DE2163897A1 - Process for dyeing or printing and simultaneously finishing cellulosic materials - Google Patents

Description

Process for dyeing or printing and simultaneously removing cellulose materials

The present invention relates to a method for dyeing or printing and simultaneously finishing cellulosic materials, the preparations used to carry out this process and, as an industrial product, the colored one or printed and finished cellulose material.

Methods are known from British patent specification 906.140 and Swiss patent specification 415.911. Textile materials with dyes that contain at least one polyhydroxyalkyl group contain or contain metal-containing phthalocyanine dyes, which include at least one bis (dihydroxyalkylamino) triazinylamino group contained, in the presence of a resin-forming intermediate and an acid in freedom to color the catalyst and to equip it at the same time. These known methods have gained no practical importance, since the dye and fixation yields achieved are too low.

A process has now been found which allows cellulosic materials to dye with azo and anthraquinone dyes in particular in strong tones and to finish at the same time. This process is characterized in that cellulose materials are mixed with an aqueous liquor containing

a) at least one dye of the formula I.

(SO ₃ H) _x -D

Z-OH

Z-OH

N
κ

Z-OH

(D

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D the remainder of an azo or anthraquinone dye, χ the numbers 1 to 4,

R is hydrogen or a lower alkyl group,

V \ \ ζ ²

E N, ,, CH or C-N,

^{f /} " ^{ff X} Z-OH

Z independently of one another is an alkylene radical having 2 to 5 carbon atoms and

η means the number 1 or 2,
or at least one dye of the formula II

(W) _1n-1 - D '- [A - XJ _n , (II)

W is an SO ₃ H or COOH group,
D ^{1 is} a chromophoric residue of a formazan. Azomethine or

Nitro and preferably an azo, anthraquinone and

Phthalocyanine dye,
A a pontic,
X is a hydroxyalkyl radical or a cycloalkyl radical

and n 'are integers with a value of 1 represents at least one hydroxyl group and m to 4,

b) a synthetic resin-forming intermediate product or an in Water-soluble or at least water-dispersible aminoplast,

c) an acid catalyst and

d) any further additives,

impregnates, dries, steams or cold storage and then the cellulose material undergoes a treatment at elevated temperature subordinates and then, if necessary, washes out.

If a printing paste is used, the usual thickening agents such as starch and starch ether, Tragacanth or methyl cellulose, but especially alginates such as sodium algirate »contain.

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As a radical of an azo dye, D in formula I is, for example the remainder of a metal-free or metal-containing monoazo, disazo and polyazo dye, including one Formazan dye.

The azo and anthraquinone dyes of the formula I which can be used according to the invention are obtained in a manner known per se Way, e.g. by reacting the corresponding di- or trihalogen, advantageously chlorotriazine or pyrimidine azo and anthraquinone dyes with dihydroxyalkylamines, especially diethanoiamine.

More to carry out the procedure? suitable dyes preferably correspond to the formula Ha

<*> ml - D '- ί A ₁ - X ₁ J _n , (Ha)

W, D ', m and n ^{1 have} the meaning given above, X _{1 is} a hydroxyalkyl radical having 1 to 10 carbon atoms or a cyclohexyl radical having at least one hydroxyl group, and

A represents a heterocyclic-aromatic radical, a substituted amino, carbonamido, sulfonamide or an alkylenaminocarbonyl radical or an —SO ₂ - and an —NHCO group.

Those dyes of the formula Hb are also particularly suitable

(W) _1n-1 - D · - [A ₂ - X ₁ I _n , (Hb)

W, D ¹ , X ₁ , m and n ^{1 have} the meaning given above and

A ₂ . the groups -NX ₁ -, -SO ₂ NX ₁ -, -CONX ₁ -, - (CH ₂ ) or the formulas

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NRo-

N. '

MT

-NHCO

corresponds to where X has the meaning given under formula Ha

ρ means 1 or 2,

R is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms,

R «. a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, a hydroxyalkyl group with 1 to 6 carbon atoms or a cycloalkyl group with at least one Hydroxyl group and

Z is a hydrogen or a halogen atom, an alkyl, aryl, Alkoxy, aryloxy, alkyl mercapto, aryl mercapto group, an unsubstituted or substituted amino group or mean a hydroxyl or thiocyanato group.

.209829 / 1094

As a chromophoric residue of an azo dye, D 'means also here, for example, the remainder of a metal-free or metal-containing monoazo, disazo or polyazo dye.

Of the anthraquinones of the formula II are the 1,4-diaminoanthraquinones mentioned, e.g. those which are further substituted on at least one amino group.

The phthalocyanine dyes of the formula II are complex compounds with heavy metals, such as manganese, Cobalt and nickel, but preferably copper. The phthalocyanine dyes contain acidic water-solubilizing groups preferably carboxylic acid, sulfonic acid or sulfonic acid amide groups, it being possible for 1 to 4, if appropriate also more, such groups to be present in the dye molecule.

The substituents R2 in the bridge link A2 of the formula Hb stand for a hydrogen atom or a lower alkyl group, such as methyl, ethyl, propyl and butyl, which in turn can be substituted again with e.g. one or more hydroxyl, Methoxy or ethoxy groups. Furthermore, R_ can be a cycloalkyl radical with at least one hydroxyl group, such as mono- or dihydroxycyclohexyl.

Examples of the substituent Z can be lower alkyl groups such as methyl and ethyl ; Halogen atoms, such as chlorine and bromine, · monocyclic aryl groups, such as phenyl and tolyl, alkoxy groups, such as methoxy and ethoxy; Aryloxy groups such as the monocyclic aryloxy groups such as phenoxy and sulfophenoxy; lower alkyl mercapto groups, such as methyl and ethyl mercapto, ary, mercapto groups, such as phenyl or tolyl mercapto groups, such as mono- and disubstituted alkylamino groups with 1 to 4 carbon atoms per alkyl radical; Hydroxyalkylamino groups, such as hydroxyethylamino and dihydroxyethylamino, also phenylamino, sulfophenylamino, disulfophenylamino, naphthylamino, sulfonaphthylamino, disulfonaphthylamino, benzylamino and cyclohexylamino.

The dyes of both the formula I and the formula II are, depending on the desired depth of color of the material, in amounts of

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about 10 to 100 g / l liquor and in particular between 40 and 80 g / l liquor, are used.

The synthetic resin-forming intermediate products are known from the literature or found in practice for the crease-resistant or the handle-modifying finishing of textiles use. Examples include: epoxies, polyisocyanates, Condensates of formaldehyde with phenols or cresols, or with acrolein, and mixtures containing the methylol derivatives or contain lower alkyl ethers of methylol derivatives of monomeric or polymeric compounds, which in turn have a plurality of amino or monosubstituted amino groups, the compounds mentioned being known or for formation of resins can be used in practice by condensation with formaldehyde. Suitable compounds are, for example, monomers Nitrogen compounds such as urea, thiourea, substituted Ureas such as alkyl or aryl urea and thioureas such as alkylene ureas or diureas, e.g. Dihydroxyethylene urea, ethylene urea, propylene urea, Oxypropylene urea and acetylene urea, dicyandiamide, dicyandiamidine, Diguanides, amides and heterocyclic compounds, such as urons, ursides, melamines, triazenes, such as N-ethyltriazon, and Hydantoins or mixtures of such compounds and polymeric nitrogen compounds, such as those obtained by reacting dibasic ones Acids with diamines made polymeric amides. The lower alkyl ethers of the methylol derivatives of these compounds are for example the methyl, ethyl, propyl and butyl ethers. Particularly suitable for increasing the crease resistance of Textiles, are tetramethylol acetylene urea, melamine formaldehyde resin and especially Ν, Ν'-dimethyloldihydroxyethylene urea. It is also possible to use aminoplasts which are dispersible in water, if appropriate with the aid of a dispersant, or, however, preferably those which are soluble in water, the water solubility not necessarily being unlimited must be, but also those aminoplasts are suitable that are uniform with water only in certain proportions Solution.

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Any other aminoplasts can be selected, addition products of formaldehyde with methylolatable nitrogen compounds being particularly suitable. These can be monomolecular or already condensed to a higher degree. As methylolatable nitrogen compounds, there may be mentioned: 1,3,5-aminotriazines, such as N-substituted melamines, for example N-butylmelamine * N-trihalomethylmelamine, oxydiaminotriazines, dioxyaminotriazines, triazones, guanamines, for example benzoguanamines, acetoguanamines or also diguanamines, · guanylurea, and guanylurea in particular 4,5-dihydroxyimidazolidone-2 and derivatives thereof, for example 4,5-dihydroxyimidazolidine-2 substituted _{in the 4-position on the hydroxyl group by the radical -CH 2} CH ₂ CO-NH-CH _{2 Oh.} The methylol compounds of urea, ethylene urea, dicyandiamide or melamine are preferably used. In general, particularly valuable products give products that are as highly methylolated as possible.

The ethers of these aminoplast precondensates can also be used together with the reaction products. Advantageous are e.g. the ethers of alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol or of pentanols.

Reaction products of methylolatable nitrogen compounds, Formaldehyde and polyalkylene polyamines are also of interest.

Mixtures of different aminoplasts can also be used.

The synthetic resin-forming intermediate products are expediently used in the form of their aqueous solutions and in quantities of about 50 to 300 g / l liquor.

The amount of aminoplast should generally not be less than that of the dye and it is recommended in As a rule, the quantitative ratio should be chosen so that the amount of aminoplast is a multiple of the amount of dye. the Aqueous preparations therefore advantageously contain 3 to percent by weight, preferably 5 to 20 percent by weight, of aminoplast.

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Examples of suitable acidic catalysts that can be used according to the invention are the salts formed from weak bases and mineral acids, such as zinc chloride, zinc nitrate, ammonium salts such as ammonium sulfate, ammonium chloride, ammonium dihydrogen phosphate, mineral acid salts of organic amines such as ethanolamine hydrochloride, weak acids, for example organic acids such as oxalic acid and neutrals which develop acidity when heated or steamed, such as magnesium chloride and ammanium thiocyanate. The acidic catalysts are advantageously used in amounts of about Q ₃₁ I to 5%.,. preferably 0.5 to 2% / l liquor used »

The aqueous dye liquor can still be used in the dye works contain usual additives, for example; improving the "grip" Agents such as polyhydroxy compounds, e.g. polyvinyl alcohols j polyvinyl acetate j cellulose ethers »starch and starch ethers, proteinaceous substances such as casein and gelatine j plasticizers, like those commonly used in textile finishing, for example silicone compounds, as well as dirt, water and anti-repellants, such as methacrylic acid resins or sarcoid polyphosphates, or the usual fluorine compounds, and finally also flame retardants, as well as wetting or dispersing agents, such as ethylene oxide reaction products with fatty acids, fatty amines or fatty alcohols.

The aqueous dye liquor can be applied to the cellulose material in a known manner. For example, it can be applied locally by printing the goods with the aqueous liquor in the form of a printing paste, or it can be applied to the entire surface of the material, for example by impregnation, advantageously at temperatures of about 20 to 50 ^° C. and then squeezing off to a liquor pick-up of about 60 to 80% are applied.

The process is particularly suitable for the continuous working method, e.g. for printing fabrics using roller printing or for impregnation on a padder.

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- 9 - 2163637

The impregnation is advantageously carried out in one stage with an aqueous liquor which at the same time contains the dye, the synthetic resin-forming intermediate or aminoplast, the acidic catalyst and, if appropriate, further additives . However, it can also be carried out in two stages by first treating the cellulose material with an aqueous liquor that only contains the dye, then squeezing the material to about 60 to 807o, drying the dyed cellulose material pretreated in this way, if necessary, and then with an aqueous liquor containing the Synthetic resin-forming intermediate product or aminoplast, the acidic catalyst and possibly other additives, impregnated and then again squeezed off to approx. 60 to 80%.

The thus impregnated cellulosic material is then dried, for example for 1 to 15 minutes subjected at a temperature between 50 and 100 ⁰ C or optionally after an intermediate drying a steaming process. As a rule, the wet goods are taken into the steam room and steamed with saturated steam at atmospheric pressure for 3 to 30 minutes or with saturated steam at a higher temperature, whereby the time can be shortened accordingly.

Another possibility, preferably for regenerated cellulose materials, such as rayon staple, is to store the impregnated material cold, for example for 8 to 48 hours, in particular for 24 hours, at room temperature. Both after steaming and after the cold storage, the material may be, for example, if necessary, dried, for 1 to 15 minutes at 50 to 100 ⁰ C.

Subsequently, the cellulose material is directly preferably up to 180 ⁰ C, subjected to a heat treatment at temperatures from 100 to 220 ⁰ C, 140th This hardening process, which can take 30 seconds to 30 minutes depending on the type of heat generated and the temperature range, is used in particular to fix the dye and synthetic resin-forming intermediate or aminoplast on the cellulose material.

209828 / 1.094

After curing, the dyed or printed cellulose material can be washed out in the usual way in order to remove unfixed dye and / or synthetic resin or aminoplast. To this end, the substrates are treated, for example, at 40 to 80 ^° C. in a solution which contains soap or a synthetic detergent, for example an ethylene oxide addition product of an alkylphenol or the sodium salt of 2-heptadecyl-N-benzylbenzimidazole disulfonic acid. In most cases, however, the dyed or printed cellulose material no longer needs to be washed.

It should be noted that as a result of the aforementioned British patent 906.140 for the method in which the cellulose material is dried after impregnation _; only those dyes of the formula I come into consideration, while for the process in which the cellulose material is either steamed or stored cold after the impregnation, both the dyes of the formula I and those of the formula II come into consideration.

Cellulosic materials are primarily natural ones or regenerated cellulose. Cotton, hemp, linen, jute as well as viscose and cellulose acetate fibers are mentioned Spun rayon, the fiber material can be in any processing stage and, for example, as loose material, in In the form of threads, yarns, fabrics or mixtures.

The cellulosic materials treated by the present process are irrelevant with very good dye yields »light- and dyed or printed washfast and depending on the type and amount of synthetic resins or aminoplasts used and others Additions have further finishing effects, such as improvement of the handle, shrinkage resistance, dry and wet wrinkle resistance or hydrophobization, the high fixing yield of the dyes is particularly noteworthy.

The following examples are intended to explain the invention in more detail without restricting it thereto. In it parts mean unless otherwise indicated, parts by weight and percentages percentages by weight.

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example 1

Impregnating at a temperature of 20 to 25 ^carbon C cotton fabrics with an aqueous liquor which Looo g per ml of the dye of the formula 50

/ CH ₉ CH ₉ OH CH ₉ CH ₉ OH

Contains 200 g of a 50% aqueous solution of N, N'-dimethyloldihydroxyethylene urea and 20 g of zinc nitrate, then squeezes the impregnated cotton fabric to a liquor content of approx. 7070, based on the dry weight of the goods, and dries for 4 minutes at 80 ° ^C C. and then heated to 150 ^° C. for 4 minutes. The goods are then rinsed and dried.

A crease-free, light and washfast, strong, bluish red cotton dye (dye yield 967o).

If instead of the 200 g of the 50% aqueous solution of N ₅ N ¹ -dimethyloldihydroxyäthylenurea 250 g of a 50% x-aqueous solution of one of the synthetic resin-forming intermediates listed in Table I below and instead of the 20 g of zinc nitrate, the one in Table II below specified catalysts in the specified amounts, then with otherwise the same procedure as described in the example, similarly strong and well finished bluish red cotton dyeings are obtained.

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Table I.

Resin-forming intermediates

N, N-dimethylol propylene urea R, N-dimethylol hydroxypropylene urea Teüramethylο1ace tylenharn s tο ff Dimethylal-N-ethyltriazone

Table II

Catalysts

12 g / l ammonium chloride 15 g / l magnesium chloride

10 g / l ammonium thiocyanate 12 g / l ammonium dihydrogen phosphate 15 g / l ethanolamine hydrochloride

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SO ₃ H

Example 2

Cotton fabric is kept at a temperature of 20 to 25 ° C with an aqueous liquor containing 50 g of the dye of the formula per 1000 ml

CH ₃

CH ₉ -CH-OH

N '

CH ₀ -CH-OH

CH ₃

1 ^ CH ₂ -CH-OH

CH ₂ -CH-OH CH ₃

contains, impregnated, to a liquor content of approx. 60%, based on the dry weight of the goods, squeezed and then a second time with an aqueous liquor containing 250 g of a 50% aqueous solution of a melamine-formaldehyde resin and 20 g per 1000 ml Magnesium chloride, impregnated, squeezed off to 75%, ^{dried at 90 °} C. for 3 minutes and then ^{heated to 160 °} C. for 3 minutes. The treated cotton fabric is then rinsed, soaped at the boil for 20 minutes, rinsed again and dried.

A crease-free, intensely red, lightfast and washfast cotton dyeing is obtained (dye yield practically quantitative).

Example 3

. Cotton fabric is at a temperature of 25 to 30 ° C with an aqueous liquor containing 40 g of the dye per 1000 ml formula

HIGH,

CH

/ \ / Il JI

HIGH

J "3

SO ₃ H

209829/109 4

Contains 180 g of a 50% aqueous solution of NjN'-dimethyloldihydroxyethyleneurea and 18 g of magnesium chloride, impregnated, then squeezed off to a liquor content of approx. 60%, ^{dried at 70 °} C. for 6 minutes and then ^{heated to 140 °} C. for 5 minutes. The cotton fabric is then rinsed and dried.

An intense yellow cotton dye is obtained (dye yield 94%).

Using g of a 50% aqueous solution of N, N'-Dimethyloldihydroxyäthylenharnstoff 250 g of a 50% aqueous solution of a urea-formaldehyde resin and not heated for 5 minutes aud 140 ° C, but 30 seconds at 210 ⁰ C instead of 180 in otherwise the same procedure as described in the example, a similarly strong and well-finished yellow cotton dye is obtained.

Example 4

Cotton fabric is at a temperature of 30 ° C with a aqueous liquor containing 40 g of the dye of the formula per 1000 ml

/ CHqCHqOH

3H ₀ CH ₀ OH 0 NH ₉

^S0 3 ^H _ / ^H ~

SO ₂ NHSO ₂ - ^ ~ Λ ^Λ Ν

Contains 220 g of a 50% strength aqueous solution of N, N'-dimethylolethyleneurea and 15 g of zinc chloride, impregnated, then squeezed off to a liquor content of 65%, ^{dried at 95 °} C. for 3 minutes and then ^{heated to 180 °} C. for 2 minutes.

An intense blue cotton dyeing with good quality is obtained Lightfastness.

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If you use 16 g ammonium sulfate instead of 15 g zinc chloride and instead of the 40 g of the dye of the above formula, the same amounts as in the following Table III, column II, The dyes listed are obtained with otherwise the same procedure as described in the example, strongly colored and good Finished cotton dyeings with the shades given in column III.

Table III

I. KH ■ N • Il HO HO S HO 3 N- /
NH - <' \\ (CH ₂ CH ₂ OH) ₂ - - 2 (CH) OH SO H ^k (CH) OH 3 III i example dye j 3 = u - fjä ^ vf 4 "Λ (CH CH OH) (CH) OH γ * 2 5 CH CH OH Hue on ■ No. o s _ / \ v \ V ²⁵ - ^ n- ν - / 22 Bavciiiolle 2 V y HO
I. ^v ^ ^Ns -S0 H ^ = ^ CH ^ CH CH OH ? \ 5 SO H
3 HO S - fr \ - K ^{= II} ~ xi 3 3 SO H JL CH CH OK
1. "^ Ml 2 2 bluish tint I. 3 oh Sh ³ oh "^! / * \ / ^CH p ^CK p ^CH Red HO S ^^^ 3 NH - // ^ $ N ^ CH CH-CH ^N CH CH OH 4M 21st 2 2 OH CH 6th / ου η Red SO ₃ H 3 | l J CH 7th Red 8th yellow

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Example 9

Cotton fabric is impregnated at a temperature of 30 ° C with an aqueous liquor containing 50 g of the dye of the formula per 1000 ml

300 g of a 50% aqueous solution of Ν, Ν'-dimethylolethyleneurea, 15 g of zinc chloride and 20 g of starch, then squeezes the impregnated cotton fabric to a liquor content of 657o, dries for 3 minutes at 95 ⁰ C and then heated for 2 minutes ^{to 1SÖ C} C. The cotton fabric is then rinsed, soaped at the boil for 10 minutes, rinsed again and dried.

A strong blue cotton dyeing with good washfastness and lightfastness and a modified handle is obtained.

Example 10

Impregnating at a temperature of 20 to 25 ^0C cotton fabrics with an aqueous liquor containing 1000 ml per g of the dye of the formula 40 _{nu rTi}

SO, H
f 3 N = N S. HO
(/ Ν / ^ H ₂ CH ₂ OH
JL M— (/ " ¹ TI fll / ΠΙ
^ n ^Λ \ / OH ₂ LH ₂ UH
t I Έ ^ZZ CH ₂ NH HO ₃ CH ₂ ^ O ₃ H ^CH 2 ^CH 2 ^OH HIGH ₉ CH ₉ X N ^ Si n " ² 10 OH ^X CH _£ i OH 209 829 / 94

180 g of a 50% aqueous solution of Ν, Ν'-dimethyloldihydroxyethylene urea, 20 g of zinc nitrate and 25 g of polyvinyl alcohol, then squeezes the impregnated cotton fabric to a liquor content of approx. 707 _O3 based on the dry weight of the goods, and dries for 4 minutes then heated four minutes at 150 ° C at 80 ⁰ C and. The cotton fabric is then rinsed and dried.

A strong red cotton dye is obtained with modified handle.

Example 11

If the procedure is as described in Example 1, but instead of the components mentioned there, 80 g of the dye are used the formula

NO,

I NY XH CH O NH-- {\ ^Δ

N- / ^N CH ₉ CH ₉ OH /% ^L

, CH ₂ CH ₂ OH

^N CH ₀ CH ₀ OH O ₃ H 2 2

300 g Ν, Ν'-Dimethyloldihydroxyäthylenharnstoff than 507 _o aqueous solution and 12 g of ammonium sulfate to obtain a high color strength, detergents and lightfast black cotton j! Dye

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Example 12

Cotton fabric is impregnated at a temperature of 30 ^° C. with an aqueous liquor containing 60 g of the dye of the formula per 1000 ml

CH ₂ ^ SO
ι ₃ H. ^H 3 ^C \ N SO
\ ₃ H. CH ₂ ^ 1 N Γ V- J Λ U -N L / Λ = I.
NH
J S.
N SO ₃ H X * N CH ₂ CH ₂ OH A _n J- CH ₉ CH ₉ OH
CH ₂ CH ₂ OH HIGH ₂ CH ₂ CH ₂ OH HIGH ₂

210 g of a 507 _o aqueous solution of tetramethylolacetyleneurea and 12 g Amrnoniumdihydrogenphosphat contains squeezed then the impregnated cotton fabric to a liquor content of about 65%, based on the dry weight of the product, dried for 3 minutes at 90 ⁰ C and then heated 3 minutes atif 170 ⁰ C. The goods are then rinsed and dried.

The result is a very well crease-free, light- and washfast, strongly colored, yellow cotton dye.

Example 13

In Example 12, 40 g of the dye of the formula are used instead of the dye mentioned

HO NH - 0 ^v

N * * - ^s CH ₂ CH ₂ OH

CH ₂ CH ₂ OH

^ CH ₉ CH ₉ OH

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and -proceeds otherwise as described in Example 12, so obtained one has a crease-free, washable, strongly colored, red cotton dye.

Example 14

A printing paste with the following composition is produced:

40 g of the dye of the formula

HIGH.

N 'HIGH ₀ CH,

^ ^X 2 ^ HIGH ₂ CH ₂ ^ \

_9x

^C ) KH H ^ Y-!

200 g melamine formaldehyde resin

400 g sodium alginate as a 5% solution

20 g ammonium sulfate 340 g water

1000 g

This printing paste is applied to cotton fabrics, for example

dried by means of templates, applied, / and the fabric is then heated ^{to 160 ° C. for 5 minutes.} The printed cotton fabric is then rinsed, soaped at the boil for 10 minutes, rinsed again and dried.

A very intensely yellow-colored and crease-free finished cotton fabric is obtained at the printed areas.

Example 15

A cell wool tissue is at a temperature of 25 to 30 ⁰ G with an aqueous liquor that per liter

40 g of the dye of the formula

Ö982S / 10SU

^Ν - < SO ₃ H CH ₂ CH ₂ OH NH— // Λ / ^ CH ₂ CH ₂ OH HO 12th f = Ν - <^ \ ^ CH ₂ CH ₂ OH ^ CH ₂ CH ₂ OH HO ₃ S

200 g of a 50% aqueous solution of Ν, Ν'-dimethylol

dihydroxyethylene urea and 15 g ammonium chloride

contains, impregnated, squeezed off to a weight increase of about 70%, ^{steamed at 103 °} C. for 4 minutes and then cured ^{at 150 ° C. for 4 minutes.} The goods are then rinsed and dried. A strong, lightfast and washfast, bluish-tinged red cellulose wool dyeing is obtained. In addition, the dyed material shows good crease resistance.

Example 16

A cotton fabric is at a temperature of 20 to 25 ⁰ C with an aqueous liquor containing 50 g per liter of the dye of the formula

" ^S0 3 ^H \ T CuPc -SO ₂ NH- --ο - ^ SO ₃ H ^ ¹ HCH ₂ CH ₂ OH HCH ₉ CH ₉ OH

200 g of a 50% aqueous solution of N, N'-dimethylol-

dihydroxyethylene urea and 12 g zinc chloride

contains, impregnated, squeezed off to about 75% weight gain, ^{steamed for 5 minutes at 103 0} C and then 2 minutes at

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Hardened 170 ° C. After rinsing and drying, the cotton is intensely lightfast and washfast turquoise, which is also crease-free.

The dyes of the formula are also suitable

CuPc

-SO ₃ H
-SO ₂ NH

N (CH ₀ CH ₉ OH) ₀
SO ₃ H ι ^{2 2 2}

turquoise

CuPc

^ CH ₂ CH ₂ OH "
^N CH ₂ CH ₂ OH / 4

N (CH ₂ CH ₂ OH)

N (CH ₂ CH ₂ OH),

turquoise

Example 17

A cotton fabric is printed with a printing paste of the following composition:

g of the dye of the formula

SO H

NHCO

0OH

NH-C-CH ₂ OH ^N CH _{2 OH}

CH ₂ OH -C-CH ₂ OH CH ₂ OH

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200 g melamine formaldehyde resin

400 g sodium alginate as a 5% solution

20 g ammonium sulfate
340 g of water

1000 g

The printed fabric is steamed for 5 minutes at 10O ⁰ C and then cured for 5 minutes at 150 ⁰ C. After washing out and drying, a strong, lightfast and washfast print of blue color is obtained. The fabric is also made crease-free.

Instead of the dye mentioned above, the following can also be used:

0 NH

CH,

NHCO-

N-CH ₂ (CHOH) ₄ CH ₂ OH

-CH ₂ (CHOH) ₄ CH ₂ OH CH ₃

(blue)

Example 18

A cotton fabric is padded at a temperature of 25 ° C with an aqueous liquor of the following composition :

50 g of the dye of the formula

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, -CH-C

N (CH ₂ -OH-OH) ₂ ■ Ν

NHCO- ^ 7 XV-N (CH ₂ -CH-OH) ₂

CH ₃

210 g of a 50% aqueous solution of tetra-

methylol acetylene urea
12 g ammonium dihydrogen phosphate
718 g of water

1000 g

The impregnated fabric is squeezed off to a weight increase of 75%, then ^{steamed at 100 ° C. for 3 minutes and cured at 170 °} C. for a further 3 minutes. A rewash is not necessary. A strong blue coloration is obtained; the fabric also shows improved grip properties and is crease-free.

Another suitable dye corresponds to the formula

CuPc

-SO ₃ H

- [SO ₉ -N

CH ₉ CH ₉ OH

(turquoise)

CuPc = copper phthalocyanine.

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Example 19

A cellular wool fabric is impregnated at a temperature of 25 to 30 ^° C. with an aqueous liquor containing 40 g of the dye of the formula per 1000 ml

s CH ₉ CH ₉ OH N
^N CH ₂ CH ₂ OH

If / / CH ₂ CH ₂ OH

Contains 200 g of a 50% aqueous solution of N ₅ N ¹ -dimethyloldihydroxyethylene urea and 15 g of ammonium chloride, squeezes to a liquor content of about 70%, the fabric is stored for 24 hours at room temperature and then heated to 150 ^° C. for 4 minutes the goods are rinsed and dried. A crease-free, lightfast and washfast, strongly colored, bluish red cellulose stain is obtained.

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Claims (27)

Claims 1. Method of dyeing or printing and simultaneous Finishing of cellulose materials, characterized in that these materials are mixed with an aqueous liquor containing; a) at least one dye of the formula I. ^ Z-OH (SO ₃ H) _x -D NO Z-OH / Z-OH Z-OH (D or II (W) m-1 (II) D the remainder of an azo or anthraquinone dye, X the numbers 1 to 4, R is hydrogen or a lower alkyl group, N, CH or ' , C-N η WD ^! independently of one another an alkylene radical with 2 to carbon atoms and the number 1 or 2, an SO ₃ H or COOH group, a chromophoric radical of a formazan, azomethine, azo, anthraquinone, nitro or phthalocyanine dye, a bridge member, a Hydroxyalkyl radical or a cycloalkyl radical with at least one hydroxyl group, and m and n ¹ mean integers with a value from 1 to, b) an intermediate product that forms synthetic resin or an aminoplast which is soluble in water or at least dispersible in water, c) an acid catalyst, 209829/1094 d) .other additions if necessary, impregnates, dries, steams or stores cold, then subjects the material to a treatment at elevated temperature and washes out if necessary. 2. The method according to claim 1, characterized in that the materials with an aqueous liquor containing: a) at least one dye of the formula I ^ Z-OH N
^X Z-OH (SO ₃ H) _x -D N ^N N .Z-OH ^(I > \ \ or \ / Z-OH Λ CH C-N // // · '/ ^X Z-OH D the remainder of an azo or anthraquinone dye, χ the numbers 1 to 4, R is hydrogen or a lower alkyl group, Z independently of one another is an alkylene radical with 2 to 5 Carbon atoms and
η is the number 1 or 2
mean, b) a synthetic resin-forming intermediate product, c) an acid catalyst, and d) any further additives, impregnates, dries, then heats the treated material and, if necessary, washes it. 3. The method according to claim 2, characterized in that the cellulose material is impregnated with an aqueous liquor, which at the same time contains the dye, synthetic resin-forming intermediate product, contains acidic catalyst and optionally other additives. 209829/1094 4. The method according to claims 2 and 3, characterized in that that the dye is used in amounts of 10 to 100 g / l. 5. The method according to claims 2 to 4, characterized in that the synthetic resin-forming intermediate product in amounts of 50 to 300 g / l used. 6. The method according to claim 2, characterized in that the squeezed-off material is ^{dried at 50 to 100 °} C. for 1 to 15 minutes. 7. The method according to claim 2, characterized in that the treated and dried material is xtf for 30 seconds heated to 100 to 220 ° C for up to 30 minutes. 8. The method according to claim 2, characterized in that the material is no longer washed after heating. 9. The method according to claim 1, characterized in that an aqueous liquor is applied to the cellulose material, the a) at least one dye of the formula I or II according to claim 1, b) one soluble in water or at least one in water dispersible aminoplast or a synthetic resin-forming intermediate pro aukt, c) an acidic catalyst and d) any other additives contains, then the impregnated cellulose material is steamed or stored cold and, if necessary, after-drying and then the Cellulosic material subjected to a treatment at elevated temperature and then optionally washed out. 209829/1094 10. The method according to claim 9, characterized in that one Dyes of the formula Ha ( ^w ) _m _l - Ο '* "IA ₁ - X ₁ J _n , (Ha) used where Vi, D ', m and n ^{1 have} the meaning given in claim 1, X, a hydroxyalkyl radical with 1 to 10 carbon atoms or 'a cyclohexyl radical with at least one hydroxyl group, and A, a heterocyclic-aromatic radical, a substituted amino, carbonamido, sulfonamido or an alkylenaminocarbonyl radical or an -SO ₂ - and an -NHCO group represents. 11. The method according to claim 10, characterized in that dyes of the formula Hb Wm-I - ^D '- I ^A 2 "A ¹ H'< ^IIb) used where W, D ¹ , X · ,, m and n 'have the meaning given in claim 1 and
A _{2 represents} the groups -NX ₁ , -SO ₂ NX ₁ -, -CONX-j-, - (CH ₂ ) NHCOX ₁ - or the formulas 209829/1094 CONH- -HNOC -HNOC corresponds to where X _{1 has} the meaning given, ρ is 1 or 2, R represents a hydrogen atom or an alkyl group from I bis Carbon atoms, R.2 is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, a hydroxyalkyl group with 1 to 6 carbon atoms or a cycloalkyl radical with at least one hydroxyl group _s and Z denotes a hydrogen atom or a halogen atom, _s denotes an alkyl, aryl, alkoxy, aryloxy, alkyl mercapto, aryl mercapto group, an unsubstituted or substituted amino group or a hydroxyl or thiocyanato group. 12. The method according to claims 9 to 11, characterized _} that metal complexes of mono- and disazo dyes are used. 209829/1094 13. The method according to claims 9 to 11, characterized in that that one uses copper phthalocyanine dyes. 14. The method according to claims 9 to 11, characterized in that that 1,4-diaminoanthraquinones are used as dyes. 15. The method according to claim 9, characterized in that adducts of formaldehyde with aminotriazines are used as aminoplasts, Oxydiaminotriazine, Dioxyaminotriazine, Triazone, Guanamines, urea or thioureas are used. 16. The method according to claim 15, characterized in that aminoplasts are methylolmelamines, methylolureas, Methylol compounds of ethylene urea and dicyandiamide or, with C 1 to C 4, alkanols partially or completely etherified methylol melamines, methylol ureas or methylolated ethylene ureas are used. 17. The method according to claim 15, characterized in that the aminoplasts methylolated, partially or completely derivatives of propylene-, guanyl-, etherified with C, to Cc-alkanols or acetylenediurea or 4,5-dihydroxyimidazolidone-2 is used. 18. The method according to claims 9 to 17, characterized in that the acidic catalyst is salts of weak Bases and mineral acids used. 19. The method according to claim 18, characterized in that ammonium or amine salts are used. 20. The method according to claim 18, characterized in that ammonium chloride is used. 209829 / 109A 21. The method according to claims 9 to 20, characterized in that that the preparations contain 3 to 30 percent by weight, preferably 5 to 20 percent by weight aminoplast. 22. The method according to claims 9 to 21, characterized in that that the preparations contain 0.1 to 5 percent by weight, preferably 0.5 to 2 percent by weight, of the acidic catalyst contain. 23. The method according to claims 9 to 22, characterized in that the dyed or printed material is either 3 Steam for up to 30 minutes or store for 8 to 48 hours at room temperature. 24. Process according to Claims 9 to 23, characterized in that ^{curing is carried out at temperatures of 130 to 210 °} C., preferably 140 to 180 ^° C., for 30 seconds to 30 minutes. 25. The method according to claim 9, characterized in that the cellulose material is not washed out after curing. 26. Preparations for carrying out the method according to claim 1, characterized in that they a) at least one dye of the formula I. (SO ₃ H) _x -D Z-OH Z-OH _ R Z-OH (D or II
wherein - D ¹ - [A - XJ _n , (II) D the remainder of an azo or anthraquinone dye, X the numbers 1 to 4, 20982Θ / 1094 R is hydrogen or a lower alkyl group, \ \ \ / Z-OH E N, CH or, C-N Z independently of one another is an alkylene radical having 2 to 4 carbon atoms and η is the number 1 or 2, W is an SO ₃ H or COOH group, D 'a chromophoric residue of a formazan, azomethine, azo, Anthraquinone, nitro or phthalocyanine dye, A is a bridge member, X is a hydroxyalkyl radical or a cycloalkyl radical with at least a hydroxyl group, and m and n 'are integers from 1 to 4, ο) an intermediate product which forms carbon resin or an aminoplast which is soluble in water or at least dispersible in water, c) an acid catalyst and d) possibly contain further additives. 27. The colored or printed according to claims 1 to 25 and finished cellulosic material. _BA D 12/14/71
Do / sh 209829/1094