Title of Invention

A PROCESS FOR THE PREPARATION OF THE DYE MIXTURE

Abstract

A process for the preparation of a dye mixture, which comprises the step of diazotising a compound of formula D-NH2and coupling the diazonium compound so obtained to a coupling component mixture comprising the coupling components of formulae wherein D is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiazole, thiadiazole, indazole, benzotriazole, pyrazole, anthraquinone. hydroxynaphthoic acid imide, chromone or diphenylene oxide series, X is in each case hydrogen, halogen, CF3, R3, OR3, NH-CO-R7, NH-CQ-ORs , T- SO2-R7 or NHCO-N~As, wherein R3 is C1-C6alkyl, ~ and Rs are each independently of the other hydrogen, C1-C4alkyl or C1-C4alkoxy-C2-C4alkyl, R7 is hydrogen, C1-C6alkyl, C1- C4alkoxy-CI,-C4alkyl or phenyl, and Rs is CI-C6alkyl or CI-C4alkoxy-C2-C4alkyl, and Y is in each case hydrogen, halogen, methoxy, ethoxy or O(CH2)n-OR9, wherein R9 is hydrogen, methyl, ~ or CH2CH2CN, and n is an integer from 1 to 6.

Full Text

The present invention relates to mixtures of azo dyes, to tlieir preparation and to their use for dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials. Azo dyes and their use for dyeing semi-synthetic or synthetic hydrophobic fibre materials are known. However, it has been found that these dyes do not always fully meet the highest demands, in particular as regards fastness to thermomigration. There is therefore a need for novel dyes or dye mixtures which provide dyeings or prints which are very fast to ther¬momigration and which have good exhaust, build-up or washing properties. Surprisingly, it has now been found that the novel mixtures substantially fulfill the above criteria. wherein D is in eacli case the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiazole, thiadlazole, indazole, benzotrlazole, pyrazole, anthraquinone, hydroxynaphthoic acid imide, chromone or diphenylene oxide series, X is in each case hydrogen, halogen, CF3, R3, OR3, NH-CO-R7, NH-CO-ORs, NH-SO2-R7 or NHCO-NR4R5, wherein R3 is Ci-CealkyI, R4 and R5 are each independently of the other hydrogen, Ci-C4alkyl or Ci-C4alkoxy-C2-C4all xy-Ci-C4alkyl or phenyl, and Rs is CrCealkyl or Ci-C4alkoxy-C2-C4alkyl, and Y is in each case hydrogen, halogen, methoxy, ethoxy or 0(CH2)n-OR9, wherein Rg is hydrogen, methyl or CH2CH2CN, and n is an integer from 1 to 6. In this invention, alkyl radicals will be understood as being generally straight-chain, branched or cyclic alkyl groups. R3, R7 and Ra defined as Ci-CealkyI are typically methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, hexyl, 1 -methylpentyl, neopentyl, cyclopentyl, cyclohexyl, as well as the corresponding isomers. R4 and R5 defined as CrC4alkyl are methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl. R4, Rs, R7 and Ra defined as Ci-C4alkoxy-C2-C4alkyl are typically methoxyethyl, methoxy-propyl, methoxybutyl, ethoxypropyl, ethoxy-iso-propyl, propoxyethyl, isobutoxypropyl or n-butoxyethyl. X defined as halogen is fluoro, bromo, iodo or, preferably, chloro. Y defined as halogen is fluoro, bromo, iodo or, preferably, cfiloro. The diazotisation of the compound of formula (4a) is carried out in per se known manner, for example with sodium nitrite in acid, typically hydrochloric or sulfuric acid, aqueous medium. The diazotisation can, however, also be carried out with other diazotising agents, conveniently with nitrosylsulfuric acid. The reaction medium of the diazotisation 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 propionic acid and acetic acid. The diazotisation is conveniently carried out in the temperature range from -10 to 30°C, for example from -10°C to room temperature. The coupling of the diazotised compound of formula (4a) to the mixture of the coupling components of formulae (5), (6) and/or (7) is also carried out in known manner, for example in acid, aqueous or aqueous-organic medium, preferably in the temperature range from -10 to 30°C, most preferably below 10°C. Suitable acids include hydrochloric acid, acetic acid, propionic acid, sulfuric acid or phosphoric acid. The diazo components of formula (4) are known and can be prepared in per se known manner. Tfie mixture of the coupling components of formulae (5), (6) and (7) is novel and is also an object of this invention. The coupling components of formulae (6) and (7) are known perse and can be prepared in a manner known per se. The coupling component of formula wherein X and Y have the meaning given above, with a mixture of methyl chloroacetate and ethyl chloroacetate in a ratio of 95:5 to 5:95. This reaction Is preferably carried out at elevated temperature, for example In the range from 60 to 130°C, preferably from 105 to 125"*C, in the presence of an add acceptor, such as sodium acetate, sodium bromide or soda, if appropriate In an Inert solvent. The novel dye mixtures can be used as dyes for dyeing or printing semi-synthetic and, In particular, synthetic hydrophobic fibre materials, especially textile materials. Textile blends containing such semi-synthetic or synthetic hydrophobic textile materials can also be dyed or printed using the novel compounds. Suitable semi-synthetic textile materials are In particular cellulose secondary acetate and cellulose triacetate. Synthetic hydrophobic textile materials consist primarily of linear aromatic polyesters, typi¬cally those from terephthalic acid and glycols, especially ethylene glycol or condensates of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane; of polycartDonates, typically those from a,a-dimethyl-4,4-dihydroxydiphenylmethane and phosgene, or of fibres based on poly¬vinyl chloride and polyamide. The novel compounds are applied to the textile materials by known dyeing methods. Typically, polyester fibre materials are dyed from an aqueous dispersion by the exhaust process in the presence of customary anionic or nonionic dispersants and in the presence or absence of customary swelling agents (carriers) in the temperature range from 80 to 140°C. Cellulose secondary acetate is preferably dyed at a temperature from about 65 to 85°C, and cellulose triacetate at temperatures of up to 115°C. The novel dyes do not stain wool and cotton simultaneously present in the dyebath or effect only minor staining (very good resist), so that they can also readily be used for dyeing polyester/wool and polyester/cellulose blends. The novel dyes are suitable for dyeing by the thermosol process, for exhaust dyeing and for printing. The textile material may be in any form of presentation, such as fibre, thread or nonwoven fabric, or wovens or knitgoods. It is expedient to convert the novel dye mixtures, before use, into a dye formulation. This is done by milling the dye mixture to an average particle size of 0.1 to 10 microns. Milling can be carried out in the presence of dispersants. Typically, the dried dye mixture is milled with a dispersant, or kneaded in paste form with a dispersant, and thereafter dried under vacuum or by spray drying. Printing pastes and dyebaths can be prepared by adding water to the formulations so obtained. The customary thickeners will be used for printing, for example modified or nonmodified natural products, such as alginates, British gum, gum arable, crystal gum, carob bean gum, tragacanth, cariDoxymethylcellulose, hydroxyethylcellulose, starch or synthetic products, including polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols. The cited materials, especially polyester material, are dyed with the novel dyes in level shades having very good end-use properties, in particular good fastness to light, thernio-fixation, pleating, chlorinating and good fastness to weat treatments, such as fastness to water, sweat and washing; and the dyeings are also distinguished by excellent fastness to rubbing. To be highlighted in particular is the good thermomigration fastness of the dyeings obtained. The novel dyes can also be readily used for obtaining mixed shades in conjunction with other dyes. In addition, the novel dye mixtures are also very suitable for dyeing hydrophobic textile material from supercritical CO2. Further objects of the invention are the aforementioned use of the dye mixtures of this invention and a process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre material, preferably textile material, which comprises applying the novel dye mixture to said material or incorporating it therein. The cited hydrophobic fibre material is preferably polyester textile material. Other substrates which can be treated by the process of this invention and preferred process conditions have been discussed above In the more detailed description of the use of the novel dyes. This invention also relates to the hydrophobic fibre material, preferably polyester textile material, which is dyed or printed by the cited process. The novel dye mixtures are also suitable for modem recording processes, for example thermotransfer printing. The invention is illustrated in more detail by the following Examples. Parts and percentages are by weight, unless othenvise stated. Temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that of the gramme and the cubic centimetre. Example 1: In a reaction vessel, 50 parts by weight of 3-amlnoacetanilide are added to a mixture con¬sisting of 98 parts by weight of methyl chloroacetate and 110 parts by weight of ethyl chloroacetate at room temperature. Subsequently, 58 parts by weight of anhydrous sodium carbonate and 5.2 parts by weight of sodium bromide are added. The reaction mixture is then slowly heated over 3 hours to 115°C and Is stirred for 9 hours at this temperature. After this time, the reaction mixture is cooled to 25°C and charged with 320 parts by weight of cold water. The resultant emulsion is stirred until the salt, which has been added earlier, is completely dissolved. The organic phase Is then separated using a separating funnel and the mixture of methyl chloroacetate and ethyl chloroacetate is distilled therefrom under vacuum. The distillation residue consists of a mixture of about 50% methyl/ethyl ester of formula What is claimed is 1. A dye mixture, which comprises as component (A) a dye of formula wherein D is in each case the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiazole, thiadiazole, indazole, benzotriazole, pyrazole, anthraquinone, hydroxynaphthoic acid imide, chromone or dipheny- lene oxide series, X is in each case hydrogen, halogen, CF3, R3, OR3, NH-CO-R7, NH-CO-ORs, NH-SO2-R7 or 8. A process for the preparation of the coupling component mixture according to claim 7, which comprises reacting an aniline of formula wherein X and Y have the meanings claimed in claim 7, with a mixture of methyl chloroacetate and ethyl chloroacetate in a ratio of 95:5 to 5:95. 9. Use of the dye mixture according to claim 1 for dyeing or printing semi-synthetic or synthetic hydrophobic fibre material. 10. Use according to claim 9, wherein the semi-synthetic or synthetic hydrophobic fibre material is a textile material. 11. Use according to claim 10 for dyeing or printing polyester fibre textile material. 12. A process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre material, which comprises applying the dye mixture claimed in claim 1 to the cited material or incor¬ porating it therein. 13. A process according to claim 12, wherein the hydrophobic fibre material consists of po¬ lyester fibres. 14. The material dyed or printed according to either claim 12 or claim 13. 15. A dye mixture substantially as herein described and exemplified. 16. A process for the preparation of the dye mixture substantially as herein described and exemplified.

Documents:

331-mas-98 abstract duplicate.pdf

331-mas-98 abstract.pdf

331-mas-98 claims duplicate.pdf

331-mas-98 claims.pdf

331-mas-98 correspondecne others.pdf

331-mas-98 correspondecne po.pdf

331-mas-98 description (complete) duplicate.pdf

331-mas-98 description (complete).pdf

331-mas-98 form-1.pdf

331-mas-98 form-19.pdf

331-mas-98 form-26.pdf

331-mas-98 form-4.pdf

331-mas-98 others.pdf

331-mas-98 petition.pdf