DE1444271A1 - Dyeing process for nitrogenous fiber materials - Google Patents

Description

Dr. Werner Hoßle?

PATENT ADVOCATE 588LODENSCHEtD Dross β I w g 2

Lüdenscheid, Jan. 31, 1969 A 6915

Official File number: P 14 44 271.8

Applicant: Hachiro Hiyama, Osaka, Japan,

No. 260 Shimohozumi, Ibaraki-shi, Osamu Manabe, Osaka, Japan,

No. 194 Higashinagai-machi ', Sumiyoshi-ku, and

Mitsubishi Kasei Kogyo Kabushiki Kaisha, No. 4, 2-Chome, Marunouchi, Chiyoda-ku, Tokyo, Japan

"Dyeing process for nitrogen-containing fiber materials"

The invention relates to dyeing processes for fiber materials. In particular, it relates to new methods of dyeing or printing of cellulose fibers and natural or artificial nitrogenous fiber materials in order to achieve, of dyeings with excellent fastness properties.

The process according to the invention is characterized in that the fibers are in the presence of an acid-binding agent colors or prints with water-soluble or water-insoluble dyes that contain at least one group in the dye molecule have the following general formula:

-NRCO - CH - CH - COY,

in which R is a hydrogen atom, an alkyl or cycloalkyl group, X ₁ and X _{2 are} a halogen or hydrogen atom, where at least one of the two X ₁ and X _{2 should be} a halogen atom, Y is a hydroxyl or alkoxy group, a halogen atom or a possibly . mean a substituted amino group containing a dye radical.

The new reactive dyes according to the invention

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- 2 can have the following general formula (1) j

[d] - NRCO - CH - CH - COT (1),

X ₁ X ₂

in which D denotes a dye residue, optionally with water-soluble groups, and R, X ₁ , Xg and Y have the above meaning. The new dyes can be obtained by condensation of a dye compound containing at least one acylatable or substituted amino group in the molecule. with halosuccinic acid or its anhydride or a compound of the general formula (2):

XOC -CH-CH- COY (2),

X ₁ X ₂

in which X is a halogen atom and X ₁ , X ₂ and Y have the meanings given, are readily obtained.

As starting dye compounds, various water-soluble or water-insoluble dye compounds, which are im Molecule of at least one acylatable or substituted amino group may be used, such as carrying at least one primary or secondary amino group as a core substituent Azo, metal-containing azo, anthraquinone, Mtr.o-, phthalocyanine-oxazine, Acridine, thioxanthene, perynon dye compound and the like ..

As halosuccinic acids, their anhydrides or compounds of the formula (2) with which the starting dye compounds mentioned are to be condensed, such as mono- or dichlorosuccinic acid, mono- or dibromosuccinic acid, Mono- or dichlorosuccinic anhydride, mono- or dibromosuccinic anhydride, ß-Carboalkoxy-mono- or dichloropropionyl chloride, ß-Carboalkoxy-mono- or dibromo-propionyl bromide, Mono- or dichlorosuccin monochloride, mono- or dichlorosuccin dichloride, Mono- or dibromosuccin-monobromide, mono- or dibromosuccin-dibromide, ß- (N-substituted amino) -carbamoyl-mono- or -dichloropropionyl chloride, ß- (N-aubsti-

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INSPECTED

tuted amine p) carbamoyl mono- or dibromopropionyl bromide and like

The condensation can be carried out in an aqueous medium or in an organic solvent at relatively low temperatures go smoothly and possibly ... by using a condensation agent such as an acid-binding agent be accelerated. In general, it is desirable to use halosuccinic acids, their anhydride or compounds of the formula (2) in excess over the starting dye compound to use.

Another process for the preparation of the new reactive dyes is that instead of the starting dye compounds mentioned their intermediates are used, these with the halosuccinic acids mentioned, their anhydrides or compounds of the formula (2) are condensed and then converted into the desired dyes. This procedure is Commonly used in the manufacture of azo dyes; For example, a diazo compound is used to obtain an azo dye or a coupling component with halosuccinic acid, the anhydride or compounds of the formula (2) thereof condensed and the condensation product thus obtained is coupled with the desired coupling component or diazo compound.

The new dyes combine as a result of the in the molecule existing reactive group: -NRCO -QH - CH - COY,

X ₁ X ₂

in particular the labile halogen atom contained therein, in an aqueous medium, expediently under the action of a acid-binding agent, solid with various fiber materials and produce real colorations on them.

The following is the dyeing process with the new dyes explained in more detail:

The dyeing process consists in dyeing or printing fiber materials with the new water-soluble or insoluble dyes using an acid-binding agent. The fiber materials can be natural or regenerative ; 9 ———

ORIGINAL INSPECTED

rated cellulose fibers and nitrogenous fiber materials such as silk, wool and synthetic polyamide fibers and as acid-binding Means of various inorganic alkalis and salts of weak acids as well as of strong alkalis such as sodium bicarbonate, carbonate, hydroxide, phosphate, metaphosphate, acetate and the like. Can be used. In addition, triethylamine can also be used and the like ora & nic bases as well as trichloromate and the like. Compounds can be used. These acid-binding agents can be used before or after the treatment of the fiber materials used with a dye liquor or printing ink or added together with the dye to the dye liquor or printing paste will.

If the dyeing process is batchwise with relatively large liquor ratios by means of a dyeing machine, such as a vat, Jigger, reel and package carried out, the dye liquor is usually made of dyes and inorganic salts, such as Sodium chloride or sulfate. After dyeing 10 minutes to an hour at room temperature or elevated Temperatures is reached, an acid-binding agent is added and dyeing is continued for a further 20 minutes to an hour.

For dyeing nitrogen-containing fibers such as nylon-polyamide synthetic fibers, the dye liquor is initially adjusted to neutral or slightly acidic and the dyeing is carried out appropriately in the presence of a leveling agent such as a nitrogen-containing nonionic surfactant at elevated levels Temperatures. The wet fastness of the dyeings obtained in this way is excellent and can be adjusted by adjusting the dye liquor to neutral or slightly acidic with the help of ammonia or other alkalis can be improved.

In the continuous implementation of the dyeing process such as ■ Rope or block dyeing with relatively small liquor ratios, The dye liquor is usually made by adding an acid-binding agent, a wetting agent and, if necessary, a solubilizing agent By means of how urea is prepared to the dyes. In this dye liquor, the fiber material is used for proportionately

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- - - ORIGINAL INSPECTED

immersed for a short time and then at room temperature or elevated Temperatures either left to stand or subjected to steaming or baking for a short time. That in advance in a Fiber material dipped in a solution of an acid-binding agent can be padded or that in a neutral dye liquor Fiber material padded in advance in a neutral dye liquor can be treated with an acid-binding agent and is then either left to stand or subjected to the heat treatment.

In the case of applying the present method to printing, sodium alginate or an emulsion paste is usually used used as a printing paste to which dyes, acid binding agents and solubilizing agents are added. With the fiber material is printed with this printing paste and then dried and subjected to the heat treatment. If necessary, this can fiber material impregnated in advance with an aqueous solution of an acid-binding agent with a neutral printing paste printed or the fiber material printed in advance with a neutral printing paste in a solution of an acid-binding Can be dipped in or overprinted with this solution.

The fiber material dyed or printed in this way is then rinsed and, if necessary, subjected to hot soaping in an aqueous solution of a nonionic detergent.

The dyeings obtained from fiber materials with the new dyes are in particular with regard to fastness properties Wet and rubbing fastness properties, excellent.

In the following, the invention is illustrated by means of exemplary embodiments explained in more detail. The term “part” should always be understood to mean a “part by weight”.

example 1

The monoazo dye compound obtained by coupling 1 mole of diazotized 2-naphthylamino-4, 8-disulfonic acid with m-toluidine is dissolved neutrally in water, this solution at 0 to 5 ° C a toluene solution of 2 moles ßc, ß-dichlorosuccinan

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added hydride and then sodium carbonate with vigorous stirring added to neutral. After the reaction has taken place, the reaction solution is acidified and the precipitates that have separated out are filtered off and the filter residues are kneaded with the addition of disodium hydrophosphate as a buffering agent and then dried. The water-soluble dye obtained in this way has the following formula:

^H0 ' ^S Cl Cl

NHCO-CH-CH-COOH

If in the above example dichlorosuccinic anhydride is replaced by 1,5 ß-carbomethoxy- #, ß-dichloropropionyl chloride, then a dye of the following formula can be obtained:

Cl Cl) -CH-CH- (

• NHCO-CH-CH-COOCH,

Example 2

20 parts of the dye obtained in Example 1, 10 parts of sodium bicarbonate, 2 parts of a nonionic dye through, 10 parts of nitrobenzene sodium sulfonate and 5 parts of sodium chloride are dissolved in 1,000 parts of water. With the dye liquor prepared in this way, mercerized cotton fabrics are padded at room temperature, then squeezed and, after predrying, steamed at 100-105 ° C. for 5-10 minutes. The stuff dyed in this way is then rinsed with water , with a 0.2 # aqueous solution

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ORIGINAL iWSPECTED

Solution of a non-ionic detergent "soaped at about 95 C, then rinsed and dried. The stuff has a reddish yellow Coloring with excellent light, washing and rubbing fastness properties. '/

Example 3

The following starting dyes A are treated analogously to Example 1 with the following compound B, whereby dyes can be obtained with which colorations C are produced on cotton material.

Al. ] E.g.

OH fjj

N = N- (y

CH ₅ Νϊζ

Cl-CH-CO ^

Oil-CH-CO

, 0

greenish yellow

2 HOS

Cl

UU

IMI

SO ₅ H

SO ₅ H

NHCOCH,

11 η

reddish orange

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SQ ₅ H

jCr / ^ -N = N

HO.

dOC-CH-CH-COOCH, reddish. Cl Cl orange

NHCH,

SO, H QH

CH,

till

scarlet red

HO

SO ₅ H

in red

Cl-CH-CO.

Ruby red

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~ i 9 -

C ₁ OC-OH-CH-COOO ₂ H ₅

Cl

NH,

HO,

NO ₂ SO ₃ H

tin.

yellowish brown

IHl

blue

HO

SO ₃ H

'CIOC-CH-CH-COOCH,

-CH-CH
Cl Cl

bluish green

lift

bluish purple

. fCu-PhJ

(SO

, nhQni Light Blue "

_ti "

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- 10 (Note: Cu-Ph means "Cu-phthalocyanine residue".)

The dyes nos. 1, 2 and 8 can also be obtained by condensation of m-phenyleijdiamine-o-sulfonic acid with the respectively indicated compound B, diazotization of the condensation product obtained and coupling of the diazotized compound with the corresponding component. Furthermore, the dye no. 13 can also be produced by condensation of p-phenylenediamine with β-carbomethoxy- 0C _t β-dichloropropionyl chloride and the thus obtained condensation product with copper-containing phthalocyanine tetrasulphochloride.

Example 4

10 parts of the dye according to Example 1, 5 parts of sodium bicarbonate, 2 parts of a nonionic dye through, 5 parts of sodium chloride and 150 parts of urea are dissolved in water solved and adjusted to 1,000 parts. With this dye liquor cotton clothes are padded at ordinary temperature, then squeezed and, after drying, baked at 120-130 ° C for 5 minutes. After rinsing, soaping, rinsing and drying, a yellow dyeing with the same fastness properties as in Example 1 can be obtained.

The same treatment can be applied to viscose cloth, but with with the exception that the baking takes place at 110 ° C yellow, the same so real coloring can be obtained.

Example 5

In 1,000 parts of an aqueous solution of 2 parts sodium hydroxide and 20 parts of sodium carbonate, cottons are dipped, squeezed off up to 65%, predried and then with a printing paste printed, which consists of 20 parts of the blue dye according to Example 3, No. 10, 50 parts of urea, 500 parts of sodium alginate thickener and 10 parts of sodium nitrobenzene sulfonate is prepared with water to 1,000 parts. That

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Stuff is then dried, steamed for 5-10 minutes, with water rinsed, soaped, rinsed again and dried, creating a clear, blue print with excellent light, washing and washing properties Friction fastness properties is obtained.

Example 6

20 parts of dye no. 13 of Example 3 are dissolved together with 150 parts of urea in a little water and 500 parts a thickening, consisting of 3-4% sodium alginate and 1% Demetallizing agents such as sodium polyphosphate, which is im 10 parts of sodium nitrobenzene sulfonate have been added beforehand, mixed. 10 parts of sodium bicarbonate are then added to the mixture and diluted with water to make the total amount 1,000 parts. With the printing paste prepared in this way then printed cotton, cotton or viscose cloth, pre-dried, then steamed for 10 minutes, rinsed with water, soaped, felt again and then dried. In this way the cloth can be dyed in a real, clear, water-blue tone.

The same print can also be made with the dye according to Example 1 and with each of the dyes listed in Example 3 are carried out in a similar manner, with corresponding real color tones being obtained.

Example 7

Cotton items are printed in the same way as in Example 6 with the printing paste, which, however, does not contain sodium carbonate, then predried and in 1,000 parts of an alkaline liquor, which by dissolving 10 parts of sodium hydroxide and Share sodium alginate thickening in water is prepared, padded, then 1 minute at 105-110 ° C using a quick steamer steamed, rinsed with water, soaped, rinsed again and dried, creating an equally real color as

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- ORIGINAL INSPECTED

- 12 is obtained in Example 6.

Example 8

50 parts of viscose yarn are immersed in a solution of 2 parts of the dye according to Example 1 and 50 parts of sodium chloride in 1,000 parts of water and ^{dyed at 80-85 ° C. for} 20 minutes, then dyed at this temperature for 1 hour after adding 4 parts of sodium carbonate, then Rinsed with water, soaped, rinsed again and dried. The yarn has a yellow coloration with excellent fastness properties. By treating the same with 2 parts of a disazo dye of the formula:

O ₅ H Q-Cu-O

raCO-CH-CH-COOH

the yarn can be dyed in a real blue 'tone.

Example 9 10 parts of a water-insoluble. Dye of the formula:

■ NHCO-CH-CH-COOH Al Cl

600 parts of a low viscosity sodium alginate thickener and 10 parts of sodium bicarbonate or ammonium chloride are made up to 1,000 parts in water. With the one so prepared Printing paste is printed on a nylon cloth, then pre-dried

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ORIGINAL INSPECTED

net, steamed for 10 minutes, then rinsed with water, soaped, then rinsed and dried again, giving a real yellow print on the JTyI on cloth.

■ '. Example '10

1 mol of diazotized N-acetyl-p-phenylenediamine is coupled with 1 mol of p-cresol and the monoazo compound obtained is heated in an aqueous solution of sodium hydroxide in order to split off the acetyl group. 46 parts of the 4 amino-2'-oxy-5'-methyl-azobenzene thus obtained are dissolved in 250 parts of acetone and 40 parts of dimethylaniline are added to the solution. After a further addition of 46 parts of d, 1-ß-carbomethoxy-0C, ß-dichloropropionyl chloride (boiling point: 78 ° C./7 mm Hg), the mixture is stirred for 1 hour and then the acetone is distilled off in vacuo. The residues are then washed with dilute HOl, rinsed with water and dried, resulting in a water-insoluble azo dye of the following formula:

N ⁼ NvX \

COOCH,

V \

\ VxIHOO — CH — OH — C

\ - / egg egg

Example 11

10 parts of the dye obtained in Example 10 are mixed with 15 parts of a nonionic dispersant of the polyethylene oxide series mixed and added 3,000 parts of water to the mixture. A material is added to the disperse liquor prepared in this way made of nylon polyamide synthetic fibers and dyed for 30 minutes at 80-85 ° C. After setting the liquor temperature on 60 ° C is an aqueous solution containing 10 parts of sodium bicarbonate contains, and the treatment continued for 40 minutes at this temperature. After rinsing, soaping and drying, a real, clear yellow color obtained.

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ORIGINAL INSPECTED

Claims (4)

• Ί 4 4 4 ^ / I claims 1. Dyeing process for fiber materials, characterized in that the fiber materials are placed in an aqueous medium Exposure to an acid-binding agent with water-soluble or water-insoluble dyes stains or prints those in the molecule have at least one grouping of the following general formula: - BTRCO - CH - CH - COY, in which R is a hydrogen atom, an alkyl or cycloalkyl group. χ and X _{2 are} a halogen or hydrogen atom, where at least one of the two X ₁ and X ₂ is intended to be a halogen atom and Y is a hydroxyl or alkoxy group, a halogen atom or a substituted amino group which may contain a dye radical. 2. dyeing process according to claim 1, characterized in that natural or regenerated cellulose is used as fiber materials or natural or synthetic nitrogen-containing fibers are used. 3. dyeing process according to claims 1 and 2, characterized in that that water-soluble or water-insoluble dyes are used, which by condensation of at least one in the molecule containing an acylatable "or substituted amino group Dye compound with halosuccinic acid, its anhydride or a compound of the general formula: - XOC-CH - CH-- COY X ₁ * 2. are obtained in which X is a halogen atom and X ^, X ₂ and Y have the meaning given. 909820/1350 ORIGINAL INSPECTED 4. dyeing process according to claims 1 and 2, characterized in that water-soluble or -insoluble dyes are used, / the by condensation of at least one acylatable or substituted amino group containing azo compound or coupling component with halosuccinic acid, its anhydride or a compound of the
general formula: XOC - CH - CH - COY, in the X, X ₁ »Xp ^{un <} * ^ ^d ^ ^{e a: ti} S ^ S ^e ^ ^{> e} ' ^{ae have} meaning and subsequent coupling of the condensation product with a
Coupling component or biazo compound are obtained. 909820/1350