HYDROXYALUMINUMPHTHALOCYANINE HAVING REDUCED GREEN ABSORPTION

Abstract: An hydroxyaluminumphthalocyanine colorant compound with reduced green absorption having peak absorption bathochromically shifted to 621 nm. In a preferred embodiment, hydroxyaluminumphthalocyanine of the invention exhibits reduced absorption on both sides of the 621-nm peak as determined by the peak width at half maximum intensity. Hydroxyaluminumphthalocyanine is useful as an electrically photosensitive component in photoelectrophoretic imaging processes, as well as in electrographic developers as a toner constituent.

Description: HYDROXYALUMINUMPHTHALOCYANINE HAVING REDUCED GREEN ABSORPTION The present invention relates to hydroxyalu¬ minumphthalocyanine colorant compounds. These com- pounds are useful in photoelectrophoretic imaging materials and as electrographic toner constituents. In various imaging systems, such as photo¬ electrophoretic (PEP) imaging systems, photosensitive colorants are employed to provide light sensitivity, as well as faithful reproduction of the light regions to which the colorants are sensitive. In PEP sys¬ tems, colorants employed are electrically photosensi¬ tive and are selected from a variety of material classes such as phthalocyanine pigments. One of these, cyan-colored hydroxyoaluminum phthalocyanine, is particularly useful for the degree of electrical photosensitivity or speed it provides. However, its coloration is not crisp, and its peak absorption at 612 nm (as determined herein) constitutes undesirable absorption in the green spectral region. Thus, when hydroxyaluminumphthalocyanine is employed in imaging applications with magenta colorants, poor color sepa¬ ration results. It is an object of the present invention to provide hydroxyaluminumphthalocyanine which exhibits improved color separation. This object has been achieved with a novel crystalline form of hydroxyalu¬ minumphthalocyanine which has an absorption peak at 621 nm as determined herein. The present hydroxyalu- minumphthalocyanine, furthermore, has a peak width of no more than 100 nm at half maximum intensity at the 621-nm peak. Among other uses such as in paints or inks, the hydroxyaluminumphthalocyanines of the present invention are electrically photosensitive and thus suited for use in photoelectrophoretic (PEP) disper¬ sions, elements and processes associated with such OMP 4IN. W wIiPr dispersions. A PEP dispersion comprises a plurality of particles composed of the present hydroxyaluminum phthalocyanine dispersed in an electrically insulat¬ ing, liquefiable or liquid carrier. Hydroxyaluminum¬ phthalocyanine colorants of the present invention are also useful as toner constituents in dry or liquid electrographic developers. The present invention provides a novel crys¬ talline form of hydroxyaluminumphthalocyanine. In this regard, hydroxyaluminumphthalocyanine has the following structure: The new crystalline form, as noted above, exhibits an absorption peak at 621 n which repre- - sents a bathochromic shift from the 612 n absorption peak of prior forms of hydroxyaluminumphthalocya¬ nine. The absorption peak, moreover, is conveniently measured when the hydroxyaluminumphthalocyanine is dispersed in a reference matrix as set forth in greater detail below. Hydroxyaluminumphthalocyanine having the above-defined spectral absorption characteristics can be prepared by treating hydroxyaluminumphthalocyanine with piperidine or certain other organic liquids at temperatures extending from room temperature (20° C) to the refluxing temperature of the solvent, or 100° C, whichever is less, as shown in the following examples. In connection with the spectral absorption of the hydroxyaluminumphthalocyanine compounds in these examples, 1 gram of the isolated hydroxyalumi¬ numphthalocyanine was milled for 5 days in a 7 per¬ cent, by weight, solution of poly(vinyltoluene-co- lauryl methacrylate-co-lithium methacrylate-co-meth- acrylic acid) in Solvesso 100". One volume part of the milled solution was combined with ten volume parts of an Isopar G" (an isoparaffinic hydrocarbon liquid) solution containing 40 percent, by weight, of the binder Piccotex 100* (a trademark for a copoly- mer of α-methylstyrene and vinyltoluene from Penn¬ sylvania Chemical Corp.) to form a dispersion. The dispersion was hand-coated on the top layer of a reflective support containing, in sequence, a polyes¬ ter substrate, a polyurethane layer containing dis- persed titanium dioxide, and a cellulose acetate top layer. Absorption measurements, in the reflection mode, were made of the hand-coated hydroxyaluminum- phthalocyanine-containing layer. The absorption mea¬ surement performed on the present novel crystalline form of hydroxyaluminumphthalocyanine in a reference matrix on a reflective support represents an identi¬ fying characteristic of the novel crystalline form per se. Example 1; Synthesis and Treatment of Hydroxyalumi- numphthalocyanine Crude hydroxyaluminumphthalocyanine (HAP) was synthesized according to US Patents 2,647,127 and 2,673,854. The crude product was acid-treated according to the following procedure: 'BU E OMPI Chemic ls 400 g (7.2 x 10" z M) crude hydroxyaluminumphthalocyanine 400 ml Reagent ACS sulfuric acid, Fisher ' Scientific Co. (specific gravity 1.83) 2600 gm ice 1300 gm distilled water 800 ml Reagent ACS ammonium hydroxide, Fisher Scientific Co. Crude hydroxyaluminumphthalocyanine was ground with a mortar and pestle, slowly added to the acid which was vigorously stirred for 1.5 hr after addition was completed. The brown solution was fil¬ tered through a 1-liter medium sintered glass fun- nel. The filtrate was precipitated by pumping it at 400 ml/min into a mixture of 2600 gm of ice and 1300 gm of distilled water with rapid stirring for 10 min. The green solid precipitate was isolated by filtration through a 2-liter medium sintered glass funnel. The solid was reslurried with 800 ml cone. NH 4 0H at 70° C for 30 min. The blue solid was isolated by hot filtration, washed 4 times with 800 ml of distilled water under the same conditions, with the final filtrate being neutral. The solid was vacuum oven-dried at 114° C for 24 hr, ground with mortar and pestle and dried an additional 24 hr under the same conditions. A blue, purified hydroxyalumi¬ numphthalocyanine was obtained. The spectral absorp¬ tion of the purified hydroxyaluminumphthalocyanine was evaluated as above to determine peak absorption and width of the absorption peak at half-maximum intensity. The purified hydroxyaluminumphthalocyanine was then solvent-treated according to the following procedure: Chemicals 13 g purified hydroxyaluminumphthalocyanine, molecular weight 556 (0.023 M) 130 ml piperidine, molecular weight 85.15 Purified hydroxyaluminumphthalocyanine was ground with mortar and pestle and refluxed with piperidine for 5 hr in a 250-ml, three-neck, round- bottomed flask fitted with a mechanical stirrer, con¬ denser with nitrogen line and a stopper. The mixture was filtered hot through a base-washed, medium, sintered-glass funnel. The solid was washed twice by reslurrying with 500 ml of ethyl acetate, twice with 500-ml reagent grade acetone, and dried in a vacuum oven at 114° C. A purple solid was obtained. The peak absorption and half-maximum peak width of the solvent-treated hydroxyaluminumphthalocyanine were determined as above and reported in the table. Table Absorption Peak Width at Half Peak Maximum Material Spectral Absorption Intensity purified HAP 612 nm >150 nm solvent-treated 621 nm =100 n HAP (invention) The data indicate that the spectral absorp- tion peak of hydroxyaluminumphthalocyanine of the invention is bathochromically shifted to 621 nm and is sharper, as evidenced by the reduced peak width. X-ray powder diffraction patterns confirm hydroxyaluminumphthalocyanine of the invention as being a novel crystalline form of this compound com¬ pared with prior-art forms of hydroxyaluminumphthalo¬ cyanine. Powder patterns, using Cu K-α radiation, - * ξxJK OMPI Is, WIP indicate, for example, that hydroxyaluminumphthalo¬ cyanine of the invention has peaks at diffraction angles (2θ) of 29.60, 28.78, 27.85, 25.75, 23.85, 22.00, 15.40, 13.80, 11.80, 9.70 and 6.68 degrees. In contrast, the x-ray powder pattern of the acid- treated hydroxyaluminumphthalocyanine (which repre¬ sents a prior form of the compound) has characteris¬ tic peaks at diffraction angles of 34.98, 27.25, 25.20, 20.70, 16.15, 13.70, 13.05 and 6.70 degrees. Hydroxyaluminumphthalocyanine of the invention, moreover, is distinguished by characteris¬ tic infrared spectral patterns. In characterizing hydroxyaluminumphthalocyanine of the invention and prior-art hydroxyaluminumphthalocyanine, the position of certain deformation bands can be considered. For hydroxyaluminumphthalocyanine of the invention, these exist at 1081 and 574 cm" 1 . In the prior forms of hydroxyaluminumphthalocyanine, these bands are shifted to the frequencies of 1064 and 610 cm" 1 . Example 2: Other Solvent Treatments The following solvents were used in place of piperidine in the treatment of purified hydroxyalumi¬ numphthalocyanine prepared as in Example 1. Treat¬ ments were performed at the reflux temperature of the solvent or at 100° C, whichever was lower. ethyl acetate α-chloronaphthalene toluene dioxane dimethylformamide 1,2-dichloroethane acetonitrile 2-butanone nitromethane 4-butyrolactone heptane pyridine methanol N-methylpyrrolidinone aniline dimethyIsulfoxide Crystal structures and spectral absorptions of hydroxyaluminumphthalocyanine treated with each of the above solvents were substantially the same as the piperidine-treated material of Example 1. Example 3: Temperature Effects To determine temperature effects, if any, on the solvent treatment of purified hydroxyaluminum¬ phthalocyanine, the following solvents were evaluated for solvent treatment of purified hydroxyaluminum¬ phthalocyanine at room temperature for 5 hr, in place of the higher temperatures employed in Example 2: Solvents dimethylformamide methanol dimethylsulfoxide N-methylpyrrolidinone Each of the treatments with the above sol¬ vents resulted in hydroxyaluminumphthalocyanine with a crystal structure and absorption substantially the same as the piperidine-treated hydroxyaluminum¬ phthalocyanine of Example 1. Example 4: Photoelectrophoretic Dispersion Piperidine-treated HAP as in Example 1 was tested for electrical photosensitivity in a liquid migration imaging dispersion, according to the proce¬ dures of US Patent 4,146,707. Samples from the images obtained were subjected to a 7-day, high- intensity daylight, 50,000-lux, fading test. The images were very good and no image fading was observed after the 7-day fading test. Example 5: Electrographic Toner Electrographic toners were prepared from pyridine-treated hydroxyaluminumphthalocyanine by first milling the pigment with steel balls for sev¬ eral days. The pigment was dispersed in a chlori¬ nated fluid, initially 1,1,1-trichloroethylene and ration. OMP was then compounded into a styrene-acrylic binder on a 2-roll rubber mill where the solvent evaporated. The toner was then ground to a particle size of 5-15 microns on a fluid energy mill. Toners of cyan hue for use in electroscopic developers were obtained.

Claims: We claim: 1. Hydroxyaluminumphthalocyanine which exhibits a reflection spectral absorption peak at 621 nm when coated from a dispersion on a reflective sup- port comprising, in sequence, a cellulose acetate layer, a polyurethane layer containing dispersed titanium dioxide and a polyester support. 2. Hydroxyaluminumphthalocyanine as in Claim 1 wherein the width of the absorption peak at 621 nm is no more than 100 nm at half-maximum inten¬ sity. 3. A migraton imaging dispersion compris¬ ing the hydroxyaluminumphthalocyanine of Claim 1 or 2 as an electrically photosensitive colorant. 4. An electrographic developer composition comprising the hydroxyaluminumphthalocyanine of Claim 1 or 2 as a toner colorant. 5. An hydroxyaluminumphthalocyanine having diffraction angles, as determined by Cu K-α X-ray diffraction analysis, of 29.60, 28.78, 27.85, 25.75, 23.85, 22.00, 15.40, 13.80, 11.80, 9.70 and 6.68 degrees. 6. A method of preparing hydroxyaluminum¬ phthalocyanine having reduced green absorption com- prising treating hydroxyaluminumphthalocyanine with an organic liquid selected from the group consisting of piperidine, ethyl acetate, α-chloronaphthalene, toluene, dioxane, dimethylformamide, 1,2-dichloroeth- ane, acetonitrile, 2-butanone, nitromethane, 4-butyrolactone, heptane, pyridine, methanol, N-meth- ylpyrrolidinone, aniline and dimethylsulfoxide at a temperature from about 20° C to about 100° C or the refluxing temperature of said organic liquid, which¬ ever is less. 7. Hydroxyaluminumphthalocyanine prepared according to the process of Claim 6. OMP vtIiPr

Inventors: REGAN MICHAEL THOMAS, WRIGHT HAL ELDON, REGAN, MICHAEL, THOMAS, WRIGHT, HAL, ELDON
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1984
Main classification: G03G17
IPC codes: C09B47, C09B67, G03G5, G03G9, G03G17