DE1419161A1 - Process for coloring polyhydroxylated materials - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Germany

Dr. Expl

Process for coloring polyhydroxy materials.

It has been found to be hard on polyhydroxy Materlallen, in particular cellulosic filler material, such as e.g. Cotton, or regenerated cellulose, or paper can be dyed if the materials to be dyed are used with aqueous solutions of monoazo dyes containing at most two 5 or 6-membered rings and which at least

909818/0960

an · acidic waterlusllohmaohand · Qrupp · And at least one Connected to the Pa »l> ttioffteiftUl via an · X * iac« group or β-γ-propylene chloride group containing treated the dyes applied to the materials used for coloring Fixed in the presence of an acid binding agent.

All dyes suitable for the present process * For example, those in Betraoht, Al «can be obtained duroh domes eiros diazotized aniline with an AoeteBsiganilld »a heterocial compound containing a • Nollable keto group, for example is we tee a pyraeoloji or a substituted aniline, at least one of the components being a water-soluble group and an epoxy or a β-γ-propylene chloride group contain musa. from Dyes of the formula are of particular interest in the processes in progress

BV-

wherein nlftAiatens an X is a radical of the formula

_Λ or

OH

and otherwise, if necessary, an H atom or an optionally substituted alkyl radical and η an integer value

■ v

■ * '

'Φ- · ■

/ [ι * Τόη mean at most 3 and in which the benzene radicals A and B

I »■ '; ■ * ■'

have further substituents customary in azo dyes

n. The Bensolkera A can, for example, also halogen, alkyl groups, alkoxy groups, acy! amino groups, cyano groups

Alkyl sulfone groups, sulfonamide groups or nitro groups ·; have pin. The nucleus B can have alkyl or alkoxy groups in the o- or a-position for A20 trupp. Such dyes can be produced using the method of American patent specification S 199 787 by coupling an aminobenzenes sulfonic acid with an "l" (H-Phenrl-! f-A? .kylMiinp-2,3-epojtypr, ppan

can be obtained. There come

öowoni metal-free dyes as well as metal complexes, especially cobalt, chromium, Hiokel or copper complexes from 0.0 * - DioxyMofs in question. The following are examples Called dyes. .

.GH-1.) / -S-IW- / ¹ > -N ^ ⁵

t SO ₃ H

> ₃ H CH ₃

JO-H

. -CH-

• x \ y ^. Tir_w i Kt '- ^ "3

Oil

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BAD OB1G »NAL

COCH ₃

SO ^ H SO

KHCH ₂ CH-CH ₂ CH

CH-C
OH Cl

The material to be colored is according to the invention in salty, aqueous solutions, preferably at most moderately increased

the / temperature and in the presence of an acid binder / agent colored,

as

such acid-binding agents are, for example, quite strongly alkaline

/ Sodium carbonate / reactive, preferably inorganic compounds / such as tri-natrluraphosphate, Kalumcyanld and especially alkali and alkaline earth "hydroxides such as sodium" and potassium hydroxide. The amount of acid-binding agent to be used of the type specified can be varied within wide limits. Ea It is advisable to use such an amount that the result is a solution with at least a Pβ value of 10. According to the present method, it is advantageous to dye in dyeing tape, which pro

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At least 0.5 g of alkali metal hydroxide must be added to the liter. The inventionsgainäs se coloring is carried out at a preferably moderately elevated temperature, for example below 90 ° and above all at about 20 to 50 °. For the purpose of exploiting the bath, it is recommended MSHR simultaneously with the dyes or during the dyeing or less neutral, especially inorganic S _a lze such as alkali chlorides or sulfates, where appropriate, in portions, add the dye bath. During the dyeing process, the specified dyes containing epoxy or chlorohydrin groups react with the material to be dyed, whereupon they are presumably fixed by chemical bonding. * ._ ^:. 0 (* x> 7jUBs.tz of foreign funds

jun: Prirbebad can already be used at the beginning of the

Follow the process; It is advisable to add these alkaline agents above ε ° so that the pw value of the initially weakly acidic ble: .iüUT; ra "I, or weakly alkaline dyebath increases gradually during the entire dyeing process.

The dyestuffs can also be applied to the material to be dyed by padding. It is advisable to use aqueous solutions of the dyestuffs in question with solutions which are more or less neutral, mainly inorganic substances ^ e such as alkali • h'.oride otter 3 \ i \ I's.üe, optionally also preferably anti-chemical agents such as alkali metal carbonates, alkali · "o, alkali metal borates or perborates or their

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BATH ORIGINAL

Mixtures, in particular buffer mixtures of such agents, are, according to the invention, the goods to be dyed preferably cold or at only moderately elevated temperature impregnated and, as usual, squeezed two-fold one from so that the impregnated goods retain 0.5 to 1.5 parts of their original weight of dye solution.

The fixation of the dyes on the goods impregnated with the dye solution is carried out after the impregnation. For this purpose, can, for example, the impregnated materials, optionally after drying and if the impregnating solution contained no inorganic acid-binding agent, a? Treatment with aqueous alkaline solutions of inorganic acid-binding agents that are at least as alkaline as sodium carbonate, e.g. with a salt-containing Alkalihyaroxydlö'sung, in the heat or in the cold and with steam or e.g. in a warm air stream or on a heated cylinder, short Time to be heated. When using practically neutral impregnation baths that do not contain any alkali-releasing substances, the goods can be left lying for a longer period of time before fixing, which can be an advantage depending on the system of the equipment available. Instead of fixing with the aid of a separate alkali bath, inan cier impregnation solution can add inorganic alkalis or alkali-releasing agents such as sodium carbonate right from the start

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BATH ORIGINAL

■ '■ /' , " ⁷ ~ · ■

impregnated materials without intermediate treatment in one Alkali bath and steam directly without intermediate drying or one '' Subject to heat treatment.

Instead of by impregnation, according to the present process, the specified dyes can also be applied to the materials to be colored by printing. For this purpose, one uses, for example, a printing ink which, in addition to the auxiliaries customary in printing, such as curing agents and thickeners, at least one of the specified dyes and a substance that is potentially alkaline, i.e. a substance that releases an acid-binding agent when heated able. Sodium bicarbonate should be mentioned as such a substance. When using printing inks that do not contain such agents, the printed goods are subjected to an alkali treatment, preferably in a highly saline alkali metal carbonate solution or , advantageously, in a highly saline alkali or alkaline earth metal hydroxide solution and subsequently to the action of heat, possibly in the presence of water vapor, exposed. If the dor printing ink already contains an inorganic acid-binding hiiiol or an inorganic substance, which, for example, is the case with iWaircer. as alkaline as sodium carbonate can ground, is vor d'2r ^ 3'wäi-miuiii bsv /. The alkali treatment of the tea-flavored goods is not necessary before steaming,

ITa-Jh present method is obtained on polyhydroxy = Iiert3ii, i ^ besciidsre cellulosic. Fabrics more fibrous

909818/0960

It IJ IWl

■ · ■.

Structure very valuable, strong, mostly very full colorations of rewarded HaBseohthettielgensohaf th und goods \ · ^;

Uohteqhtheit

ι,

For certain Pällih it can be an advantage sincei / ale käöh In the present process, high colorations are subjected to a secondary treatment EU «This is how ε · Β · the colorations obtained sweokmässlg soaped; through this post-treatment, the Not completely fixed amounts of dye removed.

In the following examples the parts * mean Unless otherwise stated, parts by weight, the Prosente Qewichteprodeente, and the temperatures are given in degrees Celsius.

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BATH ORIGINAL

, _Ν example 1

•, ι

■■ ■ I.

Share Aeo dye

formula

80 parts of trisodium phosphate are dissolved in 400 Tillen Waeeer and diluted to 4000 parts. Haoh addition of 80 parts NatrLumohlorid one goes with 100 parts of Baurawollgewebee in this dyebath, the temperature is raised within half an hour at 60 °, is again 80 parts of sodium chloride "u, the temperature increases to 80 ° and maintained for half an hour at this Temperature. The red-violet dye obtained is then rinsed and soaped for 15 minutes in a boiling 0.3 solution of an ion-free detergent. She. has excellent wet-stick properties.

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Example 2

2 parts of the dye from dlasotiertev anilin'-disuTonic acid and N, N-di- (ß-hydroxy-Y-chloropropyl) aniline dissolved in 100 parts of water. Hit the Lusung to puddle Foulard a StUoIc cotton fabric and squeezes the liquid so that the fabric 75 pounds of its weight in liquor holds back. After drying, at 20 ° with a solution containing 10 parts of sodium hydroxide and 300 parts to 1000 parts Contains sodium chloride, impregnated, squeezed, and during steamed for one minute at approx. 100 °. Then it is rinsed, Soaped at the boil and dried. This creates a very wet-fast yellow coloring. The N, N-di- (β -hydroxy - Υ-chloroproponyl-) aniline used as the coupling component is duroh condensation of aniline with 2 moles of epichlorohydrin in methyl alcoholic solution at 65 °.

Example 3

30 parts of the dye of the formula HO-

in 339 T _e ilen water, add 150 parts Barnstoff added, carries a sodium alginate from ^ in 50 parts, combined with 30 parts of potassium carbonate and 1 part by volume of a co £ strength Natriumhydrouydlö8ung. With the printing ink thus obtained, a piece of cotton is printed as usual and dried. Then steam for 5 minutes at about 100 °, rinse, soap, rinse again and ,

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BATH ORIGINAL

dries. Nan receives a purple print on these catfish «Utter of excellent cooking and washing smoothness. * The dye is usually diazotized in catfish * Clay * -! Citraniline-2-8ulfonsHure and domes on IT, N-diglycidylanil in, which e.g. according to the German patent specification 1,137,175 is obtained, produced.

» Example k

2 parts of the dye of the formula .H OVL-

HO-S ^x OHgCH-GHgCl

OH

are dissolved in 25 T _o ilen urea, 75 parts water and 2 parts of sodium carbonate. A cotton pad is impregnated with the solution and squeezed off in such a way that it retains 75 pounds of its weight in dyeing liquid. The padded goods are dried and exposed to a dry heat of 140 ° for 5 minutes. Subsequently, the 0.3 # solution of an ion-free detergent is soaped for 15 minutes, rinsed and dried. The yellow coloration has very good wet fastness.

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It ι ■ * - ■, ^ -

D _e r in paragraph 1 dye used can be obtained as follows:

25.3 parts of aniline-2,5-disulfonic acid are ale Mono-natriura salt in 100 parts of water and 30 parts of hydrochloric acid (30 # ig) in the usual way at 0 to 10 ° with a aqueous solution of 6.9 parts of sodium nitrite dlazotlert. The diazo solution obtained is at 0 to 5 ° in 18.5 parts Ä-Hethyl-K- (ß-hydroxy - ^ - chlorptOpyl-) anllln, which in 100 Parts of ln hydrochloric acid solution, partially dissolved, are added. The acid released is neutralized with sodium acetate (Congo-neutral reaction). ftaoh completed coupling will be the very easily soluble dye isolated by evaporating the aqueous solution in vacuo.

The ethyl-H- (ß-hydroxy <- -chloropropyl-) aniline used to produce the dye is produced by Condensation of Me thy! Aniline Kit Epichlorohydrin. ■

909818/0960 bad original

Claims (1)

- 13 - Claims 1. Process for dyeing polyhydroxylated materials, characterized in that the materials to be dyed with aqueous solutions of monoazo dyes containing at most two 5 or 6-sided rings and which at least an acidic water-dissolving group and at least one Epoxy- or ß ~ y ~ fropylene chlorohydrin group, treated and the dyes applied to the material to be colored in Fixed in the presence of an acid-binding agent. 2. The method according to claim 1, characterized in that that you can get dyes of the formula used, in which at least one X is a Best of the formula -CH ₂ CH CHg or * "OH and the other X is at most a Η atom or an optionally substituted alkylene radical and η is an integer Im values of at most "6 , and in which the benzene radicals A and B 809818/0960 still further 1 · ι aiso dyes Ubllohe Subatlients may have. 3 · Ancestors according to Claims 1 and 2, characterized in that the treatment is carried out in the presence of a Electrolytes, preferably in the presence of an inorganic one duroh leads. 4. The method genäss the speeches 1 to 5,. Characterized in that the treatment with the dye solutions at most moderately increased temperature. 5 «Method according to claim 1, characterized in that it is worthwhile, that ran an alkali hydroxide as the acidic agent Alkali carbonate or phosphate used. 6 "Process vegetables Anepruoh 5" Gckenns through it "pays off, data Ban tine iolohe slope · of the alkallaoh-reacting acid- * binding coat used, because the Fgrbebad has a P ₃ Afert of over 10. ?. Method sown β AneprUchexi 1 to 6, characterized in that rtan dl «P & rhstoffe duroh Foulard leren on the 505818/0960 BATH brings to coloring materials. 8. The method according to claim 7, characterized ge Ironnsa is worthwhile, that one the ait dor dye solution impregnated clay materials optionally subjected to an alkali treatment and optionally a heat treatment after drying. 9 * method according to claim 8, characterized in that that the materials impregnated with the dye solution dries, impregnated with an alkaline saline solution and dulls. 10. Turn dyeing of cellulose textile materials enjoy the test 1 to 9 « 909818/0960 _BATH