MXPA98005670A - Colors of dispers - Google Patents

Abstract

The present invention relates to describing dispersion dyes of the formula (1), wherein R is nitro or cyano, R1 is halogen, R2 is C1-C4 alkyl, which is unsubstituted or substituted by C1-C3 alkoxy, halogen, cyano or phenyl, R3 is C1-C4 alkyl, R4 is methyl or ethyl, R5 is hydrogen, methyl or ethyl, and R6 is methyl or ethyl, provided that R5 is not hydrogen if R is nitro, R1 is halogen and R2 is C1-C4 alkyl. These dyes are particularly suitable for dyeing and printing textile materials consisting of polystyrene fibers.

Description

DISPERSION COLORS DESCRIPTION OF THE INVENTION The present invention relates to dispersion dyes, to a process for their preparation, as well as to their use for dyeing or printing semi-synthetic or synthetic hydrophobic fiber materials. Dispersion dyes, ie, dyes containing no soluble group, have been known for a long time and are used to dye hydrophobic fiber materials. However, the resulting stains are generally not sufficiently resistant to thermomigration and some of their properties are also unsatisfactory, in particular their resistance to washing and perspiration. This problem occurs in particular with shades of blue and navy blue. This invention relates to dispersion dyes with which dyes are obtained which are resistant to thermomigration, as well as to washing and transpiration and which also have a good development in the exhaust and thermosol processes, as well as in the printing of textiles The dyes are also suitable for downloading printing. The novel colorants correspond to the formula: wherein: R is nitro or cyano, R1 is halogen, R2 is C1-C4 alkyl, which is unsubstituted or substituted by C1-C3 alkoxy, halogen, cyano or phenyl, R3 is C1-C4 alkyl, R is methyl or ethyl, Rs is hydrogen, methyl or ethyl, and R6 is methyl or ethyl, provided that Rs is not hydrogen if R is nitro, R1 is halogen and R2 is CrC4 alkyl. Ri defined as halogen is bromine, chlorine or iodine. R 2 and R 3 defined as C 1 -C 4 alkyl are each independently of the other typically methyl, ethyl, n-propyl, ispropyl, n-butyl, sec-butyl, tert-butyl and isobutyl. R, is chlorine or bromine. Chlorine is preferred. R is ethyl or methyl. Methyl is preferred. R3 is ethyl or methyl. Methyl is preferred. Rs is hydrogen or methyl. Methyl is preferred. The dyes of the formula (1) can be prepared by processes which are known per se. They are obtained, for example, by diazotizing a compound of the formula: and coupling the diazonium compound thus obtained to a coupling component of the formula: R, R1f R > R3 > R4, Rs, and Re having the meanings given for formula (1). The diazotization of the compounds of the formula (2) is carried out in a manner known per se, for example, with sodium nitrite in acid, typically hydrochloric and sulfuric acid, an aqueous medium. However, diazotization can also be carried out with other diazotization agents, conveniently with nitrosylsulfuric acid. The reaction medium of the diazotization may contain an additional acid, typically phosphoric acid, sulfuric acid, acetic acid, propionic acid, hydrochloric acid or mixtures of these acids, for example, mixtures of phosphoric acid and acetic acid. The diazotization is conveniently carried out on the temperature scale of -10 to 30 ° C, preferably -10 ° C at room temperature. The coupling of the diazotized compounds of the formula (2) to the coupling agent of the formula (3) is likewise carried out in a known manner, conveniently in acid, an aqueous or aqueous organic medium, preferably in the temperature range of -10 to 30 ° C, most preferably below 10 ° C. Suitable acids include hydrochloric acid, acetic acid, sulfuric acid or phosphoric acid. Diazotization and coupling can typically be carried out in the same reaction medium. Some of the diazo components of the formula (2) and the coupling components of the formula (3) are known or can be prepared in a manner known per se. The coupling component of the formula.

NHCOCH ", 3 wherein R4 and R6 have the meanings given for formula (1) is novel and is also an object of this invention The coupling component of formula (3a) is prepared, for example, by reacting 3-amino-4-methoxyacetanilide, first with a compound of the formula CH 3 -CHCI-COORß, and then with a compound of the formula CH 2 Cl-COOR. The novel dyes of the formula (1) can be used to dye and print semi-synthetic and, preferably, synthetic hydrophobic fiber materials, in particular textile materials. Textile materials made from blends containing said semi-synthetic or synthetic hydrophobic fiber materials that they contain may also be dyed or printed with the novel dyes. Suitable semi-synthetic textile materials are in particular cellulose secondary acetate and cellulose triacetate. Synthetic hydrophobic textile materials consist mainly of linear aromatic polyesters, typically those of terephthalic acid and glycoids, especially ethylene glycol, or condensates of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane.; of polycarbonates, typically those of a, a-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene, or of fibers based on polyvinyl chloride and polyamide. The novel dyes are applied to the textile materials through known dyeing methods. Typically, the polyester fiber materials are dyed from an aqueous dispersion through an escape process in the presence of customary anionic or nonionic dispersants and in the presence or absence of numbing agents (carriers) at a temperature scale of 80 to 140 ° C. The cellulose secondary acetate is preferably dyed at a temperature of about 65 to 85 ° C, and the cellulose triacetate at temperatures of up to 15 ° C. The novel dyes do not stain wool and cotton simultaneously present in the dye bath or make only a minor dye (very resistant), so that they can also be easily used to dye polyester / wool and polyester / cellulose blends. The novel dyes are suitable for dyeing through the thermosol process, continuous and escape procedures and for printing. The exhaust staining procedure is preferred. The liquor ratio depends on the apparatus used, the substrate and the form of presentation. However, it can be chosen from a wide scale, for example, from 1: 4 to 1: 100, but preferably from 1: 6 to 1: 25. The aforementioned textile material can be in any form of presentation, such as fiber, braided or non-woven fabric, or cloth or knitted articles. It is appropriate to convert the novel colorants, before use, to a dye formulation. This is done by grinding the colorant to an average particle size of 0.1 to 10 microns. The milling can be carried out in the presence of dispersants. Typically, the dried colorant is milled with a dispersant, or kneaded in paste form with a dispersant, and then dried under vacuum or through spray drying. The printing pastes and dye baths can be prepared by adding water to the formulations thus obtained. This invention also relates to dye formulations, which comprise: a) as coloring component of 30 to 50% by weight, based on the total weight of the dye formulation, of a dye of the formula: wherein R is nitro or cyano, R < is hydrogen, R 2 is C 1 -C 4 alkyl, which is unsubstituted or substituted by C 1 -C 3 alkoxy, halogen, cyano or phenyl, R 3 is C 1 -C 4 alkyl, R 4 is methyl or ethyl, R 5 is hydrogen, methyl or ethyl, and R6 is methyl or ethyl, and b) from 50 to 70% by weight, based on the total weight of the dye composition, of a dispersant. Suitable dispersants are, for example, anionic dispersants, such as aromatic sulfonic acid / formaldehyde condensates, sulfonated creosote oil / formaldehyde condensates, lignin sulfonates or copolymers of acrylic acid derivatives and styrene derivatives, preferably sulfonic acid condensates. aromatic / formaldehyde or lignin sulfonates, or dispersants based on polyalkylene oxides obtainable, for example, through the polyaddition reaction from ethylene oxide or propylene oxide. The dye formulations of this invention are preferably solid. The novel dye formulations are distinguished in that they can easily be converted to the form in which they can be applied, for example, to the printing dye or finished dye baths. Common thickeners that will be used for printing are, for example, modified or unmodified natural products, typically alginates, British gum, gum arabic, locust bean gum, tragacanth, carboxymethylcellulose, hydroxyethyl cellulose, starch or synthetic products, typically polyacrylamides, polyacrylic acids or their copolymers, or polyvinyl alcohols. The novel colorants impart to the aforementioned materials, especially the polyester material, the blue to dark blue tone levels of very good end-use properties, such as good light resistance and sublimation. Particular mention should be made of the resistance to washing and perspiration, and especially to thermomigration. The novel colorants are also distinguished by their good escape and development. The novel dyes can also be used for the preparation of blended volumes together or also together with other dyes. This invention relates to the aforementioned uses of novel dyes, as well as to a process for dyeing or printing a semi-hydrophobic fiber material. -synthetic or synthetic, in particular a textile material, said methods comprises applying to or incorporating one or more of the novel dyes into said material. The aforementioned hydrophobic fiber material is preferably a textile polyester material. Other substrates which may be treated with the process of this invention, as well as preferred process conditions, will be found above in the detailed description of the use of the novel dyes. In another of its aspects, this invention relates to the hydrophobic fiber material, preferably a polyester fabric, dyed or printed through the aforementioned process. The novel dyes of the formula (1) are also suitable for modern recording processes, such as heat transfer printing. The invention is illustrated through the following examples. Unless otherwise indicated, parts and percentages are by weight and temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is equal to that between gram and cubic centimeter.

EXAMPLE 1 In a reaction flask, 60.0 parts by weight of 3-amino-4-methoxyacetanilide was added to 200 parts by weight of methyl chloroacetate at a temperature of 20 to 30 ° C. To this mixture was then added 60 parts by weight of sodium carbonate. The resulting suspension is uniformly heated, with constant stirring, at 115 ° C and maintained for 6 hours at this temperature. After the reaction was complete, the mixture was cooled to room temperature, loaded with 330 parts by weight of water and stirred for 30 minutes until the salts were completely dissolved. After standing for a short period, 2 phases were formed in the reaction flask. The lower or organic phase was isolated and the excess ethyl chloroacetate was removed therefrom by distillation in a rotary evaporator. This gave 105 parts by weight of the compound of the formula: NHCOCH, in the form of a resinous residue, which was then dissolved in 195 parts by weight of acetic acid.

EXAMPLE 2 In a reaction flask, 72.6 parts by weight of 2-amino-3-bromo-5-nitrobenzonitrile were dissolved in 107 parts by weight of 98% sulfuric acid at a maximum temperature of 35 ° C. 104 parts by weight of 40% nitrosylsulfuric acid were added dropwise over 40 minutes to this reaction mixture, which was then stirred for 120 minutes at 25 ° C. The resulting diazo solution was then added dropwise to 300 parts by weight of 35% of the solution of the coupling component of Example 1 and to 200 parts by weight of ice for 60 minutes at 0 to 5 ° C, the reaction temperature It was maintained at a maximum of 5 ° C through the addition of ice. After the addition of the diazo solution was complete, the mixture was stirred for 2 hours, the temperature was increased to 20 ° C. The resulting precipitate was collected by filtration, washed with water and dried to give 1 35 parts by weight of a dye of the formula: Br NHCOCH, which dyes polyester textile materials in a blue shade giving good resistance properties, in particular good resistance to thermomigration and washing.

EXAMPLES 3-22 The dyes of the formulas (101) to (120) listed in Table 1 were prepared, in general analogy to the instructions in Example 2. They also dyed polyester textile materials in navy blue and blue tones having good strength properties, in particular resistance to thermomigration and washing.

TABLE 1 Preferred dyes are those of formulas (101) to (108), (110) to (113) and (117) to (120). Particularly preferred dyes are those of formulas (106), (108), (110), (117) and

Claims (1)

1. CLAIMS A dye of the formula: wherein R is nitro or cyano, R < is halogen, R 2 is C 1 -C 4 alkyl, which is unsubstituted or substituted by halogen alkoxy, cyano or phenyl, R 3 is C -C alkyl, R 4 is methyl or ethyl, R 5 is hydrogen, methyl or ethyl, and R6 is methyl or ethyl, provided that Rs is not hydrogen if R is nitro, R < is halogen and R2 is C1-C4 alkyl. 2 - A dye according to claim 1, wherein R-i is chlorine or bromine. 3. A dye according to claim 1 or claim 2, wherein R is ethyl or methyl. 4 - A dye according to any of claims 1 to 3, wherein R3 is ethyl or methyl. 5. A dye according to any of claims 1 to 4, wherein Rs is hydrogen or methyl. 6 - A dye according to claim 5, wherein Rs is methyl. 7. - A dye according to claim 1, wherein R is cyano, Ri is chlorine or bromine, R 2 and R 3 are each independently of the other methyl or ethyl, R 4 is methyl or ethyl, R 5 is methyl and R 6 is methyl or ethyl . 8. A process for the preparation of a colorant of a dye of the formula (1) according to claim 1, which comprises diazotizing a compound of the formula: and coupling the diazonium compound thus obtained to a coupling component of the formula: NHCOR2 wherein R, R ^ R2l R3, R4, Rs, and Rβ have the meanings given for formula (1). 9. A process for dyeing or printing semi-synthetic or synthetic hydrophobic fiber materials, in particular a textile material, which comprises applying to or incorporating in said material one or more of the dye according to claim 1. 10. A process according to claim 9, wherein the hydrophobic material, preferably a textile material, consists of polyester fibers. 1. The dyed or printed material according to claim 9 or claim 10. 12.- A coupling component of the formula: wherein R 4 is methyl or ethyl, and R 6 is methyl or ethyl. 13. A process for the preparation of the coupling component of the formula (3a) according to claim 12, which comprises first reacting 3-amino-4-methoxyacetanilide with a compound of the formula CH3-CHCI-COOR6 ly then with a compound of the formula CH 2 Cl-COOR 1 R 4 and R 3 having the meaning given for the formula (3a). 14. A dye formulation, comprising: a) as dye component from 30 to 50% by weight, based on the total weight of the dye formulation, of a dye of the formula: wherein R is nitro or cyano, R is halogen, R 2 is C 1 -C 4 alkyl, which is unsubstituted or substituted by C 1 -C 3 alkoxy, halogen, cyano or phenyl, R 3 is C 1 -C 4 alkyl, R 4 is methyl or ethyl, R5 is hydrogen, methyl or ethyl, and R6 is methyl or ethyl, and b) from 50 to 70% by weight, based on the total weight of the dye composition, of a dispersant.