KR0131760B1 - Phthalocyanine compound, rrocess for dyeing or printing of organic substructure by using the smae - Google Patents

Abstract

None.

Description

Phthalocyanine compounds and methods for dyeing or printing organic substrates using the same

The present invention relates to phthalocyanine compounds comprising heterocyclic reactive radicals, methods for their preparation, and the use of them as fiber reactive dyes in dyeing and printing processes.

The present invention provides the following general formula (I) compounds in free acid or free salt form and mixtures thereof.

Wherein Pc is a phthalocyanine radical; M is Cu, Ni, Co, Fe or Al; a is 1, 2 or 3, b is 0, 1 or 2, except that the sum of a and b has a maximum of 3;

R ₂ and R ₃ are each selected from hydrogen or C _1-6 alkyl, or together with the nitrogen atom bonded to them form a 5 or 6 membered ring system which may contain O- or N- atoms;

Each R ₁ is C _1-4 alkyl mono-substituted by hydroxy, halogen, —SO ₃ H, —OSO ₃ H or —COOH, unsubstituted C _1-4 alkyl, or hydrogen;

C_1-4알킬렌, -C_1-4알킬렌

또는

로부터 선택된 하나의 기가 개입된 또는 개입되지 않은 C_2-6알킬레이거나(* 는 -SO₂NR₁기에 부착된 원자를 나타냄) ; 또는 -SO₂NR₁-O₁-NR₁은

알킬렌 -NR₁- 또는 -SO₂NR₁-C_2-4알킬렌

을 형성하며;Q ₁ is —O— and —NR ₁ —, mono hydroxysubstituted C _3-6 alkylene,

C _1-4 alkylene, -C _1-4 alkylene

or

C _2-6 alkyllay with or without one group selected from (* denotes an atom attached to a —SO ₂ NR ₁ group); Or -SO ₂ NR ₁ -O ₁ -NR ₁ is

Alkylene -NR ₁ -or -SO ₂ NR ₁ -C _2-4 Alkylene

To form;

R ₄ is hydrogen, halogen, hydroxy, C _1-4 alkyl, C _1-4 alkyl, C _1-4 alkoxy, —COOH or —SO ₃ H;

(* Represents a coupling position),

R ₅ is -OH or -NH ₂ ; R ₆ is C _1-4 alkyl or —COR ₈ ; R ₈ is —OH, —OC _1-4 alkyl, or —NH ₂ ; Q ₃ is a divalent crosslinking group,

R ₉ is hydrogen, C _1-4 alkyl, C _5-6 cycloalkyl, phenyl or phenyl (C _1-4 alkyl), wherein any phenyl radical of R ₉ is unsubstituted, or C _1-4 alkyl, C Substituted with one to three substituents selected from _1-4 alkoxy, halogen, -COOH and -SO ₃ H], -COR ₈ , -C _1-4 alkyl-SO ₃ H, -C _1-4 alkyl- OSO ₃ H or —C _1-4 alkyl-COR ₈ ;

, SO₃H, -OSO₃H 또는 -NH2 에 의해 모노 치환된 C1-4 알킬 ;R ₁₀ is hydrogen, —CN, —SO ₃ H, —COR ₈ , C _1-4 alkyl; -OH, halogen, -CN, C _1-4 alkoxy,

C 1-4 alkyl mono-substituted by, SO ₃ H, —OSO ₃ H or —NH 2;

또는

이며(여기서 R₇은 수소, 할로겐, C_1-4알킬, C_1-4알콕시, -COOH 또는 -SO₃H ; R₁₁은 수소, C_1-4알킬 또는 히드록시-C_2-4알킬;

는 비발색단 음이온임);-SO ₂ NH ₂ ,

or

Where R ₇ is hydrogen, halogen, C _1-4 alkyl, C _1-4 alkoxy, —COOH or —SO ₃ H; R ₁₁ is hydrogen, C _1-4 alkyl or hydroxy-C _2-4 alkyl;

Is a non-chromophore anion);

알킬렌-, 또는 -C_1-4알킬렌

(여기서 m 은 0 또는 1)이며 ; 또는 -Q₄-NR₁- 은 -C_2-4알킬렌이며;Q ₄ is C _2-6 alkylene, monohydroxy substituted C _3-6 alkylene, _interrupted by one group selected from -O- and -NR _1- , or

Alkylene-, or -C _1-4 alkylene

Where m is 0 or 1; Or -Q ₄ -NR ₁ -is —C _2-4 alkylene;

Provided that b is not 0, M is Cu, and two R ₁ are hydrogen,

(R₄는 수소, C_1-4알킬 또는 C_1-4알콕시임)인 경우, R₂및 R₃중 적어도 하나가 수소 이외의 것이다.Q ₁

(R ₄ is hydrogen, C _1-4 alkyl or C _1-4 alkoxy), at least one of R ₂ and R ₃ is other than hydrogen.

Any alkyl or any alkylene groups which may be present in a straight or branched chain in this application are considered straight and branched unless otherwise specified. In hydroxy-substituted alkyl or alkylene groups bonded to nitrogen, the hydroxy group is preferably located at the C atom which is not directly bonded to nitrogen.

Halogen is fluorine, chlorine or bromine, preferably chlorine or bromine, more preferably chlorine.

The pyrimidine coupling position due to the non-selectivity of the coupling reaction of 5-cyano-2,4,6-trichloropyrimidine to the chromophore -NR1- group, which is caused by replacing any of the chlorine atoms on the pyrimidine Is not fixed.

Preferred compounds of formula (I) are isomer mixtures in which the substituent sites on the phthalocyanine group and the coupling site of the pyrimidine group are not immobilized.

Preferred M is M 'when M' is Cu or Ni.

Preferred R 1 is hydrogen, C _1-2 alkyl; C 1-3 alkyl substituted by a group selected from hydroxy —SO ₃ H, —OSO ₃ H and —COOH, wherein hydroxy is most preferred.

Preferred R ₁ is R _1a , wherein each R _1a is hydrogen, methyl, ethyl, 2-hydroxy ethyl, — (CH ₂ ) _p SO ₃ H, — (CH ₂ ) _p OSO ₃ H or — (CH ₂ ) _q COOH, p is 1 or 2, q is 1, 2 or 3.

More preferred R ₁ is R _1b , wherein each R _1b is hydrogen, methyl, ethyl or 2-hydroxyethyl.

Most preferred R ₁ is R _1C as R _1C and R _1C is hydrogen or methyl.

Preferred R ₂ and R ₃ are R _2a and R _3a , each of R _2a and R _3a being hydrogen or C _1-4 alkyl, or R _2a and R _3a together with the N atom bonded to them pyrrolidine, piperi To form a dean, morpholine, or piperazine ring. More preferred R ₂ and R ₃ are R _2b and R _3b , each of R _2b and R _3b being hydrogen, methyl or ethyl.

, -C1-3 알킬렌

또는

알킬렌; 또는 -SO₂-NR₁-Q_1a-NR₁- 은

, 또는

알킬렌 -NR₁-, 또는 -SO₂-NR₁-C_2-3알킬렌 ;Preferred Q ₁ is Q _{1a wherein} Q _1a is C _2-3 alkylene, monohydroxy substituted C _3-4 alkylene, C _2-3 alkylene-OC _2-3 alkylene, C _2-3 alkylene-NR _1b- C _2-3 alkylene,

, -C1-3 alkylene

or

Alkylene; Or -SO ₂ -NR ₁ -Q _1a -NR ₁ -silver

, or

Alkylene -NR _1- , or -SO ₂ -NR ₁ -C _2-3 alkylene;

R _4a and Q _2a are as defined below.

알킬렌

또는

알킬렌- (R_4b및 Q_2b는 후술되는 것과 같음) ; 또는 -SO₂-NR₁-Q_1b-NR₁- 은

을 형성한다.More preferred Q ₁ is Q _{1b wherein} Q _1b is C _2-3 alkylene, monohydroxy substituted C _3-4 alkylene,

Alkylene

or

Alkylene- (R _4b and Q _2b are as described below); Or -SO ₂ -NR ₁ -Q _1b -NR _1-

To form.

또는

(R_4b및 Q_2c는 후술된다)Most preferred Q ₁ is Q _1c and Q _1c is

or

(R _4b and Q _2c are described later)

Preferred R ₄ is R _4a , wherein R _4a is hydrogen, methyl, methoxy, -COOH, or -SO ₃ H.

More preferred R ₄ is R _4b, where R _4b is hydrogen, —COOH or —SO ₃ .

또는

이다(R_6a, R_9a및 R_10a는 후술된다).Preferred radicals Q ₂ are Q _2a and Q _2a is

or

(R _6a , R _9a and R _10a are described later).

또는

이다(R_6a, R_9b, R_10b, Q_3a및 Q_l4a는 후술된다).More preferred Q ₂ is Q _2b and Q _2b is

or

(R _6a , R _9b , R _10b , Q _3a and Q _l4a are described later).

이다(*는 커플링 위치를 나타냄).Most preferred Q ₂ is Q _2c0 and Q _2c is

(* Indicates coupling position).

R _10c and Q _4a are described later. Preferred R ₅ is -OH. Preferred R ₆ is R _6a with R _6a being methyl, -COOH or -CONH ₂ .

Preferred R ₇ is R _7a , wherein R _7a is hydrogen, chlorine, methyl, methoxy, -COOH or -SO ₃ H.

Preferred R ₈ is R _8a with R _8a being -OH or -NH ₂ .

또는

이고, R₇은 상술된 것과 같다.Preferred Q ₃ is Q _3a and Q _3a is

or

And R ₇ is as described above.

More preferably in Q _3a R ₇ is R _{7a as} defined above.

In most preferred Q _3a R ₇ is -COOH.

Preferred R ₉ is R _9a , wherein R _9a is hydrogen, methyl, ethyl, phenyl, -COR _8a , -CH ₂ SO ₃ H or -CH ₂ OSO ₃ H. More preferred R ₉ is R _9b , wherein R _9b is methyl or ethyl, most preferably methyl.

Preferred R ₁₀ is R _10a and R _10a is hydrogen, —CN, —SO ₃ H, —COR _8a or —CH ₂ SO ₃ H. More preferred R ₁₀ is

또는 -C_1-2알킬렌

(여기서 m 은 0 또는 1) 또는 -Q_4a-NR₁- 은 -C_2-3알킬렌R _10b as R _10b is hydrogen or -CONH ₂ . Preferred Q ₄ is Q _{4a wherein} Q _4a is C _2-4 alkylene, monohydroxysubstituted C _3-4 alkylene

Or -C _1-2 alkylene

Wherein m is 0 or 1 or -Q _4a -NR ₁ -is -C _2-3 alkylene

To form a group.

Preferred compounds of formula (I) are the following general formula (Ia) compounds and mixtures thereof.

Wherein each symbol is as defined above;

the sum of a1 and b1 is 3, so that a1 is 2 or 3;

b1 is 0 or 1;

Provided that b1 is not 0, M 'is Cu, R1b is hydrogen,

When Q1b is at least one of the radicals R2a and R3a is other than hydrogen.

In a preferred compound of formula (la), Q 1b is Q 1c.

More preferable Formula (Ia) compounds are those whose b1 is 0 and a1 is 2 or 3.

Most preferred Formula (Ia) compounds are those wherein R1b is hydrogen or methyl and Q1b is Q1c.

The dyes present in the salt form of the compound of formula (I) are preferably water soluble and are commonly used in reactive dye chemistry.

It also includes any non-chromophore cation used. Suitable cations are any present in sulfo groups and compounds of formula (I).

Is a carboxy group. Examples of suitable cations are alkali metal ions or unsubstituted or substituted ammonium ions, these

Examples of lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di-

And triethanol ammonium.

Preferred cations are alkali metal ions and ammonium, more preferably selected from sodium.

The dye according to the invention may be a single salt or a mixed salt of the compound of formula (I). Mixed salts are two or more different

It means a salt of a cation.

The present invention provides a process for preparing the compound of formula (I) or a mixture thereof. This method is the following general formula (II)

A mixture (where each group is as described above) or a mixture of the following general formula (II) compounds is replaced with 5-cyano-2,4,6-triclopyri

Reflecting in the appropriate molar ratio with midine, preferably in a molar ratio of 1: 1.

The reaction is preferably carried out at 0 ° -40 ° C. and pH 6.5-9. Water is usually used as the reaction medium, but acetone

The same organic solvent can be used as the solvent of 5-cyano-2,4,6-trichloropyridine.

The compound of formula (I) is used in free acid form, or preferably in conventional separation methods, for example alkali metal salts.

It can be separated into single or mixed salts by salting, filtering and vacuum drying to a slightly warmed temperature.

Starting compounds of formula (II) can be obtained using known methods from known or known compounds.

The compound of formula (I) and mixtures thereof are reactive dyes. These are organic bases containing hydroxy groups or nitrogen-containing oils.

It is suitable for dyeing or printing the base substrate. They may also be for example fibers, filaments or textiles produced therefrom.

It can be used to dye or print. The fibers, filaments or fabrics are natural or synthetic polyamides

Or composed of natural or regenerated cellulose materials, such as cotton, viscose or rayon staple fibers, or the like

And a preferred fabric is a fabric consisting of or containing cotton. They are also available by known methods

It can be used to dye or print porridge, preferably chrome-tanned leather.

Dyeing methods include the use of dye baths or printing pastes, which are mainly used as reactive dyes. For example,

Cotton is preferred by an exhaust process, for example under long or short term dye baths and at temperatures of 30-80 ° C.

Crab is dyed.

Preferred compounds according to the invention have good low temperature dyeing properties and can be used for low temperature dyeing at about 60 ° C.

The present invention may be used alone or in combination with other reactive dyes of the same class. Salt of the invention

The material has excellent dyeing properties, for example good fastness, and value of ext. By mixing with other reactive dyes

The dyeings performed show as fast fastness as if the dyes were used alone.

The compound of formula (I) exhibits good exergy values and good fixing values. Undyed

The part leaves the dye particularly easily. The resulting dyes and prints exhibit blue light fastness.

In addition, they not only have good washing and wet fastness against water, seawater and sweat, but also contain chlorine.

It has excellent properties against oxidation by water quality, chlorine bleach, peroxide bleach and perborate-containing laundry detergent.

have.

The following examples embody the present invention. Unless otherwise noted, all parts and percentages are expressed in weight, and all temperatures

Is Celsius.

Example 1

Produced by sulfochlorination of copper phthalocyanine with 1,3-diaminobenzene, with an average of 2.5-3 molecules per molecule

25.7 parts (0.025 mol) of dye base compounds for dyeing copper phthalocyanine containing a sulfonic acid group and one sulfamide group

Dissolve in 200 parts of water at pH 6.5-7.0. 150 parts of ice was added and 6.3 parts of 5- dissolved in acetone (20% excess).

An acetone solution of cyano-2,4,6-trichloropyrimidine is added in one portion. Lower the pH of the reaction mixture, the reaction continues

Continuously add 20% of soda solution to keep the pH at 7-7.5 and raise the reaction temperature to 25 ℃.

Keep standing. After 3-4 hours, the reaction is complete. The mixture is salted out with 45 parts of sodium chloride and the dye precipitate is absorbed.

After filtration, the mixture was dried at 35 ° C. The resulting dye is represented by the formula (Ia)

Dye in awkward tones. The staining results in excellent blue dyeing and wet fastnesses.

Example 2

Instead of 25.7 parts of the copper phthalocyanine dye base compound of Example (1), 2.5-3 sulfides per molecule of dye base compound

The same amount of nickel as the formula (Ia) dye can be obtained by using the same amount of nickel

Get the analog This dyes the cotton in a blue-green tint, giving the dyeing good fastness properties.

Example 3-23

Using methods analogous to those described in Examples (1) and (2) and suitable compounds as starting materials are given below in general formula (lb).

Is prepared in the form of the free acid in Table 1.

The values given for a and b are averages.

The table below shows the color of staining performed on the cotton through the examples, where the abbreviation bt is bright Turkey

Stone color tone and bg color blue-green color tone. These cotton dyeings have good fastnesses.

Table 1 Compounds of Formula (Ib)

Example

number

M

a

b

R2

R3

R4 (in ring)

Location)

In the ring

-NH-

location

dyeing

color

3

Cu

2.5

0

-

-

H

3

bt

4

Cu

2

One

CH3

CH3

H

3

bt

5

Cu

2

One

C2H5

C2H5

H

3

bt

6

Cu

3

0

-

-

4-SO3H

3

bt

7

Cu

2

One

H

H

4-SO3H

3

bt

8

Cu

2

One

C2H5

H

4-SO3H

3

bt

9

Cu

2

One

H

H

2-COOH

4

bt

10

Cu

2

One

CH3

CH3

2-COOH

4

bt

11

Cu

3

0

-

-

H

4

bt

12

Cu

2

One

C2H5

H

H

4

bt

13

Ni

2.5

0

-

-

H

3

bg

14

Ni

3

0

-

-

H

4

bg

15

Ni

2

One

H

H

H

3

bg

16

Ni

2

One

CH3

CH3

H

3

bg

17

Ni

2

One

H

H

H

4

bg

18

Ni

2

One

C2H5

C2H5

H

4

bg

19

Ni

3

0

-

-

4-SO3H

3

bg

20

Ni

2

One

H

H

4-SO3H

3

bg

21

Ni

2

One

H

H

2-COOH

4

bg

22

Ni

2

One

H

H

3-SO3H

4

bg

23

Ni

2

One

C2H5

H

3-SO3H

4

bg

Example 24

1 molecule produced by the reaction of 1,3-diaminobenzene-4-sulfonic acid after sulfochlorination of nickel phthalocyanine

25.5 parts of a nickel phthalocyanine dye base compound containing an average of 2.5 sulfonic acid groups and one sulfonamide group

Stir and mix with 1.8 parts sodium nitrite dissolved in 150 parts water. The solution is cooled to 0-2 ° and these 100 parts of

Add dropwise to 12 parts solution of 30% hydrochloric acid in ice / water. The diazonium salt suspension obtained was kept at a temperature of 0-5 °, 300 parts

In ice / water and 5.9 parts of 1- (3-methyl-aminopropyl) -6-hydroxy-4-methyl-2-pyridone.

During the coupling reaction, 20% sodium hydroxide solution is added to maintain the pH at 9-9.5. Acid according to the method of Example (1)

When the extracted green solution is reacted with 5-cyano-2,4,6-trichloropyrimidine and the product is separated, the following general formula (24a)

Dye is yielded.

The dyes dye cellulosic materials, in particular cotton, in a light greenish tint. This dyeing is excellent blue dye and excellent

It has wet fastness.

Example 25-63

Formula (Ic) and Formula (Id) (free acid form) following formula using methods similar to those of Example 24 and starting materials

Prepare the mixture.

Each group in the above formula is defined in Tables (2) and (3).

The dyes of Examples 25-63 have good fixation values and good fastnesses, for example, fairly bright fastness and wet fastness.

It gives a green dye on the cotton while giving it. Compounds in which M is nickel yield a particularly bright dyed hue.

Table 2 Compounds of Formula (Ic)

Example number

M

R4

R10

-Q4-NR1-

25

Cu

H

H

-(CH2) 3N-

CH3

26

Cu

SO3H

H

〃

27

Cu

SO3H

-CONH2

〃

28

Cu

H

CN

〃

29

Ni

H

H

〃

30

Ni

H

〃

31

Ni

H

-CONH2

〃

32

Ni

SO3H

-CONH2

〃

33

Ni

H

CN

〃

34

Ni

SO3H

-CONH2

-(CH2) 2NH-

35

Ni

SO3H

H

〃

36

Cu

SO3H

H

〃

37

Ni

H

H

〃

38

Cu

H

H

〃

39

Ni

H

H

40

Ni

SO3H

H

〃

41

Ni

SO3H

-CONH2

〃

42

Ni

SO3H

-CONH2

-(CH2) 2NH-

43

Cu

H

-CONH2

〃

44

Ni

SO3H

H

〃

45

Ni

SO3H

H

-(CH2) 2N-

CH3

Table 3 Formula (Id) Compound

Example

number

M

R4

R5

R6

R7

(Combination position)

Of -NH-

Position

46

Cu

SO3H

OH

CH3

H

3

47

Cu

H

OH

〃

2-SO3H

5

48

Cu

SO3H

OH

〃

〃

5

49

Cu

〃

OH

-COOH

H

3

50

Cu

〃

NH2

CH3

H

3

51

Ni

〃

OH

〃

H

3

52

Ni

H

OH

〃

2-SO3H

5

53

Ni

SO3H

OH

〃

2-SO3H

5

54

Ni

〃

OH

-COOH

H

4

55

Ni

〃

NH2

CH3

H

3

56

Ni

〃

〃

〃

2-SO3H

5

57

Ni

〃

〃

〃

H

4

58

Ni

〃

OH

-COOH

H

3

59

Ni

〃

OH

CH3

2-SO3H

4

60

Ni

〃

OH

〃

H

4

61

Ni

H

OH

-COOH

H

3

62

Cu

H

OH

CH3

H

4

63

Ni

H

OH

〃

H

3

Example 64-71

Using compounds analogous to Examples (1) and (2) and suitable starting materials, the compounds of formula (Ie) are prepared.

Each group in the above formula is defined in Table (4).

The dyed color shown in the cotton yarn by the dye is shown in Table (4).

bt = bright Turkish color

bg = blue-green color

These dyeings have good fastnesses.

Table 4 Formula (Ie) Compound

Example number

M

-Q1-NR1-

Dyeing

64

Cu

-CH2CH2NH-

bt

65

Ni

〃

bg

66

Cu

-CH2CHNH-

CH3

bt

67

Ni

〃

bg

68

Cu

-(CH2) 3N-

CH3

bt

69

Ni

〃

bg

70

Cu

bt

71

Ni

〃

bg

Example 72

Compounding of the following general formula (72a) in free acid form using methods and starting materials similar to those described in Example (24)

Prepare and separate water.

Using this dye, cotton fabrics of bright green dyed color are obtained, which have excellent blue dyeing and wet fastnesses.

It has

The dye of Example (1-72) prepared by the above method is obtained in the form of a sodium salt.

Examples (1-72) Dyes are a) compounds in which the chlorine substituent is a

The corresponding compound positioned at the 6-position and b) isomer position relative to the position of all substituents of the phthalocyanine group.

It is a mixture with the isomer which has.

In general, it is preferred to use the Example 1-72 dye mixtures. Therefore, separating into individual isomers

Although not required, in some cases separation may be carried out in a conventional manner.

The following application examples suitably apply the compounds of the present invention and provide suitable applications and methods for preparing their liquid-aqueous dyes.

It is described.

Application Example A

Part 10 adds bleached cotton fabric to the dye bath. This dye bath is a dye of formula (Ia) (Example 1) dissolved in 300 parts of demineralized water.

It contains 0.3 parts and 15 parts of Glauber salt (calcined). The salt bath is kept at 40 ° C for 30 minutes and then for 10 minutes

Add a total of 6 parts of soda (calcined) in 0.2, 0.6, 1.2, and 4 parts at intervals.

Staining is continued for 1 hour at 40 °. Rinse the dyed material with cool water for 3 minutes, with hot water for 3 minutes, and 0.25 parts of

Wash for 15 minutes with 500 parts of hot demineralized water in the presence of 0.25 parts of Marseille soap. Dye again with hot water for 3 minutes

Rinse, spin and dry in a 70 ° drying chamber. A bright Turquoise stain was obtained with good fastnesses. Especially

This dyeing has blue dyeing and wet fastness and is stable against oxidation.

Application Example B

10 parts of bleached cotton fabric are added to a salt bath containing 10 parts of Glarver salt (calcined) in 300 parts of demineralized water.

The bath is heated at 40 ° for 10 minutes and then 0.5 parts of dye (1a, Example 1) is added. After 30 minutes at 40 °, 3 parts of cattle

Add (calcined) and continue staining at 40 ° for 45 min. Rinse the dyeing material according to Application Example A method,

Wash and dry. The resulting bright Turkish cotton dyeings had properties similar to those obtained in Application Example (A).

It is.

Application Example C

Two parts of cattle were dyed with a 0.3 part dye bath (Eq. 24a, Example 24) using the method of Application Example (A).

Only one (calculated) is added at a time. Increase the initial temperature 40 ° to 60 ° and continue dyeing at 60 ° for 1 hour.

Belongs. The stained material is rinsed, washed and dried according to the method of example (A). Dyes settle well, good fastness

A bright green dyed cotton fabric is obtained.

Application Example D

2.5 parts of the dye of Example (6) are dissolved in 2000 parts of water. 100 parts of cotton fabric are added to the dye bath, the temperature is increased to 80 for 10 minutes.

Keep at °. 100 parts of Glauber salt (calcined) were added to the bath and 30 minutes later 20 parts of soda (calcined) were added.

All. Staining is continued at 80 ° for 1 hour. The stained material is rinsed, washed and washed according to the procedure given in Application Example (A).

To dry. Bright Turkish dyes are produced with good fastnesses.

Application Example E

The printing paste contains:

40 parts of Formula 1a (Example 1) Dye

100 parts urea

350 parts of water

500 parts 4% sodium alginate thickener

10 parts of sodium bicarbonate

100 parts in total

This is applied to cotton fabrics using known printing processes.

The printed material is steamed at 102-104 ° for 4-8 minutes, rinsed with cool water for 3 minutes and with hot water for 3 minutes. apply

The fixed cotton fabric is washed and dried according to the method given in Example (A). Bright Turkish prints are generally

Good fastness over

The salt of Example (1-72) instead of the printing paste or dye of Examples 1, 24 or 6 used in Application Examples A-E.

Any one of the dyes or an appropriate amount of these dye mixtures may be used. Calculated dyeing and printing application

Similar characteristics as in the example.

When stained with other dyes, the colors shown in Examples (1-72) were shown respectively.

Claims (11)

Phthalocyanine compounds of the following formula (I) in free acid or free salt form and mixtures thereof

Wherein Pc is a phthalocyanine radical; M is Cu, Ni, Co, Fe or Al; a is 1, 2 or 3, b Is 0, 1 or 2 except that the sum of a and b has a maximum of 3; R2 and R3 are each selected from hydrogen or C1-6 alkyl, or O- or together with a nitrogen atom bonded thereto; A 5 or 6 membered ring system having an N- atom to form a system, Each R1 is C1-4 alkyl, unsubstituted C1-4 monosubstituted by hydroxy, halogen, -SO3H, -OSO3H or -COOH Alkyl, or hydrogen; Q1 is C2-6 alkylene, monohydroxy-substituted or interrupted with one group selected from -O- and -NR1- and the like C3-6 alkylene,

Alkylene, -C1-4 alkylene

or

(* Is negative to -SO2NR1 group Represents a complexed atom), or -SO2NR1-O1-NR1

Alkylene -NR1- or -SO2NR1-C2-4 alkylene

To form; R4 is hydrogen, halogen, hydroxy, C1-4 alkyl, C1-4 alkyl, C1-4 alkoxy, -COOH or -SO3H,

(* Represents a coupling position), R5 is -OH or -NH2; R6 is C1-4 alkyl or -COR8; R8 is -OH, -O-C1-4 alkyl or -NH2 And Q3 is a divalent crosslinking group, R9 is hydrogen, C1-4 alkyl, C5-6 cycloalkyl, phenyl or phenyl (C1-4 alkyl), wherein any of the phenyl radicals in R9 are also Substituted or one to three substitutions selected from C1-4 alkyl, C1-4 alkoxy, halogen, -COOH and -SO3H Sieve; -COR8, -C1-4 alkyl-SO3H, -C1-4 alkyl-OSO3H or -C1-4 alkyl-COR8, R 10 is hydrogen, —CN, —SO 3 H, —COR 8, C 1-4 alkyl; -OH, halogen, -CN, C1-4 alkoxy,, SO3H, -OSO3H Or C 1-4 alkyl mono substituted with —NH 2; -SO2NH2, An (where R7 is hydrogen, Halogen, C1-4 alkyl, C1-4 alkoxy, -COOH or -SO3H; R11 is hydrogen, C1-4 alkyl or hydroxy-C2-4 alkyl; An Is a non-chromophore anion) Q4 is C2-6 alkylene, monohydroxy, with or without one group selected from -O- and -NR1- Substituted C3-6 alkylene,

Alkylene or -C1-4 alkylene

Where m is 0 or 1; Or -Q4-NR1- is -C2-4 alkylene

Is; B is not 0, M is Cu, two R1 are hydrogen, Q1 is

And R4 is hydrogen, C1-4 alkyl or C1-4 alkoxy, provided that the radicals R2 and R3 At least one is other than hydrogen. The compound of formula (I) according to claim 1, wherein M is Cu or Ni. The compound of formula (I) according to claim 1 or 2, wherein R 1 is R 1C and R 1C is hydrogen or methyl. 3. The compound of claim 1, wherein R 2 and R 3 are R 2b and R 3b, each of R 2b and R 3b being hydrogen, methyl or e. The compound of formula (I) which is til. 3. A compound according to claim 1 or 2, wherein Q1 is Q1a wherein Q1a is C2-3 alkylene, monohydroxy substituted C3-4 alkylene, C2-3 alkylene-O-C2-3 alkylene, C2-3 alkyl Ethylene-NR1b-C2-3 alkylene,, -C1-3 alkylene Or alkylene; Or -SO2-NR1-Q1a-NR1-

, or

Alkylene-NR1-, Or -SO2-NR1-C2-3 alkylene

R4a is hydrogen, methyl, methoxy, -COOH or -SO3H, R 1b is hydrogen, methyl, ethyl or 2-hydroxyethyl; Q2 is Q2a, Q2a is

or

Is; (Wherein R5, Q3, Q4, * are as defined in claim 1); R6a is methyl, -COOH or -CONH2; R9a is hydrogen, methyl, ethyl, phenyl, -COR8a, -CH2SO3H or -CH2OSO3H; R 10a is hydrogen, —CN, —SO 3 H, —COR 8a, or —CH 2 SO 3 H; R8a is -OH or NH2 Of compounds. The compound of formula (I) according to claim 1 or 2, wherein R4 is R4a, wherein R4a is hydrogen, -COOH or -SO3H. The compound according to claim 1, wherein the compound of formula (Ia) and mixtures thereof: Wherein Q1b is C2-3 alkylene, monohydroxy-substituted C3-4 alkylene, C1-3 alkylene

Or alkylene or -NR1-Q1b-NR1-

Form the Q2 is as defined in paragraph 1; R 4b is hydrogen, —COOH or SO 3 H; a1 is 2 or 3, b1 is 0 Or the sum of a1 and b1 as 1 has a maximum of 3; The other symbols are the same as defined in paragraph 1 except that b1 is not 0 At least one of the radicals R2a and R3a, provided that M 'is Cu, R1b is hydrogen, and Q1b is I'm other than hydrogen. 8. A compound of formula (Ia) according to claim 7, wherein b1 is 0 and a1 is 2 or 3. The following general formula (II) compound is reacted with an appropriate molar amount of 5-cyano-2,4,6-trichloropyrimidine according to claim 1 Method for preparing compound of formula (I): Wherein R1-R3, Q1, a, b, M and Pc are as defined in claim 1. A method of dyeing or printing a substrate by applying the compound of formula (I) according to claim 1 in the form of a water-soluble salt to a hydroxyl-containing or nitrogen-containing organic substrate. The method of claim 10 wherein the substrate used is composed of natural or synthetic polyamides as leather or textile fabrics or Or a substrate containing natural or regenerated cellulose.