GB2259517A

GB2259517A - Phthalocyanine compounds

Info

Publication number: GB2259517A
Application number: GB9217123A
Authority: GB
Inventors: Peter John Duggan; Dean Thetford
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1991-09-02
Filing date: 1992-08-13
Publication date: 1993-03-17
Also published as: GB9217123D0

Abstract

A polymer obtained by the polymerisation of a polymerisable phthalocyanine compound having one or more functional groups capable of taking part in polymerisation reactions, each of said groups being directly attached to an organic radical which is itself linked by an atom of an element of Group VB or Group VIB of the Periodic Table to a peripheral carbon atom of the phthalocyanine nucleus and monomeric precursors thereof. The polymers absorb strongly in the infra-red region of the spectrum and are useful for incorporation into laser-addressable optical data storage media whereby they are less prone to migration than monomeric infra-red absorbers.

Description

PHTHALOCYANINE COMPOUNDS This invention relates to phthalocyanine compounds and more particularly to polymerisable phthalocyanine compounds, to polymers derived therefrom and to the use of the polymers in optical data storage systems.

Optical data storage devices comprising a substrate supporting a film of optically deformable recording material are already known as is the use of infra-red absorbing organic dyes for the purpose of absorbing optical signals of modulated electromagnetic radiation applied to the film. Various dyes have been proposed for this purpose and our EP-A-186404 describes the use of certain phthalocyanine compounds wherein at least five of the peripheral carbon atoms are linked by atoms of Group VB or Group VIB of the Periodic Table to carbon atoms of organic radicals. The dyes are used in conjunction with amorphous polymers such as polyamides, polystyrene or polycarbonates in the form of polymer/dye composite films or, alternatively, films of pure dye can be formed on supporting substrates by solution casting techniques such as spin coating, dip coating and web coating.Unfortunately, when dyes are used in either of these ways, an undesirable migration of dye to other layers of the device can take place.

It has now been found that polymers of certain phthalocyanine compounds can be prepared and that, when the polymers are used as the active layers of optical data storage devices, the migration problem is minimised.

Accordingly, the present invention provides a polymer obtained by the polymerisation of a polymerisable phthalocyanine compound having one or more functional groups capable of taking part in polymerisation reactions, each of said groups being directly attached to an organic radical which is itself linked by an atom of an element of Group VB or Group VIB of the Periodic Table to a peripheral carbon atom of the phthalocyanine nucleus.

The polymers of the invention are preferably products of an addition polymerisation as distinct from a condensation polymerisation involving the elimination of small molecules such as water. Thus, in preferred polymerisable phthalocyanine compounds, the aforementioned functional groups comprise one or more ethylenically unsaturated groups capable of taking part in olefinic or vinyl polymerisation and/or two or more reactive groups capable of a poly-addition reaction with other reactive groups present in an appropriate co-reactant.

As examples of ethylenically unsaturated groups which may be present as functional groups in the polymerisable phthalocyanine compounds, there may be mentioned groups of the general Formula (1):

wherein X represents an atom or group linking the olefinic group to a carbon atom present in the dye molecule, n has the value 0 or 1 and each of R, R and R independently represents a hydrogen or halogen atom or a hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, cycloalkyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, nitro, cyano, acyloxy or alkoxycarbonyl group.

Alkyl groups mentioned herein, either as such or as components of larger groups such as alkoxycarbonyl, particularly include lower alkyl groups having one to four carbon atoms.

The preferred unsaturated groups are those in which each of R- and R3 is hydrogen and R1 is hydrogen, halogen, lower alkyl, cyano or alkoxycarbonyl. Especially preferred groups are those in which each of R and R3 is hydrogen and R1 is hydrogen, halogen (especially chlorine) or lower alkyl (especially methyl).

As examples of linkages which may be represented by X in Formula (1) there may be mentioned -0-, -S-, -CO-, -CS-, -NR4-CO- in which R4 is hydrogen or alkyl, -O-CO-, -S-CO-, -CO-O-, -CO-S-, -SO-.

-SO2-, -CH2-,-O-CH2-, -S-CH2-, -COCH2-, -O-CO-CH2-, -NR4-CH2 and -NR4-.

Polymers of the invention may be prepared from the phthalocyanine compounds in which the functional groups comprise one or more ethylenically unsaturated groups using conventional techniques, for example free radical polymerisation, the phthalocyanine compounds being homopolymerised or copolymerised with copolymerisable unsaturated monomers.

As examples of reactive groups which may be present as functional groups in the polymerisable phthalocyanine compounds, there may be mentioned active hydrogen containing groups, for example hydroxy, mercapto and primary and secondary amino groups.

Polymers of the invention may be prepared from the phthalocyanine compounds in which the functional groups comprise two or more active hydrogen containing groups by reacting said compounds optionally in conjunction with other compounds containing a plurality of active hydrogen atoms, with co-reactants capable of undergoing a poly-addition reaction therewith. Examples of suitable co-reactants include polyepoxides, polyisocyanates, polyisothiocyanates and polyacryloyl compounds.

Preferred starting materials for use in making the polymers of the invention by reaction with appropriate co-reactants include phthalocyanine compounds containing from 2 to 16, preferably from 2 to 12, especially from 3 to 8 active hydrogen-containing groups, each of said groups being attached to a carbon atom of an organic radical which is itself linked by an atom of an element of Group VB or Group VIB of the Periodic Table to a peripheral carbon atom of the phthalocyanine nucleus.

The organic radical to which each functional group is directly attached in the polymerisable phthalocyanine compound may be an optionally substituted aliphatic, alicyclic or aromatic radical and is preferably an optionally substituted aromatic radical, especially from the benzene, naphthalene and mono- or bi-cyclic, heteroaromatic series.

Examples of suitable aromatic radicals are optionally substituted phenyl, phenylene, naphthyl, especially naphth-2-yl, naphthylene, pyridyl, thiophenyl, furyl, pyrimidyl and benzthiazolyl. Aliphatic radicals are preferably from the alkyl and alkenyl series containing up to 20 carbon atoms, such as butyl, nonyl, dodecyl, octadecyl and octadecenyl. Alicyclic radicals are preferably homocyclic containing from 4 to 8 carbon atoms, such as cyclohexyl. The organic radical may be monovalent and attached to a single peripheral carbon atom through a single Group VB or Group VIB atom or it may be polyvalent, preferably divalent, and attached to adjacent peripheral carbon atoms through identical or different atoms from Group VB and Group VIB. Where the organic radical is polyvalent it may be attached to two or more phthalocyanine nuclei.

Examples of substituents for the aromatic and heteroaromatic radicals are alkyl, alkenyl, alkoxy and alkylthio, and halo substituted derivatives thereof, especially those containing up to 20 carbon atoms, aryl, arylthio, especially phenyl and phenylthio, halogen, nitro, cyano, carboxy, aralkyl, aryl- or alkyl-sulphonamido, aryl- or alkyl-sulphone, aryl- or alkyl-sulphoxide, or tertiary amino. Examples of substituents for the aliphatic and cycloaliphatic radicals are alkoxy, alkylthio, halo, cyano and aryl. In these substituents the alkyl and alkenyl groups preferably contain up to 20, and more preferably up to 4, carbon atoms and the aryl groups are preferably mono- or bi-homo- or hetero-cyclic. Specific examples of substituents are methyl, ethyl, dodecyl, methoxy, ethoxy, methylthio, allyl, trifluoromethyl, bromine, chlorine, fluorine, benzyl, COOH, -COOCH3, -COOCH2C6H5, -NHSO2CH3, 502 6 5' C H and N(CH3)2.

Examples of suitable atoms from Group VB and Group VIB for linking the organic radical to a peripheral carbon atom of the phthalocyanine nucleus are sulphur, oxygen, selenium, tellurium and nitrogen or any combination of these. Where an organic radical is linked to adjacent peripheral carbon atoms the second bridging atom may be any atom from Group VB or Group VIB, for example those mentioned above. Where the linking atom is nitrogen, the free valency may be attached to hydrogen or may carry, for example, an alkyl group, preferably C1 4-alkyl or an aryl group, preferably phenyl.

It will be understood by those skilled in the art that the peripheral carbon atoms of the phthalocyanine nucleus to which the atoms of Group VB and/or Group VIB are attached are the atoms numbered 1 to 16 in the Formula (2):

wherein M represents hydrogen, a metal atom, a halogeno-metal group or an oxy-metal group and k is the inverse of half the valency of M.

Examples of suitable metals, halogeno-metals and oxy-metals include copper, lead, cobalt, nickel, iron, titanium, zinc, germanium, indium.

magnesium, calcium, palladium, chloroindium, gallanyl and vanadyl. Especially useful phthalocyanine compounds for use in making the polymers of the invention may be represented by the Formula (3):

wherein Pc represents a metal-free or metal-containing phthalocyanine nucleus; each X, which is attached to a peripheral carbon atom of the phthalocyanine nucleus, represents sulphur, oxygen, selenium, tellurium or NT where T is hydrogen, alkyl or aryl; 2 and Q are optionally substituted hydrocarbon or heterocyclic radicals; Y, which is directly attached to a carbon atom present in Q1 or Q, represents a functional group capable of taking part in a polymerisation reaction; a represents an integer from 0 to 8; b represents an integer from 0 to 16 provided that the sum of 2a and b is from 2 to 16; and c represents an integer of at least 2.

When the sum of 2a and b is less than 16, the remaining peripheral carbon atom or atoms of the phthalocyanine nucleus may be unsubstituted, that is to say carry hydrogen atoms, or be substituted by other substituents, for example halogen atoms or amino groups.

Preferred phthalocyanine compounds of Formula (3) include compounds having at least one of the following features: (i) each X, independently, is oxygen, NT (as defined above) or especially sulphur; (ii) Q and Q are aromatic radicals and preferably radicals of the naphthalene or especially benzene series, which radicals may carry one or more other substituents of a non-reactive nature, for example alkyl groups; (iii) Y is an active hydrogen containing group, especially a hydroxyl or primary or secondary amino group; (iv) 2a + b is from 10 to 16, especially from 12 to 16 and more especially 15 or 16; (v) c is from 2 to 16, especially from 2 to 12 and more especially from 3 to 8; and (vi) c does not exceed a + b, and preferably is less than a + b.

Within the scope of Formula (3), particular mention may be made of compounds of the Formula (4): (Y#Q4#X#)q Pc (-X-Q )p (4) wherein Pc, X and Y have the same meanings as in Formula (3); 3 and 4 Q and Q are optionally substituted aromatic radicals; p represents an integer from 0 to 14 and q represents an integer from 2 to 16 provided that the sum of p and q is from 2 to 16.

Preferred phthalocyanine compounds of Formula (4) include compounds having at least one of the following features: (i) each X, independently, is oxygen, NT (as defined above) or especially sulphur; (ii) Q and Q4 are radicals of the naphthalene or especially benzene series, which radicals may carry one or more other substituents of a non-reactive nature, for example alkyl groups; (iii) Y is an active hydrogen containing group, especially a hydroxyl or primary or secondary amino group; (iv) p + q is from 10 to 16, especially from 12 to 16 and more especially 15 or 16; and (v) q is from 2 to 12 and more especially from 3 to 8.

Within the scope of Formula (4), particular mention may be made of compounds of Formula (5):

wherein Pc, p and q have the same meanings as in Formula (4); each X1, independently, is oxygen, sulphur or NT (as defined above); each benzene ring may carry one or more inert substituents; and Y1 is an active hydrogen-containing group.

Preferred phthalocyanine compounds of Formula (5) include compounds having at least one of the following features: (i) each X1 is sulphur; (ii) each Y1 is a hydroxyl or primary or secondary amino group; (iii) p + q is from 10 to 16, especially from 12 to 16 and more especially 15 or 16; and (iv) q is from 2 to 12 and more especially from 3 to 8.

The compounds of Formula (3) are believed to be novel and constitute one embodiment of the present invention with the exception of penta(phen-l-amino-2-thio-ylene) -penta(2-aminophenylthio) -CuPc which is disclosed in Example 43 of EP-A-155780 and proposed as an infra red absorber and not as a polymer-forming reactant.

The compounds of Formulae (4) and (5) are believed to be novel compounds and constitute further embodiments of the invention.

A number of methods may be used for the preparation of the polymerisable phthalocyanine compounds.

For example, compounds of Formula (4) may be prepared by heating a phthalocyanine compound having halogen atoms attached to peripheral carbon atoms with appropriate proportions of a compound of Formula (6): Hx y (6) optionally in conjunction with a compound of Formula (7): HX -Q3 (7) wherein Q3, Q4, X and Y have the same meanings as in Formula (4).

Suitable compounds of Formula (6) include hydroxythiophenols and aminothiophenols in which the amino group is protected by acylation.

Reaction with the halogen-substituted phthalocyanine is suitably performed at temperatures of from 1000 to 2509C in the presence of an acid-binding agent such as potassium hydroxide in an inert solvent.

Another method of preparing the polymerisable phthalocyanine compounds comprises reacting a phthalocyanine compound containing a plurality of organic radicals free of functional groups, each radical being linked by an atom of an element of Group VB or Group VIB of the Periodic Table to a peripheral carbon atom of the phthalocyanine nucleus with a compound of Formula (6) whereby to replace organic radicals having no functional groups by functionalised radicals. This reaction, which may be performed at temperatures of from 1000 to 2500C in the presence of an acid-binding agent in an inert solvent, may be used, for example, to displace arylthio substituents free of functional groups by arylthio or arylamino substituents having functional groups or to displace aryloxy substituents free of functional groups by arylthio substituents having functional groups.

In the preparation of the polymers of the invention from phthalocyanine compounds having a plurality of active hydrogen containing groups, for example compounds falling within the scope of Formulae (3), (4) and (5), the co-reactants which may be used particularly include those polyepoxy compounds, polyisocyanates and polyacryloyl compounds already known for reaction with active hydrogen compounds.

Polyepoxy compounds which may be reacted with the phthalocyanines include glycidyl ethers of polyols, for example the diglycidyl ethers of ethylene glycol and bisphenol A and oligomers thereof.

Polyisocyanates which may be reacted with the phthalocyanines include aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates, especially diisocyanates. Examples of suitable polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane4,4'-diisocyanate, m- and p-tetramethylxylene diisocyanates, phenylene diisocyanates, tolylene-2,4- and 2,6-diisocyanates and mixtures thereof, diphenylmethane-4,4'- and 2,4'-diisocyanates and mixtures and/or oligomers thereof. There may also be used polyisocyanates which have been modified by the introduction of urethane, allophanate, urea, biuret, carbodiimide, uretonimine or isocyanurate residues. The corresponding polyisothiocyanates may also be used.

Polyacryloyl compounds which may be reacted with the phthalocyanines include methylene bis-acrylamide and 1,3,5-tris-acryloyl hexahydrotriazine.

If desired, the phthalocyanines having a plurality of active hydrogen containing groups may be reacted with the aforementioned co-reactants in admixture with other active hydrogen compounds, for example low molecular weight or polymeric polyols, polyamines and the like.

Simple evidence of the production of polymers may be obtained by dissolving a small amount (0.01g) of a phthalocyanine compound containing active hydrogen groups in dimethylformamide (lml) with ethylene glycol diglycidyl ether (n/2 equivalents) and heating to 600C for 16 hours. If the resulting film does not dissolve in dimethyl formamide at room temperature, polymerisation has occurred.

The polymers of the invention, when prepared in the form of films, may be used as active layers in optical data storage devices, for example laser addressable disks, tapes, cards and the like.

The invention is illustrated but not limited by the following Examples.

Example 1 4-Hydroxythiophenol (12.6g, 0.1 mol), potassium hydroxide (4.2g, 0.075 mol) and DMF (40ml) were stirred together at 1200C for 30 minutes, then tetradecachloromonobromo copper phthalocyanine (5.7g, 0.005 mol) was added. The solution was stirred at 1200C for 2 hours, cooled to room temperature and chloroform was added. A solid precipitated and was filtered off. The solid was washed with chloroform, then dissolved in DMF. The solution was filtered through clarcelflo and chloroform was added. The filtered black solid (pentadeca-(4-hydroxyphenylthio)copper phthalocyanine) was dried (5.38g, 44%) m.p. > 250 C. max (DMF) 760nm.

Elemental Analysis: Found C 60.3; H 3.1; N 4.8% C122H76NO15S 15Cu requires C 60.1; H 3.1; N 4.6%.

Example 2 Dodecabromo copper phthalocyanine (7.62g, 0.005 mol) was added to a mixture of 4-hydroxythiophenol (12.6g, 0.1 mol) and potassium hydroxide (2.68g, 0.05 mol) in DMF (50ml) at 1200C for 2 hours. The mixture was cooled to room temperature and chloroform was added. The precipitated solid was filtered off and washed with chloroform. The solid was dissolved in DMF and the solution was filtered through clarcelflo. Chloroform was added to the solution to precipitate a solid. The black solid (penta-(4-hydroxyphenylthio)heptabromo copper phthalocyanine) was filtered off and dried (5.72g, 65%) m.p. > 250 C.

max (DMF) 736nm.

Elemental Analysis: Found C 40.3; H 2.4; N 5.2% C62H29Br7N805S5Cu requires C 42.5; H 1.7; N 6.4%.

Example 3 Octachloro dihydrogen phthalocyanine (7.9g, 0.01 mol), comprising 79X octa-3,6 and 21% octa-4,5 isomers, was added to a stirred mixture of 4-hydroxythiophenol (12.6g, 0.1 mol) and potassium hydroxide (4.48g, 0.08 mol) in DMF (50ml) at 12000. The mixture was stirred at 12000 for 2 hours, cooled to room temperature and ethanol was added.

The precipitated solid was filtered off and washed with ethanol, dissolved in DMF and the resultant solution was filtered through clarcelflo. Chloroform was added to the solution and a black solid (di-(4-hydroxyphenylthio)-hexachloro dihydrogen phthalocyanine) was filtered off and dried (2.5g, 26%) m.p. > 250 C. max (DMF) 715nm.

Elemental Analysis: Found C 51.8; H 3.3; N 9.3% C44H29Cl6N802S2 requires C 54.5; H 2.1; N 11.55%.

Example 4 A mixture of 4-hydroxythiophenol (1.26g, 10m mols), 4-thiocresol (3.72g, 30m mols) and KOH (1.68g, 30m mols) were dissolved in DMF (25ml) at 12000 with stirring. After 15 minutes at 12000, tetradecachloromonobromo copper phthalocyanine (2.28g, 2m mol) was added to the stirred mixture which was kept at 12000 for 2 hours. The mixture was allowed to cool to 8000 and then screened through clarcelflo. The filtrate was poured into water (200ml) and the precipitated solid was filtered off. The solid was dissolved in ethanol (SOml) and screened through clarcelflo.The filtrate was poured into water (300ml) and the precipitated solid was filtered off and dried (3.21g).

The solid was applied to a silica column using firstly toluene as eluent, then 1:3 toluene:chloroform (v:v), chloroform and finally 1:10 methanol:chloroform as eluent. All similar fractions were collected and the solvent removed under reduced pressure to give trichloro-tri(4-hydroxyphenylthio) -nona(4-methylphenylthio) copper phthalocyanine as a black solid (0.77g, L8%) m.p. 155-160 C.

Elemental Analysis: Found C 63.1; H 4.3; N 4.8; C1 4.0; S 16.9 C113H79Cl3N803S12Cu requires C 63.1; H 3.7; N 5.2; C1 4.9; S 17.9 Example 5 The procedure of Example 4 was repeated except that the quantities of 4-hydroxythiophenol (2.52g, 20m mols) and 4-thiocresol (2.48g, 20m mols) were altered. The isolated, crude solid (2.44g) was applied to a silica column using the same solvent systems as Example 4 to give tetrachloro-tri(4-hydroxyphenylthio) -octa(4-methylphenylthio) copper phthalocyanine as a black solid (0.9g, 22X) m.p. 185-190 C.

Elemental Analysis: Found C 60.6; H 3.7; N 5.2; C1 4.3; S 16.7 C106H72C14N803S11Cu requires C 61.7; H 3.5; N 5.4; C1 6.9; S 17.1 Example 6 The procedure of Example 4 was repeated except that the quantities of 4-hydroxythiophenol (3.79g, 30m mols) and 4-thiocresol (1.24g, 10m mols) were altered. The isolated, crude solid (3.28g) was applied to a silica column using the same solvent systems as Example 4 to give pentachlorohexa(4-hydroxyphenylthio) - tetra(4-methylphenylthio) copper phthalocyanine as a black solid (0.96g, 24%) m.p. 175-180 C.

Elemental Analysis: Found C 57.8; H 3.4; N 5.6; C1 8.7; S 14.9 C96H59Cl5N8O6S10Cu requires C 58.2; H 3.0; N 5.6; C1 8.9; S 16.2 Example 7 A mixture of 4-hydroxythiophenol (1.26g, 10m mol), 4-thiocresol (3.72g, 30m mol) and KOH (1.68g, 30m mol) in DMF (25ml) was stirred at 1200C for 15 minutes. Tetradecachloromonobromo copper phthalocyanine (2.28g, 2m mol) was added to the mixture which was stirred at 1200C for 16 hours. The mixture was allowed to cool to room temperature and then poured into water (300ml). The precipitated solid was filtered off and then dissolved in DMF (20ml) and screened through clarcelflo.The filtrates were evaporated to dryness under reduced pressure and the isolated, crude solid was slurried in boiling toluene to remove dark coloured impurities. The solid was filtered off from the solvent and the slurrying procedure was repeated. The black solid obtained, (pentachlorohepta(4-hydroxyphenylthio)-tri(4-methylphenylthio) copper phthalocyanine), was dried (2.25g, 57%) m.p. 150-155 C.

Elemental Analysis: Found C 57.9; H 3.5; N 4.4; C1 9.1; S 13.0 C95H57C15N8O7S10Cu requires C 57.5; H 2.9; N 5.6; C1 8.9; S 16.1 Example 8 The procedure of Example 7 was repeated except that the quantity of KOH used (2.8g, 50m mol) was altered and the reaction mixture was kept at 600C for 16 hours in a sonic bath. The isolated, black solid (trichloro-deca(4-hydroxyphenylthio)-di(4-methylphenylthio) copper phthalocyanine) (0.45g, 10%) had m.p. > 200 C.

Elemental Analysis: Found C 58.3; H 3.7; N 4.9; C1 5.5; S 15.2 C106H65Cl3N8010S12Cu requires C 58.7; H 3.0; N 5.2; C1 4.9; S 17.8 Example 9 A mixture of 4-hydroxythiophenol (1.26g, 10m mol), 4-thiocresol (3.72g, 30m mol) and KOH (2.24g, 40m mol) in DMF (25ml) was stirred at 120 C for 15 minutes. Tetradecachloromonobromo copper phthalocyanine (2.28g, 2m mol) was added to the mixture which was stirred at 1200C for 16 hours. The mixture was allowed to cool to room temperature and then poured into water (300ml). The precipitated solid was filtered off and then dissolved in DMF (20ml) and screened through clarcelflo.The filtrates were evaporated to dryness under reduced pressure to give a black gum which was slurried in water. A black solid (tetra(4-hydroxyphenylthio) -undeca(4-methylphenylthio) copper phthalocyanine was obtained, filtered off and dried (5.33g, 85%), m.p. 80-90 C.

Elemental Analysis: Found C 65.5; H 4.6; N 4.1; C1 < 0.2; S 1;.4 C133H98N804S15Cu requires C 66.1; H 4.1; N 4.6; C1 - ; S 19.9 Example 10 The procedure of Example 9 was repeated except that the 4-thiocresol was replaced by an equivalent quantity of 2-thionaphthol (4.80g, 30m mol). The solid was precipitated with ethanol rather than water. The isolated black solid (5.3g, 95%), m.p. 110-115 C was identified as tetra(4#hydroxyphenylthio)-undeca(naphthyl-2-thio) copper phthalocyanine.

Elemental Analysis: Found C 68.3; H 3.8; N 4.4; C1 < 0.2; S 15.0 C166H98N8O4S 15Cu requires C C 70.8; H 3.5; N 4.0; C1 - ; S 17.1 Example 11 The procedure of Example 9 was repeated except that the quantity of 4-hydroxythiophenol (2.52g, 20m mol) used was altered and 4-thiocresol was replaced by an equivalent quantity of 2-thionaphthol (3.20g, 20m mol). The solid was precipitated and slurried with ethanol rather than water. The isolated black solid (5.0g, 93X), m.p. 110-115 C was identified as octa(4-hydroxyphenylthio)-hepta (naphthyl-2-thio) copper phthalocyanine.

Elemental Analysis: Found C 64.0; H 3.3; N 4.1; C1 < 0.2; S 18.5 C166H90N8O8S15Gu requires C 67.3; H 3.4; N 4.2; C1 - ; S 17.9 Example 12 The procedure of Example 9 was repeated except that the 4-thiocresol was replaced by an equivalent quantity of 4-methoxythiophenol (4.2g, 30m mol). The solid was precipitated and slurried in ethanol. The isolated black solid (3.51g, 73%), m.p. 232-235 C was identified as tetra(4-hydroxyphenylthio) -undeca (4-methoxyphenylthio) copper phthalocyanine.

Elemental Analysis: Found C 58.9; H 3.9; N 3.7; C1 < 0.2; S 17.2 C133H98NO15S15Cu requires C 61.6; H 3.8; N 4.3; C1 - ; S 18.5 Example 13 The procedure of Example 9 was repeated except that the 4-thiocresol was replaced by an equivalent quantity of 4-chlorothiophenol (4.3g, 30m mol). The solid was precipitated and slurried in ethanol. The isolated black solid (4.lg, 78%), m.p. 235-238 C was identified as tetra(4-hydroxyphenylthio) -undeca (4-chlorophenylthio) copper phthalocyanine.

Elemental Analysis: Found C 53.9; H 2.6; N 3.7; C1 12.7; S 17.2 C122H65Cl11N804S15Cu requires C 55.5; H 2.5; N 4.2; C1 14.8; S 18.2 Example 14 The procedure of Example 9 was repeated except that the 4-thiocresol was replaced by an equivalent quantity of phenylselenol (4.71g, 30m mol). The solid was precipitated and slurried in ethanol.

The isolated black solid (4.15g, 75X), m.p. > 250 C was identified as tetra(4-hydroxyphenylthio) -undeca(phenylseleno) copper phthalocyanine.

Elemental Analysis: Found C 49.4; H 2.6; N 3.7; C1 < 0.2; S 4.6 C122H76N804S4Se11Cu requires C 52.7; H 2.7; N 4.0; C1 - ; S 4.6 Example 15 The procedure of Example 9 was repeated except that the 4-thiocresol was replaced by an equivalent quantity of 2,6-dimethylthiophenol (4.10g, 30m mol). The solid was precipitated and slurried with ethanol. The isolated black solid (3.40g, 83%), m.p.232-235"C was identified as pentachloro-hexa(4-hydroxyphenylthio) -tetra(2, 6-dimethyl- phenylthio) copper phthalocyanine.

Elemental Analysis: Found C 57.8; H 4.0; N 3.9; C1 6.0; S 13.6 C100H67Cl5N806S 10Cu requires C 58.9; H 3.3; N 5.5; C1 8.7; S 15.7 Example 16 The procedure of Example 9 was repeated except that the 4-hydroxythiophenol was replaced by an equivalent quantity of 4-acetamidothiophenol (1.67g, 10m mol) and the 4-thiocresol was replaced by an equivalent amount of 2-thionaphthol (4.80g, 30m mol). The solid was precipitated and slurried in ethanol. The isolated black solid (5.4g, 95%), m.p.180-185"C was identified as tetra(4-acetamidophenylthio)-undeca(naphthyl-2-thio) copper phthalocyanine.

Elemental Analysis: Found C 68.7; H 3.9; N 5.0; Cl 1.1; S 15.7 C174H110N12OS15Cu requires C 70.2; H 3.7; N 5.6; C1 - ; S 16.1 This product (4.7g, 1.6m mol) was stirred in a mixture of methanol (20ml), water (10ml), toluene (lOml) and concentrated hydrochloric acid (lOml) at reflux for 16 hours. The mixture was poured into water (lOO0m1). The water was decanted off a black oil and solvent (toluene) was evaporated off the oil to give a solid which was slurried several times in hot ethanol (3 x 500ml) until the filtrates were colourless.The black solid was dried (2.0g, 43%), m.p. 180-185 C and identified as tetra(4-aminophenylthio) -undeca(naphthyl-2-thio) copper phthalocyanine.

Elemental Analysis: Found C 69.4; H 3.4; N 4.4; C1 < 0.2; S 15.9 C166H102N12S15Cu requires C 70.9; H 3.6; N 6.0; C1 - ; S 17.1 Example 17 Pentadeca (4-methylphenylthio) copper phthalocyanine (2.41g, lm mol) and p-phenylene diamine (22g, 203m mol) were melted and stirred at 180 C for 16 hours and then cooled to 1000 C. Ethanol (lO0ml) was added to the stirred gum. A black/purple solid precipitated and was filtered off.The solid was washed with more ethanol (4 x 220ml) filtered and dried (1.85g, 80%), m.p. > 250 C, -l max (KBr) 3400, 3240 cm The product was penta(4-aminophenylamino) -deca(4-methyl- phenylthio) copper phthalocyanine.

Elemental Analysis: Found C 68.5; H 4.8; N 10.4; S 13.7 132 106 18 10 requires C 68.1; H 4.6; N 10.8; S 13.7 Example 18 p-Hydroxythiophenol (12.31g, 98m mol) and KOH (5.48g, 98m mol) were stirred in DMF (lOOml) at 120 C for 30 minutes. Hexadodecaphenoxy copper phthalocyanine (20g, 9.8m mol) was added to the reaction mixture which was stirred at 120 C for 2 hours. The solvent was removed under reduced pressure from the mixture to a volume of approximately Sml.

Ethanol (l0Oml) was added to the mixture and the solution was filtered to give a green solid (7.2g, 34X), m.p. > 250 C.

The product was tetra(4-hydroxyphenylthio) -dodecaphenoxy copper phthalocyanine.

Elemental Analysis: Found C 69.8; H 3.8; N 5.3; S 4.2 C128H80N8O16S4Cu requires C 70.6; H 3.7; N 5.2; S 5.9 Example 19 4-Hydroxythiophenol (4.43g, 35m mol) and KOH (1.97g, 35m mol) were stirred in DMF (50ml) at 1200C for 20 minutes and then hexadecanaphth-2-oxy copper phthalocyanine (lOg, 3.5m mol) was added to the mixture which was stirred at 1200C for 16 hours. The solution was poured into ethanol (300ml) and was then filtered to give a black solid which was slurried in boiling ethanol, filtered and dried and identified as octa(4-hydroxyphenylthio) -octa(naphth-2-oxy) copper phthalocyanine (4.lg, 43%), m.p. > 250 C.

Elemental Analysis: Found C 69.3; H 3.4; N 5.6; S 7.1 C160H96N8O16S8Cu requires C 71.0; H 3.5; N 4.2; S 9.4 The hexadecanaphth-2-oxy copper phthalocyanine used in this Example was obtained as follows: Tetrachlorophthalonitrile (30.5g, 115m mol), beta-naphthol (98.lg, 680m mol) and potassium carbonate (62.8g, 454m mol) were stirred in DMF (140ml) at 100 C for 2 hours and then the mixture was poured into water (300ml). The mixture was extracted with chloroform (3 x 300ml) and the combined organic extract was washed with aqueous 5% KOH solution (2 x 250ml), water (2 x 250ml), dried (MgSO4), filtered and the solvent was removed under reduced pressure to give a brown solid. The solid was dissolved in hot butan-l-ol (300ml) and then left to cool. The precipitated solid was filtered off giving a beige solid (40.66g, 51%), m.p. 188-189 C; m/z 696 (M+ 45.0%); Calculated: C 82.75; H 4.05; N 4.0X Found: C 81.9; H 4.0; N 4.1%.

This product (tetra-3,4,5,6-(naphth-2'-oxy) phthalonitrile) (40.6g, 58.4m mol), cupric chloride (2.35g, 17.5m mol) and urea (1.05g, 17.5m mol) were stirred in nitrobenzene (82ml) at l800C for 2 hours after which the mixture was allowed to cool to 10000 and then poured into ethanol (lOOOml). A green solid precipitated and was filtered off.The solid was slurried in aqueous 2M hydrochloric acid (500ml) at room temperature for 30 minutes, filtered off and then washed successively with aqueous 20X NH3 solution (SOOmI), water (lOOOml) and finally with ethanol (500ml) to give a green solid (34.35g, 83%), m.p. 215-220 C; max (CHC13) 735nm; Calculated: C 80.9; H 3.95; N 3.9% Found: C 76.6; H 3.5; N 3.5%.

Example 20 4-Hydroxythiophenol (4.28g, 34m mol) and KOH (1.9g, 34m mol) were stirred in DMF (50ml) at 12000 for 20 minutes and then penta/hexadeca(naphthyl-2-thio) copper phthalocyanine (lOg, 3.4m mol) was added to the mixture which was stirred at 12000 for 16 hours. The solution was poured into ethanol (300ml) and was then filtered to give a black solid which was slurried in boiling ethanol, filtered and dried and identified as octa(4-hydroxyphenylthio) -hepta(naphthyl-2.thio) copper phthalocyanine (6.24g, 69X), m.p. > 250 C.

Elemental Analysis: Found C 65.2; H 3.1; N 3.4; S 17.3 0150H90N808S15Cu requires C 67.3; H 3.4; N 4.2; S 17.9 Example 21 4-Hydroxythiophenol (5.24g, 41.5m mol) and KOH (2.35g, 41.5m mol) were stirred in DMF (50ml) at 1200C for 20 minutes and then penta/hexadeca(4-methylphenylthio) copper phthalocyanine (lOg, 4.15m mol) was added to the mixture which was stirred at 1200C for 16 hours. The solution was poured into ethanol (300ml) and was then filtered to give a black solid which was slurried in boiling ethanol, filtered and dried and identified as octa(4-hydroxyphenylthio)-hepta (4-methylphenylthio) copper phthalocyanine (5.90g, 47%), m.p. 250-255 C.

Elemental Analysis: Found C 58.3; H 3.6; N 3.3; S 19.0 C129H90N8 8S15CU requires C 59.2; H 3.3; N 4.3; S 18.4

Claims

CLAIMS 1. A polymer obtained by the polymerisation of a polymerisable phthalocyanine compound having one or more functional groups capable of taking part in polymerisation reactions, each of said groups being directly attached to an organic radical which is itself linked by an atom of an element of Group VB or Group VIB of the Periodic Table to a peripheral carbon atom of the phthalocyanine nucleus.
2. A polymer according to Claim 1 which is the product of an addition polymerisation.
3. A polymer according to Claim 1 in which the one or more functional groups comprise one or more ethylenically unsaturated groups capable of taking part in olefinic or vinyl polymerisation and/or two or more reactive groups capable of a poly-addition reaction with other reactive groups present in an appropriate co-reactant.
4. A polymer according to Claim 1 in which the ethylenically unsaturated groups which may be present as functional groups in the polymerisable phthalocyanine compounds, there may be mentioned groups of the general Formula (1):

wherein X represents an atom or group linking the olefinic group to a carbon atom present in the dye molecule, n has the value 0 or 1 and each of R, R and R independently represents a hydrogen or halogen atom or a hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, cycloalkyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, nitro, cyano, acyloxy or alkoxycarbonyl group.
5. A phthalocyanine compounds for use in making the polymers of the invention may be represented by the Formula (3):

wherein Pc represents a metal-free or metal-containing phthalocyanine nucleus; each X, independently represents sulphur, oxygen, selenium, tellurium or NT, where T is hydrogen, alkyl or aryl, which is attached to a peripheral carbon atom of the phthalocyanine nucleus; Q and Q are optionally substituted hydrocarbon or heterocyclic radicals; each Y, independently represents a functional group capable of taking part in a polymerisation reaction which is directly attached to a carbon atom present in 0 to 8; b represents an integer from 0 to 16 provided that (2a+b) is from 2 to 16; and c represents an integer of at least 2.
6. Formula (4): ( Y-Q4-X- )q Pc ( -X-Q )p (4) wherein Pc, X and Y have the same meanings as in Formula (3); Q3 and Q4 are optionally substituted aromatic radicals; p represents an integer from 0 to 14 and q represents an integer from 2 to 16 provided that the sum of p and q is from 2 to 16.
7. A phthalocyanine Formula (5):

wherein Pc, p and q have the same meanings as in Formula (4); each X1, independently, is oxygen, sulphur or NT, wherein T is hydrogen, alkyl or aryl; each benzene ring may carry one or more inert substituents; and Y is is an active hydrogen-containing group.
8. A process for the preparation of a compound of according to Claim 6 which comprises heating a phthalocyanine compound having halogen atoms attached to peripheral carbon atoms with appropriate proportions of a compound of Formula (6): HX - Q - Y (6) optionally in conjunction with a compound of Formula (7): HX - Q (7) wherein Q3, Q4, X and Y have the same meanings as in Formula (4).