Patent Grant
7358345
This application is a national stage application (under 35 U.S.C. 371) of PCT/EP2004/011590 filed Oct. 15, 2004 which claims benefit to United Kingdom application 0324584.2 filed Oct. 21, 2003.
The present invention relates to the field of disperse dyes.
Disperse dyestuffs containing cyanomethyl ester groups are known from literature and are described for example in GB 909,843, DE-A 2130992, GB 1,457,532, GB 1,536,429, FR-A 1,531,147, U.S. Pat. No. 3,776,898, JP 55161857, GB 2,104,088, EP 0 685 531 A1 and WO 95/20014.
The inventor of the present invention has surprisingly found that dyeings on polyester with very good wet fastness properties can be obtained if selected dyestuffs containing one cyanomethylester group as defined below are used.
The present invention claims dyestuffs of the formula I
wherein
Alkyl groups standing for R1, R8 or T10 may be straight-chain or branched and are preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. The same applies to alkyl groups standing for R2, which can in addition be pentyl or hexyl. Substituted alkyl groups standing for R2 are preferably substituted by hydroxyl, (C1-C4)-alkoxy or halogen.
Halogen standing for T1, T2, T3, T4, T5 or T8 are preferably chlorine or bromine.
Preferred examples for D derive from the following amines:
Preferred disperse dyestuffs according to the present invention are of the general formula (Ia)
wherein
In especially preferred dyestuffs of formula (Ia) R1 is methyl, R2 is ethyl and n is 0.
Other preferred disperse dyestuffs according to the present invention are of the general formula (Ib)
wherein
In especially preferred dyestuffs of formula (Ib) R2 is ethyl, benzyl or phenethyl.
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ic)
wherein
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Id)
wherein
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ie)
wherein
Still other preferred disperse dyestuffs according to the present invention are of the general formula (If)
wherein
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ig)
wherein
The compounds of the formula I may be obtained by usual methods for the preparation of azo compounds such as by diazotisation of an amine of the formula III
D-NH2 (III)
wherein D is defined as given above,
and coupling onto a compound of the formula IV
wherein R1, R2, R3, R4, R5 and R7 are defined as given above.
Typically the amine of the formula (III) may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from −10° C. to 10° C. Coupling onto the compound of the formula (IV) may be achieved by adding the diazotised amine to the compound of the formula (IV) under conditions described in literature and known to the skilled persons.
After coupling the compound of the formula (I) may be recovered from the reaction mixture by any convenient means such as filtration.
The compounds of the formulae (III) and (IV) are known and can be obtained by methods described in literature or known to the skilled person.
The compounds of the formula (I) are useful for dyeing and printing of synthetic textile material particularly polyester textile materials and fibre blends thereof with for example cellulosic materials like cotton, to which they impart colours which have excellent wet fastness properties.
Dyeing of the fibre goods mentioned with the dyestuffs of the formula (I) can be carried out in a manner known per se, preferably from aqueous dispersions, if appropriate in the presence of carriers, at between 80 and 110° C., by the exhaust process or by the HT process in a dyeing autoclave at 110 to 140° C., and by the so-called thermofixing process, in which the goods are padded with the dye liquor and then fixed at about 180 to 230° C.
The fibre goods mentioned can as well be printed in a manner known per se by a procedure in which the dyestuffs of the formula (I) are incorporated into a printing paste and the goods printed with the paste are treated, if appropriate in the presence of a carrier, with HT steam, pressurized steam or dry heat at temperatures between 180 and 230° C. to fix the dyestuff.
The dyestuffs of the formula (I) should be present in the finest possible dispersion in the dye liquors and printing pastes employed in the above applications.
The fine dispersion of the dyestuffs is effected in a manner known per se by a procedure in which the dyestuff obtained during preparation is suspended in a liquid medium, preferably in water, together with dispersing agents and the mixture is exposed to the action of shearing forces, the particles originally present being comminuted mechanically to the extent that an optimum specific surface area is achieved and sedimentation of the dyestuff is as low as possible. The particle size of the dyestuffs is in general between 0.5 and 5 m, preferably about 1 m.
The dispersing agents used can be nonionic or anionic. Nononic dispersing agents are, for example, reaction products of alkylene oxides, such as, for example, ethylene oxide or propylene oxide, with alkylatable compounds, such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines. Anionic dispersing agnets are, for example, lignin-sulphonates, alkyl- or alkylarylsulphonates or alkylaryl polyglycol ethersulphates. For most methods of use, the dyestuff formulations thus obtained should be pourable. The dyestuff and dispersing agent content is therefore limited in these cases. In general, the dispersions are brought to a dyestuff content of up to 50 percent by weight and a dispersing agent content of up to 25 percent by weight. For economic reasons, the dyestuff contents usually do not fall below 15 percent by weight.
The dispersions can also comprise other auxiliaries, for example those which act as oxidizing agents or fungicidal agents. Such agents are well known in the art. The dyestuff dispersion thus obtained can be used very advantageously for the preparation of printing pastes and dye liquors.
For certain fields of use, powder formulations are preferred. These powders comprise the dyestuff, dispersing agents and other auxiliaries, such as, for example, wetting agents, oxidizing agents, preservatives and dust removal agents.
A preferred preparation process for pulverulent dyestuff formulations comprises removing the liquid from the liquid dyestuff dispersions described above, for example by vacuum drying, freeze drying, by drying on roller dryers, but preferably by spray drying.
4-nitroaniline (4.1 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts). Nitrosyl sulphuric acid 40% (11.4 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution obtained was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (7.3 parts), methanol (50 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl)aniline (6.5 parts) λmax=486 nm (acetone).
When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.
The following examples of dyes of formula (Iaa):
were prepared by the procedure of Example 1 (see Table 1)
2,6-dichloro-4-nitroaniline (6.2 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (11.4 parts) was added below 5° C. and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2(cyanomethoxycarbonylethyl)-aniline (8.3 parts), methanol (50 parts), water (300 parts) and sulphamic acid (1 part). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(2,6-dichloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylethyl)aniline (9.5 parts) λmax=432 nm (acetone).
When applied to polyester materials from aqueous dispersion, yellow brown shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iba)
were prepared by the procedure of Example 65 (see Table 2)
2-amino-6-nitrobenzothiazole (3.9 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (7.6 parts) was added below 5° C. and the mixture was stirred for 1 hour. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (5.9 parts), methanol (25 parts), water (200 parts) and sulphamic acid (0.5 parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonyl ethyl)aniline (2.4 parts) λmax=545 nm (acetone).
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iab):
were prepared by the procedure of Example 80 (see Table 3)
2-amino-3,5-dinitrothiophene (3.1 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts) Nitrosyl sulphuric acid 40% (5.7 parts) was added below 5° C. and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonyethyl)-m-toluidine (4.0 parts), acetone (50 parts), water (300 parts) and sulphamic acid (0.5 parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(3,5-dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonyl-ethyl)aniline (3.0 parts) λmax=640 nm (acetone).
When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iac):
were prepared by the procedure of Example 107 (see Table 4)
7-amino-5-nitrobenzoisothiazole (2.9 parts) was added to a mixture of sulphuric acid 98% (15 parts) and phosphoric acid (4 parts) stirring at room temperature. The mixture was heated to 55° C. and was stirred at that temperature for 30 mins. Nitrosyl sulphuric acid 40% (6.1 parts) was added below 5° C. and the mixture was stirred for 2 hrs.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (4.8 parts), acetone (50 parts), water (100 parts) and sulphamic acid (0.5 parts). Sodium acetate was added to increase the pH to 4.0 and the mixture was stirred for 1 hour. The product was isolated by filtration, washed with cold water and dried to yield, 4-(5-nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl)aniline (2.4 parts) λmax=601 nm (acetone).
When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iad)
were prepared by the procedure of Example 127 (see Table 5)
2-amino-5-nitrothiazole (2.9 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts). Nitrosyl sulphuric acid 40% (7.0 parts) was added below 5° C. and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-butyl, N-2(cyanomethoxycarbonylethyl)-aniline (5.2 parts), acetone (50 parts), water (200 parts) and sulphamic acid (0.5 parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(5-nitrothiazol-yl-azo)-N-butyl-N-(2-cyanomethoxycarbonylethyl)aniline (2.9 parts) λmax=571 nm (acetone).
When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iae)
were prepared by the procedure of Example 134 (see Table 6)
2-chloro-4-nitroaniline (3.5 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (7.0 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of 3(N-ethyl, N-cyanomethoxycarbonylethyl)-amino-acetanilide (6.3 parts), methanol (40 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2-cyanomethoxy-carbonylethyl)-aniline (4.1 parts) λmax=525 nm (acetone).
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of formula (Iea):
were prepared by the procedure of Example 139 (see Table 7)
2-cyano-4-nitroaniline (3.2 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts). Nitrosyl sulphuric acid 40% (7.6 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(4-cyanomethoxycarbonylbutyl)-m-toluidine (6.0 parts), methanol (50 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(4-cyanomethoxycarbonylbutyl)-aniline. (5.3 parts) λmax=548 nm (acetone).
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iaf)
were prepared by the procedure of Example 157 (see Table 8)
2-cyano-4-nitroaniline (2.1 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (4.9 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1-cyanoethoxy)carbonylethyl)-m-toluidine (3.7 parts), acetone (50 parts), water (300 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1-cyanoethoxy)carbonylethyl)-aniline (3.5 parts) λmax=534 nm (acetone).
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ida)
were prepared by the procedure of Example 169 (see Table 9)
2-chloro-4-nitroaniline (parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (4.9 parts) was added below 5° C. and the mixture The diazo solution was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2-(cyanomethoxycarbonylpropyl)-aniline (parts), acetone (50 parts), water (300 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-chloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylpropyl)-aniline (3.5 parts) λmax=534 nm (acetone).
When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ica)
were prepared by the procedure of Example 194 (see Table 10)
4-nitroaniline (2.0 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts). Nitrosyl sulphuric acid 40% (5.7 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1-cyanoethoxy)carbonylpropyl)-aniline (4.7 parts), acetone (50 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(4-nitrophenylazo)-N-ethyl-N-(2-(1-cyanoethoxy)carbonylpropyl)-aniline (2.9 parts) λmax=473 nm (acetone).
When applied to polyester materials from aqueous dispersion, scarlet shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ih):
were prepared by the procedure of Example 213 (see Table 11)
2-cyano-4-nitroaniline (3.1 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (6.6 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(1-cyanomethoxycarbonylethyl)-m-toluidine (4.1 parts), methanol (40 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4-nitrophenylazo)-N-ethyl-N-(1-cyanomethoxycarbonylethyl)-m-toluidine (3.9 parts) λmax=510 nm (acetone).
When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0324584.2 | Oct 2003 | GB | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2004/011590 | 10/15/2004 | WO | 00 | 4/13/2006 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2005/040283 | 5/6/2005 | WO | A |
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| 5569751 | Buhler | Oct 1996 | A |
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| 21 30 992 | Dec 1971 | DE |
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| Number | Date | Country | |
|---|---|---|---|
| 20070050928 A1 | Mar 2007 | US |
