High wet fast sulphur containing cyanophenyl group containing disperse dye mixtures

Abstract

The present invention relates to dye mixtures comprising a dye of formula (1) and a dye of formula (2), to a process for the production and to the use of the dye mixtures.

Description

(I) Technical Field

[0001] This invention relates to a mixture of disperse dyes containing thiocyanate groups with high wet fastness. (II) Background Technology

[0002] Disperse azo dyes (1) with substitution patterns 2,4,5- in the diazo component are known, such as US4619993, DD209641, GB 2 020 680, US 4,379,819, WO 2005 / 056690, WO 2005 / 040283 and WO2016 / 041849. Dyes and mixtures thereof with general formula (2) are also known, such as EP 0 864 615, EP 0894 830, EP 0 555 179, WO 2006 / 131530 and WO 2002 / 081572, but their lifting power for darker shades is unsatisfactory, and / or their wash fastness and contact fastness are insufficient. (III) Summary of the Invention

[0003] It has been found that certain combinations of azo dyes of formula (1) and dyes of formula (2) can result in improved lifting power and good wash fastness and contact fastness properties in polyesters and polyester blends, especially in polyester-elastomeric / polyester-spandex fabrics. Therefore, the present invention relates to a dye mixture comprising...

[0004] At least one dye of formula (1)

[0005]

[0006] Among them, each is independent

[0007] R 1 It is hydrogen, (C1-C4)-alkyl, or (C1-C4)-alkoxy.

[0008] R 2 It is hydrogen, carboxyl, (C1-C4)-alkyl, halogen, amide, -NHCO-aryl, -NHCO-benzyl, or sulfonamide, R 3 and R 4 It is hydrogen, (C1-C4)-alkyl, (CH2) n -Phenyl, CH2-CH=CH2, (CH2) n -OH, (CH2) n -O-(C1-C4)-alkyl, (CH2) n -O-phenyl, (CH2) n -O-benzyl, (CH2) n -O-(CH2) m -OH, (CH2) n-O-(CH2) m -O-(C1-C4)-alkyl, (CH2) n -O-(CH2) m -O-phenyl, (CH2) n -O-(CH2) m -O-benzyl, (CH2) n -COOH, (CH2) n -COO-(C1-C4)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C4)-alkyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C4)-alkyl, (CH2) n -O-CO-phenyl, (CH2) n -O-CO-benzyl, COO-(CH2) n -2-Furfuryl, (CH2) m -O-(CH2) n -2-Furfuryl, CHR 9 -(CH2) p -(C1-C4)-alkyl, CHR 9 -(CH2) p Phenyl, CHR 9 -CH=CH2, CHR 9 -(CH2) p -OH, CHR 9 -(CH2) p -O-(C1-C4)-alkyl, CHR 9 -(CH2) p -O-phenyl, CHR 9 -(CH2) p -O-benzyl, CHR 9 -(CH2) p -O-(CH2) m -OH, CHR 9 -(CH2) p -O-(CH2) m -O-(C1-C4)-alkyl, CHR 9 -(CH2) p -O-(CH2) m -O-phenyl, CHR9 -(CH2) p -O-(CH2) m -O-benzyl, CHR 9 -(CH2) p -COOH, CHR 9 -(CH2) p -COO-(C1-C4)-alkyl, CHR 9 -(CH2) p -COO-phenyl, CHR 9 -(CH2) p -COO-benzyl, CHR 9 -(CH2) p -CN、CHR 9 -(CH2) p -COO(CH2) m -CO-(C1-C4)-alkyl, CHR 9 -(CH2) p -COO(CH2) m -CO-phenyl, CHR 9 -(CH2) p -COO(CH2) m -CO-benzyl, CHR 9 -(CH2) p -O-CO-(C1-C4)-alkyl, CHR 9 -(CH2) p -O-CO-phenyl, CHR 9 -(CH2) p -O-CO-benzyl, CHR 9 -(CH2) p -2-Furfuryl or CHR 9 -(CH2) p -O-(CH2) n -2-Furfuryl,

[0009] in

[0010] R 9 It is a (C1-C4)-alkyl or a (C1-C4)-alkyl substituted with -OH or halogen.

[0011] n is between 1 and 4.

[0012] m is between 1 and 4, and

[0013] p is between 0 and 3.

[0014] The condition is that at least R 3 and R 4 One of them is not hydrogen.

[0015] and

[0016] At least one dye of formula (2)

[0017]

[0018] Each of them is independent

[0019] R 5 and R 6 It is hydrogen, (C1-C4)-alkyl, (CH2) n -Phenyl, CH2-CH=CH2, (CH2) n -OH, (CH2) n -O-(C1-C4)-alkyl, (CH2) n -O-phenyl, (CH2) n -O-benzyl, (CH2) n -O-(CH2) m -OH, (CH2) n -O-(CH2) m -O-(C1-C4)-alkyl, (CH2) n -O-(CH2) m -O-phenyl, (CH2) n -O-(CH2) m -O-benzyl, (CH2) n -COOH, (CH2) n -COO-(C1-C4)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C4)-alkyl, (CH2) n -COO(CH2) m -CO-phenyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C4)-alkyl, (CH2) n -O-CO-phenyl, (CH2) n -O-CO-benzyl, COO-(CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0020] in

[0021] n is between 1 and 4, and

[0022] m ranges from 1 to 4.

[0023] The condition is that at least R 5 and R 6 One of them is not hydrogen.

[0024] R 10 It is hydrogen, (C1-C4)-alkyl, or (C1-C4)-alkoxy.

[0025] R 11 It can be hydrogen, carboxyl, (C1-C4)-alkyl, halogen, amide, -NHCO-aryl, -NHCO-benzyl, or sulfonamide.

[0026] X 5 and X 6 It can be hydrogen, halogen, nitro or cyano.

[0027] The condition is that at least X 5 and X 6 One of them is not hydrogen.

[0028] and

[0029] L represents hydrogen or

[0030] X 6 For nitro, X 5 In the case of hydrogen, L represents either hydrogen or fluorine.

[0031] Regarding dyes of formula (1) and formula (2), there are preferred dyes to form an overall preferred combination:

[0032] Regarding the selection of dyes of formula (1), the dye mixtures described above are preferred, wherein in at least one dye of formula (1), the dyes are independent of each other.

[0033] R 1 It is hydrogen, methyl, or methoxy.

[0034] R 2 It can be hydrogen, hydroxyl, COOH, COO-(C1-C2)-alkyl, (C1-C2)-alkyl, -NHCO-(C1-C2)-alkyl, -NHCO-aryl, -NHCO-benzyl, or -NHSO2-(C1-C2)-alkyl.

[0035] R 3 and R 4 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2)m -O-(C1-C2)-alkyl, (CH2)2-O-(CH2) m -O-phenyl, (CH2)2-O-(CH2) m -O-benzyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, (CH2) n -O-CO-benzyl, COO-(CH2) n -2-Furfuryl, (CH2) m -O-(CH2) n -2-Furfuryl, CHR 9 -CH=CH2, CHR 9 -(CH2) p -O-(C1-C2)-alkyl, CHR 9 -(CH2) p -O-phenyl, CHR 9 -(CH2) p -O-benzyl, CHR 9 -(CH2) p -O-(CH2) m -O-(C1-C2)-alkyl, CHR 9 -(CH2) p -O-(CH2) m -O-phenyl, CHR 9 -(CH2) p -O-(CH2) m -O-benzyl, CHR 9 -(CH2) p -COO-(C1-C2)-alkyl, CHR 9 -(CH2) p -COO-phenyl, CHR 9 -(CH2) p -COO-benzyl, CHR 9 -(CH2) p -CN、CHR9 -(CH2) p -COO(CH2) m -CO-(C1-C2)-alkyl, CHR 9 -(CH2) p -COO(CH2) m -CO-phenyl, CHR 9 -(CH2) p -COO(CH2) m -CO-benzyl, CHR 9 -(CH2) p -O-CO-(C1-C2)-alkyl, CHR 9 -(CH2) p -O-CO-phenyl or CHR 9 -(CH2) p -O-CO-benzyl,

[0036] in

[0037] R 9 It is a (C1-C4)-alkyl or a (C1-C4)-alkyl substituted with -OH or halogen.

[0038] n is 1 or 2,

[0039] m is 1 or 2, and

[0040] p is 0 or 1

[0041] The condition is that at least R 3 and R 4 One of them is not hydrogen.

[0042] More preferably, the above-mentioned dye mixture, wherein in at least one dye of formula (1), each independent R 1 It is hydrogen or methoxy.

[0043] R 2 It is hydrogen, methyl, or -NHCO-(C1-C2)-alkyl.

[0044] R 3 and R 4 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n-COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl, (CH2) m -O-(CH2) n -2-Furfuryl or CHR 9 -(CH2) p -COO-(C1-C2)-alkyl,

[0045] in

[0046] R 9 It is (C1-C4)-alkyl.

[0047] n is 1 or 2,

[0048] m is 1 or 2, and

[0049] The condition is that at least R 3 and R 4 One of them is not hydrogen.

[0050] The above-mentioned dye mixture, wherein at least one of the dyes of formula (1) is a dye of formula (1a).

[0051]

[0052] Each of them is independent

[0053] R 3 and R 4 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m-CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl, (CH2) m -O-(CH2) n -2-Furfuryl or CHR 9 -(CH2) p -COO-(C1-C2)-alkyl,

[0054] in

[0055] R 9 It is (C1-C4)-alkyl.

[0056] n is 1 or 2,

[0057] m is 1 or 2, and

[0058] p is 0 or 1

[0059] The condition is that at least R 3 and R 4 One of them is not hydrogen, and R 7 and R 8 It is ethyl or methyl.

[0060] This is a preferred embodiment of the present invention.

[0061] The above-mentioned dye mixtures, wherein at least one dye of formula (1) is a dye of formula (1b).

[0062]

[0063] Each of them is independent

[0064] R 3 and R 4 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n-COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl, (CH2) m -O-(CH2) n -2-Furfuryl or CHR 9 -(CH2) p -COO-(C1-C2)-alkyl,

[0065] in

[0066] R 9 It is (C1-C4)-alkyl.

[0067] n is 1 or 2,

[0068] m is 1 or 2, and

[0069] p is 0 or 1

[0070] The condition is that at least R 3 and R 4 One of them is not hydrogen, and R 7 It is ethyl or methyl.

[0071] This is a preferred embodiment of the present invention.

[0072] The above-mentioned dye mixture, wherein at least one of the dyes of formula (1) is a dye of formula (1c).

[0073]

[0074] Each of them is independent

[0075] R 3 and R 4 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2)n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl, (CH2) m -O-(CH2) n -2-Furfuryl or CHR 9 -(CH2) p -COO-(C1-C2)-alkyl,

[0076] in

[0077] R 9 It is (C1-C4)-alkyl.

[0078] n is 1 or 2,

[0079] m is 1 or 2, and

[0080] p is 0 or 1

[0081] The condition is that at least R 3 and R 4 One of them is not hydrogen.

[0082] This is yet another preferred embodiment of the present invention.

[0083] The preferred dye mixture is the one containing at least one dye of formula (1) selected from the following:

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] Regarding the selection of dyes in formula (2), the dye mixtures described above are preferred, wherein in at least one dye of formula (2), the dyes are independent of each other.

[0096] R 5 and R 6 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2)2-O-(CH2) m -O-phenyl, (CH2)2-O-(CH2) m -O-benzyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-phenyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, (CH2) n -O-CO-benzyl, COO-(CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0097] in

[0098] n is 1 or 2, and

[0099] m is 1 or 2

[0100] The condition is that at least R 5 and R 6 One of them is not hydrogen.

[0101] R 10 It is hydrogen, methyl, or methoxy.

[0102] R 11 It can be hydrogen, hydroxyl, COOH, COO-(C1-C2)-alkyl, (C1-C2)-alkyl, -NHCO-(C1-C2)-alkyl, -NHCO-aryl, -NHCO-benzyl, or -NHSO2-(C1-C2)-alkyl.

[0103] X 5 and X 6 It can be hydrogen, chlorine, bromine, nitro or cyano.

[0104] The condition is that at least X 5 and X 6 One of them is not hydrogen

[0105] and

[0106] L represents hydrogen or

[0107] X 6 For nitro, X 5 In the case of hydrogen, L represents either hydrogen or fluorine.

[0108] More preferably, the above-mentioned dye mixture, wherein in at least one dye of formula (2), each independent R 5 and R 6 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-phenyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0109] in

[0110] n is 1 or 2, and

[0111] m is 1 or 2

[0112] The condition is that at least R 5 and R 6 One of them is not hydrogen.

[0113] R 10 It is hydrogen or methoxy.

[0114] R 11 It is hydrogen, methyl, or -NHCO-(C1-C2)-alkyl.

[0115] X 5 and X 6 It can be hydrogen, bromine, chlorine, nitro or cyano.

[0116] The condition is that at least X 5 and X 6 One of them is not hydrogen

[0117] and

[0118] L represents hydrogen or

[0119] X 6 For nitro, X 5 In the case of hydrogen, L represents either hydrogen or fluorine.

[0120] The above-mentioned dye mixture, wherein at least one of the dyes of formula (2) is a dye of formula (2a).

[0121]

[0122] Each of them is independent

[0123] R 5 and R 6 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n-COO(CH2) m -CO-phenyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0124] in

[0125] n is 1 or 2, and

[0126] m is 1 or 2, meaning m is either 1 or 2.

[0127] The condition is that at least R 5 and R 6 One of them is not hydrogen.

[0128] R 7 and R 8 It is ethyl or methyl.

[0129] X 5 It can be hydrogen, bromine, chlorine, nitro or cyano.

[0130] X 6 It can be hydrogen, nitro or cyano.

[0131] The condition is X 5 and X 6 Not both nitro,

[0132] and

[0133] L represents hydrogen or

[0134] X 6 For nitro, X 5 In the case of hydrogen, L represents either hydrogen or fluorine.

[0135] This is a preferred embodiment of the present invention.

[0136] The above-mentioned dye mixtures, wherein at least one of the dyes of formula (2) is a dye of formula (2b).

[0137]

[0138] R 5 and R 6It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -

[0139] COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -

[0140] COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-phenyl, (CH2) n -

[0141] COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-

[0142] (CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0143] in

[0144] n is 1 or 2, and

[0145] m is 1 or 2

[0146] The condition is that at least R 5 and R 6 One of them is not hydrogen, and

[0147] R 7 It is ethyl or methyl, and

[0148] X 5 It can be hydrogen, bromine, chlorine, nitro, or cyano, and

[0149] X 6 It can be hydrogen, nitro or cyano.

[0150] The condition is X 5 and X 6 Not both nitro,

[0151] and

[0152] L represents hydrogen or

[0153] X 6 For nitro, X 5 In the case of hydrogen, L represents either hydrogen or fluorine.

[0154] This is another preferred embodiment of the present invention.

[0155] The above-mentioned dye mixture, wherein at least one of the dyes of formula (2) is a dye of formula (2c).

[0156]

[0157] Each of them is independent

[0158] R 2 It is hydrogen or -NHCO-(C1-C2)-alkyl.

[0159] R 5 and R 6 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-phenyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0160] in

[0161] n is 1 or 2, and

[0162] m is 1 or 2

[0163] The condition is that at least R 5 and R 6 One of them is not hydrogen.

[0164] X 5 and X 6 It is bromine or chlorine.

[0165] This is another preferred embodiment of the present invention.

[0166] The above-mentioned dye mixtures, wherein at least one of the dyes of formula (2) is a dye of formula (2d).

[0167]

[0168] Each of them is independent

[0169] R 5 and R 6 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-phenyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0170] in

[0171] n is 1 or 2, and

[0172] m is 1 or 2

[0173] The condition is that at least R 5 and R 6 One of them is not hydrogen.

[0174] R 7 Ethyl or methyl

[0175] R 10 It is hydrogen, methyl, or methoxy.

[0176] X 6 It can be chlorine, bromine, nitro or cyano.

[0177] and

[0178] L represents hydrogen or

[0179] X 6 In the case of a nitro group, L is either hydrogen or fluorine.

[0180] This is another preferred embodiment of the present invention.

[0181] The preferred dye mixture is the one containing at least one dye of formula (2) selected from the following:

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193] In addition, regarding the quantity of different dyes selected from the above dye mixture, there are preferred dye mixtures: the preferred dye mixture includes a dye of formula (1) and a dye of formula (2).

[0194] The preferred dye mixture includes two dyes of formula (1) and one dye of formula (2).

[0195] The preferred dye mixture includes one dye of formula (1) and two dyes of formula (2).

[0196] The preferred dye mixture includes two dyes of formula (1) and two dyes of formula (2).

[0197] The dye mixtures described above are particularly preferred, wherein the preferred formula (1) dye and the preferred formula (2) dye are combined, for example, in a dye mixture, wherein the Rs are independent of each other. 1 It is hydrogen, methyl, or methoxy.

[0198] R 2 It can be hydrogen, hydroxyl, COOH, COO-(C1-C2)-alkyl, (C1-C2)-alkyl, -NHCO-(C1-C2)-alkyl, -NHCO-aryl, -NHCO-benzyl, or -NHSO2-(C1-C2)-alkyl.

[0199] R 3 To R 6 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m -O-(C1-C2)-alkyl, (CH2)2-O-(CH2) m -O-phenyl, (CH2)2-O-(CH2) m -O-benzyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-phenyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, (CH2) n -O-CO-benzyl, COO-(CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0200] in

[0201] n is 1 or 2, and

[0202] m is 1 or 2

[0203] The condition is that R in equation (1) 3 and R 4 It is not (CH2)n-COO(CH2)m-CO-phenyl, and at least R in formula (1) 3 and R 4 One of them is not hydrogen, and at least R in equation (2) 5 and R 6 One of them is not hydrogen.

[0204] R 10 It is hydrogen, methyl, or methoxy.

[0205] R 11 It can be hydrogen, hydroxyl, COOH, COO-(C1-C2)-alkyl, (C1-C2)-alkyl, -NHCO-(C1-C2)-alkyl, -NHCO-aryl, -NHCO-benzyl, or -NHSO2-(C1-C2)-alkyl.

[0206] X 5 and X 6 It can be hydrogen, chlorine, bromine, nitro or cyano.

[0207] The condition is that at least X in equation (2) 5 and X 6 One of them is not hydrogen

[0208] and

[0209] L represents hydrogen or

[0210] X 6 For nitro, X 5 In the case of hydrogen, L represents either hydrogen or fluorine.

[0211] Therefore, even more preferred are dye mixtures as described above, wherein the Rs are independent of each other. 1 It is hydrogen or methoxy.

[0212] R 2 It is hydrogen, methyl, or -NHCO-(C1-C2)-alkyl.

[0213] R 3 To R 6 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2)2-O-phenyl, (CH2)2-O-benzyl, or (CH2)2-O-(CH2) m-O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -COO-phenyl, (CH2) n -COO-benzyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -COO(CH2) m -CO-phenyl, (CH2) n -COO(CH2) m -CO-benzyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl, COO-(CH2) n -2-Furfuryl or (CH2) m -O-(CH2) n -2-Furfuryl,

[0214] in

[0215] n is 1 or 2, and

[0216] m is 1 or 2

[0217] The condition is that R in equation (1) 3 and R 4 It is not (CH2)n-COO(CH2)m-CO-phenyl, and at least R in formula (1) 3 and R 4 One of them is not hydrogen, and at least R in equation (2) 5 and R 6 One of them is not hydrogen.

[0218] R 10 It is hydrogen or methoxy.

[0219] R 11 It is hydrogen, methyl, or -NHCO-(C1-C2)-alkyl.

[0220] X 5 and X 6 It can be hydrogen, bromine, chlorine, nitro or cyano.

[0221] The condition is that at least X in equation (2) 5 and X 6 One of them is not hydrogen

[0222] and

[0223] L represents hydrogen or

[0224] X 6 For nitro, X 5 In the case of hydrogen, L represents either hydrogen or fluorine.

[0225] The dye mixture described above is particularly preferred to include at least one dye of formula (1a) and at least one dye of formula (2a).

[0226] The preferred dye mixtures include:

[0227] - At least one dye of formula (1a) and at least one dye of formula (2b),

[0228] - At least one dye of formula (1a) and at least one dye of formula (2c),

[0229] - At least one dye of formula (1a) and at least one dye of formula (2d),

[0230] - At least one dye of formula (1b) and at least one dye of formula (2a),

[0231] - At least one dye of formula (1b) and at least one dye of formula (2b),

[0232] - At least one dye of formula (1b) and at least one dye of formula (2c),

[0233] - At least one dye of formula (1b) and at least one dye of formula (2d).

[0234] The preferred dye mixture includes at least one dye selected from dyes (1-1)-(1-43) and at least one dye selected from dyes (2-1)-(2-54).

[0235] Preferably, the dye mixture comprises one or more dyes selected from dyes of formulas (3), (4), and (5).

[0236]

[0237] Each of them is independent

[0238] X 4 It is hydrogen or nitro.

[0239] Y 2 It is (C1-C4)-alkyl, phenyl, or (CH2). m -phenyl,

[0240] Y 4 It is (C1-C8)-alkyl or (CH2) m -phenyl,

[0241] Y 6It is hydrogen, nitro, cyano, carboxyl, (C1-C4)-alkyl or (C1-C4)-alkoxy, and m is 1 to 4.

[0242] More preferably, the above dye mixture includes one or more dyes selected from dyes of formulas (3), (4), and (5), wherein

[0243] X 4 It is hydrogen or nitro.

[0244] Y 2 It is (C1-C4)-alkyl or (CH2) m -phenyl,

[0245] Y 4 It is (C1-C4)-alkyl or (CH2) m -phenyl,

[0246] Y 6 It is hydrogen, nitro, cyano or carboxyl, and m is 1 or 2.

[0247] More preferably, the above dye mixture includes one or more dyes selected from dyes of formulas (3), (4), and (5), wherein X 4 It is hydrogen or nitro.

[0248] Y 2 It is (C1-C2)-alkyl or (CH2) m -phenyl,

[0249] Y 4 It is (C1-C4)-alkyl or (CH2) m -phenyl,

[0250] Y 6 It is hydrogen, and

[0251] m is 1 or 2.

[0252] Particularly preferred are the dye mixtures comprising at least one dye of formula (3), said dye being selected from the group consisting of the following compounds:

[0253]

[0254]

[0255] Particularly preferred are the dye mixtures comprising at least one dye of formula (4), wherein the dye of formula (4) is selected from the group consisting of the following compounds:

[0256]

[0257] Particularly preferred are the dye mixtures comprising at least one dye of formula (5), wherein the dye of formula (5) is selected from the group consisting of the following compounds:

[0258]

[0259] The dyes in formulas (1) and (2) are known and can be prepared by known processes, such as those in US 4,619,993, DD 209641 and EP 0 864 615.

[0260] The dyes in formulas (3), (4) and (5) are known and can be prepared according to known processes, such as those in documents EP 0 440 072, DE 19 646 429, GB 2 300 863, US 4,140,684 and DE 1544446.

[0261] The production method of the above dye mixture includes

[0262] a) A mixture of dyes of formulas (1) and (2), and optionally dyes of formulas (3) and / or (4) and / or (5),

[0263] b) Homogenize the mixture obtained in step a). This is another aspect of the invention.

[0264] There is also a preferred range for the amount of dye in the mixture:

[0265] The preferred wt% range of the dye components in the above dye mixture is:

[0266] Formula (1) Dye 10-90,

[0267] Formula (2) Dye 90-10.

[0268] More preferably

[0269] Formula (1) Dye 25-75,

[0270] Formula (2) Dye 75-25.

[0271] When no other dyes are present in the dye mixture, the total amount of dyes from formulas (1) and (2) is 100 wt%. When other dyes are present, preferably selected from dyes of formulas (3), (4), and (5), and the amounts of dyes are preferably as follows:

[0272] Formula (1) dye 10-80 wt%,

[0273] Formula (2) dye 80-10wt%,

[0274] Other dyes 10-35 wt%,

[0275] The total amount of all dyes is 100 wt%.

[0276] Better:

[0277] Formula (1) dye 25-60 wt%,

[0278] Formula (2) dye 60-25wt%,

[0279] Dyes of formulas (3), (4) and / or (5) 15-30 wt%,

[0280] The total amount of all dyes is 100 wt%. (IV) Detailed Implementation

[0281] Example 1

[0282] a) Mix 55 parts of dye of formula (1-16) with 45 parts of dye of formula (2-2). Thoroughly mix the resulting dye mixture of the present invention with 100 parts of lignin sulfonate dispersant (Reax 85A) and 300 parts of water. Adjust the pH of the mixture to 5.5 ± 0.2 with dilute sulfuric acid, and then grind it in a glass bead mill (0.4-0.7 mm glass beads) for 4-6 hours to a size of 0.3-5 micrometers. Filter the ground dye mixture slurry from the glass beads and spray dry it in a laboratory spray dryer (Buchi) at an inlet temperature of 120°C and an outlet temperature of 60-70°C.

[0283] b) Disperse 1 g of the dye mixture obtained according to a) in 100 ml of water at 40-50°C. The dye bath is prepared by adding 5 g of polyester to 11.5 ml of this aqueous dispersion, 57.5 ml of deionized water, and 1.2 ml of buffer solution (pH 4.5). Heat the dye bath to 130°C in a Werner Mathis high-temperature dyeing machine and maintain it at 130°C for 45 minutes. After rinsing with water and reduction cleaning, the polyester material exhibits a blue / navy blue dyeing effect, suitable for darker shades.

[0284] It has good lifting power, good light fastness, and very good moisture fastness.

[0285] Example 2

[0286] Mix 30 parts of dye of formula (1-15) with 30 parts of dye of formula (1-16) and 40 parts of dye powder of formula (2-28).

[0287] According to Example 1a), the dye mixture of the present invention was formulated using a dispersant and dried by spray drying, and then the polyester or polyester blend was dyed blue / navy blue according to the dyeing conditions of 1b), exhibiting good light fastness and very good wet fastness.

[0288] Example 3

[0289] The dye mixture of the present invention was prepared by mixing 46 parts of dye of formula (1-11) with 28 parts of dye of formula (2-1) and mixing with 26 parts of dye powder of formula (2-30) according to Example 1a). The mixture was dried by spray drying and then dyed blue / navy blue on polyester or polyester blends according to the dyeing conditions of 1b). The mixture exhibited good light fastness and very good wet fastness.

[0290] Example 4

[0291] Mix 50 parts of dye of formula (1-22) with 50 parts of dye of formula (2-26).

[0292] According to Example 1a), the dye mixture of the present invention was formulated using a dispersant and dried by spray drying, and then the polyester or polyester blend was dyed blue / navy blue according to the dyeing conditions of 1b), exhibiting good light fastness and very good wet fastness.

[0293] All examples in the table below were prepared according to the above formulation.

[0294]

[0295]

[0296]

[0297] When the dye mixture of the present invention is used for dyeing, the dye mixture is dispersed in an aqueous medium in a conventional manner with the aid of a dispersant and a wetting agent to prepare a dye bath for dyeing or printing hydrophobic textile fibers.

[0298] Furthermore, the application of the dye mixtures described above in the dyeing of fibers and blends of such fibers forms one aspect of the present invention.

[0299] Preferably, the synthetic textile material can be selected from aromatic polyesters (especially polyethylene terephthalate), polyamides (especially polyhexamethylene adipamide), cellulose acetate, cellulose triacetate, and natural textile materials (especially cellulose materials and wool). Particularly preferred textile materials are aromatic polyesters or blends thereof with fibers of any of the aforementioned textile materials. Particularly preferred blends include polyester-cellulose blends, such as polyester-cotton and polyester-wool blends. The textile material or its blend can be in the form of filaments, loose fibers, yarns, or woven or knitted fabrics. In particular, in polyester fibers, not only ordinary polyester fibers (conventional denier fibers), but also microfibers (fine denier fibers, less than 0.6 denier) can be successfully dyed with the dye mixtures of the present invention.

[0300] Generally, all types of fibers can be dyed; therefore, fibers containing the above-mentioned dye mixtures combined chemically and / or physically, and blends containing such fibers constitute another aspect of the invention. The fibers are selected from: synthetic fiber materials, nylon materials, nylon 6, nylon 6.6, and aramid fibers; plant fibers, seed fibers, cotton, organic cotton, kapok, and coconut fiber; bast fibers, flax, jute, kenaf, ramie, and rattan; leaf fibers, sisal, henaquin fiber, and banana; straw fibers, and bamboo; fibers from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, angora fiber, and fur and leather materials; synthetic and regenerated fibers, cellulose fibers; paper fibers, regenerated cellulose fibers, viscose rayon fibers, acetate fibers, and triacetate fibers; and lyocell fibers.

[0301] Typical examples of dispersants are lignin sulfonates, naphthalene sulfonic acid / formaldehyde condensates, and phenol / cresol / p-aminobenzenesulfonic acid / formaldehyde condensates. Typical examples of wetting agents are alkyl aryl ethoxylates, which may be sulfonated or phosphorylated. Typical examples of other components that may be present are inorganic salts, dust-removing agents such as mineral oil or nonanol, organic liquids, and buffers. The amount of dispersant can be 30% to 500% based on the weight of the dye mixture. The amount of dust-removing agent can be 0% to 5% based on the weight of the dye mixture.

[0302] A dyeing method for a material containing formamide and / or hydroxyl groups, comprising contacting the material containing formamide and / or hydroxyl groups with the above-mentioned dye mixture and / or the above-mentioned aqueous solution, constitutes another aspect of the present invention.

[0303] For example, when dyeing polyester fibers and blended products, such as blended yarns in interwoven fabrics containing polyester fibers, good colorfastness can be obtained using conventional dyeing methods, such as high-temperature dyeing, carrier dyeing, and thermosol dyeing. In some cases, adding an acidic substance to the dye bath may improve the dyeing success.

[0304] Suitable process conditions can be selected from the following:

[0305] (i) Impregnation, carried out at pH 4 to 8.5, temperature 125 to 140°C for 10 to 120 minutes, and pressure 1 to 2 bar, with the option of adding a chelating agent;

[0306] (ii) Continuous staining at pH 4 to 8.5 and temperature 190 to 225°C for 15 seconds to 5 minutes, with the option to add migration inhibitors;

[0307] (iii) Direct printing, steaming at high temperature of 160 to 185°C for 4 to 15 minutes at pH 4 to 6.5, or baking with dry heat at 190 to 225°C for 15 seconds to 5 minutes, or steaming under pressure at 120 to 140°C and 1 to 2 bar for 10 to 45 minutes, with optional addition of 5-100% by weight of wetting agent and thickener (such as alginate);

[0308] (iv) Discharge printing (by padding dyes onto textile materials, drying and overprinting), at pH 4 to 6.5, with selective addition of migration inhibitors and thickeners;

[0309] (v) Carrier staining, pH 4 to 7.5, temperature 95 to 100°C, using carriers such as methylnaphthalene, diphenylamine or 2-phenylphenol for staining, with optional addition of chelating agents;

[0310] (vi) Atmospheric dyeing of cellulose acetate, cellulose triacetate and nylon at pH 4 to 7.5, cellulose acetate at approximately 85°C, and cellulose triacetate and nylon at approximately 90°C for 15 to 90 minutes, with optional addition of chelating agents.

[0311] In all the above methods, the dye mixture is applied in the form of a dispersion in an aqueous medium, and in the aqueous medium, the content of the dye mixture of the present invention is 0.001 to 20 wt.%, preferably 0.005 to 16 wt.%.

[0312] In addition to the above-mentioned application methods, dye mixtures can be used for inkjet printing on synthetic textile materials and fiber blends, and the substrate can be pretreated to assist printing.

[0313] An ink for digital fabric printing, comprising the aforementioned dye mixture, is another aspect of the present invention.

[0314] For inkjet applications, the application medium may contain water and a water-soluble organic solvent, preferably in a weight ratio of 1:99 to 99:1, more preferably 1:95 to 50:50, and particularly preferably in the range of 10:90 to 40:60. The water-soluble organic solvent preferably includes C1-C4-alkanols (especially methanol or ethanol), ketones (especially acetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone), glycols (especially ethylene glycol, propylene glycol, 1,3-propanediol, butane-2,3-diol, thiodiethylene glycol or diethylene glycol), ethylene glycol ethers (especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether), urea, sulfones (especially bis-(2-hydroxyethyl) sulfone), or mixtures thereof.

[0315] The dye can also be applied to textile materials using supercritical carbon dioxide, in which case the dye formulation can be selectively omitted.

Claims

1. A dye mixture comprising at least one dye of formula (1) ###0001### wherein n is 1 or 2, m is 1 or 2, and p is 0 or 1, and at least one dye of formula (2) ###0002### wherein n is 1 to 4, and m is 1 to 4, and L is hydrogen or ###0003### 2. The dye mixture according to claim 1, wherein the at least one dye of formula (1) is a dye of formula (la) ###0004### wherein n is 1 or 2, m is 1 or 2, and p is 0 or 1. R 1 is hydrogen or methoxy, R 2 is hydrogen or -NHCO-(Ci-C2)-alkyl, R 3 and R 4 is hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -CN, (CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl or CHR 9 -(CH2) p -COO-(C1-C2)-alkyl, 3. The dye mixture according to claim 1, wherein the at least one dye of formula (1) is a dye of formula (lb) ###0005### wherein n is 1 or 2, and m is 1 or 2, p is 0 or 1. R 9 is (C1-C4)-alkyl, 4. The dye mixture according to claim 1, wherein the at least one dye of formula (1) is a dye of formula (lc) ###0006### wherein n is 1 or 2, m is 1 or 2, and p is 0 or 1.

5. The dye mixture according to claim 1, wherein the at least one dye of formula (1) is selected from one of the following: ###0007### wherein n is 1 or 2, and m is 1 or 2, and L is hydrogen or ###0008### 7. The dye mixture according to claim 1 or 2, wherein the at least one dye of formula (2) is a dye of formula (2a) ###0010### wherein n is 1 or 2, and m is 1 or 2, and L is hydrogen or ###0011### with the proviso that at least R 3 and one of R 4 is not hydrogen; 8. The dye mixture according to claim 1 or 2, wherein the at least one dye of formula (2) is a dye of formula (2b) ###0012### wherein n is 1 or 2, and m is 1 or 2, and L is hydrogen or ###0013### 9. The dye mixture according to claim 1 or 2, wherein the at least one dye of formula (2) is a dye of formula (2c) ###0014### wherein n is 1 or 2, and m is 1 or 2. wherein each R independently of the others is hydrogen, (C1-C4)-alkyl, (CH2) 5 and R 6 is hydrogen, (C1-C4)-alkyl, (CH2) n -phenyl, (CH2) n -O-(C1-C4)-alkyl, (CH2) n -COO-(C1-C4)-alkyl, (CH2) n -CN or (CH2) n -COO(CH2) m -CO-(C1-C4)-alkyl, 10. The dye mixture according to claim 1 or 2, wherein the at least one dye of formula (2) is a dye of formula (2d) ###0015### wherein n is 1 or 2, and m is 1 or 2, and L is hydrogen or ###0016### 11. The dye mixture according to claim 1 or 2, wherein the at least one dye of formula (2) is selected from one of the following: ###0017### ​ with the proviso that at least R 5 and one of R 6 is not hydrogen, R 10 is hydrogen or (Ci-C4)-alkoxy, R 11 is hydrogen or -NHCO-(Ci-C2)-alkyl, X 5 and X 6 is hydrogen, halogen, nitro or cyano, with the proviso that at least one of X 5 and X 6 is not hydrogen, ​ ​ X 6 is nitro, X 5 is hydrogen, L is hydrogen or fluorine. ​ Each of the independent R 3 and R 4 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -CN、 (CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl or CHR 9 -(CH2) p -COO-(C1-C2)-alkyl, ​ R 9 is (C1-C4)-alkyl, ​ ​ ​ with the proviso that at least R 3 and one of R 4 is not hydrogen, and R 7 is ethyl or methyl, R 8 is methyl. ​ Each of the independent R 3 and R 4 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -CN、 (CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl or CHR 9 -(CH2) p -COO-(C1-C2)-alkyl, ​ R 9 is (C1-C4)-alkyl, ​ ​ ​ with the proviso that at least R 3 and one of R 4 is not hydrogen, and R 7 is ethyl or methyl. ​ Each of the independent R 3 and R 4 It can be hydrogen, (C1-C2)-alkyl, (CH2)-phenyl, CH2-CH=CH2, (CH2)2-O-(C1-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -CN、(CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, (CH2) n -O-CO-(C1-C2)-alkyl, (CH2) n -O-CO-phenyl or CHR 9 -(CH2) p -COO-(C1-C2)-alkyl, ​ R 9 is (C1-C4)-alkyl, ​ ​ ​ with the proviso that at least R 3 and one of R 4 is not hydrogen. ​ 6. The dye mixture as claimed in claim 1 or 2, wherein, in at least one dye of the formula (2), independently of one another R 5 and R 6 are hydrogen, (Ci-C2)-alkyl, (CH2)-phenyl, (CH2)2-0-(Ci-C2)-alkyl, (CH2) n -COO-(Ci-C2)-alkyl, (CH2) n -CN or (CH2) n -COO(CH2) m -CO-(Ci-C2)-alkyl, ​ ​ ​ with the proviso that at least R 5 and one of R 6 is not hydrogen, R 10 is hydrogen or methoxy, R 11 is hydrogen or -NHCO-(Ci-C2)-alkyl, X 5 and X 6 is hydrogen, chlorine, bromine, nitro or cyano, with the proviso that at least one of X 5 and X 6 is not hydrogen, ​ ​ X 6 is nitro, X 5 is hydrogen, L is hydrogen or fluorine. ​ wherein each R independently is 5 and R 6 is hydrogen, (Ci-C2)-alkyl, (CH2)-phenyl, (CH2)2-O-(Ci-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -CN or (CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, ​ ​ ​ with the proviso that at least R 5 and one of R 6 is not hydrogen, R 7 and R 8 is ethyl or methyl, X 5 is hydrogen, bromo, chloro, nitro or cyano, X 6 is hydrogen, nitro or cyano, with the proviso that X 5 and X 6 are not simultaneously nitro ​ ​ X 6 is nitro, X 5 is hydrogen, L is hydrogen or fluorine. ​ R 5 and R 6 is hydrogen, (Ci-C2)-alkyl, (CH2)-phenyl, (CH2)2-O-(Ci-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -CN or (CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, ​ ​ ​ with the proviso that at least R 5 and one of R 6 is not hydrogen, and R 7 is ethyl or methyl, and X 5 is hydrogen, bromo, chloro, nitro or cyano, X 6 is hydrogen, nitro or cyano, with the proviso that X 5 and X 6 are not simultaneously nitro ​ ​ X 6 is nitro, X 5 is hydrogen, L is hydrogen or fluorine. ​ wherein each independent R 2 is hydrogen or -NHCO-(Ci-C2)-alkyl, R 5 and R 6 is hydrogen, (Ci-C2)-alkyl, (CH2)-phenyl, (CH2)2-O-(Ci-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -CN or (CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, ​ ​ ​ with the proviso that at least R 5 and one of R 6 is not hydrogen, X 5 and X 6 is bromo or chloro. ​ wherein each R independently is 5 and R 6 is hydrogen, (Ci-C2)-alkyl, (CH2)-phenyl, (CH2)2-O-(Ci-C2)-alkyl, (CH2) n -COO-(C1-C2)-alkyl, (CH2) n -CN or (CH2) n -COO(CH2) m -CO-(C1-C2)-alkyl, ​ ​ ​ with the proviso that at least R 5 and one of R 6 is not hydrogen, R 7 is ethyl or methyl, R 10 is hydrogen or methoxy, X 6 is chloro, bromo, nitro or cyano, ​ ​ X 6 L is hydrogen or fluoro when X is nitro. ​

Images