U.S. patent application number 11/587282 was filed with the patent office on 2007-10-04 for method for dyeing or printing textile materials.
This patent application is currently assigned to Huntsman International LLC. Invention is credited to Mickael Mheidle.
Application Number | 20070226919 11/587282 |
Document ID | / |
Family ID | 34928998 |
Filed Date | 2007-10-04 |
United States Patent
Application |
20070226919 |
Kind Code |
A1 |
Mheidle; Mickael |
October 4, 2007 |
Method for Dyeing or Printing Textile Materials
Abstract
A method for dyeing or printing a textile fiber material is
disclosed, which comprises the steps of providing a digital data
processing device organizing reflectance curve data which are
associated with the corresponding dye recipes, wherein the
reflectance curve data are generated by (a) drawing up a
requirement profile for the desired dyeing, (b) selecting a group
of dyes that meet the requirement profile that has been drawn up,
(c) determining within the colour space the colour position of the
said dyes for the desired dyeing, (d) segmenting the colour space
of the dyes within a depth of shade plane into triangular areas (e)
dividing the triangular areas within a depth of shade
arithmetically into a grid.
Inventors: |
Mheidle; Mickael; (Sausheim,
FR) |
Correspondence
Address: |
HUNTSMAN INTERNATIONAL LLC
LEGAL DEPARTMENT
10003 WOODLOCH FOREST DRIVE
THE WOODLANDS
TX
77380
US
|
Assignee: |
Huntsman International LLC
10003 Woodloch Forest Drive
The Woodlands
TX
77380
|
Family ID: |
34928998 |
Appl. No.: |
11/587282 |
Filed: |
April 13, 2005 |
PCT Filed: |
April 13, 2005 |
PCT NO: |
PCT/EP05/51619 |
371 Date: |
October 23, 2006 |
Current U.S.
Class: |
8/446 ;
8/445 |
Current CPC
Class: |
D06P 1/0032 20130101;
D06P 5/30 20130101 |
Class at
Publication: |
008/446 ;
008/445 |
International
Class: |
D06P 5/30 20060101
D06P005/30 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 23, 2004 |
EP |
04101693.2 |
Claims
1. A method for dyeing or printing a textile fiber material, which
comprises the steps of (i) providing a printing or dyeing apparatus
capable of processing digital data; (ii) providing a digital data
processing device organizing reflectance curve data which are
associated with the corresponding dye recipes, wherein the
reflectance curve data are generated by (a) drawing up a
requirement profile for the desired dyeing, (b) selecting a group
of dyes that meet the requirement profile that has been drawn up,
(c) determining within the colour space the colour position of the
said dyes for the desired dyeing, (d) segmenting the colour space
of the dyes within a depth of shade plane into triangular areas
according to shade, wherein the corner points of the triangular
areas correspond to the colour position of the dyes in question,
and the said dyes define a range of shades delimited by the
triangular areas, (e) dividing the triangular areas within a depth
of shade plane arithmetically into a grid in such a manner that the
points of intersection of the grid are distributed evenly over the
triangular areas, where the points of intersection of the grid
correspond to a colour position and a reflectance curve calculated
on the basis of a dye recipe is associated with each of those
colour positions; (iii) providing a device enabling the colour
corresponding to the reflectance curve data to be rendered visible;
wherein the colour of the desired dyeing is defined by browsing the
reflectance curve data organized by the digital data processing
device (ii) using device (iii), communicating the data
corresponding to the colour defined from the digital data
processing device (ii) to the printing or dyeing apparatus (i), in
which the communicated data are used to control the printing or
dyeing apparatus (i), thereby dyeing or printing a textile fiber
material in the defined colour.
2. A method according to claim 1, wherein the printing or dyeing
apparatus capable of processing digital data is a jet- or
spray-dyeing apparatus or an ink-jet printing apparatus.
3. A method according to claim 1, wherein printing or dyeing is
carried out by unwinding a web from a support and passing it
through a dyeing or printing unit, wherein the textile fiber is
impregnated with at least one aqueous dyeing composition containing
the selected dyestuff, before it is rewinded onto another
support.
4. A method according to claim 3, wherein the dyed or printed web
is subjected to a drying or fixing operation in a drying and fixing
unit after having passed the dyeing or printing unit and before
being rewinded.
5. A method according to claim 3, wherein the dyeing or printing
unit comprises at least one dispensing device, which allows the web
to be uniformly impregnated with an aqueous dyeing composition over
its entire width.
6. A method according to claim 1, wherein the printing or dyeing
apparatus according to claim 1 comprises a reservoir for each of
the dyes selected for segmentation of the color space from the
group of dyes that meet the requirement profile according to step
(b) of claim 1.
7. A method according to claim 1, wherein mixing of the dyes is
accomplished by means of an automatic dosing system, which receives
the required commands from the digital data processing device
according to claim 1 and, in accordance with the commands received,
doses or injects the liquid compositions of the selected dyes into
a mixing chamber.
8. A method according to claim 1, wherein the digital data
processing device is a personal computer.
9. A method according to claim 1, wherein FTa*b* colour space is
used as colour space.
Description
[0001] The present invention relates to a method for dyeing or
printing textile fiber materials comprising the selection of a
colour or colour pattern and the preparation of the textile fabrics
dyed or printed with the selected colour or colour pattern in one
automated process.
[0002] Business issues, sociological and economic movements affect
the taste and buying pattern of consumers. Accordingly, business
success to a large extent is dependent on the time to market, i.e.
the period of time required from the idea of a product until its
introduction into the market. Since fashion changes rapidly, this
applies also to the textile industry. In order to cope with the
current market demands methods are required which minimize the time
period from the idea of a new fashion colour collection up to the
production of the textile fashion fabrics.
[0003] Textile professionals, such as designers, merchandisers or
product development managers know how critical colour is to the
textile business. Since it is important, a precise way to define,
select, specify, control and communicate the colour choices is
required, whether designing for apparel, accessories, home
furnishings or automotive interior.
[0004] A problem associated with the definition and communication
of colour choices, which serve as colour standards for a fashion
colour collection, is that they are generally defined only on one
textile material, for example cotton, although the defined colour
standard is also used on many other fibres, for example wool, silk,
polyester, polyamide, polyacryl, etc. or mixtures thereof. For the
dyeing or printing of different fibre materials, however, dyes from
different dye classes are used, for example reactive dyes for
cotton, acid dyes for silk, wool or polyamide and disperse dyes for
polyester. The disadvantage of the customary procedure is that it
can result in metamerism, if the dyestuffs used for the garment are
not identical with the dyes of the selected colour standard.
[0005] The market for textiles calls for specific in-use
properties, for example good fastness to light for skiwear or
summer clothing or seat covers in the automotive industry, good
fastness to chlorine for swimwear, good fastness to perspiration
for sportswear and good fastness to washing properties for
underwear etc. In general, however, such specifications are not
taken into account when defining the colour standard, with the
result that it is possible for metamerism to occur in that instance
also, especially when it is necessary to switch to dyes that take
account of in-use properties at a later stage.
[0006] Colour standards are generally defined by design
professionals who usually have no technical knowledge in the art of
industrial dyeing. In some cases, this results in the definition of
colour standards which cannot be dyed on certain textile fibers or
the recipes for which are not technically optimized or the
requisite fastness properties cannot be achieved with the colour
standard defined. As a consequence all kinds of problems throughout
the textile chain arise, from the designer of the fashion brand
through the supplier chain to the dyeing industry, occasionally
resulting in considerable financial losses.
[0007] In the definition of the standards, too little account is
also taken of the colour constancy, which has the result that the
colour of an object varies under different sources of illumination,
or again results in metamerism if the colour constancy is
improved.
[0008] Occasionally, a design professional may use a wide variety
of objects as colour standard, for example objects made from
leather, plastics, metal, paper, flowers, leaves or wood etc.
Frequently he will also select his colour standard from colour
catalogues. Colour catalogues contain colour samples on a wide
variety of materials, for example pigment-dyed paper or dyeings on
textile samples of cotton, polyester or wool. In the production of
the dyeings that are used to define the colour standard, no account
is taken of the fastness requirements for specific uses. Moreover,
the number of colours in the colour catalogues that are available
is limited, generally from 500 to 2500 different colours. In
defining the colour standard using the mentioned objects or colour
samples from catalogues, the dye recipes found have to be optimised
technically or in respect of the required fastness properties,
which can again result in problems of metamerism or colour
constancy.
[0009] An ideal colour standard does not necessarily have to be a
dyeing, but can be represented by a reflectance curve.
[0010] According to one aspect of the present invention, the
reflectance curve is produced arithmetically, starting from a
recipe that has been optimised technically and in respect of the
in-use fastness properties and using the stored data of calibration
dyeings to calculate the associated reflectance curve. The
reflectance curve, which is thus associated with an
application-optimised dye recipe, is rendered visible by means of a
suitable device, for example, a calibrated colour screen, and in
that manner is used as the defined colour standard.
[0011] By first defining the dye recipe in accordance with the
requirements of application technology and thereafter calculating
the reflectance curve corresponding to the dye recipe, it is
possible to avoid the above-mentioned problems.
[0012] Providing a convenient and reliable method to textile
professional for the definition of colour standards for a fashion
colour collection is one aspect. Another aspect is to shorten the
time from the idea of a colour standard to the preparation of the
textile fashion fabrics.
[0013] Accordingly, the problem underlying the present invention is
to provide an integrated technical solution to textile
professionals which accounts for the issues indicated above.
[0014] The present invention accordingly relates to a method for
dyeing or printing a textile fiber material, which comprises the
steps of [0015] (i) providing a printing or dyeing apparatus
capable of processing digital data; [0016] (ii) providing a digital
data processing device organizing reflectance curve data which are
associated with the corresponding dye recipes, wherein the
reflectance curve data are generated by [0017] (a) drawing up a
requirement profile for the desired dyeing, [0018] (b) selecting a
group of dyes that meet the requirement profile that has been drawn
up, [0019] (c) determining within the colour space the colour
position of the said dyes for the desired dyeing, [0020] (d)
segmenting the colour space of the dyes within a depth of shade
plane into triangular areas according to shade, wherein the corner
points of the triangular areas correspond to the colour position of
the dyes in question, and the said dyes define a range of shades
delimited by the triangular areas, [0021] (e) dividing the
triangular areas within a depth of shade plane arithmetically into
a grid in such a manner that the points of intersection of the grid
are distributed evenly over the triangular areas, where the points
of intersection of the grid correspond to a colour position and a
reflectance curve calculated on the basis of a dye recipe is
associated with each of those colour positions; [0022] (iii)
providing a device enabling the colour corresponding to the
reflectance curve data to be rendered visible; wherein [0023] the
colour of the desired dyeing is defined by browsing the reflectance
curve data organized by the digital data processing device (ii)
using device (iii), communicating the data corresponding to the
colour defined from the digital data processing device (ii) to the
printing or dyeing apparatus (i), in which the communicated data
are used to control the printing or dyeing apparatus (i), thereby
dyeing or printing a textile fiber material in the defined
colour.
[0024] In other words, the problem indicated above is solved by the
present invention by providing a digital catalogue of colour
samples that can be reproduced easily and without metamerism on any
desired textile material meeting all the desired in-use properties,
the digital catalogue being equipped with a device enabling the
colours organized by the digital colour catalogue to be rendered
visible,
and a printing or dyeing apparatus capable of processing the
digital data communicated by the digital colour catalogue, and
[0025] to interconnect the digital colour catalogue with the
printing or dyeing apparatus in a manner that the said components
form an integrated operating unit, wherein the textile fiber
material is printed or dyed with the colour or colour pattern
defined previously.
[0026] A requirement profile drawn up for the desired dyeing
according to Step (a) is understood to mean the definition of the
properties or criteria that the dyed substrate is intended to
fulfil. Such properties or criteria are, for example,
application-related properties, such as the in-use fastness
properties, for example fastness to light, chlorine, rubbing,
wetting, wet rubbing, washing, water, seawater or perspiration.
Suitable substrates are, for example, textile fibre materials,
paper, plastics or metal. Further criteria in drawing up a
requirement profile may also include the dyeing or printing process
with which the desired dyeing is to be produced, the costs, for
example of the dyes, or the pricing of the product.
[0027] In the context of the present invention, the term "dyeing"
is not limited to dyeings in the customary sense, but also includes
printing of the fabrics. The terms "dyeing" and "dyed textile fiber
material, fabric or garment etc." accordingly include both dyeing
processes and printing processes and the coloured substrates
produced by means of such processes, respectively.
[0028] According to Step (b) in the method according to the
invention, a group of dyes is selected that meet the defined
requirement profile and cover the colour space as well as possible.
A group of dyes is understood to mean, for example, three or more
dyes. The selected dyes should also be readily combinable with one
another, i.e. they should have similar affinity to the fiber, for
example, when dyeing or printing cotton, they should exhibit
similar substantivity and reactivity. The number of colours in the
colour catalogue according to the invention that can be derived
arithmetically is thus dependent inter alia upon the location of
the selected dyes in the colour space, that is to say the number
increases with the size of the colour space covered by the selected
dyes. The selection of the dyes is advantageously made by a person
skilled in the field of textile dyeing.
[0029] As colour space for the method according to the invention
there can be used, for example, the known CIE Lab colour coordinate
system, the lightness axis L* being replaced by the depth of shade
characteristic FT. The advantage of that procedure is that colour
positions of identical depth of shade or of identical colour
strength lie in one plane of the colour space. The individual
planes of the colour space are defined by the pairs of values a*,
b*, which correspond to the values of the same name in the CIE Lab
colour coordinate system. The a*, b* value pairs characterise the
hue and the colour saturation, which are known to the person
skilled in the art from the field of colour communication or
colorimetrics and constitute a measure of the shade. Instead of the
term "colour saturation", the specialist literature also uses the
terms "chroma" or "colour brilliance". In the mentioned FTa*b*
colour space, colour positions of different depth of shade or
colour strength lie one above the other on different planes. When
using a depth of shade characteristic based on reflectance
measurements, it has proved advantageous to use an additional
weighting of the data based on the colour perception of the eye or
the impression of colour produced.
[0030] As colour space for the method according to the invention,
it is also possible to use, for example, the L*C*h colour system,
which is based on the same diagram as the CIE Lab colour coordinate
system (L*a*b* system), with polar coordinates being used instead
of rectangular coordinates.
[0031] A suitable depth of shade characteristic FT is, for example,
the standard depth, as described, for example, in P. Rabe and O.
Koch, Melliand Textilberichte 38 (1957) pages 173 to 177. The
standard depth can be indicated not only in the known 2/1, 1/1,
1/3, 1/6, 1/12 and 1/25 depths, but also further sub-divided, for
example in steps of 1/10 standard depth or smaller. Depth of shade
characteristics are known to the person skilled in the art of
textile dyeing.
[0032] As depth of shade characteristic it is also possible to use
values from reflectance measurements, obtainable according to
instructions in Textilveredlung (1986), pages 299 to 304.
[0033] According to the invention, first the colour positions of
the selected dyes must be determined according to Step (c),
preferably in the FTa*b* colour space, thus defining the colour
space for the subsequent Steps. The colour positions of the dyes
suitable for the desired dyeing are so selected that they lie on a
plane of identical depth of shade, for example on a plane defined
by the pairs of values a*, b*. The colour positions are ascertained
from calibration data. If the calibration data are not known, these
must first be ascertained by measurement using a commercially
available colorimetric apparatus, for example a commercially
available spectral photometer.
[0034] Normally the dyeing behaviour of many dyes in the textile
dyeing industry, i.e. their affinity to the fiber, such as their
exhaust properties, is non-linear and it is therefore possible in
only a small number of cases to infer from a known concentration
for a specific depth of shade, for example a 1/1 standard depth,
the concentration to use for a different depth of shade. Usually,
it is necessary to ascertain the concentration to use for different
depths of shade, and from that data to produce a characteristic
calibration curve for each selected dye, the desired material to be
dyed and the dyeing or printing process applied with the printing
or dyeing apparatus indicated under (i).
[0035] The depth of shade characteristic FT can be ascertained, for
example, from a standard depth colour chart. For that purpose, a
standard depth chart or a corresponding concentration curve is
produced in a manner known per se for each of the selected dyes,
for example for the five dyes indicated in FIG. 1 which
follows.
[0036] The known depth of shade plane thus establishes the
concentration of each dye to use for that depth of shade plane.
[0037] The planes of the FTa*b* colour space are segmented into
triangular areas according to Step (d), the corner points of the
triangular areas corresponding to the colour position of the dyes
that were selected for the desired dyeing in accordance with the
requirement profile. The individual triangular areas of each depth
of shade plane do not overlap. Each colour position in the colour
space is defined by a single dye recipe, which consists, for
example, of one dye when the desired colour position corresponds to
the FTa*b* data of a single dye, or the recipe is a mixture of, for
example, two dyes when the desired colour position lies on the
usually non-straight line connecting two dyes, or the recipe is a
mixture of, for example, three dyes where the ratio of those three
dyes corresponds to the point of intersection of a regular grid
superimposed arithmetically over the triangular areas according to
Step (e).
[0038] The dyes selected for the segmentation may themselves
already be mixtures of dyes, for example a mixture of two or three
dyes, that is to say, for example, that a corner point of the
triangular area already corresponds to the colour position of a dye
mixture. In that case also, the colour positions of the mixtures
must first be ascertained from calibration data.
[0039] Once the dyes for a segmentation have been selected and
their calibration data have been ascertained in a manner known per
se from reflectance measurements at different concentrations and
thus at different depths of shade and have been stored in a
computer, the segmentation of the FTa*b* colour space according to
(d) is complete. Using that stored information, according to Step
(e) colour positions for the selected dye combination are
calculated for a defined depth of shade FT, which colour positions
are spaced at regular intervals across the range of shades defined
by the a*,b* value pairs, that is to say the depth of shade plane
is divided into a grid. Each grid point corresponds to a specific
concentration ratio between the selected dyes and thus to a
specific dye recipe.
[0040] FIG. 1 shows the segmentation of the colour space in a depth
of shade plane into three segments, the reference numerals P1 to P5
corresponding to the FTa*b* data of the selected dyes Yellow 1
(P1), Yellow 2 (P2), Red (P3), Blue 1 (P4) and Blue 2 (P5).
[0041] FIG. 2 is a further example of the segmentation of the
colour space in a depth of shade plane into twelve segments, the
reference numerals P1 to P9 corresponding to the FTa*b* data of the
selected dyes Yellow 1 (P1), Yellow 2 (P2), Orange 1 (P3), Orange 2
(P4), Red 1 (P5), Red 2 (P6), Blue 1 (P7), Blue 2 (P8) and Blue 3
(P9).
[0042] The connecting lines shown in FIGS. 1 and 2 are the result
of mixing, in each case, two dyes in specific amounts at a
predetermined depth of shade, the end points of the connecting
lines corresponding to the colour positions of the selected
dyes.
[0043] FIG. 3 shows a single segment. It is the triangular area
produced by points P2, P3 and P4 in FIG. 1. The connecting lines
between points P2, P3 and P4 are the colour positions of each of
the two-component mixtures. The grid that has been superimposed
over the entire triangular area defines colour positions of
mixtures having different concentration ratios. Points P2, P3 and
P4 define the colour positions of the respective dyes in
concentrations C.sub.2, C.sub.3 and C.sub.4. A mixture having the
concentrations X.sub.2.times.C.sub.2, X.sub.3.times.C.sub.3 and
X.sub.4.times.C.sub.4 (where X.sub.2+X.sub.3+X.sub.4=1) defines a
grid point of the same depth of shade. The grid is produced by
interpolating series of mixtures between the single dyes in such a
manner that the given spacing of the grid is obtained. For the
interpolation, the conversion between K/S values and reflectance
values is made using the customary procedure according to
Kubelka-Munk, as indicated, for example, in Colour Physics for
Industry, Ed. R. McDonald, Society of Dyers and Colourists (1987),
Chapter 5, 116 ff. In that procedure, the reflectance spectrum and
the concentrations of the dyes are stored for each calculated grid
point.
[0044] FIG. 4 shows a different segment made up of the dyes P10, P5
and P8. A grid was calculated in the same manner for the triangular
area. Points P5 and P8 correspond to points P5 and P8 of FIG.
2.
[0045] The spacings between the grid points can be preselected. The
smaller the spacings, the more colour positions can be determined
within a triangular area. The depth of shade plane defined by a
triangular area corresponds, for example, to a trichromy at a depth
of shade, the corner points of the triangular area corresponding to
the colour positions selected for the trichromy. It is thus
possible to regulate the number of colours per trichromy and thus
also the number of colours in the catalogue.
[0046] FIG. 5 shows the same segment as FIG. 4, the difference
being that the spacing between the grid points is twice as large
and thus the number of colour positions determined is reduced to
1/4.
[0047] FIGS. 1 to 5 show a plane of the FTa*b* colour space. The
depth of shade characteristic FT of those planes corresponds, for
example, to a 2/3 standard depth. For each colour position in a
plane having a specific depth of shade characteristic FT, for
example for 1/10, 2/10 or 1/1 standard depth, the reflectance curve
and the amounts of dye required to dye a specific substrate in that
depth of shade are known. The dye concentration depends, for
example, on the dye itself, the depth of shade sought, the
application procedure and the substrate to be dyed or printed.
[0048] The colour positions corresponding to the points of
intersection of the grid are in each case associated with a
reflectance curve. Behind each reflectance curve lies a specific
dye recipe, that is to say digital instructions for the printing or
dyeing apparatus (i) as to the ratio in which the dyes that are to
be combined with one another are to be mixed in order to obtain a
dyeing that corresponds to the reflectance spectrum ascertained and
that meets the requirement profile defined in advance according to
(a).
[0049] The catalogue which meets the requirement profile defined in
advance according to (a) is made up of all the reflectance spectra
calculated for all the segments in the given depths of shade.
[0050] The reflectance spectra ascertained do not, of course, give
the observer any impression of colour. According to the invention,
implementation of an operation is required by means of which the
reflectance curve is first brought into a format that enables the
corresponding colour to be rendered visible using a suitable
device. Suitable devices for visualising the reflectance curves
are, for example, a colour-calibrated screen, such as a cathode ray
tube apparatus or a liquid crystal flat screen, or a
colour-calibrated projection apparatus. It is preferred to use a
colour-calibrated screen. For that purpose, the calculated
reflectance spectra are formatted in such a manner that they can be
imported into a commercially available colour communication system,
for example Colorite ImageMaster by Datacolor or Color Talk by
GretagMacbeth. In such a system, for example ImageMaster, the
spectra can be shown as real colours.
[0051] For any dyeing problem it is possible to obtain a
comprehensive catalogue of different shades which the user can
consult. All that is required is the calibration data of the
selected dyes.
[0052] The user, for example a colour designer, can then look for
colours in the catalogue that come closest to his colour original,
which may be an idea of a colour, and that meet the previously
defined requirements, and obtains the associated reflectance curves
which correspond to specific dye recipes. The recipes obtained are
communicated to the printing or dyeing apparatus capable of
processing such digital data.
[0053] Steps (c), (d) and (e) of the method to generate a digital
catalogue of colour samples are advantageously carried with the
digital data processing device (ii). The digital data processing
device (ii) is also used to store and manage or organize the data
obtained and to control the printing or dyeing apparatus (i). The
digital data processing device (ii) is e.g. a personal
computer.
[0054] To make it easy to locate the stored reflectance curves in a
data base, they can be provided with a title that contains the dyes
used, the substrate and process data and a serial code number. On
the basis of that information, the dye recipe associated with the
reflectance curves can be recalculated or stored in a recipe data
base.
[0055] A printing or dyeing apparatus capable of processing digital
data according to step (i) of the present invention is, for
example, a jet- or spray-dyeing apparatus, an ink-jet printing
apparatus or an electrical discharge printing device, preferably a
jet- or spray-dyeing apparatus or an ink-jet printing
apparatus.
[0056] Printing or dyeing is suitably carried out by unwinding a
web from a support and passing it through a dyeing or printing
unit, wherein the textile fiber is impregnated with at least one
aqueous dyeing composition containing the selected dyestuff, before
it is rewinded onto another support. After passing the dyeing or
printing unit and before being rewinded, the dyed or printed web
may continue to travel through a drying and fixing unit, wherein
the dyeings or printings are dried or fixed on the web. A
pretreatment unit may be arranged before the dyeing or printing
unit, wherein the web is pretreated e.g. with an aqueous alkaline
liquor in the case of dyeing or printing with reactive dyes.
Pretreatment may also be carried out separately. A washing and
draining unit may be arranged after the drying and fixing unit in
order to remove unfixed dye. Furthermore, a finishing unit may be
arranged after the drying and fixing unit or in the absence of a
drying and fixing unit, after the dyeing or printing unit, which
imparts, for example, softness, water repellency, antimicrobial- or
sun protection properties to the fabric.
[0057] The dyeing or printing unit comprises at least one
dispensing device, which allows the web to be uniformly impregnated
with the aqueous dyeing composition over its entire width. As an
example there may be mentioned a tube made, for example, of metal,
the longitudinal axis of which is directed perpendicular to the
moving direction of the web. The tube suitably comprises a
multitude of small openings, i.e. nozzles or orifices, being
equally spaced along its longitudinal axis, the openings being
faced toward the web and distributed in a way that the aqueous
dyestuff composition is uniformly distributed in the form of small
droplets over the entire width of the web. A further dispensing
device which comes into consideration for the process according to
the present invention is an ink-jet print head. By means of an
ink-jet print head individual droplets of an aqueous ink are
sprayed onto the substrate in a controlled manner from a nozzle.
Predominantly, the continuous and the drop-on-demand mode of
operation are known. In the continuous mode, the droplets are
produced continuously and any droplets not required for the
printing are conveyed to a collecting vessel and recycled, whereas
in the drop-on-demand mode droplets are produced and printed as
required; that is to say droplets are produced only when required
for the printing. The production of the droplets can be effected,
for example, by means of a piezo-inkjet head or by means of thermal
energy (bubble jet). Preference is given to printing by means of a
piezo-ink-jet head for the method according to the invention.
[0058] The dyeing or printing unit may comprise one or more than
one, e.g. one, two, three, four, or up to twelve dispensing
devices, one being arranged after the other. The dyeing or printing
unit may further comprise an arrangement, wherein at least one
dispensing device is located on each side of the web, thereby
allowing for complete penetration of the dyeing composition over
the entire profile of the web. The dispensing devices on each side
of the web can be arranged either directly opposite to one another
or laterally displaced with respect to one another. In that case
the web is moved along between the dispensing devices.
[0059] The position of the dispensing device may be fixed, such as
in the case of the tube described above, or it may be installed in
a way allowing it to be moved in a direction perpendicular to the
moving direction of the web, so that any point over the entire
width of the web may be reached, such as in the case for ink-jet
printing.
[0060] The dispensing device is feeded by a reservoir containing
the aqueous dyeing composition. The printing or dyeing apparatus
capable of processing digital data according to step (i) comprises
a reservoir for each of the dyes selected for segmentation of the
color space from the group of dyes that meet the requirement
profile according to step (b) of the process of generating the
digital colour catalogue. In order to obtain a dyeing that
corresponds to the reflectance spectra ascertained, the dyes have
to be mixed in the corresponding ratio. Mixing may be accomplished
by means of an automatic dosing system, a system of valves and
pumps, which receives the required commands from the digital data
processing device (ii) and, in accordance with the commands
received, doses or injects the liquid compositions of the selected
dyes into a mixing chamber. The collected, mixed liquids leaving
the mixing chamber finally arrive at the dispensing device.
Advantageously, mixing is carried out on-line, which means that
automatic dosing system and mixing chamber are an integrated part
of the supply-line between the reservoir and the dispensing device
and only the amounts of liquid dyestuff compositions are fed into
the mixing chamber which are actually consumed in the dyeing
process. Mixing may also be accomplished directly on the web. In
that case, an automatic dosing system and a mixing chamber is not
required and each dispensing device is fed by a separate reservoir
which allows each dyestuff liquor to be sprayed on the web in the
predetermined quantity.
[0061] In an interesting embodiment of the present invention there
comes into consideration an ink-jet print head as a dispensing
device which comprises [0062] a nozzle layer (ai) defining a
plurality of ejection nozzles, [0063] an ink supply layer (bi)
which is formed from a porous material having a multitude of small
interconnected pores so as to allow passage of ink therethrough,
the ink supply layer featuring a plurality of connecting bores
(holes) from the rear surface to the front surface, each connecting
bore being aligned so as to connect between a corresponding one of
the ejection nozzles and [0064] a deflection layer (ci), comprising
a plurality of transducers related to the connecting bores for
ejecting ink droplets out through the nozzles.
[0065] The ink-jet print head applied in accordance with the
present invention may additionally comprise [0066] an ink cavity
layer (di), associated with the rear surface of the ink supply
layer (bi) having a plurality of apertures, each aperture being
positioned to correspond to one of the connecting bores of the ink
supply layer so as to at least partially define a corresponding ink
cavity.
[0067] The ink-jet print head applied in accordance with the
present invention comprises a layered structure, a key element of
which is the ink supply layer (bi) made of a porous material. The
ink supply layer (bi) is in direct communication with both the ink
reservoir and the individual ink cavities of the connecting bores
(holes) and/or the individual ink cavities of the ink cavity layer
(di), thereby acting as hydraulic linkage between the ink main
supply and the individual ink cavities.
[0068] The porous material includes, for example, sintered
material, most preferably, sintered stainless steel.
[0069] The ink cavity layer (di) may be omitted. In this case, the
deflection layer directly adjoins the ink supply layer.
[0070] The ink-jet print head used in accordance with the present
invention is described in detail in U.S. Pat. No. 5,940,099, the
disclosure of which is incorporated herein.
[0071] The ink-jet print head applied in accordance with the
present invention belongs to the category of drop on demand
systems, wherein the ink drops are ejected selectively as
required.
[0072] The transducers are, for example, piezoelectric crystals
(piezoelectric type) or thermoelectric elements (thermal bubble jet
type), preferably piezoelectric crystals.
[0073] The ejection of ink drops using a device according to one
embodiment of the present invention is accomplished as follows:
[0074] A pressure pulse is imparted to a volume of ink in an ink
cavity through the deflection of a thin deflection plate, or
diaphragm, located on top of the ink cavity. The plate is deflected
downward by the action of a piezoceramic crystal whenever a voltage
is applied across its electrodes, one of which is in electrical
contact with the usually metallic deflection plate. The pressure
pulse created by the downward bending of the deflection plate
drives the ink towards and through an outlet, having a convergent
nozzle at its outlet end, causing the ejection of a drop of a
specific size. When the piezoelectric crystal is de-energized, it
returns to its equilibrium position, reducing the pressure in the
ink cavity and causing the meniscus at the outlet end to retract.
The retracted meniscus generates a capillary force which acts to
pull ink from an ink reservoir through the porous material of the
ink supply layer (bi) into the ink cavity and into the connecting
bores (holes) related to the nozzle. The refilling process ends
when the meniscus regains its equilibrium position.
[0075] The micron grade and the surface area of the porous material
which is open for flow into the ink cavity has a crucial impact on
the refill time of the ink cavities and hence on the maximum drop
ejection rate, or frequency. The ink moves through the
interconnected pores and channels of the ink supply layer (bi) with
suitable flow resistances in order to realize system performance
which allows for high ejection frequencies, for example, 5 to 100
kHz, preferably 10 to 50 kHz and especially 20 to 40 kHz.
[0076] Further embodiments of suitable ink-jet print head
configurations comprising an ink supply layer which is formed from
a porous material are described in U.S. Pat. No. 5,940,099.
[0077] In a preferred embodiment of the present invention a
suitable ink-jet print head comprises [0078] a nozzle layer (ai)
defining a plurality of ejection nozzles, [0079] an ink supply
layer (bi) having a front surface associated with the nozzle layer
and a rear surface associated with a cavity layer (di), the ink
supply layer being formed with a plurality of connecting bores
(holes) from the rear surface to the front surface, each connecting
bore being aligned so as to connect between a corresponding one of
the ink cavities and a corresponding one of the ejection nozzles,
wherein the ink supply layer additionally features (ei) a pattern
of ink distribution channels formed in the front surface, and (fi)
at least one ink inlet bore passing from the rear surface to the
front surface and configured so as to be in direct fluid
communication with at least part of the pattern of ink distribution
channels, the pattern of ink distribution channels and the at least
one ink inlet bore together defining part of an ink flow path which
passes from the rear surface through the at least one ink inlet
bore to the pattern of ink distribution channels on the front
surface, and through the porous material to the plurality of ink
cavities. [0080] a deflection layer (ci), comprising a plurality of
transducers related to the connecting bores for ejecting ink
droplets out through the nozzles.
[0081] The location of ink distribution channels on the front
surface ensures that ink flow through the porous material of ink
supply layer occurs through the bulk of the layer. Preferably ink
distribution channels are distributed over the front surface in
such a pattern that each connecting bore is approximately the same
distance from its nearest ink distribution channel. In the typical
case that the connecting bores define an array on the front surface
having two row directions, the pattern of ink distribution channels
preferably includes a plurality of channels deployed substantially
parallel to one of the row directions and interposed between
adjacent rows of the connecting bores. The ink flow path is
particularly effective for providing a sufficient and generally
uniform ink supply to the porous layer across an entire array of
ink cavities.
[0082] The ink-jet print head which may be used in accordance with
the present invention is a multi-nozzle print head, the individual
nozzles of which are advantageously arranged as an array made up of
horizontal rows which are horizontally staggered, or skewed, with
respect to one another, comprising, for example, 512 nozzles
staggered in a 32.times.16 array.
[0083] The ink-jet print head which may be used in accordance with
the preferred embodiment of the present invention is described in
detail in U.S. Pat. No. 6,439,702, the disclosure of which is
incorporated herein.
[0084] Further embodiments of suitable ink-jet print head
configurations comprising an ink supply layer which is formed from
a porous material are described in U.S. Pat. No. 6,439,702.
[0085] The dispensing device which may be used in accordance with
the present invention comprises at least one of the ink-jet print
heads described above. Preferably, the printing device uses at
least 3 process colors, for example 3, 4, 5 or 6 process colors,
preferably 6 process colors, wherein each color is processed with
at least one print head, for example 1, 2, 3, 4, 5, 6 or 7 printing
heads, preferably 7 printing heads.
[0086] The ink-jet printing device described above allows textile
fiber materials to be printed with a speed of at least 50
m.sup.2/h, preferably in the range of 100 to 250 m.sup.2/h,
especially 150 to 250 m.sup.2/h.
[0087] In the drying and fixing unit, the web is exposed to e.g.
infra-red radiation (IR) or elevated temperatures. Fixing can be
effected, for example, by means of ultraviolet radiation (UV) or by
means of thermal energy or by subjecting the textile fiber material
to a steaming process.
[0088] Drying is carried out at temperatures of up to 150.degree.
C., especially from 80 to 120.degree. C.
[0089] In the steaming process, the printed fibrous material is
subjected, for example, to treatment in a steamer with steam which
is optionally superheated, e.g. at a temperature of from 95 to
180.degree. C., advantageously at from 95 to 130.degree. C.,
especially using saturated steam.
[0090] Fixing can be carried out batchwise at low temperature or at
elevated temperatures without passing the web through a drying and
fixing unit and rewinding it on a support after having passed the
dyeing or printing unit.
[0091] Low-temperature fixing takes place by storing the
impregnated and wound web at an ambient temperature, for example,
at a temperature between 10 and 40.degree. C., in particular
between 15 and 35.degree. C. The duration of the low-temperature
treatment can depend on the dye used and varies within wide limits,
which range from 3 to 24 hours, preferably from 4 to 10 hours,
particularly preferably from 6 to 8 hours.
[0092] A corresponding fixing treatment at elevated temperature, in
which the dye is fixed on the fiber by storage of the wound web at
a temperature above 40.degree. C., in particular of up to
70.degree. C., and preferably of up to 60.degree. C., in a storage
unit containing the impregnated and wound web, is also possible.
The duration of the treatment can depend on the dye used and varies
within wide limits. Preferably, the duration of the treatment is up
to 3 hours, in particular 0.5 to 3 hours, and preferably 1 to 3
hours.
[0093] In particular, the dyes used in the inks for ink-jet
printing according to the present invention should preferably have
a low salt content, that is to say should have a total salt content
of less than 0.5% by weight, based on the weight of the dyes. Dyes
which, as a result of their preparation and/or the subsequent
addition of diluents, have higher salt contents can be desalted,
for example, by membrane separation processes, such as
ultrafiltration, reverse osmosis or dialysis.
[0094] The aqueous dye compositions or the inks preferably have a
total dye content of from 1 to 35% by weight, especially from 1 to
30% by weight and more especially from 1 to 20% by weight, based on
the total weight of the ink. The preferred lower limit is 1.5% by
weight, especially 2% by weight, more especially 3% by weight.
[0095] The aqueous dye compositions or the inks may comprise
water-miscible organic solvents, for example
C.sub.1-C.sub.4alcohols, for example methanol, ethanol, n-propanol,
isopropanol, n-butanol, sec-butanol, tert-butanol or isobutanol;
amides, for example dimethylformamide or dimethylacetamide; ketones
or ketone alcohols, for example acetone, diacetone alcohol; ethers,
for example tetrahydrofuran or dioxane; nitrogen-containing
heterocyclic compounds, for example N-methyl-2-pyrrolidone or
1,3-dimethyl-2-imidazolidone; polyalkylene glycols, for example
polyethylene glycol or polypropylene glycol;
C.sub.2-C.sub.6alkylene glycols and thioglycols or di, tri or
tetramers of C.sub.2-C.sub.6alkylene glycols, for example ethylene
glycol, propylene glycol, butylene glycol, thiodiglycol, hexylene
glycol, diethylene glycol, triethylene glycol, dipropylene glycol,
tripropylene glycol; other polyols, for example glycerol or
1,2,6-hexanetriol; and C.sub.1-C.sub.4alkyl ethers of polyhydric
alcohols, for example 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,
2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol or
2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably
N-methyl-2-pyrrolidone, diethylene glycol, glycerol or, especially,
1,2-propylene glycol, usually in an amount of from 2 to 30% by
weight, preferably from 5 to 30% by weight and especially from 10
to 25% by weight, based on the total weight of the ink.
[0096] The aqueous dye compositions or the inks may also comprise
solubilisers, for example .epsilon.-caprolactam.
[0097] The aqueous dye compositions or the inks may comprise
thickening agents of natural or synthetic origin, inter alia for
the purpose of adjusting the viscosity.
[0098] Examples of thickeners that may be mentioned include
commercially available alginate thickeners, starch ethers or locust
bean flour ethers, especially sodium alginate on its own or in
admixture with modified cellulose, e.g. methylcellulose,
ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose,
methylhydroxyethylcellulose, hydroxypropyl cellulose or
hydroxypropyl methylcellulose, especially with preferably from 20
to 25% by weight carboxymethylcellulose. Synthetic thickeners that
may be mentioned are, for example, those based on poly(meth)acrylic
acids, poly(meth)acrylamides or polyvinyl pyrrolidones.
[0099] In a particularly preferred embodiment of the present
invention poly C.sub.2-C.sub.4-alkyleneglycol or the mono- or
di-C.sub.1-C.sub.4-alkyl ether of poly
C.sub.2-C.sub.4-alkyleneglycol is used as a viscosity adjusting
agent, the alkylene moieties of which may be straight chained or
branched, especially poly C.sub.2-C.sub.3-alkyleneglycol, such as,
polyethylene glycol, polypropylene glycol or a mixed ethylene
oxide/propylene oxide copolymerisate, and more especially a mixed
ethylene oxide/propylene oxide copolymerisate. The molar mass is,
for example, from 1,000 to 35,000 g/mol, preferably from 2,000 to
25,000 g/mol and especially from 3,000 to 20,000. The said
compounds are commercially available, for example, as P41-type
polyglycols (Clariant).
[0100] The aqueous dye compositions or the inks comprise such
thickening agents, for example, in an amount of from 0.01 to 2% by
weight, especially from 0.01 to 1% by weight, based on the total
weight of the ink.
[0101] The aqueous dye compositions or the inks may also comprise
buffer substances, for example borax, borates, phosphates,
polyphosphates or citrates. Examples which may be mentioned include
borax, sodium borate, sodium tetraborate, sodium dihydrogen
phosphate, disodium hydrogen phosphate, sodium tripolyphosphate,
sodium pentapolyphosphate, as well as sodium citrate. They are used
especially in amounts of from 0.1 to 3% by weight, preferably from
0.1 to 1% by weight, based on the total weight of the ink, in order
to establish a pH value of, for example, from 4 to 10, especially
from 5 to 9.5.
[0102] The aqueous dye compositions or the inks may comprise
surfactants or humectants as further additives.
[0103] There come into consideration as surfactants commercially
available anionic or non-ionic surfactants. In the inks according
to the invention, there come into consideration as humectants, for
example, urea or a mixture of sodium lactate (advantageously in the
form of a 50 to 60% aqueous solution) and glycerol and/or propylene
glycol in amounts of preferably from 0.1 to 30% by weight,
especially from 2 to 30% by weight.
[0104] Preference is given to inks having a viscosity of from 1 to
40 mPas, especially from 1 to 20 mPas and preferably from 1 to 10
mPas.
[0105] The aqueous dye compositions or the inks may also comprise
further conventional additives, for example antifoam agents or,
especially, substances inhibiting fungal and/or bacterial growth.
Such substances are usually used in amounts of from 0.01 to 1% by
weight, based on the total weight of the ink.
[0106] As preservatives there come into consideration
formaldehyde-releasing agents, e.g. paraformaldehyde and trioxane,
especially aqueous, for example 30 to 40% by weight formaldehyde
solutions, imidazole compounds, e.g. 2-(4-thiazolyl)benzimidazole,
thiazole compounds, e.g. 1,2-benzisothiazolin-3-one or
2-n-octyl-isothiazolin-3-one, iodine compounds, nitriles, phenols,
haloalkylthio compounds and pyridine derivatives, especially
1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one. As an
example for a broad spectrum biocide for the preservation against
spoilage from bacteria, yeasts and fungi a 20% by weight solution
of 1,2-benzisothiazolin-3one in dipropylene glycol (Proxel.TM. GXL)
can be used.
[0107] The aqueous dye compositions or the inks may comprise
further ingredients such as fluorinated polymers or telomers for
example polyethoxy perfluoro alcohols (Forafac.RTM. products) in an
amount of from 0.01 to 1% by weight based on the total weight of
the ink.
[0108] The method according to the invention is not limited to
specific dyes or specific textile substrates. Dyes of a wide
variety of dye classes can be used, irrespective of whether they
are water-soluble or disperse dyes. Preference is given to disperse
dyes, acid dyes, metal complex dyes, reactive dyes, vat dyes,
sulfur dyes, direct dyes and pigments, and also to cationic dyes.
Also suitable are natural dyes or developing dyes, such as naphthol
dyes.
[0109] As an example of the different dye classes, reference may be
made to the Colour Index; Colour Index, Third Edition, 1970/1971:
Acid Dyes, Volume 1, pages 1001 to 1562; Basic Dyes, Volume 1,
pages 1607 to 1688; Direct Dyes, Volume 2, pages 2005 to 2478;
Disperse Dyes, Volume 2, pages 2479 to 2743; Natural Dyes, Volume
3, pages 3225 to 3256; Pigments, Volume 3, pages 3267 to 3390;
Reactive Dyes, Volume 3, pages 3391 to 3560; Solvent Dyes, Volume
3, pages 3563 to 3648; Vat Dyes, Volume 3, pages 3719 to 3844.
[0110] Suitable acid dyes that can be used may belong to a wide
variety of dye classes and may contain one or more sulfonic acid
groups. They include, for example, triphenylmethane dyes having at
least two sulfonic acid groups, heavy-metal-free monoazo and disazo
dyes each having one or more sulfonic acid groups, and
heavy-metal-containing, namely copper-, chromium-, nickel- or
cobalt-containing, monoazo, disazo, azomethine and formazan dyes,
especially metallised dyes, that contain two molecules of azo dye,
or one molecule of azo dye and one molecule of azomethine dye,
bonded to a metal atom, especially such dyes containing mono-
and/or dis-azo dyes and/or azomethine dyes as ligands and a
chromium or cobalt ion as central atom, as well as anthraquinone
dyes, especially 1-amino-4-arylaminoanthraquinone-2-sulfonic acids
and 1,4-diarylamino- or
1-cycloalkylamino-4-arylaminoanthraquinonesulfonic acids.
[0111] There come into consideration as anionic acid dyes, for
example, dyes of formula ##STR1## wherein R.sub.1, R.sub.2, R.sub.3
and R.sub.4 are each independently of the others
C.sub.1-C.sub.4alkyl, and R.sub.5 is C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy or hydrogen; ##STR2## wherein R.sub.6 is
benzoylamino, phenoxy, chlorophenoxy, dichlorophenoxy or
methylphenoxy, R.sub.7 is hydrogen, benzoyl, phenyl or
C.sub.1-C.sub.4alkyl, and the substituents R.sub.8 are each
independently of the other hydrogen, phenylamino or
N-phenyl-N-methylaminosulfonyl; ##STR3## wherein [0112] the phenyl
ring B.sub.1 may be substituted by at least one substituent
selected from the group halogen, C.sub.1-C.sub.4alkyl and sulfo,
and [0113] R.sub.9 is .alpha.-bromoacryloylamino; ##STR4## wherein
R.sub.6 has the meanings given above, R.sub.10 is
C.sub.1-C.sub.8alkyl, and R.sub.11 is halogen; and ##STR5## 1:2
metal complex dyes, such as 1:2 chromium complex dyes of azo and
azomethine dyes of formulae ##STR6## wherein R.sub.12 is hydrogen,
sulfo or phenylazo, R.sub.13 is hydrogen or nitro, and the phenyl
ring B.sub.2 may be substituted by at least one substituent
selected from the group halogen, C.sub.1-C.sub.4alkyl and sulfo;
1:2 metal complex dyes, such as asymmetric (mixed) or symmetric 1:2
chromium complex dyes, preferably symmetric 1:2 chromium complex
dyes, of azo dyes of formulae ##STR7## wherein the phenyl ring
B.sub.3 may be substituted by at least one substituent selected
from the group halogen, C.sub.1-C.sub.4alkyl and sulfo, and
R.sub.14 and R.sub.15 are each independently of the other hydrogen,
nitro, sulfo, halogen, C.sub.1-C.sub.4alkylsulfonyl,
C.sub.1-C.sub.4alkylaminosulfonyl or --SO.sub.2NH.sub.2; and
##STR8## wherein R.sub.16 is hydrogen,
C.sub.1-C.sub.4alkoxycarbonylamino, benzoylamino,
C.sub.1-C.sub.4alkylsulfonylamino, phenylsulfonylamino,
methylphenylsulfonylamino or halogen, R.sub.17 is hydrogen or
halogen, and R.sub.18 is C.sub.1-C.sub.4alkylsulfonyl,
C.sub.1-C.sub.4alkylaminosulfonyl, phenylazo, sulfo or
--SO.sub.2NH.sub.2, the hydroxy group in the benzo ring D.sub.1
being bound in the o-position relative to the azo group on the
benzo ring D.sub.1; symmetric 1:2 cobalt complexes of the azo dyes
of formulae ##STR9## wherein R.sub.19 is an --OH or --NH.sub.2
group, R.sub.20 is hydrogen or C.sub.1-C.sub.4alkylaminosulfonyl,
and R.sub.21 is nitro or
C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyleneaminosulfonyl, and
##STR10## wherein R.sub.22 is carboxy or sulfo, and R.sub.23 is
halogen; asymmetric 1:2 chromium complex dyes of the azo dyes of
formulae ##STR11## wherein one substituent R.sub.24 is hydrogen and
the other is sulfo; ##STR12## wherein R.sub.25 is hydrogen or
nitro, the phenyl rings B.sub.4 and B.sub.5 each independently of
the other may be substituted by at least one substituent selected
from the group halogen, C.sub.1-C.sub.4alkyl and sulfo, and
R.sub.26 is hydrogen or halogen; and ##STR13## wherein the phenyl
rings B.sub.6, B.sub.7 and B.sub.8 each independently of the other
may in each case be substituted by at least one substituent
selected from the group halogen, C.sub.1-C.sub.4alkyl and sulfo,
R.sub.26 is hydrogen or nitro, R.sub.27 is hydrogen,
methoxycarbonylamino or acetylamino, and R.sub.28 is
C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylamino-sulfonyl,
phenylazo, sulfo or --SO.sub.2NH.sub.2; ##STR14## wherein the benzo
rings D.sub.2 are substituted by sulfo or sulfonamido;
anthraquinone dyes of formulae ##STR15## wherein R.sub.29 is
.alpha.-bromoacryloylamino, the substituents R.sub.30 are each
independently of the others hydrogen or C.sub.1-C.sub.4alkyl, and
R.sub.31 is hydrogen or sulfo; ##STR16## wherein the substituents
R.sub.32 are each independently of the other cyclohexyl or a
diphenyl ether radical that may be substituted by sulfo or by the
radical --CH.sub.2--NH--R.sub.29 in which R.sub.29 has the meanings
given above; and ##STR17## wherein R.sub.29 is
.alpha.-bromoacryloylamino, R.sub.30 has the meanings given for
formula (23), and R.sub.33 is C.sub.4-C.sub.8alkyl; ##STR18##
wherein (R.sub.34).sub.1-5 denotes from 1 to 5 identical or
different substituents selected from the group
C.sub.1-C.sub.4-alkyl unsubstituted or substituted by
C.sub.2-C.sub.4alkanoylamino (which may in turn be substituted in
the alkyl group by halogen) or by benzoylamino;
C.sub.1-C.sub.4alkoxy; C.sub.2-C.sub.4alkanoylamino and
C.sub.2-C.sub.4hydroxyalkylsulfamoyl; R.sub.35 is
C.sub.1-C.sub.4alkyl, C.sub.5-C.sub.7cycloalkyl unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, or phenyl unsubstituted or
substituted by phenoxy, C.sub.1-C.sub.4alkyl or by sulfo, the
phenoxy group in turn being unsubstituted or substituted in the
phenyl ring by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen
or by sulfo, especially by C.sub.1-C.sub.4alkyl or by sulfo;
R.sub.36 and R.sub.37 are each independently of the other sulfo,
C.sub.1-C.sub.4alkyl unsubstituted or substituted by
C.sub.2-C.sub.4alkanoylamino (which may in turn be substituted in
the alkyl group by halogen) or phenoxy unsubstituted or substituted
in the phenyl ring by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
halogen or by sulfo, especially by C.sub.1-C.sub.4alkyl or by
sulfo; and ##STR19## wherein R.sub.38 is halogen, phenylsulfonyl,
trifluoromethyl or ##STR20## in which R.sub.41 is cyclohexyl and
R.sub.42 is C.sub.1-C.sub.4alkyl, or the radicals R.sub.41 and
R.sub.42, together with the nitrogen atom linking them, form an
azepinyl ring; R.sub.39 is hydrogen or halogen, and R.sub.40 is
hydrogen or is phenoxy unsubstituted or substituted in the phenyl
ring by halogen; ##STR21## wherein R.sub.43 is hydrogen, halogen or
sulfo; R.sub.44 is hydrogen; halogen; phenoxy or phenoxysulfonyl
unsubstituted or substituted in the phenyl ring by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy or by halogen; a
radical of formula ##STR22## in which R.sub.48 is phenyl
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen or by sulfo, R.sub.49 is hydrogen or
C.sub.1-C.sub.4alkyl and R.sub.50 is halogen; or a radical of
formula ##STR23## in which R.sub.50 is as defined above; R.sub.45
is hydroxy or amino; and R.sub.46 and R.sub.47 are each
independently of the other hydrogen, C.sub.1-C.sub.4alkyl or
halogen; ##STR24## wherein R.sub.51 and R.sub.52 are each
independently of the other hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen or C.sub.2-C.sub.4alkanoylamino,
preferably hydrogen or C.sub.1-C.sub.4alkyl, R.sub.53 is phenyl
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen or by C.sub.2-C.sub.4-alkanoylamino,
preferably unsubstituted phenyl or phenyl substituted by
C.sub.1-C.sub.4alkyl; ##STR25## wherein R.sub.54 is hydrogen or
C.sub.1-C.sub.4alkyl, R.sub.55 is hydrogen or phenylsulfonyl
unsubstituted or substituted in the phenyl ring by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen or by
C.sub.2-C.sub.4alkanoylamino, preferably unsubstituted
phenylsulfonyl; ##STR26## wherein (R.sub.56).sub.0-2 denotes from 0
to 2 identical or different substituents selected from the group
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4alkoxy, halogen and phenoxy
unsubstituted or substituted in the phenyl ring by
C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.4alkoxy, sulfo, halogen or by
C.sub.2-C.sub.4alkanoylamino, preferably unsubstituted phenoxy or
phenoxy substituted by C.sub.1-C.sub.6alkyl or by halogen, and
R.sub.57 is benzoyl unsubstituted or substituted in the phenyl ring
by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, sulfo or by
halogen, preferably unsubstituted benzoyl, C.sub.2-C.sub.4alkanoyl
unsubstituted or substituted in the alkyl group by hydroxy or by
C.sub.1-C.sub.4alkoxy, preferably unsubstituted
C.sub.2-C.sub.4alkanoyl, e.g. acetyl, phenylsulfonyl or
methylphenylsulfonyl; and ##STR27## wherein R.sub.58 is hydrogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen or
C.sub.2-C.sub.4alkanoylamino unsubstituted or substituted in the
alkyl group by hydroxy, C.sub.1-C.sub.4alkoxy or by halogen;
R.sub.59 is phenyl unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, sulfo or by halogen,
preferably unsubstituted phenyl, and R.sub.60 is hydrogen or
C.sub.1-C.sub.4alkyl; and ##STR28## wherein R.sub.61 is a radical
of formula ##STR29## in which R.sub.48, R.sub.49 and R.sub.50 each
independently of the others, has the meaning given for formula (29)
above; ##STR30## wherein R.sub.62 and R.sub.63 are radicals of
formula ##STR31## wherein R.sub.45, R.sub.46 and R.sub.47, each
independently of the others, has the meaning given for formula (29)
above; ##STR32## wherein (R.sub.64).sub.0-2 denotes from 0 to 2
identical or different substituents selected from the group
C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4alkoxy, (R.sub.65).sub.0-2
denotes from 0 to 2 identical or different substituents selected
from the group sulfo, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
ureido, C.sub.2-C.sub.4alkanoylamino and ureido, and [0114]
(R.sub.66).sub.1-2 denotes from 0 to 2 identical or different
substituents selected from the group sulfo, C.sub.1-C.sub.4alkyl
and C.sub.1-C.sub.4alkoxy.
[0115] As C.sub.1-C.sub.4alkyl radicals there come into
consideration, for example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and
ethyl.
[0116] As C.sub.1-C.sub.6alkyl or C.sub.1-C.sub.8alkyl radicals
there come into consideration, for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl,
n-pentyl, sec-pentyl, isopentyl, n-hexyl, n-heptyl and n-octyl.
[0117] As C.sub.1-C.sub.4alkoxy radicals there come into
consideration, for example, methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, sec-butoxy, tert-butoxy and isobutoxy, preferably methoxy
and ethoxy, and especially methoxy.
[0118] As halogen there come into consideration, for example,
fluorine, chlorine, bromine and iodine, preferably chlorine and
bromine, and especially chlorine.
[0119] As C.sub.2-C.sub.4alkanoylamino radicals there come into
consideration, for example, acetylamino and propionylamino,
especially acetylamino.
[0120] As C.sub.1-C.sub.4alkylsulfonyl radicals there come into
consideration, for example, methylsulfonyl, ethylsulfonyl,
n-propylsulfonyl, isopropylsulfonyl and n-butylsulfonyl, preferably
methylsulfonyl and ethylsulfonyl.
[0121] As C.sub.1-C.sub.4alkylaminosulfonyl radicals there come
into consideration, for example, methylaminosulfonyl,
ethylaminosulfonyl, n-propylaminosulfonyl, isopropylaminosulfonyl
and n-butylaminosulfonyl, preferably methylaminosulfonyl and
ethylaminosulfonyl.
[0122] As C.sub.1-C.sub.4alkoxycarbonylamino radicals there come
into consideration, for example, methoxycarbonylamino,
ethoxycarbonylamino, n-propoxycarbonylamino,
isopropoxycarbonylamino and n-butoxycarbonylamino, preferably
methoxycarbonylamino and ethoxycarbonylamino.
[0123] As C.sub.1-C.sub.4alkylsulfonylamino radicals there come
into consideration, for example, methylsulfonylamino,
ethylsulfonylamino, n-propylsulfonylamino, isopropylsulfonylamino
and n-butylsulfonylamino, preferably methylsulfonylamino and
ethylsulfonylamino.
[0124] As C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkylenaminosulfonyl
radicals there come into consideration, for example,
methoxy-methyleneaminosulfonyl, methoxy-ethyleneaminosulfonyl,
ethoxy-methyleneaminosulfonyl and ethoxy-ethyleneaminosulfonyl,
preferably methoxyethyleneaminosulfonyl.
[0125] As C.sub.2-C.sub.4hydroxyalkylsulfamoyl radicals there come
into consideration, for example, .beta.-hydroxyethylsulfamoyl.
[0126] As C.sub.5-C.sub.7cycloalkyl radicals there come into
consideration, for example, cyclopentyl and cyclohexyl, preferably
cyclohexyl.
[0127] As C.sub.2-C.sub.4alkanoyl radicals there come into
consideration, for example, acetyl and propionyl, preferably
acetyl.
[0128] In a dedicated embodiment of the present invention the inks
comprise dyes of formulae (5), (9), (22), (26), (34) and (35).
[0129] Suitable dyes are, for example, the dyes of formulae
##STR33## ##STR34## ##STR35## ##STR36## ##STR37## ##STR38##
[0130] The dyes used in accordance with the present invention may
be used as single compounds or as a mixture of two or more
dyes.
[0131] Preferred are the dyes of formulae (5.1), (5.2), (9.1),
(22.1), (26.2), (26.3), (26.4), (26.5), (26.6), (26.7), (26.8),
(27.4), (28.2), (28.4), (29.3), (30.1), (31.1), (32.1), (32.2),
(32.3), (32.4), (34.1), (35.1), (37.1), (38.1) and (38.2), in
particular the dyes of formulae (5.2), (9.1), (22.1), (26.6),
(26.7), (34.1) and (35.1).
[0132] The dyes of formulae (1) to (38) are known or can be
obtained analogously to known compounds, e.g. by customary
diazotisation, coupling, addition and condensation reactions.
[0133] As the fiber reactive dyes there come into consideration,
for example, dyes of the formula A.sub.1-(Z.sub.1).sub.1-3 (39),
wherein A.sub.1 is the radical of a monoazo, disazo, polyazo,
metal-complexed azo, anthraquinone, phthalocyanine, formazan or
dioxazine chromophore having at least one sulfo group, and
(Z.sub.1).sub.1-3 is 1 to 3 identical or different fiber reactive
radicals, or dyes of the formula ##STR39## wherein Q.sub.1,
Q.sub.2, Q.sub.3 and Q.sub.4 are each independently of the others
hydrogen or unsubstituted or substituted C.sub.1-C.sub.4alkyl,
G.sub.1 and G.sub.2 are halogen, B is an organic bridge member,
A.sub.2 and A.sub.3 are each independently of the other as defined
for A.sub.1, or one of A.sub.2 and As is hydrogen or unsubstituted
or substituted C.sub.1-C.sub.4alkyl, phenyl or naphthyl and the
other one of A.sub.2 and A.sub.3 is as defined for A.sub.1,
(Z.sub.2).sub.0-1 and (Z.sub.3).sub.0-1 are each independently of
the other 0 or 1 identical or different fiber reactive radicals,
and b is the number 0 or 1.
[0134] The radicals Q.sub.1, Q.sub.2, Q.sub.3 and Q.sub.4 in the
reactive dye of formula (1) as alkyl radicals are straight-chain or
branched. The alkyl radicals may be further substituted, for
example by hydroxy, sulfo, sulfato, cyano or by carboxy. The
following radicals may be mentioned by way of example: methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and
tert-butyl, and also the corresponding hydroxy-, sulfo-, sulfato-,
cyano- or carboxy-substituted radicals. Preferred as substituents
are hydroxy, sulfo and sulfato, especially hydroxy and sulfato, and
preferably hydroxy.
[0135] Q.sub.1 and Q.sub.4 are preferably hydrogen or
C.sub.1-C.sub.4alkyl, especially hydrogen.
[0136] Q.sub.2 and Q.sub.3 are preferably each independently of the
other hydrogen or unsubstituted or hydroxy-, sulfo-, sulfato-,
cyano- or carboxy-substituted C.sub.1-C.sub.4alkyl. According to an
embodiment of interest, one of the radicals Q.sub.2 and Q.sub.3 is
hydroxy-, sulfo-, sulfato-, cyano- or carboxy-substituted
C.sub.1-C.sub.4alkyl, and the other of the radicals Q.sub.2 and
Q.sub.3 is hydrogen or C.sub.1-C.sub.4alkyl, especially
hydrogen.
[0137] Q.sub.2 and Q.sub.3 are especially preferably each
independently of the other hydrogen or C.sub.1-C.sub.4alkyl,
especially hydrogen.
[0138] G.sub.1 and G.sub.2 are preferably each independently of the
other chlorine or fluorine, especially fluorine.
[0139] The following come into consideration as organic bridge
members B, for example:
C.sub.2-C.sub.12alkylene radicals, especially
C.sub.2-C.sub.6alkylene radicals, which may be interrupted by 1, 2
or 3 members from the group --NH--, --N(CH.sub.3)-- and --O--,
especially --O--, and are unsubstituted or substituted by hydroxy,
sulfo, sulfato, cyano or by carboxy,
preferred substituents of the alkylene radicals mentioned for B
being hydroxy, sulfo and sulfato, especially hydroxy;
C.sub.5-C.sub.9cycloalkylene radicals, such as especially
cyclohexylene radicals, that are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.2-C.sub.4alkanoylamino, sulfo, halogen or by carboxy,
especially by C.sub.1-C.sub.4alkyl;
methylene-cyclohexylene-methylene radicals that are unsubstituted
or substituted in the cyclohexylene ring by
C.sub.1-C.sub.4alkyl;
C.sub.1-C.sub.6alkylenephenylene, or preferably phenylene, that is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.2-C.sub.4alkanoylamino, sulfo, halogen
or by carboxy.
[0140] Also suitable as a radical of formula
--N(Q.sub.2)--B--N(Q.sub.3)-- is a radical of the formula
##STR40##
[0141] Preferably B is a C.sub.2-C.sub.12alkylene radical which may
be interrupted by 1, 2 or 3 members from the group --NH--,
--N(CH.sub.3)-- and --O-- and is unsubstituted or substituted by
hydroxy, sulfo, sulfato, cyano or by carboxy; or
a phenylene radical that is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.2-C.sub.4-alkanoylamino, sulfo, halogen or by carboxy.
[0142] B is especially a C.sub.2-C.sub.12alkylene radical which may
be interrupted by 1, 2 or 3 members from the group --NH--,
--N(CH.sub.3)-- and --O--, especially --O--, and is unsubstituted
or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy. The
alkylene radical is preferably unsubstituted or substituted by
hydroxy, sulfo or by sulfato, especially by hydroxy.
[0143] B is more especially a C.sub.2-C.sub.12alkylene radical,
especially a C.sub.2-C.sub.6alkylene radical, which may be
interrupted by 1, 2 or 3 --O-- members and is unsubstituted or
substituted by hydroxy.
[0144] Bridge members B of special interest are
C.sub.2-C.sub.6alkylene radicals.
[0145] Fibre-reactive radicals are to be understood as meaning
those which are capable of reacting with the hydroxyl groups of
cellulose, the amino, carboxyl, hydroxyl and thiol groups in wool
and silk, or with the amino and possibly carboxyl groups of
synthetic polyamides, to form covalent chemical bonds. The
fibre-reactive radicals are as a rule bonded to the dye radical
directly or via a bridge member. Suitable fibre-reactive radicals
are, for example, those which contain at least one substituent
which can be split off on an aliphatic, aromatic or heterocyclic
radical, or in which the radicals mentioned contain a radical which
is capable of reaction with the fibre material, for example a vinyl
radical.
[0146] Preferably fiber reactive radicals Z.sub.1, Z.sub.2 and
Z.sub.3 independently of the other have the formula ##STR41## in
which Hal is chlorine or bromine; X.sub.1 is halogen,
3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl; T.sub.1
independently has the meaning of X.sub.1, or is a substituent which
is not fiber reactive or a fiber reactive radical of the formula
##STR42## in which R.sub.67, R.sub.68 and R.sub.69 independently of
one another are each hydrogen or C.sub.1-C.sub.4alkyl, R.sub.70 is
hydrogen, C.sub.1-C.sub.4alkyl which is unsubstituted or
substituted by hydroxyl, sulfo, sulfato, carboxyl or cyano or a
radical ##STR43## R.sub.71 is hydrogen, hydroxyl, sulfo, sulfato,
carboxyl, cyano, halogen, C.sub.1-C.sub.4alkoxycarbonyl,
C.sub.1-C.sub.4alkanoyloxy, carbamoyl or the group --SO.sub.2--Y,
alk and alk.sub.1 independently of one another are linear or
branched C.sub.1-C.sub.6alkylene, arylene is a phenylene or
naphthylene radical which is unsubstituted or substituted by sulfo,
carboxyl, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy or halogen, Q
is a radical --O-- or --NR.sub.69--, in which R.sub.69 is as
defined above, W is a group --SO.sub.2--NR.sub.70--,
--CONR.sub.70-- or --NR.sub.70CO--, in which R.sub.70 is as defined
above, Y is vinyl or a radical --CH.sub.2--CH.sub.2--U and U is a
group which can be split off under alkaline conditions, Y.sub.1 is
a group --CH(Hal)-CH.sub.2-Hal or --C(Hal)=CH.sub.2 and Hal is
chlorine or bromine and l and m independently of one another are an
integer from 1 to 6 and n is the number 0 or 1; and X.sub.2 is
halogen or C.sub.1-C.sub.4alkylsulfonyl; X.sub.3 is halogen or
C.sub.1-C.sub.4alkyl and T.sub.2 is hydrogen, cyano or halogen.
[0147] A group U which can be split off under alkaline conditions
is, for example, --Cl, --Br, --F, --OSO.sub.3H, --SSO.sub.3H,
--OCO--CH.sub.3, --OPO.sub.3H.sub.2, --OCO--C.sub.6H.sub.5,
--OSO.sub.2--C.sub.1-C.sub.4alkyl or
--OSO.sub.2--N(C.sub.1-C.sub.4alkyl).sub.2. U is preferably a group
of the formula --Cl, --OSO.sub.3H, --SSO.sub.3H, --OCO--CH.sub.3,
--OCO--C.sub.6H.sub.5 or --OPO.sub.3H.sub.2, in particular --Cl or
--OSO.sub.3H, and particularly preferably --OSO.sub.3H.
[0148] Examples of suitable radicals Y are accordingly vinyl,
.beta.-bromo- or .beta.-chloroethyl, .beta.-acetoxyethyl,
.beta.-benzoyloxyethyl, .beta.-phosphatoethyl, .beta.-sulfatoethyl
and .beta.-thiosulfatoethyl. Y is preferably vinyl,
.beta.-chloroethyl or .beta.-sulfatoethyl, and in particular vinyl
or .beta.-sulfatoethyl.
[0149] R.sub.67, R.sub.68 and R.sub.69 independently of one another
are each preferably hydrogen, methyl or ethyl, and particularly
preferably hydrogen.
[0150] R.sub.70 is preferably hydrogen or C.sub.1-C.sub.4alkyl,
such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl or tert-butyl, and particularly preferably hydrogen,
methyl or ethyl. R.sub.70 is particularly preferably hydrogen.
[0151] R.sub.71 is preferably hydrogen.
[0152] l and m independently of one another are preferably the
number 2, 3 or 4, and particularly preferably the number 2 or
3.
[0153] Especially preferably, l is the number 3 and m is the number
2.
[0154] Substituents T.sub.1 which are not fiber reactive are, for
example, the following radicals:
hydroxyl;
[0155] C.sub.1-C.sub.4alkoxy, for example methoxy, ethoxy, n- or
isopropoxy or n-, sec-, iso- or tert-butoxy, in particular methoxy
or ethoxy; the radicals mentioned are unsubstituted or substituted
in the alkyl moiety, for example by C.sub.1-C.sub.4alkoxy,
hydroxyl, sulfo or carboxyl;
C.sub.1-C.sub.4alkylthio, for example methylthio, ethylthio, n- or
isopropylthio or n-butylthio; the radicals mentioned are
unsubstituted or substituted in the alkyl moiety, for example by
C.sub.1-C.sub.4alkoxy, hydroxyl, sulfo or carboxyl;
amino;
[0156] N-mono- or N,N-di-C.sub.1-C.sub.6alkylamino, preferably
N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino; the radicals mentioned
are unsubstituted, uninterrupted or interrupted in the alkyl moiety
by oxygen or substituted in the alkyl moiety, for example by
C.sub.2-C.sub.4alkanoylamino, C.sub.1-C.sub.4alkoxy, hydroxyl,
sulfo, sulfato, carboxyl, cyano, carbamoyl or sulfamoyl; examples
are N-methylamino, N-ethylamino, N-propylamino, N,N-di-methylamino
or N,N-di-ethylamino, N-.beta.-hydroxyethylamino,
N,N-di-.beta.-hydroxyethylamino,
N-2-(.beta.-hydroxyethoxy)ethylamino,
N-2-[2-(.beta.-hydroxyethoxy)ethoxy]ethylamino,
N-.beta.-sulfatoethylamino, N-.beta.-sulfoethylamino,
N-carboxymethylamino, N-.beta.-carboxyethylamino,
N-.alpha.,.beta.-dicarboxyethylamino,
N-.alpha.,.gamma.-dicarboxypropylamino,
N-ethyl-N-.beta.-hydroxyethylamino or
N-methyl-N-.beta.-hydroxyethylamino;
C.sub.5-C.sub.7cycloalkylamino, for example cyclohexylamino, which
includes both the unsubstituted radicals and the radicals
substituted in the cycloalkyl ring, for example by
C.sub.1-C.sub.4alkyl, in particular methyl, or carboxyl;
[0157] phenylamino or N--C.sub.1-C.sub.4alkyl-N-phenylamino, which
includes both the unsubstituted radicals and the radicals
substituted in the phenyl ring, for example by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.2-C.sub.4alkanoylamino, carboxyl, carbamoyl, sulfo or
halogen, for example 2-, 3- or 4-chlorophenylamino, 2-, 3- or
4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or
4-sulfophenylamino, disulfophenylamino or 2-, 3- or
4-carboxyphenylamino;
[0158] naphthylamino which is unsubstituted or substituted in the
naphthyl ring, for example by sulfo, preferably the radicals
substituted by 1 to 3 sulfo groups, for example 1- or
2-naphthylamino, 1-sulfo-2-naphthylamino,
1,5-disulfo-2-naphthylamino or 4,8-disulfo-2-naphthylamino; or
benzylamino which is unsubstituted or substituted in the phenyl
moiety, for example by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
carboxyl, sulfo or halogen.
[0159] A radical T.sub.1 which is not fiber reactive is preferably
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, hydroxyl, amino,
N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino which are optionally
substituted in the alkyl moiety by hydroxyl, sulfato or sulfo,
morpholino, phenylamino or N--C.sub.1-C.sub.4alkyl-N-phenylamino
which are unsubstituted or substituted in the phenyl ring by sulfo,
carboxyl, acetylamino, chlorine, methyl or methoxy and in which the
alkyl is unsubstituted or substituted by hydroxyl, sulfo or
sulfato, or naphthylamino which is unsubstituted or substituted by
1 to 3 sulfo groups.
[0160] Particularly preferred radicals T.sub.1 which are not fiber
reactive are amino, N-methylamino, N-ethylamino,
N-.beta.-hydroxyethylamino, N-methyl-N-.beta.-hydroxyethylamino,
N-ethyl-N-.beta.-hydroxyethylamino,
N,N-di-.beta.-hydroxyethylamino, N-.beta.-sulfatoethylamino,
N-.beta.-sulfoethylamino, morpholino, 2-, 3- or
4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or
N--C.sub.1-C.sub.4-alkyl-N-phenylamino.
[0161] X.sub.1 is preferably halogen, for example fluorine,
chlorine or bromine, and particularly preferably chlorine or
fluorine.
[0162] Halogen T.sub.2, X.sub.2 and X.sub.3 are, for example,
fluorine, chlorine or bromine, in particular chlorine or
fluorine.
[0163] C.sub.1-C.sub.4alkylsulfonyl X.sub.2 is, for example,
ethylsulfonyl or methylsulfonyl, and in particular
methylsulfonyl.
[0164] C.sub.1-C.sub.4alkyl X.sub.3 is, for example, methyl, ethyl,
n- or iso-propyl or n-, iso or tert-butyl, and in particular
methyl.
[0165] X.sub.2 and X.sub.3 independently of one another are
preferably chlorine or fluorine.
[0166] T.sub.2 is preferably cyano or chlorine.
[0167] Hal is preferably bromine.
[0168] alk and alk.sub.1 independently of one another are, for
example, a methylene, ethylene, 1,3-propylene, 1,4-butylene,
1,5-pentylene or 1,6-hexylene radical or branched isomers
thereof.
[0169] alk and alk.sub.1 independently of one another are
preferably each a C.sub.1-C.sub.4alkylene radical, and particularly
preferably an ethylene radical or propylene radical.
[0170] arylene is preferably a 1,3- or 1,4-phenylene radical which
is unsubstituted or substituted, for example by sulfo, methyl,
methoxy or carboxyl, and particularly preferably an unsubstituted
1,3- or 1,4-phenylene radical.
[0171] Q is preferably --NH-- or --O--, and particularly preferably
--O--.
[0172] W is preferably a group of the formula --CONH-- or --NHCO--,
in particular a group of the formula --CONH--.
[0173] n is preferably the number 0.
[0174] The reactive radicals of the formulae (4a) to (4f) are
preferably those in which W is a group of the formula --CONH--,
R.sub.69, R.sub.70 and R.sub.71 are each hydrogen, Q is the radical
--O-- or --NH--, alk and alk.sub.1 independently of one another are
each ethylene or propylene, arylene is phenylene which is
unsubstituted or substituted by methyl, methoxy, carboxyl or sulfo,
Y is vinyl or .beta.-sulfatoethyl, Y.sub.1 is --CHBr--CH.sub.2Br or
--CBr.dbd.CH.sub.2 and n is the number 0.
[0175] A fibre-reactive radical Z.sub.1, Z.sub.2 and Z.sub.3 is
particularly preferably a radical of the formula (3a), (3c), (3d),
(3e) or (3f), in which Y is vinyl, .beta.-chloroethyl or
.beta.-sulfatoethyl, Hal is bromine, R.sub.67 and R.sub.70 are
hydrogen, m is the number 2 or 3, X.sub.1 is halogen, T.sub.1 is
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio, hydroxyl, amino,
N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino which are unsubstituted
or substituted in the alkyl moiety by hydroxyl, sulfato or sulfo,
morpholino, phenylamino or N--C.sub.1-C.sub.4alkyl-N-phenylamino
which are unsubstituted or substituted in the phenyl ring by sulfo,
carboxyl, acetylamino, chlorine, methyl or methoxy and in which the
alkyl is unsubstituted or substituted by hydroxyl, sulfo or
sulfato, or naphthylamino which is unsubstituted or substituted by
1 to 3 sulfo groups, or a fibre-reactive radical of the formula
##STR44## in particular (42b'), (42c') or (42d'), in which Y is as
defined above and Y.sub.1 is a group --CH(Br)--CH.sub.2--Br or
--C(Br).dbd.CH.sub.2.
[0176] Preferred are dyes of the formula (1) which contain 1 or 2,
in particular 2, fiber reactive radicals Z.sub.1.
[0177] Preferred are dyes of the formula (2) which do not contain
fiber reactive radicals Z.sub.2 and Z.sub.3.
[0178] When one of A.sub.2 and A.sub.3 is unsubstituted or
substituted C.sub.1-C.sub.4alkyl, phenyl or naphthyl, it may be,
for example, C.sub.1-C.sub.4alkyl that is unsubstituted or
substituted by sulfo, sulfato, hydroxy, carboxy or by phenyl; or
phenyl or naphthyl each of which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, carboxy, sulfo or by
halogen. Preference is given to phenyl that is unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
carboxy, sulfo or by halogen.
[0179] Preferably A.sub.2 and A.sub.3 are each independently of the
other the radical of a monoazo, polyazo, metal-complexed azo,
anthraquinone, phthalocyanine, formazan or dioxazine chromophore
having at least one sulfo group.
[0180] A radical A.sub.1, A.sub.2 or A.sub.3 as the radical of a
monoazo, polyazo, metal-complexed azo, anthraquinone,
phthalocyanine, formazan or dioxazine chromophore may have the
substituents customary in organic dyes bonded to its base
structure.
[0181] The following may be mentioned as examples of substituents
in the radicals A.sub.1, A.sub.2 and A.sub.3: alkyl groups having
from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl
or butyl, it being possible for the alkyl radicals to be further
substituted e.g. by hydroxy, sulfo or by sulfato; alkoxy groups
having from 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy,
isopropoxy or butoxy, it being possible for the alkyl radicals to
be further substituted e.g. by hydroxy, sulfo or by sulfato; phenyl
that is unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxy or by sulfo; acylamino
groups having from 1 to 8 carbon atoms, especially such
alkanoylamino groups, e.g. acetylamino or propionylamino;
benzoylamino that is unsubstituted or substituted in the phenyl
ring by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen or by
sulfo; phenylamino that is unsubstituted or substituted in the
phenyl ring by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen
or by sulfo; N,N-di-p-hydroxyethylamino;
N,N-di-.beta.-sulfatoethylamino; sulfobenzylamino;
N,N-disulfobenzylamino; alkoxycarbonyl having from 1 to 4 carbon
atoms in the alkoxy radical, such as methoxycarbonyl or
ethoxycarbonyl; alkylsulfonyl having from 1 to 4 carbon atoms, such
as methylsulfonyl or ethylsulfonyl; trifluoromethyl; nitro; amino;
cyano; halogen, such as fluorine, chlorine or bromine; carbamoyl;
N-alkyl-carbamoyl having from 1 to 4 carbon atoms in the alkyl
radical, such as N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl;
N-mono- or N,N-di-alkylsulfamoyl each having from 1 to 4 carbon
atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl,
N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, it
being possible for the alkyl radicals to be further substituted
e.g. by hydroxy or by sulfo; N-(.beta.-hydroxyethyl)-sulfamoyl;
N,N-di(.beta.-hydroxyethyl)-sulfamoyl; N-phenylsulfamoyl that is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxy or by sulfo; ureido;
hydroxy; carboxy; sulfomethyl or sulfo.
[0182] When A.sub.1, A.sub.2 and A.sub.3 are the radical of a
monoazo, polyazo or metal-complexed azo chromophore, the following
radicals, especially, come into consideration:
[0183] Chromophore radicals of a mono- or dis-azo dye of formula
D-N.dbd.N-(M-N.dbd.N).sub.u--K-- (43),
-D-N.dbd.N-(M-N.dbd.N).sub.u--K (44) or -D-N.dbd.N--K--N.dbd.N-D*-
(45), wherein D and D* independently of the other are the radicals
of a diazo component of the benzene or naphthalene series, M is the
radical of a middle component of the benzene or naphthalene series,
K is the radical of a coupling component of the benzene,
naphthalene, pyrazolone, 6-hydroxypyridone-(2) or acetoacetic acid
arylamide series and u is the number 0 or 1, it being possible in
the case of azo dyes for D, D*, M and K to carry customary
substituents, e.g. C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy
each of which is unsubstituted or may be further substituted by
hydroxy, sulfo or by sulfato; halogen; carboxy; sulfo; nitro;
cyano; trifluoromethyl; sulfamoyl; carbamoyl; amino; ureido;
hydroxy; carboxy; sulfomethyl; C.sub.2-C.sub.4alkanoylamino;
benzoylamino that is unsubstituted or substituted in the phenyl
ring by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen or by
sulfo; phenyl that is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxy or by
sulfo. Also suitable are the metal complexes derived from the above
dye radicals of formulae (43), (44) and (45), especially dye
radicals of a 1:1 copper-complexed azo dye of the benzene or
naphthalene series wherein the copper atom is bonded to a group
capable of metallation, e.g. a hydroxy group, on each side in the
ortho-position to the azo bridge.
[0184] The radicals of formulae (43), (44) and (45) are preferably
those of formula ##STR45## wherein (R.sub.72).sub.0-3 denotes from
0 to 3 identical or different substituents from the group
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.2-C.sub.4alkanoylamino, ureido, sulfamoyl, carbamoyl,
sulfomethyl, halogen, nitro, cyano, trifluoromethyl, amino,
hydroxy, carboxy and sulfo, (R.sub.73).sub.0-2 denotes from 0 to 2
identical or different substituents from the group hydroxy, amino,
N-mono-C.sub.1-C.sub.4alkylamino, N,N-di-C.sub.1-C.sub.4alkylamino,
C.sub.2-C.sub.4alkanoylamino and benzoylamino; ##STR46## wherein
(R.sub.73).sub.0-2 is as defined above; ##STR47## wherein
(R.sub.74).sub.0-3 and (R.sub.75).sub.0-3 independently of the
other denotes from 0 to 3 identical or different substituents from
the group C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen,
carboxy and sulfo; ##STR48## wherein R.sub.76 and R.sub.78 are each
independently of the other hydrogen, C.sub.1-C.sub.4alkyl or
phenyl, and R.sub.77 hydrogen, cyano, carbamoyl or sulfomethyl;
##STR49## wherein (R.sub.80).sub.0-3 denotes from 0 to 3 identical
or different substituents from the group C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, amino, carboxy and sulfo, and
(R.sub.79).sub.0-3 and (R.sub.81).sub.0-3 independently of the
other are as defined for (R.sub.72).sub.0-3; ##STR50## wherein
(R.sub.79).sub.0-3 and (R.sub.81).sub.0-3 independently of the
other are as defined above (R.sub.82).sub.0-2 denotes from 0 to 2
identical or different substituents from the group
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxy,
sulfo, hydroxy, amino, N-mono-C.sub.1-C.sub.4alkylamino,
N,N-di-C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.4alkanoylamino and
benzoylamino.
[0185] When A.sub.1, A.sub.2 and A.sub.3 are the radical of a
formazan dye the following radicals, especially, come into
consideration: ##STR51## wherein the benzene nuclei do not contain
any further substituents or are further substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylsulfonyl, halogen or by carboxy.
[0186] When A.sub.1, A.sub.2 and A.sub.3 are the radical of a
phthalocyanine dye the following radicals, especially, come into
consideration: ##STR52## wherein Pc is the radical of a metal
phthalocyanine, especially the radical of a copper or nickel
phthalocyanine, W' is --OH and/or --NR.sub.84R.sub.84' and R.sub.84
and R.sub.84' are each independently of the other hydrogen or
C.sub.1-C.sub.4alkyl that is unsubstituted or substituted by
hydroxy or by sulfo, R.sub.83 is hydrogen or C.sub.1-C.sub.4alkyl,
A is a phenylene radical that is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxy or by
sulfo or is a C.sub.2-C.sub.6alkylene radical and k is from 1 to
3.
[0187] When A.sub.1, A.sub.2 and A.sub.3 are the radical of a
dioxazine dye the following radicals, especially, come into
consideration: ##STR53## wherein A' is a phenylene radical that is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxy or by sulfo or is a
C.sub.2-C.sub.6alkylene radical, r independently is the number 0, 1
or 2, preferably 0 or 1, and v and v' are each independently of the
other the number 0 or 1.
[0188] When A.sub.1, A.sub.2 and A.sub.3 are the radical of a
anthrachinon dye the following radicals, especially, come into
consideration: ##STR54## wherein G is a phenylene radical that is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxy or by sulfo or is a
cyclohexylene, phenylenemethylene or C.sub.2-C.sub.6alkylene
radical.
[0189] Preferably b in the dye of formula (40) is the number 1.
[0190] Special interest is accorded to reactive dyes of formulae
##STR55## ##STR56## ##STR57## ##STR58## ##STR59## ##STR60##
##STR61## ##STR62## ##STR63## ##STR64## ##STR65## ##STR66##
##STR67## ##STR68## ##STR69##
[0191] In a particular preferred embodiment of the present
invention the dyes of formulae (39.1), (39.4), (39.9), (39.12),
(39.14), (39.15), (39-19), (39.23), (39.25), (39.27), (39.29),
(39.33), (39.35), (39.39), (39.40), (39.44), (39.45), (39.46) to
(39.49), (40.4), (40.10), (40.14), (40.15), (40.17) and (40.19) are
used.
[0192] The reactive dyes of formulae (39) and (40) are known or can
be obtained analogously to known compounds, e.g. by customary
diazotisation, coupling and condensation reactions.
[0193] Suitable disperse dyes for the process of the invention are
carboxyl- and/or sulfo-free nitro, amino, amino ketone, ketone
imine, methine, polymethine, diphenylamine, quinoline,
benzimidazole, xanthene, oxazine or coumarin dyes, and especially
anthraquinone dyes and azo dyes, such as monoazo or disazo
dyes.
[0194] As the disperse dyes there come into consideration, for
example, dyes of the formula ##STR70## in which R.sub.85 is
halogen, nitro or cyano, R.sub.86 is hydrogen, halogen, nitro or
cyano, R.sub.87 is hydrogen, halogen or cyano, R.sub.88 is
hydrogen, halogen, C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy,
R.sub.89 is hydrogen, halogen or C.sub.2-C.sub.4alkanoylamino, and
R.sub.90 and R.sub.91 independently of one another are hydrogen,
allyl, C.sub.1-C.sub.4alkyl which is unsubstituted or substituted
by hydroxy, cyano, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy,
C.sub.2-C.sub.4alkanoyloxy, C.sub.1-C.sub.4alkoxycarbonyl, phenyl
or phenoxy, ##STR71## in which R.sub.92 is hydrogen,
C.sub.1-C.sub.4alkyl, phenyl or phenylsulfonyl, the benzene ring in
phenyl and phenylsulfonyl being unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, sulfo or C.sub.1-C.sub.4alkyl-sulfonyloxy,
R.sub.93 is hydroxy, amino, N-mono- or
N,N-di-C.sub.1-C.sub.4alkylamino, phenylamino, the benzene ring in
phenyl being unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, C.sub.2-C.sub.4alkanoylamino or halogen,
R.sub.94 is hydrogen, C.sub.1-C.sub.4alkoxy or cyano, R.sub.95 is
hydrogen, C.sub.1-C.sub.4alkoxy, phenoxy or the radical
--O--C.sub.6H.sub.5--SO.sub.2--NH--(CH.sub.2).sub.3--O--C.sub.2H.sub.5,
R.sub.96 is hydrogen, hydroxy or nitro, and R.sub.97 is hydrogen,
hydroxy or nitro, ##STR72## in which R.sub.98 is
C.sub.1-C.sub.4alkyl which is unsubstituted or substituted by
hydroxy, R.sub.99 is C.sub.1-C.sub.4alkyl, R.sub.100 is cyano,
R.sub.101 is the radical of the formula
--(CH.sub.2).sub.3--O--(CH.sub.2).sub.2--O--C.sub.6H.sub.5,
R.sub.102 is halogen, nitro or cyano, and R.sub.103 is hydrogen,
halogen, nitro or cyano, ##STR73## in which R.sub.104 is
C.sub.1-C.sub.4alkyl, R.sub.105 is C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by C.sub.1-C.sub.4alkoxy and R.sub.106
is the radical --COOCH.sub.2CH.sub.2OC.sub.6H.sub.5 and R.sub.107
is hydrogen or R.sub.106 is hydrogen and R.sub.107 is the radical
--N.dbd.N--C.sub.6H.sub.5, ##STR74## where the rings A and B are
unsubstituted or substituted one or more times by halogen,
##STR75## in which R.sub.108 is C.sub.1-C.sub.4alkyl, which is
unsubstituted or substituted by hydroxy, C.sub.1-C.sub.4alkoxy,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4alkoxy,
C.sub.2-C.sub.4alkanoyloxy or C.sub.1-C.sub.4alkoxycarbonyl,
##STR76## in which R.sub.109 is C.sub.1-C.sub.4alkyl, R.sub.110 is
C.sub.1-C.sub.4alkyl, which is unsubstituted or substituted by
C.sub.1-C.sub.4alkoxy, R.sub.111 is hydrogen, C.sub.1-C.sub.4alkoxy
or halogen, and R.sub.112 is hydrogen, nitro, halogen or
phenylsulfonyloxy, ##STR77## in which R.sub.113, R.sub.114,
R.sub.115 and R.sub.116 independently of one another are hydrogen
or halogen, R.sub.117 is hydrogen, halogen, C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.4alkoxy, R.sub.118 is hydrogen, halogen or
C.sub.2-C.sub.4alkanoylamino, and R.sub.119 and R.sub.120
independently of one another are hydrogen, C.sub.1-C.sub.4alkyl,
which is unsubstituted or substituted by hydroxy, cyano, acetoxy or
phenoxy, ##STR78## in which R.sub.121 is hydrogen or halogen,
##STR79## in which R.sub.122 is hydrogen, C.sub.1-C.sub.4alkyl,
tetrahydrofuran-2-yl or C.sub.1-C.sub.4alkoxycarbonyl, which is
unsubstituted or substituted in the alkyl by C.sub.1-C.sub.4alkoxy,
##STR80## in which R.sub.123 is hydrogen or thiophenyl, which is
unsubstituted or substituted in the phenyl by C.sub.1-C.sub.4-alkyl
or C.sub.1-C.sub.4-alkoxy, R.sub.124 is hydrogen, hydroxy or amino,
R.sub.125 is hydrogen, halogen, cyano or thiophenyl, which is
unsubstituted or substituted in the phenyl by C.sub.1-C.sub.4alkyl
or C.sub.1-C.sub.4-alkoxy, phenoxy or phenyl, and R.sub.126 is
phenyl, which is unsubstituted or substituted by halogen,
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4-alkoxy, ##STR81## in which
R.sub.127 is hydrogen or C.sub.1-C.sub.4alkyl, R.sub.128 and
R.sub.129 independently of one another are hydrogen, halogen, nitro
or cyano, R.sub.130 is hydrogen, halogen, C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.4alkoxy, R.sub.131 is hydrogen, halogen or
C.sub.2-C.sub.4alkanoylamino, and R.sub.132 and R.sub.133
independently of one another are hydrogen or C.sub.1-C.sub.4alkyl,
which is unsubstituted or substituted by hydroxy, cyano,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy,
C.sub.2-C.sub.4alkanoyloxy, C.sub.1-C.sub.4alkoxycarbonyl, phenyl
or phenoxy.
[0195] As C.sub.1-C.sub.4alkyl radicals there come into
consideration, for example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and
ethyl.
[0196] As C.sub.1-C.sub.4alkoxy radicals there come into
consideration, for example, methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, sec-butoxy, tert-butoxy and isobutoxy, preferably methoxy
and ethoxy, and especially methoxy.
[0197] As halogen there come into consideration, for example,
fluorine, chlorine, bromine and iodine, preferably chlorine and
bromine, and especially chlorine.
[0198] As C.sub.2-C.sub.4alkanoylamino radicals there come into
consideration, for example, acetylamino and propionylamino,
especially acetylamino.
[0199] As C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy radicals
there come into consideration, for example, methoxy-methoxy,
methoxy-ethoxy, ethoxy-methoxy, ethoxy-ethoxy, ethoxy-n-propoxy,
n-propoxy-methoxy, n-propoxy-ethoxy, ethoxy-n-butoxy and
ethoxy-isopropoxy, preferably ethoxy-methoxy and ethoxy-ethoxy.
[0200] As N-mono- or N,N-di-C.sub.1-C.sub.4alkylamino radicals
there come into consideration, for example, N-methylamino,
N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino,
N-sec-butylamino, N-isobutylamino, N,N-dimethylamino and
N,N-diethylamino, preferably N-isopropylamino.
[0201] As C.sub.2-C.sub.4alkanoyloxy radicals there come into
consideration, for example, acetyloxy and propionyloxy, preferably
acetyloxy.
[0202] As C.sub.1-C.sub.4alkoxycarbonyl radicals there come into
consideration, for example, methoxycarbonyl, ethoxycarbonyl,
n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl,
preferably methoxycarbonyl and ethoxycarbonyl.
[0203] As C.sub.1-C.sub.4alkylsulfonyloxy radicals there come into
consideration, for example, methylsulfonyloxy, ethylsulfonyloxy,
n-propylsulfonyloxy, isopropylsulfonyloxy and n-butylsulfonyloxy,
preferably methylsulfonyloxy and ethylsulfonyloxy.
[0204] In the process of the invention, preference is given to
using the dyes of the formulae ##STR82## ##STR83## ##STR84##
##STR85## ##STR86##
[0205] The disperse dyes used in accordance with the present
invention may be used as single compounds or as a mixture of two or
more dyes.
[0206] Preferred are the disperse dyes of formulae (51.3), (51.4),
(51.5), (51.6), (51.7), (51.8), (51.9), (51.10), (51.11), (52.6),
(52.7), (52.8), (52.9), (52.10), (52.11), (52.12), (54.1), (56.2),
(58.1), (58.2), (58.3), (58.4), (60.1), (61.2), (63.1), (63.2),
(63.3), (63.4), (63.5) and (63.6), in particular the dyes of
formulae (51.3), (52.6), (52.7), (52.8), (52.9), (52.10), (52.11),
(52.12), (58.1) and (60.1).
[0207] The disperse dyes of formulae (51) to (63) are known or can
be obtained analogously to known compounds, e.g. by customary
diazotisation, coupling, addition and condensation reactions.
[0208] Suitable pigments for the process according to the invention
include both inorganic pigments, e.g. carbon black, titanium
dioxide and iron oxides, and organic pigments, especially those of
the phthalocyanine, anthraquinone, perinone, indigoid,
thioindigoid, dioxazine, diketopyrrolopyrrole, isoindolinone,
perylene, azo, quinacridone and metal complex series, for example
metal complexes of azo, azomethine or methine dyes, and also
classic azo dyes of the .beta.-oxynaphthoic acid and
acetoacetarylide series or metal salts of azo dyes. It is also
possible to use mixtures of different organic pigments or mixtures
of one or more inorganic pigments with one or more organic
pigments. Pigments of the monoazo, disazo, phthalocyanine and
anthraquinone series and also inorganic pigments, such as carbon
black and iron oxides, are of special interest.
[0209] As pigments there come into consideration, for example,
pigments of the formula ##STR87## wherein R.sub.134 is hydrogen,
halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, nitro or
cyano, R.sub.135 is hydrogen, halogen, nitro or cyano, R.sub.136 is
hydrogen, halogen or phenylaminocarbonyl, R.sub.137 is hydrogen or
hydroxy, and R.sub.138 is hydrogen or a radical of formula
##STR88## wherein R.sub.139 is hydrogen, C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.4alkoxy, R.sub.140 is hydrogen, C.sub.1-C.sub.4alkoxy
or halogen, and R.sub.141 is hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy or halogen, ##STR89## wherein R.sub.142 and
R.sub.143 are each independently of the other C.sub.1-C.sub.4alkyl
and R.sub.144 and R.sub.145 are halogen, ##STR90## wherein the
rings A, B, D and E are unsubstituted or mono- or poly-substituted
by halogen, ##STR91## wherein R.sub.146 is C.sub.1-C.sub.4alkyl,
R.sub.147 is hydrogen, halogen, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, nitro or cyano, R.sub.148 is hydrogen,
halogen, nitro or cyano, R.sub.149 is hydrogen, halogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, nitro or cyano,
##STR92## wherein the rings A' and B' are unsubstituted or mono- or
poly-substituted by halogen and the ring C' is unsubstituted or
mono- or poly-substituted by halogen, C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.4alkoxy, ##STR93## wherein (R.sub.150).sub.0-2 and
(R.sub.151).sub.0-2 each independently of the other denote from 0
to 2 substituents selected from the group halogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, nitro and cyano, and
K.sub.1 and K.sub.2 are each independently of the other a radical
of formula ##STR94## wherein (R.sub.1 52).sub.0-3 and
(R.sub.153).sub.0-3 each independently of the other denote from 0
to 3 substituents selected from the group halogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, nitro and cyano,
especially halogen, C.sub.1-C.sub.4alkyl and C.sub.1-C.sub.4alkoxy,
and ##STR95## wherein (R.sub.154).sub.0-2 and (R.sub.155).sub.0-2
each independently of the other denote from 0 to 3 substituents
selected from the group halogen, phenyl, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, nitro and cyano, especially halogen and
phenyl.
[0210] Inorganic pigments, such as carbon black and iron oxides,
are also of interest.
[0211] Of special interest are pigments of formulae ##STR96##
##STR97## ##STR98##
[0212] Further interesting pigments are C.I. Pigment Black 7, C.I.
Pigment Red 101, C.I. and Pigment Yellow 34.
[0213] In the process according to the invention it is especially
preferred to use as pigments those of formulae (64.1) to (70.2) and
C.I. Pigment Black 7.
[0214] The mentioned pigments are known or can be obtained
analogously to known preparation procedures, such as diazotisation,
coupling, addition and condensation reactions.
[0215] Advantageously, the aqueous compositions or the inks applied
in accordance with the claimed process comprise disperse dyes or
pigments, such as the dyes of formulae (51) to (63) or the pigments
of formulae (64) to (70) and (71.1), in a finely dispersed form.
For this purpose the disperse dyes or pigments are milled or
kneaded to an average particle size of between 0.1 and 10 microns,
preferably between 0.1 and 1 microns. Milling can be carried out in
the presence of dispersants. For example, the dried disperse dye or
pigment is milled with a dispersant or kneaded in paste form with a
dispersant and, if desired, is dried under reduced pressure or by
spraying. The resulting preparations can be used to prepare the
inks of the invention by addition of water and, if desired, of
further auxiliaries.
[0216] Suitable dispersants for disperse dyes are, for example,
anionic dispersants from the group (aa) acidic esters or their
salts of alkylene oxide adducts of the formula ##STR99## in which
R.sub.156 is C.sub.1-C.sub.12alkyl, aryl or aralkyl, "alkylen" is
the ethylene radical or propylene radical, R.sub.157 is the acid
radical of an inorganic, oxygen-containing acid, such as sulfuric
or, preferably, phosphoric acid, or else the radical of an organic
acid, and k is from 1 to 4 and t is from 4 to 50, (ab)
polystyrenesulfonates, (ac) fatty acid taurides, (ad) alkylated
diphenyl oxide mono- or disulfonates, (ae) sulfonates of
polycarboxylic esters, (af) an adduct of from 1 to 60, preferably
from 2 to 30, mol of ethylene oxide and/or propylene oxide with
fatty amines, fatty amides, fatty acids or fatty alcohols each
having 8 to 22 carbon atoms or with trihydric to hexahydric
alkanols having 3 to 6 carbon atoms, the said adduct being
converted into an acidic ester with an organic dicarboxylic acid or
with an inorganic polybasic acid, (ag) ligninsulfonates, (ah)
naphthalenesulfonates, and (aj) formaldehyde condensates.
[0217] As ligninsulfonates (ag) use is made primarily of those
ligninsulfonates, or their alkali metal salts, whose content of
sulfo groups does not exceed 25% by weight. Preferred
ligninsulfonates are those having a content of from 5 to 15% by
weight of sulfo groups.
[0218] Examples of suitable formaldehyde condensates (aj) are
condensates of ligninsulfonates and/or phenol and formaldehyde,
condensates of formaldehyde with aromatic sulfonic acids, such as
condensates of ditolyl ether sulfonates and formaldehyde,
condensates of naphthalenesulfonic acid with formaldehyde and/or of
naphthol- or naphthylaminosulfonic acids with formaldehyde,
condensates of phenolsulfonic acids and/or sulfonated
dihydroxydiphenyl sulfone and phenols or cresols with formaldehyde
and/or urea, and condensates of diphenyl oxide disulfonic acid
derivatives with formaldehyde.
[0219] Preferred products (ai) are [0220] condensates of ditolyl
ether sulfonates and formaldehyde, as described for example in U.S.
Pat. No. 4,386,037, [0221] condensates of phenol and formaldehyde
with ligninsulfonates, as described for example in U.S. Pat. No.
3,931,072, [0222] condensates of 2-naphthol-6-sulfonic acid,
cresol, sodium bisulfite and formaldehyde [cf. FIAT Report 1013
(1946)], and [0223] condensates of diphenyl derivatives and
formaldehyde, as described for example in U.S. Pat. No.
4,202,838.
[0224] A particularly preferred compound (aj) is the compound of
the formula ##STR100## in which R.sub.158 is a direct bond or
oxygen, R.sub.159 is the radical of an aromatic compound and is
attached to the methylene group by a ring carbon atom, M is
hydrogen or a salt-forming cation, such as an alkali metal,
alkaline earth metal or ammonium, and d and g independently of one
another are a number from 1 to 4.
[0225] A very particularly preferred compound (aj) is a compound
based on the sulfonated condensate of a chloromethylbiphenyl isomer
mixture and naphthalene, of the formula ##STR101## in which
(SO.sub.3Na).sub.1,4-1,6 denotes an average degree of sulfonation
of from 1.4 to 1.6.
[0226] The above dispersants are known or can be prepared in
analogy to known compounds by widely known processes.
[0227] Advantageously, the aqueous dye compositions or the inks
comprising disperse dyes may contain anionic copolymers, in
particular, those based on acrylic, methacrylic or maleic acid.
Among these, preference is given to those obtainable by
polymerization of acrylic and/or methacrylic acid and one or more
copolymerizable monomers selected from the group consisting of
maleic acid, N-vinylformamide, N-vinylacetamide, allylamine and
diallylamine derivatives, N-vinylpyrrolidone,
N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide,
N-vinyl-N-ethylacetamide, vinyl acetate, vinyl propionate,
acrylonitrile, styrene, methacrylonitrile, acrylamide,
methacrylamide and N-mono/N,N-di-C.sub.1-C.sub.10
alkyl(meth)acrylamide.
[0228] Particularly preferred anionic copolymers are those
obtainable by copolymerization of acrylic or methacrylic acid and
styrene.
[0229] Very particular preference is given to acrylic and
methacrylic acid-styrene copolymers having a molecular weight of
from 3000 to 16 000, in particular from 3000 to 10 000.
[0230] Suitable non-ionic dispersants for pigments are, for
example, compounds selected from the group of (ba) alkylene oxide
adducts of formula ##STR102## wherein R.sub.160 is
C.sub.1-C.sub.12alkyl, aryl or aralkyl, "alkylene" is the ethylene
radical or propylene radical and q is from 1 to 4 and p is from 4
to 50, (bb) alkylene oxide adducts with (bba) saturated or
unsaturated mono- to hexa-hydric aliphatic alcohols, (bbb) fatty
acids, (bbc) fatty amines, (bbd) fatty amides, (bbe) diamines,
(bbf) sorbitan esters, (bc) alkylene oxide condensation products
(block polymerisates), (bd) polymerisates of vinylpyrrolidone,
vinyl acetate or vinyl alcohol and (be) co- or ter-polymers of
vinylpyrrolidone with vinyl acetate and/or vinyl alcohol.
[0231] Suitable components (ba) are polyadducts of from 4 to 40 mol
of ethylene oxide with 1 mol of a phenol that contains at least one
C.sub.4-C.sub.12alkyl group, a phenyl group, a tolyl group, an
.alpha.-tolylethyl group, a benzyl group, an .alpha.-methylbenzyl
group or an .alpha.,.alpha.-dimethylbenzyl group, e.g. butylphenol,
tributylphenol, octylphenol, nonylphenol, dinonylphenol,
o-phenylphenol, benzylphenol, dibenzylphenol,
.alpha.-tolylethylphenol, dibenzyl(nonyl)phenol,
.alpha.-methylbenzyl-phenol, bis(.alpha.-methylbenzyl)phenol or
tris(.alpha.-methylbenzyl)phenol, such adducts being used on their
own or in admixture.
[0232] Of special interest as component (ba) are adducts of from 6
to 30 mol of ethylene oxide with 1 mol of 4-nonylphenol, with 1 mol
of dinonylphenol or especially with 1 mol of compounds prepared by
addition of from 1 to 3 mol of styrenes to 1 mol of phenols.
[0233] The preparation of the styrene addition products is carried
out in known manner, preferably in the presence of catalysts, such
as sulfuric acid, p-toluenesulfonic acid or especially zinc
chloride. As styrenes there come into consideration advantageously
styrene, a-methyl-styrene and vinyltoluene (4-methylstyrene).
Examples of the phenols are phenol, cresols and xylenols.
[0234] Very especially preferred are ethylene oxide adducts of
formula ##STR103## wherein f is from 1 to 3 and s is from 8 to
30.
[0235] Also preferred are ethylene oxide adducts of formula
##STR104## wherein R.sub.161 is C.sub.4-C.sub.12alkyl, phenyl,
tolyl, tolyl-C.sub.1-C.sub.3alkyl or phenyl-C.sub.1-C.sub.3alkyl,
e.g. .alpha.-methyl- or .alpha.,.alpha.-dimethyl-benzyl, and is
from 1 to 3 and w is from 4 to 40.
[0236] The non-ionic component (bb) is advantageously [0237] an
alkylene oxide addition product of from 1 to 100 mol of alkylene
oxide, e.g. ethylene oxide and/or propylene oxide, with 1 mol of an
aliphatic monoalcohol having at least 4 carbon atoms, of a tri- to
hexa-hydric aliphatic alcohol or of a phenol unsubstituted or
substituted by alkyl, phenyl, .alpha.-tolylethyl, benzyl,
.alpha.-methylbenzyl or by .alpha.,.alpha.-dimethylbenzyl (bba);
[0238] an alkylene oxide addition product of from 1 to 100 mol,
preferably from 2 to 80 mol, of ethylene oxide (wherein individual
ethylene oxide units may have been replaced by substituted
epoxides, such as styrene oxide and/or propylene oxide) with higher
unsaturated or saturated monoalcohols (bba), fatty acids (bbb),
fatty amines (bbc) or fatty amides (bbd) having from 8 to 22 carbon
atoms; [0239] an alkylene oxide addition product, preferably an
ethylene oxide/propylene oxide adduct with ethylenediamine (bbe);
[0240] an ethoxylated sorbitan ester having long-chain ester
groups, e.g. polyoxyethylene sorbitan monolaurate having from 4 to
20 ethylene oxide units or polyoxyethylene sorbitan trioleate
having from 4 to 20 ethylene oxide units (bbf).
[0241] Preferred components (bc) are ethylene oxide adducts with
polypropylene oxide (so-called EO-PO block polymers) and propylene
oxide adducts with polyethylene oxide (so-called reverse EO-PO
block polymers).
[0242] Special preference is given to ethylene oxide/propylene
oxide block polymers wherein the molecular weight of the
polypropylene oxide base is from 1700 to 4000 and the ethylene
oxide content in the total molecule is from 30 to 80%, especially
from 60 to 80%.
[0243] Also of interest are dispersants based on
naphthalenesulfonates.
[0244] Aqueous pigment compositions or pigment inks further
comprise a water-dispersible or water-soluble pigment dye binder in
order to bind the pigment to the textile fiber material.
[0245] Examples of binders that come into consideration include
pigment dye binders based on the polymerisation product of at least
one of the components acrylic acid; other acrylic monomers, e.g.
acrylic acid esters; and urethane. Preference is given to pigment
dye binders based on the polymerisation product of at least one of
the components acrylic acid and urethane. Of special importance are
pigment dye binders based on the polymerisation product of acrylic
acid; or urethane; or urethane and acrylic acid. Of special
interest are mixtures of pigment dye binders wherein one component
of the mixture is based on the polymerisation product of acrylic
acid and another component of the mixture is based on the
polymerisation product of acrylic acid and urethane. The pigment
dye binders are water-dispersible or, preferably, water-soluble.
Examples that may be mentioned include Carboset.RTM. 531 and
Sancure.RTM. AU-4010 from BFGoodrich.
[0246] In a very special embodiment of the process according to the
invention, the polymerisates that come into consideration as
binders do not contain sulfo or sulfato groups.
[0247] The pigment dye binder is present in the ink preferably in
an amount of from 2 to 30% by weight, especially in an amount of
from 5 to 20% by weight.
[0248] When ultraviolet radiation is used for fixation, the
presence of a photoinitiator is generally necessary. The
photoinitiator absorbs the radiation in order to produce free
radicals that initiate the polymerisation. Examples of
photoinitiators and photoinitiators used according to the invention
include carbonyl compounds, such as 2,3-hexanedione,
diacetylacetophenone, benzoin and benzoin ethers, such as dimethyl,
ethyl and butyl derivatives, e.g. 2,2-diethoxyacetophenone and
2,2-dimethoxyacetophenone, benzophenone or a benzophenone salt, and
phenyl-(1-hydroxycyclohexyl)-ketone or a ketone of formula
##STR105## benzophenone in combination with a catalyst such as
triethylamine, N,N'-dibenzylamine and dimethylaminoethanol and
benzophenone plus Michler's ketone; acylphosphine oxides;
nitrogen-containing compounds, such as diazomethane,
azo-bis-isobutyronitrile, hydrazine, phenylhydrazine and
trimethylbenzylammonium chloride; and sulfur-containing compounds,
such as benzenesulfonate, diphenyl disulfide and also
tetramethylthiuram disulfide, as well as phosphorus-containing
compounds, e.g. phosphine oxides. Such photoinitiators are used on
their own or in combination with one another.
[0249] The proportion of photoinitiators in the applied dye
components, immediately before irradiation, is from 0.01 to 20%,
preferably from 0.1 to 5%, based on the total amount of colourless
polymerisable compounds used.
[0250] Both water-soluble and water-insoluble photoinitiators are
suitable. In addition, copolymerisable photoinitiators, such as
those mentioned, for example, in "Polymers Paint Colour Journal",
180, page 42f (1990), are especially advantageous.
[0251] Also suitable are cationic photoinitiators, such as
triarylsulfonium salts, diaryliodonium salts, diaryl-iron complexes
or generally structures such as those described in "Chemistry &
Technology of UV & EB Formulation for Coatings, Inks &
Paints" Vol. 3, published by SITA Technology Ltd., Gardiner House,
Broomhill Road, London, 1991.
[0252] Fibrous textile materials that come into consideration for
the dyeing or printing with aqueous compositions comprising acid
dyes are nitrogen-containing or hydroxyl-group-containing fibrous
materials. As nitrogen-containing fibrous materials there come into
consideration natural or synthetic polyamide materials, e.g.
fibrous textile materials of silk, wool or synthetic polyamides.
Synthetic fibrous polyamide materials are, for example, fibrous
polyamide-6 and polyamide-66 materials.
[0253] Aqueous compositions comprising acid dyes may be used
especially for dyeing and printing of silk or silk-containing mixed
fibrous material. As silk there come into consideration not only
natural silk and cultured silk (mulberry silk, Bombyx mori) but
also the various wild silks, especially tussah silk, and also eria
and fagar silks, slub silk, Senegal silk, muga silk, and also
mussel silk and spider silk. Silk-containing fibrous materials are
especially blends of silk with polyester fibres, acrylic fibres,
cellulose fibres, polyamide fibres or with wool. The said textile
material can be in a wide variety of processing forms, e.g. in the
form of woven or knitted fabrics.
[0254] For printing silk or silk-containing fibrous material, the
fibrous material is preferably subjected to a pretreatment. To that
end the fibrous material is pretreated with an aqueous liquor
comprising a thickener and, where appropriate, a hydrotropic agent.
The thickeners preferably employed are alginate thickeners, such as
commercially available sodium alginate thickeners, which are used,
for example, in an amount of from 50 to 200 g/l of liquor,
preferably from 100 to 200 g/l of liquor. The hydrotropic agent
preferably employed is urea, which is used, for example, in an
amount of from 25 to 200 g/l of liquor, preferably from 25 to 75
g/l of liquor. The liquor may in addition comprise further
ingredients, e.g. ammonium tartrate. The liquor is preferably
applied to the fibrous material according to the pad-dyeing method,
especially with a liquor pick-up of from 70 to 100%. Preferably,
the fibrous material is dried after the above pretreatment.
[0255] Aqueous compositions comprising reactive dyes are used for
dyeing and printing of hydroxy-group-containing fibre materials.
Preference is given to cellulosic fibre materials that consist
wholly or partly of cellulose. Examples are natural fibre
materials, such as cotton, linen and hemp, and regenerated fibre
materials, for example viscose and lyocell. Special preference is
given to viscose and cotton, especially cotton. The said fibre
materials are preferably in the form of textile woven fabrics,
knitted fabrics or webs.
[0256] As already indicated above, the fibre material may be
subjected to a pretreatment with an aqueous alkaline liquor and the
treated fibre material is optionally dried.
[0257] The aqueous alkaline liquor comprises at least one of the
customary bases used for fixing the reactive dyes in conventional
reactive printing processes. The base is used, for example, in an
amount of from 10 to 100 g/l of liquor, preferably from 10 to 50
g/l of liquor. Suitable bases are, for example, sodium carbonate,
sodium hydroxide, disodium phosphate, trisodium phosphate, sodium
acetate, sodium propionate, sodium hydrogen carbonate, aqueous
ammonia or sources of alkali, such as sodium chloroacetate or
sodium formate. It is preferable to use sodium hydrogen carbonate,
sodium carbonate or a mixture of water glass and sodium carbonate.
The pH value of the alkaline liquor is generally from 7.5 to 13.5,
preferably from 8.5 to 12.5. In addition to the bases, the aqueous
alkaline liquor may also comprise further additives, e.g.
hydrotropic agents. The hydrotropic agent preferably used is urea,
which is used, for example, in an amount of from 25 to 200 g/l of
liquor, preferably from 50 to 150 g/l of liquor. In addition the
liquor for pretreating the fibre material may contain the sodium
salt of nitrobenzene sulfonic acid in an amount of 1 to 100 g/l of
liquor and a copolymer of acrylamide basis in an amount of 50 to
500 g/l of liquor as well as a silicon based softener, for example
a Megasoft.RTM. product in an amount of 0.1 to 100 g/l of
liquor.
[0258] An excellent colour performance is obtained with the
following pretreatment of the fibre material, whereby the fabric is
pretreated, for example by printing, padding, jet or spray
application, preferably pad-dyed with the liquor comprising a pad
dyeing auxiliary comprising acrylic acid amide/acrylic acid
copolymer from acrylic acid amide and acrylic acid monomer in an
amount of 0.5 to 5 g/l of liquor, urea in an amount of 50 to 150
g/l of liquor, a base, preferably soda ash, in an amount of 20 to
80 g/l of liquor, sodium salt of nitrobenzene sulfonic acid in an
amount of 5 to 50 g/l of liquor, a softener based on a amino
functional siloxane in an amount of 10 to 10 g/l of liquor and
optionally a salt, preferably sodium chloride, in an amount of 50
to 200 g/l of liquor.
[0259] Preferably the fibre material is dried after the above
pretreatment.
[0260] Aqueous compositions comprising reactive dyes or acid dyes
may also be used for dyeing and printing of synthetic polyamide
fibre materials, for example, polyamide-6
(poly-.epsilon.-caprolactam), polyamide-6,6
(polyhexamethyleneadipamide), polyamide-7, polyamide-6,12
(polyhexamethylenedodecanoamide), polyamide-11 and polyamide-12,
copolyamides with polyamide-6,6 or with polyamide-6, e.g. polymers
of hexamethylenediamine, 8-caprolactam and adipic acid and polymers
of adipic acid, hexamethylenediamine and isophthalic acid or of
adipic acid, hexamethylenediamine and 2-methylpentamethylenediamine
or 2-ethyltetramethylenediamine, and also blend fabrics or mixed
yarns of synthetic polyamide and wool.
[0261] Aqueous compositions comprising acid dyes or, in particular,
reactive dyes may also be used for dyeing and printing of
microfibres of synthetic polyamides. Microfibres are understood to
mean fibre materials constructed from threads having an individual
thread fineness of 1 denier (1.1 dTex). Such microfibres are known
and are usually produced by melt-spinning.
[0262] Aqueous compositions comprising disperse dyes may be used
for dyeing and printing of a variety of types of fibre material,
such as wool, silk, cellulose, polyvinyl, polyacrylonitrile,
polyamide, aramid, polypropylene, polyester or polyurethane.
[0263] Preference is given to polyester-containing fibre materials.
Suitable polyester-containing fibre materials are those consisting
wholly or partly of polyester. Examples are cellulose ester fibres,
such as secondary cellulose acetate and cellulose triacetate
fibres, and especially linear polyester fibres with or without acid
modification, which are obtained, for example, by condensation of
terephthalic acid with ethylene glycol or of isophthalic acid or
terephthalic acid with 1,4-bis(hydroxymethyl)cyclohexane, and also
fibres made from copolymers of terephthalic and isophthalic acid
with ethylene glycol. Suitability extends to polyester-containing
mixed-fibre materials; in other words, to blends of polyester with
other fibres.
[0264] Dyeing or printing of blends of polyester with other fibres,
for example cotton, may be advantageously carried out by supplying
at least one dispensing devise, such as one, two, three or four
dispensing devices, of the printing or dyeing apparatus with the
selected dyes suitable for the polyester part of the blend, e.g.
disperse dyes, and by supplying at least one dispensing devise,
such as one, two, three or four dispensing devices, of the printing
or dyeing apparatus with the selected dyes suitable for the cotton
part of the blend, e.g. fiber reactive dyes, it being possible to
adjust the ratio of the disperse and the fiber reactive dyes
applied to the fabric to the composition of the blend.
[0265] After printing, the fibre material is advantageously dried,
preferably at temperatures of up to 150.degree. C., especially from
80 to 120.degree. C., and then subjected to a heat treatment
process in order to complete the print, that is to say to fix the
dye, where required.
[0266] The subsequent fixing of the fibre material takes place in
general by means of dry heat (thermofixing) or by means of
superheated steam under atmospheric pressure (HT fixing). Fixing is
carried out under the following conditions: [0267] Thermofixing:
from 1 to 2 minutes at from 190 to 230.degree. C.; [0268] HT
fixing: from 4 to 9 minutes at from 170 to 190.degree. C.
[0269] The heat treatment can be carried out, for example, by means
of a hot batch process, a thermosol process or, preferably, by
means of a steaming process.
[0270] In the case of the steaming process the printed fibre
material is subjected, for example, to treatment in a steamer with
steam which is optionally superheated, advantageously at a
temperature of from 95 to 180.degree. C., more especially in
saturated steam.
[0271] Subsequently the printed fibre material is generally washed
off with water in customary manner in order to remove unfixed
dye.
[0272] Aqueous compositions comprising pigments may be used for
dyeing and printing of any of the fiber materials indicated above.
Fibrous textile materials that come into consideration are
especially hydroxyl-group-containing fibrous materials. Preference
is given to fibrous cellulosic materials that consist wholly or
partly of cellulose. Examples are natural fibrous materials, such
as cotton, linen and hemp, and regenerated fibrous materials, for
example viscose and lyocell. Special preference is given to viscose
and especially cotton. Further fibrous materials include wool,
silk, polyvinyl, polyacrylonitrile, polyamide, aramide,
polypropylene and polyurethane.
[0273] After printing, the fibrous material is advantageously
dried, preferably at temperatures of up to 150.degree. C.,
especially from 80 to 120.degree. C., and then the print is
fixed.
[0274] The print can be fixed, for example, by means of a heat
treatment, which is preferably carried out at a temperature of from
120 to 190.degree. C., the fixing preferably taking from 1 to 8
minutes.
[0275] The fixing can, however, also be carried out using
irradiation with UV light.
[0276] The printed or dyed fibrous material is advantageously
irradiated and fixed at elevated temperature, e.g. from 40 to
120.degree. C., especially from 60 to 100.degree. C. The
irradiation can take place immediately after the drying operation
or alternatively the cold printed fibrous material can be heated to
the desired temperature, e.g. in an infra-red heating apparatus,
prior to the irradiation.
[0277] The following examples serve to illustrate the invention.
Temperatures are stated in degrees Celsius, parts are parts by
weight and the percentage data are based on percentages by weight,
unless noted otherwise. Parts by weight bear the same relation to
parts by volume as the kilogram to the litre.
EXAMPLE 1
[0278] To dye polyamide, there are selected the acid dyes that, in
the form of the free acid, correspond to the formulae indicated
hereinafter:
as yellow component, the dyes of formulae (29.3), (31.1),
as red component, the dye of formula (28.4),
as blue component, a mixture of 75% by weight of the dye of formula
(26.5)
and 25% by weight of the dye of formula (26.8)
and the dye of formula (27.4).
[0279] First the calibration data of the dyes are ascertained for
the dyeing for which the colour catalogue is being produced. For
that purpose, in each case a polyamide-6.6 fiber material (Helanka
tricot) is dyed with a jet- or spray-dyeing apparatus using aqueous
compositions of different concentrations of the acid dyes specified
above. The jet- or spray-dyeing apparatus may be equipped with a
dispensing device as described above. The dyeings are measured by
spectral photometry and the CIE Lab colour coordinates are
determined. The depths of shade for the individual dyeings are
ascertained in known manner.
[0280] The depths of shade and the associated a* and b* data yield
the colour position of the above-mentioned dyes in the FTa*b*
colour space.
[0281] The colour space is then segmented within a depth of shade
plane. Such segmentation is shown for a pale shade within a depth
of shade plane in FIG. 1, where P1 corresponds to the colour
position of the yellow dye of formula (29.3) for that dyeing; P2
corresponds to the colour position of the yellow dye of formula
(31.1); P3 corresponds to the colour position of the red dye of
formula (28.4); P4 corresponds to the colour position of the blue
dye mixture of the dyes of formulae (26.5) and (26.8); and P5
corresponds to the colour position of the blue dye of formula
(27.4).
[0282] For the trichromy consisting of the dyes of formulae (28.4),
(31.1) and the dye mixture of the dyes of formulae (26.5) and
(26.8), the triangular area in that depth of shade plane is divided
arithmetically into a grid. The triangular area corresponds to the
area having the corner points P2, P3 and P4. The gridded triangular
area is shown in FIG. 3. Colour positions P2, P3 and P4 of the
selected dyes in that depth of shade plane correspond to 0.13% by
weight of the yellow dye of formula (31.1) for P2, 0.173% by weight
of the red dye of formula (28.4) for P3 and 0.194% by weight of the
blue dye mixture of the dyes of formulae (26.5) and (26.8) for P4.
The individual grid points on the connecting lines and within the
triangular area correspond to specific concentration ratios between
the dyes of formulae (28.4), (31.1), (26.5) and (26.8), that is to
say to a specific dye recipe, from which the corresponding
reflectance curves are calculated. The reflectance curves are
stored in a data base and formatted in such a manner that they can
be imported into a commercially available colour communication
system. The stored data are rendered visible as colours using a
calibrated colour screen.
[0283] A user is looking for a pale violet shade which he can use
to dye polyamide-6.6 fibre material. He decides upon the shade
denoted by Px in FIG. 3, which he locates quickly on the screen.
The dye recipe for the colour is recalculated by way of the
corresponding reflectance curve. The recipe is as follows:
0.0247% by weight of the yellow dye of formula (31.1),
0.0739% by weight of the red dye of formula (28.4) and
0.0747% by weight of the blue dye mixture of the dyes of formulae
(26.5) and (26.8).
[0284] The digital recipe data are communicated to the jet- or
spray-dyeing apparatus to control e.g. an automatic dosing system
indicated above, either directly as communicated or after being
submitted to an arithmetic operation to yield a format which may be
processed by the jet- or spray-dyeing apparatus, thereby dyeing
polyamide-6.6 fiber material.
[0285] The fabric is dried on line with an integrated hot air dryer
at 100.degree. C., fixed in saturated steam at 102.degree. C. and
is then washed off. A dyeing having good fastness properties is
obtained.
[0286] The colour of the dyed fabric is identical in terms of
shade, colour saturation and depth of shade to the shade Px from
the catalogue that was determined arithmetically.
EXAMPLE 2
[0287] To dye cotton, there are selected the reactive dyes that, in
the form of the free acid, correspond to the formulae indicated
hereinbelow:
as yellow component, the dyes of formulae (39.44), (40.17) and
(40.19),
as orange component, a mixture of the dyes of formulae (40.4),
(40.14) and (40.15) and a dye of formula (39.25),
as red component, the dyes of formulae (39.33) and (40.10),
as blue component, the dyes of formulae (39.4) and (39.12),
and a mixture of 32% by weight of the dye of formula (39.4) and 68%
by weight of the dye of formula (39.1).
[0288] First the calibration data of the dyes are ascertained for
the dyeing for which the colour catalogue is being produced. For
that purpose, in each case mercerised cotton satin fabric is dyed
with a jet- or spray-dyeing apparatus using aqueous compositions of
different concentrations of the reactive dyes specified above.
Prior to be dyed the cotton satin fabric is padded in a
pre-treatment operation with a liquor comprising 2 g/l of a pad
dyeing auxiliary comprising acrylic acid amide/acrylic acid
copolymer from acrylic acid amide and acrylic acid monomer, 100 g/l
of urea, 40 g/l soda ash, 100 g/l of sodium chloride, 20 g/l of
sodium salt of nitrobenzene sulfonic acid and 30 g/l of a softener
based on a amino functional siloxane (liquor pick-up 70%) and
dried. The jet- or spray-dyeing apparatus may be equipped with a
dispensing device as described above. The dyeings are measured by
spectral photometry and the CIE Lab colour coordinates are
determined. The depths of shade for the individual dyeings are
ascertained in known manner.
[0289] The depths of shade and the associated a* and b* data yield
the colour position of the dyes specified above in the FTa*b*
colour space.
[0290] The colour space is then segmented within a depth of shade
plane. Such segmentation is shown for a medium shade within a depth
of shade plane in FIG. 2, where P1 corresponds to the colour
position of the yellow dye of formula (39.44) for that dyeing; P2
corresponds to the colour position of the yellow dye of formula
(40.19); P3 corresponds to the colour position of the orange dye
mixture of the dyes of formulae (40.4), (40.14) and (40.15); P4
corresponds to the colour position of the orange dye of formula
(39.25); P5 corresponds to the colour position of the red dye of
formula (39.33); P6 corresponds to the colour position of the red
dye of formula (40.10); P7 corresponds to the colour position of
the blue dye of formula (39.12); P8 corresponds to the colour
position of the blue dye of formula (39.4); and P9 corresponds to
the colour position of the blue dye mixture of the dyes of formulae
(39.1) and (39.4).
[0291] For a trichromy consisting of the dyes of formulae (40.17),
(39.33) and (39.4), the triangular area in that depth of shade
plane is divided arithmetically into a grid. The triangular area
corresponds to the area having the corner points P10, P5 and P8.
The colour position P10 for the yellow dye of formula (40.17) is
not shown in FIG. 2. The gridded triangular area is shown in FIG.
4. The colour positions P10, P5 and P8 of the selected dyes in that
depth of shade plane correspond to 1.51% by weight of the yellow
dye of formula (40.17) for P10, 3.43% by weight of the red dye of
formula (39.33) for P5 and 2.84% by weight of the blue dye of
formula (39.4) for P8.
[0292] The individual grid points on the connecting lines and
within the triangular area correspond to specific concentration
ratios between the dyes of formulae (40.17), (39.33) and (39.4),
that is to say to a specific dye recipe, from which the
corresponding reflectance curves are calculated. The reflectance
curves are stored in a data base and formatted in such a manner
that they can be imported into a commercially available colour
communication system. The stored data are rendered visible as
colours using a calibrated colour screen.
[0293] A user is looking for a dull orange shade which he can use
to dye cotton tricot. He decides upon the shade denoted by Px in
FIG. 4, which he locates quickly on the screen. The dye recipe for
the colour is recalculated by way of the corresponding reflectance
curve. The recipe is as follows:
1.17% by weight of the yellow dye of formula (40.17),
0.707% by weight of the red dye of formula (39.33) and
0.0465% by weight of the blue dye of formula (39.4).
[0294] The digital recipe data are communicated to the jet- or
spray-dyeing apparatus to control e.g. an automatic dosing system
indicated above, either directly as communicated or after being
submitted to an arithmetic operation to yield a format which may be
processed by the jet- or spray-dyeing apparatus, thereby dyeing the
mercerised cotton satin fabric pretreated as given above.
[0295] The fabric is dried on line with an integrated hot air dryer
at 100.degree. C. A dyeing having very good fastness to washing is
obtained.
[0296] The colour of the dyed fabric is identical in terms of
shade, colour saturation and depth of shade to the shade Px from
the catalogue that was determined arithmetically.
DESCRIPTION OF THE FIGURES
[0297] FIG. 1 is a diagram showing a depth of shade plane in the
FTa*b* colour space, being segmented into 3 triangular areas,
points P1 to P5 being corner points of the triangular areas.
[0298] FIG. 2 is a diagram showing a depth of shade plane in the
FTa*b* colour space, being segmented into 12 triangular areas,
points P1 to P9 being the corner points of the triangular
areas.
[0299] FIG. 3 shows the gridded segment having the corner points
P2, P3 and P4 of FIG. 1.
[0300] FIG. 4 shows the gridded segment having the corner points
P10, P5 and P8, wherein P5 and P8 correspond to the corresponding
data of FIG. 2.
[0301] FIG. 5 shows the segment of FIG. 4 with a smaller number of
grid points.
* * * * *