Document dnmQ5gJ5XxdDk9eg4jX5Q6ERb

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Copy No. / T Y Y* i 4-. _ '-ii.iv-uxV CC? Period Covered: NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Final Report EVALUATION OF CPC/AUttttlTOW 8m0tft LAWS (0*8. PATENT 2,32T,4T2>, At PRXPASmOH OF CCHIBffiRPARTS. Jmxmrj 19 19*4 - lurch 14, 19<'. FILE. DATE. 223.4 4-4-#4 NJ863S N39989 8HERIAL HO. KH-44-22 Copy Ho. f Copy to* #1 - Numerical File 2 - Research Office (223*4) 3 - Library File (223*4) 4 - laperial Chemical Industries, Ltd* V *a Mi * f - Mr. C. H, Rupprecht, Wilmington (1C1 Fila) 8 - Dra. H. A. hubs, J. M. Tinker * 8. S. Roeeander, Jackson Lab., Wilmington m v^ rt IT Ta a Ih T HCTTARK PLANT PIGMENT COLOR RESEARCH REPORT Final Report Title* EVALUATION OF CFC/ALUMIHUM BSHZOATf UK* (U.8. PATENT 2,327,472), AWO FRFPARATTOW OF COTOTSRPARTS. Period Covered! January 1, 1744 - Heroh 14, 1744 SUBMITTED BY* 0. 1. Killian /AM DATS SUBMITTED* 3-23-44 N39989.01 DUP050150338 INISX I INTRODUCTION II PATENT SITUATION III SUMMARY AND CONCLUSIONS IT DISCUSSION OP EXPERIMENTAL RESULTS V EXPERIMENTAL DETAILS Pag!* i 1 2 3 i if DUP050150339 -1 arly la 1943* eeveral samples of a non-flocculating copper phthaloeysnine lake 4* by the Harmon Color Works, IasM wore obtained fro various sources in the trade, fhlo lako pigment was tooted and found to ho practically non-flocculating la lacquer and alkyd enamele, when extended with titanium dioxide white. The produet waa analysed by the analytical laboratory and found to eoaaiat essentially of 50t CPC and about $G$ aluminum benseato. With this infemotion, Brissolars and fteidinger prepared a aluminum bonsoato/BFO lako Aren "Bonaetral" Blue by precipitation of aluminum benseato la the prooeneo of tho CPC. The aluminum bonsoato was obtained by etriking a slurried mixture of CFO in a dilute solution of oodiun benseato with alum. The oenplo prepared in this way in the laboratory woo also shown to be non-flocculat ing in lacquer and alkyd enamele When tinted with titanium dioxide. A sample of the Harmon lako and our experimental match wore exposed in lacquer woroue controls made from BT-172-D plus alumina hydrate (series 6742). all tinted to tho same extent with titanium dioxide. After nix months exposure tho Herman preduet appeared superior to tho experimental match in ehalk reelstance but otherwise the three systems were equal. la addition to these evaluations, the Harmon produst was evaluated ia the Paint Laboratory under work request CD-5. (January 29. 1943. Notebook 607-192). A patent issued to tho Harmon Color Works severing this aluminum bonsoato/ CPC lako on August 24, 1943. aa tT.S. 2,327.472* nils patent is directed exclusively to the use of aluminum bonsoato to prevent the flocculation of CPC In coating films. Tho patent apoeifioo that the product mat be made by precipitation of tho aluminum bensoate ia the presence of a slurried CPC, or by a long grinding of CPC paste and aluminum bonsoato paste. Furthermore, the specification teaches that mechanical mixtures of CPC and aluminum benseato sure net equivalent to tho lake prepared by tho preferred procedure, and that leas than y&fL aluminum bensoate under any cir cumstances ia not aa affective aa 30f or mere aluminum bansoata in the product. The preferred proportions cover the range between 30^ and 7o of aluminum ben soate. There are no equivalents listed either in the spedfication or by inference in examples or claims la thie potent for aluminum bensoate. A careful examination ef the file history on thie patent indicates that no compound of on organic nature* other than aluminum bensoate was included in the original or amended specification, with the exception of barium and oalcium reoinate and alee aluminum silicate, all of which are cited as ineffective in preventing floeeulatlen ef CPC tenors* Evaluation of thie patent and a high spot eeeroti for equivalents to aluminum ben soate wae authorised under the CB-206 projeot late ia December of loot year. The work reported herein severs thie work and the study ef a faw aromatic organic acids as equivalents for aluminum bensoate to produce non-flecoulating CPC lakes. This work was done between January 1, 1944 and March 14, 1944. n. mm, masm B.6. Patent 2,327,472 (Tanas and Btalsar assignors to Harmon Color Works. Application date 1/3/41| 6/24/43).ia specifically directed toward the uee of aluminas benseato to prevent floeeulatlen ef copper phthslecyanine toner, and a preparation of aa aluminum bensoate/CPC lake which is non-floooulatlng in paint aystems. Ho equivalents are claimed or suggested. Since it eewmed un likely that bsnsoie aeid would be the only aromatic organic acid capable ef pre- DUP050150340 jf 2 ducing inpyuveitratc in flocculation of CPC in point systems, other aromatic carboxylic colds wore studied in similar lakes* is discussed in the folios* ing ooetions of this report, aluaimBB ortho-ohlor-bensoie sold has been found to bo practically equivalent to bensolo acid in preventing floeevn ation of CPC when the corresponding aluminum salt is prepared la the presence of the CPC. Alee, aluminum para-icepropyl benseata gives a CPC lake of the improved floccula tion but inferior in lacquer system either te the lake made from ortho-chlorbenzoio acid or benseie add* On the other hand, different simple substituted bensolo acids such as anthranllic acid, sulfsnilie acid, salicylic acid, end orthe-banscyl bsnsslc acid when used to prepare the corresponding aluminum salt lake cf CP fall ts give ray appreciable improvement la resistance to floccula tion of the CPC lake when extended with TiOg in lacquer er alkyd. Alee naphthoic acid and phthellc acid ware ineffective in preventing floeculation when preci pitated as the aluminum salt with CPC toner. The aluminum ortbo-chlor-bencoote/ CPC lake is considered as an equivalent to the aluminum benseate/lPC lake of the Harmon patent, but thla equivalent does not appear to bo general in character since all substituted benxoio aside do not behave in the some way to prevent the floeculation of CPC, rad in foot only ortho-eblor-ben *oic sold is of much use for this purpose among the various candidates assmlnsd te date* Per this reason the argument can be advanced that the aluminum ortho-chlor-ben so*te lake of CPC is net an obvious equivalent of the Harmon patent and therefore might be claimed as an independent discovery. Since ortho-chlor-bensoic acid is not covered by the Harmon patent, it appears tint wa are fret to manufacture the ortho-chlorben*oate/CPC lakes. in. MmjLMmm 1. The results of this work substantiates the claim of the Harmon patent. A $0% CPC/5<# aluminum hsasoate lake ia practically non-flocoulating when extended with titanium dioxide in lacquer where extanaion has net been carried toe for, and ia aoa-floeeuleting even at high TiOg extensions in alkyd enamels. This product is important and vary interacting In that it ie the first aeu-Jloeeulating copper phthaleeyanine product appearing on the market, rad ie vastly superior ts ray standard CPC toner in this respect. 2* A high spot search far equivalents ts this product net covered by the Harmon patent haa been made. Benaoatea of other metals than aluminum are net affective in preventing the flocculation of CPC, and the improvement appears te be specific te aluminum salts. Aluminum ortho-chior-ben*cate appears practically equal to aluminum benzoate in inhibiting the flooculatlen of CPC but the latter lake is still somewhat superior ia this respect in lacquer. Both lakes appear non-flocculating in alkyd enamels. A number of other organic aromatic aside have bam investigated and found of little, if any, value to provent flocculation of CPC. However, p-iaopropyl ben sole acid gives an aluminum salt lake of CPC which is non-flocculating in alkyd enamels but only slightly i*q>roved in this reapset in lacquers* 3* Me effort was made to determine whether er not the aluminum benseata CPC lake is a desirable addition to the Newark line. However, this' lake does not appear as Important now as it did before tbie evaluation etudy. Ortho-ohlor-bsBsele acid is cue material which Is capable of producing DUP050150341 >3 results practically se seed ss teasale add for tills us, sad It Is likely that / mere thorough investigation any uncover other leads of equal merit. Also, the ' f' Barmen product is not as flexible ia use as the eealeaeed phthalocyanine pigments, specifically Figment BX-CR, 4. The alusdaum tenzeata CPC lake is not as good in its resistance to flocculation ia lacquer as Pigment BX-CR. The teasoate lake when reduced 50* with titanium oxide la lacquer shows a very slight flocculation as judged by pour-out teste, whereas Pigment BX-CR fortified with CPC toner to the same color content is free of flocculation. Extension of the ben scate lake with T108 further than 5<$ redaction shows inersasing flocculation as the amount of TiOg increases) Pigment BX-CR shews no floeculstloa even at 1*100 dilutions with TiOg. The teasoate lake exhibits some tendency to inhibit the flocculation of CPC tenor ia the presence of TiOg ia lacquer, but hero again Pigment BX-CR is more effective in this respect, i.e. Pigment SX-CR will prevent the flocculation of definitely greater amounts of CPC toner than will the benzoate lake. The benzoate lake when tinted with TiO* in lacquer separates on shelf storage but not as badly as a mechanically mixed tint made from straight toner and TiO*: Pigment BX-CR in lacquer is non-separating after a year and one-half shelf storage. The benzoate lake has been reported to grow crystals in xylene which fact would indicate that it would not be can stable and would show color drift on storage. This is being cheeked at present. The eealeaeed phthalocyanine pigments are can stable. 5. It appears that the aluminum benzoate or ether organic acid aluminum lakes of GPf made from tenor paste are lose attractive economically then coalesced pigments. IV pigsyjgjoog j Mt-mma The work reported herein oan bs divided into two parts, namely, evaluation of the Harmon patent tf.S* 2,327,4?2 and a eaaroh for equivalent# to aluminum benzoate which are effective in preventing the flocculation of CPC. CPC lakes containing 50% aluminum benzoate wore made in the laboratory from both Reliogen Blue BV and "Monastral" Past Blue BK pastes. The process of example 1 of subject patent was duplicated and modified preoeduree were alee-employed in the preparation of the benzoate lakes. The effeet of colloid milling the CPC paste both with and without the sodium tenzqste heforw precipitation of the aluminum aalte was also studied. The tensedte lake was also prepared by reverse strike procedure from that of the patent example, i.e., addition of tedium benzoate to the CPC slurry containing dissolved slam. All of the teasoate lakes wore essentially equal to each other in their resistance to fUesuletien hut there was s slight variation ia this respect shown by the various products when ex tended with TiO| in laequwr. Xn slkyd enamels all ef the experimental! benzoate lakes appeared equal to each ether. Mechanical mixtures containing various proportions .of. CPC toner ,RT-172-D, and aluminum benzoate were extended by grinding in lacquer with titanium dioxide. Bone of the systems showed any improvement . in flocculation- from that obtained with regular toner CPC extended wijth titanium dioxide. Also, CPC toner paste was mixed in slurry form with a slurry'' of aluminum benzoate and the resultant product waa no tetter in flocculation than CPC toner without the added benzoate. These results substantiate disclosures in tho Barmen patent. Crude CPC waa aalt millad DUP050150342 4- with aluminum benzoate for 48 hour* and tho resultant lake was imieh bettor la Ito roolotaaoo to floeoulatioa than otaadard CPC toner hut was not quite equal to the aluminum benzoate lake made by precipitation metbode* Other metale were investigated la place ef aluminum fer preparation of metallic heaaeate CPC lakes. Lakes eeataialag $0 CPC were made with copper'' benzoate, zinc heaaeate, titanium benzoate, chromium benzoate, etenaeue benzoate, and lead benzoate. Hone ef theee lakes were ef much interest ae non-flocculating CPC pigments, and shew ae worth while Improvement in resistance to flocculation over the regular toner pigments. Titanium dioxide was ooated with aluminum bqpfejlte and thia extended TiOg was used to tint CPC toaare la laeqoer. The resultant lacquer system* were' not equal in their realstance to flocculation to the beagoete CPC lake when tinted to the same depth with TiOg. The above results agree with the elelme made in the Harmon patent. Zt appears necessary to precipitate aluminum benzoate in the proemoe of CPC toner to produce a non-flocculating lake. Example 4 of the patent describee the preparation of a non-flocculating aluminum benzoate CPC lake by ball milling a mixture of CPC and aluminum benzoate in the presence of water. This example has not been checked. A number ef ether organ!o aromatic acids have been evaluated ae their aluminum salts versus the aluminum benzoate lake to determine whether any of theee products are equal te the benzoate lakes in resistance to flooeulation. The following aside have hews studiedt Ortho-ohlor-benzoic sold, pars isopropyl benzoic acid, salicylic sold, anthreallio sold, eulfanille acid, ortho-benzoyl benzoic acid, phthalic acid, beta-oxy-aaphthoio acid, and alpha and beta naphtheia acids. Alae aluminum sill eats and aluminum hydrate were evaluated for their offset on the flocculation of CPC. The foregoing aside were added ae their sodium salts te a slurry ef CPC toner in amounts sufficient te give a 50* aluminum salt lake when struck with alum in the appropriate amounts. Theee lakes were ground as 50f> extensions with TiOg in lacquer and compared te the Herman preduet as well as laboratory samples ef aluminum benseats lakes. A lake made from ertho-ehler benseie add ia equal te the hen sole lake in its resistance te floeoulatioa in lacquer. The para isopropyl beaseate lake is better than s meohanleal mixture ef toner and TiOg but in markedly inferior te the benceete lake in lacquer. However, both these lakes appear equal te the benseete lake in reelstanes te fleeenlation ia TiOg tinted alkyd enamels. Hone ef the ether acids shew any significant improvement in their reelstanes te flocculation in lacquer or alkyd systems ever toner eeatrele. The above listed organic aside were alee used te prepare the corres ponding aluminum salt lakes ef TiOg, The seated titanium dioxides were net very effective in preventing the flocculation of CPC when tints were wade in lacquer. Mechanical mixtures ef CPC toner and aluminum ealleylate extended with TiOa in lacquer show no improvement in flooeulation over toner controls. Alee, a salt milled lake made from crude CPC and aluminum salicylate is un improved in its reelstance te flooeulation. Ono interesting observation wee made in the course of this work that the aluminum salt of beta-oxy-naphthde acid la a relatively bright greenish yellow. The lakes containing the aluminum onIt ef BOH and CPC are green. DUP050150343 Several laboratory preparations if tk aluminum ortho-eblor bensoat* itkM war# made. Theas n^irinattl product* nrli In thdr niiitinM to flocculation depending open the method need la preparing then. Tbue a lake sail by precipitation of tha ortho-eblor bonieato celt In the presence of regular "Venaetral* Bine $* panto ana praotleally equal in lie reeletanee to fleeeulatlea In lacquer to the Hansen benseate lake* However, a lake node by e similar preeeea except using CPC poet* previously eelleid milled wee lets reftietaat to flocculation tboa tbo former lake. These raenlta indicate that physical oonditiene ef manufacture ef these benseate lakes or the ertbe-ehler benseate lakes ere likely te influence the nature ef the products obtained. He thorough study hee been made of thie aspect of the problem However, it appears likely that the alusinuB ertho-Shler benseate lake e*a be prepared te equal the aluminum bestmtt lake is its rssistssss te flocculation in laeouer end nikyd enamels* It ia interesting te compere the prepertlee ef the Hsrmen produet against these ef our experimental aea-fleeettlatlag CPC pigment, Pigment iJE-CR. liter one and. one-half yeses shelf storage ef a lacquer pigmented with Pigment BX-CR no visible ssparatlea has occurred in the leequer systems end the stored leequer is just as uniform ae after grinding. A sample ef the Karmen lake ex* tendfd te the esae extent with WO# in leequer shorn considerable separation ef TJOa from the colored pigment shortly after grinding. The Karmen lake is superior in this respect, however, to meehenieelly mixed CRC toner end ?iOs ia laequdr. Technical laboratory has reported that the Barmen lake grows crystals in xylene. This fact would lead one to euapeet that the Karmen preduet would not bo can stable is paint on shelf storage. Thie property is being tested at present with the Barmen Idea tat results ere net yet available. The coalesced phtheloeyaaine plgnewte are can stable. The Karmen product ox* tended with TiO# in leequer Shove a wary slight flocculation by pour-out toato where*e Pigment BX-CR fortified with CPC to the same solar content Shove as flocculation at all. Farther eatencion of the Karmen lake with TiOg pro duces increasingly greater floseuletiea. Pigment BX-CR tea be extended te 1 te lOO.TiOa without any flocculation being evident by the pear*ewt test. A laeeuer system pigmented with fOf ef the Karmen benseate lake, ll.ff ST-172-0 end 3T.5* TlOg shewn e noticeable flecouletion by peur-eut teste whereee e similar eystem pigmented with 50? Pigment tt-GB eta tha ether components the eases la non* flocculating. This result indicates that tha Karmen product la not as good ae Pigment BX-CR in inhibiting the flocculation ef CPC tener when extended with TiOft ia leequer. The nlumiaum bensoate lake it non-floeouleting wben ex tended with TiOa even te relatively weak atade* in alkyd enamels, sad in thin respect ie equal te Pigment BX-CR. The Barmen aluminum benseate CPC lake ie #n important end interesting produet beeauee it ! the first sample af a aea-fleeeulsiiag CPC pigment which baa appeared ia the trade, la those applications ef CPC where flocculation Se a serious problem the Harmon preduet undoubtedly would be e mere desirable material te use than regular CPC tetters or lakes. However, ortho-ohler benaoie sold baa given lakes ef similar properties and thie said In net severed by the Barmen patent. Tbeee facte as well ae the development ef experimental coalesced phthalocyaninesappear te lessee the inpertanee ef Karmen's aluminum benseate lake. It appears that any ef the nluadnam celt lskea ef CPC made from regular toner pastas ere net likely te he ne eeenenieelly attractive ae the coalesced phtheloeyaaine plgKOnts. DUP050150344 v. Preparation of Aluminum Benzoate CPC lakes Notebook 1045-41, 42, 1085-19, 23, 26 WaiMitm .tf .ttf AWnmcJfeia>2a4t Ufcta In Lacquer an*. Altar* Laequer - 1045-3T, 1085-6, 1027-25, 1027-28 (Fxposure Series 6?42) Alkyd Snanele - 1001220, (Pxpoaure Seriea 6826, fteityl 807-1) 1085-3 Organic Aolde other than twaeic (Sea above evaluation teata for the benzoate lakes for grind of theee products in laoquer and alkyd). Ortbe-ohlor Benaoic Sold 1085-4, 1085-19, 1085-25 EWfrjMMflttrii. Bgpjfflg, *?** 1085-22 MfltataJUiMi 1085-4, 1085-19 1085-4, 1085-19 Mmml MmiataMlta 1085-19 m 1085-4 1045-46 1045-46 1085-4 Mm .Hy4yftl-,Mgg 1085-4 DUP050150345 7 MTSCBLLAfflgQCB WHUfflCi Salt Billed CPC aad Aluminum Benatoate 1045-47 1045-47 Preparation of Alamiomteagoate and ftlwalnwa Jall wrlAie 1045-34 TIPs floated mitfe-mrloiie AiuginmOrganlg AeM HIU 1085-12 Metalllo 8nioatfl tafeec other than Aluminum 1085-24 DUP050150346