KR0147381B1 - Dye mixtures and their use in trichromatic dyeing process - Google Patents

Abstract

The present invention optionally comprises one or more of the yellow to orange dyes of the formulas (5) to (8) together with the yellow dye of the formula (4), and the dye of the formula (6) as defined herein, and the formula A three-component mixture containing the dye of (7), wherein when these three components are combined, a preferred tricolor mixture is obtained, which means that it is possible to obtain nitrogen-containing organic substrates, in particular natural or synthetic polyamides by conventional dyeing or printing processes. It is most suitable for tricolor dyeing or printing.

Description

Dye Mixtures and Their Uses in Tricolor Dyeing Processes

The present invention relates in particular to binder anionic dye mixtures and their use for dyeing or printing nitrogen-containing organic substrates in tricolor dyeing processes. More particularly, the invention relates to a process for tricolor dyeing or printing a nitrogen containing organic substrate, preferably a natural or synthetic polyamide material, which process comprises: (i) at least one yellow component in the form of a free acid or salt; At least one dye of formula (1) as a red component in the form of a free acid or salt, and at least one dye of formula (6) and a blue component in form of a free acid or salt Together with a dye of), optionally applying an anionic dye mixture containing at least one yellow to orange dye of formulas (2) to (5) in free acid or salt form:

Wherein, R ₁ is hydrogen, C _1-4 alkoxy, C _1-4 alkyl substituted with a single beach by a C _1-4 alkyl or halogen ring, R ₂ is C _1-4 alkyl or -COR _6, R ₆ is C _1-6 alkyl, —OC _1-6 alkyl or —NR ₇ R ₈ , each of R ₇ and R ₈ is independently hydrogen, unsubstituted C _1-6 alkyl or monohydroxy-substituted C _2-6 alkyl, R ₃ is hydrogen or C _1-4 alkyl, R ₄ is hydrogen, halogen, C _1-4 alkoxy or —NR ₃ R ₉ , wherein R ₃ is as defined above but independent from it R ₉ is —COC _1-6 alkyl or —COOC _1-6 alkyl), R ₅ is C _1-4 alkyl or mono hydroxy-substituted C _2-6 alkyl, R ₁₆ is hydrogen, halogen , C _1-4 alkoxy, or —NR ₃ R ₉ , wherein R ₃ and R ₉ are as defined above but independent from it, and R ₁₁ is hydrogen, halogen, C _1-4 alkyl or C _{1- 4} alkoxy, X is hydroxy or —NHSO ₂ C _1-4 alkyl, R ₁₂ is Hydrogen or C _1-4 alkyl, each of R ₁₃ , R ₁₄ and R ₁₅ is independently hydrogen, C _1-4 alkyl or C _1-4 alkoxy and R ₁₆ is C _1-4 alkyl or C _2-4 Hydroxyalkyl, each of R ₁₇ and R ₁₈ is independently hydrogen, halogen or C _1-4 alkyl, Z ₁ is phenyl, phenoxy or —NR ₁₉ R ₂₀ , R ₁₉ is methyl or ethyl, R ₂₀ is phenyl or cyclohexyl, R ₂₁ is hydrogen, halogen or -NHCOC _1-4 alkyl, R ₂₂ is trifluoromethyl, -SO ₂ Z ₁ , wherein Z ₁ is as defined above or- SO ₂ Z ₂ , wherein Z ₂ is —N (C ₄ H ₉ ) ₂ or R ₂₃ is hydrogen or methyl, one of R ₂₄ and R ₂₅ is —SO ₂ NHC _2-4 hydroxyalkyl or —NR ₂₆ COC _1-4 alkyl, wherein R ₂₆ is hydrogen, methyl or ethyl And the other is hydrogen or methyl. In the present specification, the unsubstituted or substituted alkyl or alkoxy group described is linear or branched to any one unless otherwise specified. Preference is given to any halogen with fluorine, chlorine or bromine, in particular chlorine. In the hydroxy-substituted alkyl group bonded to nitrogen, the hydroxy group is preferably bonded to a carbon atom not directly bonded to the nitrogen atom. In the hydroxy-substituted alkyl group defined as R ₅ or R ₁₆ , the hydroxy group is preferably bonded to a carbon atom not directly bonded to the phenoxy group. In the compound of formula (1): R ₁ is preferably R _1a , wherein R _1a is hydrogen, methyl or methoxy, most preferably hydrogen. Each of R ₇ and R ₈ is preferably R _7a and R _8a , wherein each R _7a and R _8a is independently hydrogen, C _1-2 alkyl or C _2-3 hydroxyalkyl, more preferably R ₇ is R _7b , where R _7b is hydrogen or methyl, and R ₈ is hydrogen. R ₆ is preferably R _6a , wherein R _6a is C _1-2 alkyl, -OC _1-2 alkyl or -NHR _7b (where R _7b is as defined above), more preferably R _6b , wherein R _6b is C _1-2 alkyl or —NH ₂ , most preferably methyl. R ₂ is preferably R _2a , wherein R _2a is -COR _6b , wherein R _6b is as defined above, most preferably -COCH ₃ . Each R ₃ is preferably R _3a , wherein R _3a is independently hydrogen or methyl, most preferably hydrogen. R ₉ is preferably R _9a , wherein R _9a is -COC _1-2 alkyl or -COOC _1-2 alkyl, more preferably -COCH ₃ . R ₄ is preferably R _4a (wherein R _4a hydrogen, chlorine, methyl, methoxy or —NHCOCH ₂ ), more preferably R _4b (wherein R _4b is hydrogen or methyl), most preferably Is hydrogen. R ₅ is preferably R _5a , wherein R _5a is methyl, ethyl or monohydroxy-substituted C _3-5 alkyl, more preferably R _5b , wherein R _5b is methyl or monohydroxy- Substituted C ₄ alkyl), most preferably to be. R ₁₀ is R _10a wherein R _10a is hydrogen, chlorine, methyl, methoxy or —NHCOCH ₃ ), most preferably hydrogen. R ₁₁ is preferably hydrogen. The compound of formula (1) preferably corresponds to the compound of formula (8 ') in free acid or salt form:

Wherein the sulfo group is meta or para to the carbon atom to which the azo group is bonded, and R _1a , R _2a , R _3a , R _4b , R _5b and R _10a are as defined above. Compounds of formula (8 ') include (1) R _1a and R _3a are hydrogen and R _2a is —COCH ₃ ;

(2) R _10a is hydrogen;

(3) R _4b is hydrogen;

(4) R _5b in the group of (1) to (3) ego,

(5) More preferred are compounds in which the sulfo group in the group of (4) is meta to the carbon atom to which the azo group is bonded.

In the compound of formula (2):

X is preferably hydroxy or -NHSO ₂ CH ₂ , and R ₁₂ is preferably hydrogen, methyl or ethyl. In the compound of formula (3): The sulfo group is preferably meta or para to the carbon atom to which the azo group is bonded. R ₁₃ is preferably hydrogen or methoxy, and R ₁₄ is preferably hydrogen or methyl. R ₁₅ is preferably hydrogen. R ₁₆ is preferably methyl, ethyl or C _2-4 hydroxyalkyl, more preferably methyl or C _3-4 hydroxyalkyl, and the —OR ₁₆ radical is a carbon atom ortho or para bonded to an azo group. desirable. In the compound of formula (4): It is preferred that the phenyl substituents R ₁₇ and R ₁₈ are para to each other, more preferably both are chlorine. In the compound of formula (5): Z ₁ is preferably phenyl. In the compound of formula (6): R ₂₁ is preferably hydrogen, chlorine or -NHCOCH ₃ , more preferably R ₂₁ is hydrogen when R ₂₂ is -SO ₂ Z ₁ , or -SO ₂ Z ₂ . The compound of formula (7) is a compound wherein (3a) R ₂₃ is hydrogen, one of R ₂₄ and R ₂₅ is acetyl amino or propionylamino, and the other is hydrogen;

Or (3b) R ₂₃ is hydrogen or methyl, R ₂₄ is methyl and R ₂₅ is —SO ₂ NHCH ₂ CH ₂ OH. The compounds of formula (7), (3C), and R ₂₃ is hydrogen, R ₂₄ is a methyl, R ₂₅ is - most preferably SO ₂ NHCH ₂ CH ₂ OH. In the dye mixtures used in the process according to the invention, the yellow component of formula (1) is preferably used alone or in combination with the compound of formula (2). The dyes of the formulas (1) to (5), (6) and (7) used in the tricolor dyeing or printing process may be in the form of free acids or preferably salts. When they are in salt form, the cations associated with sulfo groups are not limited and may be one of the common non-chromatic cations in the field of anionic dyes. Such cations include alkali metal cations and unsubstituted or substituted ammonium cations such as lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, tri-ethylammonium and mono- , Di- and tri-ethanol ammonium. Preferred cations are alkali metal cations and ammonium, most preferably sodium. In addition, the cation bound with the sulfo group may be a mixture of the aforementioned cations meaning that these compounds may be in the form of mixed salts. Compounds of formulas (1) to (5), (6) and (7) are known or can be prepared analogously to known processes. For example, a compound of formula (1) can be obtained by etherifying a compound of formula (9) with the corresponding dialkylsulfate or alkylene oxide as described in US Pat. No. 4,384,870.

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₁₀ and R ₁₁ are as defined above.

Etherification is preferably carried out in an aqueous alkaline medium of PH 9 to 11, at a reaction temperature of 30 to 100 ° C, preferably 50 to 80 ° C.

Compounds of formula (2) may be prepared by the methods described in British Patent No. 1,454,475 and United States Patent No. 4,060,383, and compounds of Formula (3) are disclosed in United States Patent Nos. 3,862,119 and 3,932,378, and British Patent No. 1,423,629 In the process described, the compound of formula (4) can be prepared by the method described in US Pat. No. 3,891,619, and the compound of formula (5) can be prepared by the method described in EP 121495.

Compounds of formula (6) can be prepared as described in Federal Patent No. 702932, United States Patent No. 4,312,808 and British Patent No. 1,579,414.

Compounds of formula (7) can be prepared by the methods described in British Patent No. 1,568,928 and US Patent No. 3,778,453.

The invention further comprises optionally at least one of formulas (2) to (a) with at least one yellow dye of formula (1), at least one red dye of formula (6) and at least one blue dye of formula (7) It relates to a tricolor dye mixture containing the dye of 5), wherein the dyes of formulas (1) to (5), (6) and (7) are as described above. The dye is preferably used in the form of the sodium salt.

In a preferred tricolor mixture, the proportion of the individual pure dyes used in the mixture is as follows. At least 10 parts by weight of a yellow component, which is a dye of formula (1), optionally with one or more dyes of formulas (2) to (5); And 5 to 85 parts by weight of the red and blue components, respectively, which are at least one dye of formulas (6) and (7), based on 100 parts by weight of the three components in the form of sodium salts.

More preferred proportions of the individual pure dyes in the tricolor mixture are based on 100 parts by weight of the three components used in the form of the sodium salt, from 10 to 60 parts by weight of the yellow component, more preferably from 20 to 50 parts by weight, of the red component from 20 to 70 parts by weight, more preferably 20 to 45 parts by weight, and 10 to 50 parts by weight of the blue component, more preferably 15 to 40 parts by weight.

As mentioned above, dyeing or printing on natural or synthetic polyamide substrates with these tricolor dye mixtures can result in a wide range of shades from pale brown to dark blue-grey.

The individual dyes are mixed together for use in dyeing as a tricolor dye. Therefore, the dye mixtures are prepared separately as stock solutions in the dyeing process, or are preferably combined together in a single stock solution.

Such tricolor mixtures are, for example, suitable commercially available dry (powder, particulate) or liquid form mixtures, aqueous stock solutions containing such mixtures (eg dilution with water) and tricolor mixtures as described above. Salt or print pastes containing the same dye.

The dye mixture may be applied in a suitable form as described above. They may contain suitable standardizing agents such as water-soluble salts (particularly sodium chloride, sodium carbonate and sodium sulfate), non-electrolyte forms of standardizing agents such as dextrin and urea, and the like, and optionally further additives suitable for the preparation of solid or liquid formulations. In particular, if dyes with less electrolyte are required, they can be prepared by purification according to known osmotic methods.

Any substrate capable of anionic dyeing is suitable for the tricolor dyeing or printing process according to the invention, in particular natural or synthetic polyamides, in particular wool, silk, polyamide 6, polyamide 6.6, polyamide 11, Qiana (polyamide fibers obtainable by the reaction of C ₁₂ dicarboxylic acids with 4,4'-methylene-bis (cyclohexylamine)) and mixtures thereof are suitable for the tricolor dyeing or printing process according to the invention. . These substrates are commonly used in dyeing from aqueous media, e.g., loose fibers, yarns, yarns, filaments, skeins, spools, textiles, textures, felts, fleece, velvet ), In particular in the form of carpets, tufts, and semi-molded or finished products. In addition, the fibers used can be pretreated by mechanical or heat treatment. For example, they can be crimped or stretched. Moreover, other fibers or mixtures of fibers treated by other methods may also be used, in particular when other dyeing methods are used.

The above-mentioned substrates may be dyed by conventional dyeing methods, for example, by dyeing from aqueous saline or by impregnating an aqueous saline or dye formulation.

Dyeing can be carried out under conventional conditions, for example, a temperature of 40 to 120 ℃, pH 3.5 to 10, preferably pH 4 to 7. The pH of the salt bath can be adjusted by the addition of commonly used acids such as formic acid, acetic acid, tartaric acid or citric acid, or buffer solutions such as phosphate, tartrate or acetate buffers. In the case of a pH controlled dyeing process, the process may start at pH 7 to 10 and then during the dyeing process, the pH may be lowered to 3.5 to 5.5 or less. In the dyeing of the synthetic polyamide, the pH of the salt bath is preferably adjusted by a weak acid or a neutralization reaction, and more preferably maintained at a pH of 4.5 to 6. It is preferable to lower the pH in dyeing wool. Especially the range of pH 4-5.5 is preferable. Using an impregnation process, any conventional method is also suitable, so that the substrate is impregnated with an aqueous salt solution or paste, for example, by a dipping, padding or printing process. The dyeings obtained are then obtained by conventional means, for example by the cold dwell method, suitably at a temperature of 15-40 ° C., preferably at 20-30 ° C., or, for example, It can adhere by steaming at 100-105 degreeC.

The tricolor dye mixtures according to the invention are well suited for use in dyeing onto wool and / or synthetic polyamides, for example, by wool dyeing, tuft dyeing or piece dyeing, and furthermore, conventional displacements. ) Or special printing processes such as resist dyeing processes; It is well suited for use in continuous carpet dyeing, differential dyeing and space dyeing, and pH-controlled dyeing processes.

Because of the remarkably good level of homogeneity of their dyeing behavior, these dye mixtures are particularly suitable for dyeing and dipping processes.

By virtue of the dye mixtures mentioned above, dyeings, in particular on natural and synthetic polyamides, can optimally exhibit good color fastness, high yield of color strength, very good adhesion and remarkably good dyeing force. These dyeings do not exhibit contact fading. Even when performed by computer, their colorimetrically calculated methods have good reproducibility. It has been found that these properties are excellent results of certain mixtures of the dyes of the invention.

Moreover, dyes are compatible with conventional dyeing aids such as wetting agents, leveling agents, carriers, agents, and absorption aids. In addition, the dyeings obtained as described above may be treated with a universal finishing agent such as an antistatic agent, a softener, a sealability improving agent or a raising agent.

The following examples are set forth to further demonstrate the invention. In the examples, all parts and percentages refer to parts by weight and percentages unless otherwise indicated. The temperature is ° C. In the application examples, the dye component is used in conventional powder form, and the amount of dye component given in parts or percentages refers to the concentration of the pure dye based on the dry weight of the substrate.

[Production example]

44 parts of disazo dye of formula (10), which can be prepared according to the method described in Example 1 of US Pat. No. 4,384,870, are dissolved in 500 parts of water, and the mixture is added by addition of a 30% sodium hydroxide solution. The pH of was adjusted to 10, and 30 parts of n-butylene oxide -1,2 were added to this solution with stirring, and the reaction temperature was raised to 62-65 degrees. At the same time the pH was maintained at 10-10.5 by addition of 30% sodium hydroxide solution, after 15-20 hours at 62-65 ° C., the etherification was completed and precipitation of the dye was completed by addition of sodium chloride. The dye was separated by filtration, washed with 10% sodium chloride solution and dried. Disazo dyes corresponding to formula (11) in free acid form were obtained in the form of sodium salts. It dyes natural or synthetic polyamides in yellow.

A starting dye (10) is prepared by using a mixture of 1-aminobenzene-3- and 4-sulfonic acid (a ratio of about 1: 1) instead of 1-aminobenzene-3-sulfonic acid, or else, When etherification is carried out according to the described method, the corresponding dye mixture is obtained. It dyes natural or synthetic polyamides in yellow. Similar to the methods described in the preparation examples, compounds of formula (12) as listed in the following table may be further prepared using suitable starting compounds. This compound corresponds to formula (12)

In the above formula, each symbol is defined in the following table. In the last column J of the table below, the color tone of the natural or synthetic polyamide obtained with each of the compounds 2 to 10 is given as a is yellow and b is brown orange.

In the following application examples using the tricolor mixture according to the invention, the following individual dyes are used.

A yellow component of formula (12) having formula (11) according to Preparation A;

Formula of B 55% Wow

45% of chemical formula Red component of formula (6) consisting of a mixture of two dyes having a ratio of about 1: 1;

C 50% of formula (3) Wow

50% of formula (IIC) Blue component of formula (7) consisting of a mixture of two dyes having a ratio of about 1: 1;

D chemical formula Blue component of formula (7) having;

E chemical formula Red component of formula (6) having;

A blue component of formula (7) consisting of a mixture of dyes (IC) and (IIC) according to C above, except that 90% of formula (3) was used with F 10% of formula (IIC);

G chemical formula Yellow component of formula (11) having:

The individual dyes used in the dye components A to G are used in the form of sodium salts. In the tricolor mixture used in the following application examples, the dyes of formula (11) as yellow component A can be replaced by compounds 2 to 10 described in the table above, respectively. Each compound 2 to 10 is used in the form of sodium salt.

Application Example 1 (Dyeing on Polyamide Fiber)

100 parts of pre-wet synthetic polyamide, for example, polyamide 6.6 fiber in a salt bath consisting of 4000 parts of water, 10 parts of anhydrous sodium sulfate, and a dye mixture containing A 0.07%, B 0.05% and C 0.03% Was introduced. The salt solution was heated to boiling temperature for 30 minutes and maintained at that temperature for 1 hour. Then, 4 parts of glacial acetic acid was added thereto and heated for an additional 30 minutes at boiling temperature to complete dyeing. The water evaporated during dyeing was continuously changed. The nylon cloth dyed in brown was then removed from the salt solution, washed with water and dried. It is also possible to dye wool or wool / synthetic polyamide blends in the same process. The tricolor polyamide dyeings obtained were dyed uniformly, showing good sun fastness and wet fastness.

[Application Example 2]

A uniformly dyed nylon fabric was obtained according to the method described in Example 1, except for using a dye mixture containing 0.02% A, 0.025% B, and 0.025% D. .

Application Example 3 (Printing Polyamide Fiber)

15 parts of dye mixture consisting of 5.7 parts A, 6.0 parts E, and 3.3 parts F, 50 parts urea, 50 parts solubilizer (e.g. thiodiethylene glycol), 305 parts water, arc (e.g. 10% aqueous solution) Polyamide 6 is printed with a printing paste containing 500 parts of carob bean gum in the form), 20 parts of an acid donor (eg ammonium tartrate), and 60 parts of thiourea. The printed textile product is steamed (saturated steam) for 40 minutes at 102 ° C., rinsed cold, washed at 60 ° for 5 minutes with a diluent of a conventional detergent, and then rinsed again with cooling water. As a result, brown prints having good daylight and wet fastnesses were obtained.

Application Example 4 (Continuous Dyeing of Polyamide Carpet)

Polyamide (e.g., regular polyamide 6.6 fiber) carpet was wetted with a composition consisting of 1.5 parts and 998.5 parts of product obtained by reacting 1 mole of decyl alcohol with 4 moles of ethylene oxide, followed by compression to impregnate the wetting agent, (pick up) was reduced to 90% (weight of anhydrous support). A formulation based on 0.15 parts of a dye mixture containing 0.035 parts A, 0.035 parts G, 0.05 parts B, and 0.03 parts F, guar (e.g. Celca Cum D-49-D) A 500% wet pick-up of the saline solution consisting of 1.5 parts, 1.5 parts of decyl alcohol ethoxylated with 4 moles of ethylene oxide / 1 mole of alcohol, 96.85 parts of water, and a sufficient amount of monosodium phosphate to adjust the salt solution to pH 5 Based on the dry weight of the substrate) and applied to the wet polyamide carpet using a continuous applicator (e.g. kusters) and steamed the treated polyamide carpet with a vertical steamer at 102 ° for 7 minutes. Treated, rinsed with warm water and dried. If continuous impregnation with 300% or 600% pick is performed, lower or deeper dyes may be obtained. Instead of a vertical steamer, a horizontal steamer may be used. A very uniformly dyed brown dyeing with good daylight fastness (obtained even upon exposure to light by heating) and wet fastness was obtained. The following application examples 5 to 14 demonstrate a special dyeing or printing method for polyamide carpets using certain auxiliaries. These adjuvants are recorded as follows.

Leveling agent LA1) to LA6)

LA1) is a positive leveling agent based on quaternary sulfonated higher amino fatty acid amides;

LA2) is an anionic leveling agent based on saturated C _12-13 alcohol polyglycol ethersulfate as sodium salt;

LA3) is an anion homogenizer based on a mixture consisting of sulfopolyphenylsulfone, ethoxylated amino C ₂₂ fattyamines and ethoxylated higher alkyl alcohols;

LA4) is a positive leveling agent based on sulfonated ethoxylated C _18-22 fattyamines as ammonium salts;

LA5) is a cationic active leveling agent based on the reaction product of 1 mole of C ₂₂ fatty acid aminopropylamine with 105 moles of ethylene oxide;

LA6) is a nonionic leveling agent based on a mixture consisting of tridecyl alcohol polyglycol ether, LA1) and hexylene glycol.

Acid donor AD1) to AD3)

AD1) is based on butyrolactone;

AD2) is based on glycol mono- or di-esters of formic acid;

AD3) is based on a mixture of C _4-6 dicarboxylic acids.

Flame retardant RA1)

RA1) is based on the quaternary reaction product of higher fatty amines reacted with 1 mole of ethylene oxide and styrene oxide.

[Application Examples 5 to 8 / Dyeing]

In each of these application examples a salt solution in a ratio of 20: 1;

Use the product.

Example 5 Differential Staining on Polyamide 6.6

50 parts of polyamide carpet of regular basic fibers as deep dyes are used. The aqueous saline solution is a tricolor dye mixture consisting of 0.16% A, 0.15% B, and 0.30% F, 0.006% C.I. Basic Yellow 45, 0.002% of C.I. Basic Red 23, and 0.01% of C.I. Basic dye mixture consisting of Basic Blue 22, LA5) 1%, and 1 g / L of AD2) added when the dyeing process was undertaken. The pH of the salt solution is initially 7, and decreases to 5.5 during the dyeing process performed at 98 ° for 60 minutes. The resulting gray-pink polyamide is dyed very uniformly.

Example 6

Staining was performed similarly to the method described in Example 5, except that 1 g / l of AD1) was used instead of AD2) added only to the salt bath at boiling temperature. The dyeing process is undertaken to pH 8.0, then the salt solution is heated to 98 ° within 30 minutes and the appropriate amount of AD1) is added to adjust pH 8 to 6 over 30 minutes at the start.

[Solid Coloring on Example 7 / Polyamide 6.6]

50 parts of polyamide carpet of regular fibers are used. The aqueous saline solution contains a tricolor dye mixture consisting of 0.044% A, 0.035% B, and 0.028% F, LA5) 1% and AD1) 1 g / l.

Staining is performed by the method described in Example 6.

[Solid Coloring on Example 8 / Polyamide 6]

50 parts of polyamide carpet of dip dye fibers are used. The aqueous saline solution contains a tricolor dye mixture consisting of 0.014% A, 0.025% B, and 0.08% F, LA3) 1%, and 1 g / L of AD2) added at the start. Staining starts at pH 8.0 and 20 °. According to the low temperature dyeing process, the salt bath is heated to 60 ° and kept at 60 ° for 60 minutes. At the end of the salt bath process, the pH of the salt solution is 5.5. Uniformly dyed carpets are grey-blue.

[Application Examples 9 to 11 / Continuous and Semi-Continuous Dyeing]

In each of these applications (Examples 9 and 10 represent a continuous process, Example 11 represents a semi-continuous process), saline solution;

The ratio of commodities is 2.8: 1.

[Differential Staining on Example 9 / Polyamide 6]

Polyamide carpets of regular basic fibers that are dip dyes are used. 0.395 parts of a tricolor dye mixture containing 0.055 parts of A, 0.27 parts of B, and 0.07 parts of F, 0.06 parts of C.I. Basic Yellow 45, 0.10 parts of C. I. Basic Red 23, and 0.90 parts of C.I. A salt solution consisting of 1.06 parts of a basic dye mixture containing Basic Bluewoo 22, LA6) 1.5 g / L, AD3) 1.5 g / L and AD2) 2.0 g / L was applied to the polyamide carpet at pH 7.5 and 280% of Achieve pick up (based on the dry weight of the support). The dyed carpet is steamed (saturated steam) for 5 minutes at 102 °. The resulting carpet is dyed uniformly in reddish-blue tones.

[Solid Coloring on Example 10 / Polyamide 6.6]

Polyamide carpets of regular basic fibers are used.

0.62 parts tricolor dye mixture containing 0.16 parts A, 0.24 parts B, and 0.22 parts F, LA3) 1g / L, LA6) 2g / L, LA2) 2g / L, AD3) 1g / L Apply to polyamide carpet and achieve 250% pickle (based on the dry weight of the support). The dyeings are then steamed (saturated steam) at 102 °. A brown dye was obtained, which shows the same color at both ends as well as on both sides of the fiber by the uniform dispersion effect of the color promoting good ground pile tip uniformity.

[Semi-continuous monochrome staining on Example 11 / polyamide 6.6]

Polyamide carpets of regular basic fibers are used. A saline solution consisting of 0.94 parts of a tricolor dye mixture containing 0.38 parts A, 0.34 parts B, and 0.22 parts F, LA2) 2g / L, LA4) 4g / L, and 60% acetic acid 1g / L was applied to the carpet, 250 Achieve% Pickup. The residence time is 20 hours at room temperature. A uniformly dyed brown carpet was obtained, indicating no color difference on both sides and ends of the fiber.

Application Examples 12 to 15 / Printing Process

[Example 12 / Conventional Printing of Polyamide 6]

The carpet material of polyamide 6 endless velvet is used. 0.23 parts of a dye mixture consisting of 0.02 parts A, 0.10 parts B, and 0.11 parts F, LA2), 1 g / l, and 2 g / l of a hop (based on locust bean beam gum) to obtain a 10% pick up Fond staining is performed by padding at pH 5.0 with saline solution. Then, a rotating screen was used with a printing paste consisting of 0.76 parts of a dye mixture containing 0.2 parts A, 0.11 parts F, 4 kg 400 kg / kg of alginate, 4 kg / kg of LA1) and 80% 5 cm 3 / kg of acetic acid. Overprint. Dyeing is carried out by patting the carpet to yield a thin pond, then print the design using a green overprint printing paste and fix the resulting print with saturated steam for 10 minutes. A pale blue carpet pond with green printing design was obtained, showing good penetration and uniform color dispersion for the printing appearance.

Example 13 / Display Printing

The carpet material of polyamide 6.6 heat treated set yarn (belbit) is used. C.I. of 0.64 parts to yield a 100% pick up. Acid Yellow 235, 0.28 parts C.I. A salt solution containing 4.12 parts of a dye mixture consisting of acid red 399, and 3.2 parts of CI acid black 218, alginate adjuvant 4% 100 g / l, LA1) 3 g / l, and 1 g / l defoamer was padded to pH 5.0 Perform staining. The overprinting was rotated at pH 7.0 using a printing paste consisting of 1.77 parts of dye mixture containing 1.0 parts of A, 0.6 parts of B, and 0.17 parts of F, RA1) 10 kg / kg, and 500% / kg of alginate aid. Perform the screen. The printing process is similar to that described in Example 12. Carpets with dark gray ponds and transparent tan printing were obtained, which showed a uniform color distribution of the fiber structure.

Example 14 / spray printing

Polyamide 6.6 Heat Treatment Set Velvet's carpet material is used. 0.126 parts of a dye mixture containing 0.045 parts A, 0.045 parts B, 0.036 parts F, an appropriate amount of citric acid to adjust to pH 4.5, an appropriate amount of estimating agent to yield a viscosity of 300 cps, and LA5) at 2 g / l The constructed printing paste is applied to achieve 350% pick up, the carpet is partially printed using a spray printing machine and fixed with saturated steam for 10 minutes. A brown printing pattern was obtained. An optimal color distribution with no color difference for pile ground / pile tip leveling was obtained.

Example 15

A solid brown carpet was obtained using the printing process according to Example 14, except that printing was carried out on the entire surface without a pattern instead of partially printing. The entire carpet surface was stained uniformly and pile level was remarkably good.

Claims (8)

(Iii) at least one dye of formula (Ia) in the form of a free acid or salt as a yellow component, (ii) at least one dye of formula (II) in the form of a free acid or salt as a red component and (iii) blue A method for tricolor dyeing or printing of a nitrogen-containing organic substrate, comprising applying to the substrate an anionic dye mixture together with at least one dye of formula (III) in the form of a free acid or salt as a component: Wherein, R ₁ is hydrogen, C _1-4 alkoxy, C _1-4 alkyl substituted with a single beach by a C _1-4 alkyl or halogen ring, R ₂ is C _1-4 alkyl or -COR _6, R ₃ is hydrogen or C _1-4 alkyl, R ₄ is hydrogen, halogen, C _1-4 alkyl, C _1-4 alkoxy or —NR ₃ R ₉ , wherein R ₃ is as defined above but independent of it R ₉ is -COC _1-6 alkyl or -COOC _1-6 alkyl, R ₅ is C _1-4 alkyl or monohydroxy-substituted C _2-6 alkyl, and R ₆ is C _{1- 6} alkyl, -OC _1-6 alkyl or -NR ₇ R ₈ , R ₇ and R ₈ are independently hydrogen, unsubstituted C _1-6 alkyl or monohydroxy-substituted C _2-6 alkyl, R ₁₀ is hydrogen, halogen, C _1-4 alkyl, C _1-4 alkoxy, or —NR ₃ R ₉ , wherein R ₃ and R ₉ are as defined above but independent of it, and R ₁₁ is hydrogen , Halogen, C _1-4 alkyl or C _1-4 alkoxy, R ₂₁ is hydrogen, halogen or —NHCOC _1-4 alkyl, R ₂₂ is trifluoromethyl, —SO ₂ Z ₁ , wherein Z ₁ is phenyl, phenoxy or —NR ₁₉ R ₂₀ , wherein R ₁₉ is methyl or ethyl and R ₂₀ is phenyl or cyclohexyl ] Or -SO ₂ Z ₂ where Z ₂ is -N (C ₄ H ₉ ) ₂ or R ₂₃ is hydrogen or methyl, one of R ₂₄ and R ₂₅ is —SO ₂ NHC _2-4 hydroxyalkyl or —NR ₂₆ COC _1-4 alkyl, wherein R ₂₆ is hydrogen, methyl or ethyl And the other is hydrogen or methyl. The process of claim 1 wherein the dye of formula (Ia) is applied together with at least one yellow to orange dye of formula (Ib) to (Ie) in free acid or salt form: Wherein X is hydroxy or —NHSO ₂ C _1-4 alkyl, R ₁₂ is hydrogen or C _1-4 alkyl, and R ₁₃ , R ₁₄ and R ₁₅ are each independently hydrogen, C _1-4 alkyl or C _1-4 alkoxy, R ₁₆ is C _1-4 alkyl or C _2-4 hydroxyalkyl, R ₁₇ and R ₁₈ are each independently hydrogen, halogen or C _1-4 alkyl, Z ₁ is phenyl, Phenoxy or —NR ₁₉ R ₂₀ , R ₁₉ is methyl or ethyl and R ₂₀ is phenyl or cyclohexyl. The method of claim 2, wherein the dye of formula (4) is applied together with the compound of formula (5). At least one dye of formula (4) as a yellow component, at least one dye of formula (6) as a red component and at least one formula as a blue component, respectively, as defined in claim 1 Tricolor dye mixture consisting of dyes). The yellow component according to claim 4, wherein the proportion of the individual pure dyes used in the mixture is based on a total of 100 parts by weight of the three components in the form of sodium salt, and at least 10 parts by weight of the yellow component, which is the dye of formula (4). 5 to 85 parts by weight of each of the red and blue components, which are dyes of formulas (6) and (7). The method of claim 1, wherein the substrate comprises natural or synthetic polyamides. The method of claim 6 wherein the substrate is a carpet material comprising wool or synthetic polyamide. A dyeing or printing method comprising applying a tricolor dye mixture as defined in claim 5 to a substrate.