DE19816056A1 - Dispersion azo dye mixtures - Google Patents

Abstract

The present invention relates to dye mixtures comprising at least one compound of the formula (I) DOLLAR F1 and at least one compound of the formula (II) DOLLAR F2 in which the substituents have the meanings given in the description, DOLLAR A which are outstanding for dyeing and printing hydrophobic synthetic material.

Description

The invention relates to dispersion azo dye mixtures, processes for their preparation tion and their use for dyeing and printing hydrophobic synthetics materials.

The object of the present invention was to provide navy blue to black dispersions to provide dye mixtures with good application properties.

A dye mixture has now been found containing at least one dye of the formula (I)

wherein
R ^{1 represents} hydrogen, C ₁ -C ₄ alkyl, halogen, in particular Cl and Br or C ₁ -C ₄ alkoxy,
n means 1 or 2 and the
Ring A is optionally substituted, the possible substituents being one or more identical or different substituents, preferably C ₁ -C ₄ -alkyl, in particular CH ₃ and halogen, in particular Cl and Br, and at least one dye of the formula (II)

wherein
X represents halogen, in particular Cl and Br or CN,
R ² and R ⁵ independently of one another are hydrogen or C ₁ -C ₄ alkyl,
R ³ and R ⁴ independently of one another are hydrogen, optionally substituted C ₁ -C ₄ alkyl or C ₂ -C ₄ alkenyl,
preferred as possible substituents for alkyl -OH, -CN, -OCOR, -OCOC ₆ H ₅ , -OCOOR, -COOR, -OC ₆ H ₅ , -C ₆ H ₅ and / or C ₁ -C ₄ alkoxy are preferred , where R is hydrogen or C ₁ -C ₄ alkyl.

Dyes of the formula (I) are, for example, from CN-A-1 036 974 (≘ CA 114: 145 436) and dyes of the formula (II) are known, for example, from DE-A-2 818 653.

Preferred mixtures contain compounds of the formula (I) in which ring A has no further substituents. Compounds of formula (I) in which R ^{1 is} hydrogen or C ₁ -C ₄ -alkyl, in particular methyl, are particularly preferred. Mixtures according to the invention which contain the dye of the formula (I), in which n is 1, R ^{1 is} hydrogen or methyl and ring A is not further substituted, are very particularly preferred.

Preferred mixtures contain, as the dye of the formula (II), one in which X is halogen, in particular Cl or Br. Particularly preferred dyes of the formula (II) are those
wherein
R ³ and R ⁴ independently of one another are hydrogen C ₂ -C ₄ alkenyl, unsubstituted C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyl substituted by -OCOR, -CN or -COOR, in which R has the meaning given above owns.

In particular, in formula (II) R ² and R ⁵ independently of one another are C ₁ -C ₄ -alkyl, preferably CH ₃ .

Particularly preferred mixtures according to the invention are those containing at least one dye of the formula (I) selected from the group:

and at least one dye of the formula (II) selected from the group:

Mixtures according to the invention which additionally contain a further dye of the formula (III), (IV) and / or (V) are also preferred,

and or

wherein
X ^{1 is} halogen, in particular Cl and Br or CN,
X ² halogen, in particular Cl and Br, hydrogen, NO ₂ or CN,
R ^{6 is} C ₁ -C ₄ alkyl,
R ⁷ and R ⁸ independently of one another are hydrogen, unsubstituted or by -OH, -CN, -OCOR, -OCOC ₆ H ₅ , -OCOO (C ₁ -C ₄ -alkyl), -COOR, -OC ₆ H ₅ , -C ₆ H ₅ and / or C ₁ -C ₄ -alkoxy-substituted C ₁ -C ₄ -alkyl or C ₂ -C ₄ -alkenyl mean, where R has the meaning given above,
Y ¹ and Y ² independently of one another are hydrogen or halogen, in particular Cl and Br,
R ⁹ and R ¹⁰ independently of one another are hydrogen, unsubstituted or substituted by -OH, -CN, -OCOR, -OCOC ₆ H ₅ and / or C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, where R is the above Has meaning, or is C ₂ -C ₄ alkenyl,
R ^{11 is} C ₁ -C ₄ alkyl and
R ^{12 is} hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy.

Particularly preferred mixtures are those which contain a dye of the formula (III) in addition to the dyes of the formulas (I) and (II). In particular, there are dyes of the formula (III) selected from groups (IIIa) and (IIIb):

Also particularly preferred mixtures are those which, in addition to the dyes of the formulas (I) and (II), contain a dye of the formula (IV). In particular, dyes of the formula (IV) selected from the group (IVa), (IVb) and (IVc) are to be mentioned

Further particularly preferred mixtures are those which, in addition to the dyes of the formulas (I) and (II), contain a dye of the formula (V), in particular the dye of the formula (Va)

contains.  

The dye mixture according to the invention preferably contains 1 to 99, preferably 1 up to 80 wt .-%, in particular 5 to 60 wt .-% of at least one dye of the For mel (I) and 1 to 99, preferably 20 to 99 wt .-%, in particular 40 to 95% by weight of at least one dye of the formula (II), based on the dye total amount.

The dye of formula (III) is preferred in an amount of 0 to 80, in particular 2 to 60 wt .-%, based on the total amount of dye used.

The dye of the formula (IV) is preferably in an amount of 0 to 40, in particular 5 to 30 wt .-%, based on the total amount of dye used.

The dye of formula (V) is preferred in an amount of 0 to 40, in particular 5 to 30 wt .-%, based on the total amount of dye used.

The dye mixtures according to the invention result in particular in the above Quantities given to black to navy blue tones.

The mixtures according to the invention are particularly notable for distinguished sublimation fastness and good windability. Besides, that is Color yield consistently good in a wide pH range. They are particularly suitable alkaline polyester paints, especially at a pH of 8 to 11.

The dye mixture according to the invention can also contain other disperse dyes contain.

The invention further relates to a method for producing the invention Mixture, characterized in that the individual dyes (I) and (II) and give if necessary, further dyes of the dye mixture in water in the presence of a dis Powdered powder, then mixed and optionally dried  or that the dyes (I), (II) and optionally further mixed in water in Milled in the presence of a dispersant and optionally dried.

Dye mixtures according to the invention from the dyes of the formulas (I), (II) and optionally one or more of the dyes of the general formulas (III) to (V) can be achieved, for example, by simply mixing the components produce. The mixing can be done by separately finished A Mixes individual components in the dyeing liquor, or preferably by the Press cake mixes the individual components and finishes together.

The finish is characterized in that the dyes are pre-ground run in the presence of a dispersant in an aqueous dispersion, d. H. in a liquid or after drying in a powdery dye preparation, transferred the individual dyes can be finished separately first and then are mixed or the individual dyes are mixed first and then together can not be. This grinding is preferably done in mills, such as. B. Ball, vibrating, pearl or sand mills or in kneaders. After the meal the size of the dye particles is preferably approximately 0.1 to 10 μm, in particular at approx. 1 µm. The grinding is preferably carried out in the presence of dispersant agents that can be non-ionic or anionic. Nonionic dispersants are z. B. reaction products of alkylene oxides, such as. B. ethylene or propylene oxide with alkylatable compounds, such as. B. fatty alcohols, fatty amines, fatty acids, Phenols, alkylphenols and carboxamides. Anionic dispersants are for example lignin sulfonates or their salts, alkyl or alkylaryl sulfonates, Al kylaryl polyglycol ether sulfates, alkali salts of the condensation products from naphthalene sulfonic acids and formaldehyde, polyvinyl sulfonates and ethoxylated novolaks.

The invention therefore also relates to dye preparations containing
10 to 60% by weight of the dye mixture according to the invention and
40 to 90 wt .-% dispersant.

The dye preparations can be in liquid or solid form, it being the liquid preparations are preferably aqueous dye dispersions and the solid preparations are available as powder or granules.

Preferred aqueous dye preparations contain water,
15 to 50% by weight of the dye mixture according to the invention and
10 to 25 wt .-% dispersant, each based on the dye preparation.

The preferred non-ionic and anionic dispersants are preferred to name the dispersant.

The dye preparations according to the invention can also be other auxiliaries included, e.g. B. those that act as oxidizing agents such. B. sodium-m-nitrobene zolsulfonate or fungicidal agents, such as. B. sodium o-phenylphenolate and sodium pentachlorophenolate. Also wetting agents, antifreezes, dedusting agents or Hydrophilizing agents can be included.

Solid preparations such as powder or granulate settings are preferred for certain areas of application. Contain preferred solid dye preparations
30 to 50 wt .-% of the dye mixture according to the invention and
70 to 50 wt .-% dispersant.

You can also use tools such as B. network, oxidation, consumer Containing agents and dedusting agents.

A preferred manufacturing process for the solid dye preparations is in that the liquid dye preparations described above the liquid  e.g. B. by vacuum drying, freeze drying, by drying on roller rock nern, but is preferably removed by spray drying.

Dye mixtures according to the invention can, however, also preferably be carried out produce joint finishing of the mixture components.

For this purpose, the mixture components are mixed in a suitable mixing ratio described above by a grinding process dispersed in water and given if converted to a solid dye preparation by removing the water.

It can be advantageous to improve the properties of the dye preparations be liable to heat treatment the mixture components before grinding undergo. The heat treatment is carried out at 25 to 98 ° C, preferably at 30 to 80 ° C and particularly preferably at 40 to 60 ° C. It is advantageous to do so immediately to finish after heat treatment without intermediate insulation, that is in the to transfer commercially available solid or liquid preparations. To this end the heat-treated suspension is converted into a dispersion by grinding. It is expedient, the heat treatment in the presence of those dispersing and if necessary also to carry out aids in the finished fixed or Liquid preparation should be included. These are with the above surface active substances identical. Was not during the heat treatment The total amount of these dispersants and auxiliaries is added before grinding the remaining amount added. For heat treatment in this case Rule 10 to 400 wt .-%, preferably 20 to 200 wt .-% of surface-active sub punch, added based on the dye mixtures.

To produce the dye liquors, the required amounts of the dye preparations made according to the above information with the stain dium, preferably diluted with water to the extent that there is a flot for the coloring ratio of 1: 5 to 1:50 results. In addition, the fleets in general further dyeing aids such as carriers, dispersants and wetting agents are added.  

Should the dye mixture according to the invention be used for textile printing? the preferred amounts of dye preparation are preferred together with thickeners, such as. B. alkali alginates or the like, and given If necessary, other additives such. B. fixing accelerators, wetting agents and hydra kneaded into printing pastes.

The dye mixtures according to the invention, which also other colors substances can be excellent for dyeing and printing hydrophobic synthetic materials. Coming as hydrophobic synthetic materials e.g. B. into consideration: cellulose-2½-acetate, cellulose triacetate, polyamides and high molecular weight lare polyester. The dye mixtures according to the invention are preferred for dyeing and printing materials made of high molecular weight polyesters, esp especially those based on polyethylene glycol terephthalates or their mixtures gene with natural fibers, such as especially wool or cellulose, or of Materials made from cellulose triacetate are used.

The hydrophobic synthetic materials can be flat or thread-like shaped structures and z. B. to yarns or woven, knitted or ge knitted fabrics. The dyeing of the said fiber material with the Dye mixtures according to the invention can be carried out in a manner known per se, preferably from aqueous dispersion, optionally in the presence of carriers, between 80 and approx. 110 ° C according to the pull-out process or the HT process in the dyeing autoclave at 110 to 140 ° C, as well as using the so-called thermofixing method drive, the goods padded with the dye liquor and then at about 180 to 230 ° C is fixed. The printing of the materials mentioned can be known per se ter be carried out so that the dye mixtures according to the invention be incorporated into a printing paste and the goods printed with it for fixing the dyes, optionally in the presence of a carrier, at temperatures between between 180 and 230 ° C with HT steam or dry heat. You get in this way very strong olive, navy or black colors and prints with very good fastness properties, especially with very good light, rub, Thermosetting, washing, water and sublimation fastness.  

The dye mixtures according to the invention show when dyeing and Pad fleets as well as pressure dough have excellent wetting behavior and can be dis dis quickly and without complex manual or mechanical stirring pergulate. The liquors and pressure doughs are homogeneous and can be modernized Process color kitchens without problems without clogging the nozzles.

The liquid preparations according to the invention do not tend to phase separation and especially not for sedimentation and putty weaning. An also expensive It is thus possible to homogenize the dye in the container before the dye is removed omitted.

The in the preparation of solid preparations after grinding the dyes in The presence of dispersing and auxiliary grinding dough is also increased Temperature and stable over a long period. The grinding dough in the mills as well after Leaving the mills does not need to be cooled and can be done before the spray Store drying in collecting containers for a long time.

The thermal stability of the dye mixture according to the invention is also expressed in that spray drying can be carried out at high temperatures, without the material to be dried agglomerating. At the same dryer outlet temperature rature means an increase in the inlet temperature an increase in the dryer performance and thus a reduction in manufacturing costs.

The dye preparations described above can be used very advantageously of printing pastes and dyeing liquors. They offer particular advantages e.g. B. in the continuous process, in which continuous dye feed solution in the running equipment the dye concentration of the dye liquors constant must be kept.

The advantage of the dye mixtures according to the invention is particularly clear when dyeing from an aqueous dye bath under modern practical conditions.  

The mentioned modern practical conditions are characterized by high winds dense in cross-wound and tree dyeings, short liquor ratios, i.e. high Dye concentrations and high shear forces in the dye liquor due to high pump performance. Even under these conditions, those according to the invention tend Dye mixtures do not agglomerate and there is no filtering ions on the textile materials to be dyed. So there are homogeneous colors without color difference between the outer and inner layers of the Received bobbins, and the colorations show no abrasion. For block staining and printing with the dye mixture according to the invention becomes a homogeneous, get speck-free product image.

The dye mixtures according to the invention are also suitable for dyeing the pre hydrophobic materials from organic solvents listed below the known methods and for dyeing in bulk.

The invention therefore also relates to the use of the dye according to the invention mixtures for dyeing and printing hydrophobic synthetic materials, especially fiber materials and for dyeing hydrophobic synthetic Materials in bulk.

The invention is illustrated by the following examples.  

Examples example 1

• a) 13.3 g of the dye of the formula (1)
  and
  11 g of the dye of the formula (2)
  such as
  13.7 g of the dye of the formula (3)
  and
  6.0 g of the dye of the formula (4)
  were ground together with 300 ml of water and 56 g of a lignin sulfonate (Na salt) for 3 hours in a bead mill - or sand mill - and then spray-dried (inlet temperature 130 ° C, outlet temperature 60 ° C). The powder thus obtained (approx. 100 g) can be easily dispersed in water.
• b) 0.4 g of the powder prepared above was combined with 10 g of polyester Textile material at pH 4.5 and 130 ° C approx. 60 min after a normal one HT staining process treated. After washing, rinsing and drying get a deep black color with very good fastness properties.

Analogous to Example 1, further dye mixtures were prepared and the poly ester dyeing used, 13.3 g of dye 1 from Example 1 and 11 g of Dye of the general formula (II) were used in which the substituents have the meanings given in Table 1.

Table 1

Dye of formula (II) used

Example 9

Analogously to Example 1
5 g of the dye of the formula (6)

and
39 g of the dye of the formula (5)

ground and dried. The lignin sulfonate (Na salt) was in the same ratio based on the total amount of dye used as in Example 1. The obtained Dye mixture (0.1 g) was then used to dye 10 g of polyester fibers used, with clear navy blue colorations with good wash and sublimation units have been obtained.

Analogously to Example 9, the following dyes of the formulas I and II according to the Table 2 combined. The weight ratio of 1:11 from Example 9 was used to keep. Greenish to reddish navy blue colorations were obtained.  

Table 2

Example 23

24 g of the dye of the formula (6) from Example 9 and 7 g of the dye of the formula (3) from Example 1 and 22 g of the dye of the formula (5)

were analogous to Example 1 together with 300 g of water and 53 g of Na lignin sulfonate ground and dried.

If 0.35 g of this dye mixture is used to dye polyester fabric analogous to Example 1b, reddish-flowery black colorations are obtained.

The dye (5) from Example 23 was replaced in the same amount by a dye Substance of formula (II) according to Table 3 below, were further polyester Preserved reddish black colors with good fastness properties.

Table 3

Substitution meanings for the dye of the formula (II)

Example 35

17.6 g of the dye of the formula (6) from Example 9, 9.4 g of the dye of the formula (2) from Example 1 and 11.0 g of the dye (3) from Example 1 were combined ground with 62 g Na lignin sulfonate and 300 g water analogously to Example 1 and dried.

0.6 g of the powder thus obtained were together with 10 g of polyester fabric at pH 8.5 to 9 stained with a glycine / NaOH buffer at 130 ° C for 60 min. It will be a preserved deep black dyed textile material.

The dye of formula (2) in Example 35 was replaced by a dye of Formula (II) of Table 4 below in the same amount and colored with these Mixtures of polyester analogous to Example 35, so were also deep black dye gene received.

Table 4

Dye components of formula (II) used

Example 49

Analogously to Example 1, polyester fabric was dyed with a dye mixture, containing ent
16.7 g of the dye of the formula (6) from Example 9,
6.1 g of the dye of the formula (7)

11.9 g of the dye of the formula (8)

and
15.3 g of the dye of the formula (9)

This mixture was after bead milling in the presence of 50 g of Na lignin sulfonate and 650 g water spray dried.  

0.1 g of this mixture was used to dye 5 g of polyester fabric. It black colorations are obtained.

Examples 49 to 53

Staining was carried out analogously to Example 48 using the mixtures in Table 5 below. In all cases, good pH dependence, excellent results Preserve bath exhaustion and good sublimation fastness.

Table 5

Claims (11)

1. Mixture containing at least one compound of the formula (I)
wherein
R ^{1 represents} hydrogen, C ₁ -C ₄ alkyl, halogen, in particular Cl and Br or C ₁ -C ₄ alkoxy,
n means 1 or 2 and the
Ring A is optionally substituted,
and at least one compound of the formula (II)
wherein
X represents halogen, in particular Cl and Br or CN,
R ² and R ⁵ independently of one another are hydrogen or C ₁ -C ₄ alkyl,
R ³ and R ⁴ independently of one another are hydrogen, optionally substituted C ₁ -C ₄ -alkyl or C ₂ -C ₄ -alkenyl. 2. Mixture according to claim 1, comprising at least one compound of Formula (I) in which ring A has no further substituents. 3. Mixture according to claim 1, comprising at least one compound of the formula (I), in which R ^{1 is} hydrogen or C ₁ -C ₄ -alkyl, in particular methyl. 4. Mixture according to claim 1, comprising at least one compound of the formula (I), in which n is 1, R ^{1 is} hydrogen or methyl and ring A is not further substituted. 5. Mixture according to claim 1, containing compounds of formula (II), wherein X represents halogen, in particular Cl or Br. 6. Mixture according to claim 1, comprising compounds of formula (II), wherein
R ³ and R ⁴ are independently hydrogen C ₂ -C ₄ alkenyl, unsubstitu iertes C ₁ -C ₄ -alkyl or substituted by -OCOR, -CN and / or -COOR C ₁ -C ₄ alkyl, wherein R Is hydrogen or C ₁ -C ₄ alkyl. 7. Mixture according to claim 1, characterized in that it contains a compound of the formula (III), (IV) and / or (V),
and or
wherein
X ^{1 is} halogen, in particular Cl and Br or CN,
X ² halogen, in particular Cl and Br, hydrogen NO ₂ or CN,
R ^{6 is} C ₁ -C ₄ alkyl,
R ⁷ and R ⁸ independently of one another are hydrogen, unsubstituted or by -OH, -CN, -OCOR, -OCOC ₆ H ₅ , -OCOO (C ₁ -C ₄ -alkyl), -COOR, -OC ₆ H ₅ , -C _{6 is} H ₅ and / or C ₁ -C ₄ alkoxy-substituted C ₁ -C ₄ alkyl or C ₂ -C ₄ alkenyl, where R is hydrogen or C ₁ -C ₄ alkyl,
Y ¹ and Y ² independently of one another are hydrogen or halogen, in particular Cl and Br,
R ⁹ and R ¹⁰ independently of one another for hydrogen, unsubstituted or substituted by -OH, -CN, -OCOR, -OCOC ₆ H ₅ and / or C ₁ -C ₄ alkoxy-substituted C ₁ -C ₄ alkyl, where R is the has the abovementioned meaning, or are C ₂ -C ₄ alkenyl,
R ^{11 is} C ₁ -C ₄ alkyl and
R ^{12 is} hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. 8. Mixtures according to claim 1, containing 1 to 99 wt .-%, in particular 1 to 80 wt .-%, at least one compound of formula (I) and 1 to 99% by weight, in particular 20 to 99% by weight, of at least one compound of Formula (II), based on the total amount of dye. 9. Dye preparation containing
10 to 60 wt .-% dye mixture according to claim 1 and
40 to 90 wt .-% dispersant. 10. The method for producing the dye preparation according to claim 8, because characterized in that the individual dyes according to the dye mixture Claim 1 ground in water in the presence of a dispersant finally mixed and optionally dried or that the color mixture of substances according to claim 1 in water in the presence of a dispersant are ground and optionally dried. 11. Use of the dye mixtures according to claim 1 for dyeing and Printing on hydrophobic synthetic materials or for dyeing hydrophobic synthetic materials in bulk.