Document 85rvRNDzM1JbROB5v858NO60e

E, I. DU PONT DE NEMOURS 6- COMPANY PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Serial No. k k -53-15 Copy No. X Numerical File Period Covered NEWARK PLANT CHEMICAL DIVISION - COLORS Flmd Report FLOCCULATION RESISTANT PEHJALQCYANINBS PATENT EVALUATIONS 1951 - APRIL, 1953* FILE: DATE: 223.4 August 3* 1953 NJ 9747 Copy to* 1 - NUmetleal File 2 * Research Office (151) *- * (223V) 4- * Library File (151) 5 - tM " (223 A) 6 - #1*+ Building File 7 - B. F# Klenke, Jr,, Newport o - J, N. Tully/A* Siegel 9 - J. H. Cooper 10 * M. A. Perkins - Jackson Lab. 11 W. J. Clem - Chambers Wo j 12 - Extra 13 - Extra SERIAL NO, KN-53-15 Copy No. 1 NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Final Report FLOCCULATION RESISTANT PHTHALOCYANINES PATENT EVALUATIONS FEB* 1951 - APRIL* 1953. CHARGE! A-IC-20 1 BATE SUBMITTED: July 6, 1953 BATE ISSUED* August 1953 DUP050069364 The following three patents have been given some evaluation in the laboratory and a United amount of exploratory work vas done along lines suggested by these patentsi TJ.S. 2,524,672 * Lecher et al - American Gyanaaide U.S. 2,526,3^5 * Giambalvo - Interchemical B.S. 2,540,775 - Bronillard & Giambalvo - American Cyanamide PM, msmmssmi Two processes described in IJ.S. 2,524,672 and in TJ.S. 2,540,775 have not given results of any economic value with respect to floccula tion resistant phthaloeyanines. On the other hand, TJ.S. 2,526,345 which covers the use of copper phibalocyanine moaosulfooic in mixtures with copper phthalocyanlne has given substantially flocculation-free products* Subsequently, a program of research was undertaken which culminated in the release of two colors on June 1, 1953 (BP-366-D and BT-373-D) These are offered to the trade as flocculation resistant products* This work will be reported elsewhere* Such products are believed to come within the broad claims of TJ.S, 2,526,345, and DuPont now has a license to use this patent* This experimental work at Newark has also led to the prepara tion of three patent proposals of our own which are being considered by the Legal Department for filing* BfisaaiMa&tu AL DETAILSi m cyanine pigs:men *hows a process for preparing salts of phthalo- SUS] sg them in a liquid and then adding a strong acid soluble in the suspending liquid* Example 1 was evaluated in __ 1, 1424-49 by suspending CPC-LB and cl-free CPC crudes in nitrobenzene and adding xylene sulfonic add* There appeared to be complete salt formation. After 2 hours stirring, the salt was hydrolyzed with ethyl alcohol and the pigment filtered and washed with alcohol. It was finally steam distilled to remove residual nitrobenzene. The CPC-LB was about 20$ weak vs BT-304-D and the Cl- free CPC was much weaker and had the appearance of a completely crystalline product. Flocculation tests were not run, but the pro cess has little possibilityof eeonomie interest. A more practical example would have been the combination of sulfuric acid with nitro benzene, and such products might be worthy of study at a later date* u.s. 2.526*345 shows mixtures of CPC monosulfonic add and CPC to give non-flocculating compositions. The preparation of epe monosulfonic acid, after the disclosure of this patent, was done in e x p * 1393-32. though the heating cycle vas not followed exactly. Sulftcp analysls of the resulting product indicated that it contained only about 30$ CPC monosulfonic add. It was a weak, dull and greenish product by both rubout ad enamel tests* However, mixtures containing 10$ of this product and 90$ BT-3C4-D gave enamels which were quite free of flocculation and appeared strong and intense vs BT-304-D. The interesting properties of this mixture resulted in DUP050069365 an extensive line of research which has lei to the development of a mm product comprising a co-syntheslsed mixture of CPC-IB and CPC-^-aonoeiilfonic add* This has been released as a roainated lake, BP-366-D. this patent shoes the preparation of CFC-monosulfonlc add Igr direct sdfnation, hat it can also he hr synthesis from a m.ixture of p. htna. lic. anh_yd. ride and * thallc acid, this roate has been exploded by Orchea and a as contemplated hr Giambalvo has also been developed both he and by the Pigments Department. <FI-373-D). the question of the validity of U*S* 2,526,34-5 was dM with the Legal Department, particularly in dew of D*S* 2,285,359 which discloses the use of ^sulfophthalic add In mixtures vlth phtbalic anhydride to gi** asymmetric compounds containing 1. 2 r 3 sulfonic add groups oar phthalocyanine molecule. the final condo* sion was that US* 2,526,35-5 mast be considered valid* Accordingly, a license agreement has mm concluded with Interchedcal for use or this patent* Incidentally, B.S. 2 Is indict in an '9 is owned by General Aniline -free license exchange. D*8> Z+fto'lffi. was evaluated in Exo* 1393*27. Essentially, this patent contemplates atlrring a water slurry of CPC with a solvent such as carbon tetrachloride or toluene for several hours, followed by removal of the solvent by steam distillation to obtain a product which has high resistance to flocculation* The products treated were <1) add pasted chlorine-free CPC, (2) sdt silled chlorine-free CPC, and (3) solvent milled CPC-LB. By rubouts, the chlorine-free products were both wed against their controls, whereas the CPC-LB was unchanged* In alkyd enamels none of the products were free from flocculation* However, the CPC-LB was definitely improved and also appeared strong and intense vs its untreated control. The add pasted CPC flocculated badly both before and after treatment, although the treatment seemed to give a slight improvement in strength. The salt milled Blue B also was Improved slightly la strength* and there was very little flocculation either before or after treatment. As a means of obtaining flocculation resistant CPC, this process does not appear attractive either from the economic operating points of dew* Sowever, this patent Is qv* its Claims as to treatment of phthalocyanine pigments with and needs further review .as to Its relation to more recent on direct pigmentary products* ! :. r. / i DUP050069366 3 file evaluation of these patents alee led to Visited studies on other methods of preparing flocculation resistant phthaleeyanii in 1101-68 CPC polysulfonic .add ("Pontaadne* Past ftmjnoise fe) mSmwm, eater slurry of CFC-LB and predpitated with a substantially non-noctniiatiag CPC toner. This was It to include precipitation with aluminum sulfate instead of was coded b t -3^5-1). Por a combination of policy and .m Tjroduct has. not bens released for .sale* In a similar Banner, separately prepared Ideas of CPC-PtOy- sulfonic acid were tested in mixtures with CPC-LB in alkyl enamels for flocccdation -resistance,' bat nothing of interest cane of these tests. On the other hand, too CPC sulfonamides preparol at Jackson Laboratory, ears tested in mixtures with CPC-LB, and one of then gave a definite improvement in flocculation. Although -the other one shoved no improvement. it was so impure that no conclusion as to its usefulness should be drawn Other work not included in this report has also demonstrated that a co-synthcslaed mixture of CPC-LB and a CPC containing free carboxy groups (perhaps they are actually amide groups, - C0!%) is also resistant to flocculation* In view of these interesting results and the state of tie art as described in RLH-52-^-, three patent applications have been proposed and are in the hands of the Legal Department for filing* 1. the mixtures obtained by precipitating a metal salt of CPC PolysQlfonic add on CPC. 2* The preparation of mixtures of CPC mad CPC aonosulfonic add. not exceeding about 15* of the latter, by coayntheais from mixtures of phthalie anhydride and b-eUlfb p&thalic add* 3* A broad case covering the use of other polar promote !t -P(0H>2 mad their derive 'eslstamo . The above work is recorded in notebooks 1353 and 1424. DUP050069367