Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
  • C09B35/378—Trisazo dyes of the type

Definitions

• the invention relates to novel acid dyes, a process for their preparation and their use for dyeing organic substrates.
• Acid dyes are known and dyes with bridging members are known as well.
• R signifies H or a sulpho group
• R 2 signifies H or a sulpho group, R 1 has to be different from R 2 ,
• R 3 signifies H, a sulpho group, a substituted C-i to C 4 alkyi group or an
• R 4 signifies H, a substituted Ci to C alkyi group or an unsubstituted Ci to C 4 alkyi group, a substituted Ci to C alkoxy group or an unsubstituted Ci to C 4 alkoxy group,
• R 6 signifies a substituted Ci to C 9 alkyi group or an unsubstituted Ci to Cg alkyi group, an unsubstituted aryl group or a substituted aryl group.
• the preferred compounds of formula (I) bear 1 , 2 or 3 sulpho groups, of which 3 sulpho groups are particularly preferred.
• the preferred substituents of the substituted alkyl groups are selected from the following substituents -OH, -O (d to C 4 alkyl), -SO 3 H, -COOH, phenyl, -NH (d to C 4 alkyl).
• the alkyl groups having 3 or more carbon atoms are branched or linear.
• the most preferred alkyl groups are methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl (2-methylpropyl), pentyl, iso-pentyl (3-methylbutyl), hexyl, heptyl, octyl, or nonyl.
• the preferred substituents of the substituted Ci to C 4 alkoxy group are selected from the following substituents -OH, -O (Ci to C 4 alkyl), -SO 3 H, -COOH, -NH (d to C 4 alkyl).
• the alkoxy groups having 3 or more carbon atoms are branched or linear. The most preferred alkoxy groups are methoxy and ethoxy.
• Preferred substituents of the substituted aryl groups are selected from the following substituents -OH, -O (Ci to C 4 alkyl), -SO 3 H, substituted Ci to C 4 alkyl groups, unsubstituted Ci to C 4 alkyl groups, substituted Ci to C 4 alkoxy groups and unsubstituted Ci to C 4 alkoxy groups, possible substituents of the alkyl and alkoxy groups are as defined before.
• R 1 signifies H or a sulpho group
• R 2 signifies H or a sulpho group, R 1 has to be different from R 2 ,
• R 3 signifies H, a sulpho group, an unsubstituted Ci to C 2 alkyl group, an
• R 4 signifies H, an unsubstituted Ci to C 2 alkyl group, an unsubstituted Ci to C 2 alkoxy group,
• R 6 signifies a substituted Ci to Cg alkyl group or an unsubstituted Ci to C 9 alkyl group, an unsubstituted C 6 -Ci 0 aryl group or a C6-C10 aryl group substituted with 1 to 3 Ci to C6 alkyl groups.
• R 1 has to be different from R 2 ,
• Ci to Cg alkyl group signifies an unsubstituted Ci to Cg alkyl group, a Ci to Cg alkyl group substituted with phenyl or with (Ci-C 4 -alkyl)i-3 phenyl, an unsubstituted phenyl group, or a phenyl group substituted with 1 to 3 Ci to C 4 alkyl groups.
• R 1 signifies H or a sulpho group
• R 2 signifies H or a sulpho group, R 1 has to be different from R 2 ,
• R 3 signifies H, methyl, methoxy
• R 4 signifies H
• R 6 signifies an unsubstituted C 4 -C 9 alkyl group, a Ci -C 4 alkyl group
• a phenyl group e.g. benzyl, a C1-C4 alkyl group substituted with Ci-C 4 -alkylphenyl, an unsubstituted phenyl group, or a phenyl group substituted with a Ci-C alkyl group.
• the present invention further provides a process for the preparation of compound of formula (I) comprising reacting the tris-diazonium salt of a triamine of formula (II),
• Diazotisation and coupling may be effected in accordance with conventional methods.
• the coupling reaction advantageously is carried out in an aqueous reaction medium in a temperature range of from about 0 to 60 °C, preferably from 0 to 40 °C, more preferred from 0 to 10 °C, even more preferred from 0 to 5 °C, and in a pH range of from 2 to 9, preferably from pH 3 to 6. All temperatures are given in degrees Celsius.
• reaction mixtures comprising compounds of formula (I) thus obtained may be converted into stable liquid formulations with improved long term stability by desalting, e.g. by ultra filtration.
• the starting compounds i.e. the amines of formula (II) and the naphtholes of formula (III), are either known or may be prepared in accordance with known methods from available starting materials.
• Amines according to the formula (II) may be prepared according the methods disclosed in DE-4014847, thus starting from two equivalents of an aldehyde of the formula
• the reaction mixture of said aldehyde and said aromatic amine is heated in a closed autoclave at 120 to 250 °C, preferably 140 to 200 °C, more preferably 140 to 150 °C, the reaction mixture is kept at this temperature for 3 - 8 hours, preferably for 4 to 5 hours.
• the elevated temperature leads in this closed autoclave to the elevated pressure.
• the synthesis may be performed in the melt of the amino compound-hydrochloride adding the aldehyde at a temperature of from 200 to 250 °C and the pressure is atmospheric pressure.
• the dyes of the formula (I) can be isolated from the reaction medium by
• the dyes of the formula (I) can be obtained as free acid, as salt or as mixed salt which contains for example one or more cations selected from alkali metal ions, for example the sodium ion, or an ammonium ion or alkyiammonium cation, for example mono-, di- or trimethyl- or -ethylammonium cations.
• the dye can be converted by conventional techniques from the free acid into a salt or into a mixed salt or vice versa or from one salt form into another. If desired, the dyes can be further purified by diafiltration, in which case unwanted salts and synthesis by-products are separated from the crude anionic dye.
• the removal of unwanted salts and synthesis by-products and partial removal of water from the crude dye solution is advantageously carried out by means of a semipermeable membrane by applying a pressure whereby the dye is obtained without the unwanted salts and synthesis by-products as a solution and if necessary as a solid body in a conventional manner.
• the dyes of the formula (I) and their salts are particularly suitable for dyeing or printing fibrous material containing or consisting of natural or synthetic polyamides in yellow to greenish yellow shades.
• the dyes of the formula (I) and their salts are also suitable for producing inkjet printing inks and for using these inkjet printing inks to print fibrous material which contains or consists of natural or synthetic polyamides or cellulose (paper for example).
• the invention accordingly provides for the use of the dyes of the formula (I), their salts and mixtures of dyes of formula (I) for dyeing and/or printing fibrous materials containing or consisting of natural or synthetic polyamides.
• a further aspect is the production of Inkjet printing inks and their use for printing fibrous materials containing or consisting of natural or synthetic polyamides.
• Dyeing can be carried out according to known processes. Preference is given to dyeing in the exhaust process at a temperature of about 30 to 140 °C, more preferably 80 to 120 °C and most preferably 80 to 100 °C, and at a liquor ratio in the range from about 3:1 to 40:1.
• the substrate to be dyed can be present in the form of yarn, woven fabric, loop- formingly knitted fabric or carpet for example. Fully fashioned dyeings are even permanently possible on delicate substrates, examples being lambswool, cashmere, alpaca and mohair.
• the dyes of the invention are particularly useful for dyeing fine-denier fibres (microfibres).
• the dyes according to the present invention and their salts are highly compatible with known acid dyes. Accordingly, the dyes of the formula (I), their salts or mixtures thereof can be used alone in a dyeing or printing process or else as a component in a combination shade dyeing or printing composition together with other acid dyes of the same class, i.e. with acid dyes possessing comparable dyeing properties, such as for example fastness properties and exhaustion rates from the dyebath onto the substrate.
• the dyes of the present invention can be used in particular together with other dyes having suitable chromophores. The ratio in which the dyes are present in a combination shade dyeing or printing composition is dictated by the hue to be obtained.
• novel dyes of the formula (I) are very useful for dyeing natural and synthetic polyamides, i.e. wool, silk and all nylon types, on each of which dyeings having a high fastness level, especially good light fastness and good wet fastnesses (washing, alkaline perspiration) are obtained.
• the dyes of the formula (I) and their salts have a high rate of exhaustion.
• the ability of the dyes of the formula (I) and their salts to build up is likewise very good.
• On-tone dyeings on the identified substrates are of outstanding quality. All dyeings moreover have a constant hue under artificial light. Furthermore, the fastness to decating and boiling is good.
• One decisive advantage of the novel dyes is that they are metal free and provide very level dyeings.
• the invention's dyes of the formula (I) can also be used as yellow components in trichromatic dyeing or printing.
• Trichromatic dyeing or printing can utilize all customary and known dyeing and printing processes, such as for example the continuous process, exhaustion process, foam dyeing process and Ink-Jet process.
• the composition of the individual dye components in a trichromatic dye mixture depends on the desired hue.
• a brown hue for example, preferably utilizes 20 to 40 % by weight of the invention's yellow component, 40 to 60 % by weight of an orange or red component and 10 to 20 % by weight of a blue component.
• the yellow component as described above, can consist of a single component or of a mixture of different yellow individual components conforming to the formula (I). Preference is given to double and triple combinations. Particularly preferred red and/or blue components are described in
• reaction mixture was poured on 1 kg ice and 400 g sodium hydroxide solution in water (30 %).
• the organic layer was separated and residual o-anisidine separated with toluene.
• the residue was re-crystallized from toluene and the press cake washed with cold ethanol.
• the temperature of the melt fell from initially about 200 °C to 185 °C because of the reflux. The temperature was kept for one hour at 185 °C and the hot melt was poured on a mixture of 1 ,6 kg ice and 1 ,05 kg of aqueous sodium hydroxide solution (30 %).
• the organic layer was separated and washed free from salt with demineralised water.
• the dyestuff can be isolated by concentration under vacuum or by precipitation in acetone/ethanol.
• reaction mixture however can be used directly for dyeing without isolation the product.
• the dyestuff of formula (5) has surprisingly very high solubility in water and gives orange dyeings with very good fastness properties.
• the dyestuff can be isolated by concentration under vacuum or by precipitation in acetone/ethanol.
• reaction mixture however can be used directly for dyeing without isolation the product.
• the dyestuff of formula (6) has very high solubility in water and gives red dyeings with surprisingly very good fastness properties.
• a dyebath at 40 °C consisting of 2000 parts of water, 1 part of a weakly cation- active levelling agent which is based on an ethoxylated aminopropyl fatty acid amide and which has affinity for dye, 0.25 part of the dye of Example 23 and adjusted to pH 5 with 1 to 2 parts of 40 % acetic acid is entered with 100 parts of nylon-6 fabric. After 10 minutes at 40 °C, the dyebath is heated to 98 °C at a rate of 1 °C per minute and then left at the boil for 45 to 60 minutes. Thereafter it is cooled down to 70 °C over 15 minutes. The dyeing is removed from the bath, rinsed with hot and then with cold water and dried. The result obtained is a yellow polyamide dyeing possessing good light and wet fastnesses.
• a dyebath at 40 °C consisting of 2000 parts of water, 1 part of a weakly cation- active levelling agent which is based on an ethoxylated aminopropyl fatty acid amide and which has affinity for dye, 0.3 part of the dye of Example 23 and adjusted to pH 5.5 with 1 to 2 parts of 40 % acetic acid is entered with 100 parts of nylon-6,6 fabric. After 10 minutes at 40 °C, the dyebath is heated to 120 °C at a rate of 1.5 °C per minute and then left at this temperature for 15 to 25 minutes. Thereafter it is cooled down to 70 °C over 25 minutes. The dyeing is removed from the dyebath, rinsed with hot and then with cold water and dried. The result obtained is a yellow polyamide dyeing with good levelness and having good light and wet fastnesses.
• a dyebath at 40 °C consisting of 4000 parts of water, 1 part of a weakly
• amphoteric levelling agent which is based on a sulphated, ethoxylated fatty acid amide and which has affinity for dye
• 0.4 part of the dye of Example 23 and adjusted to pH 5 with 1 to 2 parts of 40 % acetic acid is entered with 100 parts of wool fabric.
• the dyebath is heated to boiling at a rate of 1 °C per minute and then left at the boil for 40 to 60 minutes. Thereafter it is cooled down to 70 °C over 20 minutes.
• the dyeing is removed from the bath, rinsed with hot and then with cold water and dried. The result obtained is a yellow wool dyeing possessing good light and wet fastnesses.
• a textile cut pile sheet material composed of nylon-6 and having a synthetic base fabric is padded with a liquor containing per 1000 parts 1 part of dye of Example 23
• the print is fixed for 6 minutes in saturated steam at 100 °C, rinsed and dried.
• the result obtained is a level-coloured cover material having a yellow and white pattern.
• Example 23 3 parts of the dye of Example 23 are dissolved in 82 parts of demineralized water and 15 parts of diethylene glycol at 60 °C. Cooling down to room temperature gives an orange printing ink which is very highly suitable for ink jet printing on paper or polyamide and wool textiles.
• Use Example F was carried out with dyes 24 to 42 with similar results.
• a dyebath consisting of 1000 parts of water, 80 parts of calcined Glauber salt, 1 part of sodium nitrobenzene-3-sulphonate and 1 part of dye from Example 23 is heated to 80 °C in the course of 10 minutes. Then, 100 parts of mercerized cotton are added. This is followed by dyeing at 80 °C for 5 minutes and then heating to 95 °C in the course of 15 minutes. After 10 minutes at 95 °C, 3 parts of sodium carbonate are added, followed by a further 7 parts of sodium carbonate after 20 minutes and another 10 parts of sodium carbonate after 30 minutes at 95 °C. Dyeing is subsequently continued at 95 °C for 60 minutes.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Coloring (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=47044951

Family Applications (1)

Country Status (11)

Families Citing this family (1)

Citations (6)

Family Cites Families (4)

• 2011
  • 2011-10-22 PT PT11008494T patent/PT2584008E/pt unknown
  • 2011-10-22 ES ES11008494.4T patent/ES2499222T3/es active Active
  • 2011-10-22 EP EP20110008494 patent/EP2584008B1/en not_active Not-in-force
• 2012
  • 2012-10-11 TW TW101137470A patent/TW201319174A/zh unknown
  • 2012-10-18 JP JP2014536140A patent/JP2014530926A/ja active Pending
  • 2012-10-18 WO PCT/EP2012/004371 patent/WO2013056837A1/en not_active Ceased
  • 2012-10-18 MX MX2014004822A patent/MX2014004822A/es not_active Application Discontinuation
  • 2012-10-18 KR KR1020147013701A patent/KR20140091011A/ko not_active Ceased
  • 2012-10-18 CN CN201280051769.5A patent/CN104011145A/zh active Pending
  • 2012-10-18 BR BR112014009398A patent/BR112014009398A2/pt not_active IP Right Cessation
  • 2012-10-18 IN IN2871DEN2014 patent/IN2014DN02871A/en unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events