WO1999051686A1 - Composes de colorants reactifs - Google Patents

Composes de colorants reactifs Download PDF

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Publication number
WO1999051686A1
WO1999051686A1 PCT/US1999/007294 US9907294W WO9951686A1 WO 1999051686 A1 WO1999051686 A1 WO 1999051686A1 US 9907294 W US9907294 W US 9907294W WO 9951686 A1 WO9951686 A1 WO 9951686A1
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Prior art keywords
dye
synthesis
reaction
compounds
dyeing
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PCT/US1999/007294
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English (en)
Inventor
Earl David Brock
David Malcolm Lewis
Taher Iqbal Yousaf
Original Assignee
The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU34665/99A priority Critical patent/AU3466599A/en
Priority to BR9909363-4A priority patent/BR9909363A/pt
Priority to JP2000542402A priority patent/JP2003524664A/ja
Priority to EP99916317A priority patent/EP1066346A1/fr
Publication of WO1999051686A1 publication Critical patent/WO1999051686A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring

Definitions

  • the present invention relates to reactive dye compounds.
  • the present invention relates to reactive dye compounds having improved dye-bath Exhaustion (E) and improved dye-fibre covalent Fixation (F).
  • Reactive dye compounds are known in the art for dyeing various substrates.
  • substrates include for example proteinaceous materials such as keratin, e.g. found in hair, skin and nails and various animal body parts such as horns, hooves and feathers, and other naturally occurring protein containing materials, e.g. silk and saccharide- derived materials such as those derived from cellulose or cellulose derivatives, e.g. natural products such as cotton, and synthetic fibres such as poly amides.
  • Examples of classes of such reactive dyes which are well known in the art include dyes containing a mono- or dichloro- or fluoro- 1,3,5-triazinyl group, mono- or dichloro or fluoro-pyrimidyl group, beta-halogen-propionyl group, beta-halogenoethyl-sulphonyl group, beta-halogenoethylsulphamyl group, chloroacetyl amino, beta-(chloro-methyl)- beta-sulphatoethylsulphamyl group, or a vinyl sulphonyl group.
  • a high Exhaustion value for a particular dye compound means that a low level of spent dye remains in the effluent after the dyeing process is complete, while a low Exhaustion value means that a high level of spent dye remains in the effluent.
  • the Fixation Value (F) of a dye compound is a measure of the dye affinity at the substrate surface.
  • a high Fixation Value can result in a simplification of the post dyeing "soaping off process" traditionally associated with fiber reactive dye compounds.
  • a high Fixation Value can result in a reduced time spent on the "soaping off process” together with a reduced cost.
  • a new class of fibre reactive dye compounds comprising a nitrogen-containing heterocycle such as pyrimidine substituted with at least one quaternized nitrogen derivative such as nicotinate, exhibit significantly increased values of Exhaustion (E) and Fixation (F).
  • E Exhaustion
  • F Fixation
  • These dyes can be used on a wide variety of substrates. They are particularly useful for cellulosic substrates, such as cotton, and show significant improvements in terms of reducing spent dyestuff in effluent, increasing dye affinity to the substrate, and simplifying the post dyeing "soaping off process" traditionally associated with reactive dyes.
  • the compounds of the present invention provide significantly more intense dyeings, and can be used for both high and low temperature dyeing, hence reducing the cost of the dyeing process.
  • the compounds of the present invention can be used together with specific chromophores for cellulose substrate dyeing leading to significantly reduced levels of salt needed for dyeing. 3
  • the compounds of the present invention exhibit increased Exhaustion (E) and Fixation (F) values and provide improvements in terms of reducing spent dyestuff in effluent, increasing dye affinity to the substrate, simplifying the post dyeing "soaping off process" traditionally associated with fiber reactive dyes and ability to dye at room tenperature and elevated temperatures.
  • the compounds of the present invention provide significantly more intense dyeings, i.e. greater colour intensity in the dyed substrate.
  • reactive dye means a dye containing one or more reactive groups, that is to say one or more groups capable of forming covalent bonds with the substrate to be dyed, or a dye which forms such a group in situ.
  • Exhaustion in relation to reactive dyes means the percentage of dye which is transferred from a solution of the dye to the substrate to be treated at the end of the dyeing process, before rinsing and soaping. Thus 100% Exhaustion means that 100% of the dye is transferred from the dye solution to the substrate.
  • Fixation in relation to reactive dyes means the percentage of dye which covalently bonds with the substrate, based on the dye originally absorbed during the dyeing process. Thus 100% Fixation means that 100% of the dye absorbed is covalently bonded with the substrate.
  • the reactive dye compounds of the present invention have a Fixation Value (F) on cellulosic substrates of 95% or greater as measured by the Fixation Value Technical Test Method described hereinbelow (at 2:1 standard depth).
  • the reactive dye compounds of the present invention have a Fixation Value on cellulosic substrates of 97% or greater, more preferably 99% or greater.
  • Preferred reactive dye compounds herein have an Exhaustion Value (E) on cellulosic substrates of 90% or greater as measured by the Exhaustion Value Technical Test Method described hereinbelow (at 2:1 standard depth).
  • the reactive dye compounds of the present invention have an Exhaustion Value of 93% or greater, more preferably 95% or greater, even more preferably 97% or greater, especially 99% or greater.
  • the total efficiency of reactive dyes can be measured by their Efficiency Value (T) which can be calculated from the Exhaustion Value (E) and Fixation Value (F) using the following equation:
  • reactive dye compounds having an Efficiency Value (T) on cellulosic substrates of about 86.5% or greater, preferably about 90% or greater (at 2:1 standard depth), more preferably about 93% or greater, even more preferably about 95% or greater, even more preferably about 97% or greater, especially about 99% or greater.
  • T Efficiency Value
  • %E percentage Exhaustion Value
  • the %E Value can be calculated using the following equation: 5
  • UV/Visible Scanning Spectrophotometer to obtain maximum accuracy of measurement it is necessary to dilute the liquor so that a sample gives an Optical Density of below 0.6 (for adherence to Beer's Law).
  • a second dye bath B was prepared in the same way as for dye bath A.
  • Bath A is agitated at 23C for 30 minutes. 2g of trisodium phosphate is then added to adjust the pH of bath A to pH 11.25 and dyeing is continued for a further 30 minutes at the end of which dyeing is complete.
  • the fabric is cut into two equal weight parts : Sample A and Sample B
  • Sample B is dried in air overnight and kept as a control.
  • Sample A is boiled for 30 minutes in 100ml of an aqueous solution of Sandozin NIE (non-ionic ethoxylated fatty alcohol detergent commercially available from Clariant) (2g/litre) in a 500ml beaker. The procedure is repeated until the extract solution is visually colourless. Sample A is then dried by hanging in air overnight.
  • Sandozin NIE non-ionic ethoxylated fatty alcohol detergent commercially available from Clariant
  • the reflectance values for Samples A and B can be used to obtain their K/S (Fixation) Values - see equation 3 below.
  • the K S or Kulbelka Munk Values are proportional to the amount of dye remaining on the samples.
  • K/S is derived from the Kulbelka Munk theory and can be used as a measure of the amount of dye on the fibre. The higher the K/S Value the more dye on the fibre.
  • the total overall efficiency of the process i.e. the fraction of dye originally applied which ends up covalently fixed to the fibre) may then be calculated as follows:
  • Preferred compounds of the present invention comprise a chromophore moiety and a nitrogen-containing heterocycle linked via a linking group.
  • the nitrogen-containing heterocycle preferably has at least one quaternized nitrogen derivative.
  • the reactive dye compounds herein can comprise one or more chromophore moieties. In reactive dye compounds comprising two or more chromophore moieties these can be the same or different. Preferably the reactive dye compounds herein comprise from one to three chromophore moieties.
  • chromophore moieties suitable for use for dyeing substrates can be used in the present invention.
  • chromophore as used herein means any photoactive compound and includes any coloured or non-coloured light absorbing species, eg. fluorescent brighteners, UV absorbers, IR absorbing dyes.
  • Suitable chromophore moieties for use in the dye compounds herein include the radicals of monoazo, disazo or polyazo dyes or of heavy metal complex azo dye derived therefrom or of an anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthene, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide dye.
  • Suitable chromophore moieties for use in the dye compounds herein include those disclosed in EP-A-0,735,107 (Ciba-Geigy), incorporated herein by reference, including the radicals described therein which contain substituents customary for organic dyes, such as sulphonate substituents which enhance the water-soluble properties of the dye compound.
  • chromophore D groups for use herein are polysulphonated azo chromophores such as those present in Procion (RTM) dyes commercially available from BASF, Drimalan (RTM) dyes commercially available from Clariant, Drimarene (RTM) dyes commercially available from Clariant and Levafix (RTM) commercially available from Dystar.
  • RTM Procion
  • RTM Drimalan
  • RTM Drimarene
  • Dystar Levafix
  • the reactive dyes of the present invention comprise at least one nitrogen containing heterocyclic moiety.
  • reactive dye compounds containing two or more nitrogen containing heterocycles these can be the same or different.
  • the reactive dye compounds herein comprise from one to three nitrogen containing heterocycles.
  • At least one of the nitrogen containing heterocycle moieties herein is substituted with at least one thio-derivative and at least one quaternized nitrogen derivative.
  • Suitable nitrogen containing heterocycles for use herein include monocyclic, bicyclic or polycyclic, unsaturated heterocycles containing at least one nitrogen heteroatom.
  • monocyclic rings are preferably selected from unsaturated rings having from about 3 to about 7 ring atoms, especially 5 or 6 ring atoms, comprising from about 1 to about 3 nitrogen heteroatoms, preferably 2 or 3 nitrogen heteroatoms.
  • bicyclic heterocycles When bicyclic heterocycles are used, they preferably comprise an unsaturated nitrogen containing heterocycle having 3 to 7 ring atoms, preferably an unsaturated nitrogen containing heterocycle having 5 or 6 ring atoms comprising 1 or 2 nitrogen atoms, fused to a 5 to 7 membered carbocycle preferably a 6-membered unsaturated carbocycle.
  • the thio- and quaternized nitrogen substituents are preferably attached to the nitrogen containing heterocyclic ring.
  • Preferred for use herein are 5 or 6 membered unsaturated nitrogen containing monocyclic heterocyclic rings comprising 2 or 3 nitrogen heteroatoms or bicyclic rings containing a 5 or 6 membered unsaturated heterocyclic ring containing 2 nitrogen heteroatom fused to a 6 membered unsaturated carbocycle.
  • heterocycles for use herein include, but are not necessarily limited to triazine, pyrimidine, quinoxaline, pyrimidinone, phthalazine, pyridazone and pyrazine.
  • Preferred for use in the compounds herein are triazine, pyrimidine and quinoxaline.
  • the compounds herein further comprise a linking moiety to link each nitrogen- containing heterocycle to each chromophore moiety.
  • Any linking moieties suitable for use in dyeing substrates can be used in the present invention.
  • the linking moiety is selected from NR, NRC-O, C(O)NR, NRSO2 and -SO2NR wherein R is H or 10
  • C1-C4 alkyl which can be substituted by halogen, preferably fluorine or chlorine, hydroxyl, cyano, C1-C4 alkoxy, C2-C5 alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato.
  • a preferred linking moiety is NR, preferably where R is H or C1-C4 alkyl, more preferably where R is H or CH3, especially H.
  • a preferred substituent of the compounds herein is a quaternized nitrogen substituent.
  • Suitable quaternized nitrogen derivatives for use herein can be represented by Q+ wherein Q is selected from amines, saturated or unsaturated, substituted or unsubstituted nitrogen containing heterocycles having from about 3 to about 8 ring members and comprising at least one nitrogen heteroatom.
  • Q groups selected from:
  • R" is C1-C4 alkyl and n is an integer of from 1 to 4.
  • Particularly preferred quaternized nitrogen derivatives for use herein are nicotinate, DABCO, dimethylaminobetaine and isonicotinate, especially nicotinate.
  • the quaternized nitrogen derivative is attached to the nitrogen-containing heterocycle via its tertiary nitrogen atom.
  • preferred reactive dye compounds comprising at least one quaternized nitrogen derivative can be represented by the formula (I):
  • D is a chromophore group as defined hereinabove
  • L is a linking moiety as defined herein above;
  • Q is a quaternized nitrogen derivative as defined hereinabove
  • X and Y are independently selected from chlorine, bromine, fluorine or hydrogen;
  • A is selected from halogen, preferably chlorine or fluorine;
  • X is selected from chlorine or hydrogen, especially chlorine and Y is fluorine.
  • thio-derivatives for use herein include, but are not necessarily limited to groups having the formula SR' wherein R' is selected from H or alkyl or preferably short chain alkyl (preferably less than about 6 carbon atoms), alkanol, alkyl carboxylate, alkylamide, alkylsulphonate, alkyl phosphonate, alkyl thiosulphonate, alkylamine, alkyl thiosulphate, aryl sulphonate, aryl carboxylate, aryl phosphate, aryl amine, cyanates, sulphonates, branched alkyl thio carboxylates, branched alkanol thiols, guanides, alkyl- ⁇ -amino- ⁇ -carboxylate, (di) thio alkyl esters of gly
  • thio-derivatives include SR' groups where R' is C1-C4 alkyl, (CH ) n COOH, (CH2) n CONH 2 , (CH 2 ) n SO 3 H, (CH2) n COOM, (CH2)nPO 3 H, (CH 2 ) n OH, (CH 2 ) n SSO 3 " , (CH2) n NR" , (CH 2 ) n N + R"3, PhSSO 3 " , PI1SO3H, PhPO3H, PhNR M 2, PhN + R"3, -CN, SO3 " , (CH2)2CH(SH)R"(CH2)3COOH, - CH2CHOHCH2SH, and
  • n is an integer in the range of 1 to 4 wherein within the same molecule n is not necessarily the same integer; and M is a cation of alkaline earth metal, alkali metal, NH4 + or NR"3 +
  • Preferred thio-derivatives for use herein have the formula SR' wherein R 1 is (CH2)nCOOH, (CH2)nOH, and (COOH)CH2CH2(COOH) ; wherein n is an integer from 1 to 4.
  • preferred reactive dye compounds of the present invention comprise at least one chromophore moiety, at least one nitrogen-containing heterocycle and a linking group to link each chromophore moiety to each nitrogen-containing heterocycle characterised in 18
  • nitrogen-containing heterocycle is substituted with at least one thio-derivative and at least one quaternized nitrogen derivative.
  • Suitable chromophore moieties, nitrogen-containing heterocycles, linking groups, thio-derivatives and quaternized nitrogen derivatives are as described above.
  • D is a chromophore group as described hereinabove
  • Z is a nitrogen containing heterocycle as defined hereinabove
  • SR' is a thio-derivative as described hereinabove
  • A is halogen, preferably chlorine or fluorine
  • B is a chromophore D as defined above, bifunctional chromophore, or other organic radical suitable for use in place of a chromophore such as those taught in the art (see for example EP-A-0,735,107), provided that the reactive dye compound contains at least one chromophore group.
  • Suitable B groups included ⁇ -sulphatoethylsulphonyl benzene, vinyl sulphonyl benzene, chloroethylsulphonyl benzene, ⁇ -s-thiosulphatoethyl sulphonyl benzene, di(ethylsulphonyl) chromophore
  • J is selected from S, O, NH
  • K is selected from Q , halogen
  • L' is a linking group which can be any suitable biradical linking group suitable for use in dye compounds and is preferably selected from B wherein B is as defined above, C1-C4 alkyl, esters having the formula (Al), diesters having the formula (Al), amides having the formula (Al), diamides having the formula (Al) wherein Al is (CH2) ⁇ -2-(C(O)-J)o l-
  • L' examples include succinate, diethyl sulphide, ⁇ - sulphatoethylsulphonyl benzene, vinyl sulphonyl benzene, chloroethylsulphonyl benzene, ⁇ -s-thiosulphatoethyl sulphonyl benzene, di(ethylsulphonyl) chromophore, ethyl, diethylsulphone, isopropanol.
  • Another preferred reactive dye according to the present invention can be represented by compounds of the formula (IV): 20
  • L is a linking group which can be any suitable triradical linking group suitable for use in dye compounds and is preferably selected from glycerol, diethylenetriamine and N,N',N" tripropanoylaminohexahydrotriazine provided that the reactive dye compound comprises at least one chromophore group.
  • Another preferred reactive dye compound according to the present invention can be represented by compounds of the formula (V):
  • each of D, L, Z, R 1 , Q are as defined above;
  • V and W are independently selected from NR, or SR 1 wherein R and R 1 are as defined hereinabove, Q , halogen.
  • Another preferred reactive dye compound according to the present invention can be represented by compounds of the formula (VI): 21
  • each of B, Z, Q, A, R', L , V and W are as defined above, provided that the reactive dye compound contains at least one chromophore group.
  • each of the defined groups may be the same or different.
  • one of the Z groups may be pyrimidine and the other Z group may be triazine.
  • the dye compounds having the formula (I) can be prepared by reacting suitable precursors of the dye of formula (I) with one another, at least one of which contains a group D-L-pyrimidine, wherein D, and L are as defined above, and at least one of which contains a Q group (wherein Q is as defined above).
  • Dye compounds having the formula (I) wherein X is fluorine and Y is chlorine can be prepared by reacting a difluoromonochloro pyrimidine dye such as those commercially available from Clariant under the tradenames Drimalan (RTM) and Drimarene (RTM), with a suitable reactant containing a Q group.
  • a difluoromonochloro pyrimidine dye such as those commercially available from Clariant under the tradenames Drimalan (RTM) and Drimarene (RTM)
  • the reactions of the starting dye compounds with the reactant containing a Q group are generally carried out at a pH of from about 5 to about 6, and at a temperature of about 40-45 °C.
  • the reactive dyes having the formula (II) above can be prepared by reacting suitable precursors of the dye of formula (II) with one another, at least one of which contains a 22
  • D-L-Z wherein D, L and Z are as defined above, at least one of which contains an R' group (wherein R' is as defined above) and at least one of which contains a Q group (wherein Q is as defined above).
  • dye compounds of the invention having a formula (II) wherein Z is a triazine heterocycle can be prepared by reacting a dichlorotriazine dye, such as those commercially available from BASF under the tradename Procion (RTM), with a suitable reactant containing an R' group and then reacting the intermediate dye compounds obtained with a suitable reactant containing a Q group.
  • RTM dichlorotriazine dye
  • Dye compounds of the invention having a formula (II) wherein Z is a pyrimidine heterocycle can be prepared by reacting a difluoromonochloro pyrimidine dye such as those commercially available from Clariant under the tradenames Drimalan (RTM) and Drimarene (RTM), with a suitable reactant containing an R' group and then reacting the intermediate dye obtained with a suitable reactant containing a Q group.
  • a difluoromonochloro pyrimidine dye such as those commercially available from Clariant under the tradenames Drimalan (RTM) and Drimarene (RTM)
  • Dye compounds of the invention having a formula (II) wherein Z is a quinoxaline heterocycle can be prepared by reacting a dichloroquinolaxine dye such as those commercially available from Dystar under the tradename Levofix(RTM), with a suitable reactant containing an R' group and then reacting the intermediate dye obtained with a suitable reactant containing a Q group.
  • a dichloroquinolaxine dye such as those commercially available from Dystar under the tradename Levofix(RTM)
  • the reactions of the starting dye compounds with the reactant containing an SR' group are generally carried out at a pH of from about 7 to about 10, and at a temperature of about 0-5 C.
  • the reactions of the intermediate dye compounds with the reactant containing a Q group are generally carried out at a pH of from about 5 to about 6 and at a temperature of from about 50-85C.
  • the reactions of the intermediate dye compounds with the reactant containing a Q group are generally carried out at temperature of from about 50- 55C when Z is triazine and 75-85 C when Z is pyrimidine.
  • dyes having the formulae (II) - (V) can be prepared by using the same general chemistry as for dyes of formula (I) by reacting together suitable starting materials, and as exemplified below.
  • the dye compounds herein are suitable for dyeing and printing a wide variety of substrates, such as silk, leather, wool, polyesters, polyurethane, polyamide fibers and 23
  • polyurethanes such as hair
  • keratin fibres such as hair
  • cellulosic materials such as the natural cellulose fibres, cotton, linen, hemp and the like, paper, and also cellulose itself and regenerated cellulose, and hydroxyl-containing fibres contained in blend fabrics, for example blends of cotton with polyester or polyamide fibres.
  • the dye compounds of the present invention can be applied and fixed to the substrate in various ways, in particular in the form of aqueous dye solutions and printing pastes.
  • a dye composition comprising one or more of the dye compounds described herein together with any carrier material suitable for use in a dye composition.
  • Preferred dye compositions herein comprise an acidic buffer material. Any acidic buffer suitable for use in dye compositions can be used herein.
  • An example of a suitable buffer is a mixed phosphate buffer.
  • a preferred ingredient is a thickening agent. Any suitable thickening agents suitable for use in dye compositions can be used herein.
  • the dye composition when the dye composition is in the form of an aqueous solution or aqueous gel/paste, the dye composition preferably has a pH of about 5 or less, preferably from about 2 to about 3.
  • the composition can comprise one or more of the compounds described herein either alone or in admixture with other well known hair dye compounds such as oxidative dyes, direct dyes, and the like.
  • the dyeing and printing processes which can be used with the dyes herein are conventional processes which are well known and which have been widely described in the technical and patent literature.
  • the dye compounds herein are suitable for dyeing both by the exhaust method and also by the pad-dyeing method, whereby the goods are impregnated with aqueous, salt-containing or salt-free dye solutions and the dye is fixed after an alkali treatment or in the presence of alkali, if appropriate with the application of heat.
  • the dye compounds herein are also suitable for the cold pad-batch method, after which the dye together with the alkali is applied to the pad-mangle and then fixed by several hours of storage at room temperature. After fixing, the dyeings or prints are 24
  • the reactive dyes of the present invention for dyeing and printing substrates such as cotton, wool, nylon, silk, keratin, leather, paper and the like.
  • the compounds herein can be used in methods of dyeing all of the substrates listed above by applying an aqueous solution of one or more of the reactive dyes of the present invention to the substrate to be dyed under suitable conditions of pH and temperature.
  • the monothioglycolatomononicotinyl triazine dye is prepared using the synthesis route as illustrated in Diagram 1.
  • the synthesis consists of two parts, the first part for the preparation of monochloro- monothioglycolato triazine and the second part for the preparation of monothioglycolatomononicotinyl triazine as shown in the reaction mechanism below.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • a variety of Procion (RTM) dyes commercially available from BASF are used as starting materials, in particular, Procion Red MX-8B, Procion Yellow MX-8G and Procion Blue MX-2G.
  • the first part of the synthesis is to obtain monochloro-monothioglycolato triazine.
  • An aqueous dye solution (O.lmol/lOOml, pH 7.5) of a purified Procion (RTM) dichlorotriazine dye is prepared.
  • a 0.1 mol solution of Mercaptoacetic acid is added by slow dripping at a temperature of between 0 and 5°C.
  • the pH of the system is adjusted to 8 using sodium carbonate and HC1.
  • the reaction is then allowed to proceed, at 0 ⁇ 5°C and pH8, for 5 ⁇ 8 hours.
  • the required reaction time is different (7 ⁇ 8 hours for Procion Red MX-8B, ⁇ 6 hours for Procion Yellow MX-8G and ⁇ 5 hours for Procion 26
  • the monochloro-monothioglycolato triazine obtained from the first part of the synthesis is reacted with nicotinic acid.
  • An stoichiometric excess of an aqueous solution of nicotinic acid (pH5 ⁇ 5.5) is added to an aqueous solution of monochloromonothioglycolato triazine dye solution.
  • the temperature of the reaction system is then raised to 50 ⁇ 55°C and the pH adjusted to 5-5.5.
  • the reaction is allowed to proceed, under these conditions, for a period of time. Again, a rapid drop in pH of the synthesis system is observed.
  • the end-of-reaction point is, again, indicated by the stabilisation of the pH for more than 5 minutes.
  • the required reaction time is different (4-5 hours for Procion Red MX-8B, -3 hours for Procion Yellow MX-8G and 2-2.5 hours for Procion Blue MX-2G). At this point, the monothioglycolatomononicotinyl triazine dye is obtained.
  • the reaction system is immediately cooled to below 5°C and its pH reduced below 2, in order to prevent the hydrolysis of monothioglycolatomononicotinyl triazine dye.
  • the solid monothioglycolatomononicotinyl triazine dye is then obtained following precipitation and filtration.
  • the solid monothioglycolatomononicotinyl triazine dye obtained is rinsed with acetone 4-5 times to ensure they are free of water and then stored at 0-5 °C.
  • the monothioglycolatomonoisonicotinyl traizine dye is prepared using the synthesis route illustrated in Diagram 2. 27
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion (RTM) Red MX-8B is used as a starting material.
  • the Procion Red MX-8B in this example can be substituted by other dichlorotriazine dyes such as Procion (RTM) Yellow MX-8G or Procion Blue MX-2G.
  • the synthesis consists of two parts, the first part for the preparation of monochloromonothioglycolatotriazine dye and the second part for the preparation of monothioglycolatomonoisonicotinyl triazine dye.
  • the monochloromonothioglycolato triazine dye obtained from the first part of the synthesis is reacted with iso-nicotinic acid.
  • 0.01 moles of the monochloromonothioglycolato triazine dye obtained from the first part of the synthesis is introduced to a flask together with 0.04 moles of isonicotinic acid in distilled water.
  • the temperature of the reaction system is then raised to 55°C and the pH adjusted to 5.5.
  • the reaction is allowed to proceed under these conditions for 30 minutes. Again, a rapid drop in pH of the synthesis system is observed which is raised again by the buffering agents.
  • the endpoint of the reaction is indicated by the stabilisation of the pH for more than 5 minutes.
  • the conditions of precipitation, filtration and acetone washing are the same as for the compound prepared in Example 1.
  • the yield is over 85%.
  • the monothioglycolatomonodiazabicyclooctane triazine dye is prepared using the synthesis route as illustrated in Diagram 3.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion (RTM) Red MX-8B is used as the starting material.
  • the synthesis consists of two parts, the first part for the preparation of monochloromonothioglycolatotriazine dye and the second part for the preparation of monothioglycolatomonoDABCO triazine dye.
  • the preparation of monochlorothioglycolatotriazine is carried out in the same manner as described in Example 1 above.
  • monochloromonothioglycolato triazine dye obtained from the first part of the synthesis is reacted with diazabicyclooctane (DABCO).
  • DABCO diazabicyclooctane
  • 0.01 moles of the monochloromonothioglycolato triazine dye is placed in a flask together with 0.03 moles of DABCO in distilled water.
  • the temperature of the resulting solution is then raised to 55°C and the pH adjusted to 5.5.
  • the reaction is allowed to proceed under these conditions for 15 minutes. Again, a rapid drop in pH of the synthesis system was observed which is brought back up to pH 5.5 by the buffering agents.
  • the 30 diazabicyclooctane
  • the monothioglycolatomonodimethylaminobetaine triazine dye is prepared using the synthesis route as illustrated in Diagram 4.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion (RTM) Red MX-8B is used as the starting material, but other suitable dichlorotriazine dye compounds can also be used as starting materials such as Procion (RTM) Yellow MX-8G and Procion (RTM) Blue MX-2G. 31
  • the synthesis consists of two parts, the first part for the preparation of monochloromonothioglycolatotriazine dye and the second part for the preparation of monothioglycolatomonodimethylaminobetaine triazine dye.
  • the preparation of monochlorothioglycolatotriazine is carried out in the same manner as described in Example 1 above.
  • monochloromonothioglycolato triazine dye obtained from the first part of the synthesis is reacted in aqueous solution with dimethylaminobetaine.
  • 0.01 moles of monochloromonothioglycolato triazine dye is placed in a flask together with 0.01 moles of dimethylaminobetaine in distilled water.
  • the temperature of the reaction system is then raised to 55°C and the pH adjusted to 5.5.
  • the reaction was allowed to proceed under these conditions for 10 to 15 minutes.
  • a rapid drop in the pH of the synthesis system was observed which is readjusted to pH 5.5 using the buffering agents.
  • the endpoint of the reaction is indicated by the stabilisation of the pH for more than 5 minutes.
  • the conditions of precipitation, filtration, and acetone washing are the same as for example 1 above.
  • the yield is over 85%.
  • the monothioethanolmononicotinyl triazine dye is prepared using the synthesis route as illustrated in Diagram 5.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion (RTM) Red MX-8G was used as the starting material, but other suitable dichlorotriazine dye compounds can also be used as starting materials such as Procion Yellow MX-8G and Procion Blue MX-2G.
  • the synthesis consists of two parts, the first part for the preparation of monochloromonothioethanol triazine dye and the second part for the preparation of monothioglycolatomonodimethylaminobetaine triazine dye.
  • the monothiosuccinatemononicotinyl triazine dye is prepared using the synthesis route as illustrated in Diagram 6.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion (RTM) Red MX-8G is used as the starting material, but other suitable dichlorotriazine dye compounds can also be used as starting materials, such as Procion (RTM) Yellow MX-8G and Procion (RTM) Blue MX-2G.
  • TSA denotes thiosuccinate attached to the ring via its sulphur atom.
  • the synthesis consists of two parts, the first part for the preparation of monochloromonosuccinate triazine dye and the second part for the preparation of monosuccinatemononicotinyl triazine dye.
  • the reaction is then allowed to proceed, at 0-5°C and pH7.5-8 (which is corrected using sodium carbonate and HCl) for 6 hours.
  • the endpoint of the reaction for this part of the synthesis is indicated by the pH of the reaction system remaining constant for more than 5 minutes.
  • the dye monochloromonothiosuccinate triazine dye is obtained.
  • KCl 35% of the total solution
  • the precipitate is then washed with acetone for 4-5 times (50ml of acetone was used each time) to obtain the final dye product.
  • 0.01 moles of the monochloromonothiosuccinate triazine dye obtained from the first part of the synthesis is introduced to a flask together with 0.03 moles of nicotinic acid in distilled water.
  • the temperature of the reaction system is then raised to 50°C and the pH adjusted to 5-5.5.
  • the reaction is allowed to proceed under these conditions for 15- 20 minutes. Again a rapid change in the pH of the synthesis system is observed which is readjusted to pH 5-5.5 by addition of buffering agents.
  • the endpoint of the reaction is indicated by the stabilisation of the pH for more than 5 minutes.
  • the conditions of precipitation, filtration and acetone washing are the same as for Example 1.
  • the yield is over 85%.
  • the mono5-chloromono4-thioglycolatomono2-nicotinyl pyrimidine dye is prepared using the synthesis route as illustrated in Diagram 7. 36
  • Drimalan (RTM) Red FB dye commercially available from Clariant is used as starting material.
  • Drimalan Red FB can be substituted for any suitable difluoromonochloro pyrimidine dye such as those commercially available under the tradename Drimalan and Drimarene dyes, in particular, Drimalan Red FB, Drimalan Yellow F-R, Drimalan Blue F-G, Drimalan Blue F-B, Drimalan Yellow F-3GL, Drimalan Black F-B, Drimarene Golden Yellow R-G2R, Drimarene Blue R-GL, Drimarene Brill Red R-8B, and Drimarene Brill Red K-4BL.
  • TGA denotes a thioglycolato moiety.
  • the synthesis consists of two parts, the first part for the preparation of mono-5- chloromono-2-fluoromono-4-thioglycolato pyrimidine dye and the second part for the preparation of mono-5-chloro-2-nicotinyl-4-thioglycolato pyrimidine dye.
  • Drimalan Red F-B dye in distilled water 0.1 moles of Drimalan Red F-B dye in distilled water are introduced into a flask. The flask is then placed in an ice-water bath. 0.1 moles of mercaptoacetic acid is then added dropwise to the reaction mixture with stirring. The total addition time is 1-1.5 hours. 37
  • the pH of the reaction mixture is maintained at pH 9.8-10 and at a temperature of 0-5°C throughout the addition of mercaptoacetic acid.
  • the reaction is then allowed to proceed at 5°C and pH 9.8-10 (which is corrected using sodium carbonate and HCl) for 15 hours.
  • the end-of-reaction point for this part of the synthesis is indicated by the pH of the reaction system remaining constant for more than 5 minutes.
  • the mono-5-chloro-2-fluoro-mono-4-thioglycolato pyrimidine dye is obtained.
  • KCl ⁇ 35% of the total solution
  • KCl ⁇ 35% of the total solution
  • the 5-chloro-4-nicotinyl-2-thioglycolato pyrimidine dye is prepared using the synthesis route as illustrated in Diagram 8.
  • Drimalan Red FB can be substituted for a variety of other suitable difluoromonochloro pyrimidine dyes or trichloro pyrimidine dyes such as those commercially available from Clariant under the tradenames Drimalan and Drimarene, including Drimalan Red F-B, Drimalan Yellow F- R, Drimalan Blue F-G, Drimalan Blue F-B, Drimalan Yellow F-3GL, Drimalan Black F-B, Drimarene Golden Yellow R-G2R, Drimarene Blue R-GL, and Drimarene Brill Red R-8B.
  • TGA denotes a thioglycolato moiety.
  • the synthesis consists of two parts, the first part for the preparation of 5-chloro-4- nicotinyl-2 -fluoro pyrimidine dye and the second part for the preparation of 5-chloro-4- nicotinyl-2-thioglycolato pyrimidine dye.
  • 0.1 moles of pure Drimarene Brill Red K-4BL dye and 150ml of distilled water are introduced into a flask.
  • 0.1 mole of nicotinic acid is then added dropwise to the reaction mixture under stirring, from a dripping funnel.
  • the total addition time is 1-1.5 hours.
  • the pH of the reaction system is maintained at pH 5-5.5 and the temperature of the reaction system 40-45°C, throughout the addition of nicotinic acid.
  • the reaction is then allowed to proceed at 40-45°C and pH5-5.5 (which was corrected using sodium carbonate and HCl) for 3-4 hours.
  • the end-of-reaction point for this part of the synthesis is indicated by the pH of the reaction system remaining constant for more than 5 minutes.
  • the 5-chloro-4-nicotinyl-2-fluoro pyrimidine dye is obtained.
  • 6N HCl the pH of the system is then reduced to below pH 2 to terminate the reaction.
  • the reaction is then allowed to proceed at 50-55°C and pH 5-5.5 (which is corrected using sodium carbonate and HCl) for 32-35 hours.
  • the end-of-reaction point for this part of the synthesis is indicated by the pH of the reaction system remaining constant for more than 5 minutes. At this point, 5-chloro-4-nicotinyl-2-thioglycolato pyrimidine dye is obtained.
  • KCl ⁇ 35% of the total solution
  • the precipitate is then washed with acetone for 4-5 times ( ⁇ 50ml of acetone used each time) to obtain the final dye product.
  • the nicotinylthioglycolato quinoxaline dye is prepared using the synthesis route as illustrated in Diagram 9.
  • the synthesis consists of two parts, the first part for the preparation of monothioglycolato quinoxaline dye and the second part for the preparation of monothioglycolatomononicotinyl quinoxaline dye as shown in the reaction mechanism below.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Levafix Goldgelb E-G commercially available from DyStar is used a starting material but this can be replaced by any suitable quinoxaline dye such as Levafix Brilliant Blue E-B, Levafix Brilliant Red E-RN and Levafix Brown E-2R.
  • the reaction is then allowed to proceed at 30-35°C and pH 9 (which was corrected using sodium carbonate and HCl) for 4-5 hours.
  • the end-of-reaction point for this part of the synthesis is indicated by the pH of the reaction system remaining constant for more than 5 minutes. At this point, thioglycolato quinoxaline dye is obtained.
  • KCl ⁇ 35% of the total solution
  • Filtration using Whatman filter paper follows. The precipitate is then washed with acetone for 4-5 times ( ⁇ 50ml of acetone used each time to obtain the dye product.
  • the dye denoted by IOC is prepared using the synthesis route as illustrated in Diagram 10.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion Red MX-8B commercially available from BASF is used a starting material but this can be replaced by any suitable triazine dye such as Procion Yellow MX-8G and Procion Blue MX-2G.
  • Compound 10B is then reacted with 0.3 moles of nicotinic acid at pH 5-5.5 at 50-55°C for 4 hours ( or until the pH remains constant).
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion Red MX-8B commercially available from BASF is used a starting material but this can be replaced by any suitable triazine dye such as Procion Yellow MX-8G and Procion Blue MX-2G.
  • Procion Red MX-5B 0.1 mole of Procion Red MX-5B is dissolved in water and slowly added to a chilled stirred aqueous solution of 0.1 moles of ethylene glycol-bis-thioglycolate.
  • the solution temperature is 0-5°C and is maintained at this temperature.
  • the solution is maintained at pH 7 throughout the reaction by the addition of sodium bicarbonate.
  • the intermediate dye 11 A is formed when the pH stabilizes.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion Yellow MX-8G commercially available from BASF is used a starting material but this can be replaced by any suitable triazine dye such as Procion Red MX-8B and Procion Blue MX-2G.
  • the dye compound 13B is synthesised according to the reaction mechanism below.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion Yellow MX-8G commercially available from BASF is used a starting material but this can be replaced by any suitable triazine dye such as Procion Red MX-8B and Procion Blue MX-2G.
  • Compound 14B is prepared by the reaction mechanism below.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Procion Yellow MX-8G commercially available from BASF is used a starting material but this can be replaced by any suitable triazine dye such as Procion Red MX-8B and Procion Blue MX-2G.
  • reaction scheme D' is a chromophore and varies depending on which starting dye is used.
  • Procion Red MX-8B was used but this can be replaced by any suitable triazine dye.
  • the 5-chloro-4-nicotinyl-2-fluoro pyrimidine dye is prepared using the synthesis route as illustrated in Diagram 15.
  • reaction scheme D is a chromophore and varies depending on which starting dye is used.
  • Drimarene Brill Red 4-KBL is used as the starting material.
  • any suitable pyrimidine containing dye can be used as a starting material including any Drimalan F dye, any Drimarene R dye and any Drimarene K dye commercially available from Clariant. 57
  • 0.1 moles of pure Drimarene Brill Red K-4BL dye in water are introduced into a flask.
  • 0.1 mole of nicotinic acid is then added dropwise to the reaction mixture under stirring, from a dripping funnel.
  • the total addition time is 1-1.5 hours.
  • the pH of the reaction system is maintained at pH 5-5.5 and the temperature of the reaction system 40-45°C, throughout the addition of nicotinic acid.
  • the reaction is then allowed to proceed at 40-45°C and pH5-5.5 (which is corrected using sodium carbonate and HCl) for 3-4 hours.
  • the end-of-reaction point for this part of the synthesis is indicated by the pH of the reaction system remaining constant for more than 5 minutes.
  • the 5-chloro-4-nicotinyl-2-fluoro pyrimidine dye is obtained.
  • 6N HCl the pH of the system is then reduced to below pH 2 to terminate the reaction.
  • the compounds prepared according to Examples 1 to 15 all have high Fixation Values on cotton fabrics (>95% as measured by the Fixation Value Technical Test Method described hereinabove).
  • the compounds prepared according to Examples 1 to 15 all have high Efficiency Values (T) on cotton fabrics (>90%) as calculated using the Fixation Values and Exhaustion Values obtained from the Fixation Value and Exhaution Value Technical Test Methods described hereinabove.
  • the compounds herein have high Exhaustion Values (E), and show significant improvements in terms of reducing spent dyestuff in effluent, increasing dye affinity to the substrate, increasing the dye-substrate covalent bonding, increasing the ability to dye substrates at room temperature, decreasing the amount of dye that is removed during the post dyeing "soaping off process” and therefore simplying the post dyeing "soaping off process” traditionally associated with dyeing cotton with fibre reactive dyes and reduction of staining of adjacent white fabrics.
  • the compounds prepared above provide more intense dyeings and require less levels of salt for dyeing cotton substrates.
  • All dye compounds prepared according to Examples 1 to 15 can be used to dye cotton using the dyeing procedures detailed below. After the cotton dyeing procedure has been carried out a soaping-off process can also be carried out on the cotton fibre.
  • An aqueous dye solution is prepared containing a dye compound according to any of Examples 1 to 15.
  • the dye solution contains 1.2% on mass of fibre of dye, 80g/L Na2SO4 and 5% on mass of fibre of sodium acetate.
  • the cotton fabrics are soaked in water and then the cotton fabrics are dyed in the above dye-bath at pH 7 at 25 °C for 30 minutes.
  • the dyed cotton fabric is then fixed in the dye-bath at pH 11.5 with addition of 30g/L of sodium formate and 5g/L Na2CO3 and dyeing continued at 25°C for 30 minutes.
  • the dyed fabric is rinsed with water.
  • a soaping off process can then be carried out by washing the dyed fabrics with an aqueous solution of Sandozine NIE (2g/L) at 100°C for 30 minutes.
  • the dyed fabrics are washed with an aqueous solution containing ECE Reference Detergent (5g/ml) and sodium carbonate (2g/ml) at 60°C for 30 minutes. 59
  • All dye compounds prepared according to Examples 1 to 15 can be used to dye nylon or wool using the dyeing procedures detailed below. After the nylon/wool dyeing procedure has been carried out a wash-test procedure can be carried out on the dyed fabric to test the wash-fastness of the dye compounds.
  • the wool/nylon fabric is soaked in a 2% Alcopol-O (40% w/w sodium-d- isooctylsulphate succinate -commercially available from Allied Colloids) solution.
  • the fabric is then dyed for 1 hour at 100°C and pH 3.5 in a dye-bath containing the following compositions: 1.2% on mass of fibre of dye prepared according to any of Examples 1 to 15, 5% on mass of fibre of sodium acetate, 1% Albegal B (commercially available from Ciba Geigy).
  • the dyed wool/nylon fabric was then rinsed with water.
  • the dyed wool/nylon fabric is washed in an aqueous solution containing 5g/L of ECE Reference Detergent (commercially available from Society of Dyers and Colourists, Bradford, UK) at 50°C for 45 minutes.
  • ECE Reference Detergent commercially available from Society of Dyers and Colourists, Bradford, UK

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  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne un colorant réactif possédant une valeur de fixation (F) sur des substrats cellulosiques de 95 % ou plus, telle que mesurée par le procédé d'essai technique de valeur de fixation (à une profondeur de référence de 2: 1). En outre, les composés selon la présente invention possèdent des valeurs d'épuisement (E) élevées, des valeurs d'efficacité (T) élevées et présentent des capacités améliorées de réduction de la quantité de colorant rejetée dans les eaux résiduaires, d'augmentation de l'affinité de teinture au substrat, d'augmentation de la liaison covalente colorant-substrat, d'augmentation de la capacité de teinture de substrats à température ambiante, de réduction de la quantité de colorant éliminée pendant le 'procédé de lavage après traitement' intervenant après la teinture, ce qui simplifie le 'procédé de lavage après traitement' intervenant après la teinture et traditionnellement associé à la teinture du coton avec des colorants réactifs, et de réduction du maculage des tissus blancs contigus. De plus, les composés préparés selon l'invention permettent d'obtenir une teinture plus intense et nécessitent des quantités de sel moins importantes pour la teinture de substrats en coton.
PCT/US1999/007294 1998-04-02 1999-04-01 Composes de colorants reactifs WO1999051686A1 (fr)

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AU34665/99A AU3466599A (en) 1998-04-02 1999-04-01 Reactive dye compounds
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JP2000542402A JP2003524664A (ja) 1998-04-02 1999-04-01 反応染料化合物
EP99916317A EP1066346A1 (fr) 1998-04-02 1999-04-01 Composes de colorants reactifs

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6713613B1 (en) 1999-05-19 2004-03-30 North Carolina State University Reactive dye compounds
US6716969B1 (en) 1999-05-19 2004-04-06 North Carolina State University Reactive dye compounds
US6723834B1 (en) 1999-10-01 2004-04-20 North Carolina State University Reactive dye compounds
US6736864B1 (en) 1999-10-01 2004-05-18 North Carolina State University Reactive dye compounds
US6790943B1 (en) 1999-10-01 2004-09-14 North Carolina State University Reactive dye compounds
US6869453B1 (en) 1999-10-01 2005-03-22 North Carolina State University Reactive dye compounds
US9091021B2 (en) 2010-10-12 2015-07-28 Oasis Dyeing Systems, Llc Method of dyeing cellulosic substrates

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CN102980861B (zh) * 2012-11-28 2014-11-26 鲁丰织染有限公司 活性染料连续染色固色率测试方法
CN105158176A (zh) * 2015-09-27 2015-12-16 河北科技大学 一种k/s值涂布法测定活性染料固色率的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6713613B1 (en) 1999-05-19 2004-03-30 North Carolina State University Reactive dye compounds
US6716969B1 (en) 1999-05-19 2004-04-06 North Carolina State University Reactive dye compounds
US6723834B1 (en) 1999-10-01 2004-04-20 North Carolina State University Reactive dye compounds
US6736864B1 (en) 1999-10-01 2004-05-18 North Carolina State University Reactive dye compounds
US6790943B1 (en) 1999-10-01 2004-09-14 North Carolina State University Reactive dye compounds
US6869453B1 (en) 1999-10-01 2005-03-22 North Carolina State University Reactive dye compounds
US9091021B2 (en) 2010-10-12 2015-07-28 Oasis Dyeing Systems, Llc Method of dyeing cellulosic substrates

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BR9909363A (pt) 2000-12-19
AU6947498A (en) 1999-10-25
WO1999051683A1 (fr) 1999-10-14

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