Title of Invention

PHTHALOCYANINE COMPOUNDS OF FORMULA (1) AND SALTS THEREOF

Abstract

Phthalocyanine compounds of Formula (1) and salts thereof: (S03H)x MvPc-(S02NH2)y (S02NR1R2)2 Formula (1) in which: M represents a metal or H; Pc represents a phthalocyanine nucleus; and R1 represents H or -(CH2)nR3; R2 represents -(CH2)nR3; or R1 and R2 together with the nitrogen atom to which they are attached represent a 5 or 6-membered ring; where: n is independently an integer from I to 30; and R3 is independently a group selected from hydroxy, sulpho, cyano, - SR4, -CO2R5, -PO3H2 and -NR6R7 where: R4, R5, R6 and R7 independently represent H, C1-3oalkyl optionally substituted by one or more groups selected from hydroxy, mercapto, sulpho, carboxy, cyano and -PO3H2; v is the valence of Pc divided by the valence of M; xis from 1.2 to 3.8; y is from 0.1 to 2.7; z is from 0.1 to 2.7; and x, y and z satisfy 2< x + y + z <4; with the provisos that: R4 and R5 are other than both H; when R1 is H or C1-4alkyl then R4 is other than C1-4alkyleneSC>3H; when R1 is H or C1-4alkyl and R6 is H, C1-4alkyl or hydroxyC1-4alkyl; then R7 is other than C1-4alkyl, hydroxyC1-4alkyl or morpholino; and when R1 is H or C1-4alkyl then R6 and R7 are other than both H or (together with the N atom to which they are attached) other than a morpholino ring.

Full Text

FORM 2 THE PATENTS ACT 1970 [39 OF 1970] & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION [See Section 10; rule 13] "Phthalocyanine compounds of Formula (1) and salts thereof FUJIFILM IMAGING COLORANTS LIMITED (formerly AVECIA INKJET LIMITED) having a principal place of business at Hexagon Tower, Blackley, Manchester, M9 8ZS, United Kingdom The following specification particularly describes the invention and the manner in which it is to be performed: ORIGINAL 459/MUMNP/2004 GRANTED 10-12-2007 24 APR 2007 SMC 60308 then added to the mixture to lower its pH to ~1. The mixture was stirred for 30 minutes at this pH. The precipitate obtained was collected by filtration and washed with 2% HCI . The resultant paste was re-dissolved in distilled water (~2 I) at pH 9 to obtain a solution which was desalinated by reverse osmosis. Water was evaporated from this solution to 5 yield 63g of the title compound. The respective ratio of S03H / SO+NH2 / S02N(C2H2)20 was determined to be 1.3 / 1.2 /1.5. Example 18 (alternative preparation of Example 7) 10 To distilled water (320ml) was added tetrahydofurfurylamine (16.7g) followed by sufficient internal ice to lower temp to ~0°C. Filter cake [380.3 g - prepared as described in Example 17(a) above] was added to the mixture and the pH adjusted to 8.5 to 9.0 using ammonia solution (SG 0.88). The mixture was stirred at this pH and ~0°C for 4 hours and then heated to 40°C and held at pH 8.5 to 9.0 for 30 minutes. Concentrated HCI was 15 added to the mixture to lower its pH to ~1, and the mixture was then stirred for 30 minutes at this pH. The precipitate obtained was then collected by filtration and washed with 2% HCI.. The resultant paste was re-dissolved in distilled water (-21) at pH 9 to obtain a solution which was desalinated by reverse osmosis. Water was evaporated from the solution to yield 71.6g of the title compound. 20 Example 19 (alternative preparation of Example 3) SMC 60308 Copper phthalocyanine (117.6g ) was added to chlorosulphonic acid (307ml, 542.9g) over 1-2 hours whilst maintaining the temperature at The solid prepared above (389g) was added to water (1 litre) followed by glycine (20.26 g) and the pH of the mixture was adjusted to ~9 by addition of caustic liquor. The mixture was stirred at this pH and heated to 70 to 80°C for ~4 hours. Then 20% w/v salt was added to the mixture and the pH adjusted to 4 by addition of concentrated HCI. The 2 o precipitate obtained was then collected by filtration, washed well with brine and then re-dissolved in distilled water at pH 9 to obtain a solution which was de-salinated by reverse osmosis. Water removed to yield, as solid, 56g of the title compound. The respective ratio of S03H / S02NH2 / S02NHC2H4NHCH2C02H was determined to be 1.3 /1.2 / 1.5 25 Further, alternative preparations Examples 4 to 5 and 8 to 15 herein can all also be prepared by an analogous route to that described in Example 19 above by replacing the glycine with an equivalent molar amount of the corresponding amine or thiol. An alternative route to the preparation of Example 1 above would be to remove 3 0 the glycine stated above and heat at pH 10 to 12 and 90°C for 4 hours which results in hydrolysis of the CI substituent to OH. Results 35 Chroma Example 1 herein was compared with the known copper phthalocyanine dye Cyan 1 [= CuPc(S03H)(S02NH2)3] in a conventional ink formulation. The chroma of an IJ print made with an ink of Example 1 was found to be 5% higher at a similar optical density than a comparative print made with Cyan 1 (the optical density of a print, can be conveniently SMC 60308 measured using an X-Rite 938 Spectrodensitometer). Chroma values were obtained in a conventional manner. Dye Chroma Example 1 40.5 Cyan 1 (known dye) 38.5 Examples 2, 6 and 7 were also tested for chroma and performed very similarly to 5 Example 1, (i.e. better than Cyan 1). Water fastness Dyes of the present invention also demonstrate a desirable combination of solubility and water fastness compared to prior art dye, as illustrated by the following test. The water fastness of Example 6 herein was compared with the known dye Cyan 1 in the conventional run down test. Water fastness (denoted herein by WF) was determined by running water (0.5 ml) down lines of print at an angle of approximately 45°C immediately after the lines had been printed. The prints were given a score of 1 to 10 where 1 indicates poor wet fastness and 10 indicates no detected ink run down (i.e. 100% water fast). ' Dye WF Example 6 6 Cyan 1 (known dye) 3 Examples 5, 6, 9 to 15 herein were also tested in the run down test and showed a comparable WF to Example 6 (i.e. better than Cyan 1). The aqueous solubility of Example 1 was found to be 29%. This compares to an aqueous solubility of 14% for its mono-sulphonic acid substituted analogue. 2 0 Thus contrary to what one would expect, the applicant has found that improved water solubility in the dyes of the present invention (which equates to greater operability in IJP) does not occur at the expense of poor WF. Prints made with the dyes of the Examples exhibit a WF comparable to or better than the corresponding zero or mono-sulphonic acid dyes. Dyes of the invention also 25 exhibit a particularly attractive cyan shade with good chroma compared to their corresponding zero or mono-sulphonic acid analogues. The dyes of the present invention are significantly easier than prior art dyes to formulate in UP inks and use in UP and yet they produce prints of comparable or improved quality to prior art dyes. Salts 30 The exemplified sodium salts (examples 1 to 19) prepared as described above, may be used after suitable purification directly in ink formulations as described below or SMC 60308 may be were converted to other IJP-effective salts as follows. Each example was dissolved in distilled water. The solution was filtered and the volume of the filtrate adjusted to 4 litres. The solution was desalinated by reverse osmosis. The dissolved sodium salt may be converted into other salt [e.g. the potassium salt] by passing the 5 solution through an ion-exchange column comprising Dowex HGRW resin saturated with a suitable solution [e.g. potassium hydroxide solution (5% w/v)]. The solution of the (e.g. potassium) salt thus obtained was then filtered and water was evaporated form the filtrate to yield a purified salt suitable for use directly in an ink as described below. 10 Inks The effectiveness in ink jet printing of compounds of. Formula (1) was demonstrated as follows. Inks separately comprising each exemplified dye were prepared by dissolving 2 parts of the sodium salt, prepared as described above, in 98 parts of a mixture of water and 2-pyrrolidone (in a respective ratio of 90:10 by volume). 15 The inks were printed onto plain paper (obtained from Felix Schoeller) using a thermal ink-jet printer to give a bright cyan prints which had excellent light fastness. Further inks comprising the exemplified dyes may be may be prepared as described in the following tables in which the number in the first column (headed Ex. no.) denotes the example number of dye to be used in the ink. The dye may be in its free 20 acid form and/or in the form of any IJP-effective salt (e.g. sodium, potassium, ammonium, or QAC salt). Numbers quoted in the second column onwards refer to the number of parts of the relevant ingredient and all parts are by weight. The inks may be applied to paper by thermal or piezo ink jet printing. The following abbreviations are used in the tables: 25 PG = propylene glycol; DEG = diethylene glycol; NMP = N-methyl pyrollidone; DMK = dimethylketone; NaST = Na stearate IPA = isopropanol; MEOH = methanol; 2P = 2-pyrollidone; MIBK= methylisobutyl ketone; CET= cetyl ammonium bromide; TBT = tertiary butanol; TDG = thiodiglycol; BDL = butane-2,3-diol; PHO = Na2HP04; P12 = propane-1,2-diol. 3 0 CHL = cyclohexanol; and PDL = pentan-1,5-diol. SMC 60308 TABLE I Ex. no. Dye Water PG DEG NMP DMK MEOH 2P MIBK 1 2.0 80 5 6 4 5 2 10.0 85 3 3 3 5 1 3 2.1 91 8 1 4 2.4 75 3 4 5 6 5 5 5.1 96 4 6 1.8 80 5 15 7 2.6 84 11 5 8 3.3 80 2 10 2 6 9 5.4 69 2 20 2 1 3 3 10 7.0 70 15 I 3 10 TABLE II J Ex. No. Dye Water — PG DEG NMP NaOH NaST IPA 2P MIBK 11 2.0 70 7 6 3 2 12 4.0 65 4 6 0.7 5 13 1.0 50 4 5 1 14 3.1 86 5 2 0.2 4 5 15 1.1 81 2 9 0.5 0.5 | 9 TABLE III Ex. no. Dye Water PG DEG NMP DMK IPA MEOH 2P MIBK 1 3.1 86 5 4 5 2 1.1 81 9 9 3 2.5 60 4 ' 15 3 3 6 10 5 4 4 3.2 65 5 4 6 5 4 6 5 5 10.0 80 2 6 2 5 1 . 4 SMC 60308 TABLE IV Ex. no. Dye Water PG DEG NMP DMK NaOH Na ST IPA 6 3.0 90 5 5 0.2 7 .5 65 5 20 10 8 4.1 80 5 2 10 0.3 9 10.8 90 5 5 10 12.0 90 7 0.3 3 TABLE V Ex. no. Dye Water PG DEG NMP CET PHO 2P P12 11 3.0 80 15 0.2 5 12 9.0 90 5 1.2 5 13 2.5 90 6 4 0.12 14 3.1 82 4 8 0.3 6 15 10.0 91 6 3 1 5.0 78 5 11 6 2 6.0 63 3 4 2.0 3 3.0 72 15 0.8 3 4 5.4 86 5 7 3.0 7 5 2.0 90 10 10 TABLE VI Ex. no. Dye Water PG DEG NMP CET TBT TDG 6 1.5 85 5 5 0.15 5.0 0.2 7 9.0 90 5 5 0.3 8 2.0 90 10 9 2.0 88 10 10 5.5 70 4 4 0.4 3 j SMC 60308 TABLE VII Ex. no. Dye Water. PG DEG NMP TBT TDG BDL PHO 2P 11 0.9 85 10 5 0.2 12 4.0 70 10 4 1 4 13 2.2 75 4 10 3 2 6 14 9.0 76 9 7 3.0 0.95 5 | 15 | 2.1 70 5 5 5 I 0.2 .0.1 | 5 0.1 5 TABLE VIII J Ex. no. Dye Water PG DEG NMP TBT TDG 2P 1 3.0 55 5 2.0 3 2 6.0 65 4 0.1 5 3 5.0 78 5 12 5 4 8.0 70 2 8 15 5 5 10.0 80 8 12 TABLE IX Ex. no. Dye Water PG DEG NMP BDL PHO 2P P12 6 10.0 75 3 5 3 3 1 7 3.5 80 6 5 8 2.0 90 7 7 0.5 9 6.0 65 5 2 10 4.0 70 10 4 1 4 11 TABLE X Ex. no. Dye Water PG DEG NMP CET TBT TDG BDL PHO 2P 11 1.5 80 1 2 3 0.5 0.4 7 2 10 12 3.0 60 4 2.0 0.5 13 4.5 90 3 6 7.0 1 3 2 14 3.0 95 7 4 3 0.5 15 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5 SMC 60308 TABLE XI Ex. no. Dye Water PG DEG NMP CHL PHO 2P PDL 1 7.0 75 3 5 3 3 1 2 3.5 60 2 5 3 2.0 90 7 7 1.5 2 4 6.0 65 5 2 5 4.0 70 5 4 1 4 12 We Claim; 1. Phthalocyanine compounds of Formula (1) and salts thereof: (S03H)x MvPc-(S02NH2)y (S02NR1R2)2 Formula (1) in which: M represents a metal or H; Pc represents a phthalocyanine nucleus; and R1 represents H or -(CH2)nR3; R2 represents -(CH2)nR3; or R1 and R2 together with the nitrogen atom to which they are attached represent a 5 or 6-membered ring; where: n is independently an integer from I to 30; and R3 is independently a group selected from hydroxy, sulpho, cyano, - SR4, -CO2R5, -PO3H2 and -NR6R7 where: R4, R5, R6 and R7 independently represent H, C1-3oalkyl optionally substituted by one or more groups selected from hydroxy, mercapto, sulpho, carboxy, cyano and -PO3H2; v is the valence of Pc divided by the valence of M; xis from 1.2 to 3.8; y is from 0.1 to 2.7; z is from 0.1 to 2.7; and x, y and z satisfy 2 with the provisos that: R4 and R5 are other than both H; when R1 is H or C1-4alkyl then R4 is other than C1-4alkyleneSC>3H; when R1 is H or C1-4alkyl and R6 is H, C1-4alkyl or hydroxyC1-4alkyl; then R7 is other than C1-4alkyl, hydroxyC1-4alkyl or morpholino; and when R1 is H or C1-4alkyl then R6 and R7 are other than both H or (together with the N atom to which they are attached) other than a morpholino ring. 2. Phthalocyanine compounds as claimed in claim 1 wherein M is Cu or Ni, R1 is selected from H and optionally substituted C1-15salkyl and R2 is a substituted Ci-isalkyl. 3. Phthalocyanine compounds as claimed in either claim 1 or claim 2 wherein M is Cu, R1 is selected from H, C1-4alkyl and hydroxyC1-4 alkyl and R2 is a hydroxyC1-4alkyl. Dated this 18th day of August, 2004. [ DIPAKMUNDRA] OF REMFRY & SAGAR ATTORNEY FOR THE APPLICANTS

Documents:

459-mumnp-2004-assignment(26-06-2006).pdf

459-mumnp-2004-cancelled pages(10-12-2007).pdf

459-mumnp-2004-claims(granted)-(10-12-2007).pdf

459-mumnp-2004-correspondence(15-02-2008).pdf

459-mumnp-2004-correspondence(ipo)-(12-03-2008).pdf

459-mumnp-2004-form 1(05-12-2007).pdf

459-mumnp-2004-form 1(18-08-2004).pdf

459-mumnp-2004-form 1(24-10-2007).pdf

459-mumnp-2004-form 13(05-12-2007).pdf

459-mumnp-2004-form 18(26-12-2005).pdf

459-mumnp-2004-form 2(granted)-(10-12-2007).doc

459-mumnp-2004-form 2(granted)-(10-12-2007).pdf

459-mumnp-2004-form 3(24-04-2007).pdf

459-mumnp-2004-form 6(26-06-2006).pdf

459-mumnp-2004-petition under rule 137(25-04-2007).pdf

459-mumnp-2004-power of authority(24-04-2007).pdf

459-mumnp-2004-power of authority(26-06-2006).pdf