Disperse azo dyes, their preparation and use

Abstract

The present invention is represented by the formula (1) [Formula 1] TIFF2023525613000040.tif45159 (in the formula, D represents formula (2) or (3), [chemical 2] TIFF2023525613000041.tif39159R1 and R2 are independently a hydrogen atom; a C6-C6 alkyl group or a C6-C6 alkoxy alkyl group that is unsubstituted or substituted with a cyano group, a carboxy group, a hydroxy group, a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. 10 Aryl group; unsubstituted or unsubstituted cyano group, carboxy group, hydroxy group, C6-C6, optionally interrupted one or more times by -O-, -S-, -NR4-, -CO-, -COO- or -OOC- 10 Aryl group or C6-C 10 C1-C substituted with aryloxy groups 12 represents an alkyl group, and the C6-C 10 Aryl group or the C6-C 10 The aryloxy group is unsubstituted or substituted with a cyano group, a carboxy group, a hydroxy group, a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group; R3 and R4 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a carboxy group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a C6-C 10 represents an arylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylsulfonyl group, a C1-C6 alkylsulfonylamino group, or a C1-C4 alkanoylamino group; and R5 is a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a carboxy group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, or a C6-C 10represents an arylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylsulfonyl group, a C1-C6 alkylsulfonylamino group, or a C1-C4 alkanoylamino group; and R6, R7, R8, and R9 each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a cyano group, a nitro group, or a C1-C4 alkanoylamino group, and groups X independently represent N or CH, provided that at least one group X represents CH. and which are distinguished by good lightfastness.

Description

[Technical field]

[0001] The present invention relates to novel diaminopyrimidine disperse azo dyes, methods for the preparation of such dyes and semi-synthetic processes. or It particularly relates to their use in the dyeing or printing of synthetic hydrophobic fibre materials, more particularly textile materials. [Background technology]

[0002] Diaminopyrimidine disperse azo dyes are known, for example, from GB 1 418 742. However, it has been found that dyeings or prints obtained with the currently known dyes do not in all cases meet the requirements nowadays, especially in terms of lightfastness. There is therefore a need for new dyes which have particularly good lightfastness properties. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] British Patent No. 1 418 742 Summary of the Invention [Means for solving the problem]

[0004] Surprisingly, we have found that nitrogen-containing heteroaromatic ring-substituted diaminopyrimidine disperse azo dyes meet the above requirements and exhibit very good light fastness, especially heat fastness. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] The present invention relates to a compound represented by formula (1) [ka] (In the formula, D represents a group represented by formula (2) or formula (3); [ka] R1 and R2 are independently a hydrogen atom; a C6-C alkyl group unsubstituted or substituted with a cyano group, a carboxy group, a hydroxy group, a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. 10 Aryl groups; unsubstituted or substituted cyano groups, carboxy groups, which may be interrupted one or more times by -O-, -S-, -NR4-, -CO-, -COO- or -OOC-; Hydroxy group, C6-C 10 Aryl group or C6-C 10 C1-C substituted with aryloxy groups 12 Represents an alkyl group, 10 Aryl group or the C6-C 10 The aryloxy group is unsubstituted or substituted with a cyano group, a carboxy group, a hydroxy group, a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group; R3 and R4 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a carboxy group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a C6-C 10 represents an arylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylsulfonyl group, a C1-C6 alkylsulfonylamino group, or a C1-C4 alkanoylamino group, and R5 is a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a carboxy group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, or a C6-C 10 represents an arylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylsulfonyl group, a C1-C6 alkylsulfonylamino group, or a C1-C4 alkanoylamino group, and R6, R7, R8 and R9 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group or a C1-C4 alkanoylamino group; and The groups X independently represent N or CH, provided that at least one group X represents CH. The present invention relates to an azo dye represented by the formula:

[0006] Any group designated as an alkyl group may be a straight or branched chain alkyl group.

[0007] The alkyl group is C1-C6 alkyl group or C1-C 12 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, i-octyl, n-decyl, and n-dodecyl groups. 12 The alkyl group may be interrupted one or more times by -O-, -S-, -NR4-, -CO-, -COO- or -OOC-, and may be interrupted by a cyano group, a carboxy group, a hydroxy group, a C6-C 10 Aryl group or C6-C 10 In an interesting embodiment, the C1-C6 alkyl group is a methyl group or an ethyl group. 12 The alkyl group is a methyl group, an ethyl group, an n-propyl group or an n-butyl group.

[0008] Any group designated an alkoxy group may be a straight or branched alkoxy group.

[0009] C1-C6 alkoxy means, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy or n-hexoxy, in particular methoxy or ethoxy.

[0010] C6-C 10 An aryl group means, for example, a phenyl group or a naphthyl group, preferably a phenyl group which may be substituted with a cyano group, a carboxy group, a hydroxy group, a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group.

[0011] C6-C 10An aryloxy group means, for example, a phenoxy group or a naphthoxy group, preferably a phenoxy group which may be substituted with a cyano group, a carboxy group, a hydroxy group, a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group.

[0012] Any radical designating a halogen atom may be a fluorine, chlorine or bromine atom, in particular a chlorine or bromine atom.

[0013] The C1-C6 alkylcarbonyl group means, for example, an acetyl group, a propionyl group, a butanoyl group, a n-pentanoyl group, an isopentanoyl group, a hexanoyl group or a heptanoyl group.

[0014] C6-C 10 Arylcarbonyl means, for example, a benzoyl or naphthoyl group, preferably a benzoyl group.

[0015] The C1-C6 alkoxycarbonyl group means, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an iso-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentoxycarbonyl group, a neopentoxycarbonyl group, or an n-hexoxycarbonyl group.

[0016] C1-C6 alkylsulfonyl means, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, n-pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl or n-hexylsulfonyl, in particular methylsulfonyl or ethylsulfonyl.

[0017] A C1-C6 alkylsulfonylamino group means, for example, a methylsulfonylamino group, an ethylsulfonylamino group, an n-propylsulfonylamino group, an isopropylsulfonylamino group, an n-butylsulfonylamino group, an isobutylsulfonylamino group, a sec-butylsulfonylamino group, a tert-butylsulfonylamino group, an n-pentylsulfonylamino group, an isopentylsulfonylamino group, a neopentylsulfonylamino group or an n-hexylsulfonylamino group, in particular a methylsulfonylamino group or an ethylsulfonylamino group.

[0018] A C1-C6 alkanoylamino group means, for example, an acetylamino group, a propionylamino group, a butanoylamino group, a n-pentanoylamino group, a isopentanoylamino group or a hexanoylamino group, in particular an acetylamino group or a propionylamino group.

[0019] In a preferred embodiment of the azo dye represented by formula (1), R1 and R2 independently represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methoxyethyl group, a 3-methoxypropyl group, a 4-methoxybutyl group, a 2-ethoxyethyl group, a 3-ethoxypropyl group, a 4-ethoxybutyl group, a phenyl group, a tolyl group, a benzyl group, or a 2-phenylethyl group.

[0020] Tolyl means o-, m- or p-tolyl.

[0021] In a more preferred embodiment of the azo dye represented by formula (1), R1 represents a hydrogen atom, and R2 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methoxyethyl group, a 3-methoxypropyl group, a 4-methoxybutyl group, a 2-ethoxyethyl group, a 3-ethoxypropyl group, a 4-ethoxybutyl group, a phenyl group, a tolyl group, a benzyl group, or a 2-phenylethyl group.

[0022] In an interesting embodiment of the azo dye of formula (1), R1 and R2 represent a hydrogen atom.

[0023] In an interesting embodiment of the azo dye of formula (1), both groups X represent CH In this case, the azo dye represented by formula (1b) [ka] The group represented by the following formula (I) is, for example, a pyridin-2-yl group, a pyridin-3-yl group, or a pyridin-4-yl group.

[0024] In another interesting embodiment of the azo dye of formula (1), one of the radicals X represents CH and the other radical X represents N. In this case, the radical of formula (1b) represents, for example, a pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl or pyrazin-2-yl radical.

[0025] In a preferred embodiment of the azo dye represented by formula (1), R3 and R4 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a methylsulfonyl group, an ethylsulfonyl group, an acetylamino group, or a propionylamino group, and R5 represents a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a methylsulfonyl group, an ethylsulfonyl group, an acetylamino group, or a propionylamino group.

[0026] In a more preferred embodiment of the azo dye represented by formula (1), R3 and R4 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group, and R5 represents a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group.

[0027] In another more preferred embodiment of the azo dye of formula (1), R6, R7, R8 and R9 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an acetylamino group, or a propionylamino group.

[0028] In an interesting embodiment of the azo dye of formula (1), D represents a group of formula (2).

[0029] The present invention also relates to a process for the preparation of an azo dye of formula (1) which comprises diazotizing an amine compound of formula (2a) or formula (3a) according to conventional procedures and then coupling the diazotized amine with a coupling component of formula (1a). [ka] [ka] (In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9 and X are as defined above.)

[0030] The diazotization of the amine compound of formula (2a) or formula (3a) is carried out in a manner known per se, for example with sodium nitrite in an acidic aqueous medium, such as with hydrochloric acid or sulfuric acid. However, the diazotization can also be carried out with other diazotizing agents, for example with nitrosylsulfuric acid. In the diazotization, an additional acid, for example phosphoric acid, sulfuric acid, acetic acid, propionic acid or hydrochloric acid, or a mixture of such acids, for example a mixture of propionic acid and acetic acid, can be present in the reaction medium. The diazotization is advantageously carried out at a temperature between -10°C and 30°C, for example between -10°C and room temperature.

[0031] The coupling of the diazotized compound of formula (2a) or (3a) to the coupling component of formula (1a) is likewise carried out in known manner, for example in an acidic aqueous or aqueous-organic medium, advantageously at temperatures between −10 and 30° C., in particular at temperatures below 10° C. Examples of acids used are hydrochloric acid, acetic acid, propionic acid, sulfuric acid and phosphoric acid.

[0032] Compounds of formula (2a) or formula (3a) are known or can be prepared by methods known per se. Precursors of coupling components of formula (1a) are known or can be prepared by methods known per se, for example, the methods described in Synthesis 2010, No. 7 pp. 1091-1096 (2010).

[0033] The coupling component of formula (1a) is novel. The present invention therefore also relates to a component of formula (1a). [ka] where R1, R2 and X are as defined above and can be used, for example, as a coupling component in the preparation of disperse azo dyes, the preparation of which is described in the experimental section.

[0034] The dyes according to the invention are semi-synthetic or They can be used in particular for dyeing or printing synthetic hydrophobic fibre materials, more in particular textile materials. Textile materials consisting of blended fabrics containing such semi-synthetic or synthetic hydrophobic fibre materials can also be dyed or printed with the dyes according to the invention.

[0035] Semisynthetic fibre materials which come into consideration are in particular cellulose 2 1 / 2 acetate and cellulose triacetate.

[0036] Synthetic hydrophobic fibre materials consist in particular of linear, aromatic polyesters, such as aromatic polyesters of terephthalic acid with glycols, in particular ethylene glycol, or condensation products of terephthalic acid with 1,4-bis(hydroxymethyl)cyclohexane; polycarbonates, such as the polycarbonate of α,α-dimethyl-4,4-dihydroxy-diphenylmethane with phosgene, as well as fibres based on polyvinyl chloride or based on polyamide.

[0037] The application of the dyes according to the invention to the fibre materials is achieved according to known dyeing procedures. For example, polyester fibre materials are dyed in the exhaust process from aqueous dispersions in the presence of conventional anionic or nonionic dispersants and, optionally, conventional swelling agents (carriers) at temperatures between 80 and 140° C. Cellulose 2 1 / 2 acetate is preferably dyed at temperatures between 65 and 85° C. and cellulose triacetate at temperatures between 65 and 115° C.

[0038] The dyes according to the invention do not stain wool and cotton which are simultaneously present in the dyebath, or only slightly stain such materials (under very suitable conditions), so that they can also be used satisfactorily in the dyeing of polyester / wool and polyester / cellulose fibre blends.

[0039] The dyes according to the invention are suitable for dyeing and printing processes by the thermosol process, the exhaust process.

[0040] In such a process, the textile material may be in various processed forms, for example in the form of fibres, yarns or non-woven, woven or knitted fabrics.

[0041] It is advantageous to convert the dyes according to the invention into dye preparations before use. For this purpose, the dyes are milled so that their particle size is on average 0.1 to 10 microns. The milling can be carried out in the presence of a dispersant. For example, the dried dyes are milled with a dispersant or kneaded with a dispersant into a paste and then dried in a vacuum or by spraying. After adding water, the resulting preparations can be used to prepare printing pastes and dye baths.

[0042] For printing, conventional thickeners are used, for example modified or unmodified natural products such as alginates, British gum, gum arabic, crystalline gum, locust bean flour, tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch, or synthetic products such as, for example, polyacrylamides, polyacrylic acids or their copolymers, or polyvinyl alcohol.

[0043] The dyes of formula (1) according to the invention are also suitable as colorants for use in recording systems. Such recording systems are, for example, commercial inkjet printers for paper or textile printing, or writing instruments such as fountain pens or ballpoint pens, in particular inkjet printers. For this purpose, the dyes according to the invention are first made into a form suitable for use in the recording system. A suitable form is, for example, an aqueous ink comprising the dyes according to the invention as colorants. The inks can be prepared in the conventional manner by mixing the individual components together in the desired amount of water, optionally in combination with a suitable dispersant.

[0044] The dyes according to the invention impart to said materials, in particular polyester materials, stable shades having very good practical fastness properties, in particular good light fastness, heat fastness, pleat fastness, chlorine fastness and wet fastness, e.g. water fastness, sweat fastness and wash fastness. the finished dyeings are furthermore characterised by very good rubbing fastness. Particular emphasis should be placed on the good fastness properties of the dyeings obtained with respect to light.

[0045] Furthermore, the dyes and dye mixtures according to the invention are also well suited for dyeing hydrophobic fibre materials from supercritical CO2.

[0046] The present invention relates to the above-mentioned use of the dyes according to the invention and to a method for dyeing or printing semi-synthetic or synthetic hydrophobic fiber materials, in particular textile materials, in which the dyes according to the invention are applied to or mixed into said materials. The hydrophobic fiber materials are preferably textile polyester materials. Further substrates that can be treated by the method according to the invention and preferred method conditions can be found above in the more detailed description of the use of the dyes according to the invention.

[0047] In the case of inkjet printing, individual droplets of ink are sprayed from a nozzle in a controlled manner onto a substrate. The main processes used for this purpose are the continuous inkjet and the drop-on-demand processes. In the case of the continuous inkjet process, droplets are generated continuously, and those not required for the printing operation are discharged into a container and reused. In the case of the drop-on-demand process, droplets are generated as needed and used for printing; that is, droplets are generated only when they are required for the printing operation. The generation of droplets can be carried out, for example, by a piezo inkjet head or by thermal energy (bubble jet). Printing with a piezo inkjet head and printing with the continuous inkjet process are preferred.

[0048] The present invention therefore also relates to an aqueous ink comprising the dye of formula (1) according to the present invention and the use of such an ink in an inkjet printing process for printing various substrates, in particular textile fibre materials, the above definitions and preferences applying for the dye, the ink and the fabric.

[0049] The present invention also relates to hydrophobic fibre materials, preferably polyester textile materials, dyed or printed by the above-described process.

[0050] The dyes according to the invention are furthermore suitable for modern reproduction methods such as, for example, thermal transfer printing.

[0051] The following examples serve to illustrate the invention. Unless otherwise stated, the parts therein are parts by weight and the percentages are percentages by weight. Temperatures are given in degrees Celsius. Parts by weight and parts by volume have the same relationship as the gram and cubic centimeter. EXAMPLES

[0052] I. Manufacturing example Example 1: Dye represented by formula (101) [ka]

[0053] Process A: The starting compound pyrazine-2-carbonitrile was converted to pyrazine-2-carboximidamide hydrochloride according to the following scheme as described in Synthesis 2010, No. 7 pp. 1091-1096 (2010). A white solid was obtained in 85% yield. [ka]

[0054] Process B: As described in Synthesis 2010, No. 7 pp. 1091-1096 (2010), the pyrazine-2-carboximidamide hydrochloride obtained by step A was converted to 2-(pyrazin-2-yl)pyrimidine-4,6-diol according to the following scheme. A light brown solid was obtained in 94% yield. 1 H-NMR (DMSO-d6, 250 MHz): δ = 9.37 (d, 1H, aromat. H), 8.87 (d, 1H, aromat. H), 8.81 (dd, 1H, aromat H), 5.48 (s, 1H, aromat H) [ka]

[0055] Process C: As described in Synthesis 2010, No. 7 pp. 1091-1096 (2010), 2-(pyrazin-2-yl)pyrimidine-4,6-diol obtained by step B was converted to 4,6-dichloro-2-(pyrazin-2-yl)pyrimidine with phosphorus oxychloride according to the following scheme. A white solid was obtained in 68% yield. 1H-NMR (DMSO-d6, 250 MHz): δ = 9.49 (d, 1H, aromat. H), 8.89 (m, 2H, aromat. H) , 8.20 (s, 1H, aromat H) [ka]

[0056] Process D: A suspension of 77.2 g of 4,6-dichloro-2-(pyrazin-2-yl)pyrimidine in 750 mL of concentrated ammonia was stirred at 87° C. and 6.5 bar for 22 hours. After cooling to room temperature, the mixture was filtered off and the filter cake was washed neutral with water. After drying, 52.8 g of 4-amino-6-chloro-2-(pyrazin-2-yl)pyrimidine was obtained as a brown solid compound. 1 H-NMR (DMSO-d6, 250 MHz): δ = 9.34 (d, 1H, aromat. H), 8.75 (m, 2H, aromat. H), 7.54 (s broad, 2H, NH2), 6.52 (s, 1H, aromat H).

[0057] Process E: 50 g of 4-amino-6-chloro-2-(pyrazin-2-yl)pyrimidine was added to 200 g of aniline. The mixture was stirred at 105° C. for 7 hours. After completion of the reaction, excess aniline was distilled by adding 1.4 L of water at a temperature of 75-100° C. within 5 hours. After addition of hydrochloric acid, the reaction mixture was filtered and the filter cake was washed with water until neutral. After drying, 63.6 g of 4-amino-6-phenylamino-2-(pyrazin-2-yl)pyrimidine was obtained as a dark solid compound. 1H-NMR (DMSO-d6, 250 MHz): δ = 10.68 (s broad, 1H, NH), 9.42 (d, 1H, aromat. H), 8.97 (d, 1H, aromat. H), 8.89 (dd, 1H, aromat. H), 8.13 (s broad, 2H, NH2), 7.54 (d, 2H, aromat. H), 7.44 (t, 2H, aromat. H), 7.18 (t, 1H, aromat. H), 5.60 (s, 1H, aromat. H).

[0058] Process F: 2 g of 4-chloro-2-trifluoromethylaniline was diazotized in a mixture of 30 g of acetic acid, 5.5 g of sulfuric acid, 13 g of water and 3.4 g of nitrosylsulfuric acid at a temperature of -3 to 6°C within 5.5 hours. The diazo solution was then added to a mixture of 2.7 g of 4-amino-6-phenylamino-2-(pyrazin-2-yl)pyrimidine obtained from step E, 100 g of acetic acid (80%), 250 g of water and 13 g of aqueous ammonia (28%) at a temperature of about 5°C within 5 minutes. The mixture was then allowed to warm to room temperature within 15 hours. After adding 100 g of ethanol, the mixture was filtered. The filter cake was washed with water. The product was stirred in 300 g of methanol, 100 g of NMP and 50 g of water to clean it. After filtering and washing with water, the compound was dried. 1.5 g of dye of formula (101) was obtained as a red solid compound. 1 H-NMR (CDCl3, 250 MHz): δ = 9.68 (d, 1H, aromat. H), 8.78 (dd, 1H, aromat. H), 8.70 (d, 1H, aromat. H), 7.79 (m, 4H, aromat. H), 7.63(dd, 1H, aromat. H), 7.46 (t, 2H, aromat. H), 7.23 (t, 1H, aromat. H).

[0059] Preparation of 4,6-diamino-2-(pyrazin-2-yl)pyrimidine: A suspension of 31.5 g of 4,6-dichloro-2-(pyrazin-2-yl)pyrimidine in 400 mL of concentrated ammonia was stirred at 175° C. and 28 bar for 21 h. After cooling to room temperature, the aqueous ammonia was removed on a rotary evaporator and the residue was dissolved in DMF / toluene. After recrystallization and drying, 20.8 g of 4,6-diamino-2-(pyrazin-2-yl)pyrimidine was obtained as a brown solid compound. 1 H-NMR (DMSO-d6, 250 MHz): δ = 9.35 (d, 1H, aromat. H), 8.79 (d, 1H, aromat. H), 8.76 (dd, 1H, aromat. H), 7.06 (s broad, 4H, NH2), 5.60 (s, 1H, aromat H).

[0060] The dyes of Production Examples 2 to 114 described in the following table can be produced in the same manner as in Production Example 1 above.

[0061] [Table 1] TIFF0007599497000012.tif211155TIFF0007599497000013.tif231155TIFF0007599 497000014.tif216156TIFF0007599497000015.tif237154TIFF0007599497000016.t if224154TIFF0007599497000017.tif230154TIFF0007599497000018.tif230155TIF F0007599497000019.tif211158TIFF0007599497000020.tif210156TIFF00075994970 00021.tif218156TIFF0007599497000022.tif224154TIFF0007599497000023.tif24 5155TIFF0007599497000024.tif232156TIFF0007599497000025.tif245154TIFF000 7599497000026.tif245155TIFF0007599497000027.tif236155TIFF00075994970000 28.tif237155TIFF0007599497000029.tif236155TIFF0007599497000030.tif168155

[0062] II. Application Examples Application example 1: 1 part by weight of the dyestuff of formula (101) according to Preparation Example 1 was ground with 4 parts by weight of a commercial dispersant and 15 parts by weight of water. This formulation was used to produce a 1% dyeing (based on dyestuff and substrate) on a woven polyester fabric by the hot exhaust process at 135°C. Test results: The lightfastness of the dyed products was good, as were the results of the VDA 75202 5 cycle and SAE J2412 488 kJ tests. The build-up of the dyes was very good.

[0063] Application examples 2 to 114: Application example 1 was repeated, but using the dyestuffs of preparation examples 2 to 114 instead of the dyestuff of formula (101) according to preparation example 1. The build-up of the dyestuffs was very good and the dyeings showed good lightfastness and very good results in the VDA 75202 5 cycle and SAE J2412 488 kJ tests.

[0064] Comparative Example Application Example 1 was repeated using dyes disclosed in GB1418742. The dyes disclosed in GB1418742 correspond to substituted diaminopyrimidine disperse azo dyes, but GB1418742 does not disclose diaminopyrimidine disperse azo dyes substituted with nitrogen-containing heteroaromatic rings. The examples of dyes disclosed in GB1418742 and used in this Comparative Example 1 and Comparative Example 2 are according to the following structures: [ka]

[0065] The lightfastness and color change after heat and light exposure obtained using dyes according to GB1418742 were compared with those obtained using dyes according to Application Example 22 and Application Example 24. [ka]

[0066] The results obtained according to the SAE J2412 488kJ standard are summarized below: [Table 2]

[0067] The loss of color strength after exposure to heat light according to the SAE J2412 488 kJ test using the dye according to the invention (corresponding to Preparation Example 22) is slightly better than that using the dye according to GB1418742.

[0068] Color change (abbreviated as dE ab* or dE* ) was calculated according to the following formula:

number

[0069] The color change after exposure to heat and light according to the SAE J2412 488 kJ test using the dye according to the present invention (corresponding to Preparation Example 22) is significantly better than the color change using the dye according to GB 1418742. This surprising result is due to the presence of the substituted nitrogen-containing heteroaromatic ring in the dye according to the present invention.

Claims

1. Formula (1) 【Chemistry 1】 (In the formula, D represents a group represented by formula (2) or formula (3); 【Chemistry 2】 R １ and R ２ are independently a hydrogen atom; an unsubstituted or substituted cyano group, a carboxy group, a hydroxy group, a halogen atom, C １ -C ６ Alkyl group, or C １ -C ６ Alkoxy-substituted C ６ -C １０ Aryl group; -O-, -S-, -NR ４ -, -CO-, -COO- or - An unsubstituted or substituted cyano group, a carboxy group, a hydroxy group, C, which may be interrupted one or more times by OOC- ６ -C １０ Aryl group or C ６ -C １０ C substituted with an aryloxy group １ -C １２ represents an alkyl group, ６ -C １０ Aryl group or the C ６ -C １０ The aryloxy group is unsubstituted or substituted with a cyano group, a carboxy group, a hydroxy group, a halogen atom, C １ -C ６ Alkyl group, or C １ -C ６ is substituted with an alkoxy group, R ３ and R ４ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a carboxy group, １ -C ６ Alkyl group, C １ -C ６ Alkoxy group, C １ -C ６ Alkylcarbonyl group, C ６ -C １０ Arylcarbonyl group, C １ -C ６ Alkoxycarbonyl group, C １ -C ６ Alkylsulfonyl group, C １ -C ６ Alkylsulfonylamino group or C １ -C ４ represents an alkanoylamino group, and R ５ is a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a carboxy group, C １ -C ６ Alkyl group, C １ -C ６ Alkoxy group, C １ -C ６ Alkylcarbonyl group, C ６ -C １０ Arylcarbonyl group, C １ -C ６ Alkoxycarbonyl group, C １ -C ６ Alkylsulfonyl group, C １ -C ６ Alkylsulfonylamino group or C １ -C ４ represents an alkanoylamino group, and R ６ , R ７ , R ８ and R ９ are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, or C １ -C ４ represents an alkanoylamino group, and The groups X independently represent N or C-H, provided that at least one group X represents C-H. An azo dye represented by the formula:

2. R １ and R ２ are independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methoxyethyl group, a 3-methoxypropyl group, a 4-methoxybutyl group, a 2-ethoxyethyl group, a 3-ethoxypropyl group, a 4-ethoxybutyl group, a phenyl group, a tolyl group, a benzyl group, or a 2-phenylethyl group.

3. R １ represents a hydrogen atom, and R ２ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methoxyethyl group, a 3-methoxypropyl group, a 4-methoxybutyl group, a 2-ethoxyethyl group, a 3-ethoxypropyl group, a 4-ethoxybutyl group, a phenyl group, a tolyl group, a benzyl group, or a 2-phenylethyl group.

4. R １ and R ２ The azo dye represented by formula (1) according to any one of claims 1 to 3, wherein represents a hydrogen atom.

5. 5. An azo dye of formula (1) according to claim 1, wherein both groups X are C-H.

6. R ３ and R ４ each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a methylsulfonyl group, an ethylsulfonyl group, an acetylamino group, or a propionylamino group, and R ５ The azo dye represented by formula (1) according to any one of claims 1 to 5, wherein represents a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, a methylsulfonyl group, an ethylsulfonyl group, an acetylamino group, or a propionylamino group.

7. R ３ and R ４ each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group, and R ５ The azo dye represented by formula (1) according to claim 6 , wherein represents a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group.

8. R ６ , R ７ , R ８ and R ９ The azo dye represented by formula (1) according to claim 1 , wherein each of the formulas represents independently a hydrogen atom, a hydroxyl group, a halogen atom, an acetylamino group, or a propionylamino group.

9. The azo dye represented by formula (1) according to any one of claims 1 to 7, wherein D represents a group represented by formula (2).

10. A process for the preparation of an azo dye of formula (1) according to claim 1, which comprises diazotising an amine compound of formula (2a) or formula (3a) according to conventional procedures and then coupling the diazotised amine with a coupling component of formula (1a). 【Chemistry 3】 【Chemistry 4】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ and X is as defined in claim 1.

11. A method for dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials, comprising the steps of: A method in which a dye of formula (1) as defined in claim 1 is applied to or incorporated into the material.

12. 2. Use of the azo dyes of formula (1) according to claim 1 in the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials.

13. The use described in claim 12, wherein the semi-synthetic or synthetic hydrophobic fiber material is a textile material.

14. 12. A semi-synthetic or synthetic hydrophobic fibre material dyed or printed by the method according to claim 11.

15. The material of claim 14, wherein the semi-synthetic or synthetic hydrophobic fiber material is a woven material.

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