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WO1995030717A1 - Teintures contenant des groupes nucleophiles et electrophiles - Google Patents

Teintures contenant des groupes nucleophiles et electrophiles Download PDF

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Publication number
WO1995030717A1
WO1995030717A1 PCT/GB1995/000887 GB9500887W WO9530717A1 WO 1995030717 A1 WO1995030717 A1 WO 1995030717A1 GB 9500887 W GB9500887 W GB 9500887W WO 9530717 A1 WO9530717 A1 WO 9530717A1
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WO
WIPO (PCT)
Prior art keywords
group
water
dye
protected
molecules
Prior art date
Application number
PCT/GB1995/000887
Other languages
English (en)
Inventor
Andrew Hunter Morris Renfrew
Michael Gordon Hutchings
Gary Neil Sheldrake
Colin Michael Brennan
Andrew Paul Shawcross
Original Assignee
Zeneca Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB9409137A external-priority patent/GB9409137D0/en
Priority claimed from GB9410484A external-priority patent/GB9410484D0/en
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to AU22622/95A priority Critical patent/AU2262295A/en
Publication of WO1995030717A1 publication Critical patent/WO1995030717A1/fr

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Classifications

    • 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
    • C09B62/503—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 the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • 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
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
    • 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
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0056—Dyeing with polymeric dyes involving building the polymeric dyes on the fibres

Definitions

  • This invention relates to dyes, their preparation and use in the coloration of substrates.
  • the dyes of the present invention contain certain nucleophilic and electrophilic groups which enable molecules of the dye to join together when an aqueous solution of the dye is heated and/or basified. In this way the dye's molecular weight increases, its water solubility can decrease, and its affinity for any textile materials present may be increased, leading to high levels of exhaustion of the dye from the dyebath, good fixation to textiles and good wash-fastness properties for textiles dyed therewith.
  • a water-soluble dye comprising molecules which contain a nucleophilic group and an electrophilic group characterised in that (i) the molecules are capable of joining together by formation of a covalent band between the nucleophilic group of one molecule and the
  • the nucleophilic group is or comprises an alkylthiol or a thiophenol.
  • nucleophilic group as used hereinafter means a nucleophilic group comprising an alkylthiol or thiophenol.
  • Fig. 1 is a flow chart showing schematically how dye molecules are joined together when heated or basified.
  • Fig. 2 is a flow chart showing how several dye molecules containing the nucleophilic group and a specific electrophilic group are joined together on basification through a combination of elimination and addition reactions.
  • Figure 1 illustrates the result of heating or basifying a water-soluble dye according to the invention.
  • the dye comprises n molecules (wherein n is >1) comprising a chromophore D, the nucleophilic group Nu and an electrophilic group EL and the molecules are joined together by formation of a covalent bond between the nucleophilic group of one molecule and the electrophilic group of another molecule vdien the dye is heated or basified.
  • An oligomerised or polymerised dye results in which the Nu' and EL' are residues of the nucleophiles and
  • Figure 2 illustrates the result of basifying or heating a water-soluble dye according to the invention containing the nucleophilic group and an electrophilic HO 3 SOCH 2 CH 2 O 2 S- group. Basificaticn or heating in the presence of base causes gradual elimination of sulphato groups to give electrophilic vinylsulph ⁇ nyl groups which form a covalent bond with the -S- groups of other molecules of the dye to give -S-CH 2 CH 2 -SO 2 -.
  • the sulphato groups in the molecules are the only or the major water-solubilising groups, elimination thereof causes a decrease in water-solubility and this assists the affinity and/or fixation of the dye to any substrates which are present.
  • the aforementioned molecules contain at least one of the nucleophilic groups and at least one electrophilic group and they join together by formation of covalent bonds between the nucleophilic group in each molecule and the electrophilic group of another molecule to give a product of higher molecular weight.
  • the water-soluble dye molecules contain a chromophore which absorbs radiation at a wavelength in the region from the ultraviolet to the infra-red, preferably in the visible region of the spectrum, especially light of a wavelength from 400 to 700nm.
  • the chromophore has an extinction coefficient of at least 5,000, more preferably at least 10,000, especially from 10,000 to 300,000, more especially from 10,000 to 150,000.
  • the chromophore preferably is as hereinafter described for D.
  • water-soluble dyes according to the invention are those which have a maximum absorption (i.e. ⁇ max) in the region 400-700nm occurring in the range 400-425nm, 425-450nm, 450-475nm, 475-500nm, 500-525nm, 550-575nm, 575-600nm, 600-625nm, 625-650nm, 650-675nm or 675-700nm.
  • the preferred extinction coefficient at the maximum absorption is as hereinbefore described.
  • nucleophilic and electrophilic groups in the molecules of water-soluble dye are on different ends of the molecule, thereby facilitating the molecules joining together in a 'head-to-tail' manner.
  • the electrophilic group must be capable of forming a covalent bond with the nucleophilic group when the dye is heated or basified and this will necessarily lead to one selecting appropriate pairs of nucleophilic and electrophilic groups which satisfy this requirement.
  • the words "are capable of joining" used when describing the present invention may therefore be replaced by "join”.
  • a skilled person may determine which pairs of nucleophilic and electrophilic groups are appropriate by heating or basifying a dye containing than and analysing the product, for example by ion spray mass spectrometry, HPLC or by gel permeation chromatography (GPC), to determine whether or not molecules of the dye have joined together to give a higher molecular weight product.
  • the nucleophilic group is preferably a thiophenol capable of forming a covalent bond with the electrophilic group of another molecule of the dye when heated or basified.
  • the alkylthiol is preferably an optionally substituted primary or secondary alkylthiol.
  • the optional substituents are preferably selected from alkyl and aryl.
  • a Preferred alkylthiol is of Formula (1) :
  • R 1 and R 2 are each independently H, optionally substituted alkyl or optionally substituted aryl, preferably H, C 1-4 -alkyl or optionally substituted phenyl, especially H or C 1-4 -alkyl.
  • R 2 is H the alkylthiol is a secondary alkylthiol, and when both R 1 or R 2 are H the alkylthiol is a primary alkyl thiol.
  • alkylthiol groups are -CH 2 SH, -CH(CH 3 )SH,
  • the thiophenol is preferably a phenylene group having an -SH substituent and optionally further substituents, for example amino, hydroxy, C 1-4 -alkyl, C 1-4 -alkoxy, sulpho, carboxy or -SH.
  • a preferred thiophenol is of the Formula (2)
  • each R 3 independently is H, -SH, amino, hydroxy, C 1-4 -alkyl, C 1-4 -alkoxy, sulpho or carboxy.
  • thiophenol groups examples include 2-, 3- and 4-thiophenol.
  • the electrophilic group may be any group capable of forming a covalent band with the nucleophilic group of another molecule of the dye when heated or basified.
  • said electrophilic group is a group capable of undergoing 1) a substitution reaction, 2) an addition reaction or 3) an elimination and addition reaction with the
  • Groups which are capable of undergoing a substitution reaction preferably comprise a carbon or sulphur atom having an electron withdrawing displaceable atom or group attached thereto, for example in the case of carbon a halo, sulpho, quaternary ammonium or a mesylate, tosylate or acetate group and in the case of sulphur an acyl group or -SO 3 - .
  • halides examples of groups which are capable of undergoing a substitution reaction there may be mentioned halides, anhydrides of acids and heterocyclic compounds which contain at least one or
  • Preferred groups capable of undergoing a substitution reaction include groups of the formula -OOCH 2 -X 1 , -COCHR 4 CH 2 -X 1 ,
  • X 1 is a labile group
  • R 4 is H or a labile group
  • R 5 is H or optionally substituted alkyl, aryl or heteroaryl
  • a labile group is a group displaceable by the aforementioned nucleophilic group when the dye is heated or basified.
  • X 1 is preferably halo, especially chloro, bromo or iodo.
  • R 4 is a labile group it is preferably halo, especially chloro.
  • R 5 is preferably H, phenyl or C 1-4 -alkyl, especially methyl or ethyl.
  • Groups which are capable of undergoing an addition reaction preferably comprise an epoxide group, an aziridine, aziridinium, azetidine or cyclopropane group or, more preferably, an activated alkene (e.g. alkenyl sudph ⁇ ne) or alkyne capable of undergoing a Michael-type addition with the aforementioned nucleophilic group.
  • an activated alkene e.g. alkenyl sudph ⁇ ne
  • alkyne capable of undergoing a Michael-type addition with the aforementioned nucleophilic group.
  • Z 1 is preferably -SO-, -SO 2 -, -CO-, especially -SO 2 -, and Z 2 is preferably -CN, -NO 2 , or an alkyl- or arylsulphonyl group or an acyl group.
  • Preferred alkylsulphonyl groups are -SO 2 -(C 1-4 -alkyl) and preferred arylsulphonyl groups are phenylsulphenyl and tosyl.
  • Preferred acyl groups are of the formula -CO-R 5 wherein R s is as hereinbefore defined, especially C 1-4 -alkyl or phenyl. It is preferred that R 7 and R 8 are both H.
  • activated alkenes include the following:
  • a preferred group capable of undergoing an elimination and addition reaction is or comprises a group of the formula
  • X 2 is a labile group and Z 1 is as hereinbefore defined, especially -SO 2 -, R 5 is as hereinbefore described, each R 11 independently is halo, -NH 2 , carboxy or a group described above for R 5 ; and m is 2, 3 or 4.
  • X 2 is a labile group and Z 1 is as hereinbefore defined, especially -SO 2 -, R 5 is as hereinbefore described, each R 11 independently is halo, -NH 2 , carboxy or a group described above for R 5 ; and m is 2, 3 or 4.
  • the labile group represented by X 2 is
  • the groups of formula -Z 1 (CR 11 R 11 ) m -X 2 may be attached to a group of formula -NR S - as defined above, in which case the CR 11 R 11 groups may be replaced by CHR 11 groups.
  • Examples of groups capable of undergoing an elimination and addition reaction include the following:
  • the dye molecules according to the present invention preferably contain 1 or 2 to 6, for example 1, 2 or 3 of the
  • nucleophilic groups and 1 or 2 to 6, for example 1, 2 or 3, of the electrophilic groups.
  • the number of nucleophilic groups may be the same as or different from the number of electrophilic groups, for example the number of nucleophilic groups may be greater than or less than the number of electrophilic groups.
  • the dye molecules of the present invention contain at least 2 of the nucleophilic groups and/or at least 2 of the electrophilic groups because this can lead to an improvement in the fixation and/or wash-fastness of the dyes to or on textile
  • the dyes can have a protecting group en the sulphur atom in the alkylthiol or thiophenol group to give what is called a protected alkylthiol or protected thiophenol.
  • the protecting group is acid or base labile or removable on treatment with a reducing agent.
  • the aforementioned sulphur atom in the alkylthiol or thiophenol group has a base labile protecting group; in this way the dye is particularly storage stable and dyeing of textiles under alkaline conditions causes removal of the protecting group and polymerisation of the dye in a single step.
  • Preferred acid labile protecting groups for the sulphur atom are p-meth ⁇ xybenzyl, 2-picolyl-N-oxide and triphenylmethyl.
  • Preferred base labile protecting groups for the sulphur atom are 2,4-dinitrophenyl, 2-nitro-1-phenylethyl, Ohe residue of
  • thiolesters for example groups of formula -CO(C 1-4 -alkyl), more preferably carbonamides, especially carbonamides of the formula -CONR ⁇ 2 wherein R 1 and R 2 are as hereinbefore defined.
  • Preferred protecting groups for the sulphur atom which are removable on treatment with a reducing agent include cyano and the residue of disulphide groups, for example groups of formula
  • dye molecules may protect one another through formation of disulphide links which act as their own protecting groups.
  • treatment with a reducing agent cleaves the disulphide bend to give two molecules of dye, each having a free -SH group.
  • the dyes of the present invention preferably have a water-solubility of at least 1%, more preferably at least 2%, especially at least 4%, more especially at least 8%.
  • Preferred dyes have a water-solubility of up to 10%, more preferably up to 50%, especially up to 100%. All percentages are by weight of dye relative to weight of water (at 20°C).
  • the joining together of the molecules by a covalent bond gives a product of lower water-solubility, more preferably less than 80%, especially less than 50%, more especially less than 25% and especially preferably less than 10% of the water-solubility of the original dye.
  • joining together of two or more of the water-soluble molecules results in a product having less than 5%, more preferably less than 1%, especially negligible solubility in water (at 20°C), wherein all percentages are by weight.
  • the aforementioned product is oligomeric or polymeric.
  • the joining together of the molecules to give a product having lower solubility than the original dye may be achieved by the presence of temporary solubilising groups in the dye, that is to say groups which enhance solubility of the dye in water which are
  • Preferred examples of such a temporary solubilising groups are ß-sulpihatoethylsulphonyl, ß-thiosulphatoethylsuilphonyl and
  • ß-phosphatoethylsulphonyl which may also act as electrophilic groups. Basificaticn and/or heating causes elimination of a solubilising group, for example an inorganic solubilising group such as a sulpho group (in the form of sulphate), bisulphate, thiosulphate or phosphate, to give a dye having fewer solubilising groups. In this way solubility of the dye may be reduced significantly thereby greatly enhancing the affinity and/or fixation of the dye for any substrate present.
  • a solubilising group for example an inorganic solubilising group such as a sulpho group (in the form of sulphate), bisulphate, thiosulphate or phosphate
  • the heating is from a first
  • the first temperature is preferably between 0°C and 40°C, more preferably between 5°C and 40°C, especially between 11°C and 29°C.
  • the dye may be heated by any means, for example by an electrical means such as a heating mantle, infra-red, microwave or ultrasound or by using steam.
  • the basifying is from a first pH to a second pH at least 0.6 pH units higher than the first pH, more preferably at least 1 pH unit higher, especially at least 2 pH units higher, more especially at least 3 pH units higher and optionally up to 6.9 pH units higher than the first pH.
  • the first pH is preferably between pH 0 and pH 8.5, more preferably between pH 2 and pH 8, especially between pH 4 and pH 8, more especially between pH 6 and pH 8 and especially preferably approximately pH 7.
  • the dye is preferably basified using an alkaline earth or alkali metal, base or salt, more preferably an alkali metal hydroxide, carbonate or bicarbonate, especially a sodium or potassium hydroxide, carbonate, bicarbonate or mixture thereof.
  • a water-soluble dye comprising molecules which contain a nucleophilic group and an electrophilic group wherein:
  • the nucleophilic group is -C(R 1 )(R 2 )-SH as described above;
  • the electrophilic group is an activated alkene or a group capable of undergoing an elimination and addition reaction;
  • the dye has at least two of the nucleophilic and/or electrophilic groups.
  • the preferred activated alkenes and groups capable of undergoing an elimination reaction are as mentioned above.
  • there are at least two of the nucleophilic or electrophilic groups there are preferably 2 to 6, more preferably 2 or 3 of these groups.
  • the molecules are capable of joining together by formation of a covalent bond between the nucleophilic group of one molecule and the electrophilic group of another molecule when the dye is heated or basified.
  • Preferred dyes according to the invention comprise molecules which are capable of being joined together in the absence of a free radical.
  • the water-soluble dyes according to the invention may contain conventional diluents found in dyes, for example salts remaining from when the dye was prepared or dedusting agents, and the dye may be mixed with other dyes.
  • the dye may also contain a colourless compound having the nucleophilic and electrophilic groups as hereinbefore defined, however this is not preferred.
  • the water-soluble dye may contain or be free from molecules of other dyes, for example dyes which have an electrophilic group but no nucleophilic group, dyes which have a nucleophilic group but no electrophilic group, and dyes which lack electrophilic and nucleophilic groups.
  • the aforementioned other dyes when present, constitute less than 40%, more preferably less than 20%, especially less than 10%, more especially less than 1.9% of the water-soluble dye (% by weight).
  • a preferred water-soluble dye according to the invention comprises molecules of the Formula (3):
  • each Nu independently is a group of Formula (1) or (2) as
  • D comprises a chromophore
  • q and r are each independently a positive integer greater than or equal to 1;
  • each EL independently is an electrophilic group as hereinbefore described.
  • the molecules of Formula (3) are generally capable of joining together by formation of a covalent bend between a group Nu in one molecule and a group EL of another molecule when the dye is heated or basified.
  • q and r are the same or different and are preferably each independently 1, 2, 3, 4 or 5, more preferably 1 or 2.
  • Examples include dyes vftierein q is 1 and r is 1; q is 1 and r is 2, q is 2 and r is 1; q is 2 and r is 2; q is 3 and r is 1; q is 3 and r is 2; q is 3 and r is 3,- q is 2 and r is 3,- and q is 1 and r is 3.
  • the electrophilic group represented by EL may be any of the aforementioned electrophilic groups provided it is capable of forming a covalent bend with the nucleophilic group of another molecule of the dye when it is heated or basified.
  • each EL independently is a group of formula -SO 2 CH 2 CH 2 OSO 3 H, -SO 2 CH 2 CH 2 SSO 3 H, -SO 2 CH 2 CH 2 OPO 3 H 2 ,
  • the chromophore represented by D is preferably of the azo, ant ⁇ iraquin ⁇ ne, phthalocyanine, triphenodioxazine, triphenylmethane, formazan, xanthene or benzodifuranone (BDF) series or a combination thereof, especially a chromophore of the azo series.
  • D is free from sulpho groups.
  • Preferred chromophores of the azo series are monoazo and disazo chromqphores.
  • each arylene radical independently is mono- or di-cyclic.
  • Preferred arylene radicals are optionally
  • heteroarylene radicals are optionally substituted pyrid ⁇ nylene, pyrazolonylene, benzthiazolene, isothiazolene, thiazolene and thiqphene.
  • the optional substituents which may be present an L 1 are preferably selected from C 1-4 -alkyl, especially methyl; cyano; C 1-4 -alk ⁇ xy, especially methoxy; hydroxy; thio; thi ⁇ ne; amino; halo, especially chloro; and amido, especially acetamido, benzamido or sulph ⁇ namido; ureido; halomethyl; carboxy,- carb ⁇ xymethyl; cyclohexyl; phenyl; and mono- and dialkylamino.
  • a preferred monoazo compound according to the invention is of the Formula (4) or a tautomer or salt thereof:
  • V is or comprises a group capable of undergoing an addition reaction or an elimination and addition reaction; n has a value of 0 or 1; and
  • each L 1 , L 2 , K and Nu independently is as hereinbefore defined.
  • a preferred disazo dye is of Formula (5):
  • each L 1 independently is as hereinbefore defined.
  • a preferred water-soluble dye of Formula (3) wherein D is a triphenodioxazine chromophore is of the Formula (6) :
  • each Y independently is a covalent bond, C ⁇ -alkylene
  • each U is H, SO 2 NR 5 R B , SO 3 R 5 , -SO 2 NHCH 2 CH 2 OSO 2 H or -SO 2 -CH 2 -CH 2 -X 2 ;
  • T 1 and T 2 are H, halo, C 1-4 -alkyl, or C 1-4 -alk ⁇ xy;
  • Nu is or comprises a nucleophilic group of formula (2) or (3) as hereinbefore defined;
  • B is H or is or comprises an electrophilic group; provided that when B is H one or both of the groups represented by U is -SO 2 -CH 2 -CH 2 -X 2 or -SO 2 NHCH 2 CH 2 -X 2 .
  • Each Y is preferably -C 2 H 4 - or -C 3 H 6 -.
  • T 1 and T 2 are preferably Cl or methyl.
  • B is preferably H or -SO 2 -CH 2 CH 2 -X 2 wherein X 2 is as
  • a preferred water-soluble dye of Formula (3) wherein D is a formazan chromophore is of the Formula (7) :
  • a preferred water-soluble dye of Formula (3) wherein D is a BDF chromophore is of the Formula (8) :
  • each Nu and El independently is as hereinbefore defined and each K independently is O, S or NR 5 ; provided that two or more molecules of
  • Formula (8) are capable of joining together by formation of a covalent bond between the nucleophilic group of one molecule and the
  • electrophilic group of another molecule when the dye is heated or basified.
  • Eyes according to the invention may be prepared by analogous methods to those described in the dyestuff art except that intermediates are selected which will result in the dye having the aforementioned nucleophilic and electrophilic groups, for example condensation of a compound having a nucleophilic group with a compound having an electrophilic group, therein one or both of the compounds contains a chromophore. It is preferred that the condensation is performed at 10-90°C, especially 20-90°C, more especially 40-90°C. Preferably the condensation is performed in a liquid medium, more preferably an aqueous medium or dimethylsulphoxide. Precise conditions used will depend upon the nucleophilic and electrophilic group and will be selected so as to prevent premature polymerisation of the desired dye.
  • the condensation is preferably performed in the presence of an acid-binding agent.
  • the function of the acid-binding agent is to neutralise any acid formed during the condensation. Accordingly any acid-binding agent may be used provided that it is not present in such a concentration that it causes hydrolysis of the reactants or causes some other side-reaction. It is preferred to use an alkali metal hydroxide, carbonate or bicarbonate, added at such a rate that the pH of the mixture stays within the range of 5.0 to 6.0.
  • dyes according to the invention containing an azo chromophore may be prepared by coupling two suitable precursors, for example coupling an azo component and a coupling component, one having an alkylthiol or thiophenol nucleophilic group and the other having an electrophilic group.
  • a coupling will normally be performed at below 5°C, in water using NaNO 2 and mineral acid to form the azo component from an amine.
  • formulae have generally been shown in their unionised or free acid form in this specification, the invention and formulae also include the dyes in the salt form, particularly their NH 4 + salts and their salts with alkali metals such as the sodium, potassium, lithium or mixed sodium/lithium salt.
  • groups shown as -SH include -S-.
  • a further feature of the present invention provides a composition comprising an inert carrier and a water-soluble dye according to the invention, preferably in a weight ratio of 99:1 to 1:99, more preferably 10:1 to 1:50, especially 5:2 to 1.1:10.
  • the inert carrier preferably comprises inorganic salts and optionally a de-dusting agent.
  • inorganic salts include alkali and alkali earth metal halides, carbonates, bicarb ⁇ nates, nitrates and mixtures thereof. Dodecylbenzene may be used as a de-dusting agent.
  • nucleophilic group is a protected thiophenol or a protected alkylthiol it is usually necessary to remove the protecting group before molecules of the dye are capable of joining together in the manner specified. This may be dene before, during or after the dye is applied to a substrate.
  • the water-soluble dye is completely dissolved in the aqueous solvent.
  • the nucleophilic group, electrophilic group and water-soluble dye are as described in the first aspect of the present invention. It is preferred that heating and/or basifying the dye causes molecules of the dye to join together by formation of a covalent band between the nucleophilic group of one molecule and the electrophilic group of another molecule of the dye. Preferably heating and/or basifying the dye forms a dye of lower water-solubility and higher affinity for the substrate.
  • the heating and basificaticn can be from first to second temperatures and pH's as described above in relation to the water-soluble dyes.
  • the mixture used in Step (a) preferably comprises 0.01 to 20 parts of dye per 100 parts of water, more preferably 0.15 to 9.9 parts of dye per 100 parts of water.
  • the water-solubility of the dye used in step (a) and the percentage of dye molecules which join together in step (b) are preferably as hereinbefore described in relation to dyes of the invention.
  • the mixture may also contain NaCl, for example 0 to 20 parts, more preferably 4 to 16 parts of NaCl per 100 parts of water. All parts are by weight.
  • the water-soluble dye used in step (a) is as described in the first or second aspect of the present invention.
  • the preferred substrate is a metal or plastic, more preferably a porous material, and especially good results are found for leather, paper and textile materials. Porous materials are preferred because the dye may permeate therein before being heated and/or basified to fix the dye.
  • the textile material is preferably a natural, semi-synthetic or synthetic material.
  • the water-soluble dyes of the invention may be in solid or liquid form.
  • the solid form is, advantageously, more storage stable because there is less opportunity for the nucleophilic and electrophilic groups to react with one another during storage.
  • the solid form is also cheaper to transport because it weighs less than a water-containing liquid form.
  • Examples of natural textile materials include wool, silk, hair and cellulosic materials, particularly cotton, jute, hemp, flax and linen.
  • semi-synthetic textiles include nitrocellulose, viscose rayon including TENCEL available from Courtaulds, England, cuprammonium raycn and cellulose acetates.
  • Examples of synthetic fibres include polyamides, polyesters, polyacryl ⁇ nitriles and polyurethanes.
  • the preferred coloration process according to the invention is a pad-batch, continuous, semi-continuous, or exhaust dyeing process or a printing process.
  • exhaust dyeing the dyes can demonstrate particularly efficient exhaustion from the dyebath.
  • Suitable printing methods include applying the dye to a substrate which has, where necessary, been pretreated, for example using an alkali.
  • the dye may be printed to the fibre and fixed by heating. Ink jet printing is one method of printing and this is of particular value where the substrate is a paper or cotton.
  • the mixture comprising an aqueous solution of the dye according to the invention is padded an a substrate at a temperature in the range 5°C to 40°C and the dye is heated to a second temperature 10°C to 75°C higher, preferably 20°C to 30°C higher than the first temperature, preferably for a period of at least 2 hours, e.g. 2.5 to 47.5 hours.
  • (a) is alkaline and the mixture is padded onto the substrate and remains in contact therewith for at least 1 hour, e.g. 2.5 to 47.5 hours.
  • Dyes of the invention may be used to prepare inks used in ink jet printing.
  • Preferred inks comprise a dye according to the invention and a liquid medium, for example an aqueous medium.
  • the ink preferably contains from 0.5% to 20%, more preferably 0.75% to 15%, especially from 1.1% to 4.9% by weight of the dye, based an the total weight of ink.
  • the liquid medium and aqueous solvent are preferably water or a mixture comprising water and a water-soluble organic solvent, preferably in the range 99:1 to 1:99, more preferably 95:1 to 50:50, especially 89:11 to 61:39.
  • the water-soluble organic solvent preferably comprises a C 1 - 4 -alkanol, especially methanol or ethanol; a ketone, especially acetone or methylisobutylket ⁇ ne; a glycol, especially diethylene glycol; 2-pyrrolid ⁇ ne; N-methylpyrrolidone; or a mixture thereof.
  • the mixture in step (a) comprises a solution of the dye in water and the mixture is applied to the substrate by immersing the substrate in a vessel containing said mixture. Heating, basifying or heating and basifying the solution in Step (b), preferably forms a dye of lower water-solubility and higher affinity for the substrate.
  • a substrate may be dyed with a mixture comprising water and a dye according to the invention at a substantially constant taiperature, for example at a temperature in the range 15 to 140°C, and the pH raised from a first to second pH as described above, preferably from a first pH in the range 4 to 8, more preferably 6.1 to 7.9, to a second pH 0.5 to 7 pH units higher, more preferably from 2 to 5 pH units higher than the first pH.
  • both the pH and taiperature may be raised during the third coloration process, preferably from the first to second temperatures and from the first to second pHs described in the preceding two paragraphs.
  • Conventional dye bath additives may be added to assist coloration of the substrate, for example salt or dyeing auxiliaries.
  • the mixture in Step (a) preferably contains a humectant and in Step (b) the dye is heated to a temperature in the range 90°C to 230°C, preferably 95°C to 220°C, preferably for a period of 0.25 minutes to 45 minutes, more preferably 0.6 minutes to 29 minutes.
  • the humectant is present in an amount of 0 to 25 parts, more preferably 2 to 20 parts per 100 parts of water, wherein all parts are by weight.
  • the mixture has a pH of 8.5 to 14, more preferably pH 9 to 11.
  • Another aspect of the fourth variation contains the extra step of drying the product of Step (a) before performing Step (b).
  • humectant there may be used polypropyleneglycol, dicyandiamide or preferably urea.
  • the water-solubility of the molecules joined together by Step (b) is less than 10%, more preferably less than 5%, especially less than 0.9%, of the water-solubility of the original dye (at 20°C, all percentages by weight relative to water) because this leads to improved wash-fastness for the dyed substrate.
  • This can be achieved by using dyes wherein any sulpho groups present in the molecules are removed by Step (b), e.g. all the sulpho groups are tarporary solubilising groups.
  • the molecules joined together by Step (b) are free from sulpho groups.
  • the process may be performed in the presence of a cellulosic substrate and, after dyeing, the cellulosic matter is digested by a cellulase enzyme to free the polymerised dye whose solubility may be measured in the normal manner.
  • the extent to which dye molecules join together may be measured by HPLC or GPC.
  • a further feature of this invention comprises a polymer or oligomer (and a process for their preparation) obtained or obtainable by heating or basifying or heating and basifying a water-soluble dye according to the present invention.
  • the aforanenti ⁇ ned oligomer and polymer preferably are free from sulpho groups preferably have negligible solubility in water at 20°C, and preferably have a molecular weight of 2 to 1000 times, more preferably 6 to 99 times the molecular weight of the original dye molecules before heating or basificaticn.
  • the heating and/or basifying is from first to second temperatures and pHs as described hereabove.
  • a still further feature of the invention is a substrate, especially a textile material, coloured using a water-soluble dye or by a coloration process according to the invention.
  • 2,2'-Dithiosalicylic acid (15.0g, 0.049 mole) and N,N-dimethyl formamide (0.5g, 0.007 mole) were dissolved in dry toluene (150ml) and the solution was heated to 50°C.
  • Thionyl chloride 11.lg, 0.093 mole was added dropwise over 30 minutes and then the mixture was heated at 80°C for 3 hours, 111°C for 30 minutes and then cooled to room taiperature.
  • 4-( ⁇ -sulphatoethylsulph ⁇ nyl) aniline (2.81g, 0.01 mole) was stirred in a mixture of water (50ml), ice (50g) and hydrochloric acid (35%; 5ml). To this mixture was added 2N sodium nitrite solution (5ml, 0.01 mole) at 0-5°C over 5 minutes and the mixture was stirred for a further 2 hours. Excess nitrous acid was then destroyed by addition of 10% sulphamic acid solution.
  • stage (a) (2.73g, 0.0046 mole) was dissolved in a mixture of 2N hydrochloric acid (20ml), acetone (25ml), acetic acid (5ml), ice (25g) and water (50ml) .
  • the product solution from stage (b) was added with stirring at 0-5°C and the pH was raised to 4.3 using sodium acetate to complete the coupling.
  • Sodium chloride (l0g) was added to precipitate the dye.
  • the title product is illustrative of dyes having a protecting group on the sulphur atom which is ranovable on treatment with a reducing agent.
  • the protecting group is another molecule of the same dye attached through a disulphide link.
  • Example 1 The product of Example 1 (0.15g, 1.27 ⁇ 10 -4 mole), sodium chloride (2.5g) and dithioerythritol (0.04g, 2.6 ⁇ 10 -4 mole, a reducing agent) were dissolved in water (50ml) in a 1 litre flask. A single piece of unmercerised cotton (5.0g) was added and the mixture was agitated by rotation at 30°C for 1 hour, thereby yielding the title product in situ as free thiol. Sodium carbonate (1.0g) was added and the taiperature ramped to 90°C over 1 hour. The dye molecules joined together and passed from the aqueous phase onto the cotton leaving the dyebath essentially colourless.
  • Example 1 The product of Example 1, stage (a), (11.88g, 0.02 moles) was dissolved in 1,4-di ⁇ xane (80ml) and water (20ml) .
  • Triphenylphosphine (6.24g, 0.024 mole) and concentrated hydrochloric acid (4 drops) were added and the mixture was stirred under a nitrogen atmosphere at 20°C.
  • Thin Layer Chromatography (silica gel plates, ethyl acetate eluant) confirmed that complete reduction of the
  • 4-( ⁇ -sulphatoethylsulphonyl) aniline (3.93g, 0.014 mole) was stirred in a mixture of water (50ml), ice (50g) and hydrochloric acid (35%; 5ml).
  • Sodium nitrite solution (2M; 7.5ml, 0.015 mole) was added and the mixture was stirred at 0-5°C for 2 hours. Excess nitrous acid was then destroyed by the addition of 10% sulphamic acid solution.
  • stage (a) (4.43g, 0.012 mole) was added to a mixture of hydrochloric acid (2M; 20ml), ice/water (100ml) and acetic acid (5ml).
  • the product solution from stage (b) was added and the pH of the mixture was raised to 4 using solid sodium acetate.
  • the coupling reaction was completed by stirring the mixture for 16 hours. NaCl (20g) was added to precipitate the dye.
  • the title product is illustrative of dyes having a
  • Example 3 The title product of Example 3 (0.15g, 2.3 ⁇ 10 -4 mole) and sodium chloride (2.5g) were dissolved in water (50ml) in a one litre flask. A single piece of unmercerised cotton (5g) was added and the mixture was agitated by rotation for 30 minutes at 30°C. Sodium carbonate (1g) was then added and the temperature was raised to 90°C over 1 hour. The basic conditions caused rapid hydrolysis of the thiocarbamate group, releasing the free thiol, and causing
  • Example 1 The method of Example 1 may be repeated except that in place of the compound specified in the first column of Table 1 there is used the compound specified in the second column.
  • Example 3 The method of Example 3 may be repeated except that in place of the compound specified in the first column of Table 2 there is used the compound specified in the second column.
  • N-2-chlorcethyl-N-ethylaniline (25.93g) and potassium thiocyanate (68.5g) were dissolved in dimethylformamide (400ml) and stirred at 100°C for 20 hours. The solvent was removed under reduced pressure and water was added to the residue. The solution was extracted three times using ether and the combined ethereal solutions were washed with water and then dried over MgSO 4 . After filtration the solution was evaporated to dryness to give an oil. Flash
  • stage (a) (2.06g) was dissolved in a mixture of water (100ml) and acetone (50ml) and cooled to 0-5°C.
  • the product solution from stage (b) was added and the pH of the mixture was raised to 5.5 by addition of sodium carbonate solution (2M).
  • the mixture was stirred for 2 hours at 0-5°C and then allowed to rise to room taiperature. NaCl solution (10% w/v) was added and the
  • the title product is illustrative of dyes having a protecting group on the alkylthiol sulphur atom which is ranovable on treatment with a reducing agent.
  • the title dye (0.2g) was dissolved in water (50ml). A piece of ⁇ nmercerised cotton (5g) was added and the mixture was agitated by rotation for 15 minutes at 50°C. Sodium chloride (2.5g) was added and the mixture was stirred for a further 30 minutes at 50°C. Sodium borohydride (0.02g) and sodium carbonate (1.0g) were then added and the mixture was agitated at 50°C for 30 minutes. The dye liquors were left essentially colourless.
  • stage (d) The dyeing method of stage (d) was repeated except that sodium borohydride was omitted. In contrast to the dyeing method of stage (d) the dye liquors remained highly coloured.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Abstract

Une teinture hydrosoluble, qui comprend des molécules qui contiennent un groupe nucléophile et un groupe électrophile, se caractérise en ce que 1) ces molécules peuvent s'associer par formation d'une liaison covalente entre le groupe nucléophile d'une molécule et le groupe électrophile d'une autre molécule quand cette teinture est chauffée ou rendue basique. Elle se caractérise aussi en ce que 2) le groupe nucléophile est un thiophénol, protégé ou non, ou un alkylthiol protégé.
PCT/GB1995/000887 1994-05-09 1995-04-20 Teintures contenant des groupes nucleophiles et electrophiles WO1995030717A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU22622/95A AU2262295A (en) 1994-05-09 1995-04-20 Dyes containing nucleophilic and electrophilic groups

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9409137A GB9409137D0 (en) 1994-05-09 1994-05-09 Chemical compounds
GB9409137.8 1994-05-09
GB9410484A GB9410484D0 (en) 1994-05-25 1994-05-25 Chemical compounds
GB9410484.1 1994-05-25

Publications (1)

Publication Number Publication Date
WO1995030717A1 true WO1995030717A1 (fr) 1995-11-16

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Country Status (2)

Country Link
AU (1) AU2262295A (fr)
WO (1) WO1995030717A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0548795A2 (fr) * 1991-12-20 1993-06-30 Hoechst Aktiengesellschaft Colorants réactif solubles, procédé de préparation et leur utilisation
WO1994012717A1 (fr) * 1992-11-27 1994-06-09 Zeneca Limited Colorants, leur preparation et leur utilisation dans la coloration de substrats

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0548795A2 (fr) * 1991-12-20 1993-06-30 Hoechst Aktiengesellschaft Colorants réactif solubles, procédé de préparation et leur utilisation
WO1994012717A1 (fr) * 1992-11-27 1994-06-09 Zeneca Limited Colorants, leur preparation et leur utilisation dans la coloration de substrats

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