US2500080A - Insolubilization of a soluble azoic dyestuff on the fiber - Google Patents

Description

Patented Mar. 7, 1950 UNITED STATES PATENT OFFICE IN SOLUBILIZATION OF A SQLUBLE AZOIC DYESTUFF ON THE FIBER No Drawing. Application January 17, 1946, Serial No. 641,873. In France February 2, 1945 6 Claims.

This invention relates to a method for the obtention, particularly on the fibres, of Water insoluble azoic dyestuifs and to the dyed fibres resulting therefrom.

It has been found that the azoic dyestuffs which possess a secondary amino group in which the hydrogen atom bound with the nitrogen atom is substituted by a sulphonic group have the property of loosing this group when submitted to an acid treatment. If they possess no other solubilizing groups, they thus become insoluble in water. If the initial soluble dyestuff is applied on any kind of fibre it becomes insoluble on the latter in the course of the acid treatment. This discovery leads, therefore, to a new and particularly simple method for preparing insoluble dyestuiis on the fibre. The application of the soluble dyestuil on the fibre may be realized by dyeing, foularding or printing. It may be obtained on vegetable fibres as well as on animal or artificial fibres.

The application on animal fibres or on artificial fibres behaving in a similar manner may be realized like that of an acid dyestuff through dyeing in a bath which should not be too acid if it is desired to avoid a simultaneous developing of the dyestuff. It is possible to add to the bath a reagent, such as borax, an acetate, e. g. sodium acetate or ammonium acetate, soap and the like maintaining the pH between favourable values. In certain cases the developing may be effected simultaneously with the dyeing in order to avoid a complementary operation.

The application through foularding or printing may be obtained by using known methods. The solutions and colours which contain the dyestuif may, besides, contain the various ingredients recommended for similar operations and more particularly solubilizing, or hygroscopic substances or the like. The developing may be effected by any known means capable of reducing the pH of the fibre: steeping in a bath showing the desired acidity at a suitable temperature,

passage through an acid atmosphere containing or not containing steam, introduction onto the fibre of a product bringing the fibre to a desired pH through a following treatment such as a steaming process. To this end, salts of volatile bases such as ammonium salts, esters regenerating their acid through hydrolysis or certain salts such as fluorosulphonates, iminodisulphonates and the like may be used.

Azoic dyestufis which possess a secondary 3 group in which the hydrogen atom bound to nitrogen is substituted by a sulphonic group may be prepared, for instance, according to the method described in our co-pending application No. 641,874, January 1'7, 1946, now abandoned, entitled Method for the preparation of diazoic derivatives and azoic dyestuffs derived therefrom, which method consists in coupling with any coupling components the diazoic derivatives obtained by diazotizing an arylene diamin both amino groups of which are substituted by a sulphonic group, one of the said groups furthermore carrying an organic radical. The co-pending application referred to discloses that the sulphonated arylene-diamines used as starting materials may be prepared by the action of sulphonating agents mixed or combined with a tertiary amine on arylene-diamines one of the amino groups of which is 'a primary group while the other is a secondary group. 1

As sulphonating agents one may use those which have already been recommended for similar operations, for instance sulphuric anhydride, sulphuric chlorhydrin, chlorosulphonic ester, oleum and pyridinium sulphate. As tertiary amines which may be mixed or combined with the sulphonating agents one can quote pyridin, dimethylaniline and other similar amines. The reaction may be eiTected in the presence of a solvent or of a diluent.

The coupling is carried out by means of the classical method which consists in dissolving the diazo in the form of a solution or an aqueous paste, in presence of an aqueous solution of the coupling component. According to the nature of said components, the operation takes place in an acid or basic medium. The coupling is carried out at ordinary temperature.

The following are non-limitative examples of realization of the invention, the parts given being parts in Weight.

Example 1 sample is removed and immersed during a quarter of an hour into a bath of 300 parts of boiling Said temperature is maintained during half an hour whereafter the:

2,60 3 water containing 1% of sulphuric acid. The dyeing which was garnet-red before this latter acid treatment turns to purplish-blue. It is then washed with water.

It is also possible to conduct the developing in the first dyeing bath through adding to the same, after the rising of the dyestufif, a quantity of acid suflicient to obtain a slightly acid reaction to Congo red which maintains during the whole operation.

Example 2 1 part of loaded or non-loaded silk is dyed in 30 parts of water containing 0.02 part of dyestufif and 1 g. of soap per litre. The temperature is maintained during 45 minutes at 85 C. and then during a few minutes at 95 C.

One develops in a boiling bath containing 2 g. of sulphuric acid per litre.

According to the dyestufi, one obtains the fol- 10 lowing hues:

Hue Coupling product of the diazo-i-phenyl-N-amlno-l-beuzene-N-sulphonic acid withbefore developing after developing (hydroxy-2-naphthoyl-3)-aminobenzone blue violet. (hydroxy-Z'-naphthoyl-3)-amino-l-Inethoxy e v10 t. (hydroxy-2-naphthoyl-3) -amino-1-methyl-2- benzene. blue violet.

Hue Coupling product of the methyl-4-phenyl-N-amino-4-dmzo-1- benzene-N-sulphonic acid w1th before developing after developing (hydroxy-2'-naphthoyl-3)-aminobenzene reddish blue. (hydroxy-2-naphthoyl-3)-amino-l-methyl-2-benzene Do.

By operating in the same manner with other dyestuffs one obtains the hereafter indicated hues:

. Hue Coupling product of diazo-4-methyl-N-amino-l-benzene-N- snlphonie acid withbefore developing alter developing (hydroxy-2-naphthoyl-3)arnino-benzene garnet-red violetblue. (hydroxy-2-naphthoyl-3)-amino-l-methyl-Z-benzene bordeaux-red. Do. (hydroxy-2naphthoyl-3)-amino-l-rnethyl-2-n1ethoxy-4-benzene. purplish-blue. (hydroxy-2'-naphthoyl-3)-aminc-l-methoxy-2-benzene viole (hydroxy-2-naphthoyl-3)-amh1o-benzene purplish-blue. (hydroxy-2'-naphthoyl-3l-amino-l-methcry-Z-benzene violet-blue. (hydroxy-2-naphthoyl-3)-amino-l-mcthyl-2-n1ethoxy-4-benzene", slightly purplish-blue. (hydroxy-2'-naphthoyl-3)-amino-l-methyl-2-benzene D0. (hydrnxy-2-naphthoyl-Ti)'amino-2-naphthalene do purplish-blue. (hydroxy-2-nephthocarbazol-earboyl-3)amino-l-rnethoxy-ebenzeneu reddish grey grey-green.

Hue Coupling product of the di-methyl-1-N-a1nin0-2-diazo-4-benzene-N- sulphonic acid with before developing after developing phenyl-methyl-py'razolone yellow sa1m0n-pink. hydroxy-2-naphtbalene mange-coloured Do. (bydroxy-2-naphthoyl-3)-am1nobenzene scarlet-red... brownish garnet. (hydroxy-2-naphthoyl-3')-arnino-l-ethoxy-Z-benzene o red brown. (hydroxy-2-naphthocarbazol-carboyl-3)-amino-l-methoxy-4-benzene. violet brown. violet brown. (hydroxy-2-carbazol-carboyl-3')-an1ino-l-chlorol-benzene brownish yellowbrown. terephthaloyl-di(acetylamino)-l-dimethoxy-2.4-chloro-5-benzene yellow orange brown.

Hue Coupling product of the methyl-4'-phenyl-N-amino-4-diazo-l-benzene-N-sulphonic acid with V before developing after developing (hydroxy-2'-naphthoyl-ii'l-aminohenzene steely blue gernet slightly reddish blue. (hydroxy-2-naphthoyl-3')-amino-l-methyl-2-benzene. do. l Do. phenyl-methyl-pyrazolone. yellow orange. brownishred. fi naphthol scarlet red... purplish brown. (hydroxy-2'-naphthoyl-3)-am nobenzene red violet bright blue. (hydroxy-2-naphthoyl-3)-amrno-l-methoil garnet-red. slightly reddish blue. (hydroxy-2-naphthoyl-3')-am no-1-rnethor red brown. Do. (hydroxy-2-naphthoyl-B)-am no-1-ethoxy-2benzene purplish-blue. (hydroxy-2-naphthoyl-3)-am no-l-xnethyl-Z-benzene. slightly greenish blue. (hydroxy-T-naphthoyl-B)-am no-l-nitro-3-benzene blue. (hydroxy-2-naphthoyl-3)-am no-1mcthyl-2-methoxyenzene slightly reddish blue. (hydroxy-2-naphthoyl-3)-anuno-l-dirnethoxy-Q.5-henzene.-.-- purplish blue. (hydroxy-2-anthracenoyl-ll)-annno-1-n1ethyl-2-benzene. green. d1(acctylaeetamino)-4.4-dimethyl-3.8-diphenyl brownish yellow. (hydroxy-2-earbazol-carboyl-S)-amino-l-chloroi-benzene violet. (hgdroxy-3-diphenylene oxide carboy1-2)-amino-l-dimethoxy-2.5- brown yellow brownish garnet.

cnzene di(hydroxy-2-nnphthoyl-3-amino)4.4-dimethoxy-3.3-diphenyl gamet-red.. grey blue.

Hue Coupling product of the methory-4'phenyl-N-amiuo-4diazo-1- benzene-N-sulphonic acid with I before developing after developing (hydroxy-2-naphthoyl-3)-a1ninobenzene red violet blue. (hydroxy2-naphthoyl-3')-amiuo-l-methyl-2-benzen Do. (hydroxy-2-nephthoyl-3)-amino-l-methoxy-Z-benzene slightly reddish blue. (hydroxy-2-naphthoyl-3)-amino-l-methoxy-4-benzene D0. 2hydroxy-2-naphthoyl-3)amino-1-methyl-Z-methoxyi-benz reddish blue.

hydroxy-2-naphthoyl-3)-arnino-l-dimethoxy-2.5-benzene Do. di-(acetylacetamino)-4.4-dimethyl-3.3-diphenyl reddish yellow.

hydroxy-2-carbazolcarboyl-3)-amino-1-chloro-4-benzene dull violet. hydroxy-3-diphenylene oxide carboyl-2)-amino-dimethox benzene dull purplish red. phenyl-methyl-pym l n red. 49 n p h bordeaux red.

Hue Coupling product of the diazoA-methyl-N-amino-l-benzene-N- sulphonic acid Withbefore developing after developing (hydroxy-2-naphthoyl-3)-au1ino-1-meth0xy-2-benzene red dull violet. (hydroxy-2-naphthoyl-3)-aminobenzene Do. (hydroxy-2-naphth0yl-3)-arnino-1-methyl-2-benzene Do. (hydroxy-2-naphthoyl-3)-amino-l-methyl-2-methoxy-tbenzene .do Do.

Hue Coupling product of the dimethyl-l-N-amino-Z-diazo-4-benzene-N- sulphonic acid before developing after developing (hydroxy-2-naphthoyl-3)-amino-1-ethoxy-2-bcnzene dull violet. (hydroxy-2-naphthoyl-3)-aminobeuzene dull red violet. (hydroxy-Zmaphthocarbazol-carboyl-3)-amino-1-methoxy-4 benzene }black violet. (hydroxy-2-ca.rbazol-carboy1-3)amino-l-chloro-4-benzene brown. (hydroxy-2-naphtl1oyl-3)-arnino-l-methyl-2-Inethoxy--i-benzene dull violet. terephthaloyl-di (acetylamiuo)-l-dimethoxy-2A-chloro-5-benzene slightly reddish yellow. phenyl-methyl-pyrazolone yellow-orange colored reddish yellow. naphthol-2 red dull red.

The hue obtained is identical if the develop- Example 4 ing is effected in the exhausted dyeing bath to which the necessary sulphuric acid is added in A colour prepared Wlth the followmg comorder to obtain a slight blue coloration on Congo posmon red indicating paper. y ff 40 Thiodiglycol 120 Example 3 Acetine 30 r Urea 1 pa of a d Silk is dy d 0n b ng n Water and starch-tragacanth thickener 760 30 parts of water containing 0.08 part of borax and 0.2 part of the dyestuff obtained by coupling 1,000

methoxy- -phenyl-N-aminol-diazobenzene- N- sulphonic acid with (hydroXy-2'-naphthoy1-3')- amino-l-methyl-Z-benzene, said couplin being One prints on a cotton fabric, dries and passes 50 during one minute through a boiling bath containing 9 g. of sulphuric acid and 100 g. of sodium.

effected following the indications given in Exsul hate or litre. One washes and soa s durm ample 2 of the above mentioned co-pendlng apan in a bath containing 3 of plicatioP- one develqps as Example 2; before and 5 g. of sodium carbonate per litre. This. developmg m hue 1s redwlolet; It turns blue operation is effected while boilin except for theafter developmglast six dyestuffs of the following list, for which.

In orde? 9 avolql the use of a speclal develop the operation is effected at C. By using the: ing bath 1t 15 Posslble to develop the hue in the various dyestuffs quoted hereafter and preparedf y dyeing bath by adding to the latter, after according to the indications of the above menex us a Sufilcient quantity of acid in Order to tioned co-pending application one obtains print that it turns he C o red paper b ue- 0 6 pings which are generally very fast with the herecrates as indicated above: the hues obtained are after indicated hues. The hues before developing: identical. have also been mentioned.

Hue

Coupling product of the methoxy-4-phenyl-N-amino-i-diazobenzene-N- sulphonic acid withbefore developing after developing hydroxy-2-naphthoyl-3)-amiuo-1-methyl-2-methoxy-4-benzene blue. (hydroxy-2-naphth0yl-3)-amino1-benzene dull v10 Do. (hydroxy-2-naphthoyl-3)-amin0-1-methoxy-2-benzene garnet red reddish blue. di (acetylacetamino)-4.4-methyl-3.3-diphenyl yellowc yellow brown. (hydroxy-2-naphthoyl-3)-amiuo-l-methyl-2benzene own ue. (hydroxy-2-carbazol-carboyl-3)-amiu0-l-chloro-4-beuzene do dull violet (hydroxy-2'-naphthoyl-3)-amino-1-methoxy-4=-benzene violet ue.

r pheuyl-methyl-pyrazolene. yellow brown red.

anemone.

Hue Coupling product of the phenylau iti ilddiazo benzene N-sulphonicacid- W1 before developing after developing (hydroxy-2-uaphtl1oyl-3 )-aminobenzene reddish blue. (hydroxy-2-naphthoyl-3)amino-Lurethoxy-2-benzene blue-violet. (hydrow-z"naphthoyl-3)-amino-l-methyl-Z-methoxyl-benzene reddish blue. (hydroxy-2-naphthoyl-3)-amino-2- nhrhalene Do; (hydroxy-2-naphthocarbazol-earboyl-3)-amino-1-methoxy-4-benzene do blue black.

Hue Coupling product of the methyl-4-phenyl-N-amino-ediazo-benzene-N- sulphonic acid with-- before developing after developing (hydroxy-2-naphthoyl-3)-aminobenzene dark brown reddish blue. (hydrozw-2-naphthoyl-3)-amino-l-methyl-2-b D0.

Hue Coupling product of the diazo-e methxlrll-N-amino-benzene-N-sulphonic acid W1 before developing after developing (hydrxy-2-naphthoyl-3)-amino-l-methoxy-2-benzene.- n... red grey blue. (hydroxy-2-naphthoyl-3)-au1in0-l-methyl-iZ-benzeno. red bro\vu brown -Vl010t. (hydroxy-2-nophthoyl-3')-arnino-1-methyl-2-ruethory brown vio1et reddishblue. (hydr0xy-2-naphthoyl-3')-aminobenzene o reddish grey blue. -di(hydroxy-2-naphthoyl13-amino)-4.4-dimethox 3.3-diphenyl brown reddish blue.

Hue Coupling product of the diazo-4-meglyl-afinino'2-methylbeuzene-N-sulphonic aci wit before developing after developing (hydroxy-2-naphthoyl-3)-aminobenzeue scarlet red brown violet. (hydroxy-2-carbazol-carhoyl-3)-aruino-benzene yellow brown Yellow l (hydr0xy-2-naphth0y1-3)-amin0-l-eth0Xy-2-benzene scarlet red brown .v1olet.. (hydroxy-zf-naphthooarbazol-carboyl-3)-amiuo-l-n1ethoxy4-benzene dark bro black. di(l1ydroxy-2-naphthoyl-3-amino)-4.4-dimethoxy-3.3-diphenyl. brown violet. terephthaloyl-di(acctylamino)-l-dimethoxy-Z.4-chloro--benzene orange-coloured. phenyl-methyl'pyrazolone .d0 Do. hydr0xy-2-naphthalene orange red red violet.

By mixing equal parts of the colours obtained:

with the dyestuffs prepared, on one hand, with methoxy-e-phenyl-N-amino-4-diazobenzene N sulphonic acid. and (hydroxy-Z'-naphthoy1-3') amino-l-methoxy-Z-benzene and,- on the other hand, With the same diazoic and di(acetylacetamino)4.4-dimethyl-3.3-diphenyl one obtains patterns the colour ofwhich verges to black.

Example 5 Fabresprinted and dried-as in thepreceding: example are developed during minutes at 100 C. in saturating steam containing acetic acid.

The obtained hues are identical with those developed by using the method according-to the said example.

Example 6 The following colour is prepared with the dyestuff obtained according to Example2 of the.

above mentioned co-pending application by coupling methoxy 4-phenyl-N-amino-4-diazobenzene-f-sulphonic acid with (hydroxy-2'- naphthoyl-3)-amino 1 methyl-2-methoxy-4-, benzene:

Dyestufi 40 I Thiodiglycol 150 10% solution of ammoniumsulphocyanide 20 Water and starch-tragacanth thickener 790* One-prints on cotton, dries, steams during 2 minutes in saturating steamat C. One washes, soaps and. dries in thezusual manner. One obtains blue-patterns.,

Example 7 wherein-A represents a benzenic nucleus, R is a radical selectediromthe group consisting of the methyl, phenyl and, methoxyphenyl radicals, and R! isthe remainder of a-hydroxylated coupling component free from any solubilizing group and which is, bound, to the-azo group in a position adjacent tothe hydroxylgroup, and thereafter subjecting said soluble dyestufi thus applied to said fibres to an acid treatment, whereby said where A represents a benzenic nucleus, R is a radical selected from the group consisting of the methyl, phenyl and methoxyphenyl radicals, and R is the remainder of a hydroxylated coupling component free from any solubilizing group and which is bound to the azo group in a position adjacent to the hydroxyl group, and thereafter subjecting said soluble dyestuff thus applied to said fibres to an acid treatment, whereby said soluble dyestufi is transformed into an insoluble dyestuff.

3. A method for printing cellulosic fibres which comprises the steps of applying to said cellulosic fibres a soluble azoic dyestuif of the general formula wherein A represents a benzenic nucleus, R is a radical selected from the group consisting of the methyl, phenyl and methoxyphenyl radicals, and R is the remainder of a hydroxylated coupling component free from any solubilizing group and which is bound to the azo group in a position adjacent to the hydroxyl group, and thereafter treating said soluble dyestufi thus applied to said cellulosic fibres in an acid bath, whereby said soluble dyestuff is transformed into an insoluble dyestufi.

4. A method for printing cotton fibres which comprises the steps of applying to said cotton fibres a soluble azoic dyestufi of the general formula wherein A represents a benzenic nucleus, R is a radical selected from the group consisting of the methyl, phenyl and methoxyphenyl radicals, and R is the remainder of a hydroxylated coupling component free from any solubilizing group and which is bound to the azo group in a position adjacent to the hydroxyl group, and thereafter treating said soluble dye-stuff thus applied to said cotton fibres in an acid bath, whereby said soluble dyestufi is transformed into an insoluble dyestufi.

10 5. A method for printing cellulosic fibres which comprises the steps of applying to said cellulosic fibres a soluble azoic dyestuif of the general formula wherein A represents a benzenic nucleus, R is a radical selected from the group consisting of the methyl, phenyl and methoxyphenyl radicals, and R is the remainder of a hydroxylated coupling component free from any solubilizing group and which is bound to the azo group in a position adjacent to the hydroxyl group, and thereafter steam treating said soluble dyestufi thus applied to said cellulosic fibres in the presence of an ammonium salt, whereby said soluble dyestufi is transformed into an insoluble dyestuff.

6. A method for printing cotton fibres which comprises the steps of applying to said cotton fibres a soluble azoic dyestufl of the general formula wherein A represents a benzenic nucleus, R is a radical selected from the group consisting of the methyl, phenyl and methoxyphenyl radicals, and R is the remainder of a hydroxylated coupling component free from any solubilizing group and which is bound to the azo group in a position adjacent to the hydroxyl group, and thereafter steam treating said soluble dyestufi thus applied to said cotton fibres in the presence of an ammonium salt, whereby said soluble dyestuif is transformed into an insoluble dyestufi.

ROBERT LAZARE LANTZ.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,362,936 Fritzche Dec. 21, 1920 1,483,798 Green et al. Feb. 12, 1924 1,536,713 Heusner et a1 May 5, 1925 1,745,676 Hoffa et al Feb. 4, 1930 1,750,057 Schirmacher et a1. Mar. 11, 1930 1,795,125 Heusner et a1 Mar. 3, 1931 2,080,043 Heckert May 11, 1937 2,172,307 Gaspar Sept. 5, 1939 2,172,308 Gaspar Sept. 5, 1939 2,241,247 Dickey May 6, 1941 FOREIGN PATENTS Number Country Date 389.758 Great Britain Mar. 23 1933

Claims (1)

1. A METHOD FOR COLORING FIBRES, WHICH COMPRISES THE STEPS OF APPLYING TO SAID FIBRES A SOLUBLE AZOIC DYESTUFF OF THE GENERAL FORMULA