US20070226919A1 - Method for Dyeing or Printing Textile Materials - Google Patents

Method for Dyeing or Printing Textile Materials Download PDF

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Publication number: US20070226919A1
Authority: US; United States
Prior art keywords: dyes; colour; dyeing; alkyl; printing
Prior art date: 2004-04-23
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Abandoned

Application number

US11/587,282

Other languages

English (en)

Inventor

Mickael Mheidle

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Huntsman International LLC

Original Assignee

Huntsman International LLC

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

2004-04-23

Filing date

2005-04-13

Publication date

2007-10-04

2005-04-13 Application filed by Huntsman International LLC filed Critical Huntsman International LLC

2007-10-04 Publication of US20070226919A1 publication Critical patent/US20070226919A1/en

2008-02-21 Assigned to HUNTSMAN INTERNATIONAL LLC reassignment HUNTSMAN INTERNATIONAL LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MHEIDLE, MICKAEL

Status Abandoned legal-status Critical Current

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Classifications

- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing

Definitions

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.
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.
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.
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.
the dyeings that are used to define the colour standard no account is taken of the fastness requirements for specific uses.
the number of colours in the colour catalogues that are available is limited, generally from 500 to 2500 different colours.
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.
An ideal colour standard does not necessarily have to be a dyeing, but can be represented by a reflectance curve.
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.
Another aspect is to shorten the time from the idea of a colour standard to the preparation of the textile fashion fabrics.
the problem underlying the present invention is to provide an integrated technical solution to textile professionals which accounts for the issues indicated above.
the present invention accordingly relates to a method for dyeing or printing a textile fiber material, which comprises the steps of
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,
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.
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.
the term “dyeing” is not limited to dyeings in the customary sense, but also includes printing of the fabrics.
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.
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.
colour saturation the specialist literature also uses the terms “chroma” or “colour brilliance”.
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.
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.
the depth of shade characteristic FT can be ascertained, for example, from a standard depth colour chart.
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.
the known depth of shade plane thus establishes the concentration of each dye to use for that depth of shade plane.
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).
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.
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.
FIG. 1 shows the segmentation of the colour space in a depth of shade plane into three segments, the reference numerals P 1 to P 5 corresponding to the FTa*b* data of the selected dyes Yellow 1 (P 1 ), Yellow 2 (P 2 ), Red (P 3 ), Blue 1 (P 4 ) and Blue 2 (P 5 ).
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 P 1 to P 9 corresponding to the FTa*b* data of the selected dyes Yellow 1 (P 1 ), Yellow 2 (P 2 ), Orange 1 (P 3 ), Orange 2 (P 4 ), Red 1 (P 5 ), Red 2 (P 6 ), Blue 1 (P 7 ), Blue 2 (P 8 ) and Blue 3 (P 9 ).
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.
FIG. 3 shows a single segment. It is the triangular area produced by points P 2 , P 3 and P 4 in FIG. 1 .
the connecting lines between points P 2 , P 3 and P 4 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 P 2 , P 3 and P 4 define the colour positions of the respective dyes in concentrations C 2 , C 3 and C 4 .
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.
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.
FIG. 4 shows a different segment made up of the dyes P 10 , P 5 and P 8 .
a grid was calculated in the same manner for the triangular area. Points P 5 and P 8 correspond to points P 5 and P 8 of FIG. 2 .
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.
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.
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.
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.
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).
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.
the reflectance spectra ascertained do not, of course, give the observer any impression of colour.
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.
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.
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.
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.
the stored reflectance curves can be provided with a title that contains the dyes used, the substrate and process data and a serial code number.
the dye recipe associated with the reflectance curves can be recalculated or stored in a recipe data base.
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.
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.
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.
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.
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.
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.
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.
the continuous and the drop-on-demand mode of operation are known.
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.
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.
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.
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.
the dyes 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.
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.
the ink-jet print head applied in accordance with the present invention may additionally comprise
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.
the porous material includes, for example, sintered material, most preferably, sintered stainless steel.
the ink cavity layer (di) may be omitted.
the deflection layer directly adjoins the ink supply layer.
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.
the transducers are, for example, piezoelectric crystals (piezoelectric type) or thermoelectric elements (thermal bubble jet type), preferably piezoelectric crystals.
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.
the piezoelectric crystal 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.
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.
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.
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.
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 ⁇ 16 array.
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.
the ink-jet printing device described above allows textile fiber materials to be printed with a speed of at least 50 m 2 /h, preferably in the range of 100 to 250 m 2 /h, especially 150 to 250 m 2 /h.
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.
UV ultraviolet radiation
thermal energy or by subjecting the textile fiber material to a steaming process.
Drying is carried out at temperatures of up to 150° C., especially from 80 to 120° C.
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° C., advantageously at from 95 to 130° C., especially using saturated steam.
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.
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° C., in particular between 15 and 35° 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.
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° C., in particular of up to 70° C., and preferably of up to 60° 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.
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.
the aqueous dye compositions or the inks may comprise water-miscible organic solvents, for example C 1 -C 4 alcohols, 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 2 -C 6 alkylene glycols and thioglycols or di, tri or tetramers of C 2 -C 6 alkylene glycols, for example ethylene
aqueous dye compositions or the inks may also comprise solubilisers, for example ⁇ -caprolactam.
aqueous dye compositions or the inks may comprise thickening agents of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity.
thickeners examples 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.
poly C 2 -C 4 -alkyleneglycol or the mono- or di-C 1 -C 4 -alkyl ether of poly C 2 -C 4 -alkyleneglycol is used as a viscosity adjusting agent, the alkylene moieties of which may be straight chained or branched, especially poly C 2 -C 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).
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.
the aqueous dye compositions or the inks may also comprise buffer substances, for example borax, borates, phosphates, polyphosphates or citrates.
buffer substances for example borax, borates, phosphates, polyphosphates or citrates.
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.
aqueous dye compositions or the inks may comprise surfactants or humectants as further additives.
surfactants commercially available anionic or non-ionic surfactants.
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.
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.
formaldehyde-releasing agents e.g. paraformaldehyde and trioxane
imidazole compounds e.g. 2-(4-thiazolyl)benzimidazole
thiazole compounds e.g. 1,2-benzisothiazol
yeasts and fungi 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 (ProxelTM GXL) can be used.
aqueous dye compositions or the inks may comprise further ingredients such as fluorinated polymers or telomers for example polyethoxy perfluoro alcohols (Forafac® products) in an amount of from 0.01 to 1% by weight based on the total weight of the ink.
fluorinated polymers or telomers for example polyethoxy perfluoro alcohols (Forafac® products) in an amount of from 0.01 to 1% by weight based on the total weight of the ink.
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.
Suitable acid dyes 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-arylaminoanthraquino
anionic acid dyes for example, dyes of formula wherein R 1 , R 2 , R 3 and R 4 are each independently of the others C 1 -C 4 alkyl, and R 5 is C 1 -C 4 alkyl, C 1 -C 4 alkoxy or hydrogen; wherein R 6 is benzoylamino, phenoxy, chlorophenoxy, dichlorophenoxy or methylphenoxy, R 7 is hydrogen, benzoyl, phenyl or C 1 -C 4 alkyl, and the substituents R 8 are each independently of the other hydrogen, phenylamino or N-phenyl-N-methylaminosulfonyl; wherein
C 1 -C 4 alkyl radicals there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and ethyl.
C 1 -C 4 alkoxy 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.
halogen there come into consideration, for example, fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and especially chlorine.
C 2 -C 4 alkanoylamino radicals there come into consideration, for example, acetylamino and propionylamino, especially acetylamino.
C 1 -C 4 alkylsulfonyl radicals there come into consideration, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl and n-butylsulfonyl, preferably methylsulfonyl and ethylsulfonyl.
C 1 -C 4 alkylaminosulfonyl radicals there come into consideration, for example, methylaminosulfonyl, ethylaminosulfonyl, n-propylaminosulfonyl, isopropylaminosulfonyl and n-butylaminosulfonyl, preferably methylaminosulfonyl and ethylaminosulfonyl.
C 1 -C 4 alkoxycarbonylamino radicals there come into consideration, for example, methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, isopropoxycarbonylamino and n-butoxycarbonylamino, preferably methoxycarbonylamino and ethoxycarbonylamino.
C 1 -C 4 alkylsulfonylamino radicals there come into consideration, for example, methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, isopropylsulfonylamino and n-butylsulfonylamino, preferably methylsulfonylamino and ethylsulfonylamino.
C 1 -C 4 alkoxy-C 1 -C 4 alkylenaminosulfonyl radicals there come into consideration, for example, methoxy-methyleneaminosulfonyl, methoxy-ethyleneaminosulfonyl, ethoxy-methyleneaminosulfonyl and ethoxy-ethyleneaminosulfonyl, preferably methoxyethyleneaminosulfonyl.
C 2 -C 4 hydroxyalkylsulfamoyl radicals there come into consideration, for example, ⁇ -hydroxyethylsulfamoyl.
C 5 -C 7 cycloalkyl radicals there come into consideration, for example, cyclopentyl and cyclohexyl, preferably cyclohexyl.
C 2 -C 4 alkanoyl radicals there come into consideration, for example, acetyl and propionyl, preferably acetyl.
the inks comprise dyes of formulae (5), (9), (22), (26), (34) and (35).
Suitable dyes are, for example, the dyes of formulae
the dyes used in accordance with the present invention may be used as single compounds or as a mixture of two or more dyes.
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.
dyes of the formula A 1 -(Z 1 ) 1-3 (39), wherein A 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 1 ) 1-3 is 1 to 3 identical or different fiber reactive radicals, or dyes of the formula wherein Q 1 , Q 2 , Q 3 and Q 4 are each independently of the others hydrogen or unsubstituted or substituted C 1 -C 4 alkyl, G 1 and G 2 are halogen, B is an organic bridge member, A 2 and A 3 are each independently of the other as defined for A 1 , or one of A 2 and As is hydrogen or unsubstituted or substituted C 1 -C 4 alkyl, phenyl or naphthyl and the other one of A 2 and A 3 is as
the radicals Q 1 , Q 2 , Q 3 and Q 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.
Q 1 and Q 4 are preferably hydrogen or C 1 -C 4 alkyl, especially hydrogen.
Q 2 and Q 3 are preferably each independently of the other hydrogen or unsubstituted or hydroxy-, sulfo-, sulfato-, cyano- or carboxy-substituted C 1 -C 4 alkyl.
one of the radicals Q 2 and Q 3 is hydroxy-, sulfo-, sulfato-, cyano- or carboxy-substituted C 1 -C 4 alkyl
the other of the radicals Q 2 and Q 3 is hydrogen or C 1 -C 4 alkyl, especially hydrogen.
Q 2 and Q 3 are especially preferably each independently of the other hydrogen or C 1 -C 4 alkyl, especially hydrogen.
G 1 and G 2 are preferably each independently of the other chlorine or fluorine, especially fluorine.
organic bridge members B for example:
C 2 -C 12 alkylene radicals especially C 2 -C 6 alkylene radicals, which may be interrupted by 1, 2 or 3 members from the group —NH—, —N(CH 3 )— and —O—, especially —O—, and are unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy,
C 5 -C 9 cycloalkylene radicals such as especially cyclohexylene radicals, that are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or by carboxy, especially by C 1 -C 4 alkyl;
C 1 -C 6 alkylenephenylene or preferably phenylene, that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or by carboxy.
B is a C 2 -C 12 alkylene radical which may be interrupted by 1, 2 or 3 members from the group —NH—, —N(CH 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 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 -alkanoylamino, sulfo, halogen or by carboxy.
B is especially a C 2 -C 12 alkylene radical which may be interrupted by 1, 2 or 3 members from the group —NH—, —N(CH 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.
B is more especially a C 2 -C 12 alkylene radical, especially a C 2 -C 6 alkylene radical, which may be interrupted by 1, 2 or 3 —O— members and is unsubstituted or substituted by hydroxy.
Bridge members B of special interest are C 2 -C 6 alkylene radicals.
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.
fiber reactive radicals Z 1 , Z 2 and Z 3 independently of the other have the formula in which Hal is chlorine or bromine; X 1 is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl; T 1 independently has the meaning of X 1 , or is a substituent which is not fiber reactive or a fiber reactive radical of the formula in which R 67 , R 68 and R 69 independently of one another are each hydrogen or C 1 -C 4 alkyl, R 70 is hydrogen, C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxyl or cyano or a radical R 71 is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkanoyloxy, carbamoyl or the group —SO
a group U which can be split off under alkaline conditions is, for example, —Cl, —Br, —F, —OSO 3 H, —SSO 3 H, —OCO—CH 3 , —OPO 3 H 2 , —OCO—C 6 H 5 , —OSO 2 —C 1 -C 4 alkyl or —OSO 2 —N(C 1 -C 4 alkyl) 2 .
U is preferably a group of the formula —Cl, —OSO 3 H, —SSO 3 H, —OCO—CH 3 , —OCO—C 6 H 5 or —OPO 3 H 2 , in particular —Cl or —OSO 3 H, and particularly preferably —OSO 3 H.
Suitable radicals Y are accordingly vinyl, ⁇ -bromo- or ⁇ -chloroethyl, ⁇ -acetoxyethyl, ⁇ -benzoyloxyethyl, ⁇ -phosphatoethyl, ⁇ -sulfatoethyl and ⁇ -thiosulfatoethyl.
Y is preferably vinyl, ⁇ -chloroethyl or ⁇ -sulfatoethyl, and in particular vinyl or ⁇ -sulfatoethyl.
R 67 , R 68 and R 69 independently of one another are each preferably hydrogen, methyl or ethyl, and particularly preferably hydrogen.
R 70 is preferably hydrogen or C 1 -C 4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and particularly preferably hydrogen, methyl or ethyl.
R 70 is particularly preferably hydrogen.
R 71 is preferably hydrogen.
l and m independently of one another are preferably the number 2, 3 or 4, and particularly preferably the number 2 or 3.
l is the number 3 and m is the number 2.
Substituents T 1 which are not fiber reactive are, for example, the following radicals:
C 1 -C 4 alkoxy 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 1 -C 4 alkoxy, hydroxyl, sulfo or carboxyl;
C 1 -C 4 alkylthio 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 1 -C 4 alkoxy, hydroxyl, sulfo or carboxyl;
N-mono- or N,N-di-C 1 -C 6 alkylamino preferably N-mono- or N,N-di-C 1 -C 4 alkylamino
the radicals mentioned are unsubstituted, uninterrupted or interrupted in the alkyl moiety by oxygen or substituted in the alkyl moiety, for example by C 2 -C 4 alkanoylamino, C 1 -C 4 alkoxy, 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- ⁇ -hydroxyethylamino, N,N-di- ⁇ -hydroxyethylamino, N-2-( ⁇ -hydroxyethoxy)ethylamino, N
C 5 -C 7 cycloalkylamino for example cyclohexylamino, which includes both the unsubstituted radicals and the radicals substituted in the cycloalkyl ring, for example by C 1 -C 4 alkyl, in particular methyl, or carboxyl;
phenylamino or N—C 1 -C 4 alkyl-N-phenylamino which includes both the unsubstituted radicals and the radicals substituted in the phenyl ring, for example by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, 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;
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 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxyl, sulfo or halogen.
a radical T 1 which is not fiber reactive is preferably C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, hydroxyl, amino, N-mono- or N,N-di-C 1 -C 4 alkylamino which are optionally substituted in the alkyl moiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino or N—C 1 -C 4 alkyl-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.
radicals T 1 which are not fiber reactive are amino, N-methylamino, N-ethylamino, N- ⁇ -hydroxyethylamino, N-methyl-N- ⁇ -hydroxyethylamino, N-ethyl-N- ⁇ -hydroxyethylamino, N,N-di- ⁇ -hydroxyethylamino, N- ⁇ -sulfatoethylamino, N- ⁇ -sulfoethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or N—C 1 -C 4 -alkyl-N-phenylamino.
X 1 is preferably halogen, for example fluorine, chlorine or bromine, and particularly preferably chlorine or fluorine.
Halogen T 2 , X 2 and X 3 are, for example, fluorine, chlorine or bromine, in particular chlorine or fluorine.
C 1 -C 4 alkylsulfonyl X 2 is, for example, ethylsulfonyl or methylsulfonyl, and in particular methylsulfonyl.
C 1 -C 4 alkyl X 3 is, for example, methyl, ethyl, n- or iso-propyl or n-, iso or tert-butyl, and in particular methyl.
X 2 and X 3 independently of one another are preferably chlorine or fluorine.
T 2 is preferably cyano or chlorine.
Hal is preferably bromine.
alk and alk 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.
alk and alk 1 independently of one another are preferably each a C 1 -C 4 alkylene radical, and particularly preferably an ethylene radical or propylene radical.
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.
Q is preferably —NH— or —O—, and particularly preferably —O—.
W is preferably a group of the formula —CONH— or —NHCO—, in particular a group of the formula —CONH—.
n is preferably the number 0.
the reactive radicals of the formulae (4a) to (4f) are preferably those in which W is a group of the formula —CONH—, R 69 , R 70 and R 71 are each hydrogen, Q is the radical —O— or —NH—, alk and alk 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 ⁇ -sulfatoethyl, Y 1 is —CHBr—CH 2 Br or —CBr ⁇ CH 2 and n is the number 0.
a fibre-reactive radical Z 1 , Z 2 and Z 3 is particularly preferably a radical of the formula (3a), (3c), (3d), (3e) or (3f), in which Y is vinyl, ⁇ -chloroethyl or ⁇ -sulfatoethyl, Hal is bromine, R 67 and R 70 are hydrogen, m is the number 2 or 3, X 1 is halogen, T 1 is C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, hydroxyl, amino, N-mono- or N,N-di-C 1 -C 4 alkylamino which are unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino or N—C 1 -C 4 alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, ace
a 2 and A 3 When one of A 2 and A 3 is unsubstituted or substituted C 1 -C 4 alkyl, phenyl or naphthyl, it may be, for example, C 1 -C 4 alkyl 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 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, sulfo or by halogen. Preference is given to phenyl that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, sulfo or by halogen.
a 2 and A 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.
a radical A 1 , A 2 or A 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.
substituents in the radicals A 1 , A 2 and A 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.
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 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or by sulfo; phenylamino that is unsubstituted or substituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or by sulfo; N,N-di-p-hydroxyethylamino; N,N-di- ⁇ -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 methyls
a 1 , A 2 and A 3 are the radical of a monoazo, polyazo or metal-complexed azo chromophore, the following radicals, especially, come into consideration:
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.
the radicals of formulae (43), (44) and (45) are preferably those of formula wherein (R 72 ) 0-3 denotes from 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, ureido, sulfamoyl, carbamoyl, sulfomethyl, halogen, nitro, cyano, trifluoromethyl, amino, hydroxy, carboxy and sulfo, (R 73 ) 0-2 denotes from 0 to 2 identical or different substituents from the group hydroxy, amino, N-mono-C 1 -C 4 alkylamino, N,N-di-C 1 -C 4 alkylamino, C 2 -C 4 alkanoylamino and benzoylamino; wherein (R 73 ) 0-2 is as defined above; wherein (R 74 )
a 1 , A 2 and A 3 are the radical of a formazan dye the following radicals, especially, come into consideration: wherein the benzene nuclei do not contain any further substituents or are further substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfonyl, halogen or by carboxy.
a 1 , A 2 and A 3 are the radical of a phthalocyanine dye the following radicals, especially, come into consideration: wherein Pc is the radical of a metal phthalocyanine, especially the radical of a copper or nickel phthalocyanine, W′ is —OH and/or —NR 84 R 84 ′ and R 84 and R 84 ′ are each independently of the other hydrogen or C 1 -C 4 alkyl that is unsubstituted or substituted by hydroxy or by sulfo, R 83 is hydrogen or C 1 -C 4 alkyl, A is a phenylene radical that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or by sulfo or is a C 2 -C 6 alkylene radical and k is from 1 to 3.
Pc is the radical of a metal phthalocyanine, especially the radical of a copper or nickel phthalocyan
a 1 , A 2 and A 3 are the radical of a dioxazine dye the following radicals, especially, come into consideration: wherein A′ is a phenylene radical that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or by sulfo or is a C 2 -C 6 alkylene 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.
a 1 , A 2 and A 3 are the radical of a anthrachinon dye the following radicals, especially, come into consideration: wherein G is a phenylene radical that is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or by sulfo or is a cyclohexylene, phenylenemethylene or C 2 -C 6 alkylene radical.
b in the dye of formula (40) is the number 1.
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.
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.
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.
R 85 is halogen, nitro or cyano
R 86 is hydrogen, halogen, nitro or cyano
R 87 is hydrogen, halogen or cyano
R 88 is hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy
R 89 is hydrogen, halogen or C 2 -C 4 alkanoylamino
R 90 and R 91 independently of one another are hydrogen, allyl, C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxy, cyano, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy-C 1 -C 4 alkoxy, C 2 -C 4 alkanoyloxy, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy
R 92 is hydrogen, C 1 -C 4 alkyl, phenyl or
C 1 -C 4 alkyl radicals there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and ethyl.
C 1 -C 4 alkoxy 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.
halogen there come into consideration, for example, fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and especially chlorine.
C 2 -C 4 alkanoylamino radicals there come into consideration, for example, acetylamino and propionylamino, especially acetylamino.
C 1 -C 4 alkoxy-C 1 -C 4 alkoxy 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.
N-mono- or N,N-di-C 1 -C 4 alkylamino 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.
C 2 -C 4 alkanoyloxy radicals there come into consideration, for example, acetyloxy and propionyloxy, preferably acetyloxy.
C 1 -C 4 alkoxycarbonyl radicals there come into consideration, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.
C 1 -C 4 alkylsulfonyloxy radicals there come into consideration, for example, methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, isopropylsulfonyloxy and n-butylsulfonyloxy, preferably methylsulfonyloxy and ethylsulfonyloxy.
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.
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.
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 ⁇ -oxynaphthoic acid and acetoacetarylide series or metal salts of azo dyes.
inorganic pigments e.g. carbon black, titanium dioxide and iron oxides
organic pigments especially those of the phthalocyanine, anthraquinone, perinone, indigoid, thioindigoid, dioxazine, diketopyrrol
Pigments of the monoazo, disazo, phthalocyanine and anthraquinone series and also inorganic pigments, such as carbon black and iron oxides, are of special interest.
pigments there come into consideration, for example, pigments of the formula wherein R 134 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro or cyano, R 135 is hydrogen, halogen, nitro or cyano, R 136 is hydrogen, halogen or phenylaminocarbonyl, R 137 is hydrogen or hydroxy, and R 138 is hydrogen or a radical of formula wherein R 139 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, R 140 is hydrogen, C 1 -C 4 alkoxy or halogen, and R 141 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen, wherein R 142 and R 143 are each independently of the other C 1 -C 4 alkyl and R 144 and R 145 are halogen, wherein the rings A, B, D and E are unsubstituted or mono- or poly-substit
Inorganic pigments such as carbon black and iron oxides, are also of interest.
pigments are C.I. Pigment Black 7, C.I. Pigment Red 101, C.I. and Pigment Yellow 34.
pigments those of formulae (64.1) to (70.2) and C.I. Pigment Black 7.
the mentioned pigments are known or can be obtained analogously to known preparation procedures, such as diazotisation, coupling, addition and condensation reactions.
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.
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.
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.
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 in which R 156 is C 1 -C 12 alkyl, aryl or aralkyl, “alkylen” is the ethylene radical or propylene radical, R 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
ligninsulfonates 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.
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.
a particularly preferred compound (aj) is the compound of the formula in which R 158 is a direct bond or oxygen, R 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.
a very particularly preferred compound (aj) is a compound based on the sulfonated condensate of a chloromethylbiphenyl isomer mixture and naphthalene, of the formula in which (SO 3 Na) 1,4-1,6 denotes an average degree of sulfonation of from 1.4 to 1.6.
the aqueous dye compositions or the inks comprising disperse dyes may contain anionic copolymers, in particular, those based on acrylic, methacrylic or maleic acid.
anionic copolymers in particular, those based on acrylic, methacrylic or maleic acid.
Particularly preferred anionic copolymers are those obtainable by copolymerization of acrylic or methacrylic acid and styrene.
acrylic and methacrylic acid-styrene copolymers having a molecular weight of from 3000 to 16 000, in particular from 3000 to 10 000.
Suitable non-ionic dispersants for pigments are, for example, compounds selected from the group of (ba) alkylene oxide adducts of formula wherein R 160 is C 1 -C 12 alkyl, 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/
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 4 -C 12 alkyl group, a phenyl group, a tolyl group, an ⁇ -tolylethyl group, a benzyl group, an ⁇ -methylbenzyl group or an ⁇ , ⁇ -dimethylbenzyl group, e.g.
component (ba) 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.
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.
catalysts such as sulfuric acid, p-toluenesulfonic acid or especially zinc chloride.
styrenes there come into consideration advantageously styrene, a-methyl-styrene and vinyltoluene (4-methylstyrene).
phenols are phenol, cresols and xylenols.
R 161 is C 4 -C 12 alkyl, phenyl, tolyl, tolyl-C 1 -C 3 alkyl or phenyl-C 1 -C 3 alkyl, e.g. ⁇ -methyl- or ⁇ , ⁇ -dimethyl-benzyl, and is from 1 to 3 and w is from 4 to 40.
the non-ionic component (bb) is advantageously
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).
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%.
dispersants based on naphthalenesulfonates are also of interest.
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.
binders examples 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® 531 and Sancure® AU-4010 from BFGoodrich.
the polymerisates that come into consideration as binders do not contain sulfo or sulfato groups.
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.
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.
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.
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.
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.
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.
Aqueous compositions comprising acid dyes may be used especially for dyeing and printing of silk or silk-containing mixed fibrous material.
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.
the fibrous material is preferably subjected to a pretreatment.
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%.
the fibrous material is dried after the above pretreatment.
Aqueous compositions comprising reactive dyes are used for dyeing and printing of hydroxy-group-containing fibre materials.
cellulosic fibre materials that consist wholly or partly of cellulose.
natural fibre materials such as cotton, linen and hemp
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.
the fibre material may be subjected to a pretreatment with an aqueous alkaline liquor and the treated fibre material is optionally dried.
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.
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.
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® product in an amount of 0.1 to 100 g/l of liquor.
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.
a pad dyeing auxiliary comprising acrylic acid amide/acrylic acid copolymer from acrylic acid amide and acrylic acid monomer in an amount
the fibre material is dried after the above pretreatment.
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- ⁇ -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.
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.
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.
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.
the selected dyes suitable for the polyester part of the blend e.g. disperse dyes
the selected dyes suitable for the cotton part of the blend e.g. fiber reactive dyes
thermofixing thermal fixing
HT fixing superheated steam under atmospheric pressure
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.
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° C., more especially in saturated steam.
the printed fibre material is generally washed off with water in customary manner in order to remove unfixed dye.
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.
the fibrous material is advantageously dried, preferably at temperatures of up to 150° C., especially from 80 to 120° C., and then the print is fixed.
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° C., the fixing preferably taking from 1 to 8 minutes.
the fixing can, however, also be carried out using irradiation with UV light.
the printed or dyed fibrous material is advantageously irradiated and fixed at elevated temperature, e.g. from 40 to 120° C., especially from 60 to 100° C.
elevated temperature e.g. from 40 to 120° C., especially from 60 to 100° 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.
the calibration data of the dyes are ascertained for the dyeing for which the colour catalogue is being produced.
a polyamide-6.6 fiber material Helanka tricot
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.
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.
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 P 1 corresponds to the colour position of the yellow dye of formula (29.3) for that dyeing; P 2 corresponds to the colour position of the yellow dye of formula (31.1); P 3 corresponds to the colour position of the red dye of formula (28.4); P 4 corresponds to the colour position of the blue dye mixture of the dyes of formulae (26.5) and (26.8); and P 5 corresponds to the colour position of the blue dye of formula (27.4).
P 1 corresponds to the colour position of the yellow dye of formula (29.3) for that dyeing
P 2 corresponds to the colour position of the yellow dye of formula (31.1)
P 3 corresponds to the colour position of the red dye of formula (28.4)
P 4 corresponds to the colour position of the blue dye mixture of the dyes of formulae (26.5) and (26.8)
P 5 corresponds to the colour position of the blue
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 P 2 , P 3 and P 4 .
the gridded triangular area is shown in FIG. 3 .
Colour positions P 2 , P 3 and P 4 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 P 2 , 0.173% by weight of the red dye of formula (28.4) for P 3 and 0.194% by weight of the blue dye mixture of the dyes of formulae (26.5) and (26.8) for P 4 .
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.
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:
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.
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.
the fabric is dried on line with an integrated hot air dryer at 100° C., fixed in saturated steam at 102° C. and is then washed off. A dyeing having good fastness properties is obtained.
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.
the calibration data of the dyes are ascertained for the dyeing for which the colour catalogue is being produced.
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.
the cotton satin fabric 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.
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.
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 P 1 corresponds to the colour position of the yellow dye of formula (39.44) for that dyeing; P 2 corresponds to the colour position of the yellow dye of formula (40.19); P 3 corresponds to the colour position of the orange dye mixture of the dyes of formulae (40.4), (40.14) and (40.15); P 4 corresponds to the colour position of the orange dye of formula (39.25); P 5 corresponds to the colour position of the red dye of formula (39.33); P 6 corresponds to the colour position of the red dye of formula (40.10); P 7 corresponds to the colour position of the blue dye of formula (39.12); P 8 corresponds to the colour position of the blue dye of formula (39.4); and P 9 corresponds to the colour position of the blue dye mixture of the dyes of formulae (39.1) 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 P 10 , P 5 and P 8 .
the colour position P 10 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 P 10 , P 5 and P 8 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 P 10 , 3.43% by weight of the red dye of formula (39.33) for P 5 and 2.84% by weight of the blue dye of formula (39.4) for P 8 .
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.
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:
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.
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.
the fabric is dried on line with an integrated hot air dryer at 100° C. A dyeing having very good fastness to washing is obtained.
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.
FIG. 1 is a diagram showing a depth of shade plane in the FTa*b* colour space, being segmented into 3 triangular areas, points P 1 to P 5 being corner points of the triangular areas.
FIG. 2 is a diagram showing a depth of shade plane in the FTa*b* colour space, being segmented into 12 triangular areas, points P 1 to P 9 being the corner points of the triangular areas.
FIG. 3 shows the gridded segment having the corner points P 2 , P 3 and P 4 of FIG. 1 .
FIG. 4 shows the gridded segment having the corner points P 10 , P 5 and P 8 , wherein P 5 and P 8 correspond to the corresponding data of FIG. 2 .
FIG. 5 shows the segment of FIG. 4 with a smaller number of grid points.

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US11/587,282 2004-04-23 2005-04-13 Method for Dyeing or Printing Textile Materials Abandoned US20070226919A1 (en)

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EP04101693.2		2004-04-23
EP04101693		2004-04-23
PCT/EP2005/051619 WO2005103369A1 (fr)	2004-04-23	2005-04-13	Procede de teinture ou d'impression de materiaux textiles

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Also Published As

Publication number	Publication date
EP1738019A1 (fr)	2007-01-03
WO2005103369A1 (fr)	2005-11-03

Publication	Publication Date	Title
US20070226919A1 (en)	2007-10-04	Method for Dyeing or Printing Textile Materials
US6723137B1 (en)	2004-04-20	Printing process, print obtained by the process and processed article
US20080187666A1 (en)	2008-08-07	Process for printing textile fibre materials in accordance with the ink-jet printing process
US6426766B1 (en)	2002-07-30	Printing process, ink set for use in such process, and print and processed article obtained thereby
US5972084A (en)	1999-10-26	Process for printing textile fiber materials in accordance with the ink-jet printing process
CN105602344A (zh)	2016-05-25	喷墨印染用水性油墨、油墨组及喷墨印染方法
US20010013149A1 (en)	2001-08-16	Process for dyeing or printing and novel reactive dyes
MXPA98010525A (en)	1999-06-01	Procedure for dyeing or stamping and colorants novedo reagents
KR101785258B1 (ko)	2017-10-16	섬유-반응성 염료들의 혼합물, 및 2색성 또는 3색성 염색 또는 프린팅 방법에 있어서의 이의 용도
KR101217646B1 (ko)	2013-01-02	반응성 염료의 혼합물 및 이의 용도
US6500247B1 (en)	2002-12-31	Black-dyeing inks and their use
JPH09188977A (ja)	1997-07-22	合成ポリアミド繊維材料の染色方法
US20080280052A1 (en)	2008-11-13	Process for Printing Textile Fibre Materials in Accordance with the Ink-Jet Printing Process
US6511535B1 (en)	2003-01-28	Method for printing fibrous textile materials using the ink jet technique
US7543926B2 (en)	2009-06-09	Process for printing textile fibre materials in accordance with the ink-jet printing process
MX2007011515A (es)	2007-10-11	Mezclas de tinturas de complejos metalicos.
CN104603214B (zh)	2017-08-08	用于喷墨印刷织物纤维材料的油墨和方法
DE19930986A1 (de)	2000-01-13	Verfahren zum Bedrucken von textilen Fasermaterialien nach dem Tintenstrahldruck-Verfahren
JP3132432B2 (ja)	2001-02-05	インクジェットプリント用インクの製造支援方法及びそれによるインクジェットプリント用インクの製造方法並びにプリント物の作製方法
Jhatial et al.	2023	Colorants for digital textile printing and their chemistry
JPWO2020017430A1 (ja)	2021-08-02	インクジェット捺染用ブラックインク組成物及び疎水性繊維の捺染方法
HOSSAIN	2022	SUSTAINABLE DIGITAL REACTIVE INKJET PRINTING ON CELLULOSIC KNIT FABRIC MODIFYING PRE-COATING PARAMETERS
KR20070017964A (ko)	2007-02-13	잉크-젯 프린팅 공정에 따라 텍스타일 섬유 물질을프린팅하는 방법
WO2000015898A1 (fr)	2000-03-23	Procede pour imprimer des materiaux fibreux textiles, selon le procede d'impression a jet d'encre
MXPA98004843A (en)	2000-08-01	Process for printing textile fiber materials according to the it jet printing process

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