Document 6wYez02K620YQLb0e0peyrZ74

E. |. DU PONT DE NEMOURS & COMPANY PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Copy No. KN-46-54 f --:JUZJi2L_______________ --.... ................. NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Final Report General Patent Survey - Fhthalocyaaine Pigments. Period Covered. May 1 - July 85, 1946 FILE. 223,4 DATE. 8-18-46 N-iaeoa N39976 Copies toi Numerical File - Research Office (2234) - Library File <2234) f - Dr* J* E* Boogo, Newport - Dr * W,, F* &pengeman8 Newark "Mr, A, Blegel, Newark Dr, B, H, Perkins| Newark " Br* F, F* Ehrioh, Newark ~ Mr Ao J, Stratton0 Newark Dr, D, B, Killian, Newark - Mr* J* P Hancock, Wilmington 12 - Orohea Patent Sorvio, Jackson Labo 13 - Extra 14 SUPPLANT TO EN~4fc-54 GENERAL PATENT SURVEY-PHTHALOCYANIKE PIQMBMTS To be attached to page 5 of the report* Since this report a* issued on August 12, 1946 attention has been called to an error in the statement en page 5 that "There it no basie product claim on metal-free phthalecyanine" It has been pointed out that olalm 18 of U.S, 2,000,052) although ooToring a product made by a different process than that commonly employed in the manufacture of metal-free phthalecyanine, never theless dominates metal-free phthalecyanine and is not limited to the process disclosed. Accordingly, the statement quoted above should be changed te read "Claim 13 of U.S. 2,000,052 Is considered a valid product olalm for matalfree phthalocyanine. This 1CI patent is available for the use of Du Pont"* | j G'%SZDX&<s^,`,M'te> AJ L STRATTON 10/11/46 APPROVED* '// r/ N39976.01 DUP050150213 Serial Ho. KH-46-54 Copy Ho* / Copy to: #1 - numerical Pile 2 ~ Research Office {223*4} 5 ~ Library Pile (223*4) 4 * Dr* J. E* Booge, Heuport 8 * Dr. W, P, Spengeman, Hewark 6 - Mr. A* Siegel, Newark 7 * CT. B. H. Perkins, Sewark 0 - Or* P. P. Ehrloh, Newark 9 * Mr* A. J. Stratton, Newark 10 - Dr. D, B. Killian, Newark 11 - Mr* J. P. Hancock, Wilmington 12 - Orohsm Patent Service, laokson Lab* u13 .- Extra jcr ?. y NEWARK PLANT PIGMENT COLOR RESEARCH REPOST Pinal Report Title: GENERAL PATENT SURVEY - PBBIALOCYABIHE PIGMENTS. Period Covered: MAT 1 * JULY 38, 1948 m APPROVED EOT: D. B. KILLIAN DATE, ISSUED 58-12-46 N39976.02 DUP050150214 am.^S2rMIKB,.liaMl - g en er al pat en t s u r v ey IMl-RODUSTIONi, Phthalocyanlne pigments have been sold in the United States by the DuPont Company since about 1935* The manufacture of the pig ment has, up to the present time, been carried out exclusively by the Organic Chemicals Department* However, the Pigments Department have used the pigment as a semi-finished product in the preparation of numerous modifications for special uses. During this period, extensive studies have been carried on in the laboratories of Orchem and of the Pigments Department and numerous reports are to be found in the files of each laboratory* These reports include a thorough review of the historical aspects of the develepmant and this will not be repeated herein* For a brief review thereof, reference is made to Newark report 0-46-7* Recently, a decision has been rendered to carry on research leading up to the full scale manufacture of phthalocyanlna pigments within the Pigments Department* This research has now progressed sub stantially to the point of pilot plant operation, and, although numerous patent surveys have been made by the Jackson Laboratory of Orchem and the patent situation is fairly well understood by those interested in it, no such survey of the art has heretofore been made at Newark and it seems highly desirable to make such a complete survey from our own point of view* With these facts in mind, the patent art has been thoroughly reviewed with particular reference to the preferred process at Newark, but a brief summary has also been included of the whole phthalocyanlne art,in anticipation of a need for broadening this survey at some future date* SCOPE OF THE REVIEW AND SOURCES: As pointed out above, this review has been directed particularly towards one process now contemplated for use at Newark but has also includedarather careful search of the art on the synthesis and finishing of copper phthalocyanlne and its chlorinated derivatives. A somewhat less careful survey has been made of use patents and of patents covering other metal phthalocyanlnes as well as9x&a#filh the benzene nuclei con tain various substituents* Although tnese latter products are not con templated for manufacture at the present time, it seems highly probable that some of them may be of interest for future study* DUP050150215 2 As to the sources of this review, an attempt has been made to inspect all U.S. and British phthalocyanine patents which have been issued to date* It is believed that all such U.S* patents are available in the Newark Library and that substantially all British patents are also available. To insure this point, a careful search was made of Chemical Abstracts and,likewise, of the Jackson Laboratory patent files. A less careful search has been made of the French, German, and Swiss patents on this subject, with considerable dependence placed upon the Abstract Journals for information with respect to many of these foreign patents* However, since we are primarily concerned with domination, these patents are of minor importance In this search* msm* y.pth9A^..af..glua... There are two fundamentally different processes which have been widely used for the manufacture of copper phthalocyanine* In one, phthalonltrile is heated with a copper salt to about 180C at which point a vigorous, exothermic reaction starts and goes to com pletion in a relatively short time* Because of the extremely vigorous nature of this reaction, it has bean difficult to control and the addition of inert material, either salt,such as sodium chloride or high boiling liquid,such as kerosene or trlchlorbentAhd* ~. has been common practice. This process has been used largely heretofore by Orchem and is still being used for the standard copper phthalocyanine pigment (BT-172-D) which is sold by the Figments Department. The other common process involves the reaction of phthalic anhydride, urea and a copper salt in the presence of certain catalysts at temperatures in the order of 200. Although this reaction may be carried out as a melt, which eventually sets up to a solid as the pig ment is formed, it has been much more successfully handled in the presence of a liquid diluent such as kerosene or trichlorbenzene. It is this process using a purified grade of kerosene as the diluent,and ammonium molybdate as the oatftl$st,whlch Newark proposes to adopt* However, it is known that this process results in the formation of a chlorine-free blue which has certain undesirable characteristics, namely a loss of strength in the presence of hydrocarbon solvent? for many uses. It is entirely satisfactory as a raw material for the subsequent manufacture of chlorinated green phthalocyanine and will be manufactured for this use* To manufacture a grade of phthalocyanine blue which is stable in the presence of hydrocarbon solvent, It is proposed to resort to the substitution of a minor proportion, about 15% to 20%t of 4-chlor phthalic acid for an equivalent amount of the phthalic anhydride used In the reaction. This results in the forma tion of a blue phthalocyanine containing approximately 4% of chlorine. DUP050150216 3- She process proposed for use at Newark is substantially identical with that used by I.C.I. in England for most of their phthalocyanine manufacture. They manufacture the chlorine-free grade under the designation "Monastral* Blue B and the grade con taining chlorine under the designation "Monastral"1 Blue LB. Where the designation "Blue B* and "Blue LB" are used throughout this report, they will have meanings similar to those used by I.C.I. ira.ftfrs.slg M Qmm .gfrlfra^QfizaBto The only phthalocyanine green marketed in this country has been a highly chlorinated copper phthalocyanine containing between 14 and 15 atoms of chlorine per molecule of copper phthalocyanine (approximately 4B% chlorine). The only process practiced commercially to our knowledge has involved the chlorination of Blue B suspended in the eutectic melt of anhydrous aluminum chloride end sodium chloride. It is an expensive process and difficult to control. Newark does not propose to use this process but will instead use sulfur dlchlorlde as a combined carrier and chlorinating agent working under pressure and at relatively high temperatures. The details of the process are rather complex, and it has been practiced only on a laboratory scale, but it has shown much promise of substantial economy because of the relative ease with which the sulfur dlchlorlde can be recovered for reuse. Finishing. Process are In the past all commercial processes of which we/aware for the manufacture of phthalocyanine pigments involvedthe "so-called1* acid pasting steps, in which the pigment is dissolved in highly concentrated sulfurie acid, or, in the case of the green, in a mixture of sulfuric acid and chlorsulfonic acid, and the pigment repreolpltated therefrom by diluting the acid solution with water. Here recently. Orehem has developed a "so-called" salt milling process in which the pigment and a relatively large amount of an Inorganic salt, such as sodium chloride or sodium sulfate,are ball milled together for a substantial period of time followed by extraction of the water soluble salt and isolation of the pure pigment. This process is under develepment for commercial operation by both Orehem and the Imperial Chemical Industries in England. The Pigments Department does not propose to use either of these processes but have developed a new process which we have eailed "Solvent Milling". In this process the pigment, either in the dry form (which may be a purified or aimply a dried out crude) , or in the form of a kerosene-containing filter cake from the synthesis step,is ground in a ball mill with a solvent such as kerosene or mineral spirits. After a suitable milling cycle (the unproven goal on a plant scale is a maximum of 48 hours), the mill charge will be dumped, separated from the solvent (probably by steam distillation) and extracted for the removal of any impurities such as the residual impurities from the synthesis stage,or,impurities result leg from abrasion or corrosion of ithe grinding device. DUP050150217 -4- In the case of the green, It seems desirable to add approximately equal quantities of an inorganic salt such as sodium sulfate to the grind and it seems necessary to use only hydrocarbon solvent for the liquid portion. The presence of even small amounts of water appears definitely harmful to the greens. On the other hand, in the case of the blue, it has been possible to get entirely satisfactory grinding with alcohols or other water soluble solvents containing up to as high as 40# of water. Sven water alone has enabled a substantial improvement in strength,although?to date, the desired strength has not been obtained in this medium. Since grinds made in the presence of an appreciable amount of water suffer from a substantial corrosion problem in steel ball mills, the proposed process is at present restricted to the use of a hydrocarbon solvent. Finally, it should be noted that the best results have been obtained when the grinds were made in the presence of an organic acid such as naphthenic acid or oleic acid, followed by steam distillation In the presence of certain treating agents, notably a combination of the TEA Ester and glyceryl mono ricinoleate. The preferred agents nave not been selected with certainty at this time,but it seems quite definite that some agent will be necessary in these steps* 1. There is no patent containing a product claim on copper phthalocyanlne as such and none is possible at this time. 2. There is a patent containing a product claim covering monochlor copper phthalocyanlne. It is assigned to I.C.I. and licensed to DuPont. 3. All practical processes for the synthesis of copper phthalocyanlne are covered in patents either owned by or licensed to DuPont. 4. All important process patents are believed to be valid and to be rather universally respected in the industry* 5* The process for the manufacture of Blue LB is disclosed but not specifically claimed aside from the general process coverage.1 1. A presumably strong product patent covering the highly chlorinated copper phthalocyanlne Is owned by General Aniline but licensed to DuPont outside of the DuPont - General CPC agreement* This is a non-exclusive license and, in tha evant that all of General's patents are thrown open to license by the Alien Property Custodian, the produot might become available to our competitors* DUP050150218 - 5 However, there appears to he ns reason to believe that our present license will be disturbed* 2* Both practical processes for the manufacture of copper ohthalocyanine green, namely the aluminum chloride sodium chloride melt and the sulfur dichloride processes, are covered by presumably valid patents owned by DuPont,so that regardless of our lack of control of the product itself, our patent position seems quite strong* IfftnikPm .Itottolgsyahlhg 1.There Is no basic product claim on metal-free phthalocyanlne. 2* The commonly known practical processes for the manufacture of metal-free phthalocyanlne are covered by patents either owned by or licensed to DuPont* Ptoigfrtaft, Pita,pa* 1* There is no basic patent covering the acid-pasting procedure and none is possible at present* However, there are numerous patents on various details of the acid-pasting and subsequent drowning steps including the use of treating agents in the drowning step. Not all of these patents are available for the use of DuPont,but It is believed that there are none which will hamper any operations now contemplated. Since we do not propose to use acid-pasting in the Pigments Department, it Is certain that none of them will disturb our operation. 2. DuPont owns a patent on the salt milling process which was issued quite recently but it is our opinion that this patent is quite weak in view of numerous references to similar processes in the art* 3* We have found no specific disclosures of solvent milling as we propose to practice it,and it is believed to be a patentable process. However, this will be made the subject of a separate report. 4. Miscellaneous Finishing Steps. It is believed tbat our process may possibly be in conflict with U.S. 2,138,049 and 2,268,144 (owned by Harmon) if any of the solvent remains after steam distillation to be removed in the oven* However, negotiations which will give DuPont rights under these patents feve been initiated at 'the present- timai '''' J We are Informed by representatives of Orchem that the use of the TEA CL. Ester is under some patent restrictions. However, we are also informed by them that they have obtained licenses for the use of this material and it, therefore. Is now open to our use. No effort has been made to locate the patent Involved. DUP050150219 - 6The general field of the use of various types of treating agents in the manufacture of pigments is one in which there are a great many patents hut substantially all of these patents are of very limited scope. Ho extended search has been made in this field at the present time. However, the field has been broadly covered in previous searches made at Newark and we feel confident in the opinion that there are no insurmountable patent bars. Some of the more important patents in this group will be discussed In connection with the detailed description of the art. MWiMSM. l,ajii In the following discussion of the patent art two main divisions will be recognised. She first will discuss in some detail those patents believed to be directly pertinent to operations of the DuPont Company in the manufacture of phthalooyanine pigments, with emphasis being laid on those which are particularly concerned with the operations of the Pigments Department. Shis group of patents will be further dub-divided under the four topics used above in the summary of the art. She second main division will include in a much less detailed fashion substantially all of the remaining U.S. patents in the phthaloeyanlne field* It will also include many of the British patents and some reference will be mad to other foreign patents. In addition to the four sain sub-divisions referred to above, it will also include references to other metal phthalocyanines, to seme patents on uses of phthelocyenines, and to,a large group of patents concerned with pro ducts in which there are substituent groups on the bensene rings of the phthalooyanine molecule. This last group of patents will be listed by descriptive title only for the most part and are being included only for a ready reference in the future. DUP050150220 A* mms^smusmmTAKCS 8,S, 2,000,081, Issued 5*7*35 to Thorpe, Llnstead & Thomas of I,C*I, This is the first phthalocyanlne patent in the united States and covers a process of reacting o-oyanobenzamide with a metal or a metal compound under the Influence of heat, A large number of metals including magnesium, copper and tin ara disclosed as effective. Their use as pigments is disclosed as well as the process of acid pasting to Obtain them in a fine state of subdivision* The possibility of re* moving some metals such as magnesium through the use of concentrated sulfuric acid to give a metal*free compound is recognised, There is no clear recognition of the structure of phth&looyaalnes as now accepted in this patent, but it la very closely approximated, Tim disclosure of this patent with respect to the compounds famed is basic to the whole phthalcoyanlne industry in the United States, However, the process is not currently used and there are no product claims independent of the process because of a prior disclosure in the literature* 8*8, 3,129,015, issued 9*6*58 to Linstead & Dent of l.C.I, then phthalonltrile and euprlo chloride sore heated {together above Shout 200G, the resulting product ie oopper monochloro phthaloeyanine, Mien cuprous chloride is used In place of cupric chloride, the product still contains chlorine but to a considerably lesser degree. The use of Inert solvent is disclosed. Claim 5 covers copper monochloro phthalocyanlne as a new product, 8,8, 2,197,458, issued 4*16*40 to Wyler of l.C.I, This patent covers broadly the phthalic anbydrlde/urea fusion process, wherein phthalic anhydride, urea and a metal salt such as cupric chloride are heated to a temperature in the order of 200nc., whereby a solid pigmentary produet is formed. The use of substituted phthalic anhydride ,as well as the use of free acid, diammonlua salts and certain other derivatives JLa disclosed. The use of boric acid or ammonium sulfaraate is recommended to improve yield and to prevent frothing. There is recognition of Improved yields resulting from add* ing the urea to a molten mixture of the phthalic anhydride and to the metal salts. There is no disclosure of the use of a liquid diluent or solvent * This patent is basic for the process proposed for use at Sewark* 8,8, 2,197,469, Issued 4*16*40 to tyier of I,C,I, A phthalocyanlne containing tin is obtained by the use of the phthalic anhydride/urea fusion process of 8,8, 2,197,468 in the presence of suitable tin salts. The patent discloses,but does not claim,the preparation of a metal-free compound by the demetallization of the tin containing phthalocyanlne through solution in concentrated sulfuric acid. DUP050150221 -aIt discloses, but dots sot alalia, the use of kerosene or ofchar high boil ing organic liquids as a diluent in the reaction. The disclosure of the use of kerosene Is important to us but there is no protection* Otherwise, there is no direct interest to Hewark at the moment but it is of direct interest to Orehsm in their manufacture of a co-salt milled copper and tin diohloride phthalocyanine* It is of potential interest to both departments as a possible route for the manufacture of metal free phthalocyanine* Such a process is now used by I.C*I, 3*3. 3,214,477, issued 9-10-40 to Riley of I.C.I. The efficiency of the phthalic anhydride/urea fusion process is materially increased through the use of certain saltr of metals of groups 5 and 6 of the periodic tables as catalysts for the reaction* itamonitar molybdate is the preferred salt and is used in very small amounts. We propose to use this process at Hewark* U.S.Application, Serial #629,981, Application Date 11-20-45 by A. Siegel, assigned to DuFont A coalesced phthalocyanine pigment is made by reacting phthalonitrile with a metal salt such as ouprlo chloride in the presence of a substantial amount of a calcined T10 pigment as a substratum* The resulting product is satisfactoryror use without any furthsr conditioning steps* British patent 453,767 is very close art against this application but has not yet been cited in the prosecu tion, and it appears probable that a patent will Issue. However, any patent which issues will probably have little value beyond that of a disclosure* The process is that formerly contemplated for use at Hewark In the manufacture of Figment BX-CR, 2* Phthalocyanine Greens U.S* 2,195,984, issued 4-2-40 to Dent and Sylvester of I.C.I. Phthalocyanine pigments may be chlorinated or broo^MN^b iJk hot molten phthalic anhydride using elementary chlorine or bromine. Although this is the first published patent on the process of halogenatIng a phthalocyanine pigment, it does not bear the earliest application date U.S. 2,214,469, issued 9-10-40 to Linatead and Dent of I.C.I. This patent has a broad claim to the process of halogenating a phthalocyanine and discloses the use of a number of halogen carriers including aluminum chloride and sulfur ohloride. This patent has the earliest application date of any patent on the direct halogenatlon of phthalocyanine but lost out as to the presently preferred product in an interference with U.S* 2,276,860 because it did not contain adequate DUP050150222 disclosure of the degree of halogenatlon necessary for tbs preferred phfchalooyanine green. 0.S* 2,247,752, issued 7-1-41 to Pox of DuPont This patent covers the aluminum ohloride/sodiu* chloride eutectic melt prooees for the halogenatlon of phthalocyanine pigments* It is the process currently used by Orohsm but is not contemplated at preamt for use at Bewwrk, 0.8, 8,383,560, issued 8*38-41 to Detrlek and Johnson of DuPont. This patent covers the successive steps of synthesis from phthalonitrile in the presence of sodium chloride, mixing the resetion product with anhydrous aluminum chloride and chlorinating directly with out any intermediate purification steps. The process is not contemplated for us at Bewark# 0*3* 2,376*880, Issued 3-17-42 to Bienann, Schmidt, Muehlhauer & Meet, assigned to General Aniline This patent has very broad coverage of halogenated phfchalooyanine containing more than eight halogen atoms per molecule obtained by direct h&l ogenafcion. It has both product and process claims. This patent issued following an Interference with 0*3. 2,314,489 mentioned above and is unquestionably a dominating patent in the field. However, the interference was settled on the basis of reyHiy free cross licenses between General Aniline and DuPont and we are free to manufacture the product. 0S, 2,377,635, issued 6-5-45 to Fox & Jackson of DuPont This patent covers the process of chlorination of phthalooyanine pigments by the use of sulfur dlohloride, followed by recovery of the sulfur dlohloride by sweeping with chlorine gas which reacts with the sulfur morxoohlorlde farmed during the chlorination with re generation of the sulfur dlohloride. This is the process contemplated for the manufacture of phfchalcoym in greens at Hewark. Attention is called to references to the manufacture of metal free phthalocyanine In some of the basic patents mentioned above. For instance, U.S. 2,000,051 discloses the demetal llzation of magicalurn phfchalooyanlne end 0,3. 2,197,459 discloses the demetallisation of tin phthalocyanine * Both of these processes have been used in the past and the second Is currently contemplated for use by I.C*I* The following patents more specifically cover the manufacture of metal free phthalocyanine* 0.8. 2,116,602, issued 5-10-38 to Hellblon, Irving & Llnatead of I.C.I. This patent covers the process of forming a metal free phthaloeyanlne by heating phthalonitrile with alkali metals or their compounds, ammonia or certain tertiary organic bases* It is understood that this DUP050150223 10 process la highly inefficient. U.S. 2,155,88%, leaned 4-18-39 to Lowe of I.C.I. In a modification of the previous patent phthalonttrile is heated with an ethanol amine to form a metal free phthalooyanine. U.S. Application, Serial #579,332, filed 2-22-48 by FaImmr & Gross of DuPont Metal free phthalooyanine may be made by reacting phfchalonitrlle, a 4 solid inert diluent such as sodium chloride or titanium dioxide and a solids alkaline agent such as calcium oxide in the presence of small mounts of methyiglueaalne at a temperature of about 20re. 'Hbi the reaction is carried eflfc In the presence of a water soluble agent as MaCl and under conditions hereby some grinding action occurs during the reaction, such as in a rotary baker, little If any condition ing of the final product other than extraction of soluble impurities is needed* It is believed that this process is currently being practiced by Orcfaea but Is not contemplated at present for use at Sewark. * ifMiigMJlm U.S. 2,138,049, Issued 11-29-38 to Vesce of Harmon A water immiscible organic liquid such as toluene Is added to a pigment slurry which la then stirred to emulsify the liquid and the Whole dried at a temperature below the fK&Iihg point of water to give a dried, pigment of improved texture. There is specifio disclosure of the application of this process to phthalooyanine pigments and it has been rather broadly interpreted as covering any process In which a water immiscible organic liquid is Intimately mixed with a pigment slurry be fore drying* This patent is Included in a cross licensing agreement undir -.negotiation'1 between DuPont and Harmon and is accordingly avail able for our use when negotiations are completed. U.S* 2,173,899, Issued 9-19-39 to A.Slegel of DuPont m is the patent covering our "Ramapo" Blue pigment and covers broadly a water insoluble phthalooyanine pigment intimately associated with an alkaline earth rosinate* Since this patent was in cluded in the Dufont/General Aniline agreement on phthalooyanine, it has been considered as available to all purchasers of phthalooyanine paste from General and no attempts have been made to enforce it by DuPont, altho it is believed that all large soale manufacturers of phthalocysnlne pigments have practiced the process* U.S. 2,213,893, issued 9-3*40 to Davies, Hailwood and Todd of I.C.I* This patent covers the use of the sodium salt of the formaldehyde condensation products of Haphthalene Sulfonic Acid (Compound #8) in the acid-pasting step of finishing phthaloeyanine pigments. There is a product claim to the combination of the pigment and the condensation product without limits to the method of manufacture and there are broad DUP050150224 - 11 process claims to the precipitation of an acid solution of phthalocyanine in the presence of a water soluble, non-hygroscopic dispersing agent. There is disclosure of ball milling in water and in the presence of the dispersing agent after acid pasting to get further particle else reduction. This patent may be sufficiently broad to cower some of our products but it is probably relatively unimportant to us. U,3. 8,268,144, issued 12-30-44 to Vesoe of Harmon This patent is similar to U.s, 2,138,049 but differs in that a definite emulsion of the volatile oil is separately prepared and added to the pigment slurry, followed by stirring until the emul sion breaks, after which the slurry is filtered and then dried. The process is disclosed and specifically claimed as applied to copper phthalocyanine as well as being claimed broadly* This patent is also included In the cross license agreement with Harmon and is available to our use.when negotiations are completed. U*S, 2,305,579, issued 12-15-42 to Cetrlok & Lang of DuPont This patent covers Orchem's use of the so-called TEACxg eater In the manufacture of a soft powder phthalooyanine pigment. The claims cover pi&sent particles coated with the Insoluble reaction product of a poly-alkanol amine with a higher el iphatie ; acid. The process is specifically applied to phthalooyanine pigments by using the agent to emulsify an organic liquid such as toluene in a process essentially similar to that of Harmon in the preceding patent* It is entirely possible that our products may come within the claims of this patent, U,S 2,327,472, issued 8-24-43 to Vesoe ,& Stalzer of Harmon A non-flocculating copper phthalooyanine Is made by in corporating therein In the wet state a major proportion of aluminum benzoate as a substratum. The disclosure of tibia patent is quite accurate and products of this type have been marketed by Harmon but they are believed to be fundamentally high in cost and not a serious threat to our business. However, the goal is highly desirable and, at present, no other good solution Is known, U,S, 2,402,167, Issued 6-18-46 to Lang & Detrick of DuPont This patent le an attempt to cover Orchem's salt-milling process for finishing phthalocyanine pigments. Because of very close prior art the claims are limited to a process using more than four parts of a water ^olubie salt per part of pigment and to the nise of an apparatus which grinds by attrition and shearing as distinguished from impact. It is doubtful if this patent has mors than a publication value. DUP050150225 12 - U*S. Application* Serial #664*434* filed 4-23-46 by Robbins of DuPont 1- naphthalene sulfonic sold is added to (or formed In situ) the sulfuric add solution of a phthalooyanlne pigment prior to drowning to give a soft-textured pigment. The agent is used in amounts of from 1 - 3-1/2 times the weight of the pigment. The true significance of this process is not clear at present but it is not now contemplated for use at Newark. British Patent 569*402* issued 5-22-45 to Mollliett and Todd of X.G.I. This is I*CI.*s 1M& milling patent and includes a small quantity of a fatty acid or ester thereof with the salt. The preferred procedure uses anhydrous sodium sulfate with a small amount of oleic or linolelo add. B* pat en t s op imsm TJ.3. 2*000*052 -I.C.I* - covers the reaction of phthallmide with a metal in the presence of ammonia. D.3. 2*075.043 - I.C.I. - CPC is formed by reacting an orthohalogen benzaraide with cuprous cyanide. IT.S. 2*124*742 - I.C.I. - Copper phthalooyanlne may be forated by heating a metal-free phthalooyanlne with copper or copper salts. tJ.S. 2,138*413 - Interohemieal - A pigment which does not need add pasting is prepared by reacting phthalonitrila and copper salts In the presence of aliphatic di- or trihydrlc alcohols or alcohol poly ethers. U.3. 2,153,300 - DuPont - The violently exothermic reaction between phthalonitrile and the copper salts is controlled by adding the reastsait portion-wise to the rotary baker. 17.3. 2*164*912 - General Aniline - Phthalonitrile is heated with a metallic oyansuntd to form a phthalooyanlne pigment. U.S. 2*160*337 - DuPont - Phthalonitrile and metallic copper may be caused to react at a temperature of 160-170C in the presence of small amounts of chloride of amphoteric metals or ammonia* 0.3* 2.166*213 -- I.C.I* -- This is the basic patent for the reaction of phthalordtrile with a copper producing agent to form copper phthal ocyanine * U*3* 3*194*850 - Interchemical -- This covers an apparatus fsp* the manufacture of phthalocyanine pl^aenta by the reaction of phthalo nitrile vapors with a polished metal surface* DUP050150226 13 0S, 2,302,632 - IC*I* - Ortho-arylene di-oyanides ape heated with a compound of a metal of the second group of the periodic table. U.S* 2,212,024 * General Aniline * Phthalonltrile is heated with an amide and a metal salt* 0S* 2,316,761 - I.CX, - Covers the use of ammonium sulfamte as a catalyst in the phtballe anhydride/urea process* tJ.S, 2,216,867 - I*CZ - Covers broadly the use of amino sulfonic acid in plane of urea in the manufacture of phthalooyanin U*8, 2,216,868 * Ic,X* - Covers the use of ammonium sulfastate in place of urea in the phthalio anhydride process for cobalt, j##w^ or iron phthalooyanlne* 0*3. 3,242,301 - I.G.X* - la a belated issuanee of one division of the basic patent for heating phthalonltrile with a copper salt sued involves the use of a neutral organic solvent* 0.S* 2,243,098 - InterOheatcal Covers the reaction of phthalonitrile vapors with a polished metal surface followed by scraping off the pigment thus formed* 0*3* 2,276,308 - 3.0,1* - The presence of small amounts of HaOH, CaO or HaoCOjj improves the efficiency of the reaction between phthalonltrile and metal compounds in the presence of liquid diluents* 0*3, 2,302,612 - American Cyanamid - Chlorine-free CPC is prepared from phthalonltrile and e^pfte chloride by reacting in the presence of anhydrous ammonia, 0.S* 2,318,783 - American Cyanamid - Chlorine-free CPC is prepared by resulting phthalonltrile with anhydrous copper sulfate In the presence of nitrobenzene and anhydrous ammonia under pressure, U.S. 2,318,737 - American Cyar.am.ld - Also covers the reaction of phthalonltrile with euprlo sulfate in the presence of ammonia. 0*3* 3,378.780 - Ikterohemlool - Shthaleoyanlnes may be pre pared by heating phthalio anhydride, ammonia and a metal salt of syanurle acid* 0*3* 3,382,441 - Interohemleal - Phthalouitri1 and metal compounds are reacted in the presence of such limited quantities of hydroxy aliphatic solvents that the major portion of the solvent is evaporated during the reaction* DUP050150227 14 - TJ,3* Application, Serial #403,866 - AFC - Bensolo aaid and related ooapounds are effeotive ia preventing the foaming of a phthalie anhpdride/nrea fusion synthesis# In listing the following British patents, those patent* which have substantially equivalent 8*S, disclosure have been, for the most part, emitted* British 882,160 - Scottish Dyes <X,c*i,) - This is the first disclosure of phfchaleoyaniaes in English and covers a prooess in which ammonia is passed lute molten phthalie anhydride in the presence of a metal to give a bluer solid which may be purified by precipitation from sulfuric aeld* British 453,707 - 1,0* Phthalonitrilc is heated with metals or metal compounds taking part in the fomaatlon of the dveatuff in the presence of m oxide or salt of a metal of groups l to 4 of the periodic systear, which salt is solid at the reaction temperature and inert and is used as a diluent, This is the best prior art against cur Figment BX**CH process, but there is no U*&# equivalent, British 467,786 - 1,0,2, Ammonium phthalate or Its deri vatives may be heated with a metal salt in the presence of an amino sulfonic sold to give a phthalooyanlne* British 468,764 - 1,0* * Phthalonitrile and copper salts are heated in the presence of tertiary bases under special conditions of pressure and concentration, British 460,780 - 1*0* - A high boiling diluent other than a tertiary base is added to the prooess of the preceding patent, British 462,$$$ - 2*0, - Phthalonitrile is heated with metal sssfdes or oyanamldee together with high molecular Wfei^h^Aloohol or ' aSlwptans* ' British 432,387 - 1,0* - Fhthalonitri1e la heated with metal compounds in the presence of diluents free from nitrogen and hydroxyl groups but under pressure, British 603,020 ttonteoatlni - Jhtholic anhydride and eopper compounds are heated in the presence of di-syano~diafitIdes* British 562,124 * DuPont - Covers the use of lnfrav>ed heating in the phthalonitrlle process for phthalooyanlne She 8*3, application has been finally rejected. imm& U,S, 2,827,628 - DuPont - Phthalooyaninea may be fluorlxmted by treatment with fluorine in liquid hydrogen fluoride* British 470,070 - 1,0. - Simultaneous hdegenation and formation of the phthalooyanlne by beating phthalonitrlle with the halogenatlng a DUP050150228 * IS agent in the preg^nce of the metal halide* British 499,415 - I.G. - Copper phthalocyanlne may be chlorinated with chlorine gas in triohloabenzen In the presence of antimony triaulfide under atmospheric pressure, British 500,471 * I.G. - Phthalocyanines are halogenated in the preserve of organic acid halides and with halogen carriers. TJ.S. 2,153,620 - I.C.I* - Phtfcaloaltrll* is heated in an atmosphere of , U.3. 2,182.763 * General Aniline * fhthalonltrile is heated with aodaml&o and dimethyl aniline in the presence of aliphatic alcohol. 0*S* 2,214,454 - I*GI* * An aUteli jhthalocyanine is treated with methyl aleqbP3. and then diluted with water to give a metal-free phthalooyanine superior to that from acid {mating* British 476,188 - I.G* - Fhthalonltrile is heated with phenols or naphthols. British 480,249 - I.G. * Fhthalonltrile is heated with a Grlgnard reagent and hydrolysed with sulfuric acid to give a metal-free phthalooyanine* 4. toes Many metal phthalocyanines other than copper are disclosed to a number of the patents listed above but the following patents are limited to certain other metal phthalocyanines. G.S* 2,058,944 - I.C*I* - Covers lead phfchaloeyanine. 7 0*3* 2,124,419 - I*C*I* - Covers iron, nickel or cobalt phthalooyanine prepared from phthalonltrlle* 0*3* 2,156,058 - IC*I* - Covers vanadyl phthalooyanine* 0*3* 2,192,704 - DuPont - Covers oo-mcld pasting of two cs* more phthalocyanines. U*S 2,225*502 * Interohemieal - Covers the formation of CFG sulfate by careful dilution of the sulfuric acid solution* tJ*S* 2,258*243 - DuPont - Covers a can stable blue paint con taining alumina hydrate end the barium lake of sulfonafced CPC* DUP050150229 16 tT*S* 2*233*273 - DuPont - Cowers the precipitation of any soluble dispersing agent prior to the addition of the oil In a pigment flushing operation. TJ,3, 2*276*178 - Allied Chemical & Dy ** Conners the treatment with a mild oxidising agent as HaOCI after aold pasting* TJ,S, 2,282,006 - DuPont - Covers the use of oatIon active agents plus volatile water immiscible organic liquids in making soft, dry pigaento including pl&h&looy&nine, TJ*5. 2,282,308 - DuPont - Covers the us of nitrogen bases to improve texture* U,S, 2*234,688 - DuPont - Is another patent on the isolation of CPC sulfate as a step In the aold pasting prooedurs* U-,S* 2,291*432 - DuPont <* Covers drowning CPC from solutions in aside in the preswnee of laurio aold and the like* C*s, 2*384*812 - DuPont * Covers turbulent How drowning of an aold pasted phthaloayanln. B.S* 2*539*787 * American Cyanamld * Covers dromlng sulfurle said solutions in water in the presence of an Inert water immiscible organic liquid not aulfonated* U*S, 2,365*464 * DuPont - Another patent on the Isolation of the crystalline CPC sulfate* U*s# 2*367,519 - Sherwin-Williams - Covers boiling the plgpent suspension resulting from the drowning of an aold pasted phfclmlocyanlne, British 454*338 * X#G# Covers drowning a sulfuric aold solution of a phfchalocyanine in the preseme of a dispersing agent and either in the presence of a substratum or under conditions which will simultaneously fom a oubstratua* British 466*042 * 1*0# - Covers broadly the mixing or milling of a phthalooyanine with dispersing agents in the presence of water* British 475,862 * 1*0* - Is similar to the preceding patent but applied to a metal-free phthalooyanine* British 502*623 - Honfceoatini - Fbthalecy&nlne pigments are converted to the sulfate with sulfuric acid below 90$ in strength and then hydrolysed with water, British 503*660 - 1*0# - CPC is treated with 78;4 sulfuric sold at 48*c. and then with water to give soft powder, British Application 5721 - 1944 - American Cyanasld - Halogen free phthalooyanine plpeents are acid pasted* exposed to a crystallising solvent* then salt-milled to the desired fineness and again exposed to the solvent, The product has 70% the strength of the acid pasted DUP050150230 17 material but no longer grows crystals la the solvent, Reference is mad# to two crystal forms of CPC, The crux of the invention seem to be an implication (without a dofinite statement) that. If crystals which haw been grawn in solvent are mechanically reduced la sise, no fwther growth la crystals will occur* So U*S, equivalent of this patent has appeared although it w^s filed id#r convention in aiglmd. 6* fflWJSj&B&ft, U.S. 2,167,514 * I.C,I, master batch* tbalocyanlnes in a rubber dispersed U.S* 2,168,376 - General Aniline - Vulcanised rubber colored with phfeh&locyanine colors, U.S* 2,192,705 - I*c,l, - Rubberised febric colored with CPC* tr,S, 2,517,371 - Inter^iataical - Use of phthalocyanlms In pigment printing using a liquid volatile pine tarpene to avoid crystal growth. U,S, 2*339,719 - 1*0,1*- Impregnating a fiber with a dlaso of an amino phfch&loayanln and developing v;ith a coupling component. U.S, 3,359,740 * - Ikgregaating a fiber with a dlaso of a poly-amino phthalocyanlne md decomposing to deposit Insoluble phthalo- cyanlne, - British 435,614 - I*c*l, - Use of phth&locyaninos in nitro cellulose coating compositions, U,3* 3,099,669 - General Aniline - Water insoluble metal salts of phthalooyanlne sulfonic acid. U,S* 2,099,390 - General Aniline - Lakes of the water insoluble salts of phthalocyanine sulfonic acid, U,s, 2,116,196 General Aniline - /Aoylated phthalooy&nina. U,S. 2,117,720 - General Aniline - Phthalonitrile is reacted with bensanthrone and aluminum chloride to give a vivid green dyestuff, U,3, 2,122,137 - General Aniline - Alkyloxy and aryloxy phthalooyaalne* U*S* 2,134,299 - General Aniline - Halogenated phthalooyanlnes react with organic hydroxy compounds to form an ether type derivative, U*S, 2,133,340 * General Aniline - Acyl casino phthalooyanlne. U.S, 2,135,653 - General Aniline - Dyeing textiles with phthalocyanine sulfonic acid* DUP050150231 18 U.S* 2,150,741 * I,CI, - A quaternary ammonium salt of a poly aulfnnafced natal phthalocyanine. U,S, 2,163,708 - DuPont - Phthaloeyanines are formed directly on the surface of a metal body to cover the same* U.S, 2,166,240 - I*C,I* - A eompownd similar to phthalocyanine but with a CH - group In*place of a * H - In the large ring, U,s 2,187,816 - General Aniline - Covers the reaction product of phthalocyanine sulfonic acid with organic basic Mmjpouads. U.S, 2,197,860 * General Aniline * Phthalooyaninee containing an oxazol, thlasol, or laldaaol group on the benzene rnifftti, 0*3# 2,213,517 - General Aniline - A CPC containing a phenyl group as a substituent on each of its four benzene nuclei* U.3, 2,215,580- I*C,I, - fhthalooyanlnes containing three oarboxy groups* U.S. 2,225,441 - General Aniline - Covers phthalocyanine con taining triehlor-methyl groups in the nuclei* U,3, 2,242,469 - General Aniline - Covers a phthalocyanine con taining both a phenyl group and a oarboxy group in each benzene nucleus* U*3* 2,266,404 - General Aniline - Covers a metal phthalocyanine with both a sulfonic acid group and a naphthylamino group in each benzene nucleus. U.S. 2,276,918 - General Aniline - Covers a metal phthalocyanine in which each benzene nucleus contains both a sulfonic acid group and an alfeoxy or aryloxy group* U.S* 2,277,688 - I*C*I, - Covers tetra-pyridyl phthalooyanlnes. U.S, 2,277,628 - I.C.I. - Covers quaternary salts of tetrapyridyl phthaloeyanines u,s, 2,277,689 - I*CI* - Covers pyridyl phthaloeyanines* U,S* 2,230,072 - I*C,I, - Covers tetra-amino-phthalocyaninea, U,3, 2,280,507 - General Aniline - Covers a sulfonated phthalo cyanine obtained by sulfonatlng a phthalocyanine containing a phenyl group on each benzene nucleus. U.S, 2,235,359 - General Aniline - Covers sulfonated phthalo oyanlnes obtained by synthesis from sulfonated phthalie acid* DUP050150232 - 19 - U.S. 2,286,679 - I.C.I. - Tetra-nitro-copper phthalooyanine, U.S, 2,288,478 - General Aniline ** Phthalocyanin sulfonic acids are treated with ehior-sulfonic aold. U.S, 2.290,906 - I.C.I. - Water soluble sulfonium derivatives of phthalocyanlnea U.S. 2,300,672 - General Aniline - Phthalocyanlnea contain ing up to four sulfonamide groups on the benzene nuclei* U.S, 2,342,663 - I.C.I. - Poly-sulfide dyes of the phfchalooyanine series. U.S* 2,342,663 - I.C.I. - A method of preparing copper phthalooyanlne containing disulfide groups. U.S* 2,349,089 - I.C.I. - Stabilized diazonium derivatives of phthalocyanine compounds. U.S, 2,349,090 - I.C.I. - Stabilized poly-dlazo phthalocyanlnea. U.S. 2 349,091 - I.C.I, - Stabilized poly-dlazo phthalocyanlnea, U.S, 2,351,118 - I.C.I, - Water soluble dyes are obtained by coupling dlazotlzed amino phthalocyanlnea with coupling c exponents con taining solubilising groups, U.S. 2.351,119 - I.C.I, - Poly-diazonlu phthalocyanlnea are coupled with pigment coupling components such as bota-naphthol or aoeto-aoet-anilide to give water insoluble dyes. British 480,152 - I.G# - Covers the preparation of pigments by the precipitation of water insoluble dyes on phthalooyanine pigments as substrate. British 471,418 - I.G. - Heterocyclic dyestuffs of the phthalocyanine series are made using dl-amlno maleic acid dinitrile as a starting ingredient. British 471,435 - I.G. - Halogen containing phthalocyanlnea may react with a primary or secondary amine to give products greener than the original. British 487,261 - I.G. - Phthalocyanlnea may be heated with trlohlor-aoetlc acid and the like to give a halogen containing alkali soluble phthalooymlna. British 490,744 - I.G, - Cyolio-ortho-dicbloro compounds ere heated with cuprous cyanide in the presence of an organic nitrogenous base. British 498,177 - I.G. - A phthalooyanine containing halogen is heated with a mercaptan. DUP050150233 * 20 British 492,194 - I.G. - Phthalonitril la floated with halides of polyvalent metals in the presence of bases such aa pyridine or quinoline* British 496,663 - I.G. - Phthalic &o id-4-sulfonamides are re acted with copper salts in the presence of area and with the usual catalysts, British 496,683 * I.G, - Fhthaloeyanlnea ere heated with aromatic compounds containing fas&ogen in a side chain to give new compounds. British 496,819 - I.G, - Diphenyl-3-4-dioarboxy1io acid con taining a further carboxy group is heated with urea and a metal salt to give a water soluble phthalooyanlne. British 514,857 - I.G. - PhthiSLocyanln sulfonic acids are treated with halogenatlng agents* The following two German patents are cited as Interesting dis closures In the general field without comparable disclosures In English. Goman 657,628 - X.G. - Discloses combinations of phthalooyanlnes with other water insoluble colors obtained by precipitating the second color on the phthalooyanlne. The disclosures include Hansa Yellow types, Red 2B, ad Chrome Yellow. German 696,592 - X.G. - Copper phthalooyanlne is heated with anthraquinone acid chloride to give vatable dyes. DUP050150234