.

11. Acetate artificial silk which contains 15 per cent of the esterification product of acetyl cellulose having per cent oi bound acetic acid and maleic acid anhydried or succinic acid anhydride is partially and permutoid saponified by exposure at a temperature of 70 C. for about 8 hours at a '75 per cent relative moisture by means of 8 per cent of ammonia in the gaseous phase. It is then after-treated with 10 per cent of ethylene imine in the form of vapor for 8 hours at C. The silk is then capable of being dyed with acid and substantive dyestufis. V

12. Viscose artificial silk is mordanted with tannin and tartrametic in the usual manner and then treated with 10 per cent of hexa- ['y-chlorop-hydroxypropyldiethylene] ammonium chloride dyestufls, for instance those oi the anthraquinone series, such as Alizarine Direct Blue A.

14. A band 01' viscose fiber is treated first with the sulfurized phenol sold in commerce under the trade mark Katanol ON" and then with a bath which contains tetra-['y-chloro-p-hydroxypropyll ammonium chloride and sodium acetate of which only about 8 to 10 per cent is taken up by. the fiber. The rinsed material is cut to staple and then after-treated with an aqueous ethylene imine solution of. 8 per cent strength at 40 C.

15. A film of cellulose ethyl ether containing 42 per cent of ethoxyl and 10 per cent of the mixed polymerizate from vinyl chloride and maleic acid anhydride is first treated for several hours with water at 60-70 C. and then aminated by means of 15 per cent 01' C-methylethylene imine in the gas phase. The film is dyed by means of Orange II 16. A film of cellulose ethyl ether containing 42 per cent of ethoxyl and 12 per cent of the mixed polymerizate from vinyl ethyl ether and maleic acid anhydride is treated for 8 hours with 15 per cent of ethylene imine at per cent of relative moisture' It now shows essentially increased afiinity for acid dyestuffs, such as Alizarine Direct Blue A or Metanil Yellow (Schultz Farbstofitabellen, 7th ed., vol. I. page 78).

17. A film of polyvinyl formal which contains 10 per cent of a "Novolak from 1 mol phenol and 6.5 mol formaldehyde is treated under conditions'given in Example 14 with ethylene imine. The film is now dyed strongly by Orange II.

18. A natural silk is mordanted with tannin and tartrametic and then treated in a solution of 30-60 C. containing 10 per cent othexa- [v-chloro-p-hydroxyethylenel diammonium chloride and the equivalent quantity of sodium acetate. It is then treated at 30-40 C. with an aqueous ethylene imine solution 01' 7 per cent.

strength. The silk is thus'given a considerably increased afilnity for acid dyestuils. Fabrics which have been made of silk treated in the manner described in this example and nitrated silk yield when dyed with acid or basic dyestufls or 'with both types of dyestufi powerful eflects.

merizate of 1 mol vinyl chloride and 1 mol maleic acid anhydride is soaked with 15 per cent of the product of reaction of ethylene diamine with 4 mol 1:2-propylene sulfide in presence of 3 per cent of sodium hydrosulfite at 50 to 70 C. After a short treatment the silk is after-treated with an ethylenelmine solution of 8 per cent strength at C. After a short time a strong elfect is produced. After acidifying the silk may be dyed with 4 per cent of Alizarinecyanine Green G Extra in presence of 4 per cent of acetic acid. The dye bath is rapidly exhausted at medium temperatures (-75 C.)

20. A film' of cellulose ethyl ether containing 42-43 per cent of ethoxyl and 10 per cent of the chlorinated resin from xylene and formaldehyde which has been caused to react with potassium hydrosulfide in alcohol and subsequently acetylated is heated in presence of alcohol vapor as a' swelling agent with 10 per cent of ethylenelmine and 3 per cent of trimethylamine for 8 hours at C. The film may now be dyed with suitable acid dyestuffs, for instance Metanil Yellow- 21. Copper silk which has been swollen by means of caustic soda lye of 4 per cent strength and then thoroughly wetted is impregnated with a solution of 10 per cent strength of ammonium glycerine-trls-phthalate at room temperature, then centrifuged, dried and acidified with dilute hydrochloric acid for fixing the acid on the fiber. A silk thus prepared is suspended for 4 hours at 60 C. in ethylenelmine vapor. It may now be dyed after preliminary acidifying in intense tints by means of acid dyestuffs. Instead of acidifying to fix the acid this object may be attained by heating. In similar manner other polycarboxylic acids and compounds equivalent in the sense of the invention, for instance aromatic trlcarboxylic acids, pyridine-polycarboxylic acids, aromatic polycarboxylic acids, such as di-hydroxynaphthalene-dicarboxylic acids, may be used.

22. Cuprammonium' artificial silk which has been swollen by means of 0.5 normal sodium hydroxide and which has subsequently been washed free of alkali, is impregnated at room temperature with an aqueous solution containing 10 per cent of the sodium salt of pentaer'ythrittetraphthalic acid, centrifuged and aftertreated after slight drying with a solution containing 1 per cent of the reaction product of dodecyltriethyiene-tetraminehydrochloride and 9 mols epichlorhydrin. Silk pretreated in this manner of formic acid at 90 to 95 C. a coloring which is fast to washing and fulling is obtained.

In case light tints are desired the silk which has sligh ly yellowed in the course of the amino.- tion may be bleached without any loss of affinity for the acid dyes.

24. Acetate artificial silk containing 10 per cent of acetyl cellulose maleic ester-acid (produced from partly acetylated acetyl cellulose and maleic acid anhydride) is treated at C. and per cent relative moisture for 7 hours with 12 per cent of ethylenelmine in vapor form. The silk contains about 1.5 to 2 per cent nitrogen. It is intensely dyed with acid dyestufi's.

25. Acetate artificial fiber containing 8 per cent of a soluble condensation product from 10 moi phenol and 8 mol formaldehyde obtained in an acid medium, is treated in the same manner as indicated in the previous examples with ethyleneimine. The fiber is intensely dyed with many acid dyestuffs such as for instance Alizarlne Direct Blue A.

26. Acetate artificial fiber containing 8 per cent of a mixed polymerizate from 1 mol vinylmethylether and 1 mol maleic acid anhydride or 1 mol vinylacetate and 1 mol maleic acid'anhydride and 4 per cent of the soluble condensation product from 10 mol phenol and 8 mol formaldehyde is aminated in the manner indicated in the previous examples at 70 C. with the aid of 5 per cent ethylenelmine. A fiber is obtained which contains up to 3 per centnitrogen and which is intensely dyed by a great many acid dyestuils.

27. A film prepared from hydroxyethyl cellulose soluble in alkali. whichv contains about 8 per cent cellulose glycolic acid is treated for 4 hours at 60 C. with 12 per cent ethyleneimine. The film now shows strong ailinity for acid dyestuil's, for instance Alizarlnecyanine Green G Extra.

1 The affinity is enhanced if the film is treated beforeamination with a solution containing 1 per cent of tetrachiorohydroxypropyl ammonium chloride.

In the claims following hereafter the expression having incorporated and fixed therein" indicates that the compounds inquestion must not is now treated for 4 hours at 60' C. and 75 per cent relative moisture with 15 per cent of ethylenelmine. The artificial silk animalized in this manner shows a marked amnity for acid dyestuffs for'wool. I

23. Acetate artificial silk produced according to the process disclosed in my copending application Ser. No. 47,638, filed October 31, 1935, which contains 10 per cent of a mixed polymerizate from 1 mol vinylmethylether and 1 mol maleic acid anhydride is heatedin a closed vessel at 75 per cent relative moisture for 12 hours at. 0. together with 15 per cent cyclohemlethyieneimine absorbed in diatomaceous earth, the content of the vessel being 60 parts of volume for'l part of the fiber by weight. After thorough acidifying with a solution of 0.5 per cent of formic acid at 60 C. the fiber contains about 1.2

percent'of potassium bichromate and 2 per cent. 7 treating said materials with not within the scope of -stuli's beremovable orat most with difficulty removable from the substratum by washing with water. Thetreatment of materials in which the acid hydroxyl group is bound to protein residues is the appended claims. What I claim is: 1

1. A process of increasing the afiinity of fibrous materials and films for acid and substantive dyematerials and films for acid and dye-J v stuffs said materials. having incorporated throughout and fixed within the body thereof an acid reacting resinous compound having in its molecule a member of the group consisting of the carboxyl groumthe phenolic hydroxy group, and

the 'mercapto-allryl group. which comprises. reacting on said materials an'amine containing in its molecule halogeno-fi-hydroxy-propyl gr'oups'aiicl said materials having incorporated throughout and fixed within the body thereof an 3. A process of increasing the afllnity of fibrous materials and films for acid and substantive dyesaid materials having incorporated throughout and fixed within the body thereof an acid reacting'resinous component having in its molecule a member of the group consisting of the carboxyl group, the phenolic hydroxy group, and the mercaptoalkyl group, which comprises reacting on said materials an amine containing in its molecule 'y-chloro-c-hydroxypropyl groups and treating said materials with an alkylene imine.

4. A process of increasing the afllnity of fibrous materials and films for acid and substantive dyestuifs, said materials having incorporated throughout and fixed within the body thereof an acid reacting resinous component containing in its molecule besides one of the group consisting of the carboxyl group, the phenolic hydroxy group and the mercapto-alkyl group halogen allryl groups, which comprises reacting on said materials an amine and treating said materials with an alkyleneimlne.

5. A process of increasing the aiiinity of fibrous materials and films for acid and substantive dyestuffs, said materials having incorporated throughout and flxed within the body thereof an acid reacting resinous component containing in its molecule besides one of the group consisting of the carboxyl group, the phenolic hydroxy group and the mercapto-alkyl group alkylating groups, which comprises reacting on said materials an amine, and treating said materials with an alkylene imine.

PAUL SCHLACK.