DE2848671A1 - REACTIVE DYES - Google Patents

Description

2343671

-f-

EAYER AKTIENGESELLSCHAFT

Central area of patents, rakes and licenses

5090 Leverkusen, Bayerwerk:

My / Th "a Nov. 1376

Reactive dyes

The invention relates to new water-soluble phthalocyanine dyes in the form of their free Acids of the formula

(SO, H) _a

(D

correspond to where

Pc = residue of a copper or nickel phthalocyanine R-, R_ = H, optionally alkyl

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R_, R., R ₅ = H, optionally substituted alkyl R ₆ , R ₇ , R ₈ = H, SO ₃ H, COOH with the proviso that at least one of the radicals = SO ₃ H or COOH, the naphthalene nucleus optionally further can be substituted

B = pontic

a = 1 to 3; b = 0 to 2; c = 1 or 2 and

a + b + c = 4.

and their mixtures and processes for their manufacture and use.

In the dyes of the formula (I), every sulfonic acid is or sulfonamide group bonded to another benzene ring of the phthalocyanine in the 3- or 4-position.

The radicals R ₁ and R-; R ₃ -R ₅ and Rg-Ro can be the same or different.

Examples of optionally substituted alkyl radicals, R ₁ and R- may be mentioned: C.-C ₅ -alkyl radicals, such as methyl, ethyl, propyl, butyl and amyl, β-hydroxyethyl and Y- hydroxypropyl.

The bridge members B can be aromatic, atic or araliphatic in nature. They can optionally be substituted, for example by C ₁ -C ₄ -alkyl groups, Cj-C ^ -alkoxy groups, halogen atoms, sulfo groups or carboxy groups, or interrupted by keto groups, sulfonic groups, carbonamido groups, urea groups, sulfonamide groups, amino groups, imino groups or oxygen atoms.

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Examples of aromatic bridge members are: 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 1,5-naphthylene, 4-methyl-1,4-phenylene, 2-methyl-1,4-phenylene, 2-methyl-5-chloro-1,4-phenylene, 4-methoxy-1,3-phenylene, 3-methoxy-1,4-phenylene, 4-chloro-1,3-phenylene, 2-chloro-1,4-phenylene, 5-carbonamido-1,3-phenylene, 2-carboxy-1,4-phenylene, 2-carboxy-1,5-phenylene, 3-carboxy-1,5-phenylene, 4-sulfo-1,3-phenylene, 3-sulfo-1,4-phenylene, 2-methyl-5-sulfo-1,3-phenylene.

Examples of aliphatic bridge members are: -CH ₂ -CH ₂ -, -CH ₂ -CH-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH-CH ₂ -,

CH.

CH.

-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH-CH ₂ -CH ₂ -CH ₂ -, -

^CH 3
-CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH-CH ₂ -CH ₂ -CH ₂

₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂

CH

Further examples of bridge members are:

-CH ₂ -CH ₂ -NH-CO-NH- / \

y, -CH ₂ -CH ₂ -NH-CO-NH- ^ y-, -CH ₂ -CH ₂ -NH-C

il ^ -A .. .f \ .rnj \.

CO-

-ΝΗ- / Λ-

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Further substituents for the naphthalene nucleus are, for example: C ₁ -C ₄

A preferred group within those of the invention Dyes are those of the general formula (I), where

Pc = remainder of a copper or nickel

phthalocyanines

R ₁ , R ₂ , R ₃ , R. - hydrogen, methyl or ethyl R ₅ = hydrogen

β = optionally by Cj-C.-alkyl-

groups, Cj-C.-alkoxy groups or halogen atoms substituted 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or C ₂ -C ₆ -alkylene (straight-chain or branched)

R ₆ , R ₇ , Rg = hydrogen, SO ₃ H, COOH, a = 1-3; b = 0-2; c = 1; a + b + c = 2-4.

A particularly preferred group within the dyes according to the invention are those of the general formula (I), whereby

Pc = remainder of a copper or nickel

phthalocyanines

R ₁ , R ₂ , R-, R- = hydrogen, methyl or ethyl Rc = hydrogen

B = optionally by C.-C ₄ -A ^ yl groups,

C ₁ -C alkoxy groups or halogen atoms substituted 1,2-phenylene, 1,3-phenylene or C ₂ -Cg -alkylene (straight-chain or branched)

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Rg, R_, Rg = hydrogen, SO ₃ Ii, COOH, where at least

one of these radicals is SO ₃ H or COOH, 1 <a <. 3, b »0, c = 1; a + b + c = 3 or 4.

Another particularly preferred group within the dyes according to the invention are those of the general formula (I),
whereby

Pc = residue of a copper or nickel phthalocyanine R ,, R. = hydrogen, methyl, ethyl R ₅ = hydrogen

B = optionally substituted by C.-C ₄ -Alky groups!, C.-C ~ ₄ alkoxy groups or halogen atoms, substituted 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or C ^ -CG-alkylene (straight-chain or branched) Rg, R ₇ , Rg = hydrogen, SO ₃ H, COOH, where at least one

this is SO ₃ H or COOH. a = 1 or 2, b = 0, c = 1, a + c = 2 or 3.

The new dyes of the formula (I) are prepared by condensing suitable starting components. That The most advantageous process consists in using dyes in the form of their free acids of the formula

Pc- (SO
²

(II)

(SO-N — B — N -H)
2 ι ι C

R ₃ R ₄

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correspond with compounds of the general formula

(III)

implements,
whereby
Pc, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , Rg, B, a, b and c

have the meaning given above.

The compounds of formula (III), which are also the subject of the present invention, are obtained by Conversion of 2,4,6-trifluoro-1,3,5-triazine with compounds the formula

(IV)

whereby

Rc, Rg, R-, and Rg have the meaning given above.

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Suitable compounds of the formula (IV) are, for example:

2-aminonaphthalene-i-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-i-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfonic acid, 7-A'thy laminonaphthalin-2-sulfonic acid, 7-butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-1,3-disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 8-aminonaphthalene-1,3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,6-disulfonic acid, 8-aminonaphthalene-1,6-disulfonic acid, 4-aminonaphthalene-1,7-disulfonic acid, 3-aminonaphthalene-2,6-disulfonic acid, 4-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 4-aminonaphthalene-2,7-disulfonic acid, 6-aminonaphthalene-1,3,5-trisulfonic acid, 7-aminonaphthalene-1,3,5-trisulfonic acid, 8-aminonaphthalene-1,3,5-trisulfonic acid, 4-aminonaphthalene-1,3,6-trisulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, 4-aminonaphthalene-1,3,7-trisulfonic acid ^ 4-aminonaphthalene-1-carboxylic acid, 5-aminonaphthalene-1-carboxylic acid, 8-aminonaphthalene-1-carboxylic acid,

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3-aminonaphthalene-2-carboxylic acid, 5-aminonaphthalene-2-carboxylic acid, V-aminonaphthalene ^ -carboxylic acid, 8-amino naphthalene-2-carboxylic acid, 4-aminonaphthalene-1,8-dicarboxylic acid.

But you can also use the dyes of the formula (II) initially with trifluorotriazine and the intermediate obtained product with a compound of the formula

(IV)

realize,
ο where

Rc, Rg, R ₇ and Rg have the meaning given above.

These reactions are acylation reactions and may constitute in an aqueous, aqueous organic or organic preferred weakly acidic to weakly alkaline medium at temperatures from -10 ⁰ C to +80 ⁰ C, preferably -5 ° C to +10 ⁰ C are performed.

The phthalocyanine compounds of the formula (II) used in the process according to the invention can thereby be prepared that a phthalocyaninesulfonic acid chloride - preferably in the form of an aqueous suspension - the formula

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- H-

(SO ₂ Cl) _n

Pc ' (V)

wherein

Pc has the meaning given above, m the numbers O, 1 or 2 and η denotes the numbers 2, 3 or 4, where the sum of m and η is not greater than 4,

with diamines or, preferably, monoacylated diamines of the formula

H-N-B-N-H or H-N-B-N-acyl

Il Il

^R 3 ^R 4 ^R 3 ^R 4

(VIa). (VIb)

and optionally with a compound of the formula

HN ^ ¹ (VII) R ₂

whereby

R ₁ , R, R ₃ , R. and B have the meaning given above,

converts and, in the case of the use of monoacylated diamines of the formula (VIb), the terminal acylamino group of the obtained Phthalocyaninverbindungen one

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subjected to acidic or alkaline saponification. In this reaction, there are unreacted sulfonic acid chloride groups converted into sulfonic acid groups.

Phthalocyaninesulfochloride or Phthalocyaninsulfochloridsulfonsäuren of the formula (V) can be obtained by using the corresponding phthalocyanine or the Phthalocyaninesulfonic acid with chlorosulfonic acid and optionally a Säu.rehalogenid such as thionyl chloride, phosphorus pentachloride, phosphorus oxychloride or phosphorus trichloride as in British Patents 708 543, 784 834 and 7 85 629 and in U.S. Patent 2 219 330 described, treated.

According to the invention, uniform phthalocyanine dyes can be used are used, those are those in which the letters a, b, and c characterize the numbers 0, 1, 2 and 3 respectively, In addition, however, mixtures of these dyes can also be used. Sometimes show such Mixtures have particular advantages in terms of solubility and substantivity. In such mixtures they vary Numbers in the mean value.

Such mixtures according to the invention are, for example, made up of two or more, in each case uniform, final dyes of formula (I) or particularly advantageously prepared by using a mixture of the starting components. The latter is often inevitable because the

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Phthalocyanine sulfonic acid chloride sulfonic acids (V) with respect to Degree of sulfonation and their ratio of sulfonic acid chloride groups and sulfonic acid groups are common technically incurred as mixtures.

As examples of "suitable monoacylated diamines Formula (VIb) and suitable diamines of the formula (VIa) may be mentioned:

2-amino-acetanilide, 3-aminoformanilide, 3-aminoacetanilide, 4-aminoformanilide, 4-aminoacetanilide, 1-amino-4-acety1-aminonaphthalene, i-Amino-S-acetyl-aminonaphthalene, 3-aminophenyloxamic acid, 4-methyl-3-amino-acetanilide, 4-methyl-3-aminophenyloxamic acid, 5-chloro-4-amino-2-methyl-acetanilide, 4-methoxy-3-amino-acetanilide, 4-amino-3-methoxy-acetanilide, 4-amino-2,5-dichloroacetanilide, N-methyl-N-4-aminophenyl-acetamide, 4-amino-2-chloro-acetanilide, 4-acetylamino-2-aminobenzoic acid, 5-acetylamino-2-aminobenzoic acid, 1,4-diaminobenzene-2-sulfonic acid, 1,3-diaminobenzene-3-sulfonic acid, 5-acetylamino-3-aminobenzoic acid, monoacetyl-ethylenediamine, Monoacetyl-propylenediamine-1,3, monoacetylbutylenediamine-1,4, N-methyl-N-3-aminopropyl-acetamide, N-methyl-N-ß-methylaminoäthy1-acetamid, N - (ß-aminoethyl) -N '- (3-aminophenyl) urea.

The new dyes are extremely valuable products that are suitable for a wide variety of applications. As water-soluble compounds, they are of interest for the dyeing of hydroxyl-containing and 'nitrogen * -

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containing textile materials, in particular textile materials made from native and regenerated cellulose, wool, silk, synthetic polyamide and Polyurethane fibers. They are particularly suitable as reactive dyes for dyeing cellulose materials according to the ones that have recently become known for this purpose Techniques. The fastness properties obtained, especially wet fastness properties, are excellent.

To dye cellulose, the dyes are preferably used in an aqueous solution to which alkaline substances, such as alkali hydroxide or alkali carbonate, or compounds which change into alkaline substances, such as alkali bicarbonate, Cl ₃ C-COONa, can be added. Further auxiliaries can be added to the solution, but these should not react in an undesired manner with the dyes. Such additives are, for example, surface-active substances, such as alkyl sulfates, or substances that prevent the migration of the dye or auxiliary dye products, such as urea, or indifferent thickeners, such as oil-water emulsions, tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes produced in this way are applied to the material to be colored, for example by padding in the Foulard (short liquor) or applied by printing and then for some time at an elevated temperature,

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preferably 40 to 150 ° C, heated. Heating can be done in the hot flue, in the steamer, on heated rollers or by placing them in heated concentrated salt baths, both on their own and in any order be executed one after the other.

When using a padding or dye liquor without alkali, passage of the dry goods through one becomes alkaline reacting solution to which common salt or Glauber's salt is added. The addition of salt reduces here in the migration of the dye from the fiber.

The material to be colored can also be pretreated with one of the aforementioned acid-binding agents treat with the solution or paste of the dye and finally, as indicated, with increased Fix temperature.

For dyeing from a long liquor, one goes into an aqueous solution of the dye (liquor ratio 1: 5 to 1:40) at room temperature and colors for 40 to 90 minutes, optionally with increasing the temperature up to 95 C and if necessary with partial addition of salt, e.g. sodium sulfate, and then alkali, for example sodium phosphates, sodium carbonate, NaOH or KOH.

This is where the chemical reaction between the dye and the fiber occurs. After chemical fixation has taken place the dyed goods are rinsed with hot water and then soaped, where-

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if not fixed residues of the dye are removed. You get excellent real, especially wet and lightfast colorations.

In the so-called block cold dwell process, one can Subsequent heating of the padded fabric can be saved by leaving the fabric for some time, e.g. 2 to 20 hours, stored at room temperature. In this process, a stronger alkali than that described above is used Dyeing process from a long liquor used.

For printing on materials containing hydroxyl groups, a printing paste is made from the dye solution, a thickener, such as sodium alginate, and a compound that reacts alkaline or releases alkali when heated , such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium hydrogen carbonate, used and the printed material rinsed and soaped.

Textile materials containing amide groups, such as wool, Silk, synthetic polyamide and polyurethane fibers are generally made using the usual dyeing methods colored in acidic to neutral range.

The colorations obtainable with the new dyes are generally good to very good Fastness properties, especially through excellent Wet fastness properties.

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example 1

6.4 g of 1-aminonaphthalene-3-sulfonic acid are added to 150 ml of water dissolved with the addition of a little sodium hydroxide solution at pH 4.0. This solution is left at 0 ° -5 ° 4.1 g of trifluorotriazine in 5 minutes while maintaining a pH of 3.2 to 3.9 with the aid of 2N soda solution add dropwise and stir while adhering to the specified

pH value for 15 minutes at 0 ° -5 ° C.

In 400 g of water, 19.7 g of the compound of the formula

(SO ₃ H)

Cu-PC- (3) - (SO ₀ NH ^) _{1 NH}

sO ₂ NH-

(obtained by reacting Cu-Pc- (3) - (SO ₂ C1 / SO ₃ H) ₄ with 3-aminoformanilide and ammonia and subsequent saponification of the formylamino group) dissolved with the aid of sodium hydroxide solution at pH 6. After the solution has cooled, the difluorotriazinylaminonaphthalenesulfonic acid solution obtained in accordance with paragraph 1 is allowed to flow in at 0 ° -5 ° C. in 5 minutes and the pH of the solution is then adjusted to 5.5 with 2N soda solution. The temperature is then increased to 25 ° -3O ° C. and the mixture is stirred until the condensation has ended. The dye is then salted out with KCl, filtered off with suction and washed with dilute KCl solution

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and dries at 50 ° -6O ° C. You get in practical quantitative yield of the dye, which is in the form of its K salt of the formula

Cu-PC-O) - (SO_NH _O

is equivalent to. He dyes cotton in turquoise blue tones.

Proceeds as described in paragraphs 1 and 2, but replaces the 1-aminonaphthalene-3-sulfonic acid used in paragraph 1 the same amount of 2-aminonaphthalene-1-sulfonic acid one, the dye is obtained in a practically quantitative yield, which is in the form of his K salt of the formula

and dyes cotton in turquoise blue tones.

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In an analogous manner, other valuable reactive dyestuffs are obtained if the ones in column 3 of the following Aminonaphthalene sulfonic acids mentioned in Table 1 are acylated with 2,4,6-trifluoro-1,3,5-triazine and the obtained Dif luortriazinyl- ^ minonaphthylsulfonsäuren with the in Column 2 formulated aminophthalocyanine derivatives condensed.

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Tabel

2648671

No. Anincphthalocyanine Dertvat anincnaphthalenesulfonic acid

Dyed on cellulose

(SO ₃ Na)

1) Cu-Pc- (3) - (SO ₉ NH ₅ ) ₁ \

4 minonaphthalene turquoise blue 2-sulfonic acid

5-ainonaphthalene-turquoise blue 1-sulfonic acid

8-aninnaphthalene-turquoise blue 1-sulfonic acid

5-toinonaphthalene-turquoise blue 2-sulfonic acid

2-micronaphthalene turquoise blue 1,5 ~ disulfonic acid

6) Qi-Pc- (3)

. (SO ₃ Na) ₃ 5-aninonaphthalene-turquoise 1-sulfonic acid

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Table 1 (continued)

No aminophthalocyanine derivative Andnonaphthalene stains sulfonic acid cellulose

_/ (SO ₃ Na) ₂

7) Cu-Pc- (3) -

2-aninnaphthalene turquoise 1-sulfonic acid

4-aminonaphthalene turquoise 2-sulfonic acid

9) Cu-Pc-O) - (SO ₂ NH ₂ ) 2-aminonaphthalene-turquoise blue 1,5-disulfonic acid

(SO ₃ Na) ₂ 10) Cu-Pc- (3) - (SO ₂ NHCH ₃ )

(SO ₂ NH- ^) -NH ₂ 5-aminonaphthalene-turquoise 1,3-disulfonic acid

(SO ₃ Na) ₂

// Λ-ι

J) -NH ₂ ). 2-AininonaEiiÜialin- turquoise 1,5- ^ iLsulfcnsäure

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Table 1 (continued) No. Etiine phthalocyanine derivative Minonaphthalene shade on sulfonic acid cellulose

12) Cu-Pc-O)

. (SO ₃ Na) ₂

7-minonaphthalene-turquoise blue 1,3-disulfanic acid

SO ₃ Na)

13) Cu-Pc- (4) - (SO ₂ NH,).

2-AninonaFhthalin- turquoise blue 1-sulfonic acid

14) Ni-Pc- (3)

y (SO ₃ Na

\ r -ι

NsO ₂ NH- ^

2-etninonaphthalene green 1-sulfonic acid

15) Ni-Pc-O)

(SO ₃ Na) ₂

2-aminonaphthalene green \ ι -ν 1,5-disulfonic acid

Ν / ™ ™, // \\ _ NH)

16) Ni-Pc-O)

(SO ₃ Na) ₃

3-minonaphthalene green 2,7-disulfonic acid

NH ₂

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Table 1 (continued)

No aminophthalocyanine derivative itainonaphthalene shade on sulfanic acid cellulose

(SO ₃ Na) ₂

17) Cu-Pc- (3) - \

NH _n 7-methylaninana; piitha- turquoise blue lin-2-sulfo: isic acid

(SO ₃ Na)

18) Cu-Pc- (3) -7-ethylaninonaphtha turquoise blue lin-2-sulfonic acid

(SO ₃ Na)

19) Cu-Pc- (3) - \

3-AnunonafÄithalin-2,7-disu] f onic acid

turquoise blue

([SO ₃ Na)

20) Cu-Pc- (3) - (SO ₂ NH ₂ )

(SO ₂ NH-

, Na 2-Minonariithalin-1-sulfonic acid

turquoise blue

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Table 1 (continued)

No amino phthalocyanine derivative minonaphthalene hue on

sulfonic acid cellulose

(SO ₃ Na) ₂

21) Qi-Pc- (3) - (SO ₉ NH ₉ ) - )., Ξ-Μΐηο-β-Μΐηοχγ- turquoise blue

\ 1_ / ^ΝΗ 2 naphthalene-2-

\ / ~ -. ^. / ΓΛ sulfonic acid

22) "e-Mino-T-ethoxy-turquoise blue

naphthalene-2-sulfonic acid

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Example 2

6.4 g of 2-aminonaphthalene-1-sulfonic acid are added to 150 ml of water adjusted to pH 4.0 with the addition of a little sodium hydroxide solution. This solution is left at 0 ° -5 ° C 4.1 g of trifluorotriazine in 10 minutes while maintaining a pH of 3.2 to 3.9 with the aid of 2N soda solution are added dropwise and the mixture is stirred for a further 15 minutes at 0 ° -5 ° C. while maintaining the stated pH.

19 g of the compound of the formula are dissolved in 300 ml of water

(SO ₃ H) ₂

Cu-Pc- (3) - (SO ₀ NH ₉ ) _Λ
χ 2 2 1

(SO ₂ NH-CH ₂ -CH ₂ -NH ₂ )

(Obtained by conversion of Cu-Pc-O) - (SO ₂ Cl) ₄ with mono acetylethylenediamine and ammonia, and subsequent saponification of the acetylamino group) dissolved with the aid of sodium hydroxide solution at pH 8.5. After the solution has cooled, the difluorotriazinylaminonaphthalene-sulfonic acid solution obtained in accordance with paragraph 1 is allowed to flow in at 0 ° -5 ° C. while maintaining a pH of 8.0 to 8.5. The temperature is increased to 25.degree. C., the pH of the solution is adjusted to 6 after the end of condensation, salted out with KCl, suction filtered, washed with dilute KCl solution and dried at 50.degree.-60.degree. The dye of the formula is obtained in very good yield

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(SO ₃ K) ₂

Cu-Pc- (3) -

SO ₃ NH

(SO ₀ NH-CH ₀ -CH ₉ -NH-

He dyes cotton in turquoise blue tones.

In an analogous manner, other valuable reactive dyestuffs are obtained if the ones in column 3 of the following Aminonaphthalenesulfonic acids mentioned in Table 2 are acylated with 2,4,6-trifluoro-1,3,5-triazine and the obtained Difluorotriazine derivatives with those shown in column 2 Aminophthalocyanine derivatives condensed.

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Tabel

No aminophthalocyanine derivative Minonaphthalene sulfonic acid

Dyed on cellulose

(SO ₃ Ha)

Cu-Pc- (3) \

(SO ₂ NH-CH ₂ -CH ₂ -NH ₂ ) 5-Aniinonaphthlialin- turquoise blue 1-sulfctic acid

4-aninnaphthalene-turquoise blue 2-sulfonic acid

2-aninonaphthalene turquoise blue 1,5-disulfonic acid

4) Cu-Pc- (3) -

(SO ₃ Na) 2-ainonaphthalene-turquoise blue 1-sulfonic acid

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Table 2 (continued)

No aminophthalocyanine derivative amine xiaphthalene hue on

sulfonic acid cellulose

(SO ₃ Na) 2

5) Cu-Pc- (3)

4-AminonaFhthalin- turquoise blue 2-sulfonic acid

CH ₃

CH ₃

(SO ₃ Na) ₂ 6) Cu-Pc- (3) - (SO ₂ NH ₂ ) ₁

(SO ₂ NH- (CH ₂ ) ₄ - * 2-aminonaphthalene- turquoise blue

• 7 \ rs,
7) Cu

- (SO ₂ NH ₂ )

- (CH ₂ ) ₃ -NH

2-aninonaphthalene turquoise blue 1-sulfQnsMure

(SO ₃ Na) 2/8) Cu-Pc- (3) - (SO ₂ NHCH ₃ ) ₁ 2-Aninonaphthal: .n- turquoise blue 1,5-disulfonic acid

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Example 3

6.5 g of the sodium salt of 8-aminoaphthalene-1-carboxylic acid are dissolved in 100 ml of water solved. After cooling to 0 ° C., the solution is adjusted to a pH of 4. so is left at 0 ° -5 ° within 10 minutes while maintaining a pH of 3.2 to 3.9 with the aid of Add dropwise 4.1 g of trifluorotriazine to 2N soda solution and stir for a further 15 minutes while maintaining the stated pH at 0 ° -5 ° C.

In 300 g of water, 19.7 g of the compound of the formula

(SO ₃ Na) ₂
Cu-Pc- (3) - (SO ₂ NH ₂ )

(obtained by reacting Cu-Pc- (3) - (SO ₂ C1 / SO ₃ H) ₄ with 3-aminoformanilide and ammonia and subsequent saponification of the formylamino group) dissolved with the aid of sodium hydroxide solution at pH 6. After the solution has cooled, the difluorotriazinylaminonaphthoic acid solution obtained in accordance with paragraph 1 is allowed to flow in at 0 ° -5 ° C. in 5 minutes and the pH of the solution is then adjusted to 5.5 with 2N Sada solution. The temperature is then increased to 25 ° -3O ° C. and the mixture is stirred until the condensation has ended. The dyestuff is salted out with KCl, filtered off with suction, washed with dilute KCl solution and dried at 50-60 ° C. The dyestuff is obtained in a practically quantitative yield, which is in the form of its K salt of the formula

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- 2Γ8 -

(SO ₃ K) ₂

Cu-Pc- (3) - (SO ₉ NH ₉ ) ₁ W- ^ T

NH-

HOO

is equivalent to. He dyes cotton in turquoise blue tones.

Dyeing example 1

In a staining beaker with a capacity of 500 ml, which is located in a heatable water bath, 220 ml of water are removed from 2O-25 ° C submitted. 0.3 g of dye is obtained according to example 1, paragraph 2, with 2 ml of cold water and add 48 ml of hot water (70 ° C). The dye solution with a pH of 7-8 is added to the water initially charged, with 10 g of cotton yarn in this The dye liquor is kept constantly in motion. The temperature of the dye liquor is increased within 10 minutes to 60 ° C, add 15 g of sodium sulfate (anhydrous) and continue dyeing for 30 minutes. Then you add the dye liquor Add 2g of sodium carbonate and dye at 60 ° C for 60 minutes. The dyed material is then removed from the dye liquor, discolor the adhering liquor by wringing out or Press off and rinse the material thoroughly first with cold water and then with hot water until

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the wash liquor is no longer bled. Then the colored material is in 500 ml of a liquor that Contains 0.5 g sodium alkyl sulfonate for 20 minutes Soaped at boiling point, dried again and at 60-70 C in a drying cabinet. The cotton is dyed in a clear, turquoise-blue shade that is fast to wet.

Dyeing example 2

3 g of dye, which is obtained according to Example 1, paragraph 2, are stirred with 5 g of urea and 1 g of sodium nitrobenzene sulfonic acid, made into a paste with 10 ml of water at 20-25 ° C and mixed with 80 ml of water at 20 ° C Stirring dissolved at pH 7-8. 20 ml of a 10% sodium carbonate solution are added to this solution. The padding liquor thus obtained is used to pad 20 g of cotton fabric on a laboratory pad, the rollers of which are pressed against one another with such a pressure that the liquor pick-up of the cotton fabric is approx. 80% of its dry weight. The thus padded fabric is stretched on a tenter frame and dried in a drying oven for 15 minutes at 60-7O ⁰ C and then steamed for 3 minutes at 102 ⁰ C. The dyed material is then rinsed thoroughly, first with cold water and then with hot water until the wash liquor is no longer bled. The colored material is then soaped in 500 ml of a liquor containing 0.5 g of sodium alkyl sulfonate for 20 minutes at the boiling point, then dried again and at 60 ° -70 ° C. in a drying cabinet.

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--8O-

The dye is absorbed in a wet-fast, clear, turquoise-blue tone.

Dyeing example 3

A 20 g wool skein is used to make a dye bath at 40 ° C received that from

0.5 g dye, obtained according to Example 1, paragraph 2 (dissolved at pH 7-8),

3.0 g of a polyglycol ether, produced according to DAS 10 41 003, example 9.

⁵ »0 g sodium and sodium sulphate 1.2 g acetic acid 30% per liter, and heated to 80 ° C within 15 minutes. The mixture is allowed to stay at this temperature for 30 minutes, is heated to the boil and this temperature is maintained for about 1 hour. After rinsing with water, a potting- and whale-fast, turquoise-blue coloration is obtained.

Print sample

A piece of cotton is coated with a printing paste consisting of 50 g of dye from Example 1, paragraph 2, 150 g Urea, 20 g of sodium bicarbonate, 10 g of sodium m-nitrobenzenesulfonic acid, 450 g of a highly viscous alginate thickener and 320 g of water, printed and steamed in a steamer, e.g. of the Mather-Platt type, at 103 ° C. The print is then flushed with cold, then with hot and finally with cold water again. You get a real turquoise blue print.

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Claims (8)

-y- claims 1. Phthalocyanine reactive dyes in the form of the free Acid of the formula correspond,
wherein
Pc = remainder of a copper or nickel phthalo- cyanins R ₁ , R ₂ = hydrogen, optionally substituted alkyl R ₃ , R., R ₅ = hydrogen, optionally alkyl B = bridge member R ₆ , R ₇ , R ₈ = hydrogen, SO ₃ H, COOH, with the proviso that at least one of the radicals = SO ₃ H or COOH, where the naphthalene core can optionally be further substituted a = 1 to 3 b = 0 to 2 ^{c =} 1 or 2 and a + b + c = Le A 19 261 030021/0208 2. Phthalocyanine reactive dyes in the form of free acid of the formula (SO, H) 1O 15th 20th correspond, wherein Pc , R_, R ₃ ^R 5 B V ^R 7 ' ^R 8 a b c = Remainder of a copper or nickel phthalo- cyanine R ₄ = hydrogen, methyl or ethyl = Hydrogen = 1,2-phenylene, 1,3-phenylene, 1,4-phenylene which is optionally substituted by Cj-C-alkyl, C ₁ -C _{4 -AlkOXy or halogen atoms} or C "-C ₆ -alkylene (straight-chain or branched) = Hydrogen, SO ₃ H, COOH, at least one of these radicals being SO ^ H or COOH. = 1 to 3 = 0 to 2 = 1 a + b + c = 2 to 4 Le A 19 030021/0208 - 43- - 3. Phthalocyanine reactive dyes in the form of free acids of the formula (SO-, Η) PC- (SO ₂ N _n ^ \ ^R2 SO ₀ N B- R-. ιΛϊϊ correspond to where Pc , i \ _o , Γ \ τ, ^R 5
B. R ₆ , = Remainder of a copper or nickel phthalocyanine = Hydrogen, methyl or ethyl = hydrogen = 1,2-phenylene, 1,3-phenylene, 1,4-phenylene which is optionally substituted by C ₁ -C ₄ -alkyl, C ₁ -C _{4 -alkyl or halogen atoms} or Cp-Cg-alkylene (straight-chain or branched) = Hydrogen, SO ₃ H, COOH, at least one of these radicals being SO ₃ H or COOH K a <3, b> 0, c = a + b-t-c = 3 or 4. Le A 19 261 030021/0208 - IA - 2848371 4. Phthalocyanine reactive dyes in the form of free acid of the formula R- a b c = Remainder of a copper or nickel phthalocyanine = Hydrogen, methyl, ethyl = Hydrogen = optionally by C ₁ -C ₄ -alkyl, C ₁ -C ₄ alkoxy or halogen atoms substituted 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or C ₂ -Cg -alkylene (straight-chain or branched) = Hydrogen, SO ₃ H, COOH where at least one of these radicals is SO ₃ H or COOH = 1 or 2, = 0, = 1, a + c = 2 or Le A 19 0 30021/0208 -Γ- 5. Process for the preparation of phthalocyanine reactive dyes characterized in that one amino group-containing phthalocyanine dyes in the form the free acid of the formula , ^(S0 3 ^H) a ^R 2 (SO ₀ NBNH) 'ι ι R ₃ R ₄ correspond to where Pc = remainder of a copper or nickel phthalocyanines R, r_, R and R, = hydrogen, optionally substituted Alkyl B = pontic a = 1 to b = 0 to c = 1 to 2 and a + b + c ^ f 4 mean. either with c moles of a compound of the formula Le A 19 261 π 30021/0208 wherein Rjj = hydrogen or optionally substituted Alkyl R ₆ , R ₇ , R ₈ = hydrogen, SO ₃ H or COOH, with the
Provided that at least one of the residues = SO ₃ H or COOH, where the
Naphthalene nucleus can optionally be further substituted or first with c mol of trifluorotriazine and then with c moles of a compound of the formula wherein Rr, R ,, Rt and R _{0 have} the meaning given above, JOlO f to react. 6. Use of the dyes of claims 1-4 for dyeing and printing hydroxyl-containing and N-containing
Materials, in particular textile materials made from native or regenerated cellulose. Le A 19 261 030021/0200 7. With the dyes of claims 1-4 dyed or printed hydroxyl-containing or N-containing Materials. 8. Difluorotriazine compounds of the formula "Ν - / ^R 6
Ί ^R 8 ^R 5 wherein c = H, optionally substituted alkyl ₆ , R ₇ , Rg = H, SO ₃ H, SOOH with the proviso that at least one of the radicals SO-H or COOH is. Le A 19 261 0 30 0 21/0208