The invention relates to novel phthalocyanine compounds and to their use as colourants. Phthalocyanines have long been known as colourants, especially as blue pigments, for example C.I Pigment Blue 15 and Pigment Blue 16. By means of substituents, the colour of the parent substance can be influenced within certain limits, substituted products generally being poorly defined mixtures of a large number of components, the composition and colour of which are greatly dependent on the preparation conditions.
Modern technologies, however, demand colourants that are ever better characterised and the shade of which can be produced under a very wide variety of conditions in as reproducible a manner as possible. Such a property is important especially in the case of colourants that are used in a readily soluble latent form and are only thereafter to be converted to the final pigment form.
The known substituted phthalocyanines do not, however, adequately meet that demand.
WO98/14520 discloses the selective preparation of formylated and acylated phthalocyanines, as well as products obtainable therefrom.
There are known from EP 648 817 phthalocyanines having alkoxycarbonylamino groups that are bonded to the phthalocyanine nucleus directly or via a C1-C4-1,1-alkylene group or a sulfone group. WO98/32802 discloses various possible applications thereof.
WO98/32802 describes the readily soluble compound of formula
and the thermal decomposition thereof.
Surprisingly, it has been found, however, that such latent phthalocyanines can lead to unexpected difficulties in practical use. In contrast to other latent pigments, thermal decomposition produces undesirable colour shades, and the fastness properties thereof are not sufficiently satisfactory, which poses a problem particularly in the case of high-quality applications, polychromatic systems and, especially, light-sensitive compositions (resists), where high demands and very precise shades must be achieved, for example in colour filters.
U.S. Pat. No. 3,972,904 describes water-soluble textile colourants which cannot, however, be used in conventional high-quality, polychromatic and light-sensitive compositions.
Example 8 of U.S. Pat. No. 4,381,261 describes the preparation of the compound of formula
which, however, owing to its high viscosity, cannot be used in conventional high-quality, polychromatic and light-sensitive compositions.
U.S. Pat. No. 4,000,158 describes alcohol- and ketone-soluble phthalocyanine compounds which, since their final solubility in the developer is too high, cannot be used in conventional light-sensitive compositions.
Surprisingly, it has been possible to solve such problems with the compounds according to the invention.
Accordingly, the invention relates to a compound of formula
M is a divalent metal, oxo metal, halogenometal or hydroxymetal, or 2 hydrogen atoms,
which may be unsubstituted or substituted by phenoxy, naphthyloxy, phenylthio or by naphthylthio,
X is a hetero atom selected from the group consisting of N, O and S, m being the number 0 when X is O or S and the number 1 when X is N,
Y is any desired substituent that is inert towards alkylating reagents,
Z is hydrogen, Z′ or COOB,
Z′ is C2-C12alkylene-N(COOB)2, C2-C12alkylene-NHCOOB, C2-C12alkylene-OCOOB or C2-C12alkylene-SCOOB,
x is a number from 1 to 4, and y is a number from 0 to 15,
wherein the sum of x and y is a maximum of 16 and, optionally, a plurality of radicals X, Y, Z and/or Z′ may be identical or different, and
B is a group of the formula
R1 is hydrogen or C1-C6alkyl,
R2 and R3 are each independently of the other C1-C6alkyl,
R4 and R8 are each independently of the other C1-C6alkyl, C1-C6alkyl interrupted by O, S or by NR12, phenyl or biphenyl unsubstituted or substituted by C1-C6alkyl, C1-C6alkoxy, halogen, cyano or by nitro,
R5, R6 and R7 are each independently of the others hydrogen or C1-C6alkyl,
is hydrogen, C1
alkyl or a group of the formula
R10 and R11 are each independently of the other hydrogen, C1-C6alkyl, C1-C6alkoxy, halogen, cyano, nitro, N(R12)2, or phenyl unsubstituted or substituted by halogen, cyano, nitro, C1-C6-alkyl or by C1-C6alkoxy,
R12 and R13 are each C1-C6alkyl, R14 is hydrogen or C1-C6alkyl and R15 is C1-C6alkyl, or phenyl unsubstituted or substituted by C1-C6alkyl,
E is p,q-C2-C6alkylene unsubstituted or mono- or poly-substituted by C1-C6alkoxy, C1-C6-alkylthio or by C2-C12dialkylamino, wherein p and q are different position numbers,
X′ is a hetero atom selected from the group consisting of N, O and S, m′ being the number 0 when X′ is O or S and the number 1 when X′ is N,
L1 and L2 are each independently of the other C1-C6alkyl or [-(p′,q′-C2-C6alkylene)-Z″-]n-C1-C6alkyl unsubstituted or mono- or poly-substituted by C1-C6alkoxy, C1-C6alkylthio, C2-C12dialkylamino, C6-C12aryloxy, C6-C12arylthio, C7-C18arylalkylamino or by C12-C24-diarylamino, wherein n is a number from 1 to 1000 and p′ and q′ are different position numbers, each Z″ independently of the other(s) is a hetero atom O, S or C1-C12alkyl-substituted N, and the C2-C6alkylene radicals in the repeating units [—C2-C6alkylene-Z″—] may be identical or different,
and L1 and L2 may be saturated or unsaturated from one to ten times, may be uninterrupted or interrupted at any positions by from 1 to 10 groups selected from the group consisting of —(C═O)— and —C6H4—, and may carry no further substituents or from 1 to 10 further substituents selected from the group consisting of halogen, cyano and nitro.
C2-C12Alkylene is, for example, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, 1,4-butylene, 2-methyl-1,2-propylene or an isomer of pentylene, hexylene, octylene, decylene or dodecylene.
C6-C12Aryloxy is O—C6-C12aryl, for example phenoxy or naphthyloxy, preferably phenoxy.
C1-C6Alkylthio is S—C1-C6alkyl, preferably S—C1-C4alkyl.
C6-C2Arylthio is S—C6-C12aryl, for example phenylthio or naphthylthio, preferably phenylthio.
C2-C12Dialkylamino is N(alkyl1)(alkyl2) wherein the sum of the carbon atoms in the two groups alkyl, and alkyl2 is from 2 to 12, preferably N(C1-C4alkyl)-C1-C4alkyl.
C7-C18Alkylarylamino is N(alkyl1)(aryl2) wherein the sum of the carbon atoms in the two groups alkyl1 and aryl2 is from 7 to 18, preferably methylphenylamino or ethylphenylamino.
C12-C24Diarylamino is N(aryl1)(aryl2) wherein the sum of the carbon atoms in the two groups aryl1 and aryl2 is from 12 to 24, for example diphenylamino or phenylnaphthylamino, preferably diphenylamino.
Substituents that are inert towards alkylating reagents are, for example, those which do not react with pyrocarbonates under the conditions indicated hereinbelow, for example those which do not contain hydroxy, amino or thiol groups.
The substituents SO2(Z)mZ′ and Y may be located at any aromatic carbon of the radicals A, for example at the peripheral positions of a phthalocyanine or naphthalocyanine and/or optionally at any desired position of the phenoxy, naphthyloxy, phenylthio or naphthylthio substituents.
The compound of formula (I) may especially be a compound of formula
In a compound of formula (II), the substituents SO2
Z′ and Y are advantageously attached at the peripheral positions of the phenyl rings, preferably at the outer positions (2, 3, 9, 10, 16, 17, 23 and/or 24 according to “Nomenklatur von Porphyrinen and Gallen-pigmente” [Nomenclature of porphyrins and bile pigments]/May 1989):
M is preferably Cu, Pd, Pb, Co, Ni, Zn, Mn or V(═O).
A is preferably a radical
X is preferably N or O, especially N.
Y is preferably Cl or Br.
Z is preferably H or COOB, especially COOB.
Z′ is preferably C2-C12alkylene-NHCOOB or C2-C12alkylene-OCOOB, especially C2-C12-alkylene-OCOOB.
C2-C12Alkylene in Z′ is preferably C2-C6alkylene, especially C2-C4alkylene, more especially 1,2-ethylene.
y is preferably 0 or from 4 to 8, especially 0.
The sum of x and y is preferably a maximum of 8.
B is preferably a group of the formula
Of the groups B according to the definition, special preference is given to those which are known as preferred groups in other latent pigments, for example the latent pigments of EP 742 255, EP 761 772 or WO98/32802.
R1 is preferably C1-C6alkyl.
The compounds of formula (I) may be prepared analogously to methods known per se, for example starting from known sulfochlorinated phthalocyanines. The sulfochlorinated phthalocyanines themselves may be prepared in a known manner by sulfochlorination of phthalocyanines. They are also obtainable, for example, by cyclisation of 4-sulfo-phthalic acid to phthalocyanine-tetrasulfonic acid and subsequent chlorination with phosphorus pentachloride, as disclosed by K. Sakamoto in Dyes and Pigments 35, 375 (1997) and A. Hong in J. Phys. Chem. 91, 2109 (1987), or by cyclisation of sulfonamido-substituted phthalodinitriles as disclosed in Houben-Weyl E9d, 725 (1998—Georg Thieme Verlag Stuttgart). Mixed syntheses with other phthalodinitriles may optionally also be carried out. The sulfochlorinated phthalocyanines may subsequently be reacted with alcohols, thiols or amines to give the desired sulfonates or sulfonamides.
The compounds of formula (I) are preferably prepared analogously to the methods described, for example, in EP 648 770, EP 648 817, EP 654 711, EP 742 255, EP 761 772 and WO98/32802. To that end, a phthalocyanine of formula (I) wherein Z′ is C2
alkylene-SH or C2
is reacted with a pyrodicarbonate of the formula
in an aprotic organic solvent in the presence of a base as catalyst, advantageously at temperatures of from 0 to 120° C., preferably from 10 to 100° C., for from 2 to 80 hours.
The molar ratio in a particular case is governed by the number of radicals B to be introduced, the dicarbonate advantageously being employed in excess, based on the theoretically required amount.
Phthalocyanines of formula (I) wherein Z′ is C2-C12alkylene-OH, C2-C12alkylene-SH or C2-C12alkylene-NH2 may be prepared from phthalocyanine sulfochlorides analogously to the methods indicated above by reaction with a C2-C12alkylene-diol, C2-C12alkylene-dithiol, C2-C12alkylene-diamine or hydroxy-C2-C12alkylene-amine.
The compounds of formula (I) according to the invention are excellently suitable for colouring in the mass high molecular weight organic material.
Examples of suitable high molecular weight organic materials that can be coloured with the compounds of formula (I) according to the invention are vinyl polymers, for example polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, poly-p-hydroxystyrene, poly-p-hydroxy-phenylstyrene, poly(methacrylate) and poly(acrylamide) and the corresponding methacrylic compounds, poly(methyl maleate), poly(acrylonitrile), poly(methacrylonitrile), poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(vinyl acetate), poly(methyl vinyl ether) and poly(butyl vinyl ether); novolaks derived from C1-C6-aldehydes, for example formaldehyde and acetaldehyde, and a binuclear, preferably mono-nuclear, phenol that is unsubstituted or is substituted by one or two C1-C9alkyl groups, one or two halogen atoms or by a phenyl ring, for example o-, m- or p-cresol, xylenol, p-tert-butylphenol, o-, m- or p-nonylphenol, p-chlorophenol or p-phenylphenol, or a compound having more than one phenolic group, for example resorcinol, bis(4-hydroxyphenyl)methane or 2,2-bis(4-hydroxyphenyl)propane; polymers derived from maleimide and/or maleic anhydride, for example copolymers of maleic anhydride and styrene; poly(vinylpyrrolidone), biopolymers and derivatives thereof, for example cellulose, starch, chitin, chitosan, gelatin, zein, ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate; natural resins and synthetic resins, for example rubber, casein, silicone and silicone resins, ABS, urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenolic resins, polyamides, polyimides, polyamide/imides, polysulfones, polyether sulfones, polyphenylene oxides, polyurethanes, polyureas, polycarbonates, polyarylenes, polyarylene sulfides, polyepoxides, polyolefins and polyalkadienes. Preferred high molecular weight organic materials are, for example, cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymerisation or condensation resins, such as aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyesters, ABS, polyphenylene oxides, rubber, casein, silicone and silicone resins, individually or in the form of mixtures.
The mentioned high molecular weight organic compounds may be present individually or in mixtures as plastic masses, melts or in the form of spinning solutions, surface coating compositions, paints or printing inks. It has proved advantageous to use the compounds of formula (I) as toners or in the form of preparations according to the intended use.
The compounds of formula (I) according to the invention are especially suitable for colouring in the mass polyvinyl chloride and, especially, polyolefins, such as polyethylene and polypropylene, as well as surface-coating compositions, and also powder coatings, printing inks and paints.
Based on the high molecular weight organic material to be coloured, the compounds of formula (I) according to the invention may be used in an amount of from 0.01 to 30% by weight, preferably from 0.1 to 10% by weight.
Colouring of high molecular weight organic substances with the compounds of formula (I) according to the invention is carried out, for example, by mixing the compound of formula (I), optionally in the form of a masterbatch, with the substrates using roll mills or mixing or grinding apparatuses. The coloured material is then brought into the desired final form by methods known per se, such as calendering, compression moulding, extrusion, coating, casting or injection moulding. In order to produce mouldings that are not rigid or to reduce their brittleness, it is often desirable to incorporate so-called plasticisers into the high molecular weight compounds prior to shaping. There may be used as plasticisers, for example, esters of phosphoric acid, phthalic acid or sebacic acid. The plasticisers may be incorporated into the polymers before or after the incorporation of the compounds of formula (I) according to the invention. In order to achieve different colour shades it is furthermore possible to add to the high molecular weight organic substances, in addition to the compound according to the invention, also fillers or other constituents imparting colour, such as white, coloured or black pigments, in any desired amounts.
For colouring surface-coating compositions, paints and printing inks, the high molecular weight organic materials and the compounds of formula (I) according to the invention, optionally together with additives, such as fillers, pigments, siccatives or plasticisers, are finely dispersed or dissolved in a common organic solvent or solvent mixture. That operation may be carried out by dispersing or dissolving the individual components separately, or several components together, and only then combining all the components.
In coloured materials, for example of polyvinyl chloride or polyolefins, or in printing inks, the compounds of formula (I) according to the invention are distinguished by good all-round properties, such as good fastness to migration, light and weathering.
Of very great importance is the conversion of compounds according to the invention incorporated in a substrate to the corresponding compounds of formula (I) wherein Z′ is C2-C12-alkylene-OH, C2-C12alkylene-SH or C2-C12alkylene-NH2. The conversion may be achieved in the simplest manner by heat treatment (heating to temperatures of from 50 to 250° C., preferably from 100 to 200° C.), in organic or aqueous media, polymer solutions or melts, of the solids, solutions or dispersions comprising the compounds according to the invention. In many cases, the desired conversion can be achieved merely as a result of the conventional conditions of incorporation.
That permits the colouring of surface-coating compositions, printing inks, plastics, especially also in fibre form, heat-sensitive recording systems, inks for ink-jet printing, toners for electrophotographic recording processes, coloured ribbons for thermal transfer printing onto smooth or woven receiver substrates, and, more especially, also in light-sensitive compositions, for example negative or positive resist formulations, with overall improved properties, such as purity, colour shade, colour strength, brilliance, transparency and fastness properties, and also valuable applications in analysis.
Accordingly, the invention relates also to a high molecular weight organic material comprising in the mass thereof a colourant of formula (I) wherein Z′ is C2-C12alkylene-OH, C2-C12alkylene-SH or C2-C12alkylene-NH2, produced in situ by thermal degradation of a compound of formula (I), as well as to a heat-, photo- or chemo-sensitive recording material, an ink for ink-jet printing, a toner for electrophotographic recording processes, a coloured ribbon for thermal transfer printing or a light-sensitive negative or positive resist composition that comprises a compound of formula (I).
Inks for ink-jet printing, toners for electrophotographic recording processes, coloured ribbons for thermal transfer printing, heat-, photo- and chemo-sensitive recording materials and light-sensitive negative or positive resist compositions are very well known to the person skilled in the art.
A very special, surprising advantage of the compounds according to the invention is that thermal conversion thereof yields products of a colour that corresponds to the colour shade cyan (blue-green), which is desirable for optical applications but has not been achieved hitherto using phthalocyanines. Thermal decomposition of the compounds according to the invention also yields products of a higher degree of purity than in the case of the compounds used hitherto.
By virtue of such improved properties, the soluble colourants of formula (I) according to the invention can be used especially advantageously in compositions that are used for the production of structured colour images or colour filters. The use of soluble pigment precursors in the production of structured colour images or colour filters is known from EP 654 711. Those compositions comprise, for example, in addition to the colourant, a positive or negative resist. Resist formulations comprising colourants of formula (I) can be irradiated in the desired pattern and developed, it being possible for the thermal conversion to colourants of formula (I) wherein Z′ is C2-C12alkylene-OH, C2-C12alkylene-SH or C2-C12-alkylene-NH2 to take place at the time of the exposure or development or, alternatively, not until later. The compounds of formula (I) may also be applied in the desired pattem directly onto a receiver layer suitable for that purpose by means of inkjet printing or thermally induced diffusion. The methods disclosed in EP 654 711 are highly suitable for the production of colour filters.
Accordingly, the invention relates also to a method of producing structured colour images or colour filters, which method comprises the pattem-wise irradiation, development and heat treatment of a positive or negative resist comprising a colourant of formula (I), wherein the heat treatment may take place at the time of the irradiation or development or later and the thermal conversion yields a colourant of formula (I) wherein Z′ is C2-C12alkylene-OH, C2-C12alkylene-SH or C2-C12alkylene-NH2.
The Examples which follow illustrate the invention without limiting the scope thereof (unless indicated to the contrary, “%” is always % by weight):