Document XBLRJy6z3eNXBezZZzRXbVyx

f v' |- r* I} E. i. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK. NEW JERSEY Serial No. KN-48-9 Copy No. 1 Nuaerical File NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Final Report SEMI-WORKS DEVELOPMENT AND PLAIT DEVELOPMENT AND STANDARDIZATION OF DIRECT LAYING PROCESS FOR RE-526-D. Poriod Covorod: FEBRUARY, 1945 - APRIL, 1948 FILE: DATE-. 222o21 10/6/48 N42158 Njeere Copy to* 1 - Numerical File 2 - aetearcH Office (222.21) 3 - Library File (222.21) 4 * #10 BmilCing File 5 - f. Chalupski, Plant Files 6 - W. F. Spongeman, Newark ? - Extra. Serial No. XN-48-9 Copy Ho. 1 mmm p l a n t PIGMENT COLOB RESEARCH REPORT Final Report SEMI-WORKS DEVELOPMENT AND PLANT DEVELOPMENT AND STANDARDTHATION OF DIRECT LAKING PROCESS FOR RE-526-D. FEBRUARY, 1945 * APRIL, 1948. CHARGEi 1100-12-31 (AIC-31) SUBMITTED BX* E. J. HESS a p p r o v e d m* j . o. DATE SUBMITTED* 6-7-48 b a t s is s u e d * /&/6/-%' DUP050066961 IHTROaqCflOKi The plant development of the direct laklng procedure for RE-526-D (extension of a dark masstone RT-443-D type toner (23^5) on Barytes) was started In February, 1945, A short laboratory study had hssn completed (See KN-44-49) and this, together with available semi-works and plant Information on the direct Inking procedures for RT-443-D (see XR-48-8), was used In selecting the starting formula. As Is evident from the following discussion, the plant development study proved to be unusually complicated. As In the case of h t -443-D, the following factors were important in the filial solution of the problem* 1. Use of Tobias Acid as an "accessory" intermediate, 2, Control of coupling and development pH. 3 Use of U Gum rosin. 4, Substitution of lithographic varnish (varnish dryer) for bodied linseed oil (H-108 vehicle) as the testing vehicle. A standard process for direct laklng "Duol" Carmine bake, RS-526~D(B), was issued in April, 1948, The RE-526-D standard, lot @4614, based on this process was set up in March, 1948* The Production Division accepted supervision of the direct laklng process for ftE-526-B manufacture in April, 1940. wm&immmjL There is no patent restriction In the manufacture of direct laklng "Duol" Carmine bake (HE-526-D). It is not believed that this study has resulted in any patentable developments. As the K-2039 toner formula (modified K-1994 using a resinous oil treatment) had already supplanted K-1994, thia"allliaeH formula was used in the first plant batch. The original laboratory pro cedure for the extended product, K-2013, was based on K-1994, The first batch ground out slightly light and dull in mas stone, close in strength, and slightly yellow and clean in tint varans the "isolated dye" HE-526-D standard, lot 4290. A second batch made in June, 1945, using crude PTMSA instead of the purified type ("bithosol" Acid DBA) was darker and duller in masstone and slightly bluer in tint than standard. DUP050066962 -2- Both of these batohes were vat washed* this say account for the low yields obtained <grind yields averaged about 5 of goal)* Meanwhile, because of its low selling price, RR-526-D was showing a paper loss of about 10* In order to correct this the Sales Division recommended that the toner content of this color be out to 20.8# from 23,1#* On the basis of this, a direct laking RE-526-D standard formula, K-2268, was written to replace the * isolated dye** procedure, K-1891. She K-2268 process was based on the R3M43-B toner formula, K-2237, and differed fron the original RE-526-D laboratory procedure, K-20131 as follows % 1* the batch size was increased to 1,47 mols from 1 mol* 2* Caustic soda was substituted for slaked lima as the alkaline solvent for the PflfBA, the resulting calcium deficiency was adjusted by adding calcium chloride to the BOB slurry* 3* Crude PtUSA was substituted for the purified material, "Lithosol" and RBA. 4. the alkaline PTMSA solution was treated with Filtercel and activated carbon black and clarified prior to dlasotlzatlon* 5. the diazo volume was increased by about 33#* 6. the normal coupling and development pH was incrsased to 10.0-10*4 Instead of 8.3-8.8. 7. Coupling was accomplished at 95F instead of 104F. 8* About 33#/mol of Resinous oil K-i, emulsified with sodiuia roslnate, was added to the color slurry before heat development. Production on the K-2268 formula was started in July, 1946* two light masstone, 20# weak tint batches were made* After dis cussing these results with Sales it was decided to return to the original 23.1# toner content for this color* this necessitated a decrease of 13# in the amount of barytes .extender used* DUP050066963 3 Manufacture was continued on the modified *2268 procedure. Fifteen batches were made during the period August. 1946 to June, 1947* Almost all of this production was light in masstons versus the misolated dps** standard, lot 4290. by the standard testing method, TF-95*12((a bodied linseed oil (1*103 vehicle) rubout)). She use of the H-108 vehicle was principally responsible for the light masstone and presented a problem similar to that experienced with the standardisation of the direct laking process for RT-443-D (see KR-48*8). However, the solution of ths RI-443-D problem (January, 194?) by the anbsti* tut ion of the varnish dryer Vehicle for H-108 was not ths answsr in ths case of HI-526-D as the standard tasting method for ths extended pigment was supplied by ths prineIpalcustomer, SloanBlabon, and could not be revised without further study. luring this period a number of variables were tried in an attempt to improve masstone and strength control* The variables tried and the results obtained follow! 1. In line with experience on the HT-443-1 toner, Tobias Acid was used as an accessory diaso Intermediate in RE-526-D to obtain dark masstone. About six pounds per 1.47 mol batch gave the maximum acceptable increase in blueness of tint but masstone remained light in the H-108 vehicle. In varnish dryer, results were fairly close to the desired depth. RB-526-D masstone standardisation is complicated by the fact that the original standard, lot 4290, was sst up out of line dark in masstone in order to meet customer requirements. 2. Close control of coupling and development pH was found to be necessary for optimum depth of masstone and strength and yellowness of tint. Fairly satisfactory strength was obtained by adjusting ths PTMSA-Tobias Acid solution pH to 10.0-10.5 (before diazotization) and the BON-lime slurry to a pH of 10.3-10.7. This gave a coupling pi in the range of 7.0*9.0 which on adjusting to a pH of 9*8*10.4 before heat developmant gave fairly satisfactory toner strength. However, masstones by H-108 subout were still on ths light side of standard and varnish dryer rubout* wars inconsistent* 3* Doubling the standard amount of Resinous oil <99# instead of 49#) gave a definitely weaker and somewhat lighter and bluar product. Decreasing the resinous oil to25 pounds hud little, if any, tinctorial offact* 4. Addition of the calcium chloride precipitant to ths diaso in tba manner of ths RT-443-D toner formula, -2489# gave improved quality control and was used in most of this production* DU P050066964 5* Early in tha work it was discovarad that the theoretical amount of extender <2950# or 76.95 based on a toner goal yield of 896#) was giving strength results in the order of 10-155 weaker than standard* Decreasing the extender *0 2500 sounds lave products about 5-105 stronger than standard* Subsequently, a goal Sleld re-cheok: indicated that the standard extender amount should s 2745 pounds (76.95 based on a toner yield of 834#). t/T A short semi-works study run during September-Oetober, 1946, in an attempt to develop a dark messtone variable was the basis for the introduction of Tobias Acid as an "accessory* intermediate. Tobias Acid substituted for PTMSA to the extent of 3 mol 5 gave a product close in depth and blue in tint versus tbs 18-526-0 standard, lot 4290* The use of PT0SA and OTESA as a replacement for the Tobias Acid in the same molar amount gave lighter, weaker and yellower products. The information which indicated the desirability of adding the calcium chloride to the diaso instead of to the BOH-lime slurry was also developed in the semi-works at this time* Almost from the start of the plant development work com plaints were received from the Control Division that the oil absorption seemed to be definitely lower than the standard. One of the customers (Armstrong), by specification, permits only a 55 variation from standard in this characteristic for normal ship ments. Examination of a number of batches during March-Apr11, 194? Indicated a range of oil absorption variation from 75 bo 295 on the low side. Oil absorption measurements of the toner components of these batches varied from 955 on the low side to 1075 on the high side of thewiaolated dye" RT-443-D toner standard, lot 32268, The direct laking process, therefore, does not seem to be responsible for the low Oil absorption. Subsequently, it was discovered that the barytes extender in use at the time showed a definitely lower oil absorption than the standard barytes sample* Datar shipments of barytes appeared to be more normal and no difficulty was reported. When poor quality performance on the RT-443-D toner made it desirable to return to the "all-lime* formula (K-2039 type) the HE-526-D toner process was changed accordingly. Plant production of BE-526-D based on the "all-lime* formula was started in July, 1947. Twenty-six batches were made during the period July, 1947 to April, 1948, Toner quality performance(by varnish dryer rubout) showed a definite improvement but H-108 results on the extended material were still on the light side of standard* DUP050066965 During tbit period (September, 1947) e second seal-works study was made using the "all-lime* formula as a basic procedure in an attempt to develop a variable to give dark masstone with the B-108 vehicle. Although all of the semi-works manufacture was darker and stronger than comparative plant production, no definite improvement was obtained bjr - 1. Separata diazotization and coupling of the Tobias Acid. 2. Separate diaaotization and coupling of PfOSA substituted for the Tobias Acid (this gave light masstone). 3* A 30$ increase in coupling volume. Plant variables and the results obtained using the K-2039 type (all-lime) toner formula follows* 1. Variation In Tobias Acid in the rang# of 4 to 6 pounds gave light masstones and blue tints versus standard in tha H-108 vehicle. In varnish dryer, %7 pounds of Tobias Acid gave a fairly close match to the desired depth of masstone and hue of tint. 2. Results indicated that better quality control was established (better pH control) if the Tobias Acid was added to the PTMSA-lima solution after clarification. Two pH adjustments of the PTBSSA solution prior to diasotlsatlon are used under these conditions* Recommended for the initial adjustment before clari fication is a pH of 9*0-9.5 and for the final adjustment after the addition of the Tobias Acid a pH of 9*5-10.5* 3. As described in the RT-443-D report (KH-48-8) rapid pro cessing of the PTBISA-line solution in the semi-works gavo Improved depth and strength. Although no marked improvement resulted In the plant the change was retained as potentially establishing a more controllable process. However, results Indicate that where PTIBA quality permits elimination of the clarifieation step a definite increase in masstone depth is obtained. 4. Separate diazotization and coupling of the Tobiae Acid showed no adventego in tho plant (checking semi-works results). 5* Substitution of M Gum for K Wood rosin gave a definite increase in depth of masstone with little or no change in tint. 6. Use of the 83# goal yield for the toner gave satis factory RE-526-D strength at the 23.1$ toner level. Tha standard extender amount for the 1.47 mol batch is 2745 pounds. 6 Failure to develop a variable that would giva tha desired dapth of masstone in tha 8-10$ (bodied linseed oil) vehicle made it necessary to consider the possibility of using varnish dryer standardisation* After a number of tests ware made using HE-J26-D alone and in combination with TE-421-D (Molybdate Orange) Sales finally decided to permit standardisation of the direct laking material using "varnish dryer* to replace the 1-108 vehicle* A blend of five batches (made during the period October . to December. 1947) lot 84614f was proposed as the first direct laking standard for RS-526-D and was set up in March, 1948* Comparisons of tha new versus the old standard follows* Famish dryer rubout (TF-132-11) Lot 84614 vs lot 4290* vs dark-trace blue-OX-blue B-108 rubout (Sloan-Blsbon rubout) (TF-95-12) Lot 84614 vs l|t 4290* light-ws strong-blue Oil Absorption* Lot 84614* l52j*$ Lot 4290* 16.0# Linoleum Composition* Lot 84614 vs lot 4290* ws blue, vs intense-5$ weakvs blue. A formula based on the process used for the standardisation material was issued in April, 194$, as standard H-$26-D(l). The *B* formula differs from the "A* process (formerly designated X-2268) as follows* 1. Hydrated lime is substituted for oaustlo soda for dissolving the PTMSA* The calcium chloride added to the BOH slurry in the *A* formula is omitted* 2. Approximately 1*5 mol# of Tobias Acid Is slbstituted for FTHSA in the diaso to obtain the desired mas stone depth* A bluer tint also results. The Tobias Acid Is added after the PTHSA solution clarification* 3* The PTMSA solution pH before clarification is maintained at pH 9.0-9.5 to decrease the "salting out* effect noted at higher alkali concentration* 4* As the addition of the Tobias Acid lowers the pH in varying amounts, the PTUBA-Tobias Acid solution Is adjusted after clarification to a pH of 9.5-10.5 to maintain control of coupling* 5* The over-all stirring time of the PTHBA solution before . diazotizatlon is held to a maximum of 2-1/2 hours for bettor quality control* DUP050066967 6. The dlazo volume is out by approximately 255* 7. M Gum rosin is substituted for K-wood rosin. 8. She Resinous Oil X-l amount is cot by approximately 505- 9. She Barytes extender amount is cut by 185 to return to the original standard toner content. Following; is a tabulation of the plant yiald performanca and the approximate savings possible with eaeh direct laking process compared with the *isolated dye" formula, K-1891* Humber of 5 of Ooal Yield Approximate Mill Cost ("A" 42|?f per 1.47 mol) Savings psr 100# SSS8SA> RB-526-DCB) 2 20 93*75 98.05 #3.50 0.50 The Production Division accepted supervision of the direct leking process for RE-526-D manufacture in April, 1948. GLOSSARYi fe,52i.dP - a 23.15 extension of dark masstone RT-443-D on barytes. Bt443-D - The rosinated calcium salt of the coupling of PTHSA diaso and beta hydroxy naphthoic acid* About 265 of calcium rosinate is present in the finished toner. PTQSA - Para Toluid ins Ortho Sulfonic Acid. PTMSA * Para Toluidina Meta Sulfonic Acid. OTIBA - Ortho Toluidine Meta Sulfonic Acid# .mum - Rifled PTMSA BOH - Beta hydroxy naphthoic acid. Tobias Acid - Beta Kaphthylamine - 1 sulfonic acid. Iff,teSft,itU-lsl - An oily product of 1005 coal tar orlgin. It has no acid number. Flash point 250F min. Supplier* Neville Co., Pittsburgh. - Calcium hydroxide * chemical grade. Minimum CaO 70.05* DUP050066968 6 Preparation of the finished pigment from the basic Intermediates without isolation or removal of the mother liquor from the dyestuff. 4 RE-526-D Semi Works DSH-48-6 BS-526-S Plant DSH-48-7 Parts 1 and 2 DUP050066969