US2131146A - Xx their a - Google Patents

Description

Patented sept. 27, 1938 y ormwmm'rommma or to I. G. Farbenindusti-le Aktien'gc cllsc gg;

FrankIort on-the-Main 'tion or a 'm' aanaflmmam,macarlal ,No.

, am. In

for'v'a'rying their amnity. v

One of its objects is a process'jot treating-ma V terials for varying their aflinlt'y. Another ob- 5 ject is the material obtained by'this-proce'ssr Fur- 'ther objects will be's'en iromthe detailed speciflcation iollowinghereinafter.-

According to the present mvehunnjlt has been found that. the chemical behaviors: naturalor l0 artificial products from proteins orof materials containing or consistin g oi highly molecular materials which are'not proteins but'c'ontain vbasic nitrogen towards dyestuffs can be considerably changed if'they are treatedwith an allgvlating agent selected from the group consisting of esters and diazoparafllnsgior instancefwith' a reactive alkylester of'a minerafacid or a mixed organicinorganic acid as for instance alkylor aryl-sulionic acid. In thiscase apparently alkylated a products'are formed the electrochemical character of which is different from that of the starting materials. The allwlation takes place at-thenitrogen atom,- however, a change-of the electro ."che'mical character is also eflected byalblation oLcarboxyl groups. as for instance in the case or w'ool. Alkylating agents of this kind are 101' iristance, ethyliodide, ethylbromide, n-butyliodide, ethylenechlorhydrine, -benzylch1oride, p-nitrobenzylchlo'ride, chloracetic methylester, .chlor- '30 acetone, chloracetaldehyde, dialkyisuliate, alkyl- 'suli'onic acid alkylesters, the sodium salt oichlormethylbenzene sulionic acid, the sodium 'salt 01 a xylol sulfonic acid halogenatedin the side. chain, toluene sulfonic'acid alkylesters, naphthalene sulfonic acid alkyl estersysalts or carboxyaryl sulionic acidalkyl esters; ttrichloroxypropylamine hydrochloride, p-tris-pechlorethyl-aminehydrochloride and tetrachloroxypropyl ammonium chloride, diazo paramns such diazoethane.

, The extent to which the material is-ichanged is mainly dependent upon three factors. namely, the swelling condition of the material. the -reae= tivity of the agent .and the temperature. The conditions of'reaction under which for instance,

a sufllcient coloring eifect is obtained may therefore vary widely. Apart irom the fact that from case to .case, the demands vary, for instance, ac- 1 cording to whether a relatively slight improve- 'ment of the dyeing. capacityis desired particularly when working. in a neutral bath orwhether a-strong coloring'contrastis desired In the, case ofgwool and other animal fibers preferablya temperature oi at least 40f; C. is applied when'work- 65 ing in non-aqueous solutions, sincewith this tem- 1, This invention relates to, a 'treatme'nt oima-' perature the-reactivity"ofthe 'materia increase. a .e M I I 11' for specialreasonsfitis desiredto \lvorlr"at v asdiazo'methanei'or' I I t t A mayber'eversed ,1, t, a

v ng the suble'ct matter oi: f the invention may be applied at ordinary or'raised' .temperature, the limits .dependingjbnthe reac-= ativi'ty of the alkylating agent and the resistance ofthe goods-under treatment, The'speedof the reaction may also be influencedby the moisture in the atmosphere or in the} goods under treatawe-- p December; 8

tem r u lowerthaj w prolong the; periodfoi reaction.

yantageously' easily'freacting, alkylating' agents i are "used, for instance, air-alkyl mama, "any case; aboiling oifdry wool witnemymrpm de mr two hours gives {no effect. lilsolwhenf imparting a stronger reactivity to wool by expaangi it to the influence or an atmosphere containing ;per cent of relative moist'uri'e the influence 1 is only very slight 'andpractically without val'ue as experlments have shown;v A-reaction period of at least 3 hours is necessary""i'or the production of; a ma1- terial' which has clear-ly a ,greaterjg amnity to acid 1 dyestufl. than; the -nontreated fmateriaL gAlso F" when treating wool; withf dimethylsulfate in" an alkaline imediu'ml at: room-temperature no.

eflect is obtained iiithe'galkylating agent; is';not

finely dispersed or emulsified in the aqueous ;me.- 'However, an effect ismmducedaii;wooljis boiled in -.'methanol in the; presence of, :10 R or =;20 7 percent or. dimethylsulfate wher by; heca ition of an' acid bindingsagentfiacilitatesthe re,- action; In-"the same manner a -strong eiiect 318 produced it woolis treated with;an;aryl,su1ionic 1;;

presence ot an acid pared chalk. v

acid allryl ester in an;aqueous, suspension.in the" treated is more ;or; less profoundly changed; in 1 i particular theadsorptivecapacity and the speed oi fixation oi! the dyestuffs, dyestumderivatives, dyestufi componentsv and other-treating agents having acid groups, are g'enerally 'considerabLv enhanced, whil inthe; case or basicdyestuiis the I reverse eflectoccurs. ,Wherijthe alkylating agent contains acid groups .Ithe foregoing relationships The treatment to merit. In the gcasi'of halogen compounds, which react slowly, the chemical change ambassajte'ned by a, smalljaddition of an' iodidejforexa'fnpie, potassium iodide, tetr'amethyl ammonium i o'-' dide ,or,trimethyldodecylarnifionium"iodide already mentioned, theprocessrnay also v ductedin the presencefofr a neutral or alka acid bindingf-ag'ent; for *example in the 'e of potassium acetate, borax, sodium phosphate, sodium silicate or of amines which are alkylated with difliculty. V obtainedwhen the treatmentis conducted with reactive esters of organic acids in the presence of alkylene'oxides or their analogues, for example propyleneoxide or epichlorhydrin. There may also be present in the processadditions 'oi'jother' reactive materials named in U. S. patent applicatlon-Ser. No. 40,352 filed September, ,12, 1935 v rurthermora'agents capablefi'oi protecting the fiber, oxidizing or reducing bleaching agents and I swelling agents such as iorma'mide, thiourea,

magnesium thiocyanate, zinc thiocyanate and methanol may be present. "The .alirylati'ng' agents may be used in the process assuch or be produced or liberated in the presence of the goods to be treated, for example by thermal decomposition of labile alkyl halides orsalts, of imine-ethers, or nitrosoalkylurethan'es. "1 v The action oi the alkylating agent can be com- .bined witha drying or printing operation; ,Also

an alter-treatment, oi. afinished dyeing may. be advantase ai r h urp e p m rov ns h iastness thereon. In both cases'it is obvious that the dyestui! mustnot be essentially changed by the alkylating agent. The fiber may be P 31- treated; before the alkylatingoperation with materials other than, dyestutls for example with mordants, tanning-agents, loading agents or in"- secticides. The after-treatment oi'finished colorings with alkylating agents is ".01 particularimportance because in, thismanner an increased da'stness is obtaineds. In both cases it must be considered thattheshadeotsome dyes is changed. By changing the pH value ot the substrate a changing oi the'shade oizthe coloring maybe pre essential extent, adsorbs Alizarine vented or lessened. *.'.-The changingoi the coloring increases generally withan increasing, pH value.

Substances which 1 are sufliciently volatile at low or moderate temperature and, if desired, under diminished pressure, are advantageously applied to thegoods in the tom 0! vapor in the manner described in'my co-p'ending application Ser. No.

48,445 filedOctOb er 23, 1935: I

The increase ofthe afllnity or-the :speed adsorption exhibited by the fibers or 'objects for certain groups oi dyestufls whichi'ollo'ws the application ofthe invention is of particular importance in'printing and in'dy'eing mixed fabrics or mixed yarns, for instance mixedyarns of wool and cellulose fibers orot wool and acetyl-cellulose fibers, particularly whenjthe dyeing is tc J be conductedunder ieebly acid or'neutral conditions at the lowest'possible temperature.

, The following; examples illustrate the invention, the parts being by weight unless stated otherwise, and the parts by weight and parts by volume bearing the relationshipjto each other asth'at oi the kilo to the liter: 3

having a moisture saturation of '15 per cent.{ The wool, which is'externally altered only to an unorOrange 11 (each 2 per cent.), in a neutralliquor much more strongly than woolwhich hasnot been treated. and is .dyedin the same dye-bath.

dyeings are also faster to washing than equally deep dyeings on untreatedwool. The samedyeing diflerences are observed ii. the wool is soaped beforedyeing. Orange 11 (Schultz, 7th edition, Vol. 1, page 86).

A particularly strong .eirect-is I sample.

I proved. 80 C. ror 14 hours in '1000 parts by volume oiiain containing 0.5 part oi vapor oi. eth l bromide and ect Blue A Alizarine Direct Blue A (Schultz, Vol. II, page 9, 7th edition).

named Idyestufis'are adsorbed by the material at an essentially lower temperature than by normal lrample 3.'Wool is impregnated with a solution of sodium benzyl-chloride-sulphonate oi! 10 per cent.strength containing mol. of potassium iodide, calculated on the benzybchldride-sulphoate. The *wool is then centrifuged and heated for 16 hours at 7010. Acid dyestufls, for instance Alizarine' Direct Blue A, are more quickly fixed by the treated material than by ordinary wool.

Example 4.Wool is heated ion 18 hours. at 80] C. in an atmosphere of 75 per cent. moisture saturation and, containing "be'nzyl (chloride. amounting to 20 percent. or the weight of the wool. The treated slrein is still puife'white. When dyed with sum-me DirectBlue A the dye is strongly adsorbedby' the treated material alreadyatBO'C. Even after anintermediate treat-j ment with ammonia, the samerelative difference u ts- Example 2.' Instead oi the ethyl bromide prescribed in the foregoing example, chloracetic acid-ethyl-ester is similarly used, the duration of the operation being 16 hours at C. and under a moisture saturation of per cent. The above-' "Ex mple 5.,-wooldyed films be as; a!

Orange, IIis treatedji'or ld hours at 50 C. in an atmosphere of '15 per cent. moisture saturation with ethyliodi'de vapor. 'Iheliastn'ess to washing is 'considerably improved. In like. manner the i'astness tol washing of a cent. dyeingoi Azofuchsin'e 'Gpn'wool m'aybeenh'ancedr .Ea:ample "6.Woo'l is (impregnated with-an n/ 5 -solution oi tetrachlorhydroxypropylammonium chloride obtainable according toU. S. pat- .ent application Ser. No. ssoosme December 5, 1935. (of. British Patent .No. 454,320); and after having been centrifuged is heated for ld hours at Direct Blue A than an untreated comparative Ezamplei-Fibroin isms i heated for 16 hours at C. in an atmosphere of moisture saturationoi, 75 per cent. in the presence '0'! ethyl- The .treated artificial-silk is dyed with Orange n not inconsiderably darker tints thanuntreated artificial silk in the same bath.

iodide vapor.

Example 8.-'-.-An acetateiartiflcial sillrcontain- 80 C. After thorough washing, thetreated wool is more powerfully dyed bymeansot -Alizarine ing a basic artificial resin 01! thepolyvinyl series (content of basic tertiary nitrogen-in the fiber being 0.4 per cent.) isdyed, with 2 per cent. of Alizarine Direct Blue A in the presence 01' acetic acid. The dyed material-is suspended for 14 hours in an atmosphere of 80 per cent. moisture saturation containing ethyliodide vapor. The iastnes's to washing'oi the dyeing is not inconsiderably im- Emmple =9.-'--Zephir 5.... is dyed in the usual manner with 3 per cent. of Amidonaphthol-Red' 7 BB -(Schuita1Farbstofltabellen' 'Ithed. suppl. vol., page 8, No. and is then'heated for 12 hours with -8 per cent or-propylene oxide and20 per cento't'ethyliodide in" an atmosphere containing about 92 "per cent of relative moi'sture in a closed vessel of '100 parts of volume at 50 C. The aftertreated wool can be washed at'80 C. withoutmaterial change in the'color and without bleeding on white material washed simultaneously. The

non-atter-treated coloring is removed to the greater part when washed under the same conditions.

colored. v Ezrample.10.10 parts of zephir yarn are treated with an aqueous dispersion of 5 parts of. prepared chalk and 5 parts of toluenesulfonic acid methylester both being dispersed with per cent of oleylpolyglycol, for 1 hour at 65? C. and for 1 hour at 75 C. in a bath containing 20 parts of liquid on one part of yarn. Then the yarn is thoroughly washed and treated with a soap solution. The treated wool-is dyed more intensely with an acid dye, for instance, with Alizarine; Direct Blue A (Schultz Farbstofitab. 7th ed. ,vo1;--

II, page 9) than the starting material.

Example IL- Zephir-Wool is treated with 15' per cent of ethyl bromide and 10 per cent of'1.2-

, propylene sulfide-for 14 hours at50 C, in an material to be treated. The thoroughly washed; material is, in a neutral bath, dyed by nieansof atmosphere with 75 per cent of relative moisture.

The wool shows an appreciable improvement of the capacity of being dyed, particularly in a neutral bath. a The colorings ,for instance, with Amidonaphthol-Red BB (Schultz Farbstofltab, 7th ed. suppl. vol., page 8, No. 110) are faster to water and washing than those of the untreated wool.

7 Example 12.--Wool is treated withan aqueous dispersion of 20 per cent of dimethylsulfate and- 20 per cent of prepared chalk made with the aid of oleyl-polyglycol, for 2 hours at C. ina' bath.

containing 20 parts of treating liquid on 1 part of acid dyes, for instance, of Orange I1 much more fibers containing a basic artificial resin, and artiintensely than untreated material dyed in the same bath. Rinsing with a cold solution of ammonia before dyeing will not make the pretreatment inefiective. If a material -.is dyed which contains treated and untreated material, strong two-color eiTects are obtained. What I claim is: v

1. A process of increasing the aifinity fcr acid' dyestuffs of wool, natural silk, leather, artificial fibers containing a basic artificial resin, and artificial fibers containing a basic cellulose derivative,

which comprises subjecting the material" to the" action of an alkylating agent selected from the group consisting of reactive alkyl esters and diazo- 2. A process of increasing the afllnity foracid dyestuffs of natural and artificial organic products containing a quaternary amino group, to-

ing of reactive alkyl esters and diazoparafiines.

'3'. A process of increasing the affinity for acid dyestuffs of wool, natural silk, leathenartificial ficial fibers containing a basic cellulose derivative, which comprises subjecting the material to the action of a reactive alkyl ester. J i e 4. A process of increasing the afllnity for acid dyestuffs of wool, natural silk, leather, artificial fibers containing a basic artificial resin, and artificial fibers containing abasic cellulose derivative, 1 which comprises subjecting the material to the action of a diazoparamne.

f-x 6;;A process-10f the alkyl radicals are methyl groups.

dyestuffs of wool,lnatural silk, leather," artificial fibers, containing a basic artificial resin, 'andar'ti flcial fibers containing a basic cellulose'derivative,

which comprises subjecting the material'to the alkyle'ne sulfides.andalkyleneimines.

group consisting of reactive alkyl-esters'anddiazo 5. :A' was is: increasing the aflinity' tor and increasing the ailinity ior acid i dyestufls of wool, natural silk, leather, artificial fibers containing abasic artificial-resin, and arti- 1 j I '1 .flclal flbers'c'ontaining arbasic' cellulose derivative,

which; comprises subjecting the material'to' the 1 parafllnes in ,the presence of a swelling agent;

17.; A process of "increasing the afilnity to acid 2 I fibers containings; basic artificial resin, and arm .n

dyestufis ofQwool, natural silk, leather, artificial ficial fibers'containing a basic cellulose derivative,

which comprises subjecting the: material to the L actionoi an alkylatingagent selectedirom' the; 1 ,groupconsisting of-reactive alkyl esters and diazoparafiines, andlsubsequentlydyeing the material 8; A process of increasing the afilnity to acid dyestuffsof. woo1',.natura1silk;leather,artificial fibers containing a basicartificial resin, .and-arti-" 'ficial fiberscontaininga basic cellulose derivative, which comprises subjecting the material to the 1 action of an alkylating, agent selected from the a group consisting of reactive alkyl esters and diazoparafilnes, and simultaneously dyeing the' material 9. A process of increasing the 'aifnity to acid dyestufisl of wool, natural silk-leather, artificial f4 a'fiberscontaining a basic artificial resin, and artificial fibers containing a basic icellulo'se, derivative,

whlch comprises dyeingthe material'with an acid;

dyestufi, and subjecting it] to the action of an alkylating agentz'selectedfrom the group consist- Q I ing of reactive alkyl esters and dialzoparafiinesi 10; An article comprising one of the group of:

4s}, materials consisting of wool, natural silk, leather;

artificial fibers containing abasicartificial resin,

derivative, said materialsbeing substituted-(by:

alkyl radicals and having a substantially increased 56 j; I afilnlty for acid dyes] gether with a carboxyl group, combined in molecules ofihigh molecular weight, which comprises subjecting the material to the action of an alkylating agent selected from the group consist- 1 fibers having'incorpo te abqsiq artificial resin, I substituted byalkylradicals,

13. Acetyl cellulose fibers havinga substantially increased aflinity for acid dyestufis, saidacetyl cellulose fibers'having'incorporated a basic artif ficial resin substituted byalkyl radicals.

- 14. An article as defined in claim1 10, infwhic1r.;

and artificial fibers'containing a basic cellulose raunscmncn.