WO2004031468A2

WO2004031468A2 - Methods of colouring materials

Info

Publication number: WO2004031468A2
Application number: PCT/GB2003/004215
Authority: WO
Inventors: Peter Jeffrey Broadbent; Philip Gareth Bentley; David Malcolm Lewis
Original assignee: Lumenia Technology Limited
Priority date: 2002-10-01
Filing date: 2003-09-29
Publication date: 2004-04-15
Also published as: AU2003269218A8; GB0222695D0; AU2003269218A1; WO2004031468A3

Abstract

The invention provides a method of colouring a material, the method comprising the steps of: (a) Inkjetting a salt of an organic acid onto the material; and (b) Inkjetting a reactive dye onto the material. The invention further provides cord materials and colouring compositions comprising salts of an organic acid and reactive dyes.

Description

Improvements In. and Relating to Methods of Colouring;

Materials

Technical Field of the Invention

The invention relates to methods of colouring materials, materials coloured thereby and compositions for colouring materials .

Background to the Invention

Reactive dye compounds are known for dyeing various substrates, such as textiles made from cellulose, cellulose derivatives, natural products such as cotton, and synthetic fibres such as polyamides. Reactive dyes are also known for dyeing substrates such as hair, skin, nails, silk and saccharide-derived materials.

There are many examples of such reactive dyes which are well known in the art, such as dyes containing a mono- or dichloro- or fluoro- 1,3, 5-triazinyl group, mono- or dichloro- or fluoro-pryimidyl group, beta-halogenpropionyl group, bet -halogenoethyl-sulphanyl group, beta-halogeno- ethylsulphamyl group, chloroacetyl amino, beta- (chloro- methyl) -beta-sulfatoethylsulphamyl group, or a vinylsulphonyl group, or α - bromoacrylamido or 1,2 - dibromopropioamide groups .

Dyes and pigments 14, 1999 pages 239-263, "Synthesis and application of reactive dyes with hetrocyclic reactive systems" discloses fibre reactive dyes containing onochloro- or dichloro- pyrimidine hetrocycles with quaternary ammonium substituents. There are many different types of commercially available reactive dyes for dyeing textile material. However a critical problem still facing the textile dye industry today is the amount of dyestuff material which remains in effluent waste solutions after the dyeing process is finished. The industry term commonly given to this problem is known as exhaustion. A high exhaustion corresponds to a low level of spent dye remaining in the effluent after the dyeing process is complete, while a low exhaustion means that a high level of spent dye remains in the effluent. There is an ongoing need for reactive dye compounds which have higher exhaustion values compared with commercially available dye compounds, and which therefore provide benefits in reducing levels of spent dye still found in the effluent water.

In addition to exhaustion values, it is also important for dye compounds to have a high dye-fibre covalent fixation. The fixation of a reactive dye compound is a measure of the amount of dye covalently bonded or in other words the percentage of dye removed from the substrate by the so- called post dyeing "soaping off" process, based on the dye originally absorbed during the dyeing process. Thus as well as having high exhaustion values, reactive dyes clearly need to have high fixation. A high fixation can result in simplification of the post dyeing soaping off process traditionally associated with fibre reactive dye compounds, and a high fixation can result in reduced time spent in removing non-fixated dye, together with a reduced cost in dyestuff. Further problems with reactive dye printing of textiles arise through the method of printing. Textile printing is conventionally carried out using screen or roller printing techniques, the most popular relying on rotary screens which are relatively expensive and time consuming to produce and operate. As a consequence, such techniques are not suited to short production runs and do not change sufficiently rapidly to meet the requirements of fashion. Thus, there is a need to develop textile printing techniques which are relatively fast, and which do not involve the use of any print plate or screen. Thus, the development of electronic printing systems over the past few years, which do not involve the use of any print plate or screen, appears to be a beneficial alternative to traditional printing processes such as screen printing, roller printing application. Inkjet technology, in particular, benefits from cost savings due to low wastage, low machine overheads and flexible design opportunities due to the availability of a potentially unlimited number of colours and the ability to create photographic quality images .

US 5759247 and US 6059870 describe inkjetting of fixation enhancing materials comprising inorganic materials such as silicate, carbonate, bicarbonate or hydroxide materials in a pre-treatment step, followed by inkjetting of reactive dyes. The fixation enhancing materials must be used at relatively high pH, above pH 8, which reduces the stability of the reactive dyes that generally requires a neutral or slightly acidic pH for maximum stability. Furthermore the fixation materials experience problems in the salting out of the reactive dyes in inkjet print cartridges and thus less vibrant prints than may otherwise be obtained in other print techniques are created.

It has been surprisingly found by the inventors that the use of reactive dyes in conjunction with salts of organic acids when inkjetted onto a material, can be used to provide compositions effective in inkjet printing of textile materials to enable the production of high resolution prints with relatively low costs and problems with clogging or damage to the inkjetting apparatus. These compositions and methods allow for printing techniques in which the dye is reacted onto a substrate, which may be a textile material or other substrate, with the dye exhibiting a high fixation value compared with commercially available dye compounds and traditional application methods.

It is therefore an object of preferred embodiments of the present invention to provide methods of colouring and compositions capable of colouring materials, which overcome or mitigate problems of the prior art, whether expressly disclosed herein or not.

Summary of the Invention

According to a first aspect of the present invention there is provided a method of colouring of a material, the method comprising the steps of:

(a) inkjet -printing a salt of an organic acid onto the material; and

(b) inkjet-printing a reactive dye onto the material. The salt of an organic acid is a compound capable of increasing the amount of fixation of a reactive dye on the material compared to when the salt of an organic acid is not present .

By "fixation" we mean the amount of the dye which reacts covalently with nucleophile sites in the material and thus remains bound to the material after post-colouring processing. Thus a high fixation will result in less dye being removed, during post-colouring processing of the material, based on the dye originally absorbed by the material in the colouring process.

Suitably the salt of the organic acid also has the property of being able to increase the exhaustion value of the dye on the material, compared to when the reactive dye activator is not present.

By "exhaustion" we mean the amount of spent dye left in effluent or dye liquor after the colouring process is completed. Thus a high exhaustion value indicates that a low level of dye will remain in the effluent or dye liquor, whereas a low exhaustion value indicates that a high level of dye will remain in the effluent or dye liquor, after colouring the material.

Suitably the salt of the organic acid is inkjetted onto the material before the reactive dye. Alternatively the salt of the organic acid may be inkjetted onto the material simultaneously with the reactive dye and thus steps (a) and (b) may be preformed simultaneously. Suitably the salt of an organic acid is a salt of a mono- carboxylic acid, di-carboxylic acid or tri-carboxylic acid.

Suitably the salt comprises a reactive anion that can be protonated to form a steam-volatile acid or comprises a reactive anion which is thermally decomposable.

We may disclaim carbonate and bicarbonate salts as not being salts of organic acids but inorganic materials.

Preferably the organic acid (and hence its corresponding salt) comprises at least two carbon atoms.

The organic acid may comprise acetic acid, formic acid, benzoic acid, carbamic acids, propanoic acid, chloroacetic acid (or other halocarboxylic acids) , lactic acid, pyruvic acid, citric acid, propionic acid, acrylic acid, methacrylic acid, thiocarbamic acid, cyanic acid, thiocyanic acid, isocyanic acid and tri-chloroacetic acid.

Suitable salts of organic acids include one or more compounds selected from the group consisting of:

M⁺X₃CCOO^"

O

₊ II

M+R— C— O- H

I

M+R— C— COO-

I

OH

M+-OOC— COO-M+

H₃N+-(CH₂)_x-COO-

M+HS-(CH₂)χ-COO-

M+N≡C— O"

M+N≡C— S- where R is hydrogen alkyl, alkenyl, or aryl, M is an alkali metal or a quaternary ammonium ion, and X is a halogen.

Preferably M is selected from sodium, potassium, lithium and a quaternary amine, and is more preferably lithium. The choice of M will be in part determined by the reactive dye to be contacted with the material and the material to be coloured. Some salts "salt-out" reactive dyes from aqueous solutions which in some applications can be highly undesirable, and in this respect lithium salts are preferred due to the low likelihood of "salting-out" . The use of salts of organic acids, and particularly lithium salts, has surprisingly been found to dramatically reduce the likelihood of "salting out" and thus improve the long- term stability of the reactive dyes and allows higher levels of dye to be incorporated into the material than known fixing agents.

Inkjet printing is particularly susceptible to failure due to particulate matter in the inks clogging up the inkjetting apparatus and thus the less "salting out" that occurs in the inks, the less likely the inks have of damaging or clogging the inkjetting apparatus and printers .

The use of salts of organic acids as fixation agents allows the use of higher concentrations of dyes to give more vibrant images without compromising ink-stability.

Suitably X is chlorine, fluorine, bromine or iodine. Preferred organic acid salts comprise a salt selected from a trichloroacetate, a cyanate, a carbamate, a carboxylate, a thiocyanate, a thiocarbamate, a formate, an acetate, a propionate, a benzoate, a chloroacetate, an acrylate, a lactate, and a pyruvate. Particularly preferred as organic acid salts are acetate or propionate salts.

Especially preferred as salts are lithium acetate and lithium propionate.

The use of salts of organic acids as reactive dyes mitigates or overcomes the need to use secondary fixation enhancers such as terting amines, but if desired they can be used in conjunction with the salts.

A tertiary amine compound may be contacted with the material during step (a) and/or (b) . Suitably the tertiary amine compound effects enhanced fixation of the reactive dye with the material in step (b) . Suitable tertiary amine compounds include saturated or unsaturated, substituted or unsubstituted nitrogen containing heterocycles. The heterocycle may comprise from between 3 to 8 ring atoms, of which at least one ring atom is a nitrogen heteroatom. Preferred substituents of nitrogen- containing heterocycles include alkyl groups, especially Cι-C₄ alkyl groups, carboxylate groups, amide groups and alkyl carboxylate groups. Particularly preferred tertiary amine compounds include alkali metal nicotinates, 1,4- diazabicyclo-2, 2,2-octane (DABCO) , dimethylaminobetaine and nicotinamide.

Suitably the reactive dye is a halogen-containing reactive dye. Suitable reactive dyes include reactive dyes comprising at least one group selected from: halotriazine, sulphatoethylsulphone/vinyl-sulphone, quaternary triazinyl, dichloro-quinoxaline, difluoromonochloropyrimidine groups, or a combination of such groups. Examples of suitable dyes include Cibacron F dyes (Ciba) [monofluoro-s-triazine] , Cibacron C (Ciba) [ onofluorotriazinevinylsulphone] , Procion P/PX (Dystar) [monochloro-s-triazine] , Remazol (Dystar)

[sulphatoethylsulphone] , Drimarene K (Clariant) [difluoromonochloropyrimidine] , Sumifix Supra (Sumitomo) [monochloro-triazine- sulphatoethylsulphone] , Levafix E (Dystar) [dichloroquinoxaline] or Kayacelon React Dyes (Nippon Kayaku) [bis-mononicotinate-s-triazine] for example. A further series of suitable reactive dyes are derived from the reaction of dichlorotriazine dyes, (such as the brand Procion MX produced by Dystar) , or difluoromonochloropyrimidine dyes, (such as the brands Drimarene R, and K produced by Clariant) , with p-phenolsulphonic acid. Although such dyes are not commercially available their synthesis is known to those skilled in the art, and the triazine derivatives can be readily formed by stirring an aqueous solution of a Procion MX dye with p- phenolsulphonic acid at 20°C, pH 6.

Preferably the reactive dye comprise a fluorine-containing reactive group, and fluorotriazones and difluoromonochloropyrimidines are especially preferred.

It has been found that the use of lithium salts of organic acids and reactive dyes comprising fluorinated reactive groups gives particularly high levels of fixation on materials .

Suitably the reactive dye and/or the salt of the organic acid is/are present in an aqueous composition, preferably water, and may be present as a dispersion, solution or suspension in the aqueous composition.

Suitably the reactive dye is present in the aqueous composition in an amount of at least 2wt%, preferably at least 5wt% and more preferably at least 10wt% of the total weight of the aqueous composition. Suitably the reactive dye is present in the aqueous composition in an amount of no more than 40wt%, preferably no more than 30wt%, and more preferably no more than 20wt% of the total weight of the aqueous composition.

A preferred range of reactive dye in the aqueous composition is therefore between substantially 10wt% and substantially 20wt% of the total weight of the aqueous composition.

Suitably the salt of the organic acid is present in the aqueous composition in an amount of at least lwt%, preferably at least 5wt% and more preferably at least 10wt% of the total weight the aqueous composition. Suitably the reactive dye activator is present in the aqueous composition in an amount of no more than 30wt%, preferably no more than 25wt% and more preferably no more than 20wt% of the total weight of the aqueous composition.

Suitably the aqueous composition further comprises an oxidising agent, such as sodium nitrobenzene sulphonate, (manufactured under the trade name Ludigol by BASF, Germany) for example. Preferably the oxidizing agent is present in an amount of between lwt% to 2wt% of the total weight of the aqueous composition. The oxidising agent may improve the vibrancy of the printed image on the material by preventing or reducing reduction of the dye during or after fixation, especially under steam conditions.

Suitably the aqueous composition further comprises a viscosity modifier, such as sodium carboxymethyl cellulose, sodium alginate or a synthetic thickening agent, for example. Preferably the viscosity modifier is present in an amount of between 0.5wt% and 5wt%, more preferably between 0.8wt% and 2wt% of the total weight of the aqueous composition.

Suitably the salt of the organic acid is present in the same aqueous composition as the reactive dye, such that steps (a) and (b) of the method are performed simultaneously.

The aqueous composition may include one or more co- solvents or humectants, such as 2-pyrrolidinone, or a polyhydric alcohol such as ethylene glycol or glycol, for example. Such humectants may have hygroscopic properties which may compensate for evaporation of water that may occur from the aqueous composition.

The aqueous composition may include a surfactant. Suitably the surfactant is present in an amount of at least 0.08wt%, preferably 0.05wt% and more preferably at least θ.lwt% of the total weight of the composition. Suitably the surfactant is present in an amount of no more than 10wt%, preferably no more than 8wt% and more preferably no more than 6wt% of the total weight of the composition. Suitable surfactants include an ethoxylated fatty alcohol such as Sandozin NIE (Clariant) .

The aqueous composition may include a biocide, preferably in an amount of between 0.02wt% and 0.4wt% of the total weight of the aqueous composition. The aqueous composition may include a fungicide, preferably in an amount of between 0.01wt% and 0.4wt% of the total weight of the aqueous composition.

Suitably the reactive dye and/or the salt of the organic acid are contacted with the material at a pH of at least

2, preferably at least 3 and more preferably at least 4 and most preferably at least 5. Suitably the reactive dye and/or salt of the organic acid is/are contacted with the material at a pH of no more than 12, preferably no more than 10, more preferably no more than 8 most preferably no more than 7.5 and especially no more than 7. Thus a preferred pH range for contacting the reactive dye and/or reactive dye activator with the material is between 4 and

7. In particularly preferred embodiments the reactive dye and/or salt of the organic acid is contacted with the material at a pH of no more than substantially 6.5.

The use of salts of organic acids, particularly acetates, and propionates enables reactive dyes to be used with a pH of around 5-7, which is important for dye stability during inkjetting and storage. Hydrosis of the reactive groups of the reactive dye may occur if the compositions used in the method of the invention are too basic or acid. Typical ink-jet printer print heads do not tolerate high or low pH compositions and so the use of salts of organic acids, particularly lithium salts, enables neutral dyes and compositions to be formulated to give long print head lifetimes, especially if the salt is jetted separately to the dye. The use of salts of organic acids as activators also enables more flexibility of dye composition formulation, including enabling the inclusion of mordants and thickeners .

Preferably the aqueous composition comprises a buffer, to control the pH of the composition to a desired pH. The buffer may comprise an organic acid, such as formic acid or acetate acid, for example.

Suitably the aqueous composition further includes a tertiary amine oxide, such as N-methylmorpholineoxide.

Preferably the method comprises a step (c) of exposing the material to heat. Step (c) may be preformed before, simultaneously or after either or both of step (a) and (b) .

Suitably step (c) may comprise exposing the material to heated air. If step (c) comprises exposing the material to dry heat such as heated air, for example, preferably step (a) and/or (b) further includes contacting the material with a tertiary amine oxide such as N- methylmorpholine oxide, nicotinicacid-N-oxide or imidazole-N-oxide, for example. Step (c) preferably comprises contacting the material with heated water, which includes steam. Suitably the water is heated to at least 90°C, preferably at least 95°C and more preferably at least 100°C. Suitably the water is heated to no more than 150°C, preferably no more than 140°C and more preferably no more than 130°C.

Preferably steps (a) and (b) are performed simultaneously, such that salt of the organic acid and reactive dye are ink-jetted onto the material simultaneously.

Suitably the salt of the organic acid and/or reactive dye are housed in a suitable container or cartridge from which they are expelled during the ink-jetting process.

According to a second aspect of the invention there is provided a material coloured by the method of the first aspect of the invention.

Suitably the material to be coloured is a textile material . Suitable natural textile materials include cotton, wool, flax, linen, hemp, paper and leather. Suitable synthetic textile materials include viscose, rayon, nylon, synthetic polyamides. The material may be an item of clothing, such as a T-shirt, shirt, hat, trousers, undergarment, or the like. Alternatively the material may be a towel, flannel, carpet, curtain, handkerchief upholstery or the like.

Preferably the method is a method of applying a coloured image to a material . According to a third aspect of the present invention there is provided a composition comprising a salt of an organic acid and a reactive dye.

Preferably the salt of an organic acid and reactive dye are as described for the first aspect of the invention. Most preferably the salt of an organic acid and reactive dye are present in an aqueous composition.

The various aspects of the invention will now be described in non-limiting fashion with reference to the following examples.

Examples :

Example 1

An aqueous liquor containing 20 gdm^-3 sodium formate and 8 gdm^"3 Cellcosan 2000 (propoxylated cellulose thickener) was prepared and set at pH 6.0 via the addition of formic acid. The liquor was ink-jet printed (using a HP Desk Jet 540 printer) on cotton so as to achieve a wet pick up of 100% and the fabric dried at 50°C for 2 min. The pre- treated fabric was inkjet printed on a HP Desk Jet 540 printer with inks containing red, yellow and blue Cibacron F (a class of reactive dyes from CIBA, Basel which contains a reactive mono-fluoro-s-triazine side chain) dyes contained in a tri-colour inkjet cartridge. The dyes employed were Cibacron Red FN-R, Cibacron Yellow FN-2R and Cibacron Blue FN-R; the dyes being formulated as follows to yield a suitable ink:

100 gdm^-3 Cibacron F dye 30 gdm^"3 Sodium bicarbonate 20 gdm^"3 2-Pyrrolidinone 25 gdm^"3 Propan-2-ol 150 gdm^"3 Ethylene glycol Distilled water to 1 litre

The printed fabric was steamed at 104°C for 10 min, rinsed with cold water and finally soaped-off at the boil with 2 gdm^"3 Sandozin NIE (non-ionic surfactant) (Clariant) . A high colour yield print exhibiting red, yellow and blue flowers on a white background was achieved.

Example 2

Cotton fabric was pre-treated with an aqueous solution containing 50 gdm^-3 sodium formate and 8 gdm^"3 Cellcosan 2000 in similar manner to that described in Example 1. The dried fabric was inkjet printed with an aqueous solution of the bisphenolsulphonate analogue of Procion Red MX-8B (100 gdm^"3) and the print steamed at 104°C for 10 min. Procion M dyes are supplied by DyStar and are a class of reactive dyes containing a dichloro-s-triazine pendant reactive group. The steamed print was rinsed with cold water and soaped-off at the boil with 2 gdm^"3 Sandozin NIE. A high colour yield print showing red flowers on a white background was achieved.

Example 3

Cotton fabric was pre-treated in a similar manner to that described in Example 2, but in this case 50 gdm^"3 1,4- diazabicyclo-2 , 2 , 2-octane was also incorporated to the pre-treatment composition. The pre-treated fabric was printed, steamed and soaped-off as in Example 2. A high colour yield print was again obtained, the strength of the print being greater than that observed in Example 2 due to the catalytic effect of the quaternary amine present.

Example 4 Cotton fabric pre-treated as in Example 2 was inkjet printed with red, yellow and blue inks containing bisphenolsulphonate derivatives of Procion Red MX-8B, Procion Yellow MX-3R and Procion Turquoise MX-G. The inks were placed in a tri-colour inkjet cartridge and used to reproduce a photographic image. The print was steamed at 104°C for 10 min, rinsed with cold water and finally soaped of at the boil as before. Good quality, high definition prints were achieved.

Example 5

Cotton was pre-treated as in Example 3, inkjet printed with bisphenolsulphonate dyes as in Example 4 and finally steamed at 104°C for 10 min. The resulting print was rinsed with cold water and soaped-off as above. A high quality print was again achieved, the colour yield of the print being higher than that achieved for Example 4 which was produced in the absence of 1, 4-diazabicyclo-2 , 2 , 2- octane .

Example 6

The procedure carried out in Example 5 was repeated, but on this occasion the quantity of l,4-diazabicyclo-2, 2, 2- octane in the pre-treatment composition was reduced to 10 gdm^"3. A photographic quality print was again achieved.

Example 7

Cotton fabric was pre-treated as in Example 2 and inkjet printed from a tri-colour cartridge with inks formulated from Cibacron Red FN-R, Cibacron Blue F-GFN and Cibacron Yellow FN-2R. The inks were formulated according to the following recipe:

100 gdm^"3 Cibacron F dye 20 gdm^"3 2-Pyrrolidinone 25 gdm^"3 Propan-2-ol 150 gdm^"3 Ethylene glycol Distilled water to 1 litre

The print was steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil with Sandozin NIE. A print exhibiting high photographic print quality and strong colour yield was achieved.

Example 8

Cotton fabric was pre-treated as in Example 6 and inkjet printed with Cibacron F based inks in a similar manner to that used in Example 7. The print was steamed at 104°C for 10 min, rinsed with cold water and soaped at the boil. A print of excellent quality was again obtained.

Example 9

The process described in Example 7 was repeated, but on this occasion the fabric was printed with inks formulated using Drimarene Brilliant Red K-4BL, Drimarene Brilliant

Blue K-2R and Drimarene Golden Yellow K-2RL. Drimarene K dyes are a class of reactive dyes manufactured by Clariant

(Basel) - they contain at least one pendant 2 , -difluoro- 5-chloro pyrimidine reactive group. The print was steamed, rinsed and soaped as before. A good quality print was achieved. Example 10

The process described in Example 8 was repeated, but this time the fabric was printed with inks containing Drimarene K dyes instead of the Cibacron F dyes. A good quality print was achieved.

Example 11

Cotton fabric was pre-treated as in Example 7 and inkjet printed with inks formulated from Procion Red PX-4B, Procion Yellow P-3R and Procion Turquoise PX-GR; the inks being formulated as in Example 7. Procion P dyes are a class of monochloro-s-triazine reactive dyes manufactured by BASF (now DyStar) - they contain at least one pendant mono-chloro-s-triazine reactive group. The printed fabrics were steamed for 10 min, rinsed with cold water and soaped-off at the boil. Good quality prints were achieved.

Example 12 Cotton fabric was pre-treated and inkjet printed in a similar manner to that described in Example 8, but in this case the printing inks were formulated using Procion P/PX dyes. Good quality prints were again achieved.

Example 13

Cotton fabric was pre-treated and inkjet printed as described in Example 7, but in this case the printing inks were formulated using Remazol Brilliant Blue R, Remazol Yellow GNL 200 and Remazol Red RB; the dyes being present in the ink formulations as their sulphatoethylsulphone form Remazol dyes are a class of reactive dyes manufactured by DyStar (Frankfurt) -they contain at least one masked or free vinylsulphone reactive group. Good prints were once more achieved.

Example 14

Cotton fabric was pre-treated and inkjet printed in a similar manner to that described in Example 8, but in this case the printing inks were formulated using Remazol dyes; the dyes being formulated in their sulphatoethyl-sulphone form. Good quality prints were again achieved.

Example 15

Cotton fabric was pre-treated in accordance with the procedure carried out in Example 7 and subsequently inkjet printed with the following ink formulation; the Remazol dye having been converted to its vinylsulphone form:

40 gdm^"3 Remazol Black NF 20 gdm^"3 2-Pyrrolidinone 25 gdm^-3 Propan-2-ol

150 gdm^"3 Ethylene glycol Distilled water to 1 litre

The print was steamed at 104°C for 10 min, rinsed with cold water and finally soaped-off at the boil . A good quality print was obtained.

Example 16

Cotton fabric was pre-treated and inkjet printed as described in Example 7, but in this case the printing inks were formulated using Cibacron Red C-R, Cibacron Yellow C- 2R and Cibacron Blue 4R. Cibacron C are a class of reactive dyes manufactured by Ciba (Basel) - they contain both a monofluoro-s-triazine and a free vinylsulphone group linked to the chromophore. Good photographic quality prints were achieved.

Example 17

Cotton fabric was pre-treated with an aqueous solution containing 50 gdm^"3 sodium trichloroacetate and 8 gdm^"3 Cellcosan 2000 in similar manner to that described in Example 1. The fabric was inkjet printed with inks formulated from Cibacron Red FN-R, Cibacron Blue FN-R and Cibacron Yellow FN-2R in a similar manner to that described in Example 7. The prints were steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil. Excellent prints exhibiting strong colour yields and photographic quality was achieved.

Example 18

Cotton fabric was pre-treated with an aqueous solution containing 50 gdm^"3 sodium cyanate and 8 gdm^"3 Cellcosan 2000 in similar manner to that described in Example 1. The fabric was inkjet printed with inks formulated from Cibacron Red FN-R, Cibacron Blue FN-R and Cibacron Yellow FN-2R in a similar manner to that described in Example 7. The prints were steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil . Excellent prints exhibiting strong colour yields and photographic quality were achieved.

Example 19 Cotton fabric was pre-treated with an aqueous solution containing 50 gdm^"3 sodium cyanate, 20gdm^"3 1,4- diazabicyclo-2,2,2-octane and 8 gdm^"3 Cellcosan 2000 in similar manner to that described in Example 1. The fabric was inkjet printed with inks formulated from Cibacron Red FN-R, Cibacron Blue FN-R and Cibacron Yellow FN-2R in a similar manner to that described in Example 7. The prints were steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the. boil. Excellent prints exhibiting strong colour yields and photographic quality were achieved; the colour yield of the print being greater than that obtained in the absence of the quaternary amine .

Example 20

Cotton fabric was pre-treated with an aqueous solution containing 50 gdm^"3 sodium lactate, 10 gdm^"3 Ludigol

(sodium nitrobenzene sulphonate oxidising agent) and 8 gdm^"3 Cellcosan 2000 in similar manner to that described in Example 1. The fabric was inkjet printed with inks formulated from Cibacron Red FN-R, Cibacron Blue FN-R and Cibacron Yellow FN-2R in a similar manner to that described in Example 7. The prints were steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil . Good prints exhibiting high colour yields and photographic quality were achieved.

Example 21

Cotton fabric was pre-treated with an aqueous solution containing 50 gdm^"3 sodium cyanate, 20gdm^"3 1,4- diazabicyclo-2,2,2-octane, 10 gdm^"3 Ludigol and 8 gdm^"3 Cellcosan 2000 in similar manner to that described in Example 1. The fabric was inkjet printed with inks formulated from Cibacron Red FN-R, Cibacron Blue FN-R and Cibacron Yellow FN-2R in a similar manner to that described in Example 7. The prints were steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil. Excellent prints exhibiting strong colour yields and photographic quality were achieved.

Example 22 Cotton fabric was pre-treated with an aqueous solution containing 50 gdm^"3 sodium formate, 10 gdm-3 Ludigol and 8 gdm^"3 Cellcosan 2000 in similar manner to that described in Example 1. The fabric was inkjet printed with inks formulated from Cibacron Red FN-R, Cibacron Blue FN-R and Cibacron Yellow FN-2R in a similar manner to that described in Example 7. The prints were steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil. Good prints exhibiting high colour yields and photographic quality were achieved.

Example 23

The process carried out in Example 21 was repeated, but in this case 8 gdm^"3 CHT Alginat MV was used instead of Cellcosan 2000. Prints of similar quality to those achieved in Example 21 were achieved.

Example 24

The process carried out in Example 21 was repeated, but in this case 8 gdm^"3 Alcoprint 7860 was used instead of Cellcosan 2000. Prints of similar quality to those achieved in Example 21 were achieved.

Example 25

Cotton fabric was inkjet printed with an ink cartridge containing sodium cyanate as the dye activator; the ink being formulated as follows:

100 gdm^"3 Sodium cyanate 20 gdm^" 2-Pyrrolidinone

25 gdm^"3 Propan-2-ol

150 gdm^"3 Ethylene glycol

10 gdm^"3 Ludigol

Adjust to pH 6.5

Distilled water to 1 litre

The pre-printed fabric was immediately over-printed with a tri-colour ink cartridge containing inks formulated from Cibacron Red FN-R, Cibacron Blue FN-R and Cibacron Yellow FN-2R. The inks were formulated according to the following recipe :

100 gdm^"3 Cibacron F dye 20 gdm^"3 2-Pyrrolidinone 25 gdm^"3 Propan-2-ol 150 gdm^"3 Ethylene glycol 10 gdm^"3 Ludigol Distilled water to 1 litre

The printed fabric was steamed at 104°C for 10 mins and soaped-off at the boil with 2 gdm^"3 Sandozin NIE. Prints exhibiting strong colour yields, photographic quality image, good handle and excellent wash-fastness were achieved; the prints being of similar quality to those obtained in Example 18, in which cotton fabrics pre- treated with an alkali donor and thickener.

Example 26 The process described in Example 25 was repeated, but in this case sodium trichloroacetate was used in the first ink as the alkali donor instead of sodium cyanate. Prints of similar quality to those obtained in Example 25 were achieved.

Example 27 The process described in Example 25 was repeated, but in this case the sodium cyanate pre-printed fabrics were over-printed with an ink cartridge containing Cibacron Red C-R, Cibacron Blue 4R and Cibacron Yellow C-2R based inks; the inks being formulated as in Example 25. Prints of similar quality to those obtained in Example 25 were achieved.

Example 28

The process described in Example 27 was repeated, but in this case sodium trichloroacetate was used in the first ink as the alkali donor instead of sodium cyanate. Prints of similar quality to those obtained in Example 25 were achieved.

Example 29

Cotton fabric was inkjet printed from a tri-colour cartridge with inks formulated from Cibacron Red FN-R, Cibacron Blue FN-R and Cibacron Yellow FN-2R; each ink also containing lithium formate as a fibre activating agent (fixation enhancer) . The inks were formulated according to the following recipe:

100 gdm^"3 Cibacron F dye 100 gdm^"3 Lithium formate 20 gdm^"3 Ludigol

20 gdm^"3 2-Pyrrolidinone

25 gdm^"3 Propan-2-ol

150 gdm^-3 Ethylene glycol Adjust to pH 6.5 with formic acid Distilled water to 1 litre

The print was steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil with Sandozin NIE. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved; the prints being of similar quality to those obtained on cotton fabrics pre-treated with a the fibre activating agent in a separate step by either inkjet or padding techniques .

Example 30

Cotton fabric was inkjet printed from a tri-colour cartridge with inks formulated from Remazol Red RB,

Remazol Turquoise G and Remazol Golden Yellow RNL; each ink also containing lithium acetate as a fibre activating agent. The inks were formulated according to the following recipe:

100 gdm^"3 Remazol dye

100 gdm^"3 Lithium acetate

20 gdm^"3 Ludigol

20 gdm^"3 2-Pyrrolidinone 25 gdm^"3 Propan-2-ol

150 gdm^"3 Ethylene glycol

Adjust to pH 6.5 with acetic acid

Distilled water to 1 litre

The print was steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil with Sandozin NIE. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved; the prints being of similar quality to those on pre-activated cotton fabrics.

Example 31 The process described in Example 30 was repeated, but in this case Sumifix Supra Turquoise Blue BGF was used instead of Remazol Turquoise G to provide an ink of enhanced water solubility. Sumifix Supra dyes are a class of reactive dyes manufactured by Sumitomo (Osaka) - they contain both a monochloro-s-triazine and a sulphatoethylsulphone (masked vinylsulphone) reactive group linked to the chromophore . Prints of similar quality to those obtained in Example 30 were achieved.

Example 32

Wool fabrics were printed with inks derived from Remazol Red RB, Remazol Golden Yellow RNL and Sumifix Supra Turquoise Blue BGF via the process described in Example 31. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 33

Silk fabrics were printed with the dyes Remazol Red RB, Remazol Golden Yellow RNL and Sumifix Supra Turquoise Blue BGF using the process described in Example 31. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 34

Wool fabrics were printed with inks formulated from Sumifix HF Red 2B, Sumifix HF Blue 2R and Sumifix HF Yellow 3R via the process described in Example 30. Sumifix HF reactive dyes are manufactured by Sumitomo (Osaka) - their structure is undisclosed but they are believed to be monochloro-s-triazine/vinylsulphone multifunctional dyes. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 35 Cotton fabric was inkjet printed from a tri-colour cartridge with inks formulated from Sumifix HF Red 2B, Sumifix HF Blue 2R and Sumifix HF Yellow 3R; each ink also containing lithium acetate as a fibre activating agent. The inks were formulated according to the recipe described in Example 30. The print was steamed at 104°C for 10 min, rinsed with cold water and soaped-off at the boil with Sandozin NIE. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 36

Wool fabrics were printed with inks formulated from Sumifix HF Red 2B, Sumifix HF Blue 2R and Sumifix HF Yellow 3R using the process described in Example 35. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 37 Wool/cotton (48:52% respectively) blend fabrics were printed with inks formulated from Sumifix HF Red 2B, Sumifix HF Blue 2R and Sumifix HF Yellow 3R using the process described in Example 35. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 38 Colour-safe nylon fabrics (Du Pont) were printed with inks formulated from Sumifix HF Red 2B, Sumifix HF Blue 2R and

Sumifix HF Yellow 3R using the process described in

Example 35. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 39

Silk fabrics were printed with inks formulated from Sumifix HF Red 2B, Sumifix HF Blue 2R and Sumifix HF Yellow 3R using the process described in Example 35. Prints exhibiting good colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 40

Ink formulations possessing higher dye concentrations were prepared from Sumifix HF Red 2B, Sumifix HF Blue 2R and

Sumifix HF Yellow 3R in accordance with the following recipe :

200 gdm^"3 Sumifix HF dye

100 gdm^"3 Lithium acetate

20 gdm^"3 Ludigol

20 gdm^"3 2-Pyrrolidinone 25 gdm^"3 Propan-2-ol

100 gdm^"3 Ethylene glycol

Adjust to pH 6.5 with acetic acid

Distilled water to 1 litre The inks were printed on cotton fabric and the prints steamed at 104°C for 10 min. The steamed prints were rinsed with cold water and soaped-off at the boil with Sandozin NIE. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved; the prints exhibiting higher print definition and clarity when compared with similar prints produced with ink formulations containing 100 gdm^"3 dye.

Example 41

Silk fabrics were printed with inks formulated from Sumifix HF Red 2B, Sumifix HF Blue 2R and Sumifix HF Yellow 3R via the process described in Example 40. Prints exhibiting good colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 42

Cotton fabrics were printed with inks formulated from Sumifix HF Red 2B, Sumifix Supra Turquoise Blue BGF and

Sumifix HF Yellow 3R using the process described in

Example 40. Prints exhibiting good colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 43

Silk fabrics were printed with inks formulated from Sumifix HF Red 2B, Sumifix Supra Turquoise Blue BGF and Sumifix HF Yellow 3R using the . process described in Example 40. Prints exhibiting good colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 44 In order to improve the colour balance of the generated prints, ink cartridges containing ink formulations of differing dye concentrations were produced; the ink formulations being produced in a similar manner to that described in Example 40. The dyes employed were Remazol Red BS (100 gdm^"3) , Sumifix Supra Turquoise Blue BGF (200 gdm^-3) and Remazol Yellow GR (100 gdm^"3) . The inks were printed on cotton and the prints steamed at 104°C for 10 mins. The steamed prints were soaped-off at the boil for 15 mins with 2 gdm^"3 Sandozin NIE. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved; the prints exhibited improved colour balance when compared with similar prints produced with ink formulations containing 100 gdm^"3 dye.

Example 45

Ink formulations containing magenta, cyan and yellow dyes were prepared as a further attempt to match the hues and colour intensities obtained from commercially available inkjet cartridges for paper printing. Ink formulations containing Remazol Brilliant Magenta HB (100 gdm^"3) , Sumifix Supra Turquoise Blue BGF (200 gdm-3) and Remazol Golden Yellow RNL (100 gdm^"3) were prepared in a similar manner to that described in Example 40. The inks were printed on cotton and the prints steamed at 104°C for 10 mins. The steamed prints were soaped-off at the boil for 15 mins with 2 gdm^"3 Sandozin NIE. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved; the prints exhibited improved colour balance when compared with similar prints produced with ink formulations containing 100 gdm^"3 red, yellow and blue dyes.

Example 46

Ink formulations containing 100 gdm^"3 Remazol Brilliant Magenta HB, 100 gdm^"3 Remazol Turquoise G and 100 gdm^"3 Remazol Golden Yellow RNL were prepared as in Example 40 and printed on cotton fabric. The prints were steamed at 104°C for 10 mins. and finally soaped-off at the boil for 15 mins with 2 gdm^"3 Sandozin NIE. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved; the prints exhibited improved colour balance when compared with similar prints produced with ink formulations containing 100 gdm^"3 red, yellow and blue dyes.

Example 47 The process described in Example 46 was repeated, but in this case the prints were produced on a wool/cotton ^"blend fabric (48:52 % respectively). Prints exhibiting strong colour yields, photographic quality images, good colour balance, good handle and excellent wash-fastness were achieved.

Example 48

Ink formulations containing mixtures of red, blue and turquoise dyes were prepared as a further attempt to match the magenta, and cyan hues obtained from commercially available inkjet cartridges for paper printing. A typical example of one the mixtures prepared is demonstrated by the following ink formulation: Magenta - 90 gdm^"3 Remazol Red BS + 10 gdm^"3 Remazol Brilliant Blue R

Cyan - 85 gdm^"3 Remazol Turquoise G + 15 gdm^"3 Remazol Brilliant Blue R

Yellow - 100 gdm^"3 Remazol Yellow GR

The ink formulations were prepared in accordance with the procedure described in Example 40 (i.e. containing lithium acetate at pH 6.5) . The inks were printed on cotton fabrics and the prints steamed at 104°C for 10 mins. The prints were soaped-off at the boil with 2 gdm^"3 Sandozin NIE for 15 mins (almost no colour removed indicating very high Fixation) . Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved; the prints exhibited improved colour balance when compared with similar prints produced with ink formulations containing 100 gdm^"3 red, yellow and blue dyes (these latter prints were very pale indicating a low level dye-fibre covalent bond formation) .

Example 49

In this example, red, yellow and blue inks were formulated from Remazol Brilliant Red F3B, Remazol Brilliant Blue R and Remazol Golden Yellow RNL using N-methylmorpholine-N- oxide as the humectant in place of ethylene glycol in accordance with the following recipe:

100 gdm^"3 Remazol dye 100 gdm^"3 Lithium acetate 20 gdm^"3 Ludigol 20 gdm^"3 2-Pyrrolidinone 25 gdm^"3 Propan-2-ol 200 gdm^"3 N-methylmorpholine-N-oxide Adjust to pH 6.5 with acetic acid Distilled water to 1 litre

The inks were printed on cotton and the prints steamed at 104°C for 10 mins; the prints being soaped-off at the boil with 2 gdm^"3 Sandozin NIE for 15 mins.

Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 50

The process described in Example 49 was repeated, but in this case the inks were formulated using Drimarene Brilliant Red K-4BL, Drimarene Golden Yellow K-2R and Drimarene Blue R-GL instead of the red, yellow and blue Remazol dyes. Previous attempts to produce such inks using ethylene glycol as the humectant rather than the N- methylmorpholine- N-oxide of this example were unsuccessful due to the dyes either being insoluble or precipitating from the ink formulation. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 51

The process described in Example 49 was repeated, but in this case the inks were formulated using Cibacron Red FN- R, Cibacron Blue FN-R and Cibacron Yellow FN-2R. The dyes exhibited higher solubility in the N-methyl-morpholine-N- oxide ink formulations than they did in the previously prepared ethylene glycol based ink formulations. Prints exhibiting strong colour yields, photographic quality images, good handle and excellent wash-fastness were achieved.

Example 52 Cotton fabric was inkjetted with a dye liquor containing 60 gdm^"3 Remazol Black NF and 50 gdm^"3 sodium acetate, set at pH 6 via the addition of acetic acid, so as to achieve a wet pick up of 100%. The treated fabric was dried at 60°C for 3 mins and steamed at 104°C for 10 mins. The dyed fabric was rinsed with cold water and finally soaped- off at the boil with 2 gdm^"3 Sandozin NIE for 15 mins. A deep black dyeing exhibiting a high degree of covalent dye fixation was achieved; the soap-off and cold water rinsing baths being virtually colourless.

Example 53

The process described in Example 54 was repeated, but in this case the drying step prior to steaming was omitted. A deep black dyeing exhibiting^' excellent levels of covalent dye fixation was again achieved.

Example 54

The process described in Example 52 was repeated, but in this case a ink composition containing 5 gdm^"3 Cibacron Blue FN-R, 8 gdm^"3 Cibacron Red FN-R, 12 gdm^"3 Cibacron Yellow FN-2R and 50 gdm^"3 sodium acetate was employed. A dark brown fabric exhibiting a high degree of dye fixation and excellent wash-fastness was achieved.

The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

All of the features disclosed in this specification (including any accompanying claims, abstract and drawings) , and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.

Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) , may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

The invention is not restricted to the details of the foregoing embodiment (s) . The invention extend to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings) , or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

1. A method of colouring a material, the method comprising the steps of : (a) inkjet-printing a salt of an organic acid onto the material ; and (b) inkjet-printing a reactive dye onto the material.

2. A method as claimed in Claim 1, wherein the salt of an organic acid is a inkjetted onto the material before the reactive dye.

3. A method as claimed in Claim 1, wherein the salt of the organic acid is inkjetted onto the material simultaneously with the reactive dye.

4. A method as claimed in any one of Claims 1 to 3 , wherein the salt of the organic acid is a salt of a mono-carboxylic acid, di-carboxylic acid or tri- carboxylic acid.

5. A method as claimed in any preceding claim, wherein the salt of the organic acid is one or more compounds selected from the group consisting of:

M⁺X₃CCOO^"

O

M+R—C—O-

H

I

M+R—C—COO- OH

M+ -OOC — COO- M+

H₃N+-(CH₂)_x-COO-

M+ HS — (CH )_X— COO-

M+ N=C— O-

M+ N≡C— S-

where R is hydrogen alkyl, alkenyl, or aryl, M is an alkali metal or a quaternary ammonium ion, and X is a halogen.

6. A method as claimed in Claim 5, wherein M is selected from sodium, potassium, lithium and quaternary amine.

7. A method as claimed in any preceding claim, wherein the salt of the organic acid comprises a salt selected from a trichloroacetate, a cyanate, a carbamate, a carboxylate, _a thiocyanate, a thiocarbamate, a formate, an acetate, a propionate, a benzoate, a chloroacetate, an acrylate, a lactate, and a pyruvate.

8. A method as claimed in any preceding claim, wherein the salt of the organic acid is lithium acetate or lithium propionate.

9. A method as claimed in any preceding claim, wherein a tertiary amine compound is contacted with the material during step (a) or (b) .

10. A method as claimed in any preceding claim, wherein the reactive dye is a halogen-containing reactive dye.

11. A method as claimed in any preceding claim, wherein the reactive dye comprises at least one group selected from a halotriazine, sulphatoethylsulphone/vinyl- sulphone, quaternary triazinyl, dichloro-quinoxaline, difluoromonochloropyrimidine groups, or a combination of such groups.

12. A method as claimed in Claim 10 or 11, wherein the reactive dye comprises a fluorine-containing reactive group .

13. A method as claimed in any preceding claim, wherein the reactive dye and/or the salt of the organic acid is/are present in an aqueous composition.

14. A method as claimed in Claim 13, wherein the aqueous composition further comprises an oxidising agent.

15. A method as claimed in Claim 13 or 14, wherein the salt of the organic acid is present in the same aqueous composition as the reactive dye, such that steps (a) and (b) of the method are performed simultaneously.

16. A method as claimed in any one of Claims 13 to 15, wherein the aqueous composition comprises one or more co-solvents or humectants.

17. A method as claimed in any one of Claims 13 to 16, wherein the aqueous composition comprises a surfactant .

18. A method as claimed in any preceding claim, wherein the reactive dye and/or the salt of the organic acid are contacted with the material at a pH of between 4 and 8.

19. A method as claimed in Claim 18, wherein the reactive dye and/or the salt of the organic acid are contacted with the material at a pH of between 5 and 7.

20. A method as claimed in any one of Claims 13 to 17, wherein the aqueous composition further includes a tertiary amine oxide.

21. A method as claimed in any preceding claim, wherein the method comprises a step (c) of exposing the material to heat.

22. A method as claimed in Claim 21, wherein step (c) comprises exposing the material to heated air.

23. A method as claimed in Claim 21, wherein step (c) comprises contacting the material with heated water.

24. A method as claimed in Claim 23, wherein step (c) comprises contacting the material with steam.

25. A method as claimed in any preceding claim, wherein the salt of the organic acid and/or the reactive dyes are housed in an inkjet print cartridge.

26. A material coloured by the method of any one of Claims 1 to 25.

27. A material as claimed in Claim 26, wherein the material is a textile material.

28. A material as claimed in Claim 25 or 26, comprising cotton, wool, flax, linen, hemp, leather, viscose, rayon, nylon or polyamide.

29. A composition comprising a salt of an organic acid and a reactive dye.

30. A composition as claimed in Claim 29, wherein the salt of the organic acid and reactive dye are as described in any one of Claims 1 to 28.

31. A method substantially as described herein.

32. A material substantially described herein.

33. A composition substantially described herein.