GB2623090A - Method of colouring - Google Patents

Abstract

A composition comprising a polymerisable diallylamine monomer and one or more functionalised dyes, wherein the polymerisable monomer is a compound of Formula (A): wherein each Q1, Q2 and Q3 represent an optionally substituted hydrocarbyl group, Q4 is an amine moiety, a tertiary ammonium cation, a quaternary ammonium cation or an optionally substituted hydrocarbyl group, q is an integer from 1-4; and wherein the functionalised dye comprises a chromophore and one or more functional groups capable of forming at least one covalent chemical bond with the polymerisable monomer. Also disclosed is a method of forming the composition and a method of colouring a substrate, in particular printing on a textile using the composition.

Description

METHOD OF COLOURING

The present invention relates to a method of colouring substrates, in particular a method of printing textiles and other substrates. There is also provided a composition including one or more functionalised dyes and a polymerisable diallylamine monomer.

BACKGROUND TO THE INVENTION

There are a variety of techniques available for the printing of textiles and other substrates. Digital printing methods use inkjets to print an image onto a substrate and offer a number of advantages over traditional techniques, such as screen printing. The image is programmed digitally giving a multitude of options for design which can be easily changed and altered resulting in cheaper and faster development, along with reduced sampling costs. The inkjets will typically fire drops of <30 picolitres, with the printer design providing high accuracy of print, resulting in high resolution prints. Other advantages over traditional printing techniques include reduced energy and water consumption, reduced waste, unlimited repeat size (not limited by the size of the screen) and reduced stock requirements. 20% of industrial water pollution comes from textile dyeing. Digital printing can significantly reduce this with some methods not creating any water pollution at all.

There are a variety of digital printing methods currently used in industry, all of which employ a different dye and fixation chemistry. There are four main classes of dye used for the digital printing of textiles, which are used to make reactive inks, disperse inks, pigment inks and acid inks. In addition to the dyes, chemical pre-treatments are often required in order to achieve satisfactory colour and fastness properties. The chemistry of each class of dye and its associated pre-and post-processing steps limits the number of types of textile or substrate that each dye class can be applied to.

Digital reactive inks are used for printing onto cellulosic substrates. Printing with reactive inks requires textile pre-treatments as well as a fixing process after application. The dyes employed create chemical bonds to cellulosic components in fibres meaning they are only applicable to textiles such as linen, rayon, nylon, cotton and other cellulosic fibres. Reactive printing requires steaming at 90-120°C for 8 minutes for dye fixation as well as washing and drying cycles, producing waste water from both processes.

Digital disperse inks printing is typically completed using a dye-sublimation technique and can be applied to textiles such as; polyester, acetate, rayon, poly-lycra and acrylics. Dye-sublimation printing involves printing a disperse ink onto a transfer sheet. The transfer sheet is then laminated to a textile surface with heat and pressure, where the dye from the parchment is sublimated into the textile fibre.

Digital pigment inks utilise pigments suspended in an aqueous ink formulation containing binders. This method can be used to print virtually all textiles, with varying levels of success, through the selection and use of the correct pre-treatments and binders. After pre-treatment and printing, the substrate is typically heated to 160-190°C to cure and fix the pigment print. As pigments are solid particles, they have a tendency to settle to the bottom of a fluid. The pigments used tend to be ground to a fine powder in order to reduce the settling properties, but the inks still require re-circulation within the printhead to maintain a homogeneous ink. Larger pigment particles get caught in the inkjet nozzle causing blockages. Inkjets require a low viscosity ink in order to achieve good flow characteristics through the nozzle, which prevents the use of high viscosity thickeners to help aid the pigment suspension. As pigment ink printing is a surface colouring technique, the colour does not penetrate into the fibres. Because of this, the print is vulnerable to more rapid wash-out, resulting in patterns losing their intensity after many washes. They also perform relatively poorly to rubbing, especially when wet. Increasing the binder content and cross-linking density of the binder can offer improvements to both the wash and rub fastness of pigment printing, but results in a stiff handle which is unsuitable for a number of industries.

Digital acid printing requires textile pre-treatments and further steaming processes after printing for fixation. The textiles must also be washed afterwards to remove any residue, creating extra water effluent. This method is only applicable to textiles such as silk, wool and nylon. Acid printing requires steaming at 20-120°C for 20-60 minutes for dye fixation as well as washing and drying cycles, producing waste water from both processes.

The present invention seeks to provide a new type of chemistry that can be used to make aqueous polymeric inks, and will be suitable to colour substrates, for example through printing, without the limitations described above with the current state of the art. This is completed by chemically incorporating dye molecules into a polymer chain. The polymer chain acts to both solubilize the dye in water, to give an aqueous polymer-ink, and to fix the dye to a textile or other substrate. The aqueous polymer-ink will be suitable for use in digital printing techniques, either on its own or with other components formulated into a digital printing ink, and will be suitable to be printed directly onto textiles and other substrates providing colour fast results, without the need for a chemical pre-treatment. The process used will have a curing stage at <160°C. This method will be applicable to all textile types.

ADVANTAGES

There are many advantages to the current invention over the traditional dye chemistries employed in digital printing. The first and most significant advantage is that this technique can be used to print all types of textile. This makes the manufacturing process simpler and easier to manage with factories only requiring one type of digital printing to process any textile. The lack of any pre-or post-treatments makes the process simpler and easier to complete, while reducing the amount of equipment required and the resulting factory floor space used. This gives advantages in terms of cost savings on equipment as well as the ability to process more textiles or other substrates per unit area. The elimination of pre-and post-treatments also gives significant savings in terms of auxiliary chemical usage, water usage and the amount of effluent created.

Other advantages include the aqueous polymer ink being homogenous with no settling properties at low viscosities. This means that no re-circulation will be required in the print-head. The lack of solid particles in the formulation will also help to ensure that the print heads remain unblocked. Other material savings are made by eliminating the use of transfer paper.

SUMMARY OF THE INVENTION

According to a first aspect of the present invention, there is provided a composition including a polymerisable monomer and one or more functionalised dyes; wherein the polymerisable monomer is a compound of Formula (A): Q4 Formula (A) wherein each of (2t2, Q2 and (20 independently represents an optionally substituted hydrocarbyl group, Q4 represents an amine moiety, a tertiary ammonium cation, a quaternary ammonium cation or an optionally substituted hydrocarbyl group, q is an integer from lto 4; and wherein the functionalised dye comprises at least one chromophore and one or more functional groups capable of forming at least one covalent chemical bond with the polymerisable monomer of Formula (A), preferably under the conditions used to polymerise the polymerizable monomer; suitable examples of functional groups include hydroxy, thiol, amine, alkene, alkyne, or silanol and where present, the alkene functional group is optionally part of an acrylate, acrylamide, or maleimide and the alkyne is optionally part of a propargylic acid ester or propargylic acid amide.

Generally, the composition is in the form of an aqueous solution. Typically, the composition is in the form of an ink or dye composition suitable for use in digital printing methods.

According to a further aspect of the present invention, there is provided a method of forming the composition disclosed herein comprising the following steps: forming a mixture including the polymerisable monomer and the funtionalised dye, initiating partial polymerisation of the polymerisable monomer and concomitant co-polymerisation of, or reaction with, the functionalised dye, which is achieved generally through the use of free-radical generators and optionally one or more cross-linking agents, for example one or more acrylic co-agents, adding an acid to the mixture, wherein the acid reacts with the product of partial polymerisation to form a water-soluble cationic polymer.

The polymerisation reaction may be terminated through cooling of the mixture.

The polymerisation reaction may be terminated through agitation of the mixture with cooling to facilitate chain termination of any remaining radicals.

According to one embodiment, water may be added to the mixture to form an aqueous solution of a partially polymerised dye-polymer composition. The composition is suitably in the form of an ink.

According to a further aspect of the present invention, there is provided a method of printing a substrate, in particular a textile including: providing the composition including the functionalised dye and polymerisable monomer, described herein, partially polymerising the composition to form a partially polymerized composition, applying the partially polymerized composition to a surface of the substrate, and fixing the partially polymerised composition to the substrate, typically by initiating further polymerization of the partially polymerized composition, or by evaporating some liquid from the partially polymerised composition.

The partially polymerised composition may be reacted with an acid to form a cationic co-polymer. According to a further aspect of the present invention, the method of printing takes the form of a digital printing method.

According to a further aspect of the present invention, there is provided a kit of parts for use in the treatment of textile fibres, in particular to promote the fixation of dyes thereon. Said kit of parts includes any of the compounds or compositions described herein and an applicator device such as a digital printer with inkjet head.

Throughout the Application, where a composition is described as having, including, or comprising specific components, or where a method is described as having, including, or comprising specific process steps, it is contemplated that the composition of the present teachings also consists essentially of, or consists of, the recited components, and that the method of the present teachings also consists essentially of, or consists of, the recited process steps.

Definitions General definitions: In the Application, where an element or component is said to be included in and/or selected from a list of recited elements or components, or where a method is said to include certain steps, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components. Further, it should be understood that elements and/or features of a composition, an apparatus, or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present teachings, whether explicit or implicit herein.

It should be understood that the expression "at least one of" includes individually each of the recited objects after the expression and the various combinations of two or more of the recited objects unless otherwise understood from the context and use.

The use of the singular herein, for example, "a," "an," and "the," includes the plural (and vice versa) unless specifically stated otherwise.

The use of the terms "include," "includes", "including,", "comprise", "comprises" "comprising", "have," "has," or "having" should be generally understood as open-ended and non-limiting unless specifically stated otherwise.

The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise.

In addition, where the use of the term "about" is before a quantitative value, the present teachings also include the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term "about" refers to a ±10% variation from the nominal value unless otherwise indicated or inferred.

It should be understood that the order of steps or order for performing certain actions is immaterial so long as the present teachings remain operable. Moreover, two or more steps or actions may be conducted simultaneously.

Features, integers, characteristics, or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.

At various places in the present specification, values are disclosed in groups or in ranges. It is specifically intended that the description include each and every individual sub combination of the members of such groups and ranges and any combination of the various endpoints of such groups or ranges. For example, an integer in the range of 0 to 40 is specifically intended to individually disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40, and an integer in the range of 1 to 20 is specifically intended to individually disclose 1, 2, 3,4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

The use of any and all examples, or exemplary language herein, for example, "such as," "including," or "for example," is intended merely to illustrate better the present teachings and does not pose a limitation on the scope of the invention unless claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the present teachings.

Hydrocarbyl: The term "hydrocarbyl" as used herein includes reference to moieties consisting exclusively of hydrogen and carbon atoms, Le. groups of the chemical formula CyHy. The moiety may comprise, for instance, 1 to 20 carbon atoms and 2 to 42 hydrogen atoms. Such a moiety may be aliphatic, aromatic of a combination of aliphatic and aromatic; may be straight or branched chain; may be cyclic, acyclic or a combination of cyclic and acyclic; may be saturated, unsaturated or a combination of saturated and unsaturated.

Alkyl: The term "alkyl" refers to an alkyl moiety, straight or branched chain, acyclic or cyclic or a combination of cyclic and acyclic, having for instance 1 to 20 carbon atoms. In particular, the term "alkyl" specifically incorporates reference to "C1-8 alkyl", with the aforementioned description, having 1 to 8 carbon atoms. The term "small alkyl group" refers to an alkyl group having a carbon backbone of 1 to 6 carbon atoms, typically 1 to 4 carbon atoms. For example, the term "alkyl" includes reference to groups, such as methyl, ethyl, propyl (n-propyl or isopropyl), cyclopropyl, butyl (n-butyl, iso-butyl, sec-butyl or tertbutyl) and the like.

Cycloalkyl: The term "cycloalkyl" refers to an aliphatic cyclic hydrocarbon moiety, including bridged, fused, or spiro cyclic compounds, preferably made up of 3 to about 12 carbon atoms, more preferably 3 to about 8. For example, the term "cycloalkyl" includes reference to groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, bicyclo[3.2.1]octyl and the like.

Haloalkyl: The term "haloalkyl" relates to an alkyl moiety having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, substituted with one or more halogen atoms, for example CH2F, CH2CI, CHF2, CHCl2, CF3, CCI3, C2H4F, C2H4CI, C2H3F2, C2H3C12, C2H2F3, C2H2C13, C2HF4, C2HCI4, C2F5, C2C15, CF2=CF2, and the like.

Alkenyl: As used herein, "alkenyl" refers to a branched or unbranched aliphatic hydrocarbon group having 2 to 20 carbon atoms, containing at least one double bond which can be terminal (i.e. ends in =CH2) or internal (i.e. does not end in =CH2) within the hydrocarbon group, and where internal, can be of either E or Z stereochemistry. The term "C2-8 alkenyl" as used herein can be used interchangeably with "alkenyl" and includes reference to a straight or branched chain alkyl moiety having 2 to 8 carbon atoms and having, in addition, at least one double bond which is terminal or internal of either E or Z stereochemistry. This term includes reference to groups such as ethenyl, n-propenyl, isopropenyl, ally!, dimethylallyl, 2-butenyl, 3-butenyl, isobutenyl, 7-octenyl, 9-decenyl, 13-tetradecenyl, and the like.

Alkynyl: As used herein, "alkynyl" refers to a branched or unbranched aliphatic hydrocarbon group having 2 to 20 carbon atoms, containing at least one triple bond which can be terminal (i.e. ends in =CH) or internal (i.e. does not end in =CH) within the hydrocarbon group. The term "C2-8 alkynyl" as used herein can be used interchangeably with "alkynyl" and includes reference to a straight or branched chain alkyl moiety having 1 to 8 carbon atoms and having, in addition, at least one terminal or internal triple bond. This term includes reference to groups such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 1-hexynyl, 2-hexynyl and 3-hexynyl and the like.

Alkoxy: The term "alkoxy' refers to an -0-R group, wherein R is a branched or unbranched C1-C20 alkyl or substituted alkyl group, preferably C1-C8, with substituents being aryl, alkoxy, aryloxy, alkenyl, alkynyl, carboxy, hydroxy, amino, thiol, etc. This term includes reference to groups such as, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, benzyloxy, phenethyloxy, allyloxy, 3,3-dimethylallyloxy, propargyloxy, 2-butenyloxy, 3-butenyloxy, 5-hexenyloxy, 7-octenyloxy, carboxymethyloxy, carboxyethyloxy, -OCH2CO2CH3, -OCH2CO2CH2CH3 and the like.

Aryl: The term "aryl" means one or more aromatic rings, each of 5 or 6 core carbon atoms, for example, phenyl. As used herein, "Aryl" also includes multiple aryl rings that may be fused, as in naphthyl, anthracenyl etc., or unfused, as in biphenyl, terphenyl etc. Aryl rings may also be fused or unfused with one or more cyclic hydrocarbon, heteroaryl, or heterocyclic rings. As used herein, "aryl' includes heteroaryl. "Substituted aryl" is aryl having one or more non-interfering groups as a substituent. For substitutions on a phenyl ring, the substituents may be in any orientation (i.e., ortho, meta, or para).

Alkylaryl: The term "alkylaryl" means a group attached via an alkyl group which bears an aryl group along the alkyl chain. Both the alkyl group and the aryl group can, themselves, be further substituted Example include benzyl, phenethyl, and the like.

Arylalkyl: The term "arylalkyl" means a group attached via an aryl group which bears an alkyl group. Both the aryl group and the alkyl group can, themselves, be further substituted. Example include phenylmethyl, phenylbutyl, and the like.

Heteroatom: The term "Heteroatom" refers to any atom other than hydrogen or carbon in a hydrocarbon analog compound. Examples include oxygen, sulfur, nitrogen, phosphorus, silicon, arsenic, selenium, tellurium, tin, boron, copper, nickel, palladium, platinum, ruthenium, rhodium, magnesium, vanadium & vanadium oxide, iron, cadmium, titanium & titanium oxide, manganese, chromium, cobalt, zinc, mercury, zirconium and molybdenum & molybdenum oxide. The term "Heteroatom" especially refers to oxygen, nitrogen and sulfur.

Metal: The term "Metal" refers to any Group 1 alkali metal, Group 2 alkaline earth metal, Group 13 metalloid or element, Group 14 metalloid or element, Group 15 metalloid or element, Group 16 metalloid, a transition metal, a lanthanoid or actinoid. The term "Metal" especially refers to lithium, sodium, potassium, caesium, magnesium, titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc, boron, aluminium and silicon.

Heterocycle: The term "Heterocycle" or "heterocyclic" means one or more rings of 5-12 atoms, preferably 5-7 atoms, with or without unsaturation or aromatic character and having at least one ring atom which is not a carbon. Preferred heteroatoms include sulfur, oxygen, and nitrogen. "Substituted heterocycle" is a heterocycle having one or more side chains formed from non-interfering substituents.

Heteroaryl: The term "Heteroaryl" is an aryl group containing from one to four heteroatoms, preferably N, 0, or S. or a combination thereof. Heteroaryl rings may also be fused with one or more cyclic hydrocarbon, heterocyclic, aryl, or heteroaryl rings. "Substituted heteroaryl' is heteroaryl having one or more non-interfering groups as Substituents.

Acrylic: The term "acrylic" as used herein generally refers to a compound which is of, or derived from acrylic acid, methacrylic acid, crotonic acid or cinnamic acid and to further substituted derivatives of those aforementioned acids.

Acrvlate: The term "acrylate" as used herein generally refers to an ester derived from formal condensation of a hydroxy group and acrylic acid or with an acrylic acid derivative, such as methacrylic acid, crotonic acid, isocrotonic acid, cis and trans-2,3-dimethylacrylic acid, 3,3-dimethylacrylic acid, 2,3-dimethylcrotonic acid, cis and trans-cinnamic acid, and further substituted cis and trans-cinnamic acids. The term "acrylate" especially refers to an ester of acrylic and methacrylic acid.

Acrvlamide: The term "acrylamide" as used herein generally refers to an amide derived from formal condensation of an amine and acrylic acid or with an acrylic acid derivative, such as methacrylic acid, crotonic acid, isocrotonic acid, cis and trans-2,3-dimethylacrylic acid, 3,3-dimethylacrylic acid, 2,3-dimethylcrotonic acid, cis and trans-cinnamic acid, and further substituted cis and trans-cinnamic acids including. The term "acrylamide" especially refers to an amide derived from acrylic and methacrylic acid.

Propargylic acid derivative: The term "propargylic acid derivatives" as used herein generally refers to compounds derived from propargylic acid. "Propargylic acid derivatives" especially include propargylic acid esters and propargylic acid amides.

Maleimides: The term "maleimide" as used herein generally refers to cyclic-imide compounds formally derived by condensation of a primary amine (R-NH2) with maleic acid or its derivatives such as 2,3-dimethylmaleic acid.

Silyl:The term "sily1" as used herein generally refers to a group containing a silicon atom.

Thiol: The term "thiol" as used herein generally refers to a moiety of structure -SH, which may also be referred to as "sulfhydryl".

Halogen: The term "halogen" as used herein includes reference to any Group 17 element. In particular, halogen is F, Cl or Br.

Substituted: The term "substituted" as used herein is in reference to a moiety and means that one or more, especially up to 5, more especially 1, 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of substituents.

The term "optionally substituted" as used herein means substituted or unsubstituted.

Additionally, it will of course be understood that the substituents described herein may themselves be substituted by any substituent, subject to the aforementioned restriction to appropriate substitutions as recognised by a person skilled in the art.

It will, of course, also be understood that substituents are only those that are chemically possible and located at positions where they are chemically possible, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular substitution is possible. For example, amino or hydroxy groups with free hydrogen may be unstable if bound to carbon atoms with unsaturated (e.g. alkenyl or alkynyl) bonds.

Typical substituents may be cyclic or acyclic, saturated or unsaturated, and include alkyl, aryl, alkylaryl, arylalkyl, alkenyl, halogen, haloalkyl, hydroxy (-OH), alkoxy (-OR), acyloxy (-0C(0)R), carbonate (-OC(0)0R), oxy-carbamoyl (-0C(0)NRR'), oxy-sulfonate ester (-0S02R), carboxylic acid (-CO2H), Carboxylate salt (CO2-X+), ester (-CO2R), amide (-CONRR'), aldehyde (-CHO), keto (-C(0)R), amino (-NRR'), amino-acyl (-NRC(0)R'), amino-carbamoyl (-NRC(0)OR'), sulfonamide (-NRS02121), sulfone (-SO2R), sulfonic acid (-503H), sulfonate salt (-SO3-X+), cyano (-CN), nitro (-NO2), thiol (-SH), thioether (-SR).

R R' R" etc: As used herein, R denotes any substituent, which is completely undefined, and used merely for clarity in general schemes and examples. Generally R represents an optionally substituted hydrocarbyl group. Where more than one R group is required, they are differentiated with apostrophes, e.g. R, R', R" etc, showing they are independent of one another. A typical example is -NRR', denoting an amine, which could be NH2, equally NHCH3, equally N(CH3)Ph, and the like. Numbered R groups, e.g. 111, 112 etc, are used herein as specifically defined substituents as described in the claims.

Non-interfering substituents: The term "Non-interfering substituents" are groups that, when present in a molecule, are typically non-reactive with other functional groups within the molecule.

Independently: Where two or more moieties are described as being "each independently" selected from a list of atoms or groups, this means that the moieties may be the same or different. The identity of each moiety is therefore independent of the identities of the one or more other moieties.

Chromophore: The term "chromophore" is an atom or chemical group whose presence in a chemical substance is responsible for the absorbance of light. Typical chromophores given here as non-limiting examples only include, an azo bond (-N=N-), a carbonyl group (C=0), a methine group (-CH=), a nitro group (NO2) and the phthalocyanine core (Pc).

Auxochrome: An auxochrome is a group of atoms that themselves do not produce colour, but are attached to a chromophore, typically via extended conjugation, which modifies the ability of that chromophore to absorb light, which intensifies the colour e.g. commonly causing a longer wavelength absorbance with increased extinction, than the chromophore alone. Typical auxochromes given here as non-limiting examples only include electron donating groups with lone pairs of electrons, like amino (-NRR') and hydroxy derivatives (-OR).

Dye: The term "dye" as used herein comprises of a chemical substance containing one or more chromophores. As well as the chromophore, the dye may bear one or more auxochromes. The chromophore and auxochrome, where present, are typically linked via extended conjugation, e.g. via aromatic and unsaturated groups. In addition, to the chromophore, auxochromes and extended conjugation, a dye typically contains other peripheral chemical groups that are non-participating in the absorbance of light, but that are useful to facilitate its synthesis and to aid in the application it is designed for, e.g. to make it sufficiently soluble.

Furthermore, the term "dye" as used herein, is a compound that absorbs light at specific wavelengths dependent on its overall chemical structure. These absorption wavelengths range from 200nm (ultra-violet) to 1400nm (near infra-red), preferably they absorb in the UV-A-visible-NIR light regions from 315-1000 nm. The wavelengths that are transmitted or reflected are the inverse of those absorbed. Additionally, some dyes may also absorb light at one wavelength and emit light at a different wavelength, which are known as fluorescent dyes.

Furthermore, a "dye" as used herein, may contain a single chromophore, with a single light absorbance/transmission spectrum. Such dyes can be used alone or mixed together in varying proportions to obtain an overall additive colour effect. Examples include, mixing yellow and cyan coloured single dyes to obtain a green colour, mixing yellow and magenta coloured single dyes to obtain an orange or red colour, mixing magenta and cyan single coloured single dyes to obtain a blue or violet colour, or mixing yellow, magenta and cyan single coloured dyes to obtain a brown or black colour. Similarly, shades can be tuned for example by adding small quantities of separate single chromophore dyes to modify the apparent colour, e.g. 95% of a yellow coloured dye and 5% of a cyan coloured dye to obtain a greener yellow shade.

Furthermore, a "dye" as used herein may also contain more than one covalently linked, but chemically independent, chromophores, in which case, the dye will, overall, have an absorbance/transmission spectrum approaching the sum of each independent chromophore.

Furthermore, in some cases, a "dye" as used herein, may contain chromophores that are not independent but are instead linked through extended conjugation, often giving broadened absorbance spectra. For example, bis-and tris-azo compounds can be used to obtain broad absorbance dyes, with observed colours such as black and grey, amber, violet, brown, olive, green, etc. Furthermore, Dyes are commonly grouped into classes, known to those skilled in the art, based on the nature of their chromophore, and are described in many standard dye related text books, for example, R. M. Christie (2015), Colour Chemistry, 2nd Edition. As such, a "dye" within this application belongs to one or more of the following classes: azo (mono, bis, tris, poly), metalated-azo, quinone, naphthoquinone, anthraquinone, indophenol, quinone-imine, naphthoquinone-imine, indigoid, thioindigoid, benzodifuranone, coumarin, naphthalimide, rylene, perylene, perinone, diketopyrrolopyrrole, acridone, quinacridone, isoindoline, metalated and non-metallated phthalocyanine, metalated and non-metallated naphthalocyanine, nitro, methine, polymethine, polyene, stilbene, cyanine, azacyanine, hemicyanine, diazahemicyanine, merocyanine, quinophthalone, squarylium, croconium, pyrroline, triarylmethane, azine, xanthene, thioxanthene, acridine, oxazine, spirooxazine, oxazone, thiazine, phenazine,safranine, rhodamine, fluorescein, dioxazine, triphendioxazine, pyrromethene, porphyrin, benzotriazole, 2-hydroxybenzophenone, 2-hydroxyacetophenone, 2-hydroxyphenyl-s-triazine, pyrazoline, a,13-di-[aryloxazoly11-ethylene, a43-dijarylimidazoly11-ethylene, a.43-di-Larylthiazoly11-ethylene, a-aryloxazolyl-p-aryl-ethylene, a-arylimidazolyl-paryl-ethylene, a-arylthiazolyl-p-aryl-ethylene, 2,5-di-Laryloxazoly1]-furan, 2,5-di-[aryloxazolyl]-thiophene, 2,5-di-Larylimidazoly11-furan, 2,5-di-[arylimidazolyI]-thiophene, 2,5-di-[arylthiazolyI]-furan, 2,5-di- [arylthiazolyll-thiophene, pyrene, metal dithiolene complexes, benzothiadiazole, benzooxadiazole, benzanthrone, anthanthrone, anthrapyrimidines, anthrypyridones, anthrypyrimidones, azabenzanthrones, benzanthrones, anthranthrones, anthrimides, anthrimidecarbazoles, isothiazole-anthrones, pyrazoleanthrones, pyrimidanthrones, sulfur, vat, UV-absorber, UVA-absorber, UVB-absorber, UVC-absorber, NIRabsorber.

The terms "dye" and "chromophore" may be used interchangeably within this invention disclosure.

Pc and related shorthands: Herein, as well as in many other literature sources, for example, as illustrated in R K. Venkataraman (1972), The Chemistry of Synthetic Dyes, Vol. VI, pp 312 -323, the shorthand "Pc" is used as a notation for the phthalocyanine core. When a metal is written before Pc, this denotes the metal complexed at the phthalocyanine centre, for example, CuPc being copper phthalocyanine, NiPc being nickel phthalocyanine and so on; whilst H2Pc implies two hydrogens, i.e. no metal, at the Pc centre. Substituted phthalocyanines may be written herein using shorthand, for example: CuPc _K (Rks (Shorthand A) (Shorthand B) in which, Shorthand A denotes four identical substituents of structure Ron one copper phthalocyanine molecule, whilst Shorthand B denotes a statistical mixture of copper phthalocyanine molecules, substituted, on average, with 4 substituents each (i.e. 2.5 + 1.5), with an average bell-curve distribution of 2.5 substituents of structure R and 1.5 substituents of structure Ron each Pc molecule. Substituents are in different aromatic rings, but in any position, i.e. being a regioisomeric mixture.

Composition According to a first aspect of the present invention, there is provided a composition including a polymerisable monomer and one or more functionalised dyes; wherein the polymerisable monomer is a compound of Formula (A): Q4 Q1 Formula (A) wherein each of al, Wand Ct2 independently represents an optionally substituted hydrocarbyl group, Q4 represents an amine moiety, a tertiary ammonium cation, a quaternary ammonium cation or an optionally substituted hydrocarbyl group, q is an integer from 1 to 4; and wherein the functionalised dye comprises at least one chromophore and one or more functional groups capable of forming at least one covalent chemical bond with a polymerisable monomer of Formula CuPc (R)4 (A), preferably under the conditions used to polymerise the polymerizable monomer; suitable example functional groups include hydroxy, thiol, amine, alkene, alkyne, alkoxysilane or silanol; where present, the alkene is optionally part of an acrylate, acrylamide, or maleimide and the alkyne is optionally part of a propargylic acid ester or propargylic acid amide.

Generally, the functionalised dye comprises at least one chromophore and one or more functional groups capable of forming at least one covalent chemical bond with a polymerisable monomer of Formula (A) under the conditions used to polymerise the polymerizable monomer. However, in some circumstances an extra species may be added to the composition to facilitate indirect bonding between the functional groups and the polymerizable monomer. For example, where the functionalised dye includes a hydroxyl functional group, extra species may be added to indirectly bond the hydroxyl group to the polymerizable monomer of Formula (A), for example extra species such as a silanol group.

Where the functional group is a silanol group, this may be formed through hydrolysis of an alkoxysilane group.

The composition may include 1 to 30 w/w% of one or more functionalised dyes; generally, 2 to 10 w/w%, typically 3 to 7 w/w%, suitably around 5 w/w% of one or more functionalised dyes.

According to one embodiment, the composition includes 20 to 60 w/w% one or more polymerisable monomer, generally 30 to 50 w/w%, typically 40 to 45 w/w% one or more polymerisable monomer.

Generally, the composition incorporates an aqueous solvent rather than an organic solvent. Typically, the amount of organic solvent in the composition is less than 1 w/w%, preferably the composition does not contain any organic solvent.

Optionally the composition is acidic. According to one embodiment, the composition includes acid at a molar excess relative to the polymerisable monomer.

The composition generally includes an aqueous solvent, typically at an amount of at least 50 vol.%. the polymerisation process is generally terminated through the addition of polymerisation inhibitors, allowing the composition to be stored including partially polymerised monomer and, co-polymerised functionalised dye, prior to application to the substrate to be dyed.

According to a further aspect of the present invention, the composition includes one or more initiator compounds. One of ordinary skill in the art would be aware of suitable initiator compounds.

According to one embodiment, the composition may include any free-radical generator. Mention may be made of azo-compounds, peroxides and persulphates.

The initiator may be oil-soluble or water-soluble and should be selected having regard to the properties of the specific composition and the solvent used.

Suitably initiator compounds are used with a relatively high half-life at low temperatures. Typically, the initiator compounds have an associated half-life of less than one hour, at temperatures of around 90°C, generally of less than 45 minutes, suitably less than around 30 minutes.

Mention may be made of one or more free radical generators such as 2,2'-Azodi(2-methylbutyronitrile) (Vazo 67).

The initiator compounds are generally used at less than 5% w/w, typically less than 3% w/w, suitably less than 1% w/w.

The composition may include one or more cross-linking agents, which take part in a co-polymerisation reaction. In particular the composition may include one or more acrylic cross-linking agents suitable to aid co-polymerisation, such as trimethylolpropane trimethacrylate (TMPTMA). Generally, the composition includes 1 to 5 w/w% acrylic cross-linking agent, typically around 1.5 to 3 w/w%.

The composition may include an acid, such as glycolic acid. According to one embodiment, the composition includes 2 to 20 w/w% acid such as glycolic acid, in particulars to 10 w/w% glycolic acid.

According to one embodiment, the composition includes 1 to 30% w/w (typically 1 to 10 w/w%) of one or more functionalised dyes, 20 to 50 w/w% (typically 30 to 45 w/w%) of one or more polymerisable monomers, less than 2% w/w (generally less than 1%w/w) of one or more initiator compounds, 5 to 10 w/w% of acid, in particular glycolic acid, and optionally less than 5 wt.% cross-linking agent, in particular around 1 to 3 w/w% acrylic cross-linking agent.

The composition of the present invention is intended to be combined by those skilled in the art with other components to produce a fully formulated digital printing ink in a range of colours.

Q4 generally represents an amine, a tertiary ammonium cation or a quaternary ammonium cation, preferably a protonated tertiary amine.

Following acidification, the compound of Formula (A) is generally converted to a compound of Formula (B): Q5 -Qs_NI C17 Formula (B) (B) Wherein one of Ce to CC represents hydrogen, and the other 0,5 to 0! independently represents hydrogen, or an optionally substituted hydrocarbyl group; generally, an aliphatic hydrocarbyl group (e.g.C1_6 alkyl, alkenyl, alkynyl), in particular an optionally substituted alkyl group, typically C1_6 alkyl.

Q3 represents an optionally substituted hydrocarbyl group, generally a C16 alkyl group such as a methylene, ethyl or propyl group, suitably a methylene or ethyl group.

Each of Oland C).3 independently represents an optionally substituted hydrocarbyl group, generally C1_6 alkyl, typically a CH2, ethyl or propyl group, preferably a CH, group.

q is an integer from 1 to 4 (generally 1 or 2), wherein where q is 2, one of Q.5 to C/7 is absent, where q is 3, two of Ce to Q.7 are absent, where q is 4, all of Q5 to C/7 are absent.

X-is a counterion, generally an anion selected from the group consisting of halide (in particular chloride or fluoride), sulfate, sulfonate (such as 2-acrylamido-2-methylpropane sulfonate (AMPS)), sulfamate, phosphonate (in particular a vinyl phosphonate), lactate, acetate, glycolate, citrate, itaconate. acrylate and methacrylate. Typically, the counter-ions are anions selected from the group consisting of sulfate, sulfonate, sulfamate, phosphonate, lactate, acetate, glycolate, citrate, acrylate, methacrylate and itaconate. Particular mention may be made of counter-ions including one or more of a phosphonate group and a basic nitrogen group.

According to one embodiment, with regard to Formula (A) or Formula (B); Q1 and Q2 generally, independently, represent a small hydrocarbyl group, generally a C2 to CB hydrocarbyl group, typically a C2 to C3 hydrocarbyl group, preferably Q1 and Q2 both represent CH2.

Q3 generally represents a small alkyl group, generally a C1 to CB alkyl group, suitably a C1 to C3 group, preferably Q3 represents a methylene group Q4 generally represents an amine, a tertiary ammonium cation or a quaternary ammonium cation, preferably a protonated tertiary amine.

According to one embodiment, with regard to Formula (A) or Formula (B): Q1 and Q2 both represent CH2, Q3 represents a methylene group, and Q.4 represents a protonated tertiary amine.

According to one embodiment the counter-ions (X-) include one or more groups polymerisable under the conditions used to polymerise the compounds of Formula (A) or Formula (B). Those such counter-ion may have the structure of the group consisting of 2-acrylamido-2-methylpropanesulfonate (AMPS); vinylphosphonate; hydrogen vinylphosphonate; lactate; glycolate; citrate; acrylate, methacrylate or itaconate.

Compounds of Formula (B) typically have a water solubility of 40% w/w or more, typically 50% w/w or more at ambient temperature and pressure.

According to one embodiment, the polymerisable monomer has the structure shown in Formula (C): r 0 0 NjC2'k)N, Formula (C) According to one embodiment, functionalised dyes present in the composition are of the Formula (1): IDYEHLI-EGnin, Formula (1) wherein DYE is a dye as described herein; L is a linking group between DYE and functional group(s) G, where L is comprised of at least one hydrocarbyl group, but may equally be comprised of several hydrocarbyl groups each linked to one-another via a bridging moiety, where each bridging moiety, individually, may comprise heteroatoms, including oxygen, sulfur, nitrogen and silicon, or functional groups including ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester; L may be terminated with a heteroatom, including oxygen, sulfur, nitrogen and silicon, which then forms the bond to G; L can be attached to DYE at any position where it is chemically possible to do so, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular attachment position is possible; G is any functional group that is capable of forming a bond with a polymerisable monomer of Formula (A) under suitable reaction conditions, that is generally the conditions used to polymerise the polymerizable monomer; G, as well as the reactive entity, may also bear other non-chemically-participating groups; G is preferably selected from hydroxyl (-OH), amine (-NHR1), thiol (-SH), trialkoxysilane (-Si(0R2)3), dialkoxysilanol (-Si(0R2)2)(OH)), alkoxysilanediol (Si(0R2)(OH)2), silanetriol (Si(OH)3), alkene including internal or terminal alkene, acrylate, acrylamide, alkylvinylsulfone, arylvinylsulfone, vinyl ester, allyl ester, allyl amide, diallyl amide, allyl sulfonamide, diallyl sulfonamide, maleimide, alkynyl including an internal or terminal alkyne, propargylic acid ester and propargylic acid amide; 1:11 is hydrogen or hydrocarbyl, preferably hydrogen or C1-C8 branched or straight-chain alkyl; R2 is hydrogen or hydrocarbyl, preferably hydrogen or Cl-C8 branched or straight-chain alkyl, and especially hydrogen or C1-C4 branched or straight-chain alkyl; m is an integer from 1 to 10; in other words, there must be at least one, or can be up to 10 functional groups G, i.e. G G2to G1°, attached to DYE directly or via one or more linking chains L, where, G1, G2... Gm are independent of one another in terms of their chemical structure; n is an integer from 0 to 10; in other words, there can be up to 10 linking groups L attached to DYE, each bearing at least one functional group G; where n > 1, each linking chain, L1, L2... Ln is independent of another linking chain in terms of its chemical structure; where n = 0, it is implied that functional groups G are bound directly to DYE without a linking group.

Especially preferred linking group L and functional group G combinations are selected from the following Formulae (Ia)-(Ip), where the dashed line denotes the position of attachment of L or G to DYE either directly or via a DYE-linked oxygen or nitrogen heteroatom, may itself be part of a larger functional group on DYE, denoted as a substituent in the claims; __A2---J1 1 DYEEAlla(0---(CH2)0)-A2_ ji leo)

-

DYE, 1 --...----A4 J11 (l bx) Formula (Ia) DYE-[Al]aol)[ R3 -- 0 0-ji c(ii) Formula [Rc(i) I (Ih) 1100 I --\ c(ii) Pi 0) \ 0-J2 DYE-IAllap)-- 1 { \J3 Pilo) Formula (Ic) Formula (Id) [R11.0) DYE-Al -[(--"...."0,3H b(w) ER14) c(II) Formula (le) Formula (If) IR1100) -(CH2)b(v) ER121c(iii) c(iv) 0 DYE-[A1]Bo)--Formula (Ig) I DYE-N mt(CH2)b(vi) 0 0 Formula (Ih) DYE-EA1141)---[-(Chl2)boiai1 Formula (Ii) IR2lcal) DYE-[Al bar -(CH2)b(v) [R1]c(i) Formula (ii) DYE-[Al]ag-[Rl]c(i) Formula (II) DYE-[Aliao-[1:111.(0 Formula (1k) 1 (CF12)0)-A2-J' cOv) -(cl12)bp, A3 A2-(01.12)b(viii)-N I 0 0

DYE-VOLK- _ -

[R16) Elrlcao Formula (Im) A3-ECH2(CH(0J3))b(A)0H20J2 1 c(iv) DYE-VOW° [R1]c0) Formula (In) DYE [A1 JaOF [Wilc(I) Formula (Ip) (CH2)to DYE -Al+ W -SKOR2)3 coo coo [R, kw Formula (Io) [74]c(iii) fi-Ew-sic0R2,3 ic(iv) (OHobm wherein is an oxygen or nitrogen heteroatom on DYE to which the functional groups G or linking group L is attached, as specified in the claims; note that the heteroatom may itself be part of a larger functional group, e.g. -502N*--, -C(0)0-**, -C(0)N* *-, etc; A2 and A' are, independently, selected from an oxygen heteroatom or NI11-; A3 is selected from an oxygen or nitrogen heteroatom; 11 is selected from hydrogen, -C(0)CH=CH2 (acryloyl), -C(0)C(CH3)=CH2 (methacryloyl), or -C(0)NH(CH2)35i(OCH 2C H3)3; 12 to 14 are, independently, selected from hydrogen, -C(0)CH=CH2 (acryloyl), or -C(0)C(CH3)=CH2 (methacryloyl); 113 is hydrogen or -CH3; Ft4 is hydrogen, Cl to C8 branched or straight chain alkyl or phenyl, preferably hydrogen or -CH3; W is C2 to C4 branched or straight chain alkyl, preferably -(CH2)3-; a(i) is 0 or 1, indicating that A' is absent or present respectively; a(ii) is 0 or 1, indicating that Al is absent or present respectively, preferably 1; b(i) is an integer from 1 to 18, preferably 1 to 12, especially 1 to 4, with the proviso that when a(i) = 1, then b(i) > 1; b(ii) is an integer from 0 to 5, preferably 0 to 3, more preferably 0 or 1, especially 0; b(iii) is an integer from 0 to 6, with the provisos that when a(ii)= 1, then b(iii) > 0, and when a(ii)= then b(iii) is preferably 0 or 1; b(iv) is an integer from 1 to 4, preferably 1; b(v) is an integer from 0 to 4, with the proviso that when a(i) = 1, then b(v) > 0, preferably 1 or 2, especially 2, and that when a(i) = 0, then b(v) is preferably 0; b(vi) is an integer from 0 to 6, with the provisos that, when A3 is oxygen, then b(vi) is preferably 0 to 2, especially 0 or 1, and when A3 is NRI then b(vi) >0, preferably 1 to 2, especially 1; b(vii) is an integer from 1 to 4; b(viii) is an integer from 2 to 6; b(ix) is an integer from 0 to 3, preferably b(ix) + b(vi) = 1 to 4; c(i) is 0 or 1, indicating that 111 is absent or present respectively, with the proviso that when Al = oxygen, or a(i) or a(ii) = 0, then c(i) = 0; c(ii) is 1 or 2, with the provisos that when Al = oxygen, then c(ii) = 1, and when Al = nitrogen then c(i) + c(ii) = 2; c(iii) is 0 or 1, indicating that R2 or R4 is absent or present respectively, with the proviso that when A2 = oxygen, then c(iii) = 0; and c(iv) is 1 or 2, with the provisos that when A3= oxygen, then c(iv) = 1, and when A3 = nitrogen then c(iii) + c(iv) = 2; In functional dyes of Formula (Ia), Formula (Ib), Formula (Ic), Formula (Id), Formula (Ti), Formula (Im) and Formula (In), where any of the functional groups GI to G6 is acryloyl or methacryloyl, these may be conveniently installed under standard ester or amide formation reaction conditions. Such ester or amide formation reactions are commonplace in organic synthesis and are well known to those suitably skilled in the art. For example, such ester or amide formation can typically be achieved by reaction of a hydroxy group, or primary or secondary amino group, which in the context of this application are connected to, or tethered by some linking moiety, to DYE, with acryloyl chloride equally with acrylic anhydride, or with methacryloyl chloride equally with methacrylic anhydride respectively, generally in the presence of an acid binder, optionally in the presence of a catalyst, such as pyridine or 4-(dimethylamino)pyridine, in a suitable solvent, or carried out in pyridine as a solvent and acting as catalyst and acid binder simultaneously. Suitable reaction conditions are exemplified in, as one example, WO 2012/019704.

In functional dyes of Formula (la), Formula (lb), Formula (1c) and Formula (Ti), where G2 is -C(0)NH(CH2)35i(OCH2CH3)3, this may be conveniently installed, for example, by reaction of a hydroxy group, or primary or secondary amino group, which in the context of this application are connected to, or tethered by some linking moiety, to DYE, with 3-(triethoxysilyl)propyl isocyanate, which is commercially available, for example from Sigma-Aldrich. Suitable reaction conditions are exemplified in, as examples, US 2009/0143598 for reaction with aliphatic alcohols and aliphatic amines, and WO 2011/045389 for reaction with aryl-alcohols and aryl-amines.

Functional dyes of Formula (fg), where A3 is 0 and b(vi) = 0, bear a vinyl ester. Vinyl esters can typically be prepared from a carboxylic acid group, which in the context of this application is tethered to DYE, by reaction with vinyl acetate in the presence of a catalyst, such as a palladium complex. Suitable reaction conditions are exemplified in, as one example, US 2013/0184423. Functional dyes of Formula (ig), where A3 is 0 and b(vi) = 1, bear an ally! ester. One typical method for the synthesis of allyl esters, well known to those skilled in the art, is from a carboxylic acid group, which in the context of this application are connected to, or tethered by some linking moiety, to DYE, by reaction with allyl bromide in the presence of an acid scavenger, such as a carbonate salt. Suitable reaction conditions are exemplified in, as one example, ACS Catalysis 2018, 8, 3016. Similarly, functional dyes of Formula (1g), where A3 is 0 and b(vi) = 2 to 6, can be prepared in an analogous fashion, exchanging allyl bromide for the requisite alkenyl bromide, i.e. using 4-bromobut-1-ene for b(vi)= 2 (exemplified in WO 2009/025388), using 5-bromopent-1-ene for b(vi) = 3 (exemplified in Angew. Chem., Int. Ed. 2020, 59, 21064), using 6-bromohex-1-ene for b(vi) = 4 (exemplified in WO 2003/041643), using 7-bromohept-1-ene for b(vi) = 5 (exemplified in J. Med. Chem. 2020, 63, 6225) and using 8-bromooct1-ene for b(vi)= 6 (exemplified in Org. Biomol. Chem. 2018, 16, 5771). Functional dyes of Formula (Tg), where A3 is N bear alkenyl-amides. These alkenyl-amides can typically be prepared by reaction of a carboxylic acid group, which in the context of this application are connected to, or tethered by some linking moiety, to DYE, with an alkenyl-amine in one of two common and general methods, well known to those skilled in the art. One method requires conversion of the carboxylic acid group to its acid chloride by treatment with a chlorinating agent, such as thionyl chloride or oxalyl chloride, which is then reacted with the alkenyl -amine in the presence of an acid binder. Suitable reaction conditions are exemplified with allylamine in, as one example, WO 2007/084450. In the second method, the carboxylic acid group and alkenyl-amine can be coupled using a carbodiimide coupling agent such as DCC or EDC. Suitable reaction conditions are exemplified with diallylamine in, as one example, US 6,511,612. These amide formation methods for dyes of Formula (1g), where A3 is N are also applicable to prepare esters of Formula (1g), where A3 is 0 and b(vi)= 2 to 6, in addition to the methods already described above.

Functional dyes of Formula (1h), Formula (1i) and Formula (1j) bear a maleimide group. Maleimides of the type found in Formula (1h) and Formula (1i) are typically prepared from the respective primary amino group (R-NH2) by reaction with a maleic anhydride compound. Suitable general reaction conditions are exemplified in Polymer Chemistry 2015, 6, 5555 for maleic anhydride and WO 2020/182636 for 2,3-dimethylmaleic anhydride as two examples respectively. Functional dyes of Formula (1h), therefore, are prepared from precursor compounds of the formula DYE-NH2, which may be commercially available for example Disperse Orange 3, Disperse Black 3 and Coumarin 120 being non-limiting commercial examples, or can be synthesised, for example, Synthetic Metals (2015), 206, 84-91 being illustrative to those skilled in the art, without limitation, of one method to how DYE-NH2 compounds may be prepared. Functional dyes of Formula (Ti), therefore, are prepared from precursor compounds of the formula DYE-[AlacoUR11,0))-[(C1-12)bor NH21,00, which can be prepared in numerous ways, with the following 3 literature methods, J. Am. Chem. Soc. 2013, 135, 17683, J. Am. Chem. Soc. 2004, 126, 4088 and Tetrahedron 2008, 64, 3168, being illustrative to those skilled in the art, without limitation, to 3 such methods and strategies. Functional dyes of Formula (IA bear maleimide groups tethered to DYE via an amide or ester functional group. Such materials can be prepared in several ways, one such way, being illustrative to those skilled in the art, without limitation, is from coupling of N-substituted maleimides bearing pendent amino or hydroxy groups, with a carboxylic acid group present on the functional dye precursor of the formula DYE-[AllawaR1Icd-[(0-12)bm-0O2H60. These ester/amide coupling reactions can be performed, for example, under conditions as exemplified above for Functional dyes of Formula (1g) where A3 is N or A3 is 0 and b(vi) = 2 to 6. Some N-substituted-maleimides bearing pendent amino or hydroxy groups are commercially available, for example N-(2-aminoethyl)maleimide hydrochloride (CAS 134272-64-3) and N-(2-hydroxyethyl)maleimide (CAS 1585-90-6), which can be purchased from, for example, Tokyo Chemical Industry UK Ltd. Alternatively, N-substituted maleimides can be synthesised by literature described means, the following literature references providing general and illustrative examples, without limitation, Tet. Lett. 2005, 46, 1181, which describes the synthesis of N-(6-hydroxyhexyl)maleimide and Bioconjugate Chemistry 2019, 30, 253 which describes the synthesis of N-(6-aminoxyhexyl)maleimide, both reactions being adaptable to other homologues by those skilled in the art.

Functional dyes of Formula (Ik), Formula (II), Formula (Im) and Formula (In) comprise ester and amide linkages to connect aminated or hydroxylated chains to DYE, the aminated or hydroxylated chains serving as a convenient scaffold to incorporate groups Gl to G6via ester, amide, urea or carbamate linkages. As with examples above, incorporation of the aminated or hydroxylated chains via ester/amide coupling reactions can be performed, for example, under similar conditions to those exemplified above for Functional dyes of Formula (1g) where A3 is N or A3 is 0 and b(vi)= 2 to 6, those methods being easily adaptable by those skilled in the art, by selecting the correct aminated or hydroxylated chain raw material. For means of exemplification only, convenient applicable aminated or hydroxylated raw materials include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethyleneglycol, tripropyleneglycol, tetraethyleneglycol, aminoethanol, Isopropanolamine, diglycolamine, triglycolamine, propanolamine, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, glycerol, 1,2,3,4-tetrahydroxybutane, 1,2,3,4,5-pentahydroxypentane, 1,2,3,4,5,6-hexahydroxyhexane, pentaerythritol, pentaerythritol monoacrylate, pentaerythritol monomethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 3-amino-1,2-propanediol, 4-amino-1,2,3-butanetriol, 2-amino-2-(hydroxymethyl)propane-1,3-diol and the like.

Functional dyes of Formula (Tp) comprise ester and amide linkages connecting a chain bearing a trihydroxysilane or trialkoxysilane to DYE. As with examples above, construction of the ester or amide linkage can be performed, for example, under similar conditions to those exemplified above for Functional dyes of Formula (Ig) where A3 is N or A' is 0 and b(vi) = 2 to 6, those methods being easily adaptable by those skilled in the art, by selecting the correct amino or hydroxy raw material. For means of exemplification only, convenient applicable amino or hydroxy raw materials include, but are not limited to, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, N[2-(trimethoxysily0ethyllbenzenamine, N-[2-(triethoxysilyflethyl]benzenamine, N-methy1-2-(triethoxysily0ethanamine, (3- aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, N-[3-(trimethoxysilyppropyllbenzenamine, N-[3-(triethoxysilyl)propyl]benzenamine, N-[3-(trimethoxysilyl)propyOrnethanamine, N13- (trimethoxysily0propyl]-1-butanamine, N[3-(triethoxysily0propyl)methanamine, N-[3- (triethoxysilyl)propy1]-1-butanamine, NL3-(trimethoxysily0propyl]cyclohexanamine, N13- (Trimethoxysily0propyl]-2-propen-1-amine, N-ethyl-2-methyl-3-trimethoxysilylpropan-1-amine, N-(1,1-dimethylethyl)-3-(trimethoxysily1)-1-propanamine, 143-(triethoxysilyppropyllpiperazine, and the like.

Some existing dyes, of various dye classes, that are listed in the Colour Index dye register (httpslicolour-index.com) are of the Formula (I) and are suitable examples of dyes for use in this application, without further structural modification, including Disperse Black 4, Disperse Black 9, Disperse Blue 7, Disperse Blue 12, Disperse Blue 23, Disperse Blue 28, Disperse Blue 30, Disperse Blue 34, Disperse Blue 41, Disperse Blue 61, Disperse Blue 70, Disperse Blue 82, Disperse Blue 85, Disperse Blue 92, Disperse Blue 93, Disperse Blue 94, Disperse Blue 96, Disperse Blue 102, Disperse Blue 106, Disperse Blue 116, Disperse Blue 119, Disperse Blue 121, Disperse Blue 127, Disperse Blue 128, Disperse Blue 144, Disperse Blue 146, Disperse Blue 149, Disperse Blue 171, Disperse Blue 177, Disperse Blue 186, Disperse Blue 187, Disperse Blue 202, Disperse Blue 205, Disperse Blue 207, Disperse Blue 319, Disperse Blue 330, Disperse Blue 351, Disperse Blue 364, Disperse Brown 1, Disperse Brown 3, Disperse Brown 4, Disperse Brown 4:1, Disperse Brown 14, Disperse Orange 5, Disperse Orange 10, Disperse Orange 17, Disperse Orange 18, Disperse Orange 19, Disperse Orange 34, Disperse Red 8, Disperse Orange 48, Disperse Orange 74, Disperse Orange 138, Disperse Red 1, Disperse Red 2, Disperse Red 3, Disperse Red 5, Disperse Red 6, Disperse Red 7, Disperse Red 12, Disperse Red 13, Disperse Red 16, Disperse Red 17, Disperse Red 19, Disperse Red 24, Disperse Red 29, Disperse Red 30, Disperse Red 32, Disperse Red 43, Disperse Red 55, Disperse Red 55:1, Disperse Red 56, Disperse Red 58, Disperse Red 64, Disperse Red 70, Disperse Red 91, Disperse Red 98, Disperse Red 103, Disperse Red 105, Disperse Red 107, Disperse Red 108, Disperse Red 109, Disperse Red 118, Disperse Red 126, Disperse Red 128, Disperse Red 129, Disperse Red 137, Disperse Red 156, Disperse Red 172, Disperse Red 178, Disperse Red 276, Disperse Red 279, Disperse Red 318, Disperse Red 320, Disperse Red 324, Disperse Red 328, Disperse Red 349, Disperse Red 350, Disperse Red 357, Disperse Violet 5, Disperse Violet 12, Disperse Violet 13, Disperse Violet 24, Disperse Violet 36, Disperse Violet 43, Disperse Violet 69, Disperse Violet 95, Disperse Yellow 132, Reactive Blue 246, Reactive Blue 247, Solvent Blue 69, Solvent Orange 72, Solvent Red 117, Solvent Red 153 and Solvent Yellow 58.

Some existing dyes, of various dye classes, that are listed in the Colour Index dye register (https://colour-index.com) bear pendent masked hydroxy groups, present as esters, which can be transformed to a hydroxy group through an ester cleavage reaction, thus becoming dyes of general Formula (1), where G = OH; which may find application directly in this invention, or can in turn be further derivatised to, for example, acryloyl or methacryloyl esters as described above. Such ester to hydroxy transformations are commonplace in organic synthesis, being described and exemplified thoroughly in many textbooks, one of which being J. March (1992), Advanced Organic Chemistry, 4th Edition, Wiley, New York, Chapter 10, page 378 -383. Examples of such ester that may be converted to hydroxy dyes of general Formula (1), where G = OH, include Solvent Green 6, Disperse Blue 79, Disperse Blue 79:1, Disperse Blue 124, Disperse Blue 130, Disperse Blue 133, Disperse Blue 142, Disperse Blue 155, Disperse Blue 173, Disperse Blue 174, Disperse Blue 214, Disperse Blue 283, Disperse Blue 284, Disperse Blue 287, Disperse Blue 294, Disperse Blue 295, Disperse Blue 369, Disperse Brown 9, Disperse Brown 10, Disperse Brown 15, Disperse Brown 16, Disperse Brown 25, Disperse Orange 30, Disperse Orange 31, Disperse Orange 43, Disperse Orange 51, Disperse Orange 62, Disperse Orange 71, Disperse Orange 73, Disperse Orange 78, Disperse Orange 79, Disperse Orange 88, Disperse Orange 89, Disperse Orange 94, Disperse Orange 101, Disperse Orange 103, Disperse Orange 119, Disperse Orange 126, Disperse Red 54, Disperse Red 54:1, Disperse Red 72, Disperse Red 74, Disperse Red 76, Disperse Red 79, Disperse Red 80, Disperse Red 82, Disperse Red 97, Disperse Red 110, Disperse Red 111, Disperse Red 113, Disperse Red 125, Disperse Red 131, Disperse Red 135, Disperse Red 136, Disperse Red 143, Disperse Red 148, Disperse Red 149, Disperse Red 151, Disperse Red 151:1, Disperse Red 158, Disperse Red 160, Disperse Red 167, Disperse Red 167:1, Disperse Red 168, Disperse Red 172, Disperse Red 176, Disperse Red 177, Disperse Red 180, Disperse Red 186, Disperse Red 188, Disperse Red 193, Disperse Red 195, Disperse Red 202, Disperse Red 203, Disperse Red 204, Disperse Red 206, Disperse Red 208, Disperse Red 218, Disperse Red 219, Disperse Red 224, Disperse Red 227, Disperse Red 272, Disperse Red 274, Disperse Red 288, Disperse Red 310, Disperse Red 315, Disperse Red 366, Disperse Red 369, Disperse Red 371, Disperse Red 376, Disperse Violet 33, Disperse Violet 58, Disperse Violet 59, Disperse Violet 60, Disperse Violet 91 and Disperse Yellow 107.

In one embodiment, according to Formula (I), it is preferred that DYE is an azo dye, of Formula (11a) or (11b), being a monoazo dye or disazo dye respectively, D1-N=N-K1 D1-N=N-E1-N=N-K1 Formula (11a) Formula (11b) wherein DI-is a diazo-component, which is either optionally substituted phenyl or optionally substituted heteroaryl; El-is optionally substituted phenyl, naphthyl or optionally substituted heteroaryl; is a coupling-component, which is selected from optionally substituted phenyl, optionally substituted naphthyl, optionally substituted heteroaryl, optionally substituted pyridonyl, optionally substituted pyrazolonyl or an optionally substituted 1,3-dicarbonyl moiety; and according to Formula (1), where n = 0, at least one of DI-, K1, or El-if present, is connected to at least one functional group G, or where n > 0, at least one of DI-, KI-or E1 if present, is connected to at least one linking group L, and L is connected to at least one functional group G. Azo dyestuffs of the formula (11a) and (11b) may also be obtained by usual diazotisation and coupling methods and strategies for the preparation of azo compounds. Such methods, and strategies are well known to those with ordinary skill in the art, and are well described in, for example, R. M. Christie (2015), Colour Chemistry, 2" Edition, The Royal Society of Chemistry, Cambridge, Sections 3.3 and 3.4, page 78 -93, and also in Organic Chemistry in Colour, P. F. Gordon and P. Gregory, Springer-Verlag Berlin Heidelberg 1987, Section 2.4, page 57 -65. Accordingly, to prepare Formula (11a) type mono-azo dyes, an amine of the Formula (111) may be diazotised and coupled with a compound of Formula (IV). Likewise, to prepare Formula (11b) type disazo dyes, an amine of the Formula (111) may be diazotised and coupled with a compound of Formula (V) to give a compound of Formula (VI), which itself may be diazotised in a second step and coupled with a compound of Formula (IV) to give the Formula (I lb) dye. In some cases, it may be preferred instead to couple the diazotised amine with an ro-methanesulfonate derivative with Formula (V), the product of which is then converted to a Formula (VI) intermediate, typically by treatment with alkali, for example, WO 2007/132152 providing a suitable example of this process. Linking group(s) L and functional group(s) G according to Formula (I) may, independently, be introduced before and/or after formation of the azo compounds of Formula (11a) and (11b), i.e. they may be built into the amine of Formula (111), coupler of Formula (IV) or central component of Formula (VI) prior to formation of the azo dye, or any of these three pre-cursor components may contain suitable functionality to allow attachment of linker and/or functional groups in subsequent synthetic steps following synthesis of the azo dye.

D1-NH2 H-K1 H-E1-NH2 H-E1-NHCH2S03Na D1-N=N-E1-NH2 Formula (Ill) Formula (IV) Formula (V) Formula (V') Formula (VI) It is further preferred that DI-is of the Formula (II la), R5 Formula (111a) wherein R5, R7 and 118 are, independently, selected from hydrogen, a functional group G according to Formula (1), a linking group L with pendent functional group(s) G according to Formula (1), optionally substituted straight or branched chain C1-C18 alkyl, C1-C4 haloalkyl, aryl, halogen, CN, NO2, OR9, CO2R9, C(0)R9, CO2N WV, S020R9, S02R9, S02NR9R10, SO2F, NR9R11, NR9COR16 or NR9S02R16; R6 R6 is selected from hydrogen, a functional group G according to Formula (1), a linking group L with pendent functional group(s) G according to Formula (I), C1-C4 alkyl, C1-C4 haloalkyl, halogen, NO2, or CN; R9 and R1° are, independently, selected from hydrogen, a functional group G according to Formula (1), a linking group L with pendent functional group(s) G according to Formula (1), optionally substituted cyclic, acyclic or a combination C1-C18 alkyl, optionally substituted cyclic or acyclic C1-C18 alkyl which is interrupted by 1 to 6 heteroatoms selected from the group consisting of -0-, -5-, -N111-and/or by functional groups including ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, C1-C4 haloalkyl, optionally substituted aryl optionally substituted arylalkyl, optionally substituted alkylaryl, or if both R9 and 111° are present then they may be part of the same cyclic group; and R11 is selected from hydrogen, -C(0)R9, -S02R9, optionally substituted -C1-C18 alkyl, optionally substituted C1-C18 alkyl which is interrupted by 1 to 6 heteroatoms selected from the group consisting of -0-, -S-, -NR'-and/or by or functional groups including ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, C1-C4 haloalkyl or optionally substituted aryl; or that D1 is of the Formula (111b), R12 R13 Formula (111b) wherein R12 is hydrogen or halogen; and RH is selected from hydrogen, a functional group G according to Formula (I), a linking group [with pendent functional group(s) G according to Formula (I), optionally substituted C1-C18 alkyl, C1-C4 haloalkyl, aryl, halogen, CN, SCN, NO2, OR9, NR9R11, CO2R9, CO2NR9R1°, S020R9, S02R9 or S02NR9R16; NR9COR16 or NR9S021116; or that D1 is of the Formula (111c), R14 N'S I / R15 Formula (111c) wherein R14is hydrogen or halogen; and R15 is selected from hydrogen, halogen or nitro; or that D1 is of the Formula (111d), Formula (111d) wherein R16 is selected from nitro, cyano, CHO or CO21219; 1:117 is selected from hydrogen, chlorine or methyl; F113 is selected from nitro, cyano, COCH3 or CO2819; and 819 is selected from C1-C4 alkyl or a linking group L with pendent functional group(s) G according to Formula (1); or that DI-is of the Formula (111e), 02N7---8 Formula (111e) or that D1 is of the Formula (111f),

N-N

S

Formula (1110 wherein 1320is phenyl or 5421; and Fel is C1-C4 straight or branched chain alkyl; or that D1 is of the Formula (111g);

CN

Formula (111g) and that K1 is of the Formula (IVa), R23 R25 R24 R22 Formula (1Va) wherein Ft22 is selected from hydrogen, methyl, chloro, OR', or 1122 and Ft' together form a 5 to 8 membered ring via a C2-C6 branched or straight chain alkyl bridge, in particular a 6 membered ring of structure C(CH3)2CH2CH(CH3) from Fin to I121; Fe' is selected from hydrogen, methyl, chloro, OR' or NHRn; R24 and R29 are, independently, selected from hydrogen, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, a linking group L with pendent functional group(s) G according to Formula (1), optionally substituted C1-C18 hydrocarbyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms or groups selected from -0-, -5-or -NR28-, C(0)F19, 502R9, C0(CH2)pCO2R29 or, in addition, R 24 forms a ring with R22 as described for R22 above, or R24 and R25 together form a 5 to 8 membered ring which is via a C2-C6 branched or straight chain alkyl or alkenyl bridge, or via a C2-05 branched or straight chain alkyl bridge which is either interrupted by a heteroatom selected from of -0-, -5-or -NR28-or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, or R24 and R25 are joined in a maleimide group, dimethylmaleimide group, succinimide group, glutarimide group or phthalimide group; R26 is selected from hydrogen, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, a linking group L with pendent functional group(s) G according to Formula (I), optionally substituted C1-C8 alkyl, C1-C4 haloalkyl or optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -S-or R22 is selected from optionally substituted C1-C10 straight or branched chain acyl, optionally substituted C1-C10 straight or branched chain carbamoyl, C1-C4 straight or branched chain halo-alkanoyl, optionally substituted benzoyl, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, C0(CH2)pCO2R29, C1-C4 straight or branched chain alkyl-sulfonyl, Cl-C4 straight or branched chain haloalkylsulfonyl or optionally substituted phenylsulfonyl; R28 is selected from hydrogen, optionally substituted C1-C18 hydrocarbyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -S-or -NR28-, C1-C10 straight or branched chain acyl, C1-C4 straight or branched chain halo-alkanoyl, optionally substituted benzoyl, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, C(0)-L where a linking group L with pendent functional group(s) G according to Formula (1), CO(CH2)pCO2R29, COCH=CHCO2R29, C0C6H4CO2R29, Cl-C4 straight or branched chain alkyl-sulfonyl, Cl-C4 straight or branched chain haloalkyl-sulfonyl or optionally substituted phenylsulfonyl; R28 is selected from hydrogen, a linking group L with pendent functional group(s) G according to Formula (I), optionally substituted C1-C18 alkyl, optionally substituted C2-C8 alkenyl, optionally substituted C1-C18 alkylaryl, optionally substituted C1-C18 arylalkyl, C1-C4 haloalkyl or optionally substituted C1-C12 alkyl which is interrupted by 1 to S heteroatoms selected from the group consisting of -0-, -S-or p is an integer from Ito 4; or that 10 is of the Formula (IVb), R32 R3° NJ kal Formula (IVb) wherein 133° is selected from hydrogen, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, a linking group [with pendent functional group(s) G according to Formula (I), optionally substituted C1-C18 hydrocarbyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -S-or -NR28-, C(0)119, 502119, C0(CH2)pCO2R29 COCH=CHCO2R28, C0C6H4CO21329, or 133° and 1331 together form a 5 to 8 membered ring which is via a C2-C6 branched or straight chain alkyl or alkenyl bridge, or via a C2-05 branched or straight chain alkyl bridge which is either interrupted by a heteroatom selected from -0-, -S-or -NR28-or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, or I33° and 1331 are joined in a maleimide group, dimethylmaleimide group, succinimide group, glutarimide group or phthalimide group; 113' is selected from hydrogen, methyl or joined to 113° as described for 133° above; 1132 is hydrogen or hydroxy; or that K1 is of the Formula (IVc), Formula (IVc) wherein R33 is selected from hydrogen, CN or CONH2; 1334 is selected from hydrogen, a linking group L with pendent functional group(s) G according to Formula (I), optionally substituted C1-C18 hydrocarbyl, optionally substituted phenyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -5-or -NR28-, or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester; or that 10 is of the Formula (IVd), R35 Formula (IVd) wherein R39 is selected from optionally substituted C1-C8 straight or branched chain, cyclic or acyclic alkyl, C1-C4 straight or branched chain haloalkyl, optionally substituted aryl, benzyl, a-methylbenzyl, phenethyl, CO21119, CO2NR9R19, preferably optionally substituted C1-C6 straight or branched chain, cyclic or acyclic alkyl, Cl haloalkyl, CO2119, CO2NR9R1°, most preferably CH3 or CO2li9; or that K1 is of the Formula (IVe), ?rR36 Formula (lye) wherein 1:(96 is selected from optionally substituted C1-C18 hydrocarbyl, optionally substituted phenyl, C1-C4 haloalkyl, 01129, NHR29, optionally substituted NH-aryl, or R39 and 1:02 form a 5 or 6 membered ring linked by CH2CH2, CH2CH2CH2, CH2C(CH3)2CH2, NHCONH, N(CH3)CON(CH3), OC(CH3)20; R32, when not part of a ring with 1136, is selected from optionally substituted C1-C18 hydrocarbyl, optionally substituted phenyl, C1-C4 haloalkyl or OR29; or that K1 is of the Formula (IVO, Formula (IVO wherein R38 is methyl or phenyl; or that K1 is of the Formula (IVg), Formula (IVg) or that K1 is of the Formula (IVh),

HN F439

Formula (IVh) wherein F(39 is, independently, as defined for R31 above; or that K1 is of the Formula (IVi), R37 Formula (IVO wherein R4° is hydrogen or Cl-C8 branched or straight chain alkyl; or that K1 is of the Formula (IVj), R9 d R4, Formula (IVD wherein R13 is selected from hydrogen, C1-C8 branched or straight chain alkyl, CO2R9, CO2NR9R19; and that El is of the Formula (Va), R42 R43 Formula (Va) wherein R92 and R43 are, independently, selected from hydrogen, fluor°, chloro, methyl, ethyl or OW; or that El is of the Formula (Vb), D1 R3 Formula (Vb) or that ['is of the Formula (Vc), Ria Di S Formula (Vc) In one embodiment, according to Formula (I), it is preferred that DYE is a metal complex azo dye, of Formula (VII), being a 2:1 azo-dye:metal complex and can also be a mixture of different variants of Formula (VII) produced as a mixture in a single chemical reaction; D2-0 Z-K3 /

N N ii II

N

K2-Y 0-D3 Formula (VII) Note: the geometry around the metal ion is schematic only and is not intended to be limiting, and the dative bond is drawn from the azo bond to imply that either of the azo nitrogen lone pairs can ligate to the metal, but not both; wherein D2 and D3 are diazo-components, independently, either optionally substituted phenyl or optionally substituted naphthyl; K2 and K3 are coupling-components, independently, selected from optionally substituted phenyl, optionally substituted naphthyl, optionally substituted heteroaryl, optionally substituted pyridonyl, optionally substituted pyrazolonyl or an optionally substituted 1,3-dicarbonyl moiety, preferably selected from optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted pyrazolonyl; Y and Z are, independently, either 0 or NR44, preferably 0; MI is any metal in the +3 oxidation state, preferably Co(III), Cr(III) and Fee II), most preferably Co(III) and Cr(III); X is a counter-cation selected from a hydrogen ion, an alkali metal ion, or an ammonium ion, of the structure R481148R47R48N+, preferably Lit, Nat, r, NH4, most preferably Nat; R44 is selected from hydrogen, a linking group L with pendent functional group(s) G according to Formula (I), optionally substituted branched or straight chain Cl-C18 alkyl, optionally substituted phenyl, ClC4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to S heteroatoms selected from the group consisting of -0-, -S-or -N1128-, or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester; R45, R46, R47 and R48 are, independently, selected from a hydrogen, optionally substituted C1-C18 alkyl including linear and branched, saturated and unsaturated, cyclic and acyclic, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -5-or optionally substituted arylalkyl where the alkyl portion of the arylalkyl group can be C1-C18 linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted and where hetero atoms, such as oxygen, nitrogen, sulfur, silicon, and the like, either may or may not be present in either the aryl or the alkyl portion of the arylalkyl group, or optionally substituted alkylaryl where the alkyl portion of the arylalkyl group can be C1-C18 linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and where hetero atoms, such as oxygen, nitrogen, sulfur, silicon, and the like, either may or may not be present in either the aryl or the alkyl portion of the arylalkyl group; optionally two or more of 1157, 1158, R59 and R6° may be joined through a cyclic structure; where the substituents on the substituted alkyl, arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxy groups, halogen atoms, amine groups, imine groups, ammonium groups, cyano groups, pyridine groups, pyridinium groups, ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonyl groups, sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups, phosphate groups, nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfone groups, acyl groups, azo groups, cyanato groups, carboxylate groups, carboxylic acid groups, urethane groups, urea groups, mixtures thereof, and the like; and if Y and Z are both 0, or, if either or both of Y and Z is N R44 but R44 is not in either case a linking group L with pendent functional group(s) G, then according to Formula (I), then, where n = 0, at least one of D2, D3, K2 or K3 is connected to at least one functional group G, or where n > 0, at least one of D2, D3, K2 or K3 is connected to at least one linking group L, and L is connected to at least one functional group G. Metal azo dye complexes of Formula (VII) are prepared in a metalation reaction from azo-dyes of the formulae (Vila) and (VI lb). Metalation reaction methods are well known to those with ordinary skill in the art, and are well described in, for example, K. Hunger (2003), Industrial Dyes, 1st Edition, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, Section 3.11.2, page 304 -311. The azo dyes of Formula (Vila) and (VIlb) can be synthesised by standard diazotisation and coupling methods already described above for compounds of Formula (11a), i.e. through diazotisation of an amine of Formula (Villa) and coupling onto a compound of Formula (IXa); likewise, Formula (VIlb) dyes being synthesised from an amine of Formula (V111b) and coupling onto a compound of Formula (IXb). Linking group(s) L and functional group(s) G according to Formula (1) may, independently, be introduced before and/or after formation of the azo compounds of Formula (Vila) and (VIlb), or after metalation to form the azo-dye metal complex of Formula (VII).

HO-D2-N=N-r-YH Formula (Vila) HO-D2-NH2 Formula (Villa) H-10-YH Formula (IXa) H0-D3-N=N-K3-YH Formula (Vilb) HO-D3-N H2 Formula (Villb) H-K3-ZH Formula (IXb) It is preferred that 02 and D3 are, independently, of the Formula (V111c) or (VIlld), R49 I, -f-----o L:.,M,,,Acr-' , R5° . o NJ 1^1 Formula (V111c) Formula (VIlld) wherein 09 and is selected from hydrogen, a functional group G according to Formula (I), a linking group L with pendent functional group(s) G according to Formula (I), optionally substituted C1-C18 straight or branched chain alkyl, C1-C4 haloalkyl, aryl, benzyl, a-methylbenzyl, phenethyl, halogen, CN, NO2, CF3, OR9, S02R9, S02NR9R10, C(0)R9 or CO2R9, CO2NR9e, preferably NO2, chloro, CO2R9, CO2NR9R1°, most preferably NO2 or CO2NR9Fff; and R5° is selected from hydrogen, NO2, C1-C8 straight or branched chain alkyl, C1-C4 haloalkyl, halogen or NO2, preferably hydrogen, NO2, CO2R9, CO2NR91110, most preferably hydrogen or NO2; and that le and le are, independently, of the Formula (IXc), R52 R" Formula (IXc) wherein R51 and is selected from hydrogen, a functional group G according to Formula (1), a linking group L with pendent functional group(s) G according to Formula (I), halogen, OR9, NR9e, preferably hydrogen, OW or NR9e, most preferably hydrogen or NR9Fff; R52 is selected from hydrogen, a functional group G according to Formula (I), a linking group L with pendent functional group(s) G according to Formula (I), optionally substituted ci-cm straight or branched chain alkyl, C1-C4 haloalkyl, optionally substituted aryl, benzyl, armethylbenzyl, phenethyl, halogen, OR9, CO2119, C(0)119, CO2N119111°, S020R9, SO2R9, SO2NR9e, SO2F, NR9C(0)Ri° or NR9S02R1°, preferably hydrogen, C1-C8 straight or branched chain alkyl, fluoro, chloro, CO2R9, CO2NR9R10, or NR9C(0)R10, most preferably hydrogen, CO2NR9R10, or NR9C(0)R10; and at least one of 1191and R52 is not hydrogen; or that K2 and K3 are, independently, of the Formula (IXd), R53 R54 Formula (IXd) wherein R53 is selected from hydrogen, a functional group G according to Formula (1), a linking group L with pendent functional group(s) G according to Formula (1), optionally substituted C1-C18 straight or branched chain alkyl, C1-C4 haloalkyl, optionally substituted aryl, benzyl, a-methylbenzyl, phenethyl, 32 halogen, OW, CO2R9, C(0)119, CO2NR9R19, 5020R9, 502R9, S02N1191119, SO2F, NR9C(0)1116 or NR9S02R19, preferably hydrogen, C1-C8 straight or branched chain alkyl, fluoro, chloro, CO2119, CO2N1191119, or NI-11127, most preferably hydrogen, CO2NR9R19, or NHR27; and R54 is selected from hydrogen, optionally substituted C1-C18 straight or branched chain alkyl, C1-C4 haloalkyl, optionally substituted aryl, benzyl, a-methylbenzyl, phenethyl, halogen, OW, preferably hydrogen, Cl-C8 straight or branched chain alkyl, bromo, OR9, most preferably hydrogen; or that K2 and 10 are, independently, of the Formula (IXe), R35 R34 Formula (IXe) or that K2 and 10 are, independently, of the Formula (IXf), R36 R37 Formula (IXf) In one embodiment, according to Formula (I), it is preferred that DYE is a phthalocyanine dye, of the Formula (X); R6O Rei Formula (X) wherein M2 is selected from a metal in the +2 oxidation state, a metal(III) halide, metal(111) hydroxide, metal(IV) dihalide or a metaleV) oxide/dihydroxide capable of being introduced, e.g. metals including Al, Cd, Co, Cr, Cr, Cu, Fe, Ga, Hf, Hg, In, Mg, Mo, Mn, Ni, Pb, Pd, Pt, Rh, Ru, Si, Sn, Ti, V, Zn, Zr, and the like, preferably selected from Al, Cu, Ni and Zn, and most preferably is Cu; Ft99 is selected from a functional group G according to Formula (I), a linking group L with pendent functional group(s) G according to Formula (I), 01163, 5R63, C(0)01164, C(0)N1164R59, SO2R64, S0201164, or SO2NR64R69; R67 R56 to R62 are, independently, selected from hydrogen, a functional group G according to Formula (1), a linking group L with pendent functional group(s) G according to Formula (1), halogen, OH, CO2H, CO2-, C(0)N H2, SO3H, 503-, OR63, 51163, C(0)0R64, C(0)NR64R65, 502R64, S020R64 or 502NR64R65; R63 is either a functional group G according to Formula (1) or a linking group L with pendent functional group(s) G according to Formula (1); R64 is a linking group L with pendent functional group(s) G according to Formula (1); R65 is selected from hydrogen, a linking group L with pendent functional group(s) G according to Formula (1), optionally substituted straight or branch chain C1-C18 alkyl, optionally substituted straight or branch chain C1-C18 alkyl which is interrupted by 1 to 6 heteroatoms selected from the group consisting of -0-, -S-, Cl-C4 haloalkyl or optionally substituted aryl, optionally substituted arylalkyl or optionally substituted alkylaryl.

Functionalised metal phthalocyanine dyes of Formula (X) that are suitable for use in this application are suitably prepared in one of two ways under well-established conditions, described in the literature, and well-known to those suitably skilled in the art. The first method follows methodology detailed in K. Venkataraman (1972), The Chemistry of Synthetic Dyes, Vol. VI, pp 312 -323, Academic Press, New York and involves modification of preformed phthalocyanine via chlorosulfonation and subsequent reaction with an amine to give a sulfonamide product or with an alcohol to give a sulfonate ester product. A mixture of regioisomers results. Use of the required amine or alcohol pre-cursor(s), and where required, with further derivatisation of the formed dyes under convenient conditions, can be used to prepare some of the phthalocyanine materials in the stated claims, i.e. the amines or alcohols reacted with the phthalocyanine sulfonyl chloride bear linking groups L according to Formula (1), and may already bear functional groups G, or the linking groups L have suitable functionality to be allow introduction of longer linking groups L and/or functional groups Gin subsequent steps. The second method follows the strategy detailed R. M. Christie (2015), Colour Chemistry, 2nd Edition, Section 5.3, pp 140-144, The Royal Society of Chemistry, Cambridge, in which a phthalocyanine is constructed, either from suitably substituted phthalic anhydride or from suitably substituted phthalonitrile. Use of the required substituted phthalic anhydride or phthalonitrile precursor, and where required, with further derivatisation of the formed dyes under convenient conditions, can be used to prepare some of the phthalocyanine materials in the stated claims i.e. the substituents on the phthalic anhydride or phthalonitrile pre-cursor are functional groups G or linking groups L according to Formula (1), or are groups with suitable functionality to allow introduction of linking groups L and/or functional groups G in subsequent steps.

In one embodiment, according to Formula (I), it is preferred that DYE is an anthraquinone dye, of the Formula (XI); R69 o R66 R76 R71 R68 0 R67 Formula (XI) wherein R66 to R69 are, independently, selected from hydrogen, halogen, nitro, OR9, NHR9 or SR9 and at least one of R66 to R69 is not hydrogen; preferably R66 is NH R9 or 5R9, and when R66 is NH R9 then R6' is NH R9 or OR9, and when R66 is SR9 then R6' to R69 are, independently, hydrogen or SR9; and Fi79 and R72 are, independently, selected from hydrogen, halogen, a functional group G according to Formula (1), a linking group L with pendent functional group(s) G according to Formula (1), -OW, -SW, CO210, -C(0)R9, -CO2N We, -5020R9, -S02R9 or -SO2NR9e, -C61-140R9, 0061-140R9, 006H4502R9, °C6I-1405021r, 0061-145020R9, 0C61-14502NR9R29, 005ELICH2OR9, 005E4CH2NR9e, 0C61-14CH2NR9C(0)e, or R7° and R22 are adjacent and form an imide ring of formula -C(0)NR9C(0)-; and according to Formula (1), where n = 0, at least one of R66 to R72 is connected to at least one functional group G, or where n > 0, at least one of Ft66 to R72 is connected to at least one linking group L, and L is connected to at least one functional group G. Numerous approaches to anthraquinone dyes with application in this invention are suitably exemplified with literature references on a case-by-case basis.

In one embodiment, according to Formula (I), it is preferred that DYE is a coumarin dye, of the Formula (XII); R72 0 R74 Formula (XII) Wherein,A3 is selected from 0,5, NH; R77 is OR9 or NR9e, preferably NR9Rm; R73 is selected from hydrogen, halogen, methyl or -CN, preferably hydrogen or -CN; 1174 is 0 or NH; R75 is selected from hydrogen, halogen, a functional group G according to Formula (I), a linking group L with pendent functional group(s) G according to Formula (I), -OW, CO2Ft9, -C(0)Ft9 -S020R6, -502R9 or -SO2NR9R19, preferably -CO2NR9R19 or -SO2NR9R19; and according to Formula (1), where n = 0, at least one of R72 and F175 is connected to at least one functional group G, or where n > 0, at least one of R22 and RTh is connected to at least one linking group L, and L is connected to at least one functional group G. Some coumarin dyestuffs may be procured commercially, many being sold under their Colour Index Generic Names or Colour Index Constitution Numbers, or synthesised by published proceudres, which can be suitably reacted to introduce the required functionality for use in this application. One non-limiting example being chlorosulfonation, and subsequent reaction with an amine-compound to give a sulfonamide product, for example, as described generally in Dyes and Pigments 2001, 51, 153, where the amine compound bears linking groups L according to Formula (1), and may already bear functional groups G, or the linking groups L have suitable functionality to be allow introduction of longer linking groups L and/or functional groups G in subsequent steps. Additionally, coumarin dyes of Formula (XII) may be suitably prepared by condensation of optionally substituted 2-hydroxybenzaldehydes with optionally substituted 2-aryl-acetonitries or alkyl 2-aryl-acetates, as described generally in Dyes and Pigments 2000, 47, 79, and US 4,892,922, where at least one of the two aforementioned condensation partners either (a) bears a suitable functional groups to allow introduction of linking groups L and/or functional groups G according to Formula (I), or (b) already bears linking groups L and/or functional groups G, or the attached linking groups L has suitable functionality to allow introduction of longer linking groups L and/or functional groups G in subsequent steps. Additionally, the absorbance wavelenghs of the coumarin dyes can be lengthened through cyanation, as described generally in Dyes and Pigments 2001, 51, 153.

In one embodiment, according to Formula (I), it is preferred that DYE is an extended coumarin dye, of the Formula (Xllh); R72 R75

CN

Formula (Xllh) Dyes of formula (Xllh) are suitably prepared from dyes of formula (Xlle) or (Xllf) by reaction with malononitrile at reflux in a high-boiling solvent, such as 2-ethoxyethanol. Such a conversion is suitably exemplified in US 2007/0122746 and DE 10 2010 031 243.

In one embodiment, according to Formula (1), it is preferred that DYE is a squaraine dye, of the Formula (XII la) to (X111e), where it will be understood by those skilled in the art that the molecules are fully delocalised and only one of many canonical forms is represented; R3K) Ral R32' 0 R78 Rm.\ R77/ IR76' R78' 0-R32 R72 R76

N \R77

Formula (X111a) Formula (X111b) Formula (X1110 Formula (XIlle) R80 Formula (X111d) wherein Fe7 and R32! are, independently, hydrogen or hydroxy; 876, 1:175, 877 and 877! are, independently, selected from hydrogen, a linking group L with pendent functional group(s) G according to Formula (1), optionally substituted C1-C18 hydrocarbyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -5-or -NR78-, or 1176 and 877, likewise 1176! and 1177, together form a 5 to 8 membered ring which is via a C2-C6 branched or straight chain alkyl or alkenyl bridge, or via a C2-05 branched or straight chain alkyl bridge which is either interrupted by a heteroatom selected from of -0-, -S-or -NR28-or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, or 876 forms a ring with F179, likewise 876 and 1179, as described for V, likewise Ft'', below; at least one of F276 and 1277, likewise one of RTh' and Rfl, is not hydrogen; Fim and 1:176! are, independently, selected from hydrogen, methyl, chloro, OR' or NHF177, preferably hydrogen, 0876 or NHR77; F179 and Ft79! are, independently, selected from hydrogen, methyl, chloro, OR', or Ft76 and 1179, likewise Ft76! and 879, together form a 5 to 8 membered ring via a C2-C6 branched or straight chain alkyl bridge, in particular a 6 membered ring of structure C(CH3)2CH2CH(CH3) from 1376 to 876, likewise Ft76! to 16176; and according to Formula (I), where n = 0, at least one of Fe6 to 876, likewise 876! to 1276, is connected to at least one functional group G, or where n >0, at least one of 876 to Ft76, likewise 876! to 1379, is connected to at least one linking group L, and L is connected to at least one functional group G; 866 is a linking group L with pendent functional group(s) G according to Formula (I); Ft61 is selected from hydrogen, a linking group L with pendent functional group(s) G according to Formula (I), optionally substituted straight or branch chain C1-C18 alkyl, optionally substituted straight or branch chain C1-C18 alkyl which is interrupted by 1 to 6 heteroatoms selected from the group consisting of -0-, -S-, C1-C4 haloalkyl or optionally substituted aryl, optionally substituted arylalkyl or optionally substituted alkylaryl.

Symmetric squaraine dyes of formula (X111a) to (X111d) are conveniently synthesised by condensation of squaric acid with a compound of structure (X111f) to (XIlli) respectively, commonly at reflux in a mixture of butanol and toluene with azeotropic removal of water. Suitable synthetic detail is provided in, for example, RSC Advances 2013, vol. 3, pp 8021-8027. Alternatively, asymmetric squaraines of the Formula (X111a) and (X111e) can be prepared in a stepwise fashion, which is suitable described in, for example, J. Am. Chem. Soc. 2014, 136, 13233 and WO 2016/154782.

R76 R78 \N R77 R79 Formula Palle Formula (Xing) Formula (XIIIh) Formula (XIlli) In one embodiment, according to Formula (I), it is preferred that DYE is a croconaine dye, of the Formula (XlVa) Or (XIVb), where it will be understood by those skilled in the art that the molecules are fully delocalised and only one of many canonical forms is represented; R79 R76 1 R78 0-R77 4I glj. N R79 R78 0 0 Formula (XlVa) R76 Rs° R80 +1 +/ R77 R81' NNR81 Formula (XIVb) Croconaine dyes of formula (XlVa) and (XIVb) are conveniently synthesised under comparable condition to those given for dyes of formula (XII la) to (X111d), but by reaction of compounds of formula (X111e) to (XIIIh) with croconic acid instead of squaric acid.

In one embodiment, according to Formula (I), it is preferred that DYE is a metal dithiolene dye, of the Formula (XV), R83 R82 S R82 S s / R83 Formula (XV) wherein M3 is selected from any metal or metal oxide capable of being introduced, e.g. V. VO, Cd, TiO, Ti, Mn, Cr, Fe, Co, Ni, Cu, Zn, Pd, Cd, Mg, Hg Zr, Al, Mo02, Pt, Ru, Rh, Hf, Sb, Sn, Pb, Pd, Au, Ag and the like, preferably Ni, Cu, Pd, and Pt, most preferably Ni; R32 is selected from a functional group(s) G according to Formula (1), a linking group L with pendent functional group(s) G according to Formula (1), -OW, -0O2119, -C(0)119, -CO2N119111°, -S020R9, -S02R9 or -S02N1191119, -C6H4119, -C6H40R9, -C6H4S119, -C6H4CO2R9, -C61-14C(0)R9, -C6H4CO2NR9R19, -C6H4S020119, -C6H4S02119 or -C6H4502N1191119; R33 is selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, optionally substituted phenyl, -C6H4119, -C6H40119, -C6H4S119, -C6H4CO2119, -C6H4C(0)119, -C6H4CO2NR91110, -C6H45020R9, -C6H4S02R9 or -C6H4S02N WV; and according to Formula (I), where n = 0, at least one of R82 and RH is connected to at least one functional group G, or where n > 0, at least one of R82 and R83 is connected to at least one linking group L, and L is connected to at least one functional group G. Serving as a means of example only, the preparation of metal dithiolene dyes of Formula (XV) is suitably exemplified in the scheme and methodology laid out in US 5,089,585, which describes the synthesis of a dye of Formula (XVa) (Example 9 in the parent literature), and in lnorg. Chem. 2014, 53, 6, 2841-2847, which describes the synthesis of a dye of Formula (XVb) (Compound HC2 in the parent literature). Suitable manipulation of synthetic pre-cursors, metal salts and further derivatisation of the formed dyes under convenient conditions described in the literature and known to those suitably skilled in the art, can be used to prepare analogous materials of Formula (1) as per the stated claims, that are suitable for use in this application.

HO OH

Formula (XVa) HO Formula (XVI3) S Ni OH

S

In one embodiment, according to Formula (1), it is preferred that DYE is a styryl dye, of the Formula Formula (XVI) wherein Rm is -CN, -0O2R29 or -C(0)NR861389; R25 R24 R22 F185 is -CN or -CO2R29; F186 and R8' are, independently, the same definition as R29; and according to Formula (1), where n = 0, at least one of R22 to R25 is connected to at least one functional group G, or where n >0, at least one of R22 to R25, F182 or R83 is connected to at least one linking group L, and L is connected to at least one functional group G. Styryl dyes of Formula (XVI) may, for example, be prepared, among other ways, in a two-step procedure. A compound of Formula (IVa), as defined above, may be formylated in a Vilsmeier-Haack reaction, for example, by using methodology based on literature reference Org. Synth. 1953, vol. 33, pp 27 -29, to give a p-aminobenzaldehyde derivative. The p-aminobenzaldehyde derivative can then be reacted with an activated methylene compound in a Knoevenagel condensation reaction, for example, by using methodology based on literature reference Chem. Mater. 1999, vol. 11, pp 1784-1791.

In one embodiment, according to Formula (I), it is preferred that DYE is a pyrroline dye, of the Formula (XVII), Formula (XVII) wherein w is 0 or 1; and according to Formula (1), where n = 0, at least one of R22 to R25 is connected to at least one functional group G, or where n >0, at least one of R22 to R25 or R29 is connected to at least one linking group L, and L is connected to at least one functional group G. Pyrroline dyes of formula (XVII) may be prepared by 1 of 2 routes, depending on whether w = 0 or 1, as shown in General Scheme 8.

Pyrrolidine dyes of Formula (XVII) where w = 0 may, for example, be prepared, among other ways, by reaction of 2-(3-cyano-4-hydroxy-5-oxo-1H-pyrrol-2(5H)-ylidene)malononitrile disodium salt with a compound of Formula (IVa), as defined above, promoted by phosphoryl trichloride, as described in, for example, US 4,845,235. Optional N-alkylation to introduce a group R29 may be achieved in a second step, for example, by treatment with an alkylating agent in the presence of a base, which may be achieved, for example, by using methodology also exemplified in the same reference. Pyrrolidine dyes of Formula (XVII) where w = 1 may, for example, be prepared, among other ways, by reaction of 2-(3-cyano-4-methyl-5-oxo1H-pyrrol-2(5H)-ylidene)malononitrile with a p-aminobenzaldehyde derivative, according to US 7,307,173; the p-aminobenzaldehyde derivative being the same compound type as that already described above for the synthesis of Styryl dyes of Formula (XVI). Optional N-alkylation to introduce a group R29 may be achieved in a second step, for example, by treatment with an alkylating agent in the presence of a base, which may be achieved, for example, by using methodology based on Example 4 of the same reference.

In one embodiment, according to Formula (1), it is preferred that DYE is a 3-dicyanomethylidene-2,3-dihydro-thiophene 1,1-dioxide dye, of the Formula (XVIII),

NC

Formula (XVIII) and according to Formula (I), where n = 0, at least one of R22 to R25 is connected to at least one functional group G, or where n >0, at least one of R22 to R25 is connected to at least one linking group L, and L is connected to at least one functional group G. 3-Dicyanomethylidene-2,3-dihydro-thiophene 1,1-dioxide dyes of formula (XVIII) may be prepared by reaction of 2-(1,1-dioxidobenzo[b]thien-3(2H)-ylidene)propanedinitrile of and a p-aminobenzaldehyde derivative, for example, using methodology described in GB 2,026,528; the p-aminobenzaldehyde derivative being the same compound type as that already described above for the synthesis of Styryl dyes of Formula (XVI).

In one embodiment, according to Formula (I), it is preferred that DYE is a Xanthene. Many known Xanthene dyes, including Rhodamine dyes, both commercially available and those developed for other means, are of the general Formula (f), and now find suitable application in this invention. Such materials include, but are not limited to, 9-(2-carboxyphenyI)-3,6-bis(di-2-propen-1-ylamino)xanthylium chloride (CN 114262335), 243-oxo-6-(2-propen-1-yloxy)-3H-xanthen-9-yllbenzoic acid (J. Appl. Polym. Sci. 2011, 122, 1968), Fluorescein 0-acrylate (Chem. Commun. 2012, 48, 8341), 2-(6-hydroxy-3-oxo-3H-xanthen-9-0-4-1(1-oxo-2-propen-1-y1)aminoThenzoic acid (WO 2022/109274), 2-(6-hydroxy-3-oxo-3H-xanthen-9-y1)-5-1(1-oxo2-propen-1-y1)aminoThenzoic acid (J. Am. Chem. Soc. 2015, 137, 13736), 2-propen-1-y12-13-oxo-6-(2-propen-1-yloxy)-3H-xanthen-9-yllbenzoate (J. Org. Chem. 2014, 79, 7665), 2-[(1-oxo-2-propen-1-yl)oxy]ethyl 2-13,6-bis(diethylamino)-3H-xanthen-9-yllbenzoate (ACS Applied Materials & Interfaces 2015, 7, 15551), 3,6-bis(diethylamino)-9-[2-[(2-propenyloxy)carbonyllphenyl]xanthylium chloride (Chem. Commun. 2009, 20, 2881), 2-propen-1-y12-[2,4,5,7-tetrabromo-3-oxo-6-(2-propen-1-yloxy) -3H-xanthen-9-yl]benzoate, 2-propen-1-y12-(6-hydroxy-3-oxo-3H-xanthen-9-yl)benzoate (WO 2006/025983), 3,6-bis(diethylamino)-942-[[(4-ethenylphenyOmethoxy]carbonyl]phenyl] xanthylium chloride (Langmuir 2006, 22, 7411), 3,6-bis(diethylamino)-9-12-[(4-ethenylphenoxy)carbonyl]phenybanthylium chloride (US 2021/0017390), 2-(2,4,5,7-tetrabromo-6-hydroxy-3-oxo-3H-xanthen-9-yObenzoic acid (4-ethenylphenyl)methyl ester (WO 2020/001864), 2-(methacryloyloxy)ethyl 2-(3,6-bis(diethylamino)-3H-xanthen-9-yl)benzoate (US 9,605,101), 9-(2-(((1,3-bis(methacryloyloxy)propan-2-yl)oxy)carbonyl)phenyI)-3,6-bis (diethylamino)xanthylium chloride (JP 2015/025971), 3,6-bis(ethylamino)-2,7-dimethy1-9-[21[2-[(2-methy1-1-oxo-2-propen-1-y1) oxy]ethoxy]carbonyliphenylixanthylium chloride (EP 2,957,578), 3,6-bis(dimethylamino)-9-[2-[[2-[(2-methy1-1-oxo-2-propen-1-yl)oxy]ethoxy] carbonyliphenyllxanthylium chloride (US 2015/0322265), 3,6-bis(diethylamino)-9-12-Umethyl[2-[(2-methyl-1-oxo-2-propen-1-yfloxy] ethyllaminolcarbonyliphenyllxanthylium tetrafluoroborate (US 2018/0171043), 3,6-bis(diethylamino)-9-[21[4-(1-oxo-2-propen-1-y1)-1-piperazinyl] carbonyliphenyllxanthylium chloride (Macromolecular Bioscience 2016, 16, 508), 3,6-bis(diethylamino)-9121[4-(2-methy1-1-oxo-2-propen-1-y1)-1-piperazinyl] carbonyllphenylixanthylium chloride (Chem. Commun. 2012, 48, 1117), 3,6-bis(diethylamino)-942-[[[2-(2,5-dihydro-2, 5-dioxo-1H-pyrrol-1-yflethyliaminoicarbonyl]phenylixanthylium chloride (KR 2020/123022), 942-carboxy-4-(2,5-dihydro-2,5-dioxo-11-1-pyrrol-1-yOphenyl]-3,6-bis (dimethylamino)xanthylium inner salt (WO 2018/111990), 912-carboxy-5-[(2-methy1-1-oxo-2-propen-1-yl)amino]phenyl]-3,6-bis (diethylamino)xanthylium inner salt (J. Polym. Sci., Part A: Polymer Chemistry 2007, 45, 2876), 942-carboxy-4-[(2-methy1-1-oxo-2-propen-1-yl)amino]phenyll-3,6-bis (diethylamino)xanthylium inner salt (J. Polym. Sci., Part A: Polymer Chemistry 2007, 45, 2876), 4-((allyloxy)carbony1)-2-(3,6-bis(dimethylamino)xanthylium-9-yl)benzoate (Nature Chemistry 2020, 12, 165), 942-carboxy-6-[[(2-propen-1-ylamino)thioxomethyl]amino]pheny1]-3,6-bis (diethylamino)xanthylium chloride (J. Fluor. Chem. 2016, 183, 92), 942-carboxy-4-[[[(4-ethenylphenyl)amino]thioxomethyl]amino]phenyl]-3,6-bis (diethylamino) xanthylium chloride (Langmuir 2012, 28, 6785), 9-[2-carboxy-5-[[[2-[(2-methy1-1-oxo-2-propen-1-yl)oxy]ethoxy] thioxomethyllamino]phenyl]-3,6-bis(diethylamino)xanthylium chloride (WO 2015/077439), 9-[2-carboxy-4-Rthioxo[[3-(trimethoxysily0propyl]aminolmethyllamino] pheny11-3,6-bis(diethylamino)xanthylium chloride (ACS Nano 2012, 6, 3954), 3,6-bis(diethylamino)-9-[2-[[2-[(1-oxo-2-propen-1-yfloxylethoxy] carbonyliphenylixanthylium chloride (J. Appl. Polym. Sci. 2011, 121, 2843), 3,6-bis(diethylamino)-9-[21[2-[(1-oxo-2-propen-1-yl)oxy]ethoxy] carbonyllphenylIxanthylium chloride (J. Appl. Polym. Sci. 2011, 121, 2843), 3,6-bis(diethylamino)-9-12-[[2-[(2-methy1-1-oxo-2-propen-1-yl)oxy]ethoxy] carbonyliphenyl]xanthylium chloride (Biomaterials 2019, 195, 38), and related analogues of these named materials not specifically named themselves, for example methacrylate ester instead of acrylate ester or vice versa, methacrylamide instead of acrylamide or vice versa, and acrylate esters, methacrylate esters, acrylamides and methacrylamides that can made from any of the named materials bearing a terminal hydroxy or primary or secondary amino group under standard conditions described for many other materials in this disclosure, with it being understood and clear to those skilled in the art that, where the Xanthene or Rhodamine dye is a salt and a counterion is specified, e.g. chloride, terafluoroborate etc., this counterion plays no role in the performance of the dye in this application and can be any counterion without changing the nature of the dye.

In one embodiment, according to Formula (1), it is preferred that DYE is a UV-absorber which may be also be Fluorescent Brightening Agent. Many known UV-absorbers/Fluorescent Brightening Agents, both commercially available and those developed for other means, are of the general Formula (1), and now find suitable application in this invention. Such materials include, but are not limited to, 212-hydroxy-512-(methacryloyloxy)ethyllpheny1]-2H-benzotriazole (TCI), 2-(2H-benzo[d][1,2,3]triazol-2-y1)-4-(2-hydroxyethyl)phenol (WO 99/58593), 2[2-hydroxy-542-(acryloyloxy)ethyl]phenyl]-2H-benzotriazole (WO 99/58593), 3-(2H-benzo[d][1,2,3]triazol-2-y1)-4-hydroxyphenethyl 6-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)hexanoate (WO 2003/029227), 3-(2H-benzo[d][1,2,3]triazol-2-y1)-4-hydroxyphenethyl (2-(3-(prop-1-en-2-yl)phenyl)propan-2-yl)carbamate (WO 2003/029227), 2-(2H-benzotriazol-2-y1)-412-(2-propen-1-yloxy)ethyl]phenol (WO 2003/029227), 243-(2H-benzotriazol-2-y1)-4-hydroxyphenyflethyl 4-pentenoate (US 2003/0133886), 2-(2H-benzotriazol-2-y1)-4-methyl-6-(2-propenyl)phenol (TCI), 2-(2H-benzotriazol-2-y1)-4-methyl-6-(2-methyl-2-propen-1-y1)phenol (US 2013/0231488), 2-(5-chloro-2H-benzotriazol-2-y1)-6-(1,1-dimethylethyl)-4-ethenylphenol (US 4,845,180), 2-(tert-butyl)-6-(5-chloro-2H-benzo[d][1,2,3]triazol-2-y1)-4- (1-hydroxyethyl)phenol (US 4,845,180), 2-(tert-buty1)-6-(5-chloro-2H-benzo[d][1,2,3]triazol-2-y1)-4- (2-hydroxyethyl)phenol (US 4,845,180), 2-(2,4-dihydroxyphenyI)-2H-benzotriazole (EP 0,751,134), 3-(4-(2Hbenzo[d][1,2,3]triazoI-2-yI)-3-hydroxyphenoxy)-2-hydroxypropyl methacrylate (Colloids and Surfaces A: Physicochem. Eng. Aspects 2019, 577, 695), 4-(2H-benzo[d][1,2,3]triazol-2-y1)-3-hydroxyphenyl acrylate (Fibers and Polymers 2019, 20, 2289), 4-(2H-benzo[d][1,2,3]triazol-2-y1)-3-hydroxyphenyl methacrylate (JP 2009/270076), 2-[[[4-(2H-benzotriazol-2-y1)-3-hydroxyphenoxy]carbonyllaminolethyl 2-propenoate (KR 2020/023578), 2-[[[4-(2H-benzotriazol-2-y1)-3-hydroxyphenoxy]carbonyllaminolethyl 2-methy1-2-propenoate (KR 2020/023578), 2-(2H-benzotriazol-2-y1)-5-[[(2E)-3-phenyl-2-propen-1-yl]oxy]phenol (WO 2003/029227), 2-(2H-benzotriazol-2-y1)-1,4-benzenediol (Aust. J. Chem. 1987, 40, 1663), 3-(2HbenzotriazoI-2-yl)-4-hydroxyphenyI 2-methyl-2-propenoate (WO 2015/115415), 2-(5-chIoro-2HbenzotriazoI-2-yl)-6-(1,1-dimethyIethyI)-4- (3-hydroxypropoxy)phenoI (EP 3,848,357), 3-11213-(1,1-dimethylethyl)-2-hydroxy-5-(3-hydroxypropoxy) pheny11-2H-benzotriazol-5-yllthio]-1,2-propanediol (EP 3,848,357), 3-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3] triazol-2-yOphenoxy)propyl methacrylate (US 4,716,234), 2-(5,6-dimethoxy-2H-benzotriazol-2-y1)-6-(1,1-dimethylethyl)-4- (3-hydroxypropoxy)phenol (US 7,803,359), 3-(3-(tert-butyl)-5-(5,6-dimethoxy-2H-benzo[d][1,2,3]triazol-2-y1) -4-hydroxyphenoxy)propyl methacrylate (US 7,803,359), 21(2-(3-(tert-buty1)-2-hydroxy-5-(3-(methacryloyloxy)propoxy)pheny1) -2H-benzo[d][1,2,3]triazol-5-y1)sulfonypethyl methacrylate (EP 3,848,357), 1-(4-(2H-benzo[d][1,2,3]triazol-2-y1)-3-hydroxyphenoxy) -3-methoxypropan-2-ylacrylate (WO 2019/080926), 1-(4-(2H-benzo[d][1,2,31triazol-2-y1)-3-hydroxyphenoxy) -3-methoxypropan-2-y1 methacrylate (WO 2019/080926), 1-(4-(2H-benzo[d][1,2,3]triazol-2-y1)-3-hydroxyphenoxy) -3-ethoxypropan-2-ylacrylate (WO 2019/080926), 1-(4-(2H-benzo[d][1,2,3]triazol-2-y1)-3-hydroxyphenoxy) -3-ethoxypropan-2-ylmethacrylate (WO 2019/080926), 1-(4-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-y1)-3- hydroxyphenoxy)-3-ethoxypropan-2-ylmethacrylate (WO 2019/080926), (WO 2019/080926), 1-(4-(5-chloro-2H-benzo[d][1,2,3]triazol-2-y1)-3-hydroxyphenoxy) -3-ethoxypropan-2-y1 methacrylate (WO 2019/080926), 4-(5-chloro-2H-benzotriazol-2-y1)-3-hydroxyphenyl 2-propenoate (JP 2009/270076), 4-(5-chloro-2H-benzotriazol-2-y1)-3-hydroxyphenyl 2-methy1-2-propenoate (JP 2009/270076), 215-[[(2E)-3-pheny1-2-propen-1-yl]oxy]-2H-benzotriazol-2-yl]phenol (WO 2003/029227), 21513-(4-ethenylphenoxy)-2-hydroxypropoxy]-2H-benzotriazol-2-yl]phenol (WO 2003/029227), 5-amino-2-(2-hydroxyphenyl)benzotriazole (Heterocycl. Commun. 2014, 20, 15), 2-(51(4-chloro-6-(diallylamino)-1,3,5-triazin-2-y0amino)-2H-benzo[d][1,2, 3]triazol-2-yOphenol, 5-amino-2-(2-hydroxy-5-methylphenyl)benzotriazole (Heterocycl. Commun. 2014, 20, 15), N42-(2-hydroxy-5-methylpheny1)-2Hbenzotriazol-5-y1]-2-methy1-2-propenamide (WO 2008/126700), 2-(5-amino-2H-benzotriazol-2-y1)-4-(1,1-dimethylethyl)phenol (WO 2008/126699), N-(2-(5-(tert-buty1)-2-hydroxypheny1)-2H-benzo[d][1,2,3]triazol5-y1) methacrylamide (WO 2008/126699), diallyl 2,2'-(thiophene-2,5-diyObis(benzo[d]oxazole-5-carboxylate) (GB 1,077,982), 2,2'-(thiophene-2,5-diy1)bis(N-(2-hydroxyethyl)benzo[d] oxazole-5-carboxamide) (GB 1,077,982), 2-(2-(5-(1H-benzo[d]imidazol-2-yl)thiophen-2-y1)-1H-benzo[d]imidazol-Fyl) ethanol (GB 879,610), 2,2'-(2,2'-(thiophene-2,5-diy1)bis(1H-benzo[d]imidazole-2,1-diy1)) diethanol (GB 879,610), 3-(2-(5-(1H-benzo[d]imidazol-2-yl)thiophen-2-y1)-1H-benzo[d]imidazol-Fyl) propane-1,2-diol (GB 879,610), 2,2'-(2,2'-(thiophene-2,5-diyObis(6-methy1-1H-benzo[d]imidazole-2,1-diy1)) diethanol (GB 879,610), 3-(6-methy1-2-(5-(5-methyl-1H-benzo[d]imidazol-2-yl)furan-2-y1)-1H-benzo [d]imidazol-Fyl)propane-1,2-diol (GB 888,209), 2,5-bis(5-(allyloxy)-6-(tert-butyl)benzo[d]oxazol-2-yl)thiophene (JP 2002/096558), 3,3'-(2,2'-(thiophene-2,5-diy1)bis(benzo[d]oxazole-5,2-diy1))bis(N- (2-hydroxyethyl)propanamide) (FR 1,343,140), bis(2-(acryloyloxy)ethyl) 2,2'-(thiophene-2,5-diy1)bis(7-(tert-butyl)benzo[d]oxazole-5-carboxylate) (KR 2015/109853), 3-(4-chloropheny1)-1-[4-(ethenylsulfonyl)pheny1]-4,5-dihydro-1H-pyrazole (DD 271,115), 2-[[4-[3-(4-chlorophenyI)-4,5-dihydro-1H-pyrazol-1-yl]phenyl]sulfonyl] ethanol (FR 6099), 2-(4-((4-(3-(4-chloropheny1)-4,5-dihydro-1H-pyrazol-1-yl)phenyl)sulfonyl) piperazin-1-ypethanol (GB 1,186,650), 3-((4-(3-(4-chloropheny1)-4,5-dihydro-1H-pyrazol-1-yOphenyl)sulfonyl) prop-2-en-1-ol (DE 2,550,548), 2-((4-(3-(4-methoxypheny1)-4,5-dihydro-1H-pyrazol-1-yOphenyl)sulfonyl) ethanol (GB 993,055), 114-(ethenylsulfonyl)pheny1]-4,5-dihydro-3-pheny1-11-pyrazole (DE 1,670,722), 3-(4-methoxyphenyI)-1-(4-((2-methylallyl)sulfonyl)pheny1)-4, 5-dihydro-1H-pyrazole (DE 2,524,927), 4,4'-bis(2-(allyloxy)styryI)-1,1'-biphenyl (CH 578,645), 4,4'-bis(3-(allyloxy)styryI)-1,1'-biphenyl (CH 578,645), 4,4'-bis(2-(but-3-en-1-yloxy)styry1)-1,1'-biphenyl (CH 578,645), 4,4'-bis(2-(but-2-en-1-yloxy)styryI)-1,1'-biphenyl (CH 578,645), 1,3-bis(2-propen-1-yloxy)-54244-(2-propen-1-yloxy)phenyliethenyl]benzene (US 8,513,374), 5-(4-(acryloyloxy)styry1)-1,3-phenylene diacrylate (US 2017/0224632), 5-(4-(methacryloyloxy)styry1)-1,3-phenylene dimethacrylate (US 2012/0052757), 2-(methyl(2-(4-nitrostyryl)benzo[d]oxazol-6-yl)amino)ethyl methacrylate (Polymer 1998, 39, 7061), N-[24412-[445,7-bis(1,1-dimethylpropy1)-2-benzoxazolyllphenyl]ethenyl] phenyl]-5-benzoxazoly1]-2-propenamide (US 4,106,941), 1-(2-(4-(4-(5-(2,4,4- trimethylpentan-2-yObenzo[d]oxazol-2-yl)styryl)phenyl)benzo[d] oxazol-5-0-1H-pyrrole-2,5-dione (JP 05127329), 4-(allyloxy)-2-hydroxybenzophenone (TCI), 2-hydroxy-4-(methacryloyloxy)benzophenone (JP 2015/01810), 2-hydroxy-4-(acryloyloxy)benzophenone (Macromolecules 2020, 53, 4465), bis[2-hydroxy-4-(2-propen-1-yloxy)phenylimethanone (EP 2,426,175), [2-hydroxy-4-[(3-methy1-2-buten-1-yfloxy]phenyliphenylmethanone (Biomedicine & Pharmacotherapy 2015, 75, 93), [2-hydroxy-4-[(2-methy1-2-propen-1-yfloxy]phenyliphenylmethanone (US 3,211,696), [41(4-ethenylphenyl)methoxy]-2-hydroxyphenyl]phenylmethanone (JP 50020059), 4-benzoy1-3-hydroxyphenyl 2-butenoate (GB 898,0650), 4-benzoy1-3-hydroxyphenyl 4-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yObenzoate (KR 2015/097180), 4-benzoy1-2-(1,1-dimethylethyl)-5-hydroxyphenyl 2-methyl-2-propenoate (BE 629,109), 2-(4-benzoy1-3-hydroxyphenoxy)ethyl acrylate (Fluorochem Ltd UK), 2-(4-benzoy1-3-hydroxyphenoxy)ethyl methacrylate (WO 2004/090030), 2-(4-benzoy1-3-hydroxyphenoxy)ethyl acrylate (CN 112029371), 4-(2-hydroxybenzoyl)phenyl methacrylate (CN 112226136), (4-(allyloxy)phenyl)(2-hydroxyphenyl)methanone (CN 109280002), (2-hydroxyphenyl)(4-(prop-1-en-1-yloxy)phenyl)methanone (CN 109280002), 6,6'-(6-(4-methoxypheny1)-1,3,5-triazine-2,4-diy1)bis(3-((2-methylally1) oxy)phenol) (J. Chem. Res. 2008, 11,664), 6,6'-(6-pheny1-1,3,5-triazine-2,4-diyObis(3-(allyloxy)phenol) (CH 484,695), 6,6'-(6-pheny1-1,3,5-triazine-2,4-diAbis(3-(2-hydroxyethoxy)phenol) (CH 484,695), 6,6'-(6-pheny1-1,3,5-triazine-2,4-diyphis(3-(but-2-en-1-yloxy)phenol) (CH 484,695), 6,6'-(6-(4-(tert-butyl)pheny1)-1,3,5-triazine-2,4-diy1)bis(3-(allyloxy) phenol) (CH 484,695), 4-(4-(4-(allyloxy)-2-hydroxypheny1)-6-(4-(tert-butyl)pheny1)-1,3, 5-triazin-2-yObenzene-1,3-diol (CH 484,695), 2-(4-(4-(tert-butyl)pheny1)-6-(2-hydroxy-4-(2-(2-hydroxyethoxy)ethoxy) pheny1)-1,3,5-triazin2-y1)-5-(2-hydroxyethoxy)phenol (CH 484,695), 6,6'-(6-(4-methoxypheny1)-1,3,5-triazine-2,4-diy1)bis(3-(allyloxy)phenol) (CH 484,695), 6,6'-(6-(4-chloropheny1)-1,3,5-triazine-2,4-diy1)bis(3-(allyloxy)phenol) (CH 484,695), 6,6'-(6-([1,1'-bipheny1]-4-y1)-1,3,5-triazine-2,4-diy1)bis(3-(allyloxy) phenol) (CH 484,695), 6,6,6"-(1,3,5-triazine-2,4,6-triyl)tris(3-(allyloxy)phenol) (CH 484,695), 5-(allyloxy)-2-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-Aphenol (CH 484,695), 2-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-5-(2-hydroxyethoxy) phenol (CH 484,695), 2-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-5-(but-2-en-1-yloxy) phenol (CH 484,695), 2-hydroxyethyl 2-(4-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) acetate (CH 484,695), 4-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenyl acrylate (CH 481,954), 4-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenyl methacrylate (CH 481,954), 4-(4-(4-chloropheny1)-6-(2,4-dimethylpheny1)-1,35-triazin-2-y1) -3-hydroxyphenyl acrylate (CH 481,954), 4-(4,6-dipheny1-1,3,5-triazin-2-y1)-3-hydroxyphenyl acrylate (CH 481,954), 4-(4,6-bis(4-chloropheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenyl acrylate (CH 481,954), 2-(4,6-dipheny1-1,3,5-triazin-2-y1)-5-((3/4-vinylbenzyl)oxy)phenol (GB 2,293,823), 1-butoxy-3-(4-(4,6-dipheny1-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) propan-2-ylacrylate (GB 2,293,823), 1-butoxy-3-(4-(4,6-dipheny1-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) propan-2-y1 methacrylate (GB 2,293,823), 1-(4-(4,6-dipheny1-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) hexan-2-ylmethacrylate (GB 2,293,823), 11-(4-(4,6-dipheny1-1,3,5-triazin-2-y1)-3- hydroxyphenoxy)undecyl acrylate (GB 2,293,823), 11-(4-(4,6-dipheny1-1,3,5-triazin-2-0-3-hydroxyphenoxy)undecyl methacrylate (GB 2,293,823), 2-(4-(4,6-dipheny1-1,3,5-triazin-2-y1)-3-hydroxyphenoxy)ethyl methacrylate (GB 2,293,823), fi(6-pheny1-1,3,5-triazine-2,4-diy1)bis(3-hydroxy-4,1-phenylene))bis(oxy) This(1-butoxypropane-3,2-diy1) diacrylate (GB 2,293,823), 11-(4-(4-(4-(hexyloxy)-2-hydroxypheny1)-6-pheny1-1,3,5-triazin-2-y1) -3-hydroxyphenoxy)undecyl methacrylate (GB 2,293,823), 11-(4-(4-(4-((11-acetoxyundecyl)oxy)-2-hydroxypheny1)-6-phenyl-1,3, 5-triazin-2-y1)-3-hydroxyphenoxy)undecyl methacrylate (GB 2,293,823), (((6-(4-chloropheny1)-1,3,5-triazine-2,4-diyObis(3-hydroxy-4,1-phenylene)) bis(oxy)This(ethane-2,1-diy1) diacrylate (GB 2,293,823), (((6-pheny1-1,3,5-triazine-2,4-diy1)bis(3-hydroxy-4,1-phenylene))bis(oxy) This(ethane-2,1-diy1) bis(2-methylacrylate) (GB 2,293,823), ((j6-pheny1-1,3,5-triazine-2,4-diyObis(3-hydroxy-4,1-phenylene))bis(oxy)) bis(undecane-11,1-diy1) bis(2-methylacrylate) (GB 2,293,823), (((6-pheny1-1,3,5-triazine-2,4-diyObis(3-hydroxy-4,1-phenylene))bis(oxy)) bis(undecane11,1-diy1) diacrylate (GB 2,293,823), (((6-phenyl-1,3,5-triazine-2,4-dias(3-hydroxy-4,1-phenylene))bis(oxy)This (hexane-2,1-diyi) bis(2-methylacrylate) (GB 2,293,823), (((6-phenyl-1,3,5-triazine2,4-dias(3-hydroxy-4,1-phenylenenbis(oxy)This (hexane-2,1-diy1) diacrylate (GB 2,293,823), (((1,3,5-triazine-2,4,6-triAtris(3-hydroxybenzene-4,1-diyintris(oxy))tris (1-butoxypropane-3,2-diyi) triacrylate (GB 2,293,823), a(1,3,5-triazine-2,4,6-triyOtris(3-hydroxybenzene-4,1-diy0)tris(oxyntris (undecane-11,1-diyi) triacrylate (GB 2,293,823), (((1,3,5-triazine-2,4,6-triyptris(3-hydroxybenzene-4,1-diyiptris(oxyntris (undecane-11,1-diyi) tris(2-methylacrylate) (GB 2,293,823), 6,6',6"-(1,3,5-triazine-2,4,6-triyOtris(3-((11-hydroxyundecyl)oxy)phenol) (GB 2,293,823), 6,6'-(6-pheny1-1,3,5-triazine-2,4-diyObis(3-((11-hydroxyundecyl)oxy) phenol) (GB 2,293,823), 2-(4-(2-hydroxypheny1)-6-pheny1-1,3,5-triazin-2-y1)-5-((11-hydroxyundecyl) oxy)phenol (GB 2,293,823), 2-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-51(3/4-yinylbenzyl)oxy) phenol (GB 2,293,823), 1-(4-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) -3-butoxypropan-2-y1 methacrylate (GB 2,293,823), 2-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-5-( (11-hydroxyundecyfloxy)phenol (GB 2,293,823), 11-(4-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) undecyl acrylate (GB 2,293,823), 11-(4-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) undecyl methacrylate (GB 2,293,823), 2-(4-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) ethyl methacrylate (GB 2,293,823), 1-(4-(4,6-bis(2,4-dimethylpheny1)-1,3,5-triazin-2-y1)-3-hydroxyphenoxy) hexan-2-ylmethacrylate (GB 2,293,823), (((6-mesity1-1,3,5-triazine2,4-diy1)bis(3-hydroxy-4,1-phenylene))bis(oxy)) his(hexane-2,1-diy1) bis(2-methylacrylate) (GB 2,293,823), (((6-mesity1-1,3,5-triazine-2,4-diy1)bis(3-hydroxy-4,1-phenylene))bis(oxy) )bis(1-butoxypropane-3,2-diy1) bis(2-methylacrylate) (GB 2,293,823), (((6-mesity1-1,3,5-triazine-2,4-diy1)bis(3-hydroxy-4,1-phenylene))bis(oxy) )bis(1-butoxypropane-3,2-diy1) diacrylate (GB 2,293,823), (((6-mesity1-1,3,5-triazine-2,4-diy1)bis(3-hydroxy-4,1-phenylene))bis(oxy) )bis(undecane-11,1-diy1) bis(2-methylacrylate) (GB 2,293,823), 6,6'-(6-mesity1-1,3,5-triazine-2,4-diy1)bis(3-01-hydroxyundecyBoxy)phenol) (GB 2,293,823), 5-(hexyloxy)-2-(4-(2-hydroxy-4-((11-hydroxyundecyBoxy)pheny1)-6-mesityl-1, 3,5-triazin-2-yOphenol (GB 2,293,823), 11-(4- (4-(4-(hexyloxy)-2-hydroxypheny1)-6-mesity1-1,3,5-triazin-2-y1) -3-hydroxyphenoxy)undecyl methacrylate (GB 2,293,823), 11-(4-(4-(4-(hexyloxy)-2-hydroxypheny1)-6-mesity1-1,3,5-triazin-2-y1) -3-hydroxyphenoxy)undecyl acrylate (GB 2,293,823), 6,61-(6-mesity1-1,3,5-triazine-2,4-diyObis(3-((3/4-vinylbenzyl)oxy)phenol) (GB 2,293,823), and related analogues of these named materials not specifically named themselves, for example methacrylate ester instead of acrylate ester or vice versa, methacrylamide instead of acrylamide or vice versa, and acrylate esters, methacrylate esters, acrylamides and methacrylamides that can made from any of the named materials bearing a terminal hydroxy or primary or secondary amino group under standard conditions described for many other materials in this disclosure. Method of Forming Composition According to a further aspect of the present invention, there is provided a method of forming the composition disclosed herein comprising: a) forming a mixture including the polymerisable monomer and the funtionalised dye, b) initiating partial polymerisation of the polymerisable monomer and co-polymerisation of, or reaction with, the functionalised dye c) adding an acid to the mixture, wherein the acid reacts with the product of step b) to form a water-soluble cationic polymer.

Typically, the cationic copolymer is diluted with water to create a polymer ink composition. Methods of initiating polymerisation of the co-monomers would be apparent to the skilled man, for instance thermal initiation, chemical initiation etc. According to one embodiment, polymerisation is initiated through the addition of initiator compounds. Generally, the initiation of polymerisation takes place in the presence of one or more cross-linking agents such as acrylic cross-linking agents.

Partial polymerisation is generally initiated through the use of free-radical generators and/or one or more cross-linking agents, in particular one or more acrylic cross-linking agents.

Generally, the monomers and, depending on the functional groups attached, the functional dye, are partially co-polymerised in the presence of a free-radical generator (such as 2,2'-azodi(2-methylbutyronitrile) Vazo 67) along with an acrylic cross-linker until a sufficient increase in solubility of the dye compound in the solvent has been achieved.

The extent of the partial polymerisation can be monitored by removing a sample from the mixture, stopping the polymerisation reaction, suitably through the addition of polymerisation inhibitors Any solvent is then removed, and the mixture is concentrated. An assessment of the extent of the polymerisation reaction can then be made.

The amount of acid to be added to the mixture depends on the identity and strength of the acid used. The addition of the acid leads to the formation of a cationic co-polymer from the co-polymerised first and second co-monomers. The cationic co-polymer is generally water miscible, typically having an associated water solubility of 40%w/w or more, typically 50%w/w or more at ambient temperature and pressure.

The amount of acid required can be determined by determining the appropriate molar ratios.

Generally the acid is added at a molar excess of over 1.1 molar equivalents based on the polymerisable monomer, suitably 1.2 to 1.5 molar equivalent, generally 1.2 to 1.4 molar equivalents, typically around 1.3 molar equivalents. According to one embodiment, the acid is glycolic acid.

According to one embodiment, 5 to 15 w/w% acid such as glycolic acid is added to acidify the co-polymerised mixture.

According to one embodiment the co-polymerisation is initially terminated by cooling the mixture to room temperature where the polymerisation rate is drastically slowed.

Upon sufficient partial co-polymerisation of the functionalised dye and after acidification of the resulting co-polymer, its water solubility increases, generally allowing the functionalised dye to become dissolved.

The further copolymerisation of the partially copolymerised mixture onto the textile or other substrate may be initiated through any suitable means. Mention may be made of chemical, thermal initiation and UV initiation.

The method may include the step of functionalizing the dye with one or more functional groups selected from acrylate (in particular methacrylate), alkene (in particular ethenyl) and allyl groups, prior to formation of the mixture.

The dye is generally functionalised prior to contact with the polymerisable monomer.

Following partial co-polymerisation and acidification, the aqueous mixture is generally a solution and may be in the form of a digital printing ink or maybe combined with further components to formulate a digital printing ink Method of Applying Colour to a Substrate According to a further aspect of the present invention, there is provided a method of colouring a substrate, in particular a textile including: providing the composition including the polymerisable monomer and the functionalised dye as described herein, partially polymerising the composition to form a partially polymerised composition, applying the partially polymerized composition to a surface of the substrate, and fixing the partially polymerized composition to the surface.

The partially polymerized composition may be fixed to the surface by initiating the further polymerization of the partially polymerized composition. Alternatively, silanols may be added to fix the partially polymerized composition to the surface. According to one embodiment, the partially polymerised surface may be dried off, with the inter-molecular forces being strong enough to adhere to the surface.

Generally, the polymerisable monomer and the functionalised dye are co-polymerised. Generally, the partially polymerised composition is reacted with an acid wherein the acid reacts with the resultant polymer to form a cationic polymer. The cationic polymer is generally water miscible.

Typically, the partially polymerised composition is diluted with water to create a polymer ink.

The method of colouring may be in the form of a method of printing, although reference may also be made to dyeing the substrate, for example through dip-dying or spray-dying.

The composition and methods of the present invention allow improved bonding of a dye onto the substrate which is particularly in the form of a textile.

Polymerisation is generally terminated before completion. The partially polymerised composition is fixed to the surface. Fixing may be through further polymerisation following application of the composition to the surface. The partially polymerised monomers bond to the textile surface during this further polymerisation step, ensuring dyeing thereof with good colour fastness, including good wash and rub resistance. Alternatively, or additionally, liquid may be evaporated from the partially polymerised composition after application to the surface, and this drying step may fix the partially polymerised composition to the surface.

Typically, the method of colouring includes the method of forming the composition disclosed herein.

Generally, the composition is in the form of an aqueous solution typically wherein the method is conducted entirely in the presence of an aqueous solvent. Typically, the composition is in the form of a polymer ink.

Generally, the partially polymerised composition is applied to the substrate in an aqueous solvent, suitably wherein the only solvent used is water; typically, wherein the method is conducted entirely in the presence of an aqueous solvent.

The partially polymerised composition is applied to the substrate, followed by fixing thereto. This may be through further polymerisation so as to produce a polymeric coating on the substrate (generally textile fibres). Alternatively, or additionally, this may be through drying of the composition after application to the substrate.

The substrate is generally in the form of a textile, including a natural or synthetic textile. Examples of synthetic textiles which may be treated in accordance with the invention are aramid, nylon, polyester or cotton. Thus, the treated textile fibres may include aramid, nylon, polyester fibres or cotton. The textile fibres may consist entirely of aramid fibres, or may comprise a mixture of aramid fibres and fibres of at least one other kind. The aramid fibres may be meta-aramid fibres and/or para-aramid fibres. Examples of suitable aramid fibres are Kevlar (RTM), Kermel (RTM) and Twaron (RTM). Examples of mixtures of aramid fibres with fibres of another kind or kinds include various mixtures of aramid fibres with viscose fibres, which may be flame retardant (FR) viscose fibres. Blends such as a 50% aramid/ 50% FR viscose mixture or a mixture of para-aramid, rayon and polybenzimidazole fibres may be used. The treatment of natural fibres is also in the scope of the invention.

Generally additional polymerisation or co-polymerisation of the partially polymerised composition is initiated thermally, or through chemical initiation. However, other types of initiation will be well known to one of ordinary skill in the art, for instance UV initiation, microwave induced polymerization and electrically induced polymerization. Initial co-polymerisation is generally initiated through chemical means, in particular chemical initiation, for instance a free-radical generator.

Typically, the partially co-polymerised mixture is applied to the substrate under conditions of elevated temperature and/or pressure and/or conditions of elevated temperature and/or pressure are applied to the substrate following application of the mixture.

As noted above, the polymerisation functionalised dye and polymerisable monomers generally requires less stringent initiation conditions than standard dyes. Accordingly, where polymerisation of the polymeric precursor is thermally initiated Specific Embodiments According to one embodiment there is provided a method of colouring textile fibres (generally a method of dying textile fibres or a method of printing onto textile fibres) including: i. providing a composition including a functionalised dye and a polymerizable monomer of the structure below;

NLNJN e H

initiating the partial co-polymerisation of the polymerizable monomer and the functionalised dye, generally through the addition of free-radical generators and cross-linking agents, allowing the polymerizable monomer and the functionalised dye to co-polymerise, adding a molar excess of acid to the composition to create an aqueous cationic co-polymer; applying the partially copolymerized mixture to the textile fibres, fixing the partially copolymerized mixture to the textile fibres, generally by initiating the further copolymerization of the partially copolymerized mixture, alternatively or additionally by evaporating liquid from the partially copolymerized mixture.

There is also provided a composition including a functionalised dye as described herein a polymerizable monomer of Formula A and an aqueous solvent. to (C s r b

Kit of Parts According to a further aspect of the present invention, there is provided a kit of parts for use in the treatment of textile fibres, in particular to promote the fixation of inks and dyes thereon. The kit is particularly useful in a method of digital printing. The kit of parts includes any of the compounds or compositions described herein and an applicator device such as a digital printer using an inkjet. The kit of parts generally includes instructions for use.

Generally, the kit includes instructions for use, for example the nature of application and the reaction conditions required to initiate polymerisation or co-polymerisation.

Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.

Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of the words, for example "comprising" and "comprises", mean "including but not limited to", and are not intended to (and do not) exclude other moieties, additives, components, integers or steps. All documents referred to herein are incorporated by reference.

Examples

The present invention will now be described by way of example only.

Unless stated otherwise, all chemicals are purchased from Sigma-Aldrich/Merck or Tokyo Chemical Industry UK Ltd at the highest grade possible and used without further purification.

The following abbreviations are used for materials: ASS = Compound of Formula (C) = 2,2'-((3-(Triethoxysily0propyl)azanediAbis(N,N-diallylacetamide) AcOH = Acetic acid CuPc = Copper phthalocyanine DCM = Dichloromethane DMAP = 4-(Dimethylamino)pyridine DMF = Dimethylformamide DMSO = Dimethylsulfoxide EDAC-HCI = N-Ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride Et0Ac = EA = ethyl acetate Et0H = Ethanol IMS = Industrial methylated spirit IPA = isopropanol Me0H = Methanol MiBK = Methyl isobutyl ketone = 4-Methyl-2-pentanone NMP = N-Methyl-2-pyrrolidone PA66 = Nylon 66 PET = Polyester textile THF = Tetrahydrofuran TMPTMA = Trimethylolpropane trimethacrylate V67 = Vazo 67 = 2,2'-Azobis(2-methylbutyronitrile) The following abbreviations are used for experimental reporting and analytical techniques: °C = degrees Celsius a/a = peak area ± total peak area, reported as % = Lambda max = Wavelength of maximum absorbance ES+ = Electrospray positive ion mode (in MS) ES-= Electrospray negative ion mode (in MS) GC = Gas chromatography GC-HS = Headspace gas chromatography GC-MS = Gas chromatography-Mass Spectrometry HPLC = High performance liquid chromatography HPLC-MS = High performance liquid chromatography-Mass spectrometry IR = Infra-red m.p. = Melting point MS = Mass spectrometry nm = nanometer NIR = Near infra-red NMR = Nuclear magnetic resonance (spectroscopy) TLC = Thin layer chromatography UV= Ultra-violet UV-vis = Ultra-violet-visible Example 1: Preparation of (phenylazanediy1)bis(ethane-2,1-diy1) diacrylate (Intermediate 1) Acryloyl chloride (358.4 g, 3.96 mol) was added dropwise to a solution of N,N-bis(2-hydroxyethyl)aniline (327.0g. 1.80 mol) in a mixture of toluene (2800 ml) and triethylamine (400.7g. 3.96 mol) at 0-5°C. The resultant suspension was stirred for 18 hours, filtered and the filtrates evaporated under reduced pressure to give 185.1 g (36%) of a yellow liquid, which was used without further purification. HPLC 90% (254 nm); 1H NMR (400 MHz, CDCI3) 8 ppm 3.71 (4H, t, 1=63), 4.37 (4H, t, 1=6.2), 5.87 (2H, d, J=10.4), 6.15 (2H, m), 6.41 (1H, s), 6.45 (1H, s), 6.76 (1H, t, J=7.2), 6.82 (2H, d, 1=8.2), 7.19-7.28 (2H, m). Example 2: Preparation of (phenylazanediyObis(ethane-2,1-diy1) bis(2-methylacrylate) (Intermediate 2) Prepared according to the method described in Example 1, using methacryloyl chloride in place of acryloy1 chloride. HPLC 89% (254 nm); 1H NMR (400 MHz, CDCI3) 6 ppm 1.97 (6H, s), 3.73 (4H, t, J=6.3), 4.37 (4H, t, J=6.2), 5.61 (2H, s), 6.13 (2H, s), 6.76 (1H, t, J=7.3), 6.84 (2H, d, J=8.3), 7.28 (2H, m).

Example 3: Preparation of 2-(ethyl(phenyl)amino)ethyl acrylate (Intermediate 3) Prepared according to the method described in Example 1, starting from 2-(N-ethylanilino)ethanol, using 1.1 mole equivalents of both acryloyl chloride and triethylamine. HPLC 92% (254 nm); 1H NMR (400 MHz, CDCI3) 5 ppm 1.28 (3 H, t, 1=7.1 Hz), 2.46(1 H, s), 3.51 (2 H, q, 1=7.0 Hz), 3.68 (2 H, t, 1=6.4 Hz), 4.42(2 H, t, 1=6.5 Hz), 5.91(1 H) dd, 1=10.4, 1.2 Hz), 6.23(1 H, dd, J=17.4, 10.4 Hz), 6.51(1 H) dd, 1=17.4, 1.2 Hz), 6.70 -6.90 (3 H, m), 7.35(2 H, m).

Example 4: Preparation of N,N-di(but-3-en-1-yl)aniline (Intermediate 4) 4-Bromo-1-butene (400.0g, 2.96mol) was added to a mixture of aniline (100.0g, 1.07mol) and sodium hydrogen carbonate (247.5g, 2.94mol) in NMP (500m1). The reaction mixture was stirred at 8789°C under nitrogen for 24 hours and then allowed to cool to ambient temperature. The resultant suspension was added to a mixture of water (1500m1) and heptane (500m1) and stirred until a solution was obtained. The aqueous phase was extracted with heptane (3 x 250m1) and then the combined organic extracts were washed with water (3 x 500m1) and dried (MgSO4). The solvent was evaporated under reduced pressure to give 218.7g (102%) of a dark amber liquid. Achieved mass over yield was attributed to residual NMP in the product and product was used without further purification; 1H NMR (400 MHz, CDCI3) 5 ppm 2.41 (4H, q, 1=7.1), 3.43 (4H, m), 5.16 (4H, m), 5.90 (2H, m), 6.73 (3H, m), 7.3 (2H, in).

Example 5: Preparation of N-(3-(di(oct-7-en-1-yl)amino)-4-methoxyphenyl)acetamide (Intermediate 5) A mixture of 8-bromo-1-octene (66.5 g, 0.348 mol), N-(3-amino-4-methoxyphenyl)acetamide (25.0 g, 0.139 mol), sodium bicarbonate (29.2 g, 0.348 mol) and NMP (125 ml) was heated at 90°C with stirring for 48 hours under nitrogen. The mixture was cooled and diluted with water (250 ml) then extracted with heptane (2 x 250 ml). The extract was dried (Mg504) and evaporated to a dark brown oil (68.0 g, 108%). Achieved mass over yield was attributed to residual NMP in the product and product was used without further purification. HPLC 95% (254 nm); 1H NMR (400 MHz, THF-d3) 8 ppm 1.18-1.55 (16 H, m), 1.98(3 H, s), 1.99 -2.10 (4 H, m), 2.98 -3.11 (4 H, m), 3.67 -3.79 (3 H, m), 4.78 -5.06 (4 H, m), 5.78(2 H, ddt) 1=17.0, 10.2, 6.8 Hz), 6.72(1 H) d, 1=8.6 Hz), 7.17(1 H) dd, 1=8.7, 2.4 Hz), 7.25 (1 H, d, 1=2.4 Hz), 8.83 (1 H, s). Example 6: Preparation of N-(3-(bis(4-hydroxybutyl)amino)-4-methoxyphenyl)acetamid (Intermediate 6)

OH OCH,

OH

A stirred mixture of 3'-amino-4'-methoxyacetanilide (18.0 g) 0.1 mol), 4-bromobutyl acetate (48.8 g, 0.25 mol), NMP (50 ml) and NaHCO3 (55.2 g, 0.66 mol) was heated at 105°C overnight, allowed to cool and was then poured into water (500 ml). After stirring for 30 minutes, the oil that separated was extracted with DCM (150 ml), the organic layer dried (MgSO4) and evaporated to a thick brown oil. The oil was dissolved in dioxane (200 ml) and 1M LiOH (300 ml) added. After 15 minutes, the reaction was neutralised with 35% FICI then evaporated to a brown oil (32 g, 100%). The crude product was used directly without purification. HPLC la 94% (254 nm); 1H NMR (400 MHz, CDCI3) 8 ppm 1.42 -1.58 (8 H, m), 2.11(3 H) s), 3.42(4 H, m), 3.63(4 H) m), 3.83 (3 H, s), 6.74(1 H, d, 1=8.7 Hz), 7.15(1 H, dd, 1=8.7, 2.5 Hz), 7.21 (1 H, d, 1=2.5 Hz), 8.83(1 H) s). Example 7: Preparation of ally! 3-(ethyl(phenyl)amino)propanoate (Intermediate 7) Prepared in accordance with the general method described for the synthesis of allyl esters in ACS Catalysis 2018, 8, 3016, starting from 3-(ethyl(phenyl)amino)propanoic acid. 1H NMR showed the sample contained residual DMF (8.6% by weight) and residual ethyl acetate (0.8% by weight); sample strength determined to be 90.6% by weight. The material was used without further purification, adjusting for strength accordingly; 1H NMR (400 MHz, CDCI3) 5 ppm 1.16 (3 H, t, 1=7.5), 2.65 (2 H, t, 1=7.0), 3.42(2 H, q, 1=7.5), 3.70(2 H, t, 1=7.0), 4.79 (2H) d, 1=5.0), 5.29 (1H, m), 5.43 (1H, dd, J=1.5,1=17.5), 6.01 (1H, m), 6.75 -7.05 (3H, m), 7.31 (2H) m).

HN

HN

Example 8: Preparation of diallyl 3,3'-(phenylazanediyOdipropanoate (Intermediate 8) o / Prepared in accordance with the general method described for the synthesis of allyl esters in ACS Catalysis 2018, 8, 3016, starting from 3,3'-(phenylazanediyfldipropanoic acid using 4 mole equivalents of K2CO3 and 2.4 mole equivalents of ally! bromide. 1H NMR showed the sample contained residual DMF (2.6% by weight) and residual DCM (1.0% by weight); sample strength determined to be 96.4% by weight. The material was used without further purification, adjusting for strength accordingly; 1H NMR (400 MHz, CDC13) 6 ppm 2.62 (4 H, t, 1=7.0), 3.76(4 H, t, 1=7.0), 4.77 (4H, d, 1=5.0), 5.27 (2H, m), 5.44 (2H, m), 6.02 (2H, m), 6.77 (2H, m), 6.94 (1H, m), 7.35 (2H, m).

Example 9: Preparation of vinyl 3-(ethyl(phenyl)amino)propanoate (Intermediate 9) o o) Prepared by modification of the method described in US 2013/0184423. 3-(Ethyl(phenyl)amino)-propanoic acid (13.3 g, 0.0686 mol) was dissolved in vinyl acetate (300 m1). With stirring, KOH (85% powder, 0.46g. 0.007 mol) and 1,4-benzoquinone (0.15 g, 0.0014 mol) were added. Pd(OAc)2 (0.15 g, 0.0007 mol) was added and the mixture was stirred and warmed at 25°C overnight. The mixture was filtered through celite (10 g), which was washed with EA (100 ml). The combined filtrates were washed with saturated NaHCO3 solution (2 x 200 ml) then brine (100 ml), dried over Mg504 (30 g) and evaporated to a red-brown oil. The oil was dissolved in DCM and filtered through a pad of silica gel (40-63 II, 100 g), eluting with DCM. The elute was concentrated to a viscous light brown oil (11.8 g, 89%); 1H NMR (400 MHz, CDCI3) 6 ppm 1.18(3 H, t, 1=7.5), 2.68(2 H, t, J=7.0), 3.44(2 H, q, 1=7.5), 3.66(2 H, t, 1=7.0), 4.59 (1H, dd,J=1.5, 1=10.0), 4.87 (1H, dd,J=1.5,J=17.0), 6.70 -7.05 (3H, m), 7.20 -7.41 (3H, m).

Example 10: Preparation of divinyl 3,3c(phenylazanediyUclipropanoate (Intermediate 10) Prepared by the method described for Example 9 from 3,3'-(phenylazanediyOdipropanoic acid (16.3 g, 68.6 mmol), vinyl acetate (300 ml Pd(OAc)2 (0.15 g, 0.0007 mol), 1,4-benzoquinone (0.15 g, 0.0014 mol) and KOH (0.92 g, 0.014 mol); brown oil (12.5g, 63%); 1H NMR (400 MHz, CDC13) 6 ppm 2.64(4 H, t, 1=7.0), 3.79(4 H, t, J=7.0), 4.56 (2H, d, 1=10.0), 4.88 (2H, d, 1=17.0), 6.79 (2H, m), 6.95 (1H, m), 7.25 -7.40 (3H, m). Example 11: Preparation of N-(4-(N,N-bis(2-hydroxyethyl)sulfamoyl)phenyl)acetamide (Intermediate 11) HO 0,

NH

II

/il 0 HO N-Acetylsufanilyl chloride (100.0g. 0.43 mol) was added in portions to a solution of diethanolamine (49.5g. 0.47 mol) in water (300 ml) at 50°C, also adding Na2CO3 portionwise to maintain pH 7.0. The pH was then adjusted to 8.5 with Na2CO3 and stirred at 50°C for 3 hours. NaCI (10% w/v) was added to the hot reaction and once dissolved, the mixture was allowed to cool. The resultant solid was collected by vacuum filtration, washed with 5% brine (2 x 50 ml) on the filter and dried in a vacuum oven at 30°C for 72 hours to provide Intermediate 11 as a white solid (102.8 g, 80%). HPLC 99.8% (260 nm); 1H NMR (400 MHz, DM50d6) 8 ppm 2.09 (3H, s), 3.12 (4H, t, J=6.3), 3.50 (4H, q, J=6.0), 4.84 (2H, t, J=5.4), 7.76 (4H, m), 10.41 (1H, s). Example 12: Preparation of N-(4-(N,N-bis(2-hydroxypropyl)sulfamoyl)phenyl)acetamid (Intermediate 12)

HO

Diisopropanolamine (29.3 g, 0.22 mol) was stirred at 60°C under nitrogen while N-acetylsulfanilyl chloride (23.4 g, 0.1 mol) was added over 2 minutes allowing the reaction to exotherm to 120°C. The resultant viscous mixture was heated overnight at 80°C. Water (100 ml) was added and the mixture wamred until the deposited gum dissolved. After sitrring for 48 hours at ambient temperature, the resutant suspended solid was filtered-off, washed with ice-cold water and crystallised from boiling water (80 ml) to give Intermediate 12 as a white crystalline solid (19.9g. 60%). Mp = 168-170°C; 1H NMR (400 MHz, DM50d6) 5 ppm 1.06, (6H, m), 2.08 (3H, s), 3.19 (4H, m), 3.42 (4H, m), 4.67 (2H, br. s), 7.74 (4H, m), 10.38 (1H, s). Example 13: Preparation of 6-hydroxy-1-(3-hydroxypropyI)-4-methyl-2-oxo-1, 2-dihydropyridine-3-carbonitrile (Intermediate 13)

NC

OH

A mixture of 3-aminopropanol (22.5 g, 0.3 mol), water (25 ml), ethyl cyanoacetate (11.3g, 0.1 mol) and ethyl acetoacetate (13.01 g, 0.1 mol) was stirred at 100°C overnight. On cooling, conc. HCI was added to pH 3 and the resulting solid was filtered-off, washed with water followed by ethyl acetate and dried to give Intermediate 13 (17.0g, 81%); m.p. 202-204°C; 1H NMR (400 MHz, DMSO-d6) 6 ppm 1.95 (2H, m), 2.68 (3H, s), 2.99 (2H, m) 3.55 (2H, m), 4.88 (1H, t, J=5.5), 5.77 (1H, s), 11.80 (1H, br. s).

Example 14: Preparation of N-(3-(bis(2-hydroxyethyl)amino)phenyl)butyramide (Intermediate 14)

OH

HN OH

A mixture of N-(3-(bis(2-hydroxyethyDamino)phenypacetamide (10.0g. 42 mmol), water (40 ml) and 37% HCl (12.5 ml) was heated to reflux overnight then evaporated. The residue was dissolved in water (100 ml) and neutralized with CaCO3. Butyric anhydride (13.3 g, 84 mmol) was added dropwise, maintaining pH 4-7 with NaHCO3solution. 2M NaOH was added to raise to pH 12, stirred 1 h, then the oily mixture was extracted with DCM (100 ml). The DCM was dried (MgSO4) and evaporated to an oil, which was purified by silica gel chromatography eluting with an increasing gradient of EA in DCM. Evaporation afforded Intermediate 14 as an oil that crystallised on standing (8.8 g, 79%). HPLC a/a 98% (254 nm); 1H NMR (400 MHz, CDCI3) 8 ppm 0.93 (3H, t, 1=7.3), 1.55 (2H, m), 2.39 (2H, t, 1=6.8), 3.33 (4H, t, 1=6.3), 3.71 (4H, q, 1=6.3), 4.55 (2H, br. s), 6.71 (1H, m), 6.84 (1H, m), 7.05 (1H, m), 7.18 (1H, m), 10.22 (1H, s).

Example 15: Preparation of N-ethyl-N-phenylethane-1,2-diamine (Intermediate 15) iNH2 Prepared according to US 3,711,546; HPLC ala 95%; 1H NMR (400 MHz) CDCI3)ö ppm 1.15-1.25(5 H, m), 2.94(2 H, t, 1=6.7), 3.38(2 H, t, J=6.7), 3.44(2 H) q, 1=7.3), 6.71 (1 H, m), 6.76(2 H, m), 7.25(2 H, m). Example 16: Preparation of 1-(2-(ethyl(phenyl)amino)ethyl)-1H-pyrrole-2,5-dione (Intermediate 16) Prepared according to Macromol. Chem. Phys. 1995, 196, 243, HPLC a/a 97% (254 nm); 1H NMR (400 MHz, DMSO-d6) 5 ppm 1.06 (3 H, t, J=7.0 Hz), 3.30(2 H, q, 1=7.1 Hz), 3.38 -3.44 (2 H, m), 3.53 -3.59 (2 H, m), 6.55 -6.61 (1 H, m), 6.68(2 H, d, J=8.1 Hz), 6.99(2 H) s), 7.11 -7.17 (2 H, m).

Example 17: Preparation of N-(2-aminoethyl)-N-phenylethane-1,2-diamine (Intermediate 17) NH2 NH2 Prepared according to Chem. Mater. 2006, 18, 4713; HPLC a/a 95%; 1H NMR (400 MHz, CDCI3) 5 ppm 1.23(4 H, br. s), 3.11(4 H) t,1=6.7), 3.41(4 H, t, 1=6.7), 6.72(1 H) m), 6.77(2 H, m), 7.25 (2 H, m).

Example 18: Preparation of ((4-((2-cyano-4-nitrophenyl)diazenyl)phenyl)azanediAbis(ethane-2,1-diy1) diacrylate (Dye 1) A 40% solution of nitrosyl sulfuric acid (33.4 g, 0.105 mol) in sulfuric acid was added dropwise to a suspension of 2-amino-5-nitrobenzonitrile [diazo] (16.3 g) 0.100 mol) in a mixture of acetic acid (65 ml) and propionic acid (25 ml) at 0-5C. The resultant yellow solution was stirred for 2 hours at 0-5°C and then added dropwise to a solution of Intermediate 1 [coupler] (28.9 g, 0.100 mol) in Me0H (300 ml) at 0-5'C. The resultant dark red suspension was stirred for 18 hours at ambient temperature, water (300 ml) was then added and the solid collected by filtration and washed with water (2 x 500 ml). The crude product was recrystallized from a mixture of DCM and Me0H and dried under vacuum at ambient temperature to give Dye 1 as a black powder (23.4 g, 51%); Amax= 508 nm (acetone); HPLC a/2 95% (540 nm); 1H NMR (400 MHz, CHLOROFORM-d) 3 ppm 3.86 (4H, t, J=6.1), 4.45(4K, t, J=6.1), 5.90 (2H, d, J=10.5), 6.15 (2h1, m), 6.45 (2h1, m), 6.94 2H, d, 1=9.2), 8.02 (3H, m), 8.46 (1H, dd, J=9.1), 8.64 (1H, d, J=2.1).

Example 19: Preparation of (N,N-di(but-3-en-1-yI)-4-((2-nitrophenyl)diazenyl)aniline (Dye 2) NO2 A mixture of 2-nitroaniline [diazo] (15.4 g, 85.6 mmol), water (310 ml) and 37% HCl (23.5 g, 300 mmol) was stirred and heated until all solid dissolved, then cooled to <5°C to give a thick slurry. A solution of sodium nitrite (6.20g. 89.9 mmol) in water (62 ml) was added and the reaction stirred for 10 minutes, until all 2-nitroaniline was consumed by TLC indicating diazotisation was complete. Excess nitrous acid was quenched by the addition of 1% sulfamic acid solution (50 ml) then the mixture was filtered to give a bright yellow solution, removing a small amount of insoluble black tar. In a separate vessel was charged Intermediate 4 [coupler] (18.1 g, 89.9 mmol) and Me0H (425 ml), and the solution was stirred with cooling to 5°C. The diazonium salt solution was added dropwise over 1 hour maintaining a reaction temperature of < 7°C throughout through external cooling, resulting in a thick orange slurry. After a further 3 hours of stirring at 5-12°C, the solid was filtered-off and washed with water and air-dried overnight. The solid was purified by filtration through silica gel as a DCM solution then recrystallisation from DCM/Me0H to give, after drying at 40°C under vacuum, Dye 2 as an orange solid (30.0 g, 62%); Amax = 444 nm (Et0Ac); HPLC ala 99% (254 nm); m.p. 61-63°C; 1H NMR (400 MHz, CHLOROFORM-d) 8 ppm 2.41(4 H, q, 1=7.1 Hz), 3.39 -3.55 (4 H, m), 5.07 -5.19 (4 H, m), 5.85 (2 H, ddt, 1=17.1, 10.2, 6.9 Hz), 6.64 -6.78 (2 H, m), 7.38 -7.49 (1 H, m), 7.57 -7.67 (1 I-I, m), 7.68 -7.76 (1 H, m), 7.79 -7.94 (3 H, m).

Example 20: Preparation of N-(5-(di(oct-7-en-1-yl)amino)-4-methoxy-2-((4-nitrophenyl)diazenyl)phenyl) acetamide (Dye 3) 02N ocH:

HN \ -

A mixture of 4-nitroaniline [diazo] (8.58 g, 62.2 mmol), water (935 ml) and 37% HCI (21.4 g, 217 mmol) was stirred and heated until all solid dissolved, then cooled to <5°C to give a thick slurry. A solution of sodium nitrite (4.42 g, 64.0 mmol) in water (45 ml) was added and the reaction stirred for 10 minutes, until all 4-nitroaniline was consumed by TLC indicating diazotisation was complete. Excess nitrous acid was quenched by the addition of 10% sulfamic acid solution (3 ml). In a separate vessel was charged Intermediate 5 [coupler] (28.0 g, 62.2 mmol), sodium acetate trihydrate (42.3 g, 311 mmol) and Me0H (925 ml), and the mixture was stirred with cooling to 5°C. The diazonium salt solution was added dropwise over 2 hours maintaining a reaction temperature of < 7°C throughout through external cooling, resulting in a thick slurry. After a further 2 hours of stirring at <5°C, the solid was filtered-off and washed with water. The solid was triturated in IMS (270 mol), filtered-off and washed with further IMS (30 ml). Drying at 40°C under vacuum gave Dye 3 as a dark green solid (23.2 g, 62%); kma" = 543 nm (EA); HPLC a/a 98% (254 nm); 1H NMR (400 MHz, CDCI3) 6 ppm 1.10-1.49 (12 H, m), 1.60 -1.75 (4 H, m), 2.05(4 H, q, J=6.7 Hz), 2.28(3 H, s), 3.32 -3.52 (4 H, m), 3.87(3 H, s), 4.94(2 H, d, J=10.1 Hz), 5.00(2 H, dd, J=17.1, 1.5 Hz), 5.81(2 H, ddt, J=17.1, 10.1, 6.7 Hz), 7.33(1 H, s), 7.83(2 H, d, J=8.9 Hz), 8.18(1 H, s), 8.34(2 H, d, J=8.9 Hz), 10.17(1 H, br. s.). Example 21: Preparation of 44(5-cyano-1-ethy1-2-hydroxy-4-methyl-6-oxo-1, 6-dihydropyridin-3-yndiazeny1)-N,N-bis(2-hydroxyethyl)benzenesulfonamide (Dye 4)

CN

A mixture of sodium hydroxide (12.0 g, 0.30 mol) and Intermediate 11 [diazo] (15.1 g, 0.05 mol) in water (150 ml) was stirred at 80°C for 2 hours and then cooled to 0°C. To this mixture at 0°C, was added concentrated hydrochloric acid (45 ml) followed by the dropwise addition of a solution of sodium nitrite (3.6 g, 0.05 mol) in water (15 ml). The resultant orange solution was stirred for 30 minutes at 0-5°C and then added dropwise to a solution of 1-ethy1-6-hydroxy-4-methy1-2-oxo-1,2-dihydropyridine-3-carbonitrile [coupler] (8.9 g, 0.05 mol) in a mixture of IMS (135 ml), acetone (135 ml), NMP (50 ml) and water (200 ml) at 0-5'C. The resultant bright yellow suspension was stirred for 18 hours at ambient temperature and then the solid was collected by filtration and washed with water (3 x 200 ml). The solid was dried under vacuum at 30°C for 48 hours to give Dye 4 as an orange powder (20.1 g, 93%). HPLC a/a 95% (420 nm); Xinaa = 425 nm (acetone); 1H NMR (400 MHz, DMSO-d6) 8 ppm 1.14 (3H, t, J=7.1), 2.53 (3H, s), 3.17 (4H, t, 1=6.4), 3.51 (4H, t, 1=6.3), 3.88 (2H, q, 1=7.0), 7.88 (4H, m) 14.42 (1H, s).

Example 22: Preparation of 6-hydroxy-54(4-(2-hydroxyethyflphenyl)diazeny1)-1-(3-hydroxypropyl) -4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (Dyes) Sodium nitrite (0.69 g, 0.01 mol) was added to a stirred, ice cold, solution of 4-aminophenethyl alcohol [diazo] (1.37 g, 0.01 mol) in ice cold dilute hydrochloric acid. After 30 min diazotisation was complete and excess nitrous acid was destroyed by adding a small amount of sulphamic acid. Intermediate

HO

13 [coupler] (2.08 g 0.01 mol) was added as a solid and coupling was allowed to proceed at pH 2.0-2.5. After coupling was complete, the resultant yellow solid was collected, washed with water and dried to give Dye 5 as a yellow powder (3.6 g, 100%). Amax = 437 nm (Me0H).

Example 23: Preparation of N-(5-(bis(4-hydroxybutyl)amino)-24(2-bromo-6-cyano-4-nitrophenyl)diazeny1) -4-methoxyphenypacetamide (Dye 6)

CN OH OCH3

02N N/ Br HN -ThOH Sulfuric acid (80% w/w, 75 ml) was cooled to 5°C and 6-bromo-2-cyano-4-nitroaniline [diazo] (9.7 g, 40 mmol) was added and stirred for 10 minutes at <5°C until fully dispersed. Nitrosyl sulfuric acid 40% (w/w) in sulfuric acid (15.3 g, 0.048 mol) was added in portions at 3-5°C, then stirred for 1h at <5°C. Intermediate 6 [coupler] (13.6 g, 42 mmol) was diluted with Me0H (100 ml), cooled to 5°C and solid ice (50 g), water (50 ml) and 10% sulfamic acid solution (10 ml) were added. The above diazonium salt solution was added dropwise over 1h, maintaining at pH 3.5-4.5 by adding solid sodium bicarbonate. The reaction was stirred overnight, then the solid filtered-off and dried overnight at 40°C (13.4 g, 50%). The crude product was recrystallised from DCM and Me0H to give Dye 6 as a green crystalline solid (12.7 g, 55%). it," = 603 nm (acetone); HPLC ala 99% (254 nm); 'H NMR (400 MHz, CDCI3) 5 ppm 1.38 -1.65 (8 H, m), 2.21(3 H, s), 3.47(4 H, m), 3.62(4 H, m), 3.82 (3 H, s), 7.57 (1 H, s), 8.36(1 H, s), 8.48(1 H, d, J=1.0 Hz), 8.59 (1 H, d, J=1.0 Hz), 10.16(1 H, s.). Example 24: Preparation of N-(5-(bis(4-hydroxybutyl)amino)-2-((2,6-dicyano-4-nitrophenyl)diazeny1) -4-methoxyphenyl)acetamide (Dye 7) 02N

OH

HN \OH A mixture of Dye 6(7.5 g, 13.0 mmol), zinc cyanide (0.82 g, 7 mmol) and copper(I) cyanide (40 mg, 0.45 mmol) in NMP (15 ml) was heated to 100°C for 4h. External heating was removed and Me0H (45 ml) was added slowly to the hot reaction, allowing to reflux and gradually cool. The resultant crystalline solid was filtered-off and washed with Me0H (100 ml) on the filter. The solid was stirred for 1 hour in 0.2 N HCI (200 ml), filtered-off, washed with water then Me0H on the filter and dried. The solid was boiled in toluene (100 ml) for 5 mins then allowed to cool to ca. 50°C before filtering-off. The solid was recrystallised from DCM/Et0H, to provide Dye 7 as a violet-green crystalline solid (5.5 g, 81%); Amax = 648 nm (acetone); HPLC a/a 99% (254 nm); 1H NMR (400 MHz, CDCI3) 8 ppm 1.38 -1.66 (8 H, m), 2.22(3 H, s), 3.49(4 H, m), 3.64(4 H, m), 3.86 (3 H, s), 7.49 (1 H, s), 8.30(1 H, s), 8.68(2 H, s), 10.01(1 H, br. s.).

Example 25: Preparation of N-(5-(bis(2-hydroxyethyl)amino)-24 (4-cyano-3-methylisothiazol-5-yndiazenyl)phenyl)butyramide (Dye 8)

OH

ON N'8

HN OH

>-C31-17 A stirred suspension of 5-amino-3-methylisothiazole-4-carbonitrile [diazo] (4.9 g, 35 mmol) in a mixture of acetic acid (25 ml) and propionic acid (100 ml) was cooled in an ice bath and diazotized by the addition of 40% nitrosylsulfuric acid (7.0 ml, 41 mmol) at 0-5°C to give a brown solution of diazonium salt. In a separate vessel, Intermediate 14 [coupler] (9.3 g, 35 mmol) was dissolved in Me0H (50 ml) with stirring, then 10% sulfamic acid solution (10 ml) and crushed ice (50 g) were added. The diazonium salt solution was added dropwise to the coupler solution over 20 minutes, adding further small portions of ice, such that some was present throughout the addition. After stirring for 30 minutes, the pH was increased to 4 by the addition of ammonium hydroxide, keeping temperature < 10°C by adding further solid ice. The resultant dark violet solid suspension was stirred overnight. The solid was collected by vacuum filtration and washed copiously on the filter with hot water until the filtrates ran colourless and neutral. Drying afforded a dark violet solid (11.8 g, 81%). The dried solid was purified by Soxhlet extraction with IPA (150 ml), then allowing to crystalise at ambient temperature, to give Dye 8, after isolation and drying under vacuum at 40°C, as violet-bronze crystals (7.0 g, 48%). Xmax = 546 nm (Et0Ac); HPLC ala 99.6% (550 nm). Example 26: Preparation of 2,2c1[4-[2-12,5-diethoxy-4-12-(4-nitrophenyl)diazenyl]phenyl]cliazenyl] -3-methylphenylpmino]bis-ethanol (Dye 9) OEt 0,14 / /OH

DO

OH

Step 1-2,5-Diethoxy-4-((4-nitrophenyl)diazenyl)aniline: 4-Nitroaniline (6.9 g, 0.050 mol) was suspended in water (150 ml) and 35% HCI (17.3 g, 0.165 mol) added. To this was added a solution of sodium nitrite (3.6 g, 0.053 mol) at 0-5°C. Once all solid had dissolved, excess nitrous acid was destroyed by adding sulfamic acid and the solution added dropwise to solution of 2,5-diethoxyaniline (9.4 g, 0.052 mol) in water (300 ml) containing 35% HCI (6.0 g, 0.057 mol). The resultant suspension was stirred overnight, filtered-off, washed copiously with water and dried. The dried solid was crystallised from ethyl cellosolve (400 ml), collected by filtration, washed with IMS and dried to a fine red crystalline solid (15.4g. 93%).

Step 2-Dye 9: 2,5-Diethoxy-4-((4-nitrophenyl)diazenyl)aniline (3.3 g, 10 mmol) was stirred in NMP (45 ml) and warmed to 60°C to dissolve. The solution was then cooled with stirring to 5°C to give a thick precipitate. 40% Nitrosylsulfuric acid (3.2 g, 10 mmol) was added dropwise causing all solid to dissolve, then reprecipitate. Stirring was continued for a further 2 hours at room temperature. In a separate vessel, m-tolyldiethanolamine (1.95 g, 10 mmol) and sulfamic acid (0.5 g) were dissolved in a mixture of butanol/water, and the prepared diazonium salt solution was added. The mixture was stirred overnight, allowing to warm to room temperature. The resultant black solid was filtered-off and dried in a vacuum oven at 40°C. The solid was purified by dissolving in ethyl cellosolve (200 ml) at 100°C then adding water (100 ml) dropwise. On cooling, a precipitate formed, which was filtered-off, washed with water, 1MS and dried to give Dye 9 a fine blue-black solid (2.9 g, 54%). Xrnax = 560 nm (Et0Ac); HPLC 99.6% (550 nm).

Example 27: Preparation of 2,2'1(2-((4-(diortylamino)-2-methylphenyl)diazeny1)-5-((4-nitrophenyl) diazeny1)-1,4-phenylene)bis(oxy))diethanol (Dye 10) (OH 0 0,N p61-117 bel-117 HO-r° Step 1-((2-amino-5-((4-nitrophenyl)diazeny1)-1,4-phenylene)bis(oxy)This (ethane-2,1-diy1) diacetate: 4-Nitroaniline (6.9 g, 0.05 mol) was suspended in dilute HCI and to this was added a solution of sodium nitrite (3.6 g, 0.053 mol) at 0-5°C, pH < 1. Excess nitrous acid was destroyed sulfamic acid and the solution added dropwise to solution of 2,2'-(2-amino-1,4-phenylene)bis(oxy)bis(ethane-2,1-diy1) diacetate (EP 1,147,153) in aqueous acetone. The resultant orange suspension was stirred overnight at ambient temperature and the solid filtered-off, washed with water and aqueous 1MS, then recrystallised from ethyl cellosolve, washing the isolated red solid with 1MS and drying at 40°C (16.0 g, 72%), mp = 197-200°C.

Step 2-Dye 10: 2,2'-(2-Amino-5-((4-nitrophenyl)diazeny1)-1,4-phenylene)bis(oxy)bis (ethane-2,1-diyl) diacetate (4.5 g, 10 mmol) was stirred in NMP (45 ml) and warmed to 60°C to dissolve. The solution was then cooled with stirring to 5°C to give a thick fine precipitate. Nitrosylsulfuric acid (40% w/w) (3.2 g, 10 mmol) was added dropwise causing all solid to dissolve, then stirred for a further 1.5 h warming slowly to 40°C. N,N-Dioctyl-m-toluidine (3.3 g, 10 mmol) (WO 2013/127494) and sulfamic acid (0.5 g) were dissolved in a mixture of acetone and 1MS and to this was added ice/water, causing a fine suspension to form. The prepared diazonium salt solution was then added and the mixture stirred o/n allowing to warm to room temperature The black solid was filtered-off and dried (6.4 g, 81%) then dissolved in THE (100 ml) with stirring for 5 minutes. To this solution was added 1N LiOH (25 ml, 25 mmol) and the reaction was stirred at ambient temperature overnight. Acetic acid (5 ml) was added followed by water (150 ml) which caused on oil to separate. After stirring for lh, the oil had solidified. Solid was filtered-off and washed with water (500 ml). The solid was crystallised from DCM (200 ml) by addition of Me0H (300 ml) and allowing to evaporate overnight to a final volume of co 100 ml. The resultant black micro-crystalline solid was filtered-off and washed with Me0H (30 ml). Pulled dry under vacuum then dried for 2 h in a desiccator (2.1g, 54%). The material was used directly without further purification.

Example 28: Preparation of 2,2'1(44(4-((2,4-dinitrophenyl)diazeny1)-2,5-bis((2-ethylhexyl)oxy)phenyl) diazeny1)-3-methylphenyflazanediyUdiethanol (Dye 11) 02N 4-((2,4-Dinitrophenyl)diazeny1)-2,5-bis(2-ethylhexyloxy)aniline (WO 2013/127494) (0.54g. 1 mmol) was dissolved in NMP (10 ml) and to this was added 40% (w/w) nitrosyl sulfuric acid in sulfuric acid (0.38 g, 1.2 mmol) allowing the mixture to exotherm. After 30 minutes, the mixture was added to a solution of 2,2'-(m-tolylazanediy1)diethanol (0.20 g, 1 mmol) and sulfamic acid (0.5 g) in 74 0.P IMS (100 m1). A dark oily solid separated which was extracted into DCM, dried (MgSO4) and purified over silica gel, eluting with DCM containing an increasing concentration of ethyl acetate. Evaporation provided Dye 11 as a black oil that solidified on standing (0.54 g, 72%). Amax = 595 nm (Et0Ac).

Example 29: 2-((44(2-aminoethyl)(ethyflamino)phenyl)diazeny1)-5-nitrobenzonitrile (Dye 12)

CN

02N \-Th NH, A 40% solution of nitrosyl sulfuric acid (33.4g. 0.105 mol) in sulfuric acid was added dropwise to a suspension of 2-amino-5-nitrobenzonitrile [cliazo] (16.3 g, 0.100 mol) in a mixture of acetic acid (65 ml) and propionic acid (25 ml) at 0-5C. The resultant yellow solution was stirred for 2 hours at 0-5°C, sulfamic acid (0.2 g) was added and stirred 15 minutes before adding dropwise to a solution of Intermediate 15 [coupler] (16.4 g, 0.100 mol) in Me0H (300 ml) at 0-5'C. The resultant dark red suspension was stirred for 1 hour, allowing to warm to room temperature. Water (500 ml) was then added causing a solid to separate. The mixture was stirred for 1 hour then the solid was collected by filtration and washed with water (100 ml). The filter cake was re-suspended in water (500 ml) and adjusted to pH 9 by adding 2M NaOH, stirred 1 hour, then filtered-off, washed on the filter with water (2 x 100 ml) and dried in a vacuum oven at 35°C. THE crude product was recrystallized from a mixture of THF and toluene by slow distillation of THF from the mixture on a rotary evaporator, then cooling of the resultant suspension in an ice bath before collecting the crystallised solid by vacuum filtration. Drying in a vacuum oven at 35°C afforded Dye 12 as a black powder (22.1g. 65%); Xma"= 537 nm (acetone); 1H NMR (400 MHz, DMSO-d6) 8 ppm 1.15 (3H, m), 2.77 (2H, m), 3.46 (2H, m), 3.57 (2H, m), 6.98 (2H, m), 7.88 (3H, m), 8.47 (1H, m), 8.79 (1H, br. s).

Example 30: Preparation of N-(5-(bis(2-hydroxyethyl)amino)-2-((2-chloro-4-nitrophenyl)diazenyl) phenyl)acetamide (Dye 13)

OH CI Cl

N N 02N N

AcHN OH Disperse Red 167:1 (50.6 g, 0.1 mol) was dissolved in THF (500 ml), 1 M LiOH (300 ml) was added and the mixture stirred vigorously overnight to ensure thorough mixing of the phases. The phases were separated and the organic layer was washed with brine then dried (MgSO4) and evaporated. The residue was triturated with Me0H until a red solid suspension was formed. The solid was collected by vacuum filtration, washed with Me0H on the filter and dried in a vacuum oven at 45°C to afford Dye 13 as a dark red powder (40.1g. 95%); Xma"= 518 nm (IMS).

Example 31: Preparation of N-(5-(bis(2-hydroxyethynamino)-2-((2-chloro-4,6-dinitrophenyl)diazeny1) -4-methoxyphenypacetamide (Dye 14) 02N NO, Prepared from Disperse Blue 79:1 according to Example 30; Xr","= 608 nm (acetone).

Further azo-dyes, listed in Table 1, were synthesised according to the Method stated, wherein the coupler and diazo in the indicated Method were replaced instead by those shown in the Table. Dye Amax measured in acetone, unless stated otherwise.

-re e 1 Example Dye Number Dye structure Coupler Diazo Method as for: Xmas/mu Example Dye 15 0 Intermediate 2 2-amino-5- Example 18 509 32 ON. nitrobenzo N nitrile 02N It N Example Dye 16 CN 4e. ,--/- Intermediate 4 2-amino-5- Example 18 533 33 02N It \-\_ nitrobenzo nitrile Example Dye 17 OH 2-(Ethyl 2-amino-5- Example 18 534 34 CN it phenylamino) Et0H nitrobenzo N nitnle 02N N * Example Dye 18 OTh 2-(2-(ethyl(m- 2-amino-5- Example 18 535 CN tolyl)amino) nitrobenzo N HO) ethoxy)ethanol nitrile 02N. N it Bioconj.Chem.2017, Example Dye 19 OH 3-(ethyl(phenyl) 2-a mino-5- Example 18 538 36 ON it amino)propane-1,2- nitrobenzo N OH dial nitrile 02N 1, N WO 2009/003867 Example Dye 20 OH N-Phenyl di etha nol 2-a mino-5- Example 18 533 37 ON. amine nitrobenzo N nitrile 02N. NOH Example Dye 21 OH 1,1'-(phenylazane 2-a mino-5- Example 18 536 38 ON diy1)bis(propan-2-ol) nitrobenzo N * N nitrile 02N * N

H

Example Dye Number Dye structure Coupler Diazo Method as for: Xnexiss, 39 Dye 22 Example Intermediate 9 2-amino-5- Example 18 523 ON * C nitrobenzo 02 * bi \-\Or nitrile Example Dye 23 ON * C Intermediate 16 2-a mino-5- Example 18 522 02N * N] N nitrobenzo 0....- nitrile Example Dye 24 NH2 Intermediate 17 2-amino-5- Example 29 539 41 ON nitrobenzo N nitrile 02N. N * NH2 Example Dye 25 CN * C Intermediate 7 2-a mino-5- Example 18 520 42 / nitrobenzo Oil * N nitrile Example Dye 26 ON * Intermediate 8 2-amino-5- Example 18 508 43 N nitrobenzo 02N * N nitrile Example Dye 27 ON * C Intermediate 9 2-amino-5- Example 18 519 44 02N tlik /- nitrobenzo 0 nitrile Example Dye 28 CH * Intermediate 10 2-amino-5- Example 18 506 * N r}cf= nitrobenzo 02N o/= nitrile Example Dye 29 OH m-tolyl 2-amino-5- Example 18 547 46 ON * diethanolamine nitrobenzo N nitrile 02N If N OH Example Dye 30 OH 2,2'-(((m-tolylazanediyl) bis(ethane-2,1- diyI))bis(oxy)) 2-a mino-5- Example 18 549 47 0 j- di ethanol nitrobenzo CN * WO 2009/087034 nitrile

N

011 st N -\ -OH 48 Dye 31 Example N-[3-[Bis(2- 2-amino-5- Example 18 555 OH hydroxyethyl)a mine nitrobenzo ON N * N] phenybacetamide nitrile 011 it ''HN OH Example Dye 32 0 N,N-Diethylaniline N-(3-Amino Example 20 414 49 HN phenyl)-2' N e N'- propenamide \_ Example Dye 33 0 N,N-Diethylaniline N-(4-Amino Example 20 413 N li C phenyl) k maleimide I N lik Example Dye 34 N It TM C N,N-Diethylaniline 4-(Allyloxy) Example 20 434 51 O (gp \_ aniline Example Dye 35 OH m-tolyl 2-Amino-6- Example 25 558 52 0 hi, NN * N diethanolamine nitrobenzo 02N S OH thiazole Example Dye Number Dye structure Coupler Diana Method as for: Example Dye 36 OH m-tolyl 2-Amino-6- Example 25 547 53 N diethanolamine thiocya no 00 N. ill * benzothiazole Nos 5 oH Example Dye 37 OH m-tolyl 2-Amino-6- Example 25 545 54 0 l' FIN it N diethanolamine s (methyl ulfonyl) H,CO,S S OH benzothiazole Example Dye 38 OH m-tolyl 2-Amino-S- Example 25 599 N N It N diethanolamine nitrothi a zole 1,-N' 02N S OH Example Dye 39 OH N-Phenyldiethanol 3,5-Dinitro Example 25 632 56 NO2. amine thioph en-2-N amine

I N

02N S OH Example Dye 40 NO, OMer e 02N $ AcHN 3,5-Dinitro Example 25 672 (EA) N *N N [3 (Di 2 propen 1-ylamino)-4-methoxyphenyl] acetamide thioph en-2-amine Example Dye 41 CN 2-Ethylhexyl Intermediate Example 21 425 58 HO pyridone 11 N- iti \ (US 2004/0007155) N__ \HO 0 C/ HO Example Dye 42 CN 1-Butyl-6-hydroxy4 methyl 2 oxo 1,2 dihyd ropyri dine-3-carbonitrile Intermediate Example 21 425 59 HO - 11 \--\S to " \

N-

HOC' 6 HO Example Dye 43 ON 1-Butyl-6-hydroxy4-methyl-2-oxo-1,2-dihyd ropyri dine-3-carbonitrile Intermediate Example 21 426 (EA) HO 12 --)-\ 9 \ 0 N-h if N

HO

Example Dye 44 CN Intermediate 13 3,4-Dichloro aniline 427 61 ClCl _ Example 22 (THE) It N HO \ r°H Example Dye 45 OMe OH 3'-[Bis(2- 2-Bromo-4,6- Example 18 606 62 NO2 hydroxyethyl) dinitroaniline N. N amino]-41-methoxy 02N1 It El acetanilide

OH Br

Example Dye 46 NO2 m-tolyl 3-Amino-5nitro-2,1-benziso thiazole Example 25 619 63 40 NActHN N diethanolamine

OH

N-s OH Example 64: Preparation of 3-(ethyl(44(5-nitrobenzo[c]isothiazol-3-yDdiazenyflphenyl)amino) propanoic acid (Intermediate 18) 1M LiOH (250 ml) was added to a stirred solution of Disperse Blue 148 (41.3 g, 0.1 mol) in 1,4-dioxane (1200 ml) causing some dye to precipitate. The mixture was stirred vigorously overnight at 40°C to give a deep blue solution, which was filtered to remove insoluble particles and acidified to pH 2 with cHCI. The resultant blue solid was filtered-off under vacuum, washed neutral with water then dried overnight in a vacuum oven at 70°C to afford Intermediate 18 (34.3 g, 87%); 1H NMR (400 MHz, CDCI3) 6 ppm 1.30 (3H, t, I = 7.5 Hz), 2.68 (2H, t, I = 7.0 Hz), 3.61 (2H, q, I = 7.5 Hz), 3.79 (2H, t, 1 = 7.0 Hz), 6.84 (2H, d,J= 9.0 Hz), 7.77 (1H, d, 1=9.5 Hz), 7.99 (2H, d, J= 9.0 Hz), 8.21 (1H, dd, 1=2.0, 9.5 Hz), 9.21 (1H, d, 1=2.0).

Example 65: Preparation of 3,3'1(4-((2-bromo-6-chloro-4-nitrophenyl)diazenyl) phenypazanediyUclipropanoic acid (Intermediate 19) CI /CO21-I 02N -ThCO2H Br Disperse Brown 19 was hydrolysed according to Example 74 using twice the volume of 1M DOH. Example 66: Preparation of 2-((acryloyloxy)methyl)-2-(((3-(ethyl(4-((5-nitrobenzo[c]isothiazol-3-yl) diazenyl)phenyl)amino)propanoypoxy)methyl)propane-1,3-diyldiacrylate (Dye 47)

NC CYCk °

Intermediate 18(4.0 g, 0.010 mol), pentaerythritol triacrylate [coupling partner] (3.6 g, 0.012 mol) and DMAP (0.12g. 0.001 mol) were dissolved in DCM (200 ml) and EDAC-HCl (2.3 g, 0.012 mol) was added. The mixture was stirred for 48 hours then washed twice with 0.01 M HCl, water, brine, then dried (Mg504). The organic layer was evaporated and the residue purified by silica chromatography eluting with an increasing concentration of EA in DCM. The product enriched fractions were pooled and evaporated, and the resulting semi-solid was triturated with Me0H to give a blue solid, which was filtered-off, washed with Me0H on the filter and dried under vacuum to give Dye 47 as a dark blue powder (3.3 g, 49%); krra" = 592 nm (acetone); 1H NMR (400 MHz, CDCI3) 6 ppm 1.30 (3H, t, I = 7.5 Hz), 2.68 (2H, t, I = 7.0 Hz), 3.61 (2H, q, I = 7.5 Hz), 3.79 (2H, t, 1 = 7.0 Hz), 4.19 (2H, s), 4.25 (6H, s), 5.93 (3H, m), 6.14 (3H, m), 6.44 (3H, m), 6.84 (2H, d, J= 9.0 Hz), 7.77 (1H, d, 1=9.5 Hz), 7.99 (2H, d, I= 9.0 Hz), 8.21 (1H, dd, 2.0, 9.5 Hz), 9.21 (1H, d, 1=2.0).

Example 67: Preparation of 2,3,4-trihydroxybutyl 3-(ethyl(44(5-nitrobenzo[c]isothiazol-3-yOdiazenyl)phenyl)amino)propanoate (Dye 48) Prepared according to Example 66 except pentaerythritol triacrylate was replaced with mesoerythritol (10 mole eq.), DCM was replaced with THE and the reaction was worked up by washing with 2 x 0.01 M HCI containing 15% w/w NaCI, then 5 times with 15% w/w NaCI to remove excess meso-erythritol. No further purification was done; kmax = 592 nm (acetone).

Further azo-dyes, listed in Table 2, were synthesised according to Example 66, starting from either Intermediate 18 or Intermediate 19 using the specified coupling partner in place of pentaerythritol triacrylate. Where Intermediate 19 was the starting material, twice the amount DMAC*HCI was used. Dye Xmax measured in acetone.

Example Dye Number Dye structure Coupling Partner Example 68 Dye 49 S N If C 1-(63-yHrryodireoxzsiedxioyInhe1H- 593 1 0,.... (Bioconj. Chem. 2015, 26, N 2554) N o Example Dye 50 S N. C PE 1-(6-Aminohexyl)-1H- 592 69 H pyrrole-2,5-dione IIII 0 (Bioconj. Chem. 2019, 30, \/ 0 253) " N-Example Dye 51 N'S N le C 1-(6-Hydroxyhexyl)-3,4- 593 I dimethy1-1H-pyrrol e-2,5- 0 dione 0 ---. U520030096265 N \ / o Example Dye 52 I N \ 0 Glycerol DI methacrylate 593 71 -0-161 FC12-0 IP 0 NO2 Example Dye 53 S N It C 4-Hydroxybutyl acrylate 593 72 110 0 \ Example Dye 54 S N 2-(2-Hydroxyethoxy) ethyl 593 73, It C acrylate 0 (Polym. Chem. 2019, 10, Jr° 5778) N 0 1-% Example Dye 55 CI 0 2 2-Hydroxyethyl acrylate 420 74 N N (CH2)2 02N lit N it -%-.--\ \ Br 0 \ Example Dye 56 CI 0 2-Hydroxyethyl 420 02N a N" *N (CF12)2- methacrylate Br °"1 o Example Dye 57 ci _ 2 N-(2-Hydroxyethyl) 421 76 N*N o maleimide 02N aIf o)\---Br (0-12)2- j-N I 1 -1)T o Example 77: Preparation of 2-((4-((2-cyano-4-nitrophenyl)diazenyl)phenyl)(ethyl)amino)ethyl methacrylate (Dye 58)

CN 02N

To a solution of Dye 17 (17.0g. 50 mmol) in DCM (204 ml) was added methacryloyl chloride (5.8 g, 55 mmol) followed by dropwise addition of triethylamine (9.6 g, 95 mol) at <35°C. After stirring overninght at room temperature, the mixture was filtered through a small pad of Celite® 545 and concentrated in vacuo to ca. 100 ml. The concentrated solution was filtered through a small pad of silica gel, eluting with DCM until the elute was pale red. Concentration of the elute provided a dark green oil, which was crystallised from DCM (100 ml) and Me0H (100 ml) by slow removal of DCM on a rotary evaporator, until a thick slurry had formed. After stirring in an ice bath for 1 hour, the solid was collected by vacuum filtration, and washed with ice cold Me0H (25 ml). Drying provided Dye 58 as dark blue crystals (15.9 g) 78%). X,"a" = 524 nm (acetone); HPLC 98% (520 nm); 'H NMR (400 MHz, CHLOROFORM-d) 6 ppm 1.30(3 H) t, J=7.0 Hz), 1.95(3 H, s), 3.59(2 H, q, J=7.0 Hz), 3.78 (2 H, t, J=6.1 Hz), 4.40(2 H, t, J=6.1 Hz), 5.61 (1 H, s), 6.12(1 H, s), 6.84(2 H, d, J=9.0 Hz), 7.90 -8.07 (3 H, m), 8.41(1 H) dd,J=9.0, 1.6 Hz), 8.59(1 H) d, J=1.6 Hz).

Example 78: Preparation of N-(2-((4-((2-cyano-4-nitrophenyl)diazenyl)phenyl)(ethyl)amino)ethyl) acrylamide (Dye 59) To a mixture of Dye 12(3.4 g, 10 mmol) and N,N-diisopropylethylamine (2.1 ml) 12 mmol) in DCM (85 ml) at 0°C was added acryloyl chloride (1.0 g, 11 mmol). After 1 hour, the reaction was filtered and the filtrates washed with dil. HCI, dried (Mg504) and evaporated. The material was recrystallised from DCM and Me0H, to provide Dye 59 as a violet solid (2.7 g, 69%). Xmax = 529 nm (acetone); HPLC a/a 99.6% (500 nm). Example 79: Preparation of N-(24(4-((2-cyano-4-nitrophenyl)diazenyl)phenylflethyDamino)ethyl) propiolamide (Dye 60) 02N Prepared according to Example 78 except acryloyl chloride was replaced with 2-propynoyl chloride (Bioorg. Med. Chem. Lett. 2015, 25, 3975). X,"a" = 529 nm (acetone); HPLC a/a 98.9% (500 nm).

Example 80: Preparation of (((44(5-cyano-l-ethy1-2-hydroxy-4-methyl-6-oxo-1, 6-dihydropyridin-3-yndiazenyl)phenyl)sulfonyl)azanediyObis(ethane-2, 1-diy1) diacrylate Dye 61) Dye 4(9.5 g, 21.1 mmol) was stirred in DCM (120 ml) at 35°C. N,N-Dimethylaniline (7.7 g, 63.4 mmol) was added followed by acryloyl chloride (5.8 g, 63.4 mmol), allowing to exotherm to reflux then held at reflux. After 4 hours, HPLC showed all starting material had been consumed and <1% by area of monoacrylate remained. The reaction was filtered and the filtrates were washed with dilute HCl, dried over magnesium sulfate and evaporated. The material was purified over silica gel eluting with an increasing gradient of EA in DCM. Product enriched fractions were evaporated to dryness and the solid was recrystallised from DCM and Me0H, to provide Dye 61 as a yellow powder (4.48 g, 71%). Xnia" = 425 nm (acetone); HPLC a/a 99.6% (254 nm); 1H NMR (400 MHz, CHLOROFORM-d) 5 ppm 1.26 (3H, t, 1=7.0), 2.63 (3H, s), 3.55 (4H, t, 1=5.9), 4.05 (2H, q, 1=7.1), 4.34 (4H, t, 1=5.9), 5.86 (2H, d, 1=10.5), 6.09 (2H, dd, 1=17.3, 1=10.5), 6.44 (2H, d, 1=17.3), 7.57 (2H, d, 1=8.7), 7.91 (2H, d, 1=8.7), 14.93 (1H, s).

Example 81: Preparation of (4((2-cyano-4-nitrophenyl)diazenyl)phenyl)azanediyIbis(ethane-2,1-diy1) dipropiolate (Dye 62) Prepared from Dye 20 according to Example 80 except acryloyl chloride was replaced with 2-propynoyl chloride (Bioorg. Med. Chem. Lett. 2015, 25, 3975). Xr," = 509 nm (acetone).

Example 82: Preparation of 2-((4-((2-chloro-4-nitrophenyl)diazenyl)phenyl)(ethyl)amino)ethyl acrylate (Dye 63) CI 0 To a stirred mixture of Disperse Red 13 (10.0 g, 29 mmol) and N,N-dimethylaniline (4.0 ml, 43 mmol) in DCM (100 ml) at 35°C, was added acryloyl chloride (3.5 ml, 43 mmol), allowing to exotherm to reflux then held at reflux. After 4 hours, the reaction was filtered, the filtrates washed with dil. HCI, dried (MgSO4) and evaporated. The material was purified over silica gel eluting with an increasing gradient of EA in DCM. Product enriched fractions were evaporated and the solid recrystallised from DCM and Me0H, to provide Dye 63 as a red solid (7.6 g, 65%). Amax = 480 nm (toluene); HPLC aia 99.4% (525 nm); 1H NMR (400 MHz, CDCI3) 8 ppm 1.28 (3 H, t, 1=7.1 Hz), 3.57(2 H, q, 1=7.1 Hz), 3.75(2 H, t, 1=6.3 Hz), 4.40(2 H, t, 1=6.3 Hz), 5.88(1 H, dd, J=10.4, 1.2 Hz), 6.08 -6.20 (1 H, m), 6.44(1 H, dd, 1=17.3, 1.2 Hz), 6.84(2 H, d, 1=9.2 Hz), 7.79(1 H, d, 1=8.9 Hz), 7.96(2 H, d, 1=9.2 Hz), 8.17(1 H, dd, 1=8.9, 2.4 Hz), 8.41 (1 H, d, J=2.4 Hz).

Example 83: Preparation of (((44(1-buty1-5-cyano-2-hydroxy-4-methy1-6-oxo-1, 6-dihydropyridin-3-yndiazenyl)phenyl)sulfonyl)azanediyObis(ethane-2, 1-diy1) bis(2-methylacrylate) (Dye 64)

CN

Methacrylic anhydride (12.3g, 75 mmol) was added to a solution of Dye 42 (11.9g, 25 mmol) in pyridine (110 ml) at 65°C and stirred overnight. The reaction was allowed to cool, then water (5m1) was added. After standing overnight the precipitated material was filtered-off, IMS (150 ml) was added to the mother liquor and allowed to stand 1h to precipitate further material, which was also filtered-off. The combined solids were purified over silica gel, eluting with 95:5 toluene:acetone. The product enriched fractions were pooled and concentrated in vacuo to ca 80 ml, causing precipitation of a solid, which was redissolved by heating to the boil. The solution was allowed to stand overnight and the resultant crystalline solid filtered-off, washed with a small portion of cold toluene and dried to give Dye 64 as a crystalline orange solid (6.0g, 39%). M.p. 177-179°C; Xmax = 424 nm (EA) 424nm; 1H NMR (400 MHz, CDCI3) 5 ppm 0.95 (3H, t,1=7.0), 1.30-1.70(4H, m), 1.90 (6H, s), 2.65 (3H, s), 3.55 (4H, t, 1=5.9), 3.95 (2H, t, /=7.1), 4.30(4H, t, 1=5.9), 5.55 (2H, s), 6.05 (2H, s), 6.44 (2H, d,1=17.3), 7.55 (2H, d,1=8.7), 7.90 (2H, d,1=8.7), 14.95 (1H, s). Example 84: Preparation of 4-((5-cyano-2-hydroxy-1-(3-(methacryloyloxy)propy1)-4-methy1-6-oxo-1, 6-dihydropyridin-3-yOdiazenyl)phenethyl methacrylate (Dye 65) Methacrylic anhydride (4.63 g, 0.03 mol) was added to a stirred solution of Dye Sin pyridine (36 ml) at 65°C. After 4 hours, further methacrylic anhydride (1.54 g, 0.01 mol) was added and stirring continued at 65°C for another 16 hr. The solution was cooled and water was added dropwise until the mixture became cloudy, then stirred for 3 hr. The precipitated solid was filtered-off, washed with water and dried. The crude product was purified over silica gel, eluting with an increasing gradient of DCM in hexane (60 to 80%). Product enriched fractions were pooled and evaporated, and the obtained material was re-crystalised from DCM/n-propanol by slow evaporation of DCM to yield Dye 65 as a yellow solid (2.50 g, 50%). M.p. 133-135°C; Amax 439nm (Me0H);1FINMR (400 MHz, CHLOROFORM-d) 8 ppm 1.90 (6H, s), 2.05 (2H, m), 2.60 (3H, s), 3.05 (2H, m), 4.10 (2H, m), 4.20 (2H, m), 4.35 (2H, m), 5.55 (2H, 2 x overlayed s), 6.08 (1H, s), 6.10 (1H, s), 7.35 (2H, m), 7.45 (2H, m), 15.05 (1H, s).

Example 85: Preparation of ((2-((4-(dioctylamino)-2-methylphenyl)diazeny1)-5-((4-nitrophenyl) diazeny1)-1,4-phenyleneThis(oxy))bis(ethane-2,1-diy1) diacrylate (Dye 66) o

HO

P8F117 baNi7 A mixture of Dye 10(3.5 g, 5.0 mmol), K2CO3 (2.6 g, 18.8 mmol) and 3-chloropropionyl chloride (3.8 g, 30 mmol) in DCM (40 ml) with stirring and warmed in an oil bath at 35°C overnight, then for a further 72 h at ambient temperature. Water (10 ml) and NaHCO3 (co 1 g) were added (aq. layer pH 7) and stirred for lh. The organic layer was separated, dried (MgSO4) and evaporated. The crude product was purified over a silica gel, eluting initially with DCM, which eluted the required product (bis-chloropropionyl ester), retaining the slower running mono-ester. The pure fractions were evaporated to a black oil, which was solidified by triturating with Me0H overnight. The solid was filtered-off, pulled dry to give a black solid. After drying overnight in a desiccator, the solid and 2,6-di-t-butylphenol (5 mg) were dissolved in DCM (20 ml) and triethylamine (1.16 g, 11.5 mmol) was added. The reaction was shaken to mix then stood overnight. The reaction was washed with 0.01M HCl (20 ml), dried (Mg504) and evaporated. The residue was re-dissolved in DCM (10 ml) and Me0H (50 ml) was slowly added with stirring. The precipitate was filtered-off, washed with Me0H and dried in a desiccator to provide Dye 66 as a black powder (3.0g, 75%.). Ima" (EA) 565 nm; HPLC: 100% (550 nm); 1H NM R (400 MHz, CDCI3) 5 ppm 0.95 (3H, t,1=7.0), 1.25 -1.45 (20H, m), 1.65 (4H, m), 2.75 (3H, s), 3.40 (3H, t, 1=6.1), 4.48 (4H, m), 4.65 (4H, m), 5.85 (2H, dd, 1=1.2,1=10.5), 6.15 (2H, dd, /=10.5, 1=17.3), 6.40-6.60(4H, m), 7.48 (1H s), 7.57 (1H, s), 7.80(1H, d,1=8.8), 8.05 (2H, d, J=8.9), 8.41 (2H, d, J=8.9). Example 86: Preparation of ((44(2-cyano-4-nitrophenyl)diazenyflphenyl)azanediyObis(ethane-2,1-diy1) bis((3-(triethoxysilyl)propyl)carbamate) (Dye 67) HN Si(OCH2Chi3)3 CN /-/ 0 02N FIN-/ \ Si(OCH2Chlah 0-' Dye 20 (7.1 g, 20 mmol) was dissolved in THF (71 ml) and 3-(triethoxysilyppropylisocyanate (10.9g. 44 mmol) was added followed by a drop of dibutyltin dilaurate. After stirring overnight at room temperature, TLC showed complete consumption of the starting material. The solution was evaporated, the reside redissolved in DCM (200 ml) at 30°C and filtered through a short pad of Celite 545 to remove insoluble material. Evaporation gave Dye 67 as a dark red powder (13.1 g, 77%); = 524 nm (EA).

Example 87: Preparation of 2,2'-(4-((4-(2,4-dinitrophenyl)diazeny1)-2,5-bis(2-ethylhexyloxy)phenyl) diazeny1)-3-methylphenylazanediyObis(ethane-2,1-diy1) diacrylate (Dye 68) 02N A mixture of Dye 11 (3.5 g, 5 mmol), NaHCO3 (12.6 g, 0.15 mol) and 3-chloropropionyl chloride (1.9 g, 15 mmol) in DCM (50 ml) was stirred and heated at 40°C overnight. The solid was filtered-off, the filtrate was evaporated and the resultant oil was solidified by adding IMS (3.7 g). A 2.7 g portion of the solid was dissolved in DCM (50 ml) and Et3N (0.9 g, 8.7 mmol) added. The mixture was heated at 30°C overnight and a solid was precipitated by adding IMS. The solid was recrystallised from hot IMS and Dye 68 was isolated as a violet/black powder (1.6 g, 65%); m.p 128-130°C, Ama" (EA) 574nm; 1H NMR (600 MHz, CDCI3) 5 ppm 0.83 -0.93(6 H, m), 0.98(6 H, q, J=7.3 Hz), 1.29 -1.66 (18 H, m), 1.80 -1.93 (2 H, m), 2.76(3 H, s), 3.81(4 H, t, J=6.1 Hz), 4.05 (2 H, d, 1=5.9 Hz), 4.14(2 H, d, 1=5.8 Hz), 4.42 (4 H, t, 1=6.1 Hz), 5.88 (2 H, dd,J=10.5, 1.2 Hz), 6.14 (2 H, dd,J=17.3, 10.5 Hz), 6.44(2 H, dd,1=17.3, 1.2 Hz), 6.66 -6.73 (2 H, m), 7.37 (1 H) s), 7.41 (1 H, s), 7.83 (1 H, d, 1=8.8 Hz), 7.88(1 H, d,1=8.8 Hz), 8.50(1 H, dd, 1=8.8, 2.4 Hz), 8.80(1 H, d,1=2.4 Hz).

Further azo-dyes, listed in Table 3, were synthesised according to the Method Example stated, where the Precursor Dye in the indicated Method Example was replaced instead by the Precursor Dye stated in the Table. Where the synthesis of the Dye stated in the Table is not exemplified herein, then these materials are commercially available. Dye Amax was measured in acetone, unless stated otherwise.

Tab]e 3 Example Dye Number Dye Structure Precursor Dye Method as for: Example Dye 69 CN 0 2 Dye 7 Example 90 644 88 ocH3r (CH2)40 02N a N a NI*N

CN AcHN

Example Dye 70 Dye 3 Example 90 532 89 ON (EA) I CI °

N \_..\ HN 0

-C3H3 o o Example Dye 71 ON Dye 44 Example 87 426 Cl 0 N 0, < Cl i * HO Example Dye 72 o ON _ Dye 41 Example 90 424 91 **\ 0 (EA) N-# o/il HO Example Dye 73 0E1 Dye 9 Example 95 544 92 02N. 7-C (EA) N a N

N

Et0 \-\o_r

T

Example Dye Number Dye Structure Precursor Dye Method as for: Lim inm Example Dye 74 CN 02N * N * Ch 0 Dye 18 Example 92 534 93 \Tho_r Example Dye 75 02N CNN * N _ Dye 21 Example 90 515 94 It N CH2CH(CHa)0 Example Dye 76 0o- Dye 19 Example 90 524 CR it N _o)_ c _, c 02N. N_ Example Dye 77 0 Dye 29 Example 90 523 96 CN * -

N

02N * N p -I\ Example Dye 78 02N CNN. N Dye 30 Example 90 548 97 IF N \-0 Example Dye 79 0 Dye 31 Example 90 531 98 0-_

CN

0 N * NI Nit N AcHN _c0_ Example Dye 80 ON 7-c° - Dye 6 Example 90 602 99 OCH3 / NI 02N a N 4 N Br \Th HN \ 0 Example Dye 81 OEt Dye 9 Example 93 545 0- 011 11 N le ff it

N

DO

Example Dye 82 \\ 4) N. NC Ind. Eng. Chem. Example 78 422 101 0 It N" \ _ Res. 2019, 58, Example Dye 83 7_74: Dye 35 Example 80 533 102 0 IV N,N a 02N S s= E xample Dye 84 0 0-/ Dye 36 Example 80 523 103 c /C N\ rt * \ _Th NOS S 0 Example Dye 85 r_i_c0 Dye 37 Example 80 520 104 0 N' Nlyi a \_Th RaCO2S S 0 0/ s= if Example Dye Number Dye Structure Precursor Dye Method as for: Xi,/nm Example Dye 86 0 Dye 38 Example 83 576

CI

-N \-\ 0 02N_{E N N * 0-/ Example Dye 87 0 Dye 39 Example SO 608 106 NO2 * ,

N 0,N

Example Dye 88 C Disperse Red 1 Example 77 456 107. N. 02N Example Dye 89 or Disperse Red Example SO 456 108 N. 17 02N * " \-\ 0 0-c= Example Dye 90 0 Dye 45 Example 83 582 109 CM: NO2 *

N N

02N It N. AcHN o Br 0 Example Dye 91 0 Dye 46 Example 80 594 cf0-_ N'S PI t I \-.., 0 11110 / NO2 Example Dye 92 N_s N. ft - Dye 48 Example 93 593 111 N Using 4 mole 111/ 0 Ot le 0 equivants of ooNf..0- -0 0 o methacrylic :\>\ -\( anhydride Example 112: Preparation of 2((4-(diethylamino)phenyl)diazeny1)-5-nitrobenzonitrile (Dye 93, Comparative Negative Control Dye Example) Prepared according to the above method for Dye 1, where Intermediate 1 was replaced with N,Ndiethylaniline. Dye 112 was obtained as a dark green powder (16.0g. 50%); Xmaa= 535 nm (acetone); HPLC ala 97% (560 nm); 1H NMR (400 MHz, CDCI3) 8 ppm 1.29 (6H, t, 1=7.1), 3.53 (4H, q, 1=7.1), 6.74 (2H, d,1=9.2), 7.96 (3H, d,1=9.0), 8.39 (1H, m), 8.57 (1H, m).

Example 113: Preparation of N-butyl-3-hydroxy-44(2-hydroxy-4-nitrophenyndiazeny1)-N-(2-hydroxyethyl) -2-naphthamide (Intermediate 20) Step 1-N-Butyl-3-hydroxy-N-(2-hydroxyethyl)-2-naphthamide: Thionyl chloride (6.54g, 0.055 mol) was added drop-wise to a stirred suspension of 3-hydroxy-2-naphthoic acid (9.4 g, 0.05 mol) in toluene (15 ml), then heated for 90 minutes at 55°C, evaporated in vacuo, and the residue co-evaporated twice with toluene. Toluene (75 ml) was added to the residue (11 g) followed by 2-(butylamino)ethanol (17.6 g, 0.015 mol) and the mixture was stirred at 75°C for 90 minutes, allowed to cool and acidifed with cHCI. Solid was collected, washed with cold water and dried (11.0 g, 77%); m.p. = 137-139°C; ES-m/z 286, 100% ([M-1-11-).

Step 2-Intermediate 20: 2-Amino-5-nitrophenol (1.54 g, 0.01 mol) was diazotized with 2M NaNO2 solution in a mixture of ice/water (25 ml) and 35% hydrochloric acid (5 ml). The diazonium salt suspension was added slowly to a cold stirred suspension of N-butyl-3-hydroxy-N-(2-hydroxyethyl)-2-naphthamide (3 g, 0.0104 mol) at pH >9. The mixture was stirred at pH 9 and room temperature for 16 hr. Solid was filtered-off, washed with cold water and dried to yield Intermediate 20 as a deep red-brown solid (3.5 g, 77%). Example 114: Preparation of N-butyl-3-hydroxy-44(2-hydroxy-5-nitrophenyndiazeny1)-N-(2-hydroxyethyl) -2-naphthamide (Intermediate 21) Prepared according to Example 113, except 2-amino-4-nitrophenol was used in place of 2-amino-5-nitrophenol.

Example 115: Preparation of sodium bis[3-hydroxy-4-[(2-hydroxy-4-nitrophenyflazo]-N-butyl-N-(2-hydroxyethyl) -2-naphthalenecarboxamidato(2-)] chromate(1-) (Dye 94) Na.

Intermediate 20(3.5 g, 7.7 mmol) and chromium(III) acetate hydroxide (1.0 g, 1.7 mmol) were heated at reflux in a mixture of water (50 ml) and ethoxyethanol (50 ml) for 16 hours. The pH was increased from pH 5 to 7 with 1M Na2CO3 and refluxing continued for a further 18 hours. The dye solution was filtered and diluted with water to separate Dye 94 as black tar (3.6 g, 95%); Amax (Me0H) 585 nm.

Example 116: Preparation of sodium bis[3-hydroxy-4-[(2-hydroxy-4-nitrophenyl)azol-N-butyl-N-(2-hydroxyethyl) -2-naphthalenecarboxamidato(2-)] chromate(1-) bis-methacrylate ester (Dye 95) Na' A mixture of Dye 94(3.5 g, 3.67 mmol), pyridine and methacrylic anhydride (2.27g. 14.7 mmol) was stirred at 55°C for 18 h, then cooled and water was added. The separated tar was dissolved in a minimum volume of DCM, passed through silica gel, eluting with 2% IPA in DCM, and the coloured elute evaporated to give Dye 95 as a blue-black tar (2.1 g, 53%); Xmax (Et0Ac) 603 nm; ES-rniz 1088, 100% ([M-Nat).

Example 117: Preparation of sodium bis[3-hydroxy-4-[(2-hydroxy-5-nitrophenyflazol-N-butyl-N-(2-hydroxyethyl) -2-naphthalenecarboxamidato(2-)] chromate(1-) (Dye 96) Nat Prepared according to the procedure described in Example 115, except Intermediate 20 was replaced with Intermediate 21. Dye 96 was isolated as a black solid (94%); 1),,a" (Me0H) 569 nm. Example 118: Preparation of sodium bis[3-hydroxy-4-[(2-hydroxy-5-nitrophenyl)azo]-N-butyl-N-(2-hydroxyethyl) -2-naphthalenecarboxamidato(2-)] chromate(1-) bis-methacrylate ester (Dye 97) Ne Prepared according to the procedure described in Example 116, except Dye 94 was replaced with 96 124. Dye 97 was isolated as a black tar (63%); ltrna" (EA) 375, 442, 570 nm; ES-miz 1088, 100% UM-Nat). Example 119: Preparation of chrome complex mixture (Dye 98) 0 o HO Cr 0 / NO, Na+ Prepared according to the procedure described in Example 115, except 50 mole% of Intermediate 20 was replaced with 50 mole% of Intermediate 21; isolated as a black solid (95%); Amax (Me0H) 575 nm. Example 120: Preparation of chrome complex mixture bis methacrylate ester (Dye 99) Na Prepared according to the procedure described in Example 116, except Dye 94 was replaced with Dye 98. Dye 99 was isolated as a tarry-solid (55%); Amax (Et0Ac) 379, 573 nm; ES-m/z 1088, 100% QM-Na]). Example 121: Preparation of CuPc tetra(N,N-bis(2-hydroxyethyl)sulfonamide) (Dye 100) CuPc H(S02N(CH2CH20H2)4 Copper phthalocyanine tetrasulfonyl chloride wet paste, prepared from copper phthalocyanine (14.4g, 25 mmol) according to US patent 6,456,845, was added in portions over 10 minutes to a solution of diethanolamine (52.6 g, 500 mmol) in water (150 ml) with stirring. After stirring for 30 minutes at ambient temperature, the mixture was heated at 60°C for 6 hours, diluted to 1 L total volume and salted to 25% w/v with NaCI at 60°C. After cooling to room temperature, the resultant solid was filtered-off then re-dissolved in water (500 ml) at 50°C. The solution was transferred to visking tubing and dialysed for 2 hours until the waste water was <50 LtS/cm conductance. The solution was poured into a glass dish and dried down in a fan-assisted oven at 60°C to give Dye 100 as a dark purple solid (20.3g, 65%); Xmax = 670 nm (DMF). Example 122: Preparation of CuPc tetra(N-butyl-N-(2-hydroxyethyl)sulfonamide) (Dye 101) CuPc (SO2N(C4H9)CH2CH2OH)4 Prepared according to the procedure described in Example 121, except 2-(butylamino)ethanol was used in place of diethanolamine. Dye 101 was isolated as a dark purple solid; Xrndx= 671 nm (DMF). Example 123: Preparation of CuPc bis(N,N-dibutylsulfonamide) bis(N-butyl-N-(2-hydroxyethyl)sulfonamide) (Dye 102) (SO2N(C4H9)2)2 -ISO2N(C4H9)CH2CH2OH)2 Copper phthalocyanine tetrasulfonyl chloride wet paste, prepared from copper phthalocyanine (2.9 g, 5 mmol) according to US patent 6,456,845, was suspended with stirring in water (250 ml) at room temperature. 2-(Butylamino)ethanol (1.3 g, 11 mmol) was added, the pH rising toll, and the reaction mixture stirred at room temperature for 5 h, during which time the pH dropped slowly to 9. Dibutylamine (2.6 g, 20 mmol) was added and the mixture was stirred at room temperature overnight. Further di-nbutylamine was added drop wise until the pH was 10 and the reaction was then stirred at 40°C for 3 h. The product was collected by filtration, washed with cold water and then stirred consecutively in hot 0.1 N caustic soda solution, hot 0.1 N HCI and then cold water, filtering-off after each treatment and washing with water. Drying overnight yielded Dye 102 as a dark blue solid (5.6 g, 85%); Xmax= 670 nm (DMF). Example 124: Preparation of CuPc tetra(N-butyl-N-(2-hydroxyethyl)carboxamide) (Dye 103) CU PC H(CON(C4F1g)CH2CH20F04 Copper phthalocyanine tetracarbonyl chloride (8.3 g, 0.01 mol), prepared according to US patent 6,508,873, was added in portions to a solution of 2-(butylamino)ethanol (11.7 g, 0.1 mol) in pyridine (83 ml) with ice cooling. The reaction mixture was stirred for 30 minutes at ambient temperature and then heated to 80°C for two hours. After allowing to cool the reaction mixture was added to water (830 ml) with stirring then sodium chloride (10% w/v) was added. The resultant precipitate was collected by vacuum filtration and washed with 5% NaCI solution (500 ml) on the filter. Drying to constant weight in a vacuum oven at 60°C afforded Dye 103 as a dark blue-green solid (7.3 g, 64%), X",ax= 675 nm (DMF).

Example 125: Preparation of CuPc bis(N,N-dibutylsulfonamide) bis(N-butyl-N-(hydroxyethyl)sulfonamide) bis-methacrylate ester (Dye 104) c(502N(D4H02)2 CuPc (502N(C4H9)CH2CH20C(0)C(CH3)=CH2)2 Dye 102 (5.6 g, co 4.2 mmol) was dissolved in pyridine (56 ml) and methacrylic anhydride (1.85 g, 12 mmol) was added. The solution was stirred at 60°C overnight then allowed to cool to room temperature. Water (5 ml) was added and the reaction stirred at room temperature for 30 minutes before further water was added drop wise until the product precipitated as a blue-black semi-solid. The material was collected by filtration, washed with cold water and dried. The solid was Soxhlet extracted with DCM, concentrated in tiocuo and re-precipitated by drop-wise addition of Me0H. The precipitate was filtered-off, washed with Me0H on the filter then dried to give Dye 104 as a blue solid (4.1 g, 67%); X",a"= 673 nm (DCM).

Example 126: Preparation of CuPc tetra(N,N-bis(2-hydroxyethyl)sulfonamide) octa-methacrylate ester (Dye 105) CuPc HSO2N(CH2CH20C(0)C(CH3)=C_H2,12,14 CuPc Prepared from Dye 100 instead of Dye 102 according to the procedure described in Example 125, except double the volume of pyridine was used and 12 mole equivalents of methacrylic anhydride were added per mole of Dye 100. Dye 105 was obtained as a blue solid; Xrna"= 672 nm (DCM).

Example 127: Preparation of copper phthalocyanine tetra(N-butyl-N-(2-hydroxyethyl)sulfonamide) tetramethacrylate ester (Dye 106) CuPcH(SO2N(C4HOCH2CH20C(0)0(CH3)=0F12)4 Prepared from Dye 101 instead of Dye 102 according to the procedure described in Example 125, except 6 mole equivalents of methacrylic anhydride were added per mole of Dye 101; Amax = 673 nm (DCM). Example 128: Preparation of copper phthalocyanine tetra(N-butyl-N-(2-hydroxyethyl)carboxamide) tetramethacrylate ester (Dye 107) CuPc (CON(C4HOCH2CH20C(0)C(CH3)=CF12)4 Prepared from Dye 103 instead of Dye 102 according to the procedure described in Example 125, except 6 mole equivalents of methacrylic anhydride were added per mole of Dye 103; Xma"= 678 nm (DCM). Example 129: Preparation of 1,4-bis((4-(2-hydroxyethyl)phenyl)amino)anthracene-9,10-dione (Dye 108)

OH OH

Leucoquinizarin (4.84g, 0.02 mol) and boric acid (3.71 g, 0.06 mol) were stirred under reflux for 30 minutes in IPA (100 ml) then allowed to cool. 2-(4-Aminophenyl)ethanol (8.23 g, 0.06 mol) was added and the mixture was then stirred under reflux overnight. The reaction was concentrated in vacuo, the residue was tritrated in Me0H (100 ml) and filtered-off. The material was purified over silica gel, eluting with an increasing gradient of EA (5-100%) in DCM. The pure blue-coloured fractions were evaporated, and the obtained solid recrystallised from EA to give the Dye 108 as green crystals (0.81 g, 21%); X (EA) 637 nm.

Example 130: Preparation of 1,4-dihydroxy-5,8-bis((4-(2-hydroxyethyl)phenynamino)anthracene-9,10-dione (Dye 109) OH 0 HN

OH OH

OH 0 HN Step 1-9-Chloro-10-hydroxyanthracene-1,4-dione: Prepared by modification of the procedure described in J. Chem. Soc., Perkin Trans. 1, 1981, 689-696. Commercial unpurified grade 1,4-dihydroxyanthraquinone (ca. 90% spec, 15 g, 0.0624 mol) was heated at reflux in thionyl chloride (60 ml) overnight, cooled and evaporated to dryness. Recrystallisation from toluene afforded 9-chloro-10-hydroxyanthracene-1,4-dione as deep red needles (11 g, 68%); m.p. 232-233°C.

Step 2-1,4-Dichloro-5,8-dihydroxy-9,10-anthracenedione: 9-Chloro-10-hydroxyanthracene-1,4-dione (5.0 g, 0.019 mol) was stirred with thionyl chloride (10.1 ml, 0.139 mol) to give a thick paste. Fuming sulfuric acid (20% S03, 190 g) was added gradually followed by portion-wise addition of boric acid (2.5 g, 0.040 mol), causing effervescence and an exotherm. Iodine (0.5 g, 0.002 mol) was added and the mixture stirred for 1 hour at 70°C, then sulfuryl chloride (10 ml, 0.123 mol) was cautiously added, before stirring overnight at 70°C. After allowing the mixture to cool to ambient temperature, it was slowly poured onto crushed ice giving an insoluble solid, which was filtered-off and washed acid-free with water before drying to a dark red powder. Recrystallisation from chlorobenzene gave 1,4-dichloro-5,8-dihydroxy-9,10-anthracenedione as deep red crystals (5.2 g, 88%); m.p. 273-275°C.

Step 3-Dye 109: A mixture of 1,4-dichloro-5,8-dihydroxy-9,10-anthracenedione (2.0 g, 6.5 mmol), 4-aminophenethyl alcohol (10.0 g, 72.9 mmol) and Na0Ac (2.0 g, 25 mmol) were melted with stirring at 130°C bath temperature for 4 hours at which point, a small volume of NMP was added until the mixture became mobile. The bath temperature was raised to 150°C and stirred overnight. After cooling, 2M HCI (120 ml) was added and stirred for 30 minutes before collecting the solid by filtration and washing acid free with water. After drying, the crude product was recrystallized three times from ethoxyethanol, removing a violet-blue impurity, to give Dye 109 as green-black crystals (1.4 g, 42%); Amax (EA) 679, 632, 415 nm.

Further anthraquinone dyes with application in this invention, listed in Table 4, were synthesised according to the procedure described in the cited literature source.

Example 134: Preparation of 4,11-diamino-2-(2,3-dihydroxypropy1)-1H-naphth[2,311isoindole1,3,5,10(2H) -tetrone (Dye 113) Dye 112

Example 133

US 8,192,937 T e 4

Example Number

Dye Number Dye structure Literature source / Notes

Example 131

Example 132

Dye 110 Dye 111

OH

OH

US 5,362,812 US 4,778,742 0 HN"..."------OH NH2

OHO OH NJ

O NH2 0 Prepared from 4,11-diamino-1H-naphtho[2,3-f]isoindole-1,3,5,10(2H)-tetraone (US 2,628,963) according to the 2-step procedure described in US 5,362,812, except 2-(3-bromopropoxy)tetrahydro-2H-pyran was replaced by (2,2-dimethy1-1,3-dioxolan-4-yOmethyl 4-methylbenzenesulfonate. (2,2-Dimethyl1,3-dioxolan-4-yl)methyl 4-methylbenzenesulfonate was prepared in 1 step from Solketal as described in Journal of Molecular Liquids (2018), 218-224, and was used crude; knia" = 674 nm (DCM).

Example 135: Preparation of 44(1-amino-4-hydroxy-9,10-dioxo-9,10-dihydroanthracen-2-yl)oxy)-N,Nbis (2-hydroxyethyl)benzenesulfonamide (Dye 114)

S-N OH

8 \-\OH

O OH

A solution of diethanolamine [amine] (7.9 g, 75 mmol) in water (50 ml) and THF (100 ml) was cooled to 10°C. With stirring, 1-amino-2-(4'-chlorosulfonyl)phenoxy-4-hydroxyanthraquinone [sulfonyl chloride] water wet solid (25 mmol, prepared according to US 6,022,944) was added portion-wise, then heated at 50°C for 2 h. The heating block was removed and ice (200 g) was added to cool. Once the ice had melted, the resultant solid was collected by vacuum filtration, washed with water until neutral, then vacuum dried over CaCl2 to give Dye 114 as a dark red solid (11.0g. 88%); Amax (DCM) 518 nm. Example 136: Preparation of N,N-dially1-44(1-amino-4-hydroxy-9,10-dioxo-9,10-dihydroanthracen-2-ynoxy) benzenesulfonamide (Dye 115)

O OH

A solution of diallylamine [amine] (7.3 g, 75 mmol) in water (50 ml) and THF (100 ml) was cooled to 10°C. 1-Amino-2-(4'-chlorosulfonyl)phenoxy-4-hydroxyanthraquinone hydroxyanthraquinone [sulfonyl chloride] water wet solid (25 mmol, prepared according to US 6,022,944) was added portion-wise, then heated at 50°C for 2 hours. The heating block was removed and ice cold 0.1 M HCI (200 ml) was added. After stirring for 30 minutes, the resultant solid was collected by vacuum filtration, washed with water until neutral, then vacuum dried over CaCl2 to give Dye 115 as a red solid (9.7 g, 79%); Amax (DCM) 519 nm. Example 137: Preparation of 4,4c((1,4-diamino-9,10-dioxo-9,10-dihydroanthracene-2,3-diy1)bis(oxy))bis (N,N-bis(2-hydroxyethyObenzenesulfonamide) (Dye 116) oOH O NH,

S-N OH \-/ °

S-N OH

A solution of diethanolamine [amine] (15.8 g, 150 mmol) in water (100 ml) and THF (200 ml) was cooled to 10°C. 1,4-Diamino-2,3-dil(4'-chlorosulfonyl)phenoxy)anthraquinone [sulfonyl chloride] water wet solid (25 mmol, prepared according to US 6,022,944) was added portion-wise, then heated for at 50°C for 2 hours. The heating block was removed and ice (200 g) was added causing the reaction to cool. Once the ice had melted, the resultant solid was collected by vacuum filtration, washed with water until neutral, then vacuum dried over CaCl2 to give Dye 116 as a dark violet-black solid (11.9g. 63%); Amax (DCM) 546 nm. Example 138: Preparation of 3,3'4(9,10-dioxo-9,10-dihydroanthracene-1,4-diyObis(azanediyl))his(N, Ndially1-2,4,6-trimethylbenzenesulfonamide) (Dye 117) 0 HN SO2NH(CH2CH=O1-12)2 0 HN SO2NH(CH2CH=CH2)2 A solution of diallylamine [amine] (14.6 g, 150 mmol) in water (100 ml) and THF (200 ml) was cooled to 10°C. 1,4-Bis[31-chlorosulfony1-2',4',6'-trimethylanilino]anthraquinone [sulfonyl chloride] water wet solid (25 mmol, prepared according to US 6,022,944) was added portion-wise, then heated at 50°C for 2 hours. The heating block was removed and ice cold 0.1 M HCI (200 ml) was added causing the reaction to cool. After stirring for 30 minutes, the resultant solid was collected by vacuum filtration, washed with water until neutral, then vacuum dried over CaCl2 to give as a dark blue solid (16.9 g, 85%); Xina" (DCM) 629 nm.

Further anthraquinone dyes, listed in Table 5, were synthesised according to the Method stated, where the sulfonyl chloride and amine in the indicated Method were replaced instead with those shown in the Table. All sulfonyl chlorides were prepared according to the procedures given in US 6,022,944, unless stated otherwise. All amines were commercially available. Dye Xrra" measured in DCM.

Table"]

Example Dye Number Dye structure sulfonyl chloride Amine Method as for: Xn,./..

Example Dye 118 0 NH2 o I-Amino-2-(Wchlorosulfonyl) phenoxy-4-hydroxyanthraquinone Diisopropa Example 135 518 139.00 8 \ -C nolamine

OH 0 OH

Example Dye 119 0 NH2 * 9 (cr 1,4-Di a mino-2,3-di-((4'- 2-(Butyl Example 137 546 S-N OH chlorosulfonyl) phenoxy) amino) 8 -/ anthraquinone ethanol 000 0 aS-NrOH 0 NH2 0 'Th_ Example Dye 120 0 NH. SO2N(13u)CH2CH2OH 1,4-bis[3'- 2-(Butyl Example 137 628 141 00. Chlorosulfony1-21,41,61 - amino) 0 HN 0 SO2N(Bu)CH2CH2OH trimethyl aniline] ethanol anthraquinone Example Dye 121 142 1,4 Diamino 2,3 di WI] N-Allyl Example 138 546 0 NH 9,Ph chlorosulfonyl) phenoxy) aniline It a rk, anthraquinone 0 ii 0 NH2 * a $-N1A 0 Ph Example 143: Preparation of 3-(4,11-diamino-1,3,5,10-tetraoxo-1H-naphtho[2,31Psoindol-2(3H,5H,10H) -yflpropyl methacrylate (Dye 122) NH2

SOO

O NH, 0 Dye 110 (1.46 g, 4 mmol) was stirred for 30 minutes in pyridine (36 ml) at 60°C. Methacrylic anhydride (0.77 g, 5 mmol) was added and the solution stirred overnight at 60°C. After cooling, water (5 ml) was added and the reaction stirred at room temperature for 30 minutes before further water was added drop-wise until the product precipitated as a dark blue-black tar. The supernate was decanted-off and the tar was rinsed with Me0H then dried under a purge of nitrogen. The residue was dissolved in DCM (250 ml) and filtered through a small pad of silica (7 g). The blue elute was concentrated to -100 ml and Me0H (100 ml) was added dropwise. The resultant suspension was cooled in an ice bath for 1 hour before filtering off the solid and washing with Me0H. Drying gave Dye 122 as a blue solid (0.83g. 48%); 674 nm (DCM).

Example 144: Preparation of 3-(4,11-diamino-1,3,5,10-tetraoxo-1H-naphtho[2,3;flisoindol-2(3H,5H,10H) -yl)propane-1,2-diy1 bis(2-methylacrylate) (Dye 123) o NH, 0 Dye 123 (3.81 g, 10 mmol) was stirred for 30 minutes in pyridine (100 ml) at 60°C. Methacrylic anhydride (3.4 g, 22 mmol) was added and the solution stirred at 60°C overnight. After cooling, water (5 ml) was added and the reaction stirred at room temperature for 30 minutes. The bulk of the pyridine was removed by rotary evaporation then water was added with swirling until the product separated as a dark blue-black tar. The water was decanted and the tar was rinsed with Me0H then dried under a purge of nitrogen. The residue was dissolved in DCM (50 ml) and purified over a silica gel column eluting with DCM then an increasing gradient of EA in DCM. Fractions enriched in the faster running of two blue products were combined and concentrated to -100 ml, then Me0H (100 ml) was added dropwise with stirring. The resultant suspension was stirred for 1 hour before filtering-off the solid. The solid was washed with Me0H on the filter then dried to give Dye 123 as a dark blue solid (1.50 g, 29%); X,"= 673 nm (DCM).

Example 145: Preparation of (((9,10-dioxo-9,10-dihydroanthracene-1,4-diyObis(azanediyl))bis(4, 1-phenylene))bis(ethane-2,1-diy1) diacrylate (Dye 124)

O HN

SOO

O HN

A suspension of Dye 108 (1.9 g, 4.0 mmol), in DCM (50 ml) was treated with N,N-dimethylaniline (1.94 g, 16 mmol) and acryloyl chloride (1.45 g, 16 mmol) at 30°C overnight. The reaction was cooled to room temperature, washed with 0.2 N HCI (3 x 50 ml), water (50 ml) and then dried (Na2504). The solution was applied to a pad of silica gel, washed with DCM then eluted with an increasing gradient of ethyl acetate (1025%) in DCM. The pure fractions were combined and evaporated, and the resultant solid was recrystallised from isopropanol to give Dye 124 as blue crystals (1.70 g, 72%); Amax (Et0Ac) 636, 598, 402 nm.

Example 146: Preparation of 1,4-bis((4-(allyloxy)phenethyDamino)anthracene-9,10-dione (Dye 125)

O HN

O HN

A mixture of Dye 111 (26.3 g, 0.055 mol), K2CO3 (19.0 g, 0.138 mol), ally! bromide (39.9 g, 0.33 mol) and butanone (400 ml) was heated at reflux for 6 hours, cooled off the boil then filtered and evaporated to dryness. The residue was dissolved in DCM (200 ml) and filtered through a silica pad eluting with DCM, collecting elute once beginning to run blue and continuing to collect until the elute was pale blue. The collected elute was concentrated to dryness and the residue re-precipitated from DCM/Me0H by slow evaporation of DCM. The resultant solid was filtered-off, washed with Me0H and dried overnight at.50T in a vacuum oven to give Dye 125 as a blue powder (20.0 g, 65%); m.p. 112-114T; Amax (EA) 642 nm.

Example 147: Preparation of (((5,8-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-1,4-diyObis(azanediy1)) bis(4,1-phenylene))bis(ethane-2,1-diy1) diacrylate (Dye 126) Prepared according to procedure described in Example 145 replacing Dye 108 with Dye 109 and purifying over silica gel, eluting with an increasing gradient of EA (0-8%) in DCM. The pure fractions were combined and evaporated, and the resultant solid was recrystallised from DCM/Et0H to give Dye 126 as green-black crystals (84%); m.p. 171-172°C; Am,. (Et0Ac) 678, 631, 414 nm.

Further anthraquinone dyes, listed in Table 6, were synthesised according to the Method Example stated, except the precursor dye in the Method Example was replaced instead with that shown in the Table. Dye Amax measured in DCM.

OH 0 HN 00, /

SOO

OH O HN

Example 148

Dye 111 Dye 127

Example 148

Example Number

Dye Number Dye structure Precursor Dye Method as for: 71E Example Number Dye Number Dye structure Precursor Dye Method as for: km,/nm Example 149 Dye 128 0 Dye 112 Example 144 642 0 HNOjCi

SOO

0 HN,,,"-,,O,..(L. o

Example 150 Dye 129 0 NH2 0 Dye 114 Example 145 517 o VC-04 It OS 0 \-\ 0 % 10 0 OH \\O Example 151 Dye 130 0 S1-12)20 2 Dye 116 Example 144 546 0 NH2. -N (C 2 Using 4.4 mole 0 0 equiv. of SOO 0 0 methacrylic as g-N (CF12)20 anhydride 0 NH2 0 Example 152 Dye 131 0 NH2 9 Dye 118 Example 144 518 SOO 0. S-N 8 / -'---\\. jo 0 0 OH C \\O Example 152: Preparation of 3-(benzo[d]oxzol-2-y1)-7-(bis(2-hydroxyethyDamino)-2H-chromen-2-one (Dye 132) lb \ HOC/ 0 0 Prepared according to methodology described in US 4,892,922; Ar"," (DCM) 435 nm.

Example 154: Preparation of 3-(benzo[d]thiazol-2-y1)-7-(bis(2-hydroxyethyflamino)-2H-chromen-2-one (Dye 133)

HO \ \

HO

Prepared according to methodology described in US 4,892,922 except ethyl cc-(2-benzothiazolyl)acetate was used in place of ethyl a-(2-benzoxazolyl)acetate; Anna" (DCM) 451 nm.

Example 155: Preparation of 3-(1H-benzo[d]imidazol-2-y1)-7-(bis(2-hydroxyethyl)amino)-2H-chromen-2-one (Dye 134)

HO \ \

Prepared according to methodology described in US 4,892,922 except ethyl a-(2-benzimidazolypacetate was used in place of ethyl a-(2-benzoxazolyl)acetate; An,ax (DCM) 438 nm. Example 156: Preparation of 2-(7-(diethylamino)-2-oxo-2H-chromen-3-yI)-N,N-bis(2-hydroxyethyl)benzo[d] thiazole-6-sulfonamide (Dye 135) Prepared according to general methodology described in Dyes and Pigments 2001, 51, 153. 2-(7-(Diethylamino)-2-oxo-2H-chromen-3-yObenzo[d]thiazole-6-sulfonyl chloride (4.5 g, 10 mmol), was added to an ice cold solution of diethanolamine (3.2 g, 30 mmol) in water (25 ml) and stirred overnight at ambient temperature. The solid was collected by vacuum filtration and washed on the filter with water until the filtrates ran colourless. Drying afforded Dye 135 as an orange solid (4.2 g, 81%); Xma" (DCM) 475;1H NMR (400 MHz, DMSO-d6) 5 ppm 1.14 (6H, t, J=7.0), 3.55 -3.80 (12H, m), 4.79 (2H, t, J=5.5), 6.63 (1H, d, J=1.7), 6.82(1K, dd,J=9.2, J=1.7), 7.75 -7.85 (2H, m), 8.06(1K, d, J=8.8), 8.53(1K, d, J=1.8), 8.99(1K, s). Example 157: Preparation of 2-(7-(diethylamino)-2-oxo-2H-chromen-3-y1)-N,N-bis(2-hydroxyethyl)-4-oxo3, 4-dihydroquinazoline-6-sulfonamide (Dye 136) OH r_f 0 N S-N 0 0 'OH Acid Yellow 227 (US 3,979,389) was treated with chlorosulfonic acid according to the general chlorosulfonation conditions described in Dyes and Pigments 2001, 51, 153. The resultant sulfonyl chloride was reacted with diethanolamine under conditions described in Example 156 to give Dye 136 as an orange solid; A.,"a" (DCM) 460; 1H NMR (400 MHz, DMS0-(16) was broad indicating a mixture of isomers.

Further coumarin dyes, listed in Table 7, were synthesised according to Example 156 using the amine stated in place of diethanolamine. The requisite sulfonyl chlorides were prepared according to the procedures given in Dyes and Pigments 2001, 51, 153. Dye Xma" measured in DCM.

Table

Example Dye Number Dye structure Amine L../ .., Example Dye 137 N Diethanolamine 463 158 ---* * * S-N

O

---/ 0

OH

Example Dye 138 N 0 Diethanolamine 460 159 ---* , N 41 *

OH

Example Dye 139 ---\ ---/ * N * 2-(Butylamino)ethanol 473 160,°-N 0 OH mble 7 Example Dye Number Dye structure Amine Xmax / nni Example Dye 140 N * jr some Diallylamineco-solvent) (with THF 472 161 'NI Example Dye 141 --""). * N * Diallylamine (with 460 162 some THF co-solvent) Example Dye 142 ---). * N * p, Diallylamine (with THF 458 163 --/ \ ,, 'N \ some co-solvent) o o A selection of coumarin dyes were converted to the extended coumarin dyes listed in Table 8 according to the general procedure described in DE 10 2010 031 243. Dye kma" measured in DMF.

A selection of coumarin dyes were converted to the cyanated derivatives listed in Table 9 according to the general procedure described in Dyes and Pigments 2001, 51, 153. Dye Amax measured in DCM.

Dye Number Dye 143 Dye 144 Dye 145 Precursor Dye X.,../.., Dye 137 559 Dye 141 557 Dye 134 539 Dye structure

Example

Example

Example

Example

Dye Number Dye 146 Dye 147 Dye 148 Precursor Dye X.,../.., Dye 135 547 Dye 143 644 Dye 144 643 Dye structure

Example

Example

Example

Example

A selection of coumarin dyes, listed in Table 10, were synthesised according to the Method stated, replacing the precursor dye in the Method with that shown in the Table. Dye kma" measured in DCM.

Table ila

Example Dye Number Dye structure Precursor Dye Method as for: Xmax/nm Example Dye 149 / Dye 132 Example 145 425 \_---\ . \ N /41 0 o 0 o o Example Dye 150 / Dye 133 Example 145 442 171 o o S / o Example Dye 151 ---\ it N 11 0 0 Dye 135 Example 145 477 172 ---/ S N 0 0 o ' -__ o Example Dye 152 -\N 0 Dye 136 Example 144 461 173 _/ a HN 0 o N a S-N Example Dye 153 n N fie 9 0 0 Dye 138 Example 145 463 174 ---* P"NI 0 o \ d, Example Dye 154 ---\ ---I * \ NS ill dO_Nr_/, 0 Dye 139 Example 144 474 o using 1 1 eq's of 0 methacryl lc n hydride Example Dye 155 --NN CN. 0. 0 Dye 146 Emple 145 Example 548 176 ---/ , N 0 0 * S o -__ 0 0 The styryl dyes shown in Table 11 were prepared according to the general conditions described in Chem. Mater. 1999, 11, 7, 1784-1791. The starting benzaldehyde derivative was as stated in the table, and was reacted with one of malononitrile, ethyl cyanoacetate or allyl cyanoacetate, which one being apparent to those skilled in the art from the product structure. The starting benzaldehydes were commercially available or prepared according to the method described in US 4,757,130. Dye imax measured in Me0H.

Rible 11 Example Dye Number Dye structure Benzaldehyde derivative Xeusiee, Example Dye 156 OH 4-(bis(2-Hydroxyethyl) a mi no)-2- 433 177 N methyl benzaldehyde It NC *

CN OH

Example Dye 157 OH 4-(bis(2-Hydroxyethyl) a mi no)-2- 424 178, It N methyl benzaldehyde NC ' CO2Et OH Example Dye 158. N 4-(Diallylamino)-2- 446 179 NC \--% methylbenza I dehyde

CN

Example Dye 159 4* Ni- 4-(Diethylamino)-benzaldehyde 436 NC \_ CO2CH2CH=CH2 The pyrroline dyes shown in Table 12 were prepared according to the methods described in US 4,845,235, from the aniline derivatives stated. Dye Xn,,,,measured in acetone.

* * * * * iable.1 Example Dye Number Dye structure Aniline derivative Leasieie Example Dye 160 0 /- Intermediate 4 602 HN / NC le CN CN \ -Example Dye 161 0 Intermediate 4 637 182 --"."---NN /-/ NC \ CN CN \\ _ Example Dye 162 0 Intermediate 4 636 183 r-/-

N

* NC \

CN CN

Example Dye 163 o Intermediate 2 622 184 o

N

lik NC \-\ 0

CN CN 01

Example Dye 164 o Intermediate 3 630 N....;"....-.,

N C It

NC \-\ 0 CN CN 11)-Example Dye 165 0 N-Ethyl-N-2- 639 186 HO hydroxyethylaniline N"----xN 41* NC NC \__,\

CN CN OH

The pyrroline dyes shown in Table 13 were prepared according to the methods described in US 7,307,173, from the benzaldehyde derivatives stated. The starting benzaldehydes were commercially available or prepared according to the method described in US 4,757,130. Dye Xmax measured in DCM.

Table 1

Example Dye Number Dye structure Benzaldehyde derivative Xmaiiiii.

Example Dye 166 CN CN r 7/ 4-(N,N-Dially1 735 187 NC a mino)benzaldehyde \ It N \--'

HN o

Example Dye 167 CN /7 4-(N,N-Dially1 739 188 C a mino)benzaldehyde NC If NI \-71/4

N

Example Dye 168 OH 4-(N,N-lois(2-Hydroxyerhyl) 690 189 CN CN a minoThenzaldehyde NC N It N

N

*,,,r--/ OH Example Dye 169 CN CN 4-(Erhyl(2-hydroxyerhyfla mi no) 701 NC N C benzaldehyde \ * \ N _Th

OH 0 0

The dyes shown in Table 14 were prepared according to the methods described in GB 2,026,528, from the commercially available benzaldehyde derivatives stated. The starting benzaldehyde derivatives were or prepared according to the method described in US 4,757,130 Dye Amax measured in Me0H.

Further styryl, pyrroline and 3-dicyanomethylidene-2,3-dihydro-thiophene-1,1-dioxide dyes listed in Table 15, were synthesised according to the Method stated, except the precursor dye in the Method was replaced by that shown in the Table.

4-(bis(2-Hydroxyerhyl) a mi no)-2-methyl benzaldehyde Dye 170

Example

Example

Dye 171 methylbenzaldehyde

Example

Dye Number Dye structure Benzaldehyde derivative X.6,1 nei Tabre 5

Example

Dye Number Dye structure Precursor Dye Method as for: Dye 172

NC

Dye 156

Example

Example 144

423 (Me0H)

table 15

Example Dye Number Dye structure Precursor Dye Method as for: Imam inni Example Dye 173 0 Dye 157 Example 145 413 194 0 (Me0H) / * N / NC 0 CO2E1 / Example Dye 174 1 0 Dye 165 Example 145 633 N C aceone ( t) NC * \

CN C

Example Dye 175 C 0-\ Dye 168 Example 145 678 196 N CN ci 0 (DCM) NC \ It \-N \ o Example Dye 176 CN CN Dye 169 Example 145 653 197 N (DCM) 0 \ 41). C \--\-\ yo-r--./N C) 0 0 Example Dye 177 NC 04CN Dye 170 Example 145 590 198 ci 0 (Me0H) / It 0 02 NO-Example 199: Preparation of 2,4-bis[2,2,4,7-tetramethy1-3,4-dihydroquinoline-6,1(2H)-diyObis(ethane2, 1-diy1)] squaraine diacrylate (Dye 178) Step 1-2,4-Bis[N-(2-hydroxyethyl)-2,2,4,7-tetramethy1-3,4-dihydroquinoline-6,1 (2H)-diy1] squaraine: A stirred mixture of 1-butanol (100 ml), toluene (50 ml), squaric acid (2.3 g, 0.02 mol) and 2-(2,2,4,7-tetramethy1-3,4-dihydro-1(2H)-quinolinypethanol [starting material] (8.8 g, 0.04 mol), was heated for 16 h under reflux, removing generated water with a Dean-Stark trap. The reaction was allowed to cool, diluted with diethyl ether (300 ml) and the resultant crystalline solid was filtered-off, washed with further diethyl ether and dried at 40°C. The material was purified by recrystallisation from chlorobenzene, to give the pure title compound as a green crystalline solid (10.0 g, 91%).

Step 2-Dye 178: A mixture of 2,4-bis[N-(2-hydroxyethyl)-2,2,4,7-tetramethy1-3,4-dihydroquinoline-6,1 (2H)-diy1] squaraine (2.7 g, 5 mmol), DCM (50 ml), N,N-dimethylaniline (2.4 g, 20 mmol) and acryloyl chloride (1.8 g, 20 mmol) was stirred under reflux for 16 h, further N,N-dimethylaniline (2.4 g, 20 mmol) and acryloyl chloride (1.8 g, 20 mmol) were added and heating continued for 24 h. After cooling, the reaction was washed with 0.2 M HCI, dried (Mg504) and applied to a pad of silica gel. The 92 required product was eluted with an increasing gradient of EA (10-25%) in DCM. Pure Dye 178 was obtained, following recrystallisation from DCM/IPA, as olive crystals (2.5 g, 76%); Xmax (Et0Ac) 654 nm.

Table 16 shows squaraine and croconaine dyes that were prepared from the starting material stated, according to Example 199, using croconic acid in place of squaric acid for croconaine dyes, and replacing the methodology described in Step 2 with that described in Example 144 for methacrylate dyes. Starting materials were commercially available or prepared according to the provide literature reference. Dye krna" measured in toluene, unless stated otherwise.

L.HIplp[0.1.k.

Example Dye Number Dye structure Starting material X../..

Example Dye 179 0 0 2-(Ethylphenylamino)ethanol 614

--

4004P zcrk----Example Dye 180 0 0 2-(2,2,4,7-Tetramethy1-3,4- 844 201 -,0. dihydro-1(2H)-quinolinyl)ethanol -----/.._ + ilk 110

N N o o 0

Example Dye 181 ---- 1 OH 3-(Buty1(2-hydroxyethyl) 640 202 --- Nz f-- amino)phenol N HO 0-'o US 6,126,867 Example Dye 182 0 OH 0 0 HO 0--lh 3-(Buty1(2-hydroxyethyl) 822 203 amino) phenol US 6,126,867 o/ -0 *---111 iip 5' . Nj Example Dye 183 0 Intermediate 4 625 204 CC Example 271, Step 1 only e a, -/ \ _ Example Dye 184 '\ 0 ce N,N-DiallyI-3-methylaniline 654 205 - 4 N Journal of Chemistry 2013, -4*. Article 989285.

Example 271, Step 1 only Example Dye 185 o 3-Acetyla mino-N-butyl-N-(2- 673 206 o --(NH 0 hydroxyethyl) aniline ----1 + itt. * -LTC" US 4,139,528 N _ HN 0 1r- 0 Example Dye 186 0 N [3 (Di 2 propen 1 yl 684 207 ry amino)phenyl]acetamide -ANN 0 * N Org. Biomol. Chem., 2012, 5119 \----% Example 271, Step 1 only \ + .--4._ HN )r--/ 0 Example Dye 187 % \ OH 0 HO 5 (Di 2 propen 1 ylamino) 1,3 675 (EA) 208 benzenediol 4.-.

ri OH r HO \--% Table 17 shows squaraine dyes disclosed previously, which now find application in this invention, that were prepared according to the parent literature. Acrylate esters were prepared according to Example 271, Part 2. Methacrylate ester were prepared according to Example 144. Dye Xmas measured in toluene.

Table 18 shows asymmetric squaraine dyes with application in this invention that were prepared from 1-(p-dibutylaminophenyI)-2-hydroxycyclobuten-3,4-dione (1. Am. Chem. Soc. 2014, 136, 13233) and the starting material stated, according to the procedure described in WO 2016/154782. Acrylate esters were prepared according to Example 199, Part 2. Methacrylate ester were prepared according to Example 144. Dye Xmas measured in toluene, unless stated otherwise.

1-AllyI-1H-indole Org. Lett. 2012, 14, 4614 Dye 188

Example

Dye 189 1H-Indole-1-hexanol Pharmaceuticals 2020, 13, 469

Example

Tablet

Example

Dye Number Dye structure Starting material X...

Dye 190

Example

US 2011/0159483 US 2011/0159483 Dye 191

Example

Dye 192

Example

Prepared from the bis-hydroxy dye exemplifed in Organic Electronics 2017, 382.

Table f)

Example

Dye Number Dye structure

Disclosure document Tabre

Example

Dye Number Dye structure Starting material kmax/nm 2,21-(m-Tolylazanediy1)diethanol

Example

Dye 193

Table 18

Example Dye Number Dye structure Starting material Xmax/nm Example Dye 194 0 0-C N[3-[Bis(2-hydroxyethyl)a ml no] 644 215 ci ° phenyljacetamide -4I/ * * \_Th 0-HN 04 I? 0 Example Dye 195 \ 0 ri 3-(Diallylamino)phenol 628 (EA) 216 \ J. Heterocyclic Chem. 2018, 1183.

-a * a 0-HO \--% Example Dye 196 0 HO 5-(Di-2-propen-1-ylarnino)-1,3- 630 (EA) 217 / benzenedial N WO 2016/154782 45) N\ 0-HO % Example Dye 197 0 54Bis(2-hydroxyethyl)a mino41,3- 616 (EA) 218 0 HO 04 benzenediol \_ Chem. Commun. 2014, 4438 * 4 N _41, 0

CT HO

Example Dye 198 0 * 1413u43-en-1-y1)-2,3,34rim ethyl- 633 219 --7-j -40-1k / ) 3H-indo1-1-ium bromide US 2011/0159483 Example Dye 199 --\--\ 0* 1 42-(2-2,3,3-trim ethyl-3H-indo1-1-ium bromide 628 220 14E 0 --r-j 1111-* , N -o Metal dithiolene dyes with application in this invention, listed in Table 19, were synthesised according to the cited literature, with relevant notes given. Amax measured in DCM unless stated otherwise.

Table 19

Example Dye Number Dye structure Literature sources and Notes 1..../..

Example Dye 200 HO a s 1. OH US 5,089,585 842

S

Example Dye 201 ill OH Inorg. Chem. 2014, 53, 2841 870 222 is S S. Ni HO. s is Example Dye 202 HO OH US 5,182,409 871 223 *1. s * Ni ip s s is

HO OH

Example Dye 203 0 0. OH 4'-(2-Hydroxyethoxy)acetophenone was 881 224 di S -41-S prepared according to J. Med. Chem. 2009, (PhMe) 52, 6394. This was converted to 4'-(2-hydroxyethoxy)-2-bromoacetophenone according tot. Chem. Soc. 1951, 255 This was converted to Dye 279 as per methodology in US 5,089,585.

z. :Table:19-z z:-

Example Dye Number Dye structure Literature sources and Notes Xmas Ai.

Example Dye 204 o 41(2-Hydroxyethoxy)ethoxy)acetophenone 882 225 HO 24 S was prepared according to J. Med. Chem. (PhMe) S-0--s 2009, 52, 6394-6401. This was converted to S OH 4'-(2-hydroxyethoxy)ethoxy)-2- 1111 0 J2 bromoacetophenone according to J. Chem. Soc. 1951, 255. This was converted to Dye 280 as per methodology in US 5,089,585.

Example Dye 205 0 0 4,4'-Di a Ilyloxybenzoin was prepared from 931 226 -111. 7 commercial 4-allyloxybenzaldehyde according S S o Tetrahedron 2010, 68, 523. This was Ni converted to Dye 282 as per methodology in C el S ' S) US 5,182,409 Example Dye 206 0 1-(4-Hydroxyph eny1)-2-phenyl ethane-1,2-dione was prepared according to Macromolecul es 2001, 34, 2427. This was converted to 1-(4-(allyloxy)pheny1)-2-phenylethane-1,2-dione using allyl bromide according to J. Am. Chem. Soc. 2019, 141, 16237 (Synthesis of n-Ketoacid, Method C) 894 227 I* S., ,S 41 V This was converted to Dye 283 as per methodology in US 5,182,409 Ni I V "s iv. 40 Example D 207 0 Methods as per Example 308 using 888 228 ye 1111 S S 1411 HO chloroethanol in place of a Ily1 bromide OH so s' . 401 a Example Dye 208. . Methods as per Example 307 using 926 229 OH* S, ,S 110 HO 4-(2-hydroxyethoxy)benzaldehyde I Ni I in place of 4-allyloxybenzaldehyde OH 401 S 'S 40) HO 0 0 Example Dye 209 Har'"-e-N 40 1(41(2-Hydroxyethyl)(methy Damino) 1013 230 S ph enyl)eth enon e was prepared according to S-141.,s US 2018/0186815. This was converted 2-s' ..." bromo-1-(4-U2-2 10.,,,,OH hydroxyethyl)(methyl)amino)phenyl) ethenone according to.10C 2018, 83, 1095 This was converted to Dye 286 as per methodology in US 5,089,585.

N

I

Example D 210 1 1 Methods as per Example 307. 1174 231 ye N N 4-(N-Methyl-N-hydroxyethyl)amino OH 101 S S 10 HO benzaldehyde was used in place of 14 4-allyloxybenzaldehyde OH is S' S 0 HO

N N S 1

Example 232: Preparation of bis[4-(1,2-dimercaptoethenyl)benzeneethanolato(2-)-S,STnickel dimethacryloyl ester (Dye 211) Dye 200 was reacted under conditions described in Example II of US 5,089,585, except the described 1 mole equivalent of sebacoyl chloride was replaced with 2.2 mole equivalents of methacryloyl chloride. The crude product was dissolved in DCM, filtered through celite, then through a silica gel pad (6 weight equivalents) and eluted until all green colour had passed through. Heptane was added to the dye solution and the mixture concentrated in vacuo gradually removing DCM, resulting in crystallization of the desired product. After cooling the solid was filtered-off and washed with heptane. Dye 211 was obtained as green-black crystals after drying; Xmax (toluene) 835 nm;1-1-1NMR (400 MHz, CDCI3) 6 ppm 1.95(6 H, s), 2.64 (4 H, t, 1=7.7 Hz), 4.49(4 H, t, 1=7.7 Hz), 5.68(2 H, s), 6.11 (2 H, s), 7.28(4 H, m), 7.93(4 H, m), 9.70(2 H, s). Further metal dithiolene dyes, listed in Table 20, were synthesised from the specified precursor dyes following Example 232, using 2.2 or 4.4 equivalents of methacryloyl or acryloyl chloride, as required for each structure shown, being apparent to those skilled in the art. Ava, DCM unless stated otherwise.

Example Dye Number Dye structure Precursor Dye X..in.

Example Dye 212 0 Dye 207 886 233 Si s. S 0

I NI I 0 $ 0

Example Dye 213 I,Ni I Dye 208 921 234 0 1 c0 0 o. S 101 f ij Example Dye 214 0 Dye 201 866 235 Si s 411 ft

NI I 8. 0 0

Example Dye 215 0 Dye 209 991 236 \ S 0 / a S-girs / 8 / N it 0 \ Example Dye 216)Nir-0 0 Dye 202 868 237 0 It S"S 101 INiI * S 'S * 0 0 Example Dye 217, Dye 210 1131 238 0 0') Lek-. I'NII

Lsco 0-L * S' 'S *110 N'i --ac-i I /

Table 20

Example Dye Number Dye structure Precursor Dye X.,../.., Example Dye 218 a:I'S 07/ Dye 200 835 239 * 0 (PhMe) \O S" 1 S / Example Dye 219 a / ...S O Dye 203 875 240 C r---/ S f_J-Co (PhMe) 0 0 0 fie Example Dye 220 '_0 /-0, Dye 204 880 241 ' (PhMe) 0 j-0 0 S a S 7 It 0 0_ __ 0" Example 242: General method for preparation of polymer inks A) Composition by weight%; * 20 -30% ASS * <3% Crosslinking co-agent * <0.2% Polymerisation Initiator * < 0.2% Catalyst * <3.0% Functionalised Dye * Remainder Solvent B) Reaction Conditions; <s hours @ 80-90°C then cooled C) Post reaction treatment; * Addition of 50-350 ppm Hydroquinone * Composition vacuum distilled until no more than a few % of solvent remaining * Optional addition of glycolic acid (up to 1.4 mole equivalents with respect to ASS) * Diluted with water to SO% polymer ink Example 243: Preparation of Dye 1-ASS Polymer Ink A) Composition by weight%; * 44.3 g ASS (25.6%) * 2.6 g TMPTMA (1.5%) * 0.1 g V67 (0.1%) * 4.9 g Dye 1 (2.8%) * 121.2 g Solvent (70.0%) [DMF] B) Reaction Conditions; 3.5 hours @ 80-90T then cooled C) Post reaction treatment; * Addition of 53 ppm Hydroquinone * Vacuum distilled to 0.9% DMF (GC-HS) * Addition of 14.2 g Glycolic acid (67%) * Diluted with water to 50% polymer ink Dry-down check; 10.00 g polymer ink gave 5.09 g non-volatiles = 50.9% w/w polymer ink Viscosity; Rotor#2, T=18.4°C, w=60 rpm, Viscosity=35 cP Example 244: Preparation of Dye 4-ASS Polymer Ink A) Composition by weight%; * 45.5 g ASS (21.6%) * 3.2 g TMPTMA (1.5%) * 0.2 g V67 (0.1%) * 0.4 g Tin(II) 2-ethylhexanoate (0.2%) * 5.0 g Dye 4(2.4%) * 156.7 g Solvent (74.2%) [119.9 g DMF, 14.4 g glycolic acid (67%), 22.4 g water] B) Reaction Conditions; 4 hours @ 80-90°C then cooled C) Post reaction treatment; * Addition of 71 ppm Hydroquinone * Vacuum distilled * Addition of 14.6 g Glycolic acid (67%) * Diluted with water to 50% polymer ink Dry-down check; 10.00 g polymer ink gave 5.00 g non-volatiles = 50.0% w/w polymer ink Viscosity; Rotor#2, T=24.3°C, w=12 rpm, Viscosity=1822 cP Example 245: Preparation of Dye 20-ASS Polymer Ink A) Composition by weight%; * 44.56 g ASS (23.8%) * 3.21 g TMPTMA (1.8%) * 0.21 g V67 (0.1%) * 0.40 g Tin(II) 2-ethylhexanoate (0.2%) * 1.96 g Dye 20(1.1%) * 133.82 g Solvent (72.7%) [99.80 g MiBK (54.5%), 14.01 g 67% glycolic acid (7.6%), 20.01 g water (10.9%)] B) Reaction Conditions; 4 hours @ 80-90°C then cooled C) Post reaction treatment; * Addition of 242 ppm Hydroquinone * Vacuum distilled * Diluted with water to 50% polymer ink Dry-down check; 10.00g polymer ink gave 5.00 g non-volatiles = 50.0% w/w polymer ink Viscosity; Rotor#4, T=25.0°C, w=60 rpm, Viscosity=80 cP Example 246: General method for Dye and Dye-Polymer Ink water solubility measurement Part 1 -Dye water solubility (before incorporation into ink) 1) Prepare dye 'solution' a) Add 0.25g Dye to 4.75g water (5%) b) Mix for 30 minutes at room temperature 2) Dry filter paper in over for 2 minutes at 150°C 3) Measure mass of dried filter paper 4) Add filter paper to vacuum filter set-up, wet with water and apply vacuum 5) Pour in the dye solution made in step (1) 6) Rinse filter cake through with 100 g water 7) Remove filter paper and air dry at ca 50°C 8) Remove final moisture in oven for 2 minutes at 150°C 9) Measure mass of filter paper to determine mass of un-dissolved dye Part 2-Dye-Polymer Ink water solubility 1) Dry filter paper in over for 2 minutes at 150°C 2) Measure mass of dried filter paper 3) Add filter paper to vacuum filter set-up, wet with water and apply vacuum 4) Add 5 g of a 50% Dye-Polymer aqueous ink concentrate (0.25g of dye @ 100% basis) 5) Rinse filter cake through with 100 g water 6) Remove filter paper and air dry at ca 50°C 7) Remove final moisture in over for 2 minutes at 150°C 8) Measure mass of filter paper to determine mass of undissolved dye, i.e., dye not incorporated into the Dye-Polymer ink.

Example 247: Comparative Example Part 1-Positive control: Dye 1-ASS Polymer Ink water solubility comparison Dye 1 is of the general Formula (1) claimed in this invention.

Dye-polymer ink produced according to the method described in Example 243 Solubility measurements carried out using the general method described in Example 246 When filtered, the Dye 1-ASS Polymer Ink filtrate was a very deep red-purple colour and no visible solid remained on the dried filter.

Material Dye mass input Mass recovered on filter Mass Dye incorporated %Dye Dye wt% solubility in water incorporation Dye 1 0.25 g 0.25 g - - 0% Dye 1-ASS Polymer Ink 0.25 g 0.01 g 0.24g ? 96% 4.8% These results show that Dye 1 is incorporated to a minimum of 96% into the polymer ink produced under conditions described in Example 243 and that the dye, when incorporated into the polymer, has an aqueous solubility of at least 4.8% in water.

Part 2-Negative control: Dye 93-ASS Polymer Ink water solubility comparison Dye 93 is in NOT of the Formula (1) claimed in this invention, and is included as a negative control.

When filtered, the Dye 93-ASS Polymer Ink was a pale brown colour (not deep purple) with significant retained granular solid retained on the dried filter.

Dye-polymer ink produced according to the general method described in Example 242 Solubility measurements carried out using the general method described in Example 246 Material Dye mass input Mass recovered on filter Mass Dye incorporated %Dye Dye wt% water solubility incorporation Dye 93 0.25g 0.25 g 0% Dye 93-ASS Polymer Ink 0.25 g >0.25 g ? 0 g 0% 0% These results show Dye 93 is not incorporated into the polymer ink produced under conditions described in Example 242.

Example 248: Dye 20-455 Polymer Ink water solubility Dye-polymer ink produced according to the method described in Example 245 Solubility measurements carried out using the general method described in Example 246 except the dye loading was 2% instead of 5% (Le. 0.10 g dye in test) When filtered, the Dye 20-ASS Polymer Ink filtrate was a very deep violet with a sail amount of visible solid remaining on the dried filter.

Table n

Material Dye mass Mass recovered Mass Dye %Dye Dye wt% solubility input on filter incorporated incorporation in water Dye 20-ASS Polymer Ink 0.101 g 0.027 g 0.074 g 73% 1.46 % These results show that Dye 20 is incorporated to a minimum of 73% into the polymer ink produced under conditions described in Example 245 and that the dye, when incorporated into the polymer, has an aqueous solubility of at least 1.46% in water.

Example 249: Spray Atomiser Application Methodology The following general application method and thermal fixation process were employed for testing textile colouration by the Dye-Polymer Ink; 1) Textile sample to be sprayed is taped to a suitable vertical surface.

2) Spraying solution is prepared; 2.1) 50% ink concentrate diluted to 5%; 2.2) 3 drops of Ultravon® Jun wetting agent added per 10g of spray solution.

3) Spraying solution added to 10 ml manual atomiser.

4) Atomiser used to mist textile in layers, with drying in between, until a deep colour is achieved.

5) Textile fully dried and cured in a convection oven (no fan) for 10 minutes at 150°C.

Example 250: Wash Testing Methodology The following general washing method was used in order to identify whether a suitable wash fastness has been achieved; 1) The edges of the sample, prepared according to Example 249, are glued to prevent the textile fraying during the wash 2) A portable washing machine (ZENY MINI Portable Single Bucket Wash Machine Washing Drying 2 in 1 Washer) is filled with c.a. 18 L of tap water (45-50°C) and ca 35 g of a standard domestic washing powder (Ariel Original) added.

3) Sample is placed in the washing machine and the machine's wash setting is turned on. The wash timer is for 15 minutes and so the dial needs turning four times to complete the full 1 hour wash cycle used for this test. The wash temperature is maintained at 40-50°C during the 1 hour wash cycle.

4) After the 1 hour of washing, the sample is removed and rinsed thoroughly with tap water.

5) Sample is patted dry with tissue paper before being fully dried in an oven for 2 minutes at 150°C. Example 251: Colour Quantification Methodology The following method is used to quantify the colour of the sample prepared according to Example 249. This method also details how the change in colour is quantified after washing according to Example 250; 1) The colour of a textile sample prepared according to Example 249 has its colour measured and quantified, using a CS-10 colorimeter, with a black card backing material. A total of 5 readings are taken and averaged, measure xyY colour coordiantes.

2) After the sample has been washed according to Example 250, the colour of the textile is quantified in the same way as outlined during step (1).

3) The dE is then determined from the average xyY results of the washed and unwashed samples. The dE is calculated using the CIE76 algorithm. A result of less than 2 is generally considered to be perceptually equivalent.

4) If a dE if greater than 2 is observed after the washing, a further wash test is done. This is continued until a dE<2 between washes were achieved.

Example 252: Wash results of Dye 1-A55 Polymer Ink on Polyester Dye 1-ASS Polymer Ink prepared according to Example 247.

Dye 1-ASS Polymer Ink applied to PET (Arville P4033) according to Example 249.

Colour and wash fastness of the resulting sample determined according to Examples 250 and 251. Table 21 shows Dye 1-ASS Polymer Ink colour measurements on PET after application and after two wash cycles.

Table 24

After Application and fixation After lx Wash Cycle +lx Wash Cycle I Y I Y x I Y I Y x I Y I Y I Reading if 1 0.4044 0.2838 12.31 0.3928 0.2801 13 0.3936 0.2793 13.05 2 0.4063 0.2832 11.92 0.3956 0.2787 12.21 0.3966 0.2781 12.37 3 0.4064 0.2822 11.85 0.3964 0.278 12.6 0.3964 0.278 12.6 4 0.4086 0.2827 11.64 0.3979 0.2786 12.14 0.3942 0.2787 12.87 0.4055 0.2829 12.03 0.3893 0.281 13.55 0.3918 0.2811 13.59 Mean 0.4062 0.283 11.95 0.3944 0.2793 12.7 0.3945 0.279 12.9 Error (a=0.05) 0.0014 0.0005 0.22 0.0034 0.0012 0.51 0.0018 0.0011 0.4 56 Error (a=0.05) 0.30% 0.20% 1.80% 0.90% 0.40% 4.00% 0.50% 0.40% 3.10% dE n/a 2.55 0.44 These results show there is no perceptual change in colour after the second wash cycle, showing all unfixed dye is fully removed in a single low temperature wash and the remainder is fixed to the fiber. Example 253: Wash results of Dye 1-A55 Polymer Ink on Nylon 66 Dye 1-ASS Polymer Ink prepared according to Example 247 Dye 1-ASS Polymer Ink applied to Nylon 66 (ArviIle P4011) according to Example 249 Colour and wash fastness of the resulting sample determined according to Examples 250 and 251. Table 22 shows Dye 1-A5S Polymer Ink colour measurements on Nylon 66 after application and after two wash cycles.

Table 25

After Application and fixation After lx Wash Cycle +lx Wash Cycle Reading if x Y Y x Y r x y r 1 0.3888 0.3008 10.58 0.3805 0.2943 9.81 0.3765 0.2928 10.75 z 0.3838 0.3004 11.26 0.3771 0.2950 10.57 0.3734 0.2945 11.07 3 0.3901 0.3011 10.38 0.3804 0.2933 9.84 0.3778 0.2920 10.17 4 0.3905 0.3010 10.39 0.3841 0.2929 9.26 0.3722 0.2949 10.64 0.3838 0.3018 11.62 0.3768 0.2947 10.38 0.3776 0.2956 9.95 Mean 0.3874 0.3010 10.85 0.3798 0.2940 9.97 0.3755 0.2940 10.52 Error (a=0.05) 0.0029 0.0004 0.49 0.0026 0.0008 0.45 0.0022 0.0013 0.4 % Error (a=0.05) 0.7% 0.1% 4.5% 0.7% 0.3% 4.6% 0.6% 0.4% 3.8% dE n/a 2.69 1.19 These results show there is no perceptual change in colour after the second wash cycle, showing all unfixed dye is fully removed in a single low temperature wash and the remainder is fixed to the fiber.

Example 254: Wash results of Dye 20-A55 Polymer Ink on Polyester Dye 20-ASS Polymer Ink prepared according to Example 248.

Dye 20-ASS Polymer Ink applied to PET (Aryille P4033) according to Example 249.

Colour and wash fastness of the resulting sample determined according to Examples 250 and 251. Table 23 shows Dye 20-ASS Polymer Ink colour measurements on PET after application and after two wash cycles.

Tattle 20 After Application and fixation After lx Wash Cycle +lx Wash Cycle I Y I Y x I Y I Y x I Y I Y I Reading if 1 0.3408 0.2654 9.96 0.3330 0.2629 11.42 0.3319 0.2665 11.45 2 0.3400 0.2649 9.98 0.3343 0.2634 11.19 0.3343 0.2672 12.74 3 0.3386 0.2646 10.41 0.3345 0.2619 10.49 0.3330 0.2665 11.90 4 0.3392 0.2642 10.22 0.3315 0.2628 10.75 0.3300 0.2679 12.44 0.3401 0.2640 10.23 0.3358 0.2627 10.58 0.3311 0.2675 11.41 Mean 0.3397 0.2646 10.16 0.3338 0.2627 10.89 0.3321 0.2671 11.99 Error (a=0.05) 0.0007 0.0005 0.17 0.0014 0.0005 0.35 0.0015 0.0005 0.52 % Error (a=0.05) 0.2% 0.2% 1.6% 0.4% 0.2% 3.2% 0.4% 0.2% 4.3% dE n/a 3.12 1.64 These results show there is no perceptual change in colour after the second wash cycle, showing all unfixed dye is fully removed in a single low temperature wash and the remainder is fixed to the fiber. Example 255: Wash results of Dye 20-ASS Polymer Ink on Nylon 66 Dye 20-ASS Polymer Ink prepared according to Example 248 Dye 20-ASS Polymer Ink applied to Nylon 66 (Arville P4011) according to Example 249 Colour and wash fastness of the resulting sample determined according to Examples 250 and 251 Table 24 shows Dye 20-ASS Polymer Ink colour measurements on Nylon 66 after application and after two wash cycles.

Table 27 *

After Application and fixation After lx Wash Cycle Reading it x y Y x y r 1 0.3418 0.2761 10.21 0.3386 0.2781 10.63 Z 0.3482 0.2767 8.87 0.3394 0.2784 9.80 3 0.3460 0.2747 8.71 0.3410 0.2821 11.23 4 0.3538 0.2838 9.83 0.3366 0.2753 10.40 0.3456 0.2771 9.36 0.3442 0.2799 9.47 Mean 0.3471 0.2777 9.40 0.3400 0.2788 10.31 Error (a=0.05) 0.0039 0.0031 0.55 0.0025 0.0022 0.61 % Error (a=0.05) 1.1% 1.1% 5.9% 0.7% 0.8% 5.9% dE n/a 1.18 These results show there is no perceptual change in colour after the first wash cycle. This shows that all dye is essentially fixed to the textile with no wash out.

Various modifications and variations of the described aspects of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes of carrying out the invention which are obvious to those skilled in the relevant fields are intended to be within the scope of the following Claims.

Claims (28)

1. CLAIMS1. A composition including a polymerisable monomer and one or more functionalised dyes, wherein the polymerisable monomer is a compound of Formula (A): Q34 NTh=Q2 Q1 Formula (A) wherein each of al, Wand Q.2 independently represent an optionally substituted hydrocarbyl group, Q4 represents an amine moiety, a tertiary ammonium cation, a quaternary ammonium cation or an optionally substituted hydrocarbyl group, q is an integer from 1 to 4; and wherein the functionalised dye comprises a chromophore and one or more functional groups capable of forming at least one covalent chemical bond with the polymerisable monomer, preferably under the conditions used to polymerise the polymerizable monomer.
2. 2. A composition of claim 1 wherein the one or more functional groups on the functionalised dye are selected from the group consisting hydroxy, thiol, amine, alkene, alkyne, alkoxysilane, and silanol; and where present, the alkene functional group is optionally part of an acrylate, acrylamide, or maleimide and where present, the alkyne is optionally part of a propargylic acid ester or propargylic acid amide.
3. 3. A composition as claimed in either one of claim 1 and claim 2 wherein the one or more functional groups are not bonded to the chromophore.
4. 4. A composition as claimed in claim 1 wherein Q'T represents a protonated tertiary amine group.
5. 5. A composition as claimed in claims 1 to 3, wherein the functionalised dye compound is of Formula (I): IDYEHL11Grn], Formula (1) Wherein: DYE is a dye compound; Lisa linking group comprising at least one hydrocarbyl group, where each [group can be the same or different; G is a functional group that is capable of forming a bond with the polymerisable monomer of Formula (A), preferably under the conditions used to polymerise the polymerizable monomer of Formula (A), where each G group may be the same or different; n is an integer of from 0 to 10; and Q4 m is an integer of from 1 to 10.
6. 6. A composition as claimed in claim 5 wherein the functionalised dye compound has the structure of any one of Formulae (la)-(Ip); DYE-EA1la(i)---[-(CH2)1,(0-A2-J1 IcaoDYE[R1]0{I) Formula (Ia) Formula (Ib) R3 [Ir](i) DYE-[Alboo-- FDYE-V^11300--\ 1 o o-J2 _ \J3 c(II) [1:11]0) Formula (lc) DYE-[Alk(11)1-(CH2)b(iii)j1 [RIO) Formula (Ie) Formula (Id) (1:111.0) DYE-Al --[(-aH b(w) 0(11)Formula (If) [R110(i) (721b(iii) 0 DYE-P.1].0)-- A3-1-(C1-12)b(viC/71 DYE-N -(C112)b(v) c(Iv) e.NR3 0 Formula (Ih) Formula (Ig) (Rim DYE-I/014r Formula (1i) * (a-12)b(viii)-O 0 DYE-(Alle(iy--((H2)b(v (1:111b(0 Formula (1j) DYE-Wilacy -(cH2)b(v [R2k(iii) DYE-EAl]aff-ml A3 (CH2)bU)-A2-JI boo Formula (1k) 0 c(N) [R1]o) Formula (II) DYE-[A1 Pric(in [al]o) A3-ECH2(CH(0J3pb(vinCH20,12 Lov) 0 Formula (1m) /J3 o DYE-V\lia(i) CH2)b(,) [R110) Formula (In) - DYE -Al+ W -Si(OR2)3 1 c(ii) I coo [FO]c(i) Formula (1o) DYE-(Maor-- (CH2)bm rem [R1]0) /A34W-Si(OR2)31 Formula (1p) \\ c(iv) wherein A1 is an oxygen or nitrogen heteroatom on DYE to which the functional group G or linking group L is attached,; A2 and A' are, independently, selected from an oxygen heteroatom or NR'; A' is selected from an oxygen or nitrogen heteroatom; _I' is selected from hydrogen, -C(0)CH=CH2 (acryloyl), -C(0)C(CH3)=CH2 (methacryloyl), or -C(0)NH(CH2)3Si( OCH 2C H3)3; 12 to 14 are, independently, selected from hydrogen, -C(0)CH=CH2 (acryloyl), or -C(0)C(CH3)=CH2 (methacryloyl); R1 is hydrogen or hydrocarbyl, preferably hydrogen or C1-C8 branched or straight-chain alkyl; R2 is hydrogen or hydrocarbyl, preferably hydrogen or Cl-CS branched or straight-chain alkyl, and especially hydrogen or C1-C4 branched or straight-chain alkyl; 113 is hydrogen or -CH3; R4 is hydrogen, Cl to C8 branched or straight chain alkyl or phenyl, preferably hydrogen or -CH3; W is C2 to C4 branched or straight chain alkyl, preferably -(CH2)3-; a(i) is 0 or 1; a(ii) is 0 or 1, preferably 1; b(i) is an integer from 1 to 18, preferably 1 to 12, especially 1 to 4, with the proviso that when a(i) = 1, then b(i) > 1; b(ii) is an integer from 0 to 5, preferably 0 to 3, more preferably 0 or 1, especially 0; b(iii) is an integer from 0 to 6, with the provisos that when a(ii)= 1, then b(iii) > 0, and when a(ii) = 0, then b(iii) is preferably 0 or 1; b(iv) is an integer from 1 to 4, preferably 1; b(v) is an integer from 0 to 4, with the proviso that when a(i) = 1, then b(v) > 0, preferably 1 or 2, especially 2, and that when a(i) = 0, then b(v) is preferably 0; b(vi) is an integer from 0 to 6, with the provisos that, when A3 is oxygen, then b(vi) is preferably 0 to 2, especially 0 or 1, and when A3 is N111 then b(vi) >0, preferably 1 to 2, especially 1; b(vii) is an integer from 1 to 4; b(viii) is an integer from 2 to 6; b(ix) is an integer from 0 to 3, preferably b(ix) + b(vi) = 1 to 4; c(i) is 0 or 1, indicating that R1 is absent or present respectively, with the proviso that when A1 = oxygen, or a(i) or a(ii) = 0, then c(i) = 0; c(ii) is 1 or 2, with the provisos that when Al= oxygen, then c(ii) = 1, and when Al= nitrogen then c(i) + c(ii) = 2; c(iii) is 0 or 1, with the proviso that when A3= oxygen, then c(iii) = 0; and c(iv) is 1 or 2, with the provisos that when A3 = oxygen, then c(iv) = 1, and when A3 = nitrogen then c(iii) + c(iv) = 2.
7. 7. A composition as claimed in either one of claim 5 and claim 6 wherein DYE has the structure of formula (11a) or (11b), being a monoazo dye or disazo dye respectively, 01-N=N-K1 D1-N=N-E1-N=N-K1 N=N-E1-N=N-K1 Formula (11a) Formula (11b) wherein 1D1 is a diazo-component, which is either optionally substituted phenyl or optionally substituted heteroaryl; E1 is optionally substituted phenyl, naphthyl or optionally substituted heteroaryl; K1 is a coupling-component, which is selected from optionally substituted phenyl, optionally substituted naphthyl, optionally substituted heteroaryl, optionally substituted pyridonyl, optionally substituted pyrazolonyl or an optionally substituted 1,3-dicarbonyl moiety; and according to Formula (I), where n = 0, at least one of D1, K1, or El, is connected to the at least one G group, or where n > 0, at least one of D1, K1 or El., is connected to the at least one L group, and the at least one L group is connected to the at least one G group.
8. 8. A composition as claimed in claim 7 wherein D is of the Formula (111a), R7 R5 Formula (111a) Wherein R5, 117 and F19 are, independently, selected from hydrogen, the G group, the L group substituted with one or more G group(s), optionally substituted straight or branched chain C1-C18 alkyl, ClC4 haloalkyl, aryl, halogen, CN, NO2, OR9, CO2R9, C(0)R9, CO2NR9R19, S020R9, S02R9, S02NR9R10, SO2F, NR9R12, NR9COR19 or NR9S02R19; R6 is selected from hydrogen, the G group, the L group substituted with one or more G groups, Cl-C4 alkyl, C1-C4 haloalkyl, halogen, NO2, or CN; R9 and 1129 are, independently, selected from hydrogen, the G group, the L group substituted with one or more G group(s), optionally substituted cyclic, acyclic or a combination C1-C18 alkyl, optionally substituted cyclic or acyclic C1-C18 alkyl which is interrupted by 1 to 6 heteroatoms selected from the group consisting of-O-, -S-, -NW--and/or by functional groups including ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, C1-C4 haloalkyl, optionally substituted aryl, optionally substituted arylalkyl, or optionally substituted alkylaryl, wherein if both R9 and 1119 are present, they may form part of the same cyclic group; and is selected from hydrogen, -C(0)119, -S02R9, optionally substituted -C1-C18 alkyl, optionally substituted C1-C18 alkyl which is interrupted by 1 to 6 heteroatoms selected from the group consisting of -0-, -5-, -NR'-and/or by or functional groups including ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, C1-C4 haloalkyl or optionally substituted aryl; and R1 is as defined in claim 6; D1 is of the Formula (111b), R.12 \ N R13 Formula (111b) wherein R12is hydrogen or halogen; and R13 is selected from hydrogen, the G group, the L group substituted with one or more G group(s), optionally substituted C1-C18 alkyl, Ca-C4 haloalkyl, aryl, halogen, CN, SCN, NO2, OR9, NR9R11, CO2R9, CO2N1191129, S020119, S02119 or S02N1191:219; NR9CORTh or NR9S02R19; D1 is of the Formula (111c), R14 N-S / R15 Formula (111c) wherein R14is hydrogen or halogen; and R15 is selected from hydrogen, halogen or nitro; D1 is of the Formula (111d), Formula (111d) wherein Ribis selected from nitro, cyano, CHO or CO21319; Rl'is selected from hydrogen, chlorine or methyl; R'8 is selected from nitro, cyano, COCH3 or CO2R19; and R19 is selected from C1-C4 alkyl or the L group substituted with one or more G groups; D1 is of the Formula (111e),N 02N SFormula (111e); D1 is of the Formula (111f), N -----R2o S Formula (111f) wherein R20is phenyl ors-R21; and R21 is C1-C4 straight or branched chain alkyl; or that DI-is of the Formula (111g);CN N'SFormula (111g) 9. A composition as claimed in claim 7 wherein K1 is of the Formula (IVa), Formula (IVa) wherein R22 is selected from hydrogen, methyl, chloro, OR', or R22 and R24 together form a 5 to 8 membered ring via a C2-C6 branched or straight chain alkyl bridge, in particular a 6 membered ring of structure C(CH3)2CH2CH(CH3) from R22 to R24; R23 is selected from hydrogen, methyl, chloro, OR26 or NHR27; R24 and R29 are, independently, selected from hydrogen, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, the L group substituted with one or more G groups, optionally substituted C1-C18 hydrocarbyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms or groups selected from -0-, -S-or -Ne-, C(0)R9, S02R9, C0(CH2)pCO2R29 or, in addition, R24 forms a ring with R22 as described for R22 above, or R24 and R29 together form a 5 to 8 membered ring which is via a C2-C6 branched or straight chain alkyl or alkenyl bridge, or via a C2-05 branched or straight chain alkyl bridge which is either interrupted by a heteroatom selected from of -0-, -S-or -NRTh-or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, or R24 and R29 are joined in a maleimide group, dimethylmaleimide group, succinimide group, glutarimide group or phthalimide group; R25 is selected from hydrogen, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, the L group substituted with one or more G groups, optionally substituted C1-C8 alkyl, ClC4 haloalkyl or optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -S-or R27 is selected from optionally substituted Cl-C10 straight or branched chain acyl, optionally substituted C1-C10 straight or branched chain carbamoyl, C1-C4 straight or branched chain halo-alkanoyl, optionally substituted benzoyl, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, CO(CH2)pCO2R29, C1-C4 straight or branched chain alkyl-sulfonyl, C1-C4 straight or branched chain haloalkylsulfonyl or optionally substituted phenylsulfonyl; R28 is selected from hydrogen, optionally substituted C1-C18 hydrocarbyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -S-or -NR28-, C1-C10 straight or branched chain acyl, C1-C4 straight or branched chain halo-alkanoyl, optionally substituted benzoyl, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, C(0)-L where the L group is substituted with one or more G group, CO(CH2)pCO2R29, COCH=CHCO2R29, C0C61-14CO2R29, C1-C4 straight or branched chain alkyl-sulfonyl, C1-C4 straight or branched chain haloalkylsulfonyl or optionally substituted phenylsulfonyl; R29 is selected from hydrogen, the L group substituted with one or more G groups, optionally substituted C1-C18 alkyl, optionally substituted C2-C8 alkenyl, optionally substituted C1-C18 alkylaryl, optionally substituted C1-C18 arylalkyl, C1-C4 haloalkyl or optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -5-or p is an integer from 1 to 4; RI-is as defined in claim 6; and R9 is as defined in claim 8; KI-is of the Formula (IVb), R3 R30 F231 Formula (IVb) wherein R3° is selected from hydrogen, acryloyl, methacryloyl, crotonoyl, 2,3-dimethacryloyl, 2,3,3-trimethacryloyl, the L group substituted with one or more G group, optionally substituted C1-C18 hydrocarbyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -S-or -N1233-, C(0)R9, S02R9, CO(CH2)pCO21129, COCH=CHCO2W9, C0C61-14CO2R29, or R3° and R31 together form a 5 to 8 membered ring which is via a C2-C6 branched or straight chain alkyl or alkenyl bridge, or via a C2-05 branched or straight chain alkyl bridge which is either interrupted by a heteroatom selected from -0-, -5-or -NR29-or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, or R3° and R31 are joined in a maleimide group, dimethylmaleimide group, succinimide group, glutarimide group or phthalimide group; R31 is selected from hydrogen, methyl or joined to R3° as described for I13° above; R32 is hydrogen or hydroxy; K1 is of the Formula (IVc), Formula (IVc) wherein R33is selected from hydrogen, CN or CONH2; R34 is selected from hydrogen, a linking group L with pendent functional group(s) G according to Formula (f), optionally substituted C1-C18 hydrocarbyl, optionally substituted phenyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to S heteroatoms selected from the group consisting of -0-, -5-or -NR28-, or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester; K1 is of the Formula (IVd), R35 R34 Formula (IVd) wherein R35 is selected from optionally substituted CFCs straight or branched chain, cyclic or acyclic alkyl, C1-C4 straight or branched chain haloalkyl, optionally substituted aryl, benzyl, cc-methylbenzyl, phenethyl, CO2R9, CO2NR91316, preferably optionally substituted C1-C6 straight or branched chain, cyclic or acyclic alkyl, Cl haloalkyl, COO, CO2NR9R19, most preferably CH3 or COO; and 119 is as defined in claim 8.K2 is of the Formula (lye), 3:-R38 R32 Formula (lye) wherein R36 is selected from optionally substituted Cl-C18 hydrocarbyl, optionally substituted phenyl, C1-C4 haloalkyl, 01329, NHR29, optionally substituted NH-aryl, or R35 and 1:02 form a 5 or 6 membered ring linked by CH2CH2, CH2CH2CH2, CH2C(CH3)2CF12, NHCONH, N(CH3)CON(CH3), OC(CH3)20; I122, when not part of a ring with 1135, is selected from optionally substituted C1-C18 hydrocarbyl, optionally substituted phenyl, C1-C4 haloalkyl or OR29; K1 is of the Formula (IVO, Formula (IVO wherein R38 is methyl or phenyl; K1 is of the Formula (IVg), Formula (IVg) is of the Formula (IVh),HN R39
9. Formula (IVh) wherein R39 is, independently, as defined for IR34 above; IC' is of the Formula (IVi), R40 R9 Formula (IVi) wherein R4° is hydrogen or C1-C8 branched or straight chain alkyl; and R9 is as defined in claim 8; K1 is of the Formula (IV]), R9 R41 Formula (IVj) wherein R41 is selected from hydrogen, C1-C8 branched or straight chain alkyl, CO2R9, CO2NR9R10; and R9 is as defined in claim 8.
10. 10. A composition as claimed in claim 7 wherein El is of the Formula (Va), R43 Formula (Va) wherein R42 and R43 are, independently, selected from hydrogen, fluor°, chloro, methyl, ethyl or OR9; and R9 is as defined in claim 8.or that El is of the Formula (Vb), R42 -K1 Formula (Vb) or that El is of the Formula (Vc), Ria 1112 is a defined in claim 8. Formula (Vc)
11. 11. A composition as claimed in either one of claim Sand claim 6 wherein the functionalised dye has the structure of Formula (VII), being a 2:1 azo-dye:metal complex, D2-0 7,3 mi " K2-Y o-D3 Formula (VII) wherein ID2 and D2 are diazo-components, independently, either optionally substituted phenyl or optionally substituted naphthyl; K2 and 10 are coupling-components, independently, selected from optionally substituted phenyl, optionally substituted naphthyl, optionally substituted heteroaryl, optionally substituted pyridonyl, optionally substituted pyrazolonyl or an optionally substituted 1,3-dicarbonyl moiety, preferably selected from optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted pyrazolonyl; Y and Z are, independently, either 0 or NR44, preferably 0; M1 is any metal in the +3 oxidation state, preferably Co(III), Cr(III) and Fee II), most preferably Co(III) and Cr(III); X+ is a counter-cation selected from a hydrogen ion, an alkali metal ion, or an ammonium ion, of the structure 13458451342848N., preferably Li', Na, r, NH4, most preferably Na"; R44 is selected from hydrogen, the L group substituted with one or more G groups, optionally substituted branched or straight chain C1-C18 alkyl, optionally substituted phenyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -5-or -NR28-, or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester; 1:145, 1146, 1:142 and 1148 are, independently, selected from a hydrogen, optionally substituted C1-C18 alkyl including linear and branched, saturated and unsaturated, cyclic and acyclic, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -S-or -NR22-, optionally substituted arylalkyl where the alkyl portion of the arylalkyl group can be C1-C18 linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted and where hetero atoms, such as oxygen, nitrogen, sulfur, silicon, and the like, either may or may not be present in either the aryl or the alkyl portion of the arylalkyl group, or optionally substituted alkylaryl where the alkyl portion of the arylalkyl group can be C1-C18 linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and where hetero atoms, such as oxygen, nitrogen, sulfur, silicon, and the like, either may or may not be present in either the aryl or the alkyl portion of the arylalkyl group; optionally two or more of 1145, n461147 and R48 may be joined through a cyclic structure; where the substituents on the substituted alkyl, arylalkyl, and alkylaryl groups may be (but are not limited to) hydroxy groups, halogen atoms, amine groups, imine groups, ammonium groups, cyano groups, pyridine groups, pyridinium groups, ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonyl groups, sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups, phosphate groups, nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfone groups, acyl groups, azo groups, cyanato groups, carboxylate groups, carboxylic acid groups, urethane groups, urea groups, mixtures thereof, and the like; and if Y and Z are both 0, or, if either or both of Y and Z is NR44 but R44 is not in either case the L group substituted with one or more G groups, then where n = 0, at least one of D2, D3, K2 or K3 is connected to at least one G group, or where n >0, at least one of 02, D3, K2 or K3 is connected to at least one L group substituted with at least one G group substituent; and R28 is as defined in claim 9.
12. 12. A composition as claimed in claim 11 wherein 02 and D3 are, independently, of the Formula (VII 1c) or (VII Id), R49 R49 / R5° Formula (V1110 Formula (VIlld) wherein 09 and is selected from hydrogen, the G group, the L group substituted with one or more G groups, optionally substituted C1-C18 straight or branched chain alkyl, C1-C4 haloalkyl, aryl, benzyl, amethylbenzyl, phenethyl, halogen, CN, NO2, CF3, 0119, S02R9, S02NR91:140, C(0)119 or CO21:19, CO214129R10, preferably NO2, chloro, COO, CO2NR3F(1°, most preferably NO2 or CO2NR9R1°; and F(5° is selected from hydrogen, NO2, C1-C8 straight or branched chain alkyl, C1-C4 haloalkyl, halogen or NO2, preferably hydrogen, NO2, COO, CO2NR91140, most preferably hydrogen or NO2; and R9 and RTh are as defined in claim 8.
13. 13. A composition as claimed in claim 11 wherein r and 10 are, independently, of the Formula (IXc), R52 R" Formula (IXc) wherein R51 and is selected from hydrogen, the G group, the L group substituted with one or more G groups, halogen, (DRY, NR5R15, preferably hydrogen, OW or NR5R15, most preferably hydrogen or NR5R15; R52 is selected from hydrogen, the G group, the L group substituted with one or more G groups, optionally substituted C1-C18 straight or branched chain alkyl, C1-C4 haloalkyl, optionally substituted aryl, benzyl, a-methylbenzyl, phenethyl, halogen, 0139, CO2R9, C(0)139, CO2N1191319, S020119, S02119, S02N1191119, SO2F, NR9C(0)R19 or NR9S02R19, preferably hydrogen, C1-C8 straight or branched chain alkyl, fluoro, chloro, CO2119, CO2N1391310, or NR9C(0)R19, most preferably hydrogen, CO2N1191119, or NR9C(0)1319; and at least one of R51 and R52 is not hydrogen; and 139 and Rim are as defined in claim 8; K2 and 10 are, independently, of the Formula (IXd), R5\3 R514 Formula (IXd) wherein R53 is selected from hydrogen, the G group, the L group optionally substituted with one or more G groups, optionally substituted C1-C18 straight or branched chain alkyl, C1-C4 haloalkyl, optionally substituted aryl, benzyl, a-methylbenzyl, phenethyl, halogen, OR9, CO2R9, C(0)139, CO2NR91319, S020R9, S02139, SO2NR91319, SO2F, NR9C(0)1319 or NR9S021319, preferably hydrogen, C1-C8 straight or branched chain alkyl, fluor°, chloro, CO2R9, CO2NR91319, or NHR27, most preferably hydrogen, CO2NR91319, or NHR27; and R54 is selected from hydrogen, optionally substituted Cl-C18 straight or branched chain alkyl, C1-C4 haloalkyl, optionally substituted aryl, benzyl, a-methylbenzyl, phenethyl, halogen, OW, preferably hydrogen, C1-C8 straight or branched chain alkyl, bromo, OR9, most preferably hydrogen; R9 and Rim are as defined in claim 8; and R27 is as defined in claim 9; K2 and K3 are, independently, of the Formula (IXe), rl R35 R34 Formula (IXe) wherein R34 and R35 are as defined in claim 9; K2 and K3 are, independently, of the Formula (IXf), R36 R37 Formula (IXf) wherein F235 and Ft' are as defined in claim 9.
14. 14. A composition as claimed claim 5 and claim 6 wherein the functionalised dye is a phthalocyanine dye of formula (X): R57 R56 Rsi Rso Formula (X) wherein M2 is selected from a metal in the +2 oxidation state, a metal(III) halide, metal(111) hydroxide, metal(IV) dihalide or a metaleV) oxide/dihydroxide capable of being introduced, e.g. metals including Al, Cd, Co, Cr, Cr, Cu, Fe, Ga, Hf, Hg, In, Mg, Mo, Mn, Ni, Pb, Pd, Pt, Rh, Ru, Si, Sn, Ti, V, Zn, Zr, and the like, preferably selected from Al, Cu, Ni and Zn, and most preferably is Cu; R55 is selected from the G group, the L group substituted with one or more G groups, OR63, 51363, C(0)0R64, C(0)NR641165, S02R64, 5020R64, or 502NR64R65; 1356 to R62 are, independently, selected from hydrogen, the G group, the L group substituted with one or more G groups, halogen, OH, CO21-1, CO2-, C(0)NH2, 503H, 503-, 01363, 51363, C(0)0R64, C(0)N1364R65, 502R64, 5020R64 or SO2NR641365; R53 is either the G group or the L group substituted with one or more G groups; R64 is the L group substituted with one or more G groups; 1165 is selected from hydrogen, the L group substituted with one or more G groups, optionally substituted straight or branch chain C1-C18 alkyl, optionally substituted straight or branch chain Cl-C18 alkyl which is interrupted by 1 to 6 heteroatoms selected from the group consisting of -0-, -5-, C1-C4 haloalkyl or optionally substituted aryl, optionally substituted arylalkyl or optionally substituted alkylaryl.
15. 15. A composition as claimed in either one of claim S and claim 6 wherein the functionalised dye is an anthraquinone dye, of the Formula (XI), R69 o R66 rice' R68 0 R67 Formula (XI) wherein R66 to R69 are, independently, selected from hydrogen, halogen, nitro, OR9, NHR9 or SR9 and at least one of R66 to R69 is not hydrogen; preferably R66 is NHR9 or 5R9, and when R66 is NHR9 then R6' is NHR9 or OR9, and when R66 is SR9 then R6' to R69 are, independently, hydrogen or SR9; and Fi79 and R71 are, independently, selected from hydrogen, halogen, the G group, the L group substituted with one or more G groups, -0R9, -SR9, CO2R9, -C(0)R9, -0O2NR9R19, -S020R9, -502R9 or -502NR9R19, -C61-140R9, 0061-140R9, 0061-14502R9, 0061-140502R9, 0061-145020R9, 0C6H4S02NR9R19, 0C61-14CH2OR9, 0C61-14CH2NR9R19, OC6H4CH2NR9C(0)R19, or Viand R71 are adjacent and form an imide ring of formula -C(0)NR9C(0)-; R9 and 1119 are as defined in claim 8; and according to Formula (I), where n = 0, at least one of I256 to R71 is connected to at least one G group, or where n > 0, at least one of R36 to R7.1 is connected to at least one L group, and L is connected to at least one G group.
16. 16. A composition as claimed in either one of claim S and claim 6 wherein the functionalised dye is a coumarin dye, of the Formula (XII), or an extended coumarin dye, of the Formula (Xllh); \ R75 R73 N R7 0 R74 Formula (XII) 72 W6CNFormula (Xllh) wherein A3 is selected from 0, S, NH; R72 is OR9 or NR9R19, preferably NR9R19; R73 is selected from hydrogen, halogen, methyl or -CN, preferably hydrogen or -CN; Ft74 is 0 or NH; R71 RTh is selected from hydrogen, halogen, the G group, the L group substituted with one or more G groups, -0R9, -SR9, CO2R9, -C(0)R9, -CO2NR9R19, -S020R9, -S02R9 or -SO2NR9R19, preferably -CO2NR9R19 or -SO2NR9R19; R9 and R1° are as defined in claim 8; according to Formula (1), where n = 0, at least one of 1172 and 1178 is connected to at least one G group, or where n >0, at least one of 1172 and 1178 is connected to at least L group, and L is connected to at least one G group.
17. 17. A composition as claimed in either one of claim Sand claim 6 wherein the functionalised dye R78 R77/ R79' R32' 0 is a squaraine dye, of the Formula (X111a) to (X111e), F178' 0 R76-R32 R79 R78'\ -N + \R77 R8K R81 Roo N+ Formula (X111a) Formula (X111b) R80 Formula (X1110 Formula (X111d) Formula (Xlle) wherein Iffis, independently, as defined for 1132 in claim 9; R75, R76, 1277 and 1177 are, independently, selected from hydrogen, the L group substituted with one or more G groups, optionally substituted C1-C18 hydrocarbyl, C1-C4 haloalkyl, optionally substituted C1-C12 alkyl which is interrupted by 1 to 5 heteroatoms selected from the group consisting of -0-, -5-or -NR28-, or R76 and R77, R78 and R771, 1378 and R'9, and/or R78 and R79 together form a 5 to 8 membered ring via a C2-C6 branched or straight chain alkyl or alkenyl bridge, or via a C2-05 branched or straight chain alkyl bridge which is either interrupted by a heteroatom selected from of -0-, -S-or -NR28-or interrupted by a functional group selected from ketone, ester, amide, carbonate, carbamate, sulfoxide, sulfone, sulfinic acid ester, sulfonic acid diester, silanol, ammonium salt, phosphoric acid ester, phosphonic acid ester or phosphinic acid ester, ; at least one of R76 and R77, and at least one of 1176! and R77, is not hydrogen; 1178 and F178' are, independently, selected from hydrogen, methyl, chloro, OR26 or NHR27, preferably hydrogen, OR26 or NHR27; R79 and R79! are, independently, selected from hydrogen, methyl, chloro, OR26, or 1176 and R79, and/or 1176! and R79, together form a 5 to 8 membered ring via a C2-C6 branched or straight chain alkyl bridge, in particular a 6 membered ring of structure C(CH3)2CH2CH(CH3) from R79 to R76; and where n = 0, at least one of IV6 to R78, and at least one of R76! to 1179, is connected to at least one G group, or where n >0, at least one of R78 to R79, and at least one of R78' to R79, is connected to at least one L group substituted by at least one G group; Ft86 is the L group substituted with one or more G groups; R81 is selected from hydrogen, the L group substituted with one or more G groups, optionally substituted straight or branch chain C1-C18 alkyl, optionally substituted straight or branch chain C1-C18 alkyl which is interrupted by 1 to 6 heteroatoms selected from the group consisting of -0-, -S-, C1-C4 haloalkyl or optionally substituted aryl, optionally substituted arylalkyl or optionally substituted alkylaryl; and R26, R27, 11 *-*28, R32 and R38 are as defined in claim 9.
18. 18. A composition as claimed in either one of claim sand claim 6 wherein the functionalised dye is a croconaine dye, of the Formula (XlVa) or (XIVb), R76 R78 0-R77 ret We R78 0 0 R8° R80 N. W7 NNR81 R79 R76 Formula (XlVa) Formula (XIVb) R76 to R81 are as defined in claim 17;
19. 19. A composition as claimed in either one of claim sand claim 6 wherein the functionalised dye is a metal dithiolene dye, of the Formula (XV), or a a styryl dye, of the Formula (XVI), R83ShipR82 *S-yS R93Formula (XV) R85 Formula (XVI) wherein NI9 is selected from any metal or metal oxide capable of being introduced, e.g. V, VO, Cd, TiO, Ti, Mn, Cr, Fe, Co, Ni, Cu, Zn, Pd, Cd, Mg, Hg Zr, Al, Mo02, Pt, Ru, Rh, Hf, Sb, Sn, Pb, Pd, Au, Ag and the like, preferably Ni, Cu, Pd, and Pt, most preferably Ni; R82 is selected from the G group, the L group substituted with one or more G groups, -0R9, -SR9, -CO2R9, -C(0)R9, -CO2NR9R19, -5020R9, -S02R9 or -SO2NR9R19, -C61-09, -C6F140R9, -C6H4SR9, -C61-14CO2R9, -C61-14C(0)R9, -C61-14CO2NR9R19, -C61-145020R9, -C6H4502R9 or -C61-14502NR9R18; Fi83 is selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, optionally substituted phenyl, -C6H4R9, -C61-140R9, -C61-145R9, -C61-14CO2R9, -C61-14C(0)R9, -C61-14CO2NR9R29, -C61-145020R9, -C6H4S02R9 or -C61-14502NR9R29; R9 and RTh are as defined in claim 8; according to Formula (1), where n = 0, at least one of R" and I189 is connected to at least one G group, or where n >0, at least one of 1182 and I182 is connected to at least one L group substituted with one or more G groups; R84 is -CN, -CO2R29 or -C(0)NR9187; Ras is -CN or -CO2R29; 1:189 and 118' are, independently, the same definition as R29; R22 to R29 and R29 are as defined in claim 9; and according to Formula (I), where n = 0, at least one of R22 to R29 is connected to at least one G group, or where n > 0, at least one of R22 to R29, R82 or 1183 is connected to at least one L group substituted with one or more G groups.
20. 20. A composition as claimed in either one of claim sand claim 6 wherein the functionalised dye is a pyrroline dye, of the Formula (XVII), or a 3-dicyanomethylidene-2,3-dihydro-thiophene 1,1-dioxide dye, of the Formula (XVIII), R23CN CNNC R29 0Formula (XVII) R29 R24 R22NCFormula (XVIII) wherein w is 0 or 1; R22 to R25 and R29 are as defined in claim 9; according to Formula (I), where n = 0, at least one of R22 to R25 is connected to at least one G group, or where n > 0, at least one of R22 to R25 or R29 is connected to at least one L group substituted with one or more G groups; R22 to R25 are as defined in claim 9; and according to Formula (I), where n = 0, at least one of R22 to R25 is connected to at least one G group, or where n >0, at least one of R22 to R25 is connected to at least one L group substituted with one or more G groups
21. 21. A composition as claimed in either one of claim Sand claim 6 wherein the functionalised dye is a Xanthene dye, which may be a Rhodamine dye, or wherein the functionalised dye is a UV-absorber, and optionally a Fluorescent Brightening Agent, and is of the general Formula (1).
22. 22. A composition as claimed in any preceding claim wherein the polymerisable monomer has the structure below: to r / o 0 N,A,,N,),N""
23. 23. A composition as claimed in any preceding claim comprising 1 to 30%w/w (typically 1 to 10 w/w%) of one or more of the functionalised dyes, 20 to 50w/w% (typically 30 to 45 w/w%) of one or more of the polymerisable monomers, less than 2%w/w (generally less than 1%w/w) of one or more initiator compounds, 5 to 10 w/w% acid, in particular glycolic acid, and optionally less than 5 wt.% cross-linking agent, in particular around Ito 3 w/w% acrylic cross-linking agent.
24. 24. A method of forming the composition as claimed in any preceding claim comprising: a. forming a mixture including the polymerisable monomer and the functionalised dye of any preceding claim; b. initiating partial polymerisation of the polymerisable monomer and co-polymerisation of, or reaction with, the functionalised dye; c. adding an acid to the mixture, wherein the acid reacts with the reaction product of step b to form a cationic co-polymer.
25. 25. A method as claimed in claim 24 including co-polymerisation of the polymerizable monomer and the functionalised dye.
26. 26. A method as claimed in either one of claim 24 and claim 25 wherein the cationic copolymer is diluted with water to create a partially polymerised dye-polymer composition, such as an ink composition, suitably wherein 20 to 80 w/w% water is added to the mixture, typically 40 to 60 w/w% water.
27. 27. A method as claimed in any one of claims 24 to 27 wherein the acid is added at a molar excess of over 1.1 molar equivalents based on the polymerisable monomer, suitably 1.2 to 1.4 molar equivalents.
28. 28. A method of colouring a substrate, in particular a method of printing on a textile including: providing the composition including the polymerisable monomer and the functionalised dye as claimed in any one of claims 1 to 23, partially polymerising the composition to form a partially polymerized composition, applying the partially polymerized composition to a surface of the substrate, fixing the partially polymerized composition to the surface, suitably by initiating the further polymerization of the partially polymerized composition; suitably wherein the partially polymerised composition is reacted with an acid to form a cationic copolymer.