Method of preparation of dyeings and solid impressions on cellulosic feedstocks.

PATENT AS AFRICAN AND MALAGASY

INDUSTRIAL PROPERTY

P. 887

yaoundê (Cameroon) International Patent Classification: 06 no. 02331 D.

o-mspmsp.i GBP.

' VFs

Request 18 February 1967 to 18 TB 40 ∩ΐη

the OAM.P.I. (G.P. no. 52,770) by

the company said: FARBWERKE and Hoechst AKTIENGESELLSCHAFTVormals set limits Lucius Richard & BRUNING, residing in Germany.

5 May 1970 delivered

Publishes official ballot № 1 of 1970

PRIORITY:

Patent application deposited in Germany in the n° F. 34036 Cvi/8m 27 May 1961 on behalf of the applicant.

The present invention showed a method

preparation of dyes and d * solid prints

on cellulosic materials.

The applicant has been found to be pre -

5 parry tinctures and impressions solid articles such as fibers, flakes filSjj, knitted fabrics, fabrics or sheets in natural cellulose-or regenerated, in sizing the articles mentioned with ' an aqueous alkaline solution of a coupling component, drying, and then

10 in sizing or printing with a solution or paste -, printing acid-containing aqueous colqrant ATs reactive diazonium compound, and then by treatment with an aqueous alkaline solution. The pH of the solution

printing paste or acid-aqueous can vary in

' and

t5 wide, limits, it is say, about 1/about 7,

The degree of acidity of optimum must, in each particular case ., be adjusted at diazonium compound and at reactive dye used "

In accordance with the method of the present invention is obtained, on cellulosic materials, interesting dyes or prints having excellent strength,¹ more particularly very good light fastness and wet. In addition, obtainable in this way all shades of the pallet.

As reactive dyes are advantageously used for example dyes containing moieties as hydroxyéthylsulfonyle the group esterified with sulfuric acid or a nitrogen-containing heterocyclic ring carrying reactive halogen atoms. In addition, one can use reactive dyes containing other moieties so long as they are sufficiently strong in acid medium. aqueous.

As components of coupling compounds are used ^ ulant coextruded in neighbor position of a hydroxy group, more particularly arylides of o-aromatic hydroxycarboxylic acids or heterocyclic or acylacetic hydroxylic compounds as well as other aromatic or heterocyclic, compounds containing a group enolizable ketomethylene or enolized in a heterocyclic ring. Such compounds are for example acid arylides 2.3-to-hydr'oxynaphtoïque or its derivatives substituted in position 6, acid 2 a-hydroxyanthracene and 3-carboxylic acid, cresotic acids, acids of halo -. geno-salicylic, acid 4 a-hydroxydiphenyl ether and 3 a-crrboxylique, acid 2 hydroxy-carbazole 3-carboxylic, D. © acid 5 L-" 2.1 '.2'-benzoimidazole carbazole 4-carboxylic, D. © acid 3 hydroxy-dibenzofuran and 2-carboxylic, acid derivatives © 3 hydroxy-dibenzothiofuranne and 2 a-carboxy lic, acetoacetic acid, acid derivatives © benzoylacétiqu © or acid téréphtaloyl-to-bisracétique, hydroxybenzenes © n-substituted para-position, for example the 4 chloro-1 a-hydroxybonzène, the 4-methyl 1-hydroxybenzene, the 4-isopropyl 1; - hydroxybenzene, the 4 tert-butyl peroxy - * - 1-hydroxybenzene, the 4 acylamino-1 a-hydroxybenzenes or 5-amino 4-methyl 1-hydroxybenzene, of polyhydroxybenzènes, by

example the 1.3-dihydroxybenzene, the 1.3.5-to-EPA -

or the

benzene, the 2.4 a-dihydroxybenzophéno udder/1.4 di - (2'. 4 ' - dihy -

droxybenzoyl) - benzene, hydroxynaphthalenes of, e.g. 2 hydroxynaphthalene, the 6 a-bromo 2 hydroxynaphthalene, the 6-methoxy-2" hydroxynaphtalêne, the 7-methoxy-2 a-hydroxynaphtalêne, of 1 a-acyiamino-a 7 a-hydroxynaphthalenes, the 5 chloro - 1 hydroxynaphthalene, the 4 chloro-1 - hydroxynaphtalèpe, the 5.8-dichloro 1 hydroxynaphthalene, of 1 - acylamïno-a 7 a-hydroxynaphthalenes, the 7 a-substituted benzoylamino-a 2 a-hydr.oxynapht awl, 1' acid amide 1 hydroxynaphthalene-to-5 sulfonic, the

1 - hydroxy 4 a-methoxynaphthalene, le .1 - hydroxy 4 a-benzoylnaphtalene, the est6r © acid methyl-d 2 a-hydroxynaphthalene-3-carboxylic, arylamides of 2 a-hydroxynaphta-to-lèno-to-6-carboxylic, acid amide 2 a-hydroxynaph-to-talene and 6 a-suifonic or 2 a-hydr oxy 6 a-alky1suifonyl tetrahydronapthalenes, dihydroxynaphtâlènes of, e.g. 1.3 -, 1 ©. 2.6<!•or 2é7-a dihydroxynaphthalene, pyrazolones, by■example acid amide 1 phenyl 5-pyrazolone derivative and 3-carboxylic acid, the 1- phenyl -3- methyl -5the pyrazolone -, web 1- (4tchlo -, the I

rophényl) -3- methyl -5the pyrazolone -, the 1- (2'-' 5 dichloride.3- methyl -/

phenyl>$therein is AZ ο R.1^ οη℮ · ( 5 )>the 1 - (naphthyl-2 ') -3- methyl -5- willwill pyra -

zolone or derivatives of barbituric acid *

As diazonium compounds can be used all compounds which, with the components of the above-mentioned coupling, give. dyes of mono -, polyazo disou water insoluble, thus for example also the compounds of aromatic diamines tétrazoniüm *

When size (or printed) in a bath of foulardago (or with a printing paste) containing the diazonium compound and the reactive dye, the material which has been treated with a. aqueous alkaline solution of a component ' coupling and dried, it is first formed on the substrate the azo dye insoluble in water; and then, when altering the. pH from the substrate by plating a sizing or an aqueous alkaline solution which, to resist migration of the reactive dye readily soluble existing on the substrate, may contain relatively large amounts of salt, e.g. sodium sulfate or sodium chloride, the reactive dye reacts with the hydroxyl groups of the cellulose.

The subsequent processing described above made alkaline

should be/canvas so that generation of the bond 1q

chemical between the reactive dye and assumes the cellulose. not on the saponification of the reactive dye reactive groups. This requirement can be met by

•example as follows: the impregnated material with VLT coupling component is sized and dried or plated with an acidic solution containing the diazonium compound and the dye réadbif, and the reactive dye is fixed in a bath containing an alkali, caustic or an alkali carbonate, optionally after a short exposure to the air in which the azo dye water insoluble OS form through population.

' Whether to print the mertière which has been imptégnée component with the coupling and dried, with a printing paste containing the diazonium salt and the reactive dye, the azo dye insoluble in water is formed already during printing and drying, while the secure attachment of the dye reagent occurs during alkaline treatment which must follow. This alkaline treatment is advantageously performed in the following manner is size or plate or frame overlay the printed material, with saline or print paste alcalinaéqueusealoaline aqueous and thereafter subjected to a short exposure to air at room temperature or at an elevated temperature, to a steaming during 5 to 60 seconds to about 100° q^ a passage through a.

5 churning aqueous alkaline salt solution to 60 about seconds

at a temperature between/ 50 and 100°C, preferably

at a temperature between ' 70 i 't 95 °c, or to a passage on heated surfaces, for example the drums of drying to about 150°C, the. temperature and processing time being in inverse ratio. In^- •aqueous concentrated solutions of alkali is caustic.

fixing may also perform cold in a short time.

In depositing the compound of diazoniuéi and

;

reactive dye in the form of a print paste, can be applied an alternative method by incorporating the diazonium compound and the reactive dye in ' soft printing pastes and printing of these two different printing pastes successively in any order and, if necessary, lfune on the other.

The fact that some components of coupling, such as acylacetic acid arylides, react with certain reactive dyes, more particularly with dyes containing groupoahydroxyéthylsulfonyles sulfated, with formation of unwanted water-soluble dyes, is unimportant in operation mode in which size or simultaneously performs the diazonium compound and the reactive dye. - provided that the component coupling does not exist in excess relative to the diazonium compound - because the component coupling reacts faster with the diazonium compound than with the reactive dye. The reactive dye reagent that does incidentally during subsequent alkaline treatment. At that time. the diazonium compound is already consumed by coupling with the coupling component.

Whether to print, however, according to variant as possible, it is to say whether to print the successively. diazonium compound and the reactive dye in. pètes different print while printing first the reactive dye, there may be a substantial attenuation of. shade by the undesired reaction between•- coupling component and the reactive dye which ' trips, in fixing alkali subsequent, well 50 there is firstly under acidic conditions. This reaction φ *

trips also when, in a printing paste together containing the reactive dye and the diazonium compound, the diazonium compound is in an amount smaller than the coupling component, because when treating alkali excess coupling component reacts with the reactive dye. For avoiding such loss, is to ajouto. the paste containing the dye reagent impres SiON film with small amounts of a water soluble aldehyde, for example 1 to 25 grams of formaldehyde to 50% (wt.) per kilogram of printing paste. Instead of formaldehyde may also be used for example 1' acetaldehyde or furfural. It is advantageous to add an amount of aldehyde such that the portion of the coupling component which is on the substrate and does not coupling the products with the diazonium compound is prevented from further react with the reactive dye, by methylolating quantitatively to the position capable of copulate.

If the reactive colorant is deposited and ' the diazonium compound pêtos as two different print, this should be added the aldehyde to the reactive dye, also upon a primary repository of the diazonium compound, whether by the positive coupling exists in excess relative to the diazonium compound. It is, therefore, indicated add aldehyde even in the case where the deposited the diazonium compound and the reactive dye together, but that the diazonium compound OS is in defect with respect to the component

the I

coupling used. By adding aldehyde ' lend itself * opera between the diazonium compound and by the positive coupling is not prevented.

Since the azo dyes' are mainly yellow dyes, to rougos. violet, the field of application of the water-insoluble azo dyes which, due to their fastness properties, are valued, th3t-considerably extended by the method of the present invention. The possibility given by the invention prepare on cellulosic materials, in a simple manner, dyes and prints very solid comprising, the entire color gamut by some combination technique with reactive dyes and components OD 'water-insoluble azo dyes, is surprising and represents a considerable technical priogrès'.

The following examples - - - -■' - illustrate the present invention without limiting its scope scope..

EXAMPLE 1

•T-

■ The scarf® poton tissue with an aqueous alkali solution containing 10 grams per liter of 2 a-acétoacétylamino-to-6-ethoxy-benzothiazole and 12 grams of sodium hydroxide solution (32° Be) and dried. Then neckties with an aqueous acidic solution containing 15 grams per liter of the diazonium chloride 1 amino -, 2 - chlorobenzene, 20 grams of aluminum sulfate and 20 grams of acetic acid (6° Be) as well as 10 grams of the reaction product of 1 mole of culvre-to-phthalocyanine-3 - sulfochloride aveo 1 moles of I ' sulfuric ester L-amino 4 - (P hydroxyéthylsulfony]) - benzene, it expresses and " after exposure to air for 20 seconds, treated it during 20 seconds to 90°C in a bath, containing aqueous 30 grams of sodium hydroxide solution (32° Be), 100 grams of sodium chloride and 200 grams of potassium carbonate. Rinsed, soaping is hot and rinsed, again. A green dye is obtained, very bright, white rongeable, having excellent light fastness and wet, ..

EXAMPLE 2

Size is a fibrate tissue with an aqueous alkali solution containing. 15 grams per liter 4 - (2 '.3' a-hydroxynaphtoylamino) - L chlorô above 2.5 to-dimethoxybenzene and 15 grams of sodium hydroxide solution (32° Be) and - the dry. Is the size then with an aqueous acidic solution containing 15 grams per liter diazonium chloride of the L-amino 3-chlorobenzene, 20 grams of the phloruro of zino, 20 grams aoetic acid (6^I Be) and 10 grams of the condensation product of

1 mole of the sulfuric ester L-amino 3 - (hydroxyéthylsulfonyl) - benzene with l.mole acid L-amino 4 a-mono moanthraquinone-to-2 sulfonic, and expresses it vigorously * after exposure to air for 5 seconds to warm to about 60Approximately 32 is applied to the tissue, with a scarf to two rollers, an aqueous solution containing 10 grams per liter of sodium hydroxide solution (38° Be), 100grammeB sodium carbonate and 100 oD grams sodium sulfate, it expresses weakly and vaporized for about 20 seconds to 102°C.

After the finishing operation performed as described in example I, obtained-a red-brown dyeing having very good fastness properties.

EXEMPIE3

First one is impregnated tlesü. oD cotton with an aqueous solution containing 15 grams per liter of 2.3 to-hydroxynaphtoylaminobenzène and 20 grams of sodium hydroxide solution (32° Be), and dried. And then to printing with a P ^ Te of printing oontenant 20 grams per kilogram of the diazonium chloride 5 amino -2- substituted benzoylamino -1.4- diéthoxybenzène, .30 grams of acetic acid (6° Be), 500 grams of thickener of amidonadraganthe, 15 grams of the coupling of the sulfuric ester L-amino 2.5 a-diméthoxÿ-to-4~(w-hydro xyéthylsulfony3) - bonzènê diazotized with the 3methyl-L - (4" - eulfophényl) - 5 pyrazolon derivative and 435 grams of water.

The tissue is then sèohe and subjected to the process' mercerization common in caustic soda lye OD. 30° Be.

After 1g finishing performed as described to 1 Example 1 excellent sensation green on a white background having very good fastness properties.

EXAMPLE!' 4-

Printed cotton fabric, previously impregnated by the method described in the example 3 $ with two printing pastes having each time the composition of the printing paste mentioned in the example 3 * the AV<. 7 the restriction that, each fols, only NOU coloring components is incorporated into les.pâtes printing. The performed first with the paste containing the dye reagent. The printed surfaces with both printing pastes may overlap in whole or in part.

üprès drying is thus printed fabric strip size, on a scarf, with an aqueous solution containing 10 per liter grammesde laundry de caustic potash (50^I Be), 100èe grams sodium chloride, 150 grams of sodium carbonate and 1 gram of sodium dithionite, and passed then on a heated roll 130° C., thereby fixing the dye reagent in a short seconds.

After the finishing operation performed as described in " two the example 1 is obtained, where the CS/improssions. cover, green printing having very good fastness properties.

- Whether to print first improsèion paste containing the diazonium compound while OD in the manner described above is substantially the same result.

FOR EXAMPLE, 5

Is foulr.rde a tissue staple OD with " an aqueous solution containing 15 grams per liter 3.3' - dimethyl -4.4^T- - diaoetoacétylaminodiphényle and 12 grams of sodium hydroxide solution {32° Be), and dried. And then to printing with a printing paste containing by ' kilogram diazonium chloride 30 grams of the L-amino 2-methyl 4-chlorobenzene, lo and grams, acetic acid (6° Be), 500 grams of a thick -•thickener based starch ether to 10, 10 grams of the condensation product of 1 mole of the product OD coupling acid 1.3-to-diaminbbonzène-a 4 a-sulfoniquo diazotized and OD 1 mole of L-substituted benzoylamino-to-8 a-naphtôl-to-3.6 disulfonic with the product of condensing. primary 1 mole of acid with 1 mole of sulfaniliquocyanurylo chloride, ' 500 grams of thickener 5' alginate 4, 10 grams of formaldehyde to 30 $

•V.

and " 430 grams of water. the fabric is treated liprès drying

during 60 seconds to 90Approximately 32 on the vessel rolls with NOU aqueous solution containing 200 grams per liter sodium carbonate OD, and 100 grams of sodium chloride

After the finishing operation performed as described in example I, obtained on white background printing reactive dyes gloss having very good fastness rere.et candlelight the lavage,

EXAMPLE 6

A blended fabric is impregnated cotton and viscose staple OD in the manner described to the example 3 and is then printed with a print paste containing 10 grams per kilogram of the diazonium compound of the 4' a-raéthoxy-to-4-amino diphenylamine, 10 grams acid acétiqte (6®Be), 15 grams of the coupling w - ("4" 3 a-BulfO^, ^ amino-pH nyl) - 1 ** 9mido of β - - ohloro acid

⁴ *. '

diazotized propioniquo TDC OD 1 * acide L hydroxynaphtalèno-to-3•6 a-disuifonic ., 500 grams of d♦alginate thickener to 4 % and 465 water grammosthe Iüprès is drying processes. ponrdant60 than1 seconds to0°C danB a chamber OD # heating

After the finishing process as described cffootué 1' example 1 excellent sensation dark black having NOU very good light fastness to washing TDC, g. 7

Is foulardc tissue OD viscose rayon avoo solution, containing aqueous by 15 grams of L - litro (2♦.3^, - hydroxynaphtoylamino) - 3 a-môthylbenzènc and 15 grams of sodium hydroxide solution (32Be®), and is sèoho, printing

Puii is 1' printed with a paste containing/

20 per kilogram grammos diazonium sulfate have reached L-amino 3 methyl 4-methoxy-6 a-benzoylaminobenzène, . ïû grams acetic acid (6° Be), 10 grams of the coupling OD OD L-aminobcnzène and 2 a-sulfoniquo diazotized with the acid 2 - (4^{the R} . 6 'a-dichlorotriazinyl-to-'amino 2)~5- - naphthol7- Sulfoniquo, 600 grams of thickener of adragaptho ^ and 6 to 360 grams of water.

Æprèsfoulardo is drying with an aqueous solution containing per liter 50 grams of barium hydroxide and 200•grammos OD OD of sodium chloride, dried again d'imposition subsequently vaporized churning 30 seconds. 100°C (this steaming semiconductor nanoparticles, . however 6trc omitted without disadvantages)..

After 1gm finishing performed oomme described

<

1' example 9.ï excellent sensation fonoé brown with excellent properties OD solidity.

EXAMPLE 8'

Size is a fibrate OD tissue aqueous alkaline solution of NOU avoooontonant 15 per liter grammos OD 3•3 ' - d-im-ethyl-4•4^{the R} - diaoétoaoétylnmino-to-diphénylo and 12 grams of lye OD braze welding oaustiquo (32Bô degrees) and the sècho. Then 1' printed avoo paste containing a 30 a diazonium chlorfcro grams of the OD of the L-amino 2 a-tnéthyl-a 4 a-chlorobûnzène, 30 grams of acetic acid (6° Be), 500 grams'd ' thickener 10 # starch ether, 10 grams of the OD coupling n - (*3- sulpho -4- aminophenyl) - amide-die. acrylic acid diazotized and L-naphthalene 3, .6 to-disulfonïque and 430 grams of water. '

After printing and lo and séohago treated tissue churning 60soeo ' wrinkles 70Approximately 32 on the vat roller with a-'uno.. aqueous solution containing 200 grams per liter sodium carbonate and OD OD chloruro 100 grams sodium.

After the finishing operation performed as described in example 1 is obtained on white background printing écarlato gloss having very good OD solidity.

EXAMPLE 9

- A blended fabric is impregnated cotton and viscose staple in the manner described to the example 3 and NGF the prints' then with a printing paste containing by 30 kilogram 10 grams of the compound OD diazonium the 4' - Hïiéthoxy * ^ Mino-to-diphény laminate 10 grams acetic diacid (6° Be), 5 the grams. coupling product W - (3-sulfo 4-amino-phenyl) - amide acidc acrylic diazotized and L - ^ '- methyl-I-'-sulfo e ' a-ohlorophényl) - 3 a-môthyl-to-5-pyrazolone derivative, 500 grams of thickener of * alginato and 475 grams of water.

After drying is treated during 60 seconds to 80Degrees c in each heating chamber, processing in which a bag for accelerating the lightening by irradiation with infrared 1' input of the apparatus.

After the finishing operation performed as déorlt corresponding to example 1 excellent sensation verto with excellent properties OD solicited.

EXEMHE10

The fibrate foulardo tissue aqueuso with an alkaline solution. côhtenânt 15 grams per liter 4 - (2 * .3 ' - hydroxynaphtoyl amino) - L chloror. 2, .5-to-diméthoxybenz ^ NO and 15 grams de.-to-lossiye ^ e of caustic soda (32* Be) V and is the sèôttG ^: 9.ï üiô!_: RN.) concerns|^: the FPU&rlô with an acidic solution aqueuso ' ebûtftântM ^. 10 grams of the compound.

• f... ***■•

a diazonium OD OD the 4'hn^thbjéÿ^ $^ amino diphénylaaiimy.

20. grams of acetic acid ^ 6° Be) oo.t 10 grams of the coupling fluoride OD L ^ * anjinobonzèhe and 3 a-sulfûniquo, L ^ ^ cUazotmphtalène-to-Vfîiftsdlfoiilque ^, and the ^ ^ I gqjijçewsemdntfcexpa. after

•air exposure pondan T-^ ^ L-fiondes to about

is applied to the tissue, with a scarf to two rollers, a solution containing 30 grams per liter sodium hydroxide liquor OD OD (32Be *), 100 grams of sodium oarbopate TDC 100 grammos OD sodium sulfate, or expresses faijblèmont TDC is vaporized for about 20 seconds to 102° C..

Iprès finishing performed as described&

.•- 'i 1'. example 1 there is obtained a brown dyeing having very good fastness properties.

11 EXETPIE

•size is cotton fabric with an alkaline solution containing per liter aqueous••10 grams of 2 a-acétoacétylamino and 6 a-éthoxybenzothiazole and 12 grams of lye dede.soude caustic (32SB degrees), and the dry R4II " boxwood origins. size with an aqueous acidic solution containing per liter .15 the diazonium chloride grams L-amino 2-chlorobenzene, 20 grams of aluminum sulfate, 20 grams of acetic acid (6° Be), 10 grams of the product of coupling the diamine/CIO) OD-n-methyl-n-éthionyl P-phénylèno-to-diaminopyridine diazotized acid and L-hydroxy 8 a-acétylaminonaphtalène and 5.6-to-disulfôniquo, on_•expresses it and, after exposure to ' air churning 10 seconds, treated it during-20 seconds to 90Degrees c in an aqueous bath contenâht per liter 1q - grams of sodium hydroxide solution (38° Be) ., 100 oD grams of sodium chloride and 200 grams of potassium carbonate OD.

' After finishing as described in example 1 is obtained orange-dyeing having very good do-washfastness.;