Patent Grant
9493657
This application is a national stage application (under 35 U.S.C. §371) of PCT/EP2014/050067, filed Jan. 6, 2014, which claims benefit of European Application Nos. 13000169.6, 13151174.3, 13151183.4, all filed Jan. 14, 2013, and 13000205.8 filed Jan. 15, 2013, all of which are incorporated herein by reference in their entirety.
This invention relates to disperse azo dye mixtures, which have Navy or Black colour.
Disperse AOX-free dyes are of growing interest due to ecological reasons. Disperse AOX-free disperse dyes and their use for dyeing polyester and its blends with other fibres such as for example cellulose, elastane/spandex, nylon and wool by normal exhaust dyeing, continuous dyeing and direct printing techniques are already known from e.g. DE 30 04 655, EP 0 827 988 or DE 26 23 251.
They have, however, certain application defects, such as for example an insufficient colour buildup on polyester (good colour build-up results from the ability of a dye to provide a proportionally stronger dyeing when used in higher concentrations in the dye bath), or unsatisfactory fastness properties.
Thus there is a need for disperse dyes which provide dyeings of improved colour depth and good fastness properties of dyed polyester or its blends with other fibres such as cellulose, nylon and wool being free of halogen substituents due to ecological reasons.
Surprisingly the problems can be solved by certain dye mixtures and the present invention therefore is directed to a mixture comprising
at least one dye selected from the group consisting of the dyes of formula (1) and (2)
and
at least one dye selected from the group consisting of the dyes of formula (3a), (3b), (3c), (3d) and (3e)
and
one dye of formula (4a)
and optionally
at least one dye selected from the group consisting of the dyes of formula (5a) and (5b)
wherein independent from each other
R2 and R3 is hydrogen, (C1-C4)-alkoxy or (C1-C4)-alkyl,
R4 to R11 is (C1-C4)-alkyl, —(CH2)n—O—(C1-C4)-alkyl, —(CH2)n—O—CO—(C1-C4)-alkyl or —(CH2)n—COO—(C1-C4)-alkyl,
X1 and X2 is nitro, cyano, carboxy or CO—NR2R3,
X3 and X4 is hydrogen, cyano or nitro,
Y1 is —(CH2)m-phenyl substituted by Y2, wherein
Preferred is a dye mixture comprising at least one dye of formula (2)
and
at least one dye selected from the group consisting of the dyes of formula (3a), (3b), (3c), (3d) and (3e)
and
one dye of formula (4a)
and
optionally at least one dye selected from the group consisting of the dyes of formula (5a) and (5b)
wherein independent from each other
R2 and R3 is hydrogen, (C1-C4)-alkoxy or (C1-C4)-alkyl,
R4 to R11 is (C1-C4)-alkyl, —(CH2)n—O—(C1-C4)-alkyl, —(CH2)n—O—CO—(C1-C4)-alkyl or —(CH2)n—COO—(C1-C4)-alkyl,
X1 and X2 is nitro, cyano, carboxy or CO—NR2R3,
X3 and X4 is hydrogen, cyano or nitro,
Y1 is —(CH2)m-phenyl substituted by Y2, wherein
Even more preferred is a dye mixture comprising
at least one dye of formula (I)
and
at least one dye of formula (2)
and
at least one dye selected from the group consisting of the dyes of formula (3a), (3b), (3c), (3d) and (3e)
and
one dye of formula (4a)
and optionally
at least one dye selected from the group consisting of the dyes of formula (5a) and (5b)
wherein independent from each other
R2 and R3 is hydrogen, (C1-C4)-alkoxy or (C1-C4)-alkyl,
R4 to R11 is (C1-C4)-alkyl, —(CH2)n—O—(C1-C4)-alkyl, —(CH2)n—O—CO—(C1-C4)-alkyl or —(CH2)n—COO—(C1-C4)-alkyl,
X1 and X2 is nitro, cyano, carboxy or CO—NR2R3,
X3 and X4 is hydrogen, cyano or nitro,
Y1 is —(CH2)m-phenyl substituted by Y2, wherein
There also exist preferred dyes for such mixtures and consequently also preferred mixtures and a dye mixture as described above, wherein independent from each other
R2 is hydrogen, methoxy or methyl,
R3, R6 and R7 is (C1-C4)-alkyl,
R4 and R5 is —(CH2)n—O—(C1-C4)-alkyl,
R8 to R11 is —(CH2)n—O—CO—(C1-C4)-alkyl or —(CH2)n—COO—(C1-C4)-alkyl,
X1, X2 and X3 is cyano or nitro,
X4 is hydrogen,
Y1 is —(CH2)m-phenyl substituted by Y2, wherein
Even more preferred is a dye mixture as described above, wherein independent from each other
R2 is hydrogen or methoxy,
R3 is methyl or ethyl,
R4 and R5 is —(CH2)n—O—(C1-C2)-alkyl,
R6 and R7 is (C1-C4)-alkyl,
R8 and R9 is —(CH2)n—COO—(C1-C2)-alkyl,
R10 and R11 is —(CH2)n—O—CO—(C1-C2)-alkyl,
X1, X2 and X3 is cyano or nitro,
X4 is hydrogen,
Y1 is —(CH2)m-phenyl,
n is 1 or 2 and
m is 1 or 2.
A dye mixture as described above, wherein independent from each other
R2 is hydrogen,
R3 is methyl or ethyl,
R4 and R5 is —(CH2)2—O—CH3,
R6 and R7 is ethyl,
R8 and R9 is —(CH2)n—COO—CH3,
R10 and R11 is —(CH2)—O—CO—(C1-C2)-alkyl,
X1, X2 and X3 is cyano or nitro,
X4 is hydrogen,
Y1 is —(CH2)m-phenyl,
n is 1 or 2 and
m is 1 or 2
is most preferred.
The dyes of the dye mixtures of the present invention are known and can be prepared according to known procedures, for example from the documents:
EP 0 167 913, DE 27 15 34, DE 26 10 675, WO 00/040656, U.S. Pat. No. 3,980,634, EP 0 051 563, EP 0 667 376, EP 2 032 524, DE 29 36 489, EP 0 161 665, EP 0 440 072, WO 02/068539, WO 02/074864 and WO 04/044058.
Ranges of weight % of the components of the inventive dye mixtures are e.g.:
1: 0-60
2: 5-85
3a-3e: 5-40
4: 5-40
5a and/or 5b: 0-20.
Preferred ranges of weight % of the components of the inventive dye mixtures are
2: 15-80
3a-3e: 7.5-35
4: 7.5-35
5a and/or 5b: 0-15
and even more preferred ranges of weight % of the components of the inventive dye mixtures are
2: 30-75
3a-3e: 5-30
4: 0-30
5a and/or 5b: 0-10
for those dye mixtures, which do not comprise a dye of formula (I).
Preferred ranges of weight % of the components of the inventive dye mixtures are
1: 1-45
2: 15-80
3a-3e: 7.5-35
4: 7.5-35
5a and/or 5b: 0-15
and even more preferred ranges of weight % of the components of the inventive dye mixtures are
1: 5-30
2: 30-75
3a-3e; 5-30
4: 0-30
5a and/or 5b: 0-10
for those dye mixtures, which comprise at least one dye of formula (I).
In each dye mixture the components 1 to 5b add up to 100% in case the dye mixture consists of the dyes mentioned above or to less than 100% in case additional dyes are added e.g. as shading components. In such a case the amount of shading components preferably is less than 10, more preferred less than 5 and most preferred less than 2 weight % based on the weight of all dyes of the dye mixture.
By mixing the single dyes the mixture(s) according to the present invention can be obtained.
Thus also a process for the production of a dye mixture as described above comprising
In general there are three preferred possibilities:
A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with a dye mixture as described above and/or an aqueous solution as described above forms yet another aspect of the present invention.
When the dye mixture of the present invention is used in dyeing, the dye mixture is dispersed in an aqueous medium by means of a dispersing agent and wetting agent in the usual way to prepare a dye bath for dyeing or a printing paste for textile printing.
Typical examples of a dispersing agent are: lignolin-sulphonates, naphthalene sulphonic acid/formaldehyde condensates and phenol/cresol/sulphanilic acid/formaldehyde condensates, typical examples of wetting agents are: alkyl aryl ethoxylates which may be sulphonated or phosphated and typical examples of other ingredients which may be present are: inorganic salts, de-dusting agents such as mineral oil or nonanol, organic liquids and buffers. Dispersing agents may be present in amounts of 30 to 500% based on the weight of the dye mixture. Dedusting agents may be used in amounts from 0 to 5% based on the weight of the dye mixture.
In the case of dyeing e.g. polyester fibres and fibre mixture products such as blended yarn fabrics of union cloth products comprising polyester fibres those fibres and/or fibre mixture products can be dyed with good colour fastness by common dyeing methods, such as the high temperature dyeing method, the carrier dyeing method and the thermosol dyeing method. In some cases, the addition of an acid substance to the dye bath may lead to more successful dyeing.
Suitable process conditions may advantageously be selected from the following
In all the above processes, the dye mixture is applied as a dispersion comprising from 0.001 to 20%, preferably from 0.005 to 16%, of the dye mixture in an aqueous medium.
An aqueous solution for dying comprising a dye mixture as described above forms another aspect of the present invention.
In addition to the above-mentioned application processes, the dye mixture may be applied to synthetic textile materials and fibre blends by ink-jet printing, the substrates optionally having been pre-treated to aid printing. For ink-jet applications, the application medium may comprise water and a water-soluble organic solvent, preferably in a weight ratio of from 1:99 to 99:1, more preferably from 1:95 to 2:1 and especially in the range 1:90 to 1:1. The water-soluble organic solvent preferably comprises a C1-C4-alkanol, especially methanol or ethanol, a ketone, especially acetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially ethylene glycol, propylene glycol, trimethylene glycol, butane-2,3-diol, thiodiglycol or diethylene glycol, a glycol ether, especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether, urea, a sulphone, especially bis-(2-hydroxyethyl)sulphone or mixtures thereof.
Thus an ink for digital textile printing, comprising a dye mixture as described above forms another aspect of the present invention.
The inventive dye mixture may also be applied to textile materials using supercritical carbon dioxide, in which case the dye formulating agents may optionally be omitted.
Another aspect of the present invention is the use of a dye mixture as described above and/or an aqueous solution as described above for dying fibres, as well as blends of such fibres selected from the group consisting of: synthetic fibres: nylon, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibres, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fibre, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibres and Lyocell fibres.
Accordingly fibre and blends containing such fibre selected from the group consisting of: synthetic fibre materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibres, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fibre, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibres, and Lyocell fibres comprising a dye mixture as described above either in chemically and/or physically bound form is another aspect of the present invention.
An especially preferred textile material for being dyed with the dye mixture of the present invention is an aromatic polyester or fibre blend thereof with fibres of any of the above mentioned fibre or blend materials. Especially preferred fibre blends include those of polyester-cellulose, such as polyester-cotton, and polyester-wool. The textile materials or blends thereof may be in the form of filaments, loose fibres, yarn or woven or knitted fabrics.
Particularly, among polyester fibres, not only ordinary polyester fibres (regular denier fibres) but also microfibres (fine denier fibres, which are less than 0.6 denier) are to be mentioned as fibres, which can successfully be dyed with the dye mixture of the present invention.
The following examples shall further illustrate the invention, without limiting the scope. Parts and percentages are by weight unless noted otherwise. The relationship of parts by weight to parts by volume is that of the kilogram to the liter
10 parts dye of the formula (1-1)
were mixed with 45 parts of a dye of the formula (2-1)
and mixed with 20 parts of a dye powder of the formula (3a-1)
and mixed with 15 parts of a dye powder of the formula (4-1)
and mixed with 10 parts of a dye powder of the formula (5b-1)
The resulting dye mixture was formulated using dispersing agent and dried via spray drying and gives very deep black dyeings and prints, on polyester or polyester blends for example, under the dyeing conditions typical for Disperse dyes.
13 parts dye of the formula (1-2)
were mixed with 45 parts of a dye of the formula (2-2)
and mixed with 20 parts of a dye powder of the formula (3b-1)
and mixed with 22 parts of a dye powder of the formula (4-2)
The resulting dye mixture was formulated using dispersing agent and dried via spray drying and gives very deep black dyeings and prints, on polyester or polyester blends for example, under the dyeing conditions typical for disperse dyes.
9 parts dye of the formula (1-3)
were mixed with 36 parts of a dye of the formula (2-3)
and mixed with 20 parts of a dye powder of the formula (3c-1)
and mixed with 25 parts of a dye powder of the formula (4)
and mixed with 10 parts of a dye powder of the formula (5a)
The resulting dye mixture was formulated using dispersing agent and dried via spray drying and gives very deep black dyeings or prints, on polyester or polyester blends for example, under the dyeing conditions typical for disperse dyes.
12 parts dye of the formula (1-2)
were mixed with 36 parts of a dye of the formula (2-1)
and mixed with 20 parts of a dye powder of the formula (3d-1)
and mixed with 32 parts of a dye powder of the formula (4-4)
The resulting dye mixture was formulated using dispersing agent and dried via spray drying and gives very deep black dyeings and prints, on polyester or polyester blends for example, under the dyeing conditions typical for disperse dyes.
5 parts dye of the formula (1-3)
were mixed with 78 parts of a dye of the formula (2-3)
and mixed with 10 parts of a dye powder of the formula (3d-1)
and mixed with 5 parts of a dye powder of the formula (4)
and mixed with 2 parts of a dye powder of the formula (5a)
The resulting dye mixture of the invention was formulated using dispersing agent to and dried via spray drying and gives very deep navy dyeings or prints, on polyester or polyester blends for example, under the dyeing conditions typical for disperse dyes.
10 parts dye of the formula (1-2)
were mixed with 70 parts of a dye of the formula (2-1)
and mixed with 15 parts of a dye powder of the formula (3e-1)
and mixed with 5 parts of a dye powder of the formula (4-4)
The resulting dye mixture was formulated using dispersing agent and dried via spray drying and gives very deep navy dyeings and prints, on polyester or polyester blends for example, under the dyeing conditions typical for Disperse dyes.
All examples of the following table are prepared as formulations as explained above, using dispersing- and dedusting agents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 13000169 | Jan 2013 | EP | regional |
| 13151174 | Jan 2013 | EP | regional |
| 13151183 | Jan 2013 | EP | regional |
| 13000205 | Jan 2013 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2014/050067 | 1/6/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2014/108357 | 7/17/2014 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3980634 | Weaver | Sep 1976 | A |
| 4348319 | Hamprecht | Sep 1982 | A |
| 4681932 | Kruckenberg | Jul 1987 | A |
| 4734490 | Schwander et al. | Mar 1988 | A |
| 5102425 | Buhler et al. | Apr 1992 | A |
| 5688288 | Akatani | Nov 1997 | A |
| 5910624 | Wanken et al. | Jun 1999 | A |
| 6008332 | Herzig et al. | Dec 1999 | A |
| 6555664 | Lauk et al. | Apr 2003 | B1 |
| Number | Date | Country |
|---|---|---|
| 101735663 | Jun 2010 | CN |
| 101760046 | Jun 2010 | CN |
| 101768375 | Jul 2010 | CN |
| 101955691 | Jan 2011 | CN |
| 101974255 | Feb 2011 | CN |
| 102153890 | Aug 2011 | CN |
| 102391680 | Mar 2012 | CN |
| 27 15 34 | Mar 1914 | DE |
| 26 23 251 | Dec 1976 | DE |
| 26 10 675 | Sep 1977 | DE |
| 29 36 489 | Mar 1980 | DE |
| 30 04 655 | Aug 1981 | DE |
| 0 051 563 | May 1982 | EP |
| 0 161 665 | Nov 1985 | EP |
| 0 167 913 | Jan 1986 | EP |
| 0 440 072 | Aug 1991 | EP |
| 0 667 376 | Aug 1995 | EP |
| 0 827 988 | Mar 1998 | EP |
| 2 032 524 | Mar 2009 | EP |
| 1535334 | Dec 1978 | GB |
| 2030169 | Apr 1980 | GB |
| WO-0040656 | Jul 2000 | WO |
| WO-02068539 | Sep 2002 | WO |
| WO-02074864 | Sep 2002 | WO |
| WO-2004044058 | May 2004 | WO |
| WO-2004056925 | Jul 2004 | WO |
| WO-2007118818 | Oct 2007 | WO |
| WO-2008074719 | Jun 2008 | WO |
| WO 2012095284 | Jul 2012 | WO |
| Entry |
|---|
| STIC Search Report dated Dec. 29, 2015. |
| U.S. Appl. No. 14/760,832, filed Jul. 14, 2015, Vermandel et al. |
| International Search Report for PCT/EP2014/050067 mailed Jun. 6, 2014. |
| Number | Date | Country | |
|---|---|---|---|
| 20150353735 A1 | Dec 2015 | US |
