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.#/ s &%> HgSfo .\k : b ?4 M&-fe.V 3$~-sr* \ '"a^ 5-- J*&^.: HSWASK FLA2JT PIG3S2NT COLOR RESEARCH REPOSTS f ISAY - 1935 ,,-W -. , :.;.... IV " >. v-''~- gRSkJ./ ;;.,, r*-! Lv h ' 'V" ' /* PIGMENT COLOR RESEARCH REPORTS MAY - 1935 I - PIGMENT GREEN B Pigment Green B Pulp GT-68-P (EJH) ........................ * * for Paper Coating & Dyeing {AS) Page 1-4 5 II- RUBBER COLORS . Rubber Colors (AJS) ............................................................... 6-11 Ext. Green PTA Colors for Rubber: GP-399-d (CS-7789) and GP-400-D (CS-7863}EJH 12-13 Green Lake for Rubber GL-7854-D {EJH) ..................... 14 Rubber Colors RL-407-D, RL-408-D, RP-409-D (ADR) 15 III- PERMANENT BED ZB Barium Lithosol Red 2B - CS-7895 (AAB) ................... 16 IV - LITHOL REDS fa) Azo-Sulphite Derivatives (SWR) ............................ 17-19 (bj Calcium Lithol Toners RT-379-D & RT-300D (EJTH) 20-21 (c) Barium Lithol, RT-364-D (ADR) ............................... 22-23 V - CHROME GREENS (a) Preparation of Greens from Unwashed Blue(SCH) (bj Lightfast Kilori Green CS-7889 (JDM) ............... (c) CP Chrome Green G-389-d Line (ADR) ................. (d) Strong Meadows Green CS-7192-7194 (ADR) .... 24 25-86 27 28-29 VI- CHROHB YELLOWS & ORANGES a Press Washing of Chrome Yellows (VC) !b Medium Yellow Y-359-D (FLP) ................. e Primrose Yellow (FLP) ............................... d Excelsior Yellow CS-7903 (FLP) .......... e Study of Lead Cyanamide (SCH) ............ t Study of Y0-38-D Process (SCH) .......... 30-32 33-34 35 36-37 38 39-40 VII- IRON BLUES (a) Iron Blue Yields (RED, HCli) ............................ (bj Study of Iron Blues (SCH) .......................... ............. 41-43 44-45 VIII- PREP. OF PIGMENT-OIL MIXTURES BY MECHANICAL METHODS - June 7, 1935 (GWJ) (Special Report) 46 a-f IX - WORKING PROPERTIES OF PIGMENTS (a) Treatments to Improve Flow of Pigments (RKH) (bj Dry Dispersed Colors (SCH) ..................................... X - PHOSPHOTUNGSTIC ACID PIGMENTS a) improvements in PTA Pigments (SCH) ................... !bj BT-125-D & BT-150-D (EJH) ....................................... cj Plant PTA Yield Studies (EJH) ............................... XI - MFdC). BSTTU-1D2IE2S-D (New) (EJH) .......................................... .. Grinding of Pulps (JDM) 47 48 49 50 51-52 53-54 55 Eli- ALUMINA HYDRATE Preparation of Alumina Hydrate Ink from Pulp (r e d ) 56 i : ______ ;____________________________________ ______________ DUP050315769 _ .2 * v XIII- MISC. ORGASTIC PIGMENTS (a) Para Chior Ortho Nitraniline- Beta Naphthol (CS-7873) (AAB) (b) Toluidine Toner RT-232-D, RT-349-D, RT-200-D (c) RT-242-B (BJH) ............................................................... (d) RT-399-D (EJH) ............................................................... (e) tfisc. Toners Pigment Ruhine G- RT-S59-B (AXB) ............. Pigment Rubine Toner RT-359-D, Extended Color R1-390-B (ADR) ..... Improved Eire Toner, CS-7873 (ADR) .... (f) Mi sc. Lakes Dispersion Studies on Vat Dyes and the Preparation of Lakes (AS) ................... Miscellaneous Lakes & Toners (AS) ...... Blue Pigments for Lacquer- Drift in Shade (c k b ) Peacock Blue Lake BL-151-D (BJH) gage 57 58-60 61-63 64-65 66-68 69-70 71-72 73-74 75 76-83 84-85 XIV - SEMI-WORKS PRODUCTION (HA) 86-92 i'j'S-'V" 2 DUP050315770 PIGMENT RESEARCH REPORT PI GROTT GREEN B PULP GT-S8-P ________ SUBMITTED BY: t-M-V**** APPROVED BY: FILE: MIOO.TONETK? DATE: Mf 1935 INTRODUCTION Production on this color was quite high during the month eight batches being mad3 to fill an order for 1.000 pounds dry far rubber and to build up a stock of 5.000 pounds of pulp for paper* All outstanding sub standard stock (lots 48841 and 4049 ) was consumed during the month in mixes shipped to fill the order for rubber. SUMMARY & CONCLUSION The first three batches made during the month were made to check Lot 41873 except that an equivalent amount of caustic soda was used to replace the soda ash in the Cadmium-Turkey -^ed Oil soap. The use of caustic soda seems to give a more stable soap. All three batches were satisfactory by rubber test and were used to mix off outstanding sub-standard stock (lots 4S841 and 4049). The usual salting and pul verizing method was followed in mixing these lots which were shipped to fill an order for 1,000 pounds dry for rubber. The next three batches were made to check the previous three except that in the case of the last batch a little difficulty was encountered in making the Ferric Oxalate. A change to a different vat smaller in size (change made on request of the plant) caused a precipi tating of the Sodium Oxalate due to low volume and con siderable difficulty was encountered in redissolving. Finally after heating and increasing the volume a fairly good solution was secured but which had a cloudy appear ance as compared with previous Sodium Oxalate solutions. After salting and pulverizing all three of these batches were satisfactory in rubber and pre-shipment samples have been sent to the Technical Laboratory at the Dye Works for test in paper. On the basis of duplicate paper tests made at this plant the first two batches were in dicated as being satisfactory far paper but the last batch (the batch where trouble was encountered in making the Ferric Oxalate^ was 15$ weak on paper test. These tests of course are not final and are only an indication of the possible results that may be secured by the Technical Laboratory on which reports are not available as yet. DUP050315771 2 The final two batches made during the month were made to exactly check Batch 41873 except that the small vat was continued in use for preparing the Ferric Oxalate, By careful control of volume and temperature, actual precipitation was prevented but the Sodium Oxalate solution again gave the undesirable cloudy appearance. These batches are still in process and will be re ported next month together with the final results on the three batches being tested for paper. All eight of these batches were pressed in 40 cakes in a 30x1" press and satisfactory dry contents aver aging 26# were secured. All the pulps broke down to a thin slurry on stirring but set up to a satisfactory soft pulp on the addition of 1/2# of salt with subsequent mixing by pulver ization. Yields on the six batches reported were fairly satisfactory averaging 96# of estimate checking last month's yield result. GT-68-P production for the mcnth is tabulated in Table 1 and shipments from stock tabulated in fable II. DUP050315772 Shipped does not break % cCO rH Ci-Oe lO rH H t CO o rH 0 to <bDO ft CO CO O E MO <6rc3eq3j t+UBJ g- o ft CO <0 I? X rH rH ft ft U t rl u X H *4 5 (4 P u i3 m P u SO 3v c 43 T3 CO e *cJ rlOH ft rl a o j> P S- u 0 V g rl T3 3 S O L> Ok 10 & rH d u (4 0 V id O S3 rl 0 S W C O O 0 O b4* rH 3 C U 0 V g + 9 p. a . rl V 43 S 0 u u 0 V & 0 P c -p S 5O ft V *n n a u *4 r&* U 0 V bd 0 p c s i^ a* * *H Jh 0 ft ft V ft 0 m3 ft -P O CQ u S3 P # 4-3 : rH p rH ft rH a rH ft >> cCHD <0 rH fl O O 0 rH -P > cm U C> co Sn rHj P S >> B > 4L3 H 3 24 O U P -p rsHi > > B (4 P c 3 5 44 rH 8* 0 as > 3< m H O> W O 3< rH in O O rH >O CM u JO OLH fftt rl O to rH 43 > 6? o o 8 rl B U a`d rH O f+t rH f3t oP 3ft 00 Sm 0$ g oo o W 4& w n 43 ft rH dft 4> p Vi p OO GO nfl *fe O CD CO 44 P 42 rfHt fdt p g VP 0O CQ d fe 00 fO J4 U ft H sft p S3 V 0O CQ d a a 9t ft rH P ft -P g V ?s O0 CQ *d 4te O CO CO id u * rHft P ft P C Vg 0O CQ xs f CO CO Of O #H h S kQ Pi -p > O ^S a & 00 d rfHt Sh * GO d 3? 2= CM s in ft > s 42 4fc & t 1 b- fc~ 0 co CO CO m l* in to CO in o 1 t m in m *0 V CM CM CM CM <4 4fe CO $ 2? =te 50 s CO <0 C- in in CO CO CO CO CO CO 1 3= =*fc CO CO 5l* 4 10 e- CO in in cm cm in c m CD TO \n ** M3 in t- w CM CM CM > CM CO rH M i1 ft 8 + CO 3 00 c m 4H o X O rH rH X O frin CO <f4 IO <0 CO o tCO CO 30 00 00 ft 2 d* a CO Din* co tin CO <4* 44 binr CO * M em CO ** t- H CO * 44 uU fti CO CO rH <d CO ? CO 1-H cS Sr <0o0 b s B.24 -d 0o id 0 O 43 O 0 O rH O ft CM S cf O go $ a, <d< 0 O> O o O *H O 1 CO CO CM O 0% <0 co 5 ti>n in <0 O t- CO 0 0% b- CO CO t10 12 co CO CO co co ro 30 d* & rH DUP050316773 TABLE II GT-68-P Shipped during May Lot Comoosition Rubber Test vs Lot 13926 Paper Test vs. Lot 41873 Remarks & Disposition 42841 Plant batch 42841 10% wk,vs dirty - - Sub-standard stock. Consumed in mixes 14678 and 14679. Total con sumption 266# dry. 42893 43227 43296 43342 42893 ws str,vs cl. OK by Paper lab . OK for paper. Consumed in shipment for paper 1235# at 27.25% = 334# dry. * 43227 OK, ws clean Shipped for paper. 1221# at 28.4% = 347# dry. " 43296 m h OK for paper. Consumed in shipment for paper. 1300# at 25.7# * 334# dry 43342 M* OK for paper. Consumed in shipment for paper. 1318# at 26.4% 348# dry 43578 * 43578 5% str,ws el. "" consumed in mix 14678. OK for rubber. Total consump tion 388# dry 43658 * 43658 OK,v t s bl, ws drty - - Consumed in mix 14679. OK for rubber. Total consump tion 374# dry 43702 " 43702 OK, OK m OK for rubber. Consumed in mix 14700. Total consump tion 360# dry 4049 29# SW-6783, 74# 42841 treated in SW, 6#stump 41873 5% wk,vs yel&drty -- Sub-standard stock. Consumed in mix 14700. Total con sumption 110# dry 14678 388# 43578, 133# 42841 2% wk, vs yel & cl. - - OK for rubber. Consumed in rubber shipment. 1874^ at 26.9% = 504# dry 14679 374# 43658, 133# OK, m bl. 42841 OK for rubber. Consumed in rubber shipment. 1869# at 25.75% = 481# dry 14700 360# 43702, 110# ws str, ws bl. 4049 OK for rubber. Consumed in rubber shipment. 1832# at 25.8% = 473# dry. 3s5' DUP050315774 pimmT COLOR RBSSAB.CS BSPORT mms B ffB PAPBR GOATIKff ASB Pima .SUBMITTED 5ft Ksmmm b y * X*3*?/ PILE Hiac. lOKBg DAIS HAY- 1988 iHfacsgQffgar The development of a water dispersible Figment Green B powder for paper coating and dyeing has been practically completed in tbe laboratory, A large final sample is in the course of preparation, and semi-works development is in order, SUMMARY & GQXGLmmm The preparation ef a 50% pigment of excellent dispersing and wetting properties has been successfully accomplished in the laboratory using only rosin sine, She good dispersing and wetting properties of dry rosin sine has made the U3e of the more expansive leuoanol unneces sary, in order to obtain the water dispersible Pigment Green B powder it is necessary te mix intimately the rosin size with the pigment paste to a very homogeneous mass, which can be accomplished in the laboratory by werner and Pfleiderer milling, colloid milling and even by ordinary agitation, She paste prepared In these manners increases In bulk te approximately four to five tines its original volume owing to the foam ing of the rosin sine, and drys rapidly and to a friable form. For Obvious reasons it is advantageous te pulverise the material to a coarse granular form* the dispersible pigment powder is from IS to 20% stronger, slightly yellower and appreciably brighter than the corresponding stand ard GT-68-P paste as Judged by paper dyeing tests conducted by the Du Font Technical laboratory, and appreciably stronger, slightly yel lower and appreciably brighter than the standard paste as Judged by paper coating tests, SXPERiaSBSTAL DETAILS Notebook 460, expts. 22, 26 and 30, pages 90, 104 and 30 respect ively* Records, procedures, experimental results, and Technical Labora tory reports* DUP050315775 SUBMITTED BY: APPROVED BY: PICMBNT COLOR RESEARCH REPORT RUBBER COLORS HIE: ftUDDEn COLORS DATE: MAX-1935 INTRODUCTION This problem has continued active in the laboratory with the emphasis still on Ca Lithol and to some extent on the PTA Lake of Victoria Blue R. The Semi Works has been active in the development of the six colors already sub mitted to it and they are now ready for release subject to the approval of the Rubber laboratory. SUMMARY & CONCLUSIONS The Semi Works development of the following colors is now complete with results as indicated. 1. CS 7664 - extended Ba Lithol - approved by the Rubber Laboratory and ready for sale - given our code RL-407-D and the trade name Rubber Red TXE. 2* CS 766.5 - Extended Ca Lithol - submitted to the Rubber Laboratory under the code RL-408-D. 3. CS-7836 - Extended Ba Lake Red C. Subject to final approval by the Rubber Laboratory as Rubber Red BAE (our code RF-409-D). 4. CS 7789 - Specially treated GT-347-D. The Semi Works material is 15$ strong; vs yellow and s. dirty vs CS 7789. It has been submitted to the Rubber Lab oratory as GP-399-D for Rubber Green EG. 5. CS 7863 - Specially treated GT-354-D. The Semi Works mix is 20$ strong, sli. yellow and sli. dirty vs CS 7863. It has been submitted as GF-400-D. 6. CS 7854 - Lake of Brilliant Blue L and Naphthol Yellows to match Imperials Green -1292 (C-37280). The Semi Works mix is vs strong and t v s clean - vs CS 7854 and extremely close to C-37280. It has been submitted as GM-401-D. This completes the development work on Rubber colors before the Semi Works at the present time. DUP050315776 -2- Difficulty is still being experienced in obtaining satisfactory material for shipment of both RT-344-D and RT-300-D. It appears that the difficulty is at least as much the result of inaccuracies in the method of testing when applied to these two colors, as it is to anything actually wrong with the colors. It calls our attention once again to masterbatch technique or to its counterpart, refining of the colored rubber, as the only means of get ting reproducible results with certain colors of the toner class. We believe the difficulty will be largely overcome as the extended colors rqjlace the toners, but it is probably inherent whenever the maximum possible disper sion in rubber is not obtained. Nothing of especial interest has been developed on the FTA of Victoria Blue R. An acid variable disclosed the expected fact that low acid gives poor lightfastness. It is recognized that the dye analysis is inaccurate and a dye variable showed that a considerably higher amount could be used which has been adopted for future work. Three general formulas have been used in the work on the Ca Lithol for rubber. 1. RT-379-D type as used in 461-16 series. 2. Buffered Alkaline coupling with TOB regular 3. Buffered Alkaline coupling with 50# TOBW RT-379-D type gives rather erratic results both in rubber and in rubouts. Method #2 gives consistent results and excellent dispersion in rubber but it is inherently weaker (by rub out) than RT-379-D and somewhat dull and flat. Method #3 also gives consistent results and is stronger and bluer than RT-379-D by rubout but shows poor dispersion in rubber* In the April report a method of treating with kerosene to get softer texture is discussed. It consists of incorporating kerosene or other fairly volatile oily material with the slurry of the color, filtering and drying. The water evaporates first and leaves the oil which then goes off leaving a soft bulky cake. When the kerosene or mineral spirits are added by sinply stirring in, there is some effect in certain cases but is feather small in any case. However, when the oil is added and the material passed thru the colloid mill, the color floats on the liquid and filters to an entirely different cake. The dried material is remarkably soft and bulky and there is no increase in yield. 7 DUP050315777 -3 We have also tried extending the various colors with CaC03 struck in the mixture from Soda ash added to the Soda Salt and of course, have treated these colors with mineral spirits in the colloid mill. It seems fairly safe to conclude that any of these colors will respond to the Colloid Mill oil treatment to give the extremely soft texture. There is, however, a great difference in the degree to which this is feflected in the dispersion in rubber. The RT-372-D type shows some response to the treatment end some to extending with CaC03 but it is disappointingly small. The buffered alkaline coupling from TOB regular shows very little im provement in rubber due to any of the treating methods tried. As a toner, however, it gives the best results of any method thus far tried with Ca Mthol tho by rubout it is weaker and duller than RT-379-D. The buffered alkaline coupling with 50$ TOBW gives poor dispersion in rubber and, as would be expected, re sponds well to the various treating methods and gives with the combination of CaC03 with the oil-colloid mill treat ment, a very excellent product which is stronger and cleaner and sli. bluer than CS 7665. As a toner it is dark, strong and clean vs RT-379-D. An attempt to improve the dispersion by adding a non-volatile oil with the mineral spirits was unsuccessful under the conditions employed tho the idea has not been completely abandoned. There have been some rather mysterious inconsisten cies in the controls which have appeared to coincide with times when the color was left for an unusually long time in the oven* It has been shown that baking for 3-4 hours at 110OC will make the rubout dark, blue, strong and dirty and the rubber slab strong and blue. The rubout gradually regains the characteristics of the control but the rubber does not. As a further check on this drying, a sample of RT-300-D from the plant was dried in the P & S Dryer at constant humidity 140$ humidity, 1400]?) but no advantage was apparent. The future course with Ca Lithol is not exactly clear but we feel that the present RT-379-D method must he modified and that the buffered alkaline coupling appears to offer the best point of attack. We also feel that the use of isomers.with the TOB is dangerous as far as dispersion in rubber is concerned but seems at this stage to be necess ary for the desired depth, strength ana blueness. The ideal DUP050315778 t 4 color would appear to be cne made from TOB regular and pure Beta Naphthol by some method which will give the desired tinctorial properties. EXPERIMENTAL DETAILS - see notebook 461 pp 50-91 461-16 Treatment of Ca Lithol (Buffered Alkaline coupl ing' 50$ TOBW as in 461-8C) with Kerosene and Mineral spirits. Various amounts of the oils were used in the form of emulsions with Diglycol Stearate and also with out the emulsifying agent. The results were somewhat erratic but in every case the treated product was dis tinctly better in rubber than the control while substanti ally alike in rub-outs. However, the product containing Kerosene without the DGS was the best in the series. It appears to be significant improvement and is probably caused by the fact that the Kerosne is taken up by the color and held until most of the water is evaporated. The oil then evaporates and leaves a softer color largely free from oemented aggregates. 461-16 An alkali variable in RT-379-D method together with -a-erosaie treatment as in 15 series without emulsifying agent. Due to considerable "burning" in the oven, any conclusions are dangerous. There appears to be some tend ency for the more alkaline products to show better disper sion in rubber. The kerosene treatment as used here appears to be of no benefit. 461-17 To try precipitating CaC03 with a Ca Lithol of HT-379-D type together with Kerosene treatment as in 16 series. This was tried because CaS04 is too soluble and washes out of the color. Various amounts of N82C03 were added to the Na salts before the strike to give CaC03 ranging from 20fo to 40<k of the final product. There was a marked improvement in dispersion in the case of the smaller amount. There was some additional improvement with larger amounts but it was slight. The lakes are sub stantially equal to CS 7665 in dispersion. The kerosene treatment gives definite improvement to the control, only slight in B and none at all with the better products. 461-18 A study of the PTA of Victoria Blue H - Acid variable altho the series is slightly out of line by rubout, it is quite obvious that lower acid gives stronger products of poor lightfastness in ruhout, hut with slight differences in rubber. No change is indicated. 461-19 To study the effect of colloid milling on the oil treatment as tried in 15 series and also on the CaC03 lake DUP05031 5779 - 5 ' as in 17 series. Both the toner and the lake were treated by colloid milling alone (A1 and B4) with mineral spirits alone (A2 and B2) and with mineral spirits followed by colloid milling (A3 and B3). A3 and B3 were greatly changed in physical properties and quickly floated to a layer on top the slurry* They dried to a soft bulky lump with no increase in yields over the controls (A&B). The results show little effect in any direction by the colloid milling alone. The mineral spirits alone give a percept ible improvement in texture but the combination of the two gives a remarkable change in physical properties which are partially reflected by the dispersion in rubber. The ex tended colors are only slightly better than the toners in any case. The improvement in texture is so pronounced that it will be studied further. An interesting phenomenon was observed when a sample of the control (19 A' was heated for 3-4 hours at 110 C. By rubout, it was then dark and muddy, strong and blue but after several days the rubouts changed so that there was little difference. In rubber the heated product is strong and slightly blue and the slab is apparently unchanged on standing. This effect of heating may explain some irregularities in the results obtained, especially when the products have been left in the oven for a loigsr period than usual. 461-20 In this series an attempt was made to produce dark blue Lithols by using small amounts of BON in place of comparable amounts of Beta Naphthol in a buffered Alkaline coupling from TOB regular. In rubouts the BON does give depth, blueness and strength. However, in rubber, it appears to give inferior dispersion and does not appear to be the proper solution to the problem. The colloid mill - mineral spirits treat ment was also applied and gives a remarkable improvement in texture and some improvement in dispersion in rubber? especially in the case of those which are poorer to begin with* 461-21 In this series an attempt was made to add 5# of non volatile oil to the mineral spirits before colloid mill treatment of an RT-379-D type Lithol. The yields indicate that the various oils used - Cotton seed Oil, biglycol Stearate, Butyl Stearate, Butyl Oleate and Paraffin - re mained in the pigment but in no case was there any improvement over the product treated in the colloid mill with mineral spirits alone. However, the whole series was somewhat out of line by rubout and may be an illustration of the heating effect as noted under the 19 series. 461-gg Variation in alkalinity of coupling on 20A method. Also extend part with CaC03 and treat both parts with mineral spirits in the colloid mill. DUP050315780 -6- Higher Alkalinity gives definitely inferior results and the lower amount as used here is not advantageous. The extended products are not appreciably different from the toners and the treatment in the colloid mill shows only slight improvement. All are equal or superior to CS 7665 in rubber and very close in shade. However, by rubout, they are inferior to RT-379-D. Nevertheless, products made by the same method, except using 50% TOBW are superior to RT-379-D but poor in dispersion in rubber. 'Therefore, some work will be done in an attempt to improve the dispersion of this latter type, 461-25 A product such as that mentioned above under 22 series (like 461-8C was prepared and treated with mineral spirits in the colloid mill. It was also extended with CaC03 and likewise treated in the colloid mill. In texture the treated products (23B and 23D) gave very soft bulky cakes whereas the controls (23A and 23C) were hard and canpact, By rubout the toners are dark, yellow, strong and clean vs RT-379-D while the lakes (20% CaC03) are only slightly weaker, all better in lightfastness. In rubber the CaC03 and the mineral spirits each give some improvement when used alone but the use of both gives a very desirable product which is stronger, bluer and cleaner than CS 7665. On refining in rubber all these products as well as GS 7665 were considerable improved in strength hut D was still slightly the best. It will he given further study. 461-24 An alkalinity study on 23 D with a special treatment of the control with Dibutyl Phthalate. This leA shows nothing of value and the change in alkalinity over a small range does not seem significant. In A the alkali was defi cient for coupling hut this was taken care of by the soda ash added before the strike. The product was quite dis tinctly strong and should be studied further. 461-25 Variation of Para Soap seems of no significance in rubber. Additional NH4C1 in the strike seems to cause poor dispersion. Inasmuch as the control is dark by rubout the results are open to some doubt. 461-26 The volume of development on 23D was studied and there seems to he no reason for changing it. 461-27 This series attempts to check 24A with only moderate success as is not unexpected in sucha formula. Certain modifications were tried which indicate that Soda Ash pre sent during the coupling is slightly harmful. There is also some doubt as to whether 24A is as good as it first appeared to be. 461-28 A variation in the amount of dye used in the Victoria Blue R-PTA-Lake gives increased yield and somewhat extra strength with the higher amounts of dye used. As lakes the products are all alike in rubber and the higher amount will be used in the future. // DUP050315781 PIG-MEM? COLOR RESEARCH REPORT EXTENDED GREEN PTA COLORS FOR RUBBER: GP-399-D [C3-7789) AND GP-400-D (CS-7863) SUBMITTED BY: APPROVED BY: FILS: .nUBBER COLORS DATE: MAY - 1935 Sips'- IlfPRCDUCTION Production of Both of these colors was continued in the 3emiV/orks during the month. In both cases satisfactory mixes were made and new rubber standards set up and coded. SUMMARY & CONCLUSIONS Pour batches of GP-399-D (C3-77S9) are reported this month in cluding two outstanding from last month. Two of these batche^sere made increasing the ratio of Thioflavine to Brilliant Green over the standard formula in order to give a yellower lake to be used for shading. A satisfactory mix was made containing practically all GP-399-D production to date, and v.ras set up as the Rubber Green EG standard, GP-399-D. replacing CS-7789. Results are tabulated in Table I. Three batches of.GP-400-D (C3-7863) were made during the month checking the standard CS-7863 formulation but making batches five times the size of those made last month. Satisfactory rubber testss were secured'on the individual batches. A mix was made consuming all production to date and set up as the new rubber standard GP-400-D replacing CS-7863. Results are tabulated in Table II. . ... - Jw ii'.aTrii wZSSi* jv.- A ' mUZUmmSSsSmam. DUP050315782 EXPERIMENTAL DETAIIS TABLE I GP-399-D(CS 7789) N.B. 408 cages 118-1E3 Batch Dyes 100# wt. 100# Wt, N-338 N-S91 Rubout Results vs CS 7789 Yield Est. Lump Masstone Drawdown Str. Tint Rubber test vs CS 7789 7014 1.3# 7.0# RMC 373 RMD 275 30# 29# Lt. Yel. O.K. Yel. 8-10# yel 7OT5 5.16# 19.2# RMC 373 RMD 275 90# 88# tr.lt. vs bl. tr.wk. vs bl. 15# vs str.equal dirty tint 7036 5.16# 19.2 # HKD 368 RMD 364 90# 88# vs dk. vs bl. O.K. vs bl* 20# str. vs bl. 7037 3.9# 21.0# RMD 368 HMD 364 90# 88# lt. yel. wk. yel. 10# str yel. Mix 4119 Composition: 6943(all) vs.It.clean vs yel. wk. s.yel. 15# str. 6976(all),7014(all),7015 vs yel. (all) ,7036( all) , 7037(part-44#). s.dirty |Migration OK Std. GP-399-D TABLE II GP-400-D(CS7863) N.B. 408 pages 116-123 Batch Type Dye Yield Rubout Results vs CS 7863 Rubber test vs Formula Lot Sat. Lump Masstone Drawdown Str. Tint cs 7863 7007 Check CS7863 RMC 142# 132# Lt. dirty wk. dirty, yel. more than 5X SW 6947 373 20# str.yel 7009 Check 7007 RMC 142# 139# 373 Lt. dirty s.wk. dirty, yel. 7034 Check 7007 RMD 142# 134# brown 368 wk. wk. dirty Mixes 4112;| composition: 69471 all) ,6980(all,TO4(all), 4113-1 7007(all) ,7009(all) Lt. s.yel.dirty wk . dirty yel. Migration O.K. Std. GP-400-D. Z0% str. vs yel. 20-25# str. vs.yel. 20% str. s.yel. s. di rty Hu: DUP050315783 /P PIGMENT COLOR RESEARCH REPORT GREEN LAKE FOR RUBBER GL-7854-D SUBMITTED BY: 6.0^ APPROVED BY: /7^ PILE: RUDDER OOI-OflS DATE: MAY 1935 INTRODUCTION Production on this color was continued during the month a total of three hatches being reported. A satis factory mix has been made during the month! set up as stand ard^ and coded Gfcf-401-D. SUMMARY & CONCIUSION The first batch was made increasing the ratio of LithosoJ. Brilliant Blue to Naphthol Yellow S in order to secure a blue batch to be used for shading. Tested in rubber this material was 5-8$ str. and blue versus CS 7854 as com pared with the slightly yellow test secured when using the standard amount of the <^res. In order to secure another supplier for the Naphthol Yellow two batches were made substituting Naphthol Yellow SXX from General Dyestuffs for the Naphthol Yellow S supplied by National Aniline Company. The products were satisfactory and this source of supply for the Naphthol Yellow was approved. A satisfactory mix has been made consuming all Semi Works production to date and has been set up as rubber stand ard at 401 D. Results are tabulated in Table I. EXPERIMENTAL DETAILS - N.B. 430, pages 104-107 Batch SW752I SW7 62*7 TABLE I Rubber test Dyes Rubout Result vs CS7854 vs CS 7854 Yield N-311 Naphthol Yell. Masstone Drawdown Str. Tint Lot Wt-, Type Wt._____________ ____________________________________ Est. 8 12570 S 11.6# deep bl. OK bl. 5-8% str.bl.79 79 0U 2188E "^8 10.4# SXX 14.6# vs deep str. str. yel. + 10$ str, 79 73 OU 2521 tr.yel._______ SW7045 JOB 10.4# SXX 14.6"# vs It. yel* vs str. yel. 79 74 ___________ OU 8521 _____________________ ________ vs dirty____________________ Mix 4116) composition: All of lots,vs It. vs clean vs str. clean vs.str. - 4116) 6971,6985,6988,7021, Ws clean 7027,7043. clean vs C#37280 ws str.vns clean _______________________________________________________ OK migration DUP050315784 J&'-'-zssv /r PIGteEMT COLOR RESEARCH REPORT RUBBER COLORS RI-407-D, RL-408-D. RP-409-D SUBMITTED BTSi^WT^, APPROVED BY: ' FILE; HUJWA1W UU'HlRS DATE: MAY 1935 INTRODUCTION Sani Works standardization of these rubber colors was completed during May. No new work was done on the extended Lithols but mixes of each type were made up for standard. Four hatches of the extended Lake Red C toner were made following the Laboratory formula, CS 7836. SUMMARY & CONCLUSION The following tentative standards were set Up: CS 7664 - Coded as RL-407-D - Barium Lithol - Lot 4086 CS 7665 - B RL-408-D - Calcium Lithol- n 4101 CS 7836 - " RP-409-D - Lake Red C - " 4106 The four batches of CS 7836 were close to each other and to the CS standard by rubber test altho all but one were darker by rubout. No variations were made except In batch size and in flooding temperature which showed no distinct difference, EXPERIMMTAL DETAILS - Notebook 430 p. 74. 5ST836 - RP-409-D SW 6919 - l/lOth of CS 7836 - used Lithosol Red CIt. paste Lot 13 Rubout-s.dark and rauddy; ok; vvs wh; vs dirty Rubber - s weak and dirty SW-7023 - 1.5 X SW 6919 Rubout- dark and s brt. s. yel; s. str; vvs yel. Rubber - vs yel and strong SW-7026 - 3 x SW 6919 Rubout - dark and s. brt; yellow; s strong; vs yel Rubber - vs yel & strong SW-7030 - 3 x SW 6919 except quench to 150 instead of 180op Rubout - dark and s brt; yellow; vs str; vs yel. Rubber - vs yel & strong. Lot 4086 - CS 7664. Mix of SW 6858 - 6867 - 6884 Rubber test - s. yellow and clean Lot 4101 - CS 7665 mix of SW 6455 - 6873-6879-6937 - Rubber test - O.K. in-strength; trace blue Lot 4106 - CS 7836 - Mix of SW 6915-7023,7026,7030. Rubber test - vvs strong; vs yellow DUP050315785 gr-ss-t // PIGMENT COLOR RESEARCH REPORT BARIUM LITHOSOL REP 2B - C3-7895 SUBMITTED BY APPROVED BY: .a.2.2. FILS: MIOC. TOMES DATE: JAY- 1935 INTRODUCTION A process. CS-7895. for the preparation of the barium toner of Lithosol Red 2B has been developed in the laboratory and a one pound sample has been prepared for evaluation purposes. SU:TA-Y & CONCLUSIONS Eight different preparations were made on a modified 447-16C for mula, varying in size from 0.05 mol to 0.2 mol, for the purpose of determining the consistency of the method. All eight runs were sub stantial checks to each other and to 447-16C, an indication of the stability of the formula. This procedure was assigned CS-7895 and the eight runs were combined and set up as the CS-7895 sample. Samples were submitted to Parlin and Philadelphia for evaluations in Duco and Dulux respectively; a sample is also being evaluated in printing ink by the General Laboratory. By way of review, the results of some of our own tests on C3-7895 are given below: Lithographic Varnish Rubouts: CS-7895 is v.sl. dull (yellow cast) in maslitone, clean in printing tone finish, v.sl. weak, si,blue and clean, distinctly better on zinc oxide reduction fadeometer exposure than HT-313-D (Ba Red for Lake C). Lacquer: CS-7895 is non-bleeding in Duco and darkens (masstone) in 24 hours in fadeometer. Versus ET-313-D, the C3 is dull and about' equal in lightfastness. Rubber: CS-7895 is distinctly worse in lightfastness (6 hrs.fadeometer) than the calcium toner of Red 23 (C3-7853), and is only about equal to RT-313-D. EXPERIMENTAL DETAILS Notebook 447; series 24 and 25. vf DUP050315786 ^S~~/5ry PIGMENT COLOR RESEARCH REPORT AZO-SULPHITE DERIVATIVS5 SUBMITTED BY: APPROVED BY: t>JL PILE: MHmOL-ffflP DATE: MAY 1935 INTRODUCTION Further work on the improvement of the texture of the Calcium Toner of the Azo-Sulphite derivative of Lithol Red was continued during the month. The conversion of Toluidine Red to the Azo-Sulphite derivative was tried. SUMMARY & CONCLUSION Improvement of the texture of the Calcium toner of the Azo-3ulphlte derivative of Lithol Red was tried by treating the slurry and finished pulp with various agents. The dispersing agent diglycol stearate added both to the slurry and the finished pulp gave a slight improvement over control 446-47E(similar to C.3.7801 with the exception of developing at the boil); Para Soap added to the strike and the slurry both in the acid and neutralized condition had no effects; tri-ethanol amine added to the slurry and finished pulp gave considerably inferior results, very hard texture with very poor dis persion in rubber, ^ hey were all inferior to C.S.7665 in rubber. Treating the finished press cake with glycerine prior to drying gave poor results while the addition of mineral spirits and colloid milling gave very good re sults, soft texture with equal strength and clean tint in rubber versus. C.S .7665. Thus,this treatment appears to be the best to date altho the results were no better than C.s.7665. Overdrying and humidified drying of the toner had no apparent effects. The temperature of the alkali addition had very little effects from 350C to 80oc while at the boil an entirely different type product was obtained, very soft in texture, dark and brown in masstone, blue in tint and slightly inferior in lightfbstness versus CS 7801 in varnish driers, very blue, approx, equal strength versus CS 7665 in rubber. // DUP050315787 - 2- The formation of the azo sulphite derivative of toluidine red was tried by varying the treatment from all sulfurous acid to all sodium sulphite at high tem perature. A small amount of conversion (20%) was ob tained when the molar ratio of the sodium bisulphite to sodium sulphite was Cl*l). Further work is not contem plated along this line at present. "EXPERIMENTAL DETAILS - K.B. 446 (Pp. 140-153) Series"~446-51-55,56 tried to improve the texture of the Calcium toner of the azo-sulphite derivative of Lithol Red by treating with dispersing agents and various dry ing methods, and the addition of mineral spirits with colloid milling. The addition of tri-ethanolamine to the slurry and finished pulp gave inferior results, very hard texture with practically no dispersion in rubber, para soap both to the addition of the strike and to the finished slurry in the acid and neutral condition had no effects, diglycolstearate added to the slurry and finished press cake gave slightly improved results but was weak versus CS 7665 in rubber. Over-drying and humidified drying had no apparent effects on the results The addition of glycerine to the press cake prior to drying gave hard texture with very little dispersion in rubber. The addition of 20% Mineral spirits and colloid milling gave very good texture with equal strength and clean versus C.s.7665 in rubber. Series 446-52 varied the temperature of addition of caustic soda from 35C to boiling. Slight differences were obtained on increasing the temperature from 350 to near boiling. At boiling a different type product was obtained, very soft texture, dark reddish appearance and was brown, blue, ,and slightly poorer in lightfastness versus CS 7801 in varnish driers, very blue and equal strength to C.S.7665 in rubber. Series 446-53 tested the ageing qualities of the azo-sulphite derivative of Lithol Red both as paste or press cake and dry powder. Only slight variations were obtained after ageing one month. Thus, it appeared evident that it can be stored either way satisfactorily. Series 446-54 repeated a double series in order to determine the uniformity of the product obtained. Un doubtedly, a slight variation occurred in the depth of the masstone, only slight differences in tint and strength. msnnnuuu^ DUP050315788 -3 - <v f 3 Series 446-57 tried the formation of the azo sulphite derivative of toluidine red, RT-158-D, pulp, by varying the treatment from all sulfurous acid to all sodium bisulphite* Boiling several hours a slight amount of conversion was obtained when the molar ratio . of sodium bisulphite to sodium sulphite was (lil). ' Per haps this formation was Impurities, then again, it might be possible to obtain complete conversion by determining the optimum reaction condition for this type of material* . DUP050315789 PIGMENT COLOR RESEARCH REPORT CALCIUM LITHOL fOtfERS RT 379 D AND HT 500 D____________ SUBMITTED BY: 9 ai^o APPROVED BY: FILE: irraeta SATE: MAY 1935 INTRODUCTION There was no production on RT-379-D during the month. The plant hatches reported are outstanding from last month. Five hatches of RT-300-D were made in the plant during the month results on all of which are available. SUMMARY & CONCLUSION batches Both of the RT-379-D/outstanding from last month were satisfactory in that they were easily shadeable in fao'^i one batch has already been consumed in a mix for rubber. Both were made to check a previous batch, 41501, except that the first batch was struck before dilution to development volume while the second batch was diluted^to development volume before strike (an exact check to 41501j. The higher dilution on striking gave darker, stronger and yellower results which is desirable quality for shading. Results in Table I are tabulated on these batches. All five batches of RT-300-D made in the plant were satisfactory, tinctorially. The first three batches made on a modified RT-379-D formulation were light and yellow with OK strength. The last two, which were sat isfactory for rubber, were made on the old standard BT-300-D formulation, CS 7038 and were vs dk. vs brown and vs blue versus the standard by rubout. Results are tabulated in '-`'able II DUP050315790 _______________________________________________ & y a l* OK but 175* l/ Z W ^YS.'dk. v a d ir ty OK vs b l . Q%V t r W a ' 205 NB 433 pagas 180-181 hold 20* s.brown r--I A 83 r-f U PA g^ u H a T? ^ O CoOo 3 H W i--I m OAo ^sro OO S3 CO A> 4sJh* S3 > l-->tfk 0$ * P nao3cS' T> c rl a ft 4*08 in C4Ms <0 tn fO <n CM 1 4U0"i P o o 5 1335 CM 40 icno o> CM <on CC*O2 3I3 A a, CO CO w a $. goo Eh co S 9 CM a Kca E-< ca| ts a Mg co C3C >CO (O co CM * r$l Uoi > tA + ssi ,,(OL, Cel >363 >Si43 5 5O> ao o& h ,4 siHs i2*n*. mo 43 1O Ok r-i 8 8 o ? 3 &3 O N rl Ok <_&C0O as Ott 0a O4Oi3d -fOXPt PH i5oI2J ttioon *CO U > a 30 O rH p P P s sO H CM >k O o si ^ p CM >> iH > * CO in o CM >A * p C8O*. Mo o * t a H >t in-+i pm '|j *ts iicnH ro-t i o Ok .MP E * P O co o 8 o CHM r4<-*rf IX t* . S XK 40 in MoS w hO: \ 1100 tr> co 4a H bl TJ P ^ JO4 Ao \rH Pp^4t1n00 o c*$o' s t* -*PTg3* O *PH X O xoAt icno fo rm u la CS 7038 -143 hold 20* va br Sat, fo r rubber s ____________ ____ ______________________d ir t y to o s tro n g TABLE I RT 379 D 127-140 1800 -144 43866 chack 43841 EXPERIMENTAL DETAILS DUP050315791 PICMENT COLOR RESEARCH REPORT BARIUM LITHOL. RT-364-D SUBMITTED BYX>. APPROVED BY: FILE: DATE: "TSTZITTlTJTVflAT)-- May 1935 INTRODUCTION Production, of this Lithol was continued in the plant checking the last hatch reported in April, The form ula, except for development temperature, is identical with the acid coupling formula C.S. 7290, SUMMARY & CONCLUSION Practically all the material made was normal in character, averaging v.s. to *. dark in mass tone and v.s. to s, yellow in tint. Use of the standard amount of far a sag? and Caustic soda in the coupling and development at 170" F appear to he most suitable* Low temperature drying (140F in either Hurricane or P&3 Dryersi prevents darkening of masstone during this process. Other precautions such as a thoroughly clear diazo vat and elimination of use of iron drums for dissolving Ammonium Chloride probably help in obtaining a normal product. Bringing to development temperature in one hour Instead of 20 minutes appeared to be favorable on vat control but the batch which was dried in the Brick Dryer became dark when finished. Increasing development volume from 1700 to 2500 gallons may add slightly to depth. However, results are uncertain because the batch stood in press cake for over the week end. Both of these variables should be re checked. A mix of / 5oo pounds was made up of some of the month's production and a blend of RT-403-D was also made for shipment. DUP050315792  fa 0o rH *P X Pi o rH > to c *rt rH P P O o p o Pi erf X O ca o H -P ca 3 o -*r A P. o CO p CU CO to p 5 o rH : in ts o >* rH *P P z . <H H SX P > 41 zc 6H o 44 z* S3 to * > CO P +* to 5 p p n > CO 44 CO P 4 erf sx o rH H > rH >> > -h> 44 P P > 4 > * n3 rH B^rH >o a > 43 P P rH > > 44 P a -P Xp ,,o p o z >% M * >* gs 40 Q 44 rl Si P 33 r-1 ^ s > O r W z o M H Ps X H >p Pt X p at X? c at -p CO 3 X erf -P S3 H 3 43 rH C H fa o* s- 5 ^s X O 4* CQ , (D Pi O p fa >> Po Q to rH 1 o rH r| P P3 a: p 3 X o o p Pi X P CO \ rH >> r-1 O . > *3 4 P P rH fa *> 44 P3 -pP X . * > fa ) O 4< rH P fa & CO s fa rH fa P P D rH fa > rH .Q M c 5 o cS 44 P X > * s * 8 # rH > P P > rH >* > 44 P X f o O S3 o rH 44 Pi o Ss xp Po E H OP O Pi in csi p H P_ rl X O Xo + P.CO o rH 'S Q teO s rH A OH o e 4> Q u > 44 c3 X a > P >> & c fa a> oo H 4* P rH P3 S3 o rH Pi O X e s H IS rH P O *3 S Sh X o5 S> o o& a CO CO CO rH Eh m <o fc- fc- b <$ CO CO CO CO co eo CO a> t 14733 One t h ir d o f 43913 JBrick Dryer 140VF dark vs blue i N.B.335 EXPERIMENTAL DETAILS DUP050315793 FIGMENT COLOR RESEARCH REPORT PREPARATION OF GREENS FROM UNWASHED BLUE SUBMITTED BY: f.C- APPROVED BY: FILE: CHROME OH1SMT" DATE: MAX' 1935 INTBODUCTION A brief study has been made of the possibility of using pnwglied Blue liquor for preparing greens of the G-389-D line. The preliminary work indicates it may be possible to use unwashed blue in these colors. SUMMARY Sc CONCLUSION Greening yellow prepared by the G-389-D process was treated with washed and unwashed B-63-D blue liquor. An extended green was also prepared using unwashed blue liquor. There was no indication that the unwashed blue produced a more olive green. The green slurry contain ing unwashed blue showed no increase in oliveness af ter standing 24 hours . EXPERIMENTAL DETAILS - see notebook 439 Experiments 78,79. Preparation of G.P. and extended Chrome Greens using unwashed blue. Results: No appreciable differences in light fastness or appearance were noted. slightiy lower yield was obtained with unwashed blue. b DUP050315794 PIGMENT COLOR R533ARCH REPORT LIGHTFA3T KILORI GREEN CS-7SS9 SUBMITTED BY APPROVED BY: i'lLE: Gimois! g u is e DATS: MY - 1935 INTRODUCTION Three hatches of this color were struck in the factory on the low hi chromate formulation introduced last month to increase the stability. The temperature of strike was raised in each case in or der to ascertain the effect of a temperature more nearly approximating that which is practical during the summer season. oiJMIARY & CONCLUSIONS All of these hatches were struck at 75&:F instead of 70CP. The first of these, although yellow and olive against the corresponding member of the G-389-D line, was brighter and bluer than that of the hilori line, with increased lightfastness as compared to the latter. The second batch, identical to the first except for being light er for shading purposes, was light and olive against the Ililori green of the same depth. The third batch gave a yellow similar to the preceding one. An attempt was made $6 get rid of the redness of the yellow, and the consequent oliveness of the green^by adjusting the pK of the yellow with acid. This procedure was not carried to a sufficient extent to obtain the desired blue and bright product. 3emi-works shading to the G-7891-D depth using plant yellcwwas tried both on laboratory scale and on somewhat larger scale to check the results of the laboratory work. It was found that the laboratory material left overnight, became very changeable. In the larger check run, one third of the material was pressed and dried immediately, one third pressed and left as wet cake over night, and one third left as slurry overnight. ill of these were changeable, the sample dried immediately being very slaty in appear ance. The other samples were olive, and the one left in slurry form overnight was much darker. The undertones were blue except for she sample iiried immediately, in which case it was yellow. This study is being continued and it is hoped that more favor able results will be available within the month. EXPERIMENTAL DETAILS 3at ch 43537 43924 43960 Variation Check 42945 but strike at 75CF Check lot 43537 but use 301> of Blue Check 43924 See N.3. 437 - r-u. 157-159 N.3. 436 - p'. 144 Lt.fastness 3td. Mass. Under. vs. G-315D G-389-1) dk.v.s. yellow olive II olive h better II tl It t! DUP050315795 Batch SW-7054 Variation Leave in vat over night after shad ing Std. Gr-392-D Mass. dk.ol. chgble Under. s.blue S?-7055 Pi Iter and dry immediately S^-7056 Leave press cake moist over night If n slaty, yellow changeable olive,slaty s.dirty changeable DUP050315796 PIGMSYX COLOR RESEARCH REPORT CP CHftOMB GREER G-389-P LIK3 s u b mit t e d b y CUt-A-X^ c ^. AP: .OV3D BY: FILS: CJUt IUIj J G.nEE'is DATE: J/DY - 1935 i:::.toDUCTiosr Supervision of this line of greens has been turned over to the p!~nt staff and the only attention given by the Development Section v."v in the production of some olive material for shading G-389-D. SY. 11 :Y & COITCLUSIQI' A slight increase in Bichromate with corresponding reduction in sul hates (ratio of 237 to 16 instead of 232 to 22) ->vas not sufficient to -ivs any definite increase in oliveness of the G-389-D masstone. A four mol charge on this formula resulted in a red changeable yetlow but it is possible that some other variation was the cause of the abnormal product. Other four mol charges were made in which the ratio of 237 bichro mate to 18-1/2 sodium sulphate was used. (An intermediate amount of sodium sulphate). A very slightly olive masstone was obtained when the yellow was treated in the standard manner. 3y use of soda ash lately omitted from the treatment, oliveness was increased satisfactorily and the blueness of undertone and tint now occurring in G-389-D was cor rected. Twelve batches of G-3B9-D and one batch each of the other members of this line were made, hires totalling 14,000 pounds of G-3B9-D and 4,820 pounds G-391-D were made up during the month. EXPERIAL PSTAIDS - see plant control boohs. r DUP050315797 SS~-/C3 PIGMENT COLOR RESEARCB REPORT STRONG MEADOWS GREEN CS 7192 - 7194 SUBMITTED BY: c>- APPROVED BY: ^CAa/u^s^ A// HLE: GimOKS QH-gBNS DATE: MAY 193 5 INTRODUCTION One batch of this green was struck in the plant in sane equipment used last month with a variation in the formula to increase blueness and brightness of masstone. Three batches of C.S.7194 made in the Semi Works during April and not reported at that time are included in this report. SUMMARY & CONCLUSION Doubling the amount of sodium sulphate precipit ated with the bichromate added to brightness in the light shade 7192 and increased blueness of masstone in the dark shade 7194. The latter was v.s. dirty on final grind end some further changes may be required to stabilize this shade. For the other shades, the improved agitation together with the rapid strike and the variation made, this month, will undoubtedly give satisfactory results. Production of the dark shade in the Semi works was not successful. One batch was blue and dirty in masstone and a second batch in wh ch lead nitrate crystals were used was olive and changeable. Another batch wMch was shaded only to a light depth was also olive and changeable because the agitation was shut down during the strike. * five minute addition of bichromate was used on all batches. EXPERIMENTAL DETAILS Plant N.B. #437 pages 15 and 36 43538 - C.S.7192 - Like 43255 except increase sulphates in bichromate from 12 to 24# is C.S. 71i2 - light vs bright; yellow 43253 - C.S. 7194 - Part of 43538. Treated and shaded is CS 7194 - v. blue vs dirty; vs yel. G.K. vs yellow Semi Works N.B. 436 p. 14 and 22. S.W. 6950 - yellow as in CS 7192, SW 6779 (Feb. Report) is CS 7194 - dark dirty; blue S.W. 6965 - check S.W. 6950 but use lead nitrate crystals instead of liquor. Is CS 7194 - olive changeable; blue v-~ W****fi*?^__ DUP050315798 - 2S.W. 6960 - Same as 6965 but agitator was shut down during strike. Yellow was very red and was shaded to XL depth. Is CS 7192 - very olive; yellow DUP050315799 I 'v:; jZy vV < ! ;#4, m Map E ifS*.- v, w* PISHBHT COLOR RESEARCH REPORT PRESS WASHING OP CHROMB VgT.TJnsa SUBMITTED BY* /. , APPROVED BY* A//- f p iis i cnROMS Yffiaews DATE: MAY - 1935 IffTRODUCTIOIT A number of plant batches of Medium Yellows were split and por tions filtered and washed in the press immediately after the strike. In the case of Y-359-D, press washing gave an increase in strength at the expense of cleanness of masstone. Ink properties were not appreciably affected, the controls and the press washed portions being satisfactory. HTo further work is planned until summer conditions pre vail. Y-299-P and Y-316-D showed a much smaller effect on tinctorial properties* SUMMARY & gQggUISIOHS Pour batches of Y-359-D were press washed. In each case, the press washed portion was greenish ad dirty in nassrfeone, slightly strong, and slightly green in tint compared to the corresponding con trol. Press washed portions were equal to the controls in lightfast ness . The time of washing was varied from complete washing, to washing equivalent to the ordinary vat washing. The degree of washing showed little .effect. Two batches of Y-299-D were press washed. This yellow showed very little difference between vat washed and press washed portions. One batch of Y-316-D also showed very little effect. SXESRIMgRTAL RETAILS A tabulation follows. The times of washing on these yellows were: { 43452 Y-359D( 43490 { 43565 ( 4355? 1hour 20 min. 10 - - 30 - - 20 y-299-B( 43386 lhour 4 min. ( 43647 1 40 Y-316--D 43423 1 10 'tf'W ; DUP050315800 3t 2. rubout Ini: mill test Break- (1) t s . standard mix body length flow down Code lot (2] vs. control ciig.' ' ' ' Vs better Y-359-2> 43428 (1) t s dk, s.red, t s red thin- OK 0.01 OK control 0K red 2:45 ner t t s better 43452 (1) s.dk&drty,OK,OK, * OK P.W. s.red,TS drty * t s worse {2)s.drty;Ts drty; s.str equal lightfastness 43477 (1)t s dk&chg;s.gr;str. control green & cl. t s worse 43490 (l)drty.chg, s.gr; str P.W. green & clean <2)s.drty; OK; t s str; t s gm, Itfastness 5:50 9:45 s.hry * s.short 0.34 OK 0.35 * $> OS lightfastness 43535 (1)t t s red ehg; t s wk; 4:55 TS soft * 0.03 eohtrol t t s wk, t s red OK lightfastness 43565 (l)dty,ehg 3:05 TS hry * 0.06 P.W. s.dk&gr, t s str; s.str.,s.gr. (2)s.drty;drty;s.str; t s grn, =ltfastness t t s worse 43561 (1)t s flat chg;s.gr; 5:15 t t s hry control s.str,s.grn t s worse 43557 drty.chg. 7:30 heaTy P.W. (1) a.dk,gr; s.gr, str., gr (2) s.drty; s.str; t s str s.grn, Itfastness " " 0.08 * 0.16 * VB W0TS8 Y-299-D 43385 (l) lt.gr.chg,gr,-,-, 1:30 t s soft 9 0.11 " . X? control * 43386 (1) * " 1:25 * 9 0.04 9 P.W. OK Itfastness (2)t s el$TT8 red, OK, t t s wk, t s red t s worse 43448 (1) lt.gr.chg,gr,-, control 1:45 43467 (1) * * 1:20 P.W. (2}t t s dk&drty; t t s grn; t t s str; t t s green * lightfastness * n9 9 0.08 *> * ' DUP050315801 /r^r 3* Codie ruboftt (l) t s standard lot (2i t s control mix lift mill test Breakbody length flow down OK lightfastness y-316-D 43410 {1)t t s It&dty; vs gr, t s str 3*30 hvy. control s.grn 4 drty OK none OK vys worse 43423 (1) chg.vs gr&dty; t s cl; P*W* t s str; s.clean 2*40 s.hvy. * & (2) v t s red; OK; vrs str; OK equal lightfastness .sir. w: DUP050315802 PIGMENT COLOR RESEARCH REPORT ISSDIUM YELLOW Y 359 D ss--ft' *r SUBMITTED BY: APPROVED BY FILE: CHROME YELLOW DATE: MAX' 1935 INTRODUCTION Plant production of tills color was continued under the supervision of the Development Staff. The production was generally satisfactory, except far a few batches which were slightly below standard in their tinctorial proper ties. All batches were satisfactory in lithographic re sistance. The tendency toward a slightly darker, dirtier shade seems to be due to a lower acidity of the lead ni trate solution. An effort was made to correct this by addition of a small amount of Hydrochloric acid to the sodium chromate solution; this results in cleaner, brighter material of better lightfastness. All batches were made with lead nitrate solution made from pig lead. SUMMARY & CONCLUSION Seventeen batches were struck during this month. Fourteen were made on the modified standard formula; six of these ended with a final Ph of 8-8.2 (Ph of 7.8 being normal). The batches with higher final Ph were v.s. to s. darker and dirtier in masstone and vs to vvs worse in light fastness. Three batches were made with the addition of a small amount of Hydrochloric Acid added to the sodium chromate lowering the final Ph to 6.2-6.7; cleaner brighter material of better lightfastness was obtained. The best condition for this color seems to be a final Ph'close to the neutral point as at a Ph of 6.7 material of superior cleanliness and good strength was obtained whereas a higher acidity seems to he detrimental to the strength. Tabulation of plant batches attached: Details N.B. 448 page 73-74 '-gf-Tg.--- ................................ ,fesstf*' DUP050315803 a.green a.worse w a red equal vs green vs s tr. s .s tr. vs drty vs s tr equal w s s tr. vs s tr. d irty ,v s grn vvs red rvs clean w s clean I 1 u bO h 0 O o *4 os ft ft s ft ft ft ft ft ft ft i X P SS 3 X H U Q <0 Jh Ip {* O p 14 p0 p P a t4 ea a 0 t4 P UP if fa +3 O bO X H 1 J Vi C o ft X > * 43 rH e 00 30 > > 0* > > > > O P0 p > )ft P > PX e > >X 43 J* c H e-* * > c fe ft ft 0 E E0 s 0 0 fc *0 {4 *4 rH 0 00 to b0 rH O rH *4 O t O &o n rH u F > >> b0 O bO ai t cinn cio X CO rl O U * CO rH X^ rl Q 0 o> 3 CO *>!< rH CO X} p p CO 0 s p ft 43 *N ft +3 > a CO > ft a 0u 2X p rH 3 0 > & > 0 U b0 m X bO 0 rl *rt *o u3 > OS 0 rH nO a 1 X ofi u C4 o o u + >* >4 P P4 u X3 * at X X TJ > p 0 tc M rl 0 O 04 ft ft > > xi (4 + CO fc- to u 0p ue p > 0' if a > 0 rH O s > >* X P SU 0 u ft 3 Tj *15 d a u bO U ? > > a {> > >. > /-s ^ ++ + 0 s = CO + CO ++ tf # u p* u p ft ft rH 0 0 ft P > m > > C31 > 0 0 li t t* 0 u h0 > > X 0 + ++ 0 u bO * >* P bO *rl X O > - ++ 0 0$ rH E OP > > rH O p # C TO X *G a + 0 0 rH rH O O a rH 0 O rH t O P #v up X rH a ++ t- W CO 03 fc- f * 33 00 t> GO 10 to iH s Oto sft* *4 ft E0atDH H M t ft ft ft ft CtoO Cto3 0to 000 0m i<no 0e- 0to ft 0b- at ft CoO> ft 0o> s s s C01O s ft ft ft s & TS iO-<s3S +a3t +u3 rH o fc<X03 O orH S3 O -oH ixss o* aX: Hx 0 ort OorH pp & $014 T3 0 o X tft CicnOo X rCHO at tcno 0 * s ft s e S s sts c 0 o orH 0 XA rl O rH *CodO O O r~i 5 wso > ^ *M 010 V* S* o O OC7 00 fits 3S ft s ft ft hi 20; p0 CmmO co X tUCoO) inn CO rmVHO t*t Oe1wv0t C0cVOoO 0Ct5oOj*t cCtcoOah 0SC142OO10 t0CV>2OO Eit0n-0- bc0rtHo-s 0f<riH~00 CO 0 3.0 SCO ofirn> CtiOt oCxO C^O rOH pu 0ibnco tc0no tj <0 0CO VF Crossraounts 43958 v s . 43957 44036 v s .43957 44035 va .44036 DUP050315804 PIGMENT COLOR RESEARCH REPORT PRIMROSE YELLOW SUBMITTED BY: ?iAPPROVED BY: FILE: 8HR0HE YELLOW DATE: May 1935 INTRODUCTION A Plant trial based on CS 7888 made last month re sulted in red and strong material, presumably due to ab normal drying conditions* Another trial was made in Hay which also resulted in offshade material, in spite of normal drying conditions. SUMMARY & CONCLUSION The operation on the trial batch made during this month was normal; drying was done in the plant, Proctor & Schwartz Dryer, regulated to a temperature of 140F with relative humidity of 20$ the color was in the dryer for 44 hours. A drying study with plant press cake of this hatch was made in the Semi Works in the Proctor & Schwartz Ex perimental Dryer with the same temperature adjustment as on the Plant Dryer. The material was partly dried on paper covered wire tr*ys and partly the usual way on Aluminum pans. The plant dried material as well as the one dried in the experimental dryer was offshade. The material dried on wire trays was vs green and light versus control but still much redder vs CS 7888. Semi Works batches made on the CS 7888 formula were satisfactorily dried in the experimental dryer at the temperature of 140F and relative humidity regulations of 20$. An explanation may be found in the speed of drying vsfci ch was faster in the case of the Semi Works batches (26 - 28 hours) as these batches filled only two trays whereas in the case of the plant batch the drying period was over 4 0 hours. Because of the extreme sensitivity of this Yellow to drying, further study was recommended in the Research Laboratory* EXPERIMENTAL DETAILS - see notebook 448 page 138-139 -Ms**....... ............ ............... ................. WmBfe DUP050315805 3^*6? SUHSITTED BY: APPROVED BY: PIGMENT COLOR RESEARCH REPORT EXCEL5I OR YELLOW CS 7905 *./// FILE: CSRqg'B-TfflttPWB DATE: MAY 1935 INTRODUCTION Development of a new Chrome Yellow begun in May was continued in the Semi '`forks and several batches were tried in the plant* Results were promising and the work will be continued. SUMMARY & COKC IDS ION A Semi kforks batch using lead nitrate liquor instead of crystals was satisfactory, being close to the laboratory product tinctoriaily and satisfactory in lithographic re- ' sistance. Three plant batches were made, varying the develop ment temperature from 150F to room temperature. This re sulted in little or no change in the product; omitting the development may have decreased the lightfastness. Part of a batch was left in the filter press overnight, instead of putting into the dryer immediately]? this did not affect the quality. All of the plant batches were redder in masstone and tirif*`thsn the Semi 'forks product. EXPERIMENTAL DETAILS - notebook 448 p. 30 A tabulation follows* , u .HSksl DUP050315806 i H p o s <a *4 ** 3d 2d * 3d id id S3 . H O D o p at a S3 oD ooO O u H U b0 P d H | Si S. P u p Si Si 9 ot =5 P1 E P CO pP p Id id s s to o o o o J t St *H d i*sj J3 a *3 c m S3 O n3 i-f -CJ -a S3 s- U d P >i S* P Si id o > H u U > St - > a rH > S* Si CO 13 P S* P CO O p u p vs id Si p o Si >p >m O ^ Si rao 3 04 ,3 o5 'd Si T5 S3 J=> > & > TJ to u E p o u p u * 03 pH O K CO + fbOt g OK a * Si 'C Si o id o a Si H e u3 E d ts -- >* 2 +* E d c > S. Q tj fr. Si 03 d H u T3 T3 d a ta tn ti * m> i--I >> o T3 iH Si 9s S* b0 T3 tt Si fcO p $ p Si o 09 o 'd OJ d bO O O' d E Si C- o (&S Si rl > 1 "5 CO 1 CO CO 0 o> t** 1 to o d ^ g PS033 O t. I P fS3 CO 33 r-J d S. LO P* d p a 4 w cn R p H H o H G> tn -P H nod a SCOt 43E-* 3 'H <D o 02 1 >3 * &3 at t. St <D O S# & P. p *iH ) i 6h p _ HP Si *0 Cw p do o tn rH CO (=X CO 1 o O' t~ o 1 CO 1 >< s E a o to _ +Se>i -sbHo Ud 43 as m t3 o tn p, as t s to es it V> 4a3) -H SpB,W -. 13 l i--(3I 1c o rH op *4 o ja, So3 p3d3 C4 tn a> d* 1 rl 1 E !o P Si Pi d o dp E o o* o K rH p rH o CjJ O EO O & CO CO O t> o P d s, EP cO S ^sl CO P CO Si o p c- 1 p> E CO 3 rH E O. O CO -3H3 CO wQ ol o CO O' t- pH o J CO CO m CO d* 1 > E rH a tn 03 > O rH rH rH 4 tn * P"> 3O .Q rH rH 00 rH O 00 p CQ T3 P d >H-4 E2 frr-i o> CO 1** a t- t> 1 rH rH O' o o> o CO CO CO -3t rurt 13 St P o 5 CO tn CO P rH E O' bO E CO *rH P ^ Si Si *w > P O O rH rl P P <H Si Vi d E rH -rH s oCO & P E E bO CO E rH rl CO P CO d E H a iH 'H rH r-3 ccno o <# 5** =M= DUP050315807 PIGMENT COLOR RESEARCH- REPORT STUD! OF LEAD CYANAMIDE SUBMITTED BY APPROVED BY: FILE: eHROME YELLOW DATE: MAY 1931 INTRODUCTION Several experiments were run in an attempt to dup licate B-1979 or D-1980,samples of lead cyanamide supplied by the R. & H. Chemicals Division. SUMMARY & CONCnJSION It was found that the use of an excess of Calcium Cyanamide was necessary to obtain the yield and appearance obtained by the R. & H. Laboratory. Apparently complete extraction of the Crude Cyanamide did not result after several hours stirring possibly due to incomplete wetting, A sample of the best material obtained was sent to the Experimental Station for test as a possible rust inhibitive pigment. EXPERIMENTAL DETAILS - see notebook 453 Experiments 51, 52. Preparation of lead cyanamide from calcium cyanamide. Results: The best products were obtained what a considerable excess of Calcium Cyanamide was used. r'" DUP050315808 PIGMENT COLOR RESEARCH REPORT STUD! OF Y0-56-D PROCESS SUBMITTED BIl APPROVED BY: FILE: -CimONE ORANGE DATE: MAY 1955 INTRODUCTION A general study of the Yo-38-D process has been started. Some progress has been made and the work is being continued as rapidly as possible. SUMMARY & CONCLUSION A stucfy has been made of the effect of numerous variables on the Yo-38-D process. The usual method of changing the shade is to vary the amount of bicarbonate used since the latter depends on the amount of lead in solution at the time of the strike. In the standard pro cess the bicarbonate is added dry and the base is then stirred for forty-five minutes. The amount of soluble lead decreases during the stirring period and may not reach a constant amount. he amount of Acetic -a-cid in the lead liquor must of course, be considered, when sufficient bicarbonate is added to precipitate all of the lead a further increase in bicarbonate has only a slight effect. The strike temperature has only a slight effect on the final product. As the strike temperature increases the depth of masstone decreases slightly. The temperature of formation of the base is more important. the temp erature increases the depth decreases. The addition of acid or alkali to the bichromate solution results under some conditions in a considerable increase in depth. When a considerable amount of acid or alkali is added with the bichromate it may be inecessary to increase the quantity of bichromate used. A possible control on Y0-38-D might be. a test for the amount of lead in solution before the strike. EXPERIMENTAL DETAILS - see notebook 421. Experiment 34. Effect of varying the bicarbonate on Y0-38-D Results: Experiment off because of use of insufficient stirring period after bicarbonate. Experiment 35. Results: Use of dissolved bicarbonate and effect of striking the base cold and then heating. Striking the base cold results in a darker masstone than when the base is struck at an elevated temperature. Using a bicarbonate DUP050315809 -2- Experiments 36,38,39. Study of effect of strike tempera ture. Results: Increasing the strike temperature lightens the mas stone. Experiment 37. Effect of slight variations In bicarbonete. Results* Slight variations effective only where the lead is in completely precipitated by the bicarbonate. Experiment 40. Further study of strike temperature. Results* Temperature of formation of base seems more im portant than strike temperature. Experiments 41,42,43. Effect of using a mixture if bi carbonate and soda ash in the preparation of the base. Results: The use of soda ash results in a somewhat duller pigment. Experiments, 44,45. Modification of the 10-260-0 process to give Y0-38-D. Results* Modifying the 10-260-D process results in dark but changeable products. Experiment 46. Effeot of developing over a two hour period vs 20 min. Results* Heating for a long period results in a light some what dull oigment. Experiments, 47,48,49. Effect of using small amounts of Acetic Nitric and sulphuric acid in the strike solu tion. Results: The results were irregular but no products equal to Y0-38-D were obtained. Experiment 5o. Use of dry versus issolved bicarbonate. Results* The use of dry bicarbonate seems to offer no ad vantage over dissolved bicarbonate. Experiments 51,58,53,54. Study of the use of sodium chroma and of mixtures of sodium chromate and bichromate. Results: The use of appreciable amounts of sodium chromate tends to give a very dark weak pigment. Experiments 55,56. Effect of acetic acid added after develop ment and of a short development period. Results: -acetic -acid after development had no effect. A short development results in a slightly darker masstone. . c -5 DUP050315810 PIGMENT COLOR RESEARCH REPORT 3 S'-/ 91 IRON BLUE YIELDS SUBMITTED BY: APPROVED BY: INTRODUCTION czLc**-- v r- A/3 PILE* IROIT BEtflS DATS: MAY-1935 A laboratory study has been completed on the yields of both the B-6-B and PB-6-D types of soluble blue. SUMMARY & CONCLUSIONS The studies on B-6-D gave very consistent figures and a yield very close to the book value. In the case of PB-6-D the agreement was not as close and the final average figure was about 2.5^ less than the estimate. The method used in reaching these conclusions is explained below in considerable detail. According to our standard formulas, soluble blue is made by treating pulp equivalent to 500 lbs. 3-63-D ("100?^ basis") with 1S5 pounds of dispersing material,- Y.P.S. (and a little sulfuric acid) in the case of B-6-D; ammonium oxalate in the case of PB-6-D. The yield is estimated at 625 lbs. in each case. In the laboratory, pulp equivalent to 125 grams "100^ blue" was used for each experiment. The necessary weight was determined by simply drying a sample at 1403P. The dried "lOO^" material was analyzed by toluene distillation and found to contain 3.5% water. *In other words, the 125 grams represented material similar to the usual' run of B-63-D and corresponded to 120.6 grams of "dry basis material". The conversion was carried out by simple mechanical stirring of the mixture and drying {with the jar and paddles) at 140 CP, The re sulting blues were in general somewhat low in moisture (toluene dis tillation) compared with standard but OK in solubility and fairly close in color by rubout. B-6-P - (YPS type) TPS was analyzed by toluene distillation and found to contain 56,65% H20, and this figure is used below. (The theory for KaAFefCN)* 10 H2O is'37,5%), Standard B-6-D (SD-46846) was found to contain 8.82>s H2O. The theoretical yield is estimated as follows: 100# Blue* YPS 100^ H2SG4 Weights used T These represent 31.5 ordinary dry 1.0 Weights as 157.5 given in for mula Weights on anhydrous basis ISoTe 20.0 1.0 141.6 BIWUICT* DUP050315811 2 Experiment number 468- ID 2A 2B 2C 2D Weight of product ~155.5 152.5 152.0 150.0 153.5 $ HsO by Yield on distillation dry basis 9.0 141.5 7.2 141.5 6.9 141.5 5.8 141.3 7.6 141.8 Avg. 14175 Yield at 8.8$ H20 ...155'. 4 155.4 155.4 155.1 155.7 155.5 For 500 15s. of "100$ blue" (containing however 3.5$ H20) the yieia is therefore 622 lbs. of soluble blue of 8.8$ H2O content. This substantially confirms the present estimate - 625 lbs. te- FB-6-D (Oxalate type) Ammonitim oxalate was analyzed by toluene distillation and found to contain 12.7$ HsO, a figure practically identical with the theor etical one for (EEte)2C2O4.H2O. Standard PB-6-D (SD-46888) was found to contain 5.39$ H2C. The theoretical yield is estimated as follows: Blue Oxalate Weights used 125 ) as with B-6-D 31.5) these represent 156.5 ordinary dry weights as given in the formula Weights on anhydrous basis l5oT6 27.5 148.1 Experiment Weight of $ H2O by Yield on Yield at Humber product distillation dry basis 5.4$ HsO 468 - 1A 152.0 4.3 145.5 153.9 LB 147.0 4.0 141.0 149.0 . * 7A 153.5 4.0 147.4 155.9 ?B 152.0 7C 148.5 4.6 3.2 145.0 143.8 153.3 152.0 7D 148.0 3.4 143.0 151.0 Avg. 144.3 152.5 For 500 lbs. of 1100$ blue" (containing however 3.5$ H2O) yield is therefore 610 lbs. of soluble blue of 5.4$ water content or about 2.5$ less than the estimated figure of 625 lbs. This is be lieved due to a loss of ammonium oxalate in the drying operation. It was observed in the toluene distillation of blues of this type that an appreciable amount of the latter salt was carried up with the vapors and deposited in the condenser. BXEBHIMMTAL DETAILS See notebook #468, Expts. 1, 2, 7. aS8SB. DUP050315812 3 Readings (rttbout) t s . B-6-D SD-46846 3D vs light as. TTS light 2B t t s light 2C y s light 2D vs light ws red vs green ft U ft vvs wk vs strong II t* .*/ Reddings vsi, PB-6 -D SD-46888 1A vs dark IB vs red 7A ws dark 7B w 7C ' 7D ft vs green vs red vs green vs clean ws dirty ws dirty vs strong si. weak si. strong si.weak si.strong vs strong Solubility OK on all. r '"v ' DUP050315813 PI GHENT CC1DB RESEARCH REPORT STUDY OF IRON BHJB5 SUBMITTED BY APPROVED BY SL/3 FILE: IRON-.BLUBS DATE: MAY 1935 INTRODUCTION The general study of iron blue pigments was con cluded during the past month. The information obtained may be useful in future work. SUMMARY & CONCLUSION During the previous month the effect of different oxidizing agents, of different amounts of Copperas, and of Acid in the Copperas solution, was studied. A study of the use of ammonium sulphate in the copperas solution was concluded during the past month. It appears that ammonium ferrous ferroeyanide is much less soluble than sodium ferrous ferroeyanide and in the presence of suf ficient ammonium sulphate it is probable that only a negligible amount of sodium fenous ferroeyanide is formed. It is probable that hydrogen ferrous ferroeyan ide is likewise present in only small amounts. Ferrous ferrous ferroeyanide Fe2Fe(CN)6 is apparently of the same order of solubility as ammonium ferrous ferroeyanide. The quantity of acid added after the strike in fluences the strength and if large amounts are used the masstone is altered. The strength increases with in crease in acid to an optimum probably without much change in masstone. Treatments with oil of iron blue pigments having a hard texture and low strength failed to result in an appreciable increase in strength indicating there is no direct connection between strength and texture. The possible effect of various substances on the particle size, shape and composition of iron blue was investigated. No marked changes in tinctorial properties were observed. It is possible that because of the small particle size of the iron blue pigments large changes in size or shape of the pigment or a change in compsdftiiLon will cause only a small change ir. tinctorial properties. FTPERIMSNTAL DETAILS - see notebooks 376 and 468 Experiment 376-76. Effect of various amounts ofsuluhuric acid. Results* The strength increases with an increas in the sulphuric acid. IRON BLUBS Experiment 376-77. Effect of various amounts of ammonium sulphate and copperas. Results* The white precipitate appears to consist almost entirely of ammonium ferrous ferrocyanide. Additional copperas had little effect. Experiment 376-79. Effect of Mazoot Oil on a hard texture blue. Results* The'use of Mazoot On aid not result in an appre ciable increase in strength. Experiments 468-3-4-6. Effect of various substances such as salt, sodium phosphate, potassium thiocyanate, hydroxylamine, hydrazine, etc. on iron blues. Results* Only slight tinctorial changes were noted. DUP050315815 PIGMENT COLOR RESEARCH REPORT TREATMENTS TO IMPROVE PLOW OR PIGIEHTS 30'-/7>' ifl SUBKITTED BY: APPROVED BY <5R/z &L~.-L. PILE: PILE: PIGMENT TRC^TIENT TREAT ILC- AGENTS DATE: MAY- 1935 INTRODUCTIOR The study of the effect of various treating agents on the flow of inks was continued during the month. The effect of Glucamine and Methyl Glucamine on the flow of RT-283-D was investigated, Doth alone and in combination with Barium Hydrate. SUMMARY & CONCLUSIONS 3arium Hydrate was more effective in producing flow than either Glucamine or Methyl Glucamine. Mixtures of Barium Hydrate with these compounds were less effective, "ethyl Glucamine v/as not as effective as Glucamine. It is expected that the effect of these agents will be much greater on Lithols than Duols. Both will be tried in RT-364-D in con junction with Barium Hydrate. EXPERIMENTAL DETAILS Experimental Details are covered in N.3. 458-4 and inlc grind 3034. DUP050315816 PIGMENT COLOR RESEARCH RSPORT DRY DISPERSED COLORS 3-'/ >3 SUBMITTED BY: APFR07ED BY: -t M***?/ /6o FILE: PIGMENT-'TREATMENTS DATE: MAY 1935 IRT RODUCTION The study of the new process for preparing dry.dis persed colors of improved texture is being continued. No improvement has been obtained in the dry dispersed colors to date. SUMMARY & CONCLUSION Three dry dispersed colors Y-366-D, Y0-263-D, and Y-31B-D have been used during the last month in a study of a new process for preparing products of improved texture. The colors are treated with an emulsion of a volatile oil and then filtered and dried. In each case the treatment results in a dirty appearance the tinctorial change being most marked with a kerosene, triethanolanine oleate emul sion and probably least marked with a varnoline, triethan olanine oleate mixture. Preparation of a pigment oil mix ture by passing a mixture of pigment and volatile oil thru the colloid mill has somewhat les3 tinctorial effect. No improvement in dispersion was obtained in Y-366-D and Y0-263-D. With 1-318-D a very slight improvement was probably present. Since it apoears that the new process being investi gated cannot be applied to the inorganic dry dispersed colors it is proposed to continue the work using the organic dry dispersed colors. BXPERIMBHTAL DETAILS - see notebook 466 Experiments 4,5,6. Treatment of Y-318-D, Y0-263-D, and Y-366-D with emulsions of volatile mineral oils. Treatments of the same colors with volatile mineral oils in the colloid mill. Results i Only in the case of ^-318-D was even a slight im provement in dispersion obtained. In most cases a notice able decrease in strength and a more dirty masstone was obtained. DUP050315817 PIGMENT COLOR RESEARCH REPORT IMPROVEMENTS IN P. T. A. PIGMENTS SUBMITTED BY: APPROVED BY? FILE: DATE: A * 3. a- / J.T.A.riCMEMKT MAY 1935 INTRODUCTION An investigation was made of the possible formation of mixed crystals of potassium or ammonium phospho molyb date with the phosphomolybdates of Victoria Pure Blue BO and Victoria Green. Some evidence was obtained of mixed crystal formation. SUMMARY & CONCLUSION Several strikes were made in which a mixture of dye and potassium or ammonium salt were added to a phosphomolybdate solution. In the case of Victoria Pure Blue Bo and Victoria Green an increase i n strength was produced by the potassium and ammonium salts. EXPERIMENTAL DETAILS - see notebook 426 Experiments 58, 59. Effect of potassium and ammonium salts on the phosphomolybdates of Victoria Pure Blue BO and Victoria Green. Results ' In both cases an increase in strength was obtained thru the use of the -ootassium and ammonium salts. DUP050315818 PIGMENT COLOR RESEARCH REPORT BT-125-D & BT-150-D SUBMITTED BY: APPROVED BY: ^ Jl*S. 2-/ FILE: PTA riOMEiffS DATE: MAY 193 5 INTRODUCTION There was no production in the Semi works on these colors during the month. The results reported are those outstanding from last month's production. SUMMARY & CONCLUSION A satisfactory mix was made on the BT-150-D produc tion of last month consuming all the Semi Works manufacture together with 238# of plant sub-standard. Rubout results versus BT-150-D were as follows: s. dk.-vs green-2^ str. O.K. The two batches of BT-125-D (new) outstanding since last month were made checking Sw 6940, the temporary stand ard, except that a direct strike (BVA solution into dye) was used instead of a reverse strike (dye into FMVA solu tion) as formulated. This variable had no apparent effect by vat control results but both batches ground out weak versus SW 6940. More work will be done on this color as soon as equipment is available. Results on the BT-150-D mix are tabulated in Table I Results on the BT-125-D (new) are tabulated in Table II. EXPERIMENTAL DETAILS TABLE I - Notebook 408 page 9 2 Rubout results vs BT 150 D Std. Color Mix#Components______ ______ Mas stone Drawdown Str. Tint BT 150 D 4090) 6925(all)6934( all )6963( all)s.dk. vs green 2$str. O.K. 6f70(all)78#Lot 42635 4091) 82#lot 41911,78#Lot 41616, 17# DPG SW Lot 6989 6997 Yield Est. Lump 10# 30# 28# TABLE II - Notebook 408 pages 90-91 BT 125 D (new) Rubout Results vs SW 6940 Light Mas stone Drawdown Strength Tint Stability O.K. s. wk. vs worse vs clean finish O.K. wk. vs clean finish -v vs worse DUP050315819 35"-/^ PIGMENT COLOR RESEARCH REPORT PLANT PTA YIELD STUDIES SUBMITTED BY: C.J APPROVED BY: / *-/ FILE :PTA PIGMENTS DATE :MAY 1935 INTRODUCTION Work was continued during the month on the survey of plant PTA Toner yields. Production continued high with average yields fair hut individual batch yields remaining erratic. This yield study remains a survey of operating data with no attempt being made to improve these yields. SUMMARY & CONCLUSION Three batches of RT-389-D are reported this month including one held over from last month. The plant continues to re-estimate the yield downward without making an equivalent decrease in the formula size. Average yields are a trifle better than last month but still remain poor being 93-# based on plant estimated yield and 89-|$ based on corrected estimated yield. Tinctorial properties are satisfactory. Of the four batches of BT-1S5-D reported, two are outstanding from last month. Yields improved slightly averaging 94|$ of estimate an improvement of 6% over the yield of the last batch made. As reported last month, how ever, 100$ yields should be secured on this color as an average yield of 102ft of estimate was Secured in the Semi Works on batches one-half plant size. Tinctorial proper ties on the plant batches were satisfactory. Two batches of BT-96-D outstanding from last month gave a low average of 84ft of estimate a decrease of 7$ under the percent yield of the last batch made. Rubout results were satisfactory. Four batches of BT-92-D were made during the month. Fairly satisfactory yields were secured averaging 96$ of estimate an improvement of 1ft over last month. Quality was satisfactory. Three batches of BT-100-D were made during the month. Yields were satisfactory averaging practically 100ft of estimate. Quality was satisfactory. Yield and rubout results are tabulated in Table I. -at - ' .K: M, DUP050315820 & 2 EXPERIMENTAL DETAILS TABLE I N.B. 434 pages 51-54 Color Batch Yield $ of . Est. Lump Mas stonei Drawdown Str. Tint Remarks RT-329-D 43417 95(96) 96 1 43838 92(97) 88 99i 91 It 43865 92(97) 76 88i BT-125-D 43435 88 82 93 ft 43460 88 86 98 n 43706 ft. 43734 BT-96-D 43498 n 43522 BT-92-D 43546 43886 n 43907 n 43936 BT-100-D 43781 tf 43804 ft 43827 88 88 100 -88 76 86-g 68 50 73 68 64 94 96 91 95 96 96 100 96 . 96 100 96 86 89* 90 84 93i 90 92 iosi 90 93 103 g s it. It. It. It. gray It.green It. gray vs. dk. s.dk. s.dk. It.gray vs.dk. It.gray It.gray It.gray It. It. O.K. s.yel. total aver, yield of all hi. u bl. PTA toners for April 96. 8$ of Es t. bl. -- bl. Total aver* yield of all vs. vrk. s. wk. vs red PTa toners for May 93. 9f0 of ^st. vs.wk. vs.wk. vs red 2.9$ decrease for May under April O.K. s.str. vs green vs.str. s.str. vs clean v.bbl. str. v.bl. bl. s .str. bl. vs.green str. s.green vs.green s.str .s.green wk. wk. green wk. wk. s.green s .str. s.str . red & red green s.wk. green green O.K. green I DUP050315821 PlOMBHT COLOR BBSSARCH REPORT BT-122-S (h e w ) 3<r-/ ?7 SUBMITTED BY* APPROVED BY* PILE* PTJfc-TCfflBHS BATE* MAY-1935 IUTROPUCTIOK Production was started in the semi-Worlcs during the month on a new non-bleeding BT-122-D type color. Six batches were made, but results on only five of these are available. SUMMARY & CQHCLUSIOSS The first variable studied in the Semi-Works consisted of four batches* made increasing the dye gradually from the standard amount (426-40B formula) to a 12-1/2# increase in order to secure optimum strength, prom the results obtained it would appear that optimum strength is secured with the standard amount of dye or with less than a 5# increase as both the control batch and the batch made using a 5# increase in dye checked quite closely in strength. The last batch reported also made to check standard formula did not check the previous control batch, being v.v.s. weaker and distinct ly redder. All these batches were cleaner and weaker than the BT-122-D stan dard, and on treatment with 5# DPff the first two batches (control and 5# increase in dye) showed no ink bleed, while the batches made using a 10# and a 12-1/2# increase in dye together with the check to the control and the BT-122-D standard showed noticeable bleedd on varnish bleed tests* ~ Yields were satisfactory, averaging 105# of estimate. Work will be continued in the Semi Works on this color inai effort to produce strong material for shading. Results are tabulated in Table I. DUP050315822 09 evO- t CO <0 <0 bO aPi oco ta * S3 I xl i-9 Hco H >1 (0 &3 e>t > I c* C9 CO w Q9 CO cvt CcO cS t, -g n > 1^8 O + O <9 Cft r^OH >SH3 O rH OM d H 43 O P d rH X> s t* w 3 rH 43 r} 4b s* + > *P 'g^ g 5 ta b *d {2 4* s3 a ? r h -cpo t CQ s 43 T< 5 <5* 3 I* H a a H >_ CO TO3 5g S 'Ll ri > il r-i H O *n II S 9 <H Og * o OS g S3 4sO3 -g d d f n H 3 OO *Edh CO ft I *1 CM H m i'. -' .v:J i>. 0 >e; DUP050315823 PIGMENT COLOR RES3ARCH REPORT s SUBMITTED BY APPROVED BY: GRINDING OP PULPS // ^ * PILE: MPO . GTUB IBS' DATE: MAY- 1935 INTRODUCTION Two semi-works batches of RT-126-P were ground through the 12" LliRropulverizer during the month. One hatch each of Y-73-P and Y-81-P were ground through the Straub mill to decrease lumpiness in the pulp. SUMMARY AND CONCLUSIONS The first hatch of RT-126-P was ground satisfactorily, and one third of it subsequently reground with the next batch to give the reouired tinctorial properties. The two plant lots, Y-78-? and Y-81-P were ground satisfactor ily through the Straub mill. EXPERIMENTAL DETAILS See N.B. 291, pp. 77-78. DUP050315824 PIGMENT COLOB RESEARCH REPORT > 5i PREPARATION OF ALUMINA HYDRATE IKK NRCM PULP / /b-- SUBMITTED BY: /Ur-) * m APPROVED BY: PI IB: ALUMINA irjDRATB DATE: MAY- 1935 INTRODUCTION A small amount of work was carried out, continuing that reported in September 1934. The results were not satisfactory. s u i;:.`a ,y & c o n c l u s io n s Earlier work had shown the following: 1) Drying a hydrate-varnish-water mixture is objectionable be cause of a tendency to body. 2) Colloid milling of pulp Tarnish mixture develops heat and a tendency for the ink to body. It was believed that a procedure might be used comprising mixing the correct proportion of pulp and varnish, filtering to as dry a cake as possible, and working out the rest of the water on the ink mill. This was tried but the results T/ere not promising. No further work is planned on this problem. A review of all the past studies appears to indicate that the preparation of a flushed hydrate ink will involve one or all of the following: A special strike or special vehicles. Use of transfer agents. Pressing the pulp to a very high solid content. Use of special equipment (e.g. vacuum mixer) for the transfer. Avoidance of high temperatures. EXPERIMENTAL DETAILS Notebook 360-33. NL pulp from Philadelphia 10-15* solids. 400 - 800 gram portions mixed with 100 grams #0 Transparent Varnish and filtered to as dry a cake as possible. With less than S00 grams, the oil tended to separate. The sample of hydrate-oil-water from 800 grams of pulp was homo geneous and was run over a cold mill but a "whipped cream* emulsion was formed which would not break. DUP050315825 PIGM3M1 COLOR RESEARCH REPORT 34T-/re> n par a c h l o r o r t h o n it r ah iiik e fcs-78731 SUBMITTED BY* APPROVED BY* IKTRCDUCTION BETA KAPHTHOL a*/- *y 7h e : ;gac.--geMsts- DATE: KAY- 1935 Some additional studies were carried out in the laboratory on C3-7"73 (para chlor ortho nitraniline - beta naphthol) for the purpose of increasing the diazotisation efficiency of the formula. SUT.O'.AKY & CONCLUSIONS The original 03-7873 formula included a diazo clarifica.tion with norit and filtercel. However when semi-works development was started, it was thought advisable to attempt to eliminate this step since it resulted in loss of time and additional handlin' of the diazo. On allowing the diazo to settle, it was found that the residue amounted to about 4$ (on the basis of the P.C,0.lx .A.) and that it settled quite rapidly and that the supernatant liquid was quite clear. Consequently a study was made in the laboratory to determine the effect of higher temperature of diazotisation both upon the amount of residue and upon the tinctorial properties. Higher temperatures of diazotisation had the effect of decreas ing the amount of residue and at the same time had an almost negli gible effect upon tinctorial properties. Diasotising at 10cC instead of OcC decreased the residue from 51 to 2d; 20cC decreased the residue further to about 0.2%. Slower addition of nitrite (30 minutes) resulted in a slight reduction in residue. Reducing the time of stirring, after the addition of nitrite, from 2 hours to 1 hour gave an increase in residue. However, a com bination of aLower addition of nitrite and less time of stirring (20cC diazotisation) gave a small amount of residue (0.34$). This latter method, including a 20rC diazotisation, 30 minute addition of nitrite, and a 1 hour stirring period, was selected for semi-works trial. EXPERIKEIJTAL DETAILS Notebook So. 219 Series S19-64 tried diazotisation at O'C, 10cC, 20cC. All colors were practical checks to each other. 0cC gave 5.1J residue? 10'C gave 2.2%% 20C gave 0.2-1. Series 219-65 was a study of time of diazotisation and time of nitrite addition. The effect on the colors was practically negligible. 20C diazo - 2 hr. stirring - quic2< addition of nitrite - 0.17,1 residue " " " nitrite added in l/2 hour - 0.10j " " 1 hr. " quick addition of nitrite - 0.88,1 " nitrite added in 1/2 hour - o.34;1 DUP050315826 & 3 PIGMENT COLOR RESEARCH REPORT TOLUIDINE TONER RT-232-D, RT-349-D, RT-200-D SUBMITTED BY: (jjtMxXck. APPROVED B a */ V FILE; -TOLUI BINES' DATE; May 193 5 INTRODUCTION A study of the manufacture of Toluidines was made in the plant this month. Lack of strength or lack of depth has characterized recent production of this color. The type of diazo and method of drying were observed and some variations were made in these conditions and in the coupling in order to obtain material closer to standard. Seven batches of RT-232-D, two of RT-349-D and two of RT-2G0-D were made. SUMMARY & CONCLUSION While it is not yet possible to determine the cause of the weakness being obtained, there is fairly positive evidence from the present series and from past work that drying conditions can be regulated so as to pre vent much of the loss in strength. The drop in strength between a press cake sample dried in the laboratory dryer and a lump sample from the plant Brick Dryer mounts to at least 5%, In the Proctor & Schwartz Driers at a temperature of 155F^ wo noticeable improvement was obtained but at 140F the loss in strength was very slight. As results ere based on a few batches of RT-232-D further study is required. How ever laboratory tests show that overdrying causes weakness and blueness and this is very likely to occur under the usual drying conditions obtaining in the Brick Dryers. One batch of RT-232-D and both batches of RT-349-D to which additional Para Soap was added, before pressing, appeared to have increased stability during drying. Increasing the speed of agitation during coupl ing from 12 to 20 RIM did not show a definite improvement but is nevertheless a desirable change. Use of Mono Acid L was effective in obtaining Increased depth in both RT-232-D and RT-349-D but dia not give the additional strength desired. DUP050315827 2 The current lot of MNPT (Lot 420) gives satis factory diazos with only a relatively small amount of sediment. Addition of nitrite in 10 minutes instead of 1/2 hour did not improve the appearance of the diazo or of the finished product, A small mix of RT-232-D has been made using the batch dried at 140F in the P & S Dryer. DUP050315828 E X P E R IM E N TA L D E T A IL S N .B .3 8 5 P . 1 3 0 <Js o CO 30 o <T J O .n rH ?n Q* H -H rH CM o ro O.o CO o ft- .o o rH H CO O O .-o c P 3 rH rH . & o rH a p rH O rH rH O 3 p A 3 rH Hn > > > H 43 > >* to >* CD >> > i* 44 to >> O n > r 24 M * M O &* uu p p b4 44 O > > & m rH rH P 8 rH P p o rH rH H rH > a 43 > m > > m > > >i > H P > >> 24 O > ja t> *8P X 00 bO rl P 42 p bj rl P 43 rH bO *5) H p 43 bO Jtt S Si P W P P Si P Si 43 JO 43 P rH H H *H rH * rH bO H > bo 4t H bO P > > > rH > rH > H H c u S- v Pi > > Xs Pc S3 ^5 Si o %ocr * m 44 oo 4* t> rH O1 rl rH *H O u Si ^ t* CUP )*o rH CO rH 3 2SU? > * uQ > 44 O i O iP O H rH * 8 8* CS CQ +1 23 +erf 00 rH (T> n P H bO C rH -H O Si S. P 43 Oh rH fea p b( P 0 rl rl S3 rl Po 43 1) faOP CO T3 O C O P H to Pi P B & Jo ti in 3 mo rH a p 0 iH *rH rl H T3 I *P *c cd bl Pi ti O Pp O rH O P 33 N -4 Q TJ *H H O fe o 3 *H P p 3 P 45 S* oo o * O t, ^ CO O Si o in CO c ft- S= ffl Pi tsbO s sSi P rH a o &S W S3 O O o> P 43 * rt _ a *2 p ffi 3 as P *0 03 *2 ^rH P M bl P S3 H o P JO &i U o rH a a TJ p fcf *0 r*Hte Oo a * rH P P p oo 8<rf P 43 P p P P p n a X! 3 o 43 *H 73 p fe P 43 0 43 JO o Oro* &p-rH O Tto3 co O42 43 43 P + rH 4* P O H 3 p C3 aP rH <o P 03 CO CM o 3 00 p S rH P O CO & CO rH O 'Cj* P H* 44 O 42 O rH ~ a 44 a U o p M O 'iH E M Oo o o t 43 ^ h 4^3 P1 4- &- o ^ i-3 S,, *H rl CO O P Si fc. ^ O p O H S p P bO P Si rl P * p 2 HN rH 1-3 H *H rH ,, rH 2 3Q tyst CT (C P> . $O |?f>c O to M H J3 -P -H O *S <C 00 M Qa g wC0O3 tcPo tr> CO CM CO IP tft 30 CO <0 ft- CO 00 CO Ok f* CO 3) 05 CO <* CO co CO rf4 Ci^O4 o o t> o in to o CO rH D CO E-i co 30 CO .6-J OCO' c* CO ftS H* oc! ol DUP050315829 SUBMITTED BY: APPROVED BY: S6~-/ * CJ PIGMENT COLOR .RESEARCH REPORT BT-242-D SlU A '/// FILE: DUCIS DATE: KAY 1935 INTRO DUCH OH Plant production was started during the month to secure yellow lav bronze shading material* total of four batches were made. Two batches of this color were made in the semi works to check the result of substitut ing Lithosol Acid TO 3F( a TOB type intermediate contain ing 4% Isomers) fctr Lithosol Acid TOB regular* SUMMARY & CONCLUSIONS The first plant batch was made to check SW 6982 except omitting the sodium phosphate in the coupling. This formula is a modified RT-242-D formulation using Sherwin Williams TOB and striking at 175F with subsequent development at a boil. A dark vs strong and yellow but very bronzy product was secured practically checking Semi Works results. In the next batch the caustic in the Beta Naphthol solution was lowered 5# to decrease the depth but the product remained dark, strong, yellow and very bronzy versus the standard. A 10# cut in rosin and addition of 6 pounds per mol of sodium phosphate in the coupling also resulted in dark, str. and s. yellow material with bronze showing little of any decrease. Finally a batch was made checking sw 6944 using duPcntTOB substituing B rosin for, 60# of the 1 rosin and gsing 8 pounds per mol of sodium phosphate in the coupling. The striking temperature remained at 1750F with subsequent development at a boil. The slurry control cn this batch was light O.K. strength and s. yellow, with satisfactory bronze versus the standard but on grinding gave light and muddy, a. weak and blue, vs dirty results the bronze re maining satisfactory. All of these batches except one of the dark, yellow high bronze products, have been consumed in a plant blend. Results are tabulated in Table I. The first Semi Works batch was made to check the SW 6982 formulation using all TOBF to replace the Sherwin Williams TOB. In the second batch TOB regular (_* 20#) was used to make weight on a check to the first formula except striking at a boil. Both of these batches were .ISS'T- } DUP050315830 2 light and muddy, vs strong, vs blue and dirty, and s high in bronze versus RT-242-B standard. From these results it would appear that this material gives a product not unlike that given by TOBy/ on this formulation. This product is therefore, unsatisfactory for use in entirely replacing TOB in the RT-242-'u formulation but the use of small amounts of TOBF will be studied to check the possibility of using it in the manufacture of material for shading purposes. Results are tabulated in Table II. DUP050315831 O EXPERIMENTAL DETAILS BATCH TOB N-7 IN AMT* ROSIN N-6 TABLE I RT 243 PLANT NB 433 pages 150-154 RUBOUT RESULTS VS RT 242 D S td . YIELD REMARKS CM X 03 <Q <o 1 44 C + *H xg --3 5 2 33 CM ** P H ro <3 t 44 2 u 5-S 13 O S3 iH 0* -P n aj <o *rl CO u xj* > M o -p -C3 Oc H5i fc3% I 2 44 P O t! 5 ?6 i 33 CO o 105 *o CM to o trH * EH tn in o co pa 10 M <o 1C0O sR in 10 J Jj p rH j V *5 Qtf (9 e-4 ^ ^ K rH M > i 2 H Ch K >* 8 pi > w8 rH O i-H ffl jz M * as > P Ua o P 2 a * ^ t s- > 03 > P >! H E-* > *3 N P CO P 3 P P o Oo t. U L. S rO aO 43 rH O r-H rH H rH 43 Bi r*i * U} > >i U > P 43 > as > > > a >> i o a e-< 44 44 44 g sQ Q a a *P 3 rH 1 I S 4 CO 03 1C- fcO1 O2 to 2 m in CO JH CO CM O CO 3r O CM Sr a> >^=sO CM CO I fc 2: rH 03 CQ CM # t CM lO C1M0 o CM -P 1"jS CO S CO S rH C EH 35 O S ia 9^ Ji ^ cu n CC W K 93 rH -0 rH He o <o s ro H4 rH 03 rH tn o to S 5CO * * rH CO o cw CM CO b* CO 6I- -Q3 r-t M bO as P* f* * s CM GO O(O* 4* fo&Sit3** o c* OPfc o CO >5 4o3 iCnO to <> rH rH $ 03 55 0cnH cm m e- CM & HCM4 >co H05 CO *SU331 HH &q as SB- BECC0 o S3 03 r4AH3 pH -O 93 > ao 5 > 3o tn x> fcrH S' CM CHM S fca o Eci btifn> in co H4 co Eh 3 Oft s 5 ob- 3Q 5a t a.high bronze except note ______________________________________________v a r ia tio n s AS DUP050315832 PIGMENT COLOR RESEARCH REPORT HT-599-D "~ SUHAITTED BY: > APPROVED BY: ' FILE: JTBS-MjeCHS DATE: MAX' 1935. INTRODUCTION Work has been resumed during the month on the improved non-bleeding RT-297-D type color whch has been coded RT-399-D. Tn this series of batches special lots of duPont Naphthanil BS were used to replace the General Dyestuffs Naphthanil BS as used in the standard formula tion (see January 1935 report). SUMMARY & CONCLUSION A total of from 0.2 mol batches were made during the month, two using duPont purified NBS loti and two us ing duPont specially treated NBS Lot 307. A batch from each of these two sets was split in half and one half treated with GT-69-P (Pigment Green & toner) to produce very dark material ftor shading. The second half of each of these batches remained untreated. The batches made with these two different lots of NBS were substantially the same resulting in products slightly light and bright with OK bleed in lacquer versus the standard RT-399-D. A satisfactory mix has been made using all of the straight batches together with a snail amount of the special dark shading material. This blend amounting to about 300 pounds of material was vs It. vs brown and satisfactory in bleed in lacquer versus the RT-399-D standard. Upwards of 60 pounds of dark shading material are still on hand and will be used up in subsequent mixes. Results are tabulated in Table T. DUP050315833 N B 441 pages 44-51 >3 ns rH XH * P T5 P to O' CTV CO Eh *0 OC w r-i > CQ p a c-* u $H O CTrH o .3 o p S3 H P Eh CO Jfl aP bC <3% ST uOk CO p Eh <o S3 03 t> o 1 Pd pH cd P so p 8 o 05 * Oh CO 40 If <d Eh O CQ P S o *4 S IS CQ in a> Ho o> rH in C4J X CM Hs B pT pH O pH Ok Oin* O*0' o 23 5* CM rH rT mt d* B f * I * u p p a tas5 Id OO >m id o ad *4 2d oo O O Up t jo JPu3 JO 3* E as p as p rH P rH uO> >9 * *C3 rH 'S s rH >> >* P rH rH Sh > > nHS tt* P u* P p > 1 11 P Bh *rt T3 -Q gi *H > p A t5 rH 'p a rH p > t* H T? U Ptt 1 > t 1 rH T3 Pi i< P JO rH J> >> rH >> Q > ad o rH > > ^ c TS JSt >1 4P S rH *rl J3 T3 U > >v P V. H TJ rH JO C p XI xlo&>i as s 085 S3 o M ab JH T3 XI TJ & * % Pu XI ts SC t o > pup t H H rH p fc- ^ PU rH> pH rH o o CO o SO ^ >o O fr~ roH 8 t- b- nS 3 -rt t s zs M *1 & p O rH 1 rt P CM r-l +> H rl rH *ts * Po rH rH H d H *4 v< H H o H o O % 3d. CO rl O b 8 H *H rH rH O P.'-- H O H CM H J- 3 Oi oSr CO P. w rH Sh d a. oa rH H t- t> CM p H &o A CQ Np^Ob- 04 CM r*> E CO i O rH 0 01- ^m O O b CO rr <H O Oo fr* 3 eo~ CM rH Ob" CO obrH- e- robH" rH O fr* rH rH 4* CM rH s Si 5s to B &5 X g a TABLE I EXPERIMENTAL DETAILS jy *+ DUP050315834 PIGM5KT COLOR RESEARCH REPORT PIG23MT RTJ3IK3 G'- AT-335599A-D #s--/ry SUBMITTED BY: APPROVED BY: IITTRODUCTIOB PIES: 1113 Q t TOUTJIfrS BATS: EY- 1935 The RT-359-D formula was studied further this month to brighten the masstone and to determine the factors which cause bronze in the printing tone of this pigment. -X1IARY & CONCLUSIONS It was found last month that a 50.'? reduction in para soap and total elimination of para soap gave brighter masstones and lower bronze. This month's studies were carried out on the basis of formula U33-SA-1 (no para soap). Decreasing the time of coupling from 20 minutes to 10 minutes gave a darker masstone and bluer tint, while increasing the time to 50 minutes was practically without effect. Elimination of sodium sulphite and increasing the amount 200;A in the strike had practically no effect. Increase in the excess of 3011 in the coupling tended to give lighter duller masstones, more bronze, less strength and yellower tints, A deficiency in BOB', giving rise to excess diazo, caused the masstone to become darker and browner. A 50;^ reduction in strontium nitrate gave lighter brighter masstones with slightly yellower tints. Strontium chloride was substituted satisfactorily for the ni trate salt. A 50% reduction in tine volume of strike gave a lighter duller masstone and less strength. A 100 - increase in volume was negligible in its effect. Ammonium chloride in the strike darkened the masstone and made the tint bluer. The general effect of increased temperature of strike was to lighten the masstone, increase the bronze, decrease the strength and to yellow the tint. Increase in the soda ash alkalinity of coupling and addition of soda ash to the soda salt before strike made the masstones lighter and duller and weakened the color slightly. Gradual neutralization of the soda salt with '-cetic acid tended to give lighter masstones, more bronze and yellower tints. However, upon making the soda salt slightly acid, the color went distinctly darker and bluer in tint. It was discovered that washing of the finished pigment increased the bronze. It was also found that baking of the color at 100cC gave n i' r~ DUP050315835 P 2 less bronze and that this lower bronze persisted even after rehumidify ing to about 4^ moisture content. The other properties were apparently unaffected. To briefly summarise the above, the following factors should be avoided in order to obtain brighter raasstones with very little change in strength and tint and less bronze: 1. Too high para soap content. 2. Too fast coupling. 3. Too high an excess of BON 4. Excess diazo in the coupling 5. Low volume of strike 6. Too high temperature of strike 7. Too high soda ash alkalinity of coupling. 8. Too much washing of finished pigment. 9. Too low temperature of drying. EXPERIMENTAL DETAILS Notebook No. 463. Series 463-7 studied the effect of variation in Strontium nitrate in formula 463-64-1 (no para soap). It was found that 10 g. strontium nitrate were required to com pletely precipitate an 0.05 mol coupling. The results also showed that a 50 m decrease (from 20 to 10) in strontium nitrate gave lighter and slightly brighter masstones, slightly -mellower tint and decreased yield. Series 463-8 studied effect of rate of coupling on 463-6A-1. Decreasing the time from 20 minutes to 10 minutes made the color darker and bluer. Increasing the time of coupling from 20 minutes to 60 minutes had very little effect. Series 463-9 studied variation in BON on formula 463-6A-1. A 2?S deficiency in BON. accompanied by excess diazo in the coupling, gave dark brown masstone and blue tint. Increase in BON from a Q% excess to a 22^ excess tended to give lighter duller masstones. bronsier printing tones, weaker and yellower tints, with no increase in yield. Series 463-10 tried to eliminate sodium sulfite from the strike; replaced strontium'"nitrate with strontium chloride and checked the effect of reducing the strontium nitrate by 50.U. Omitting the sodium, sulfite had a negligible effect. The effect of cuttin - the strontium nitrate 50 was checked; i.e. slightly lighter and yellower color. Strontium chloride gave a substantial check to the control. Series 463-11 studied the volume of strike; also checked the ef fect of strontium chloride. A 50^ reduction in volume gave light dull and slightly weaker color. A 100increase was practically without effect. Strontium chloride gav= a sati.factory check to the control. DUP050315836 3. K Series 465-13 tried the effect of increasing the soda ash both in the coupling and in. the strike. Increasing the soda ash either in the coupling or by adding to the soda salt resulted in lighter, slightly duller masstones and slightly weaker colors. Series 463-13 studied reduction in alkalinity of coupling. Inconclusive because of faulty control. Series 463-14 varied the sodium sulfite in method 463-SA-l; also studied effect of ammonium chloride in the strike. Increase in sodium sulfite from 2 g. to 6 g. made very little difference tinctorially. Ammonium chloride made the color slightly dark a nd blue. Series 463-15 studied the effect of gradually neutralizing the soda salt with acetic acid before striking. Gradual neutralization tended to give lighter masstones. more bronze and yellower tints. However, upon making the coupling sOLightly acid, the color became distinctly dark and blue. Series 463-16 studied temperature of strike (67c to 97cC). The~trend of increasing temperature of strike was lighter masstones, more bronze, decreased strength and yellower tints. Decreasing the temperature from 77cC to 67cC made the color browner, less bronzy and bluer. DUP050315837 PI GMT CO LOB RESEARCH REPORT PI CLIENT RUBINS TONER RT-359-D EXTMDED COLOR RE-590-D SUBMITTED APPROVED BY: a*a- as PILE; JgSC. TONERS DATS: MAY 1935 INTRODUCTION Three additional batches of RT-35otD were made in the Semi Works in continuation of the problem of improving brightness of this product. In the plant production of RE-390-D, the barytes ex tension of RT-359-D, was continued, four batches being made. SUMMARY & CONCLUSION All the Soai Works material was close to standard in tint but muddy in masstone. One batch was O.K.'d for ship ment. A 50# reduction in amount of Para soap which was $sed in all batches may be cf some help in reducing bronziness but appears to reduce stability in grinding with re sulting loss in strength. Lot 14 of P Chloraniline-M-sulphonic acid gave a ruddier masstone than Lot 13, checking Laboratory results in this respect. A combination of variables found to be beneficial in the laboratory showed pratically no improvement on finished grind altho the vat control was stronger and yellower . The changes made were increase in BoN excess and in coupling time and a reduction in amount of strontium nitrate used. Results obtained in the plant on RE-390-D were simi lar to those observed in the Sard Works in respect to muddi ness of masstone. However, if the proper tint and strength is obtained the former can probably be disregarded. Lot 13 of P.C.A.M.S.A. gave products of this type on two batches, one of which was O.K. to ship as is. An abnormally dark blue and dirty product was obtain ed with one barrel of P.C.A.M.S.A. labelled Lot 12 but analyzing 97.8# by nitrite value instead of 65 and 71# ob tained on other barrels. It was necessary to increase the batch size by 40# due to the higher analysis. The diazo has the appearance of being made from a different intermedi ate . DUP050315838 -2 ' / * A fire occurred while mixing one batch which was as cribed to poor was3rfagg.ar general instability of the pigment, the clay-like condition of the press cake probably makes thorough washing of this color difficult. However, RE-6Q57-D which is a 6$ extension of the same toner receives no working and does not show instability. EXPERIMENTAL DETAILS RT-359-D Semi works N.B. 351 P. 94 0.1 mol charges were made and dried in P&S Dryer at 140P - 40$ humidity. SW 7031 - 2xSW 6955 except reduce Para Soap 50$ P.C.A.M.S.A. Lot 12 vs RT 358 D vs dark muddy; OK; vvs wk; vvs bl & dirty sw 7035 - Check 7031 except use P.C.A.M.S.A. Lot 14 vs RT 359 D - s dark muddy;: vs yel; O.K. s. blue vs SW 7031 - muddy; s. bl & dirty; O.K.: s. blue SW 7060 - Like 7035 except 1) increase soda ash from 9.5 to 10# 2) Increase BoN from 20 to 21# Z) Couple in 1/2 hour instead of 20 min. 4) Reduce strontium nitrate from 40 to 30# vs RT 359 D s. dark muddy; vs yel; O.K.; s. dirty vs SW 7035 - O.K. O.K. vs str; vs yel. RE 390 D Plant N.B. 318 P. 27 43646 - check 42840. Caught fire in mixer, was wet and then redried in Brick Dryer. Va RE-390-D - dark; blue; strong; blue 43908 - check last. Error in analysis and probably in type of intermediate result ed in abnormsC product. Batch size increased 40$ due to use of too much P.C.A.M.S.A. Lot 12. Diazo-yellow in color with dark backwater, vs RE 390 D - dark brown dirty; blue strong and dirty. 43967 - check 43646 using P.C.A.M.S.A. Lot 13 vs RE-390-D - s. brown; s. yel; vs. strong; s. yellow 44001 - check last vs RE 390 - vs dark & brown; ws yel; ns str; vvs dirty DUP050315839 SUBMITTED BY: APPROVED BY: JS~- / <P -r/ PIGMENT COLOR RESEARCH REPORT IMPROVED FIRE TONES, CS 7875 . ULu 4j ~~**, * ** FILS: KIOO. TON MET DATE; MAY 19 35 INTRODUCTION Semi Works development of the Improved RT-208-D formula CS 7873 was begun in April. P-chlor-e-nitraniline is used in this type. Thirteen batches have been made.Variations from the laboratory formula were chiefly for the purpose of obtaining more complete diazotization. SUMMARY AND CONCLUSION The first Sami Works run In which the diaeo was clarified was too muddy in masstone. As this procedure involves too much handling of the diazo, it was omitted and the sediment was allowed to settle out with a result ing increase in brightness. No further improvement was obtained by reduction in amount of nitrite used. Use of the theoretical amount of nitrite and omission of urea resulted in an abnormal brown product. Brightness was slightly increased by adding extra acid to the diazo and reducing the amount used to precipitate the Beta Naphthol. In all the preceding cases the completed diazo solutions contained undiazotized sediment amounting in some cases to 4% of the weight of intermediate. It was found to be practicable to diazotize at a temperature of 68F instead of 32F. A clear diago was obtained with only a slight muddiness of masstone. At 50F, the diazo was slightly less clea r, but a slightly brighter masstone was obta.ined 60P will be used for the present. Increasing the coupling time from 1 to 1-1/2 hours gave a slightly brighter and weaker product. Increas in batch size from 0.1 to 0.3 mol had very little effect except for a slight increase in depth which can probably be corrected. A composite mix of all except the abnormal batch was close in masstone and vs blue In tint compared to the laboratory C.S. standard. This type is darker and bright versus RT-396-D (Calco product) but considerably weaker. DUP050315840 vvs wk. vvs blue OK vvs yel.caet s CM 4= 25 CM Ov CM y> CM 8 p o> [eo** 3 * o S H, gn 9 P >> > *4 O 3 3H PP > >4 Q 33 P jQ j O & 3 > bO g CO u p U 8 C5 J3 ED H >> M JX o o > t p3 3 3 p uH p i XP p o TJ > > >> > .x > Ui ! o > 33 P 33 >> > s > tiO c 5 fx p < ft H A > i j M >> CO T3 > 0c0- > CO p TJ S T5 p * P c- MCO CO, g H a ga o ts C o T%3 c a to Q P p P p B u B oP P P >> P > > > P O t j *ri P > T3 P 73 $4 3 * jD a m a > > ft > > tsi s> > 08 t* > > > > P U) ho p no *H P p B a boT* p o H a >4 1 u * p u *H p O * 3 cU B Vi o Pu oB UP a 1>ft 43 04 41 CM c- n P s * 3 so t- H B p E* p AP o CM p 3 o T5 \ rs o i CO ft N o 8 Pa >p CO > P P o U OS P t* P < B 8 > o ISp O <Vh u mp + 3 P 43 01 W p p p Pp oB t O ja p C O JD Ps a05 oPP 03 P p 33 P 23 P X CM Jx -rl u tt p ft J? o V p tfc fc- BP P P s, PP N P P p P u p tn X5 H o a 3 3 aP o X P >> u P H p *H B PP o fH u a sc ou NP ai -h P 53 N 01 p TS a o p'-- * TS in p --* N S3 P > 3 P o p t3 PP oT3 CO H XJ .> POp + H p p TS a aw *4 ft w Eh C-- 00 P Ug 3 3p P no P-t St P +> i a o Pft c (h s a(S5i s bu0 43 o P fc- fid <S <o0 > Vt o s: \xs Pd 3 p P CM 3p pP P 43 3 X cn O OO3 3 P X 43 A * O H Vr <0y4> to M joa O TJ P S to C0T4> to O S c o CtMb O P Sm 3 cfrMO p o a P o oP o A! o JS o to o0>4 to B! CO p p <<~-ti u! ofr- j O C0M5 -o Vo P TP? B CM COcMJX jLoa3 P X P XP P TS P P N CM Oc- CMsO,3: B P PC tn CM P CM P-P o C- W oXO a CM a B 3 u 3 Ao vCJ. P1 P COCfrMO- CO XCO aX oeao; o -Oa O > 00 H O<to7>' c 0044 to <* i8 Ootn o p ot- p p ofr* CCMM o> cKvb? ot- m CoM CCMO Ofr- oeCinM* 7062 Check 7057 except couple in one hour N B 455 P 100 EXPERIMENTAL DETAILS DUP050315841 PIGM3HT COLOR RBSEARCH REPORT 7> PI35BH310H STUDIES OH VAT DYES ASP THE EBSPARA.TIOH OP IAKBS SUBMITTED BY* APPROVED BY* A A3 >6 PILE* gISOT-3iAi3B DATS* MAY-1935 IHTRQDUCTIOS- Investigations were continued In the laboratory on the prepara tion of improved 1ak pigments of rat dyes* especially the new water- dispersible type dye powders, with the object of determining the scope of this problem, The studies this month were confined chiefly to Ponsol Blue GZ and GD. Sulfonated Ponsol Blue R prepared by Jackson Lab oratory, was evaluated for the preparation of toner and lake pigments. SUMMARY & GOKCLU8IOBB The orientation experiments conducted with rat dyes hare resulted in several specific eases in outstanding improvements but the data ac cumulated to date is insufficient to predict the exact magnitude of this problem* However, it appears that t he tinctorial and other proper ties of lakes from vat dyes in general cannot be predicted by the pro perties these dyes possess when dyed or printed on textiles. Our ex perience cn the preparation of lakes from vat dyes is the result of taking by known methods, several vat dyes, and selecting those most desirable In tinctorial properties. The resultsof recent work indicate that several dyes which in our very early studies were discarded owing to poor tinctorial properties are not only equal but superior to those previously selected, when laked by the recently improved methods. There for, in order to obtain a more complete picture of this general problem it appears essential to investigate the various types of dyes which are cf Interest tlnctorially and from the data accumulated, select those of outstanding merit for evaluation as pigment colors. The preparation of alumina hydrate lakes from Ponsol Blue (ED and Ponsol Jade Green water dispersible powders has resulted in pigments of increased strength and brilliancy compared with the best obtained front the regular dye pastes. However, in the case of Ponsol Blue GZ the dispersible type dye gives a lake superior to the corresponding regu lar paste but only equal to the lake prepared from the corresponding crude paste* Lakes prepared from Ponsol Blue GDS Grains, which is a water dispersible dry dye, are appreciably superior to lakes prepared from the regular standard double paste and slightly superior to the best lakes obtained from crude paste and dispersible powder of Ponsol Blue GZ* The water dispersible dyes precipitate on alumina hydrate and Clay probably by adsorption, but do not precipitate on a blano fime sub stratum. It has now been found that these dispersible dyes can be pre cipitated on the blane fixe by acidification and boiling, which breaks the colloid or auspensold and coagulates the dye. However, the results with blano fixe have in general, been less satisfactory than with alu- mina hydrate, particularly with dyes originally poor in dispersing qual- Itiaa Yh blatte fixe lakes are very hard in texture, which can be greatly improved by the precipitation of some barium rosinate in the presmuM ? dy* and substratum. DUP050315842 2 Bovina and calcium toners and lakes of sulfoaated Ponsol Blue R bare been prepared* The dry toner pigments are exceptionally hard in texture and poor tlnetorially. The barium lakes are very much greener than the lakes of Ponsol Blue GZ and <D and possess seme merit* BXTOIMSBTAL BBTAXL3 Alumina Hydrate Lakes of Ponsol Blue QZ expt. 19, h .B, 460 page 76, Toners and Lakes of Sulfonated Ponsol Blue R, expt. 23, H.B. 460* page 94* Bland Fixe Lakes of Ponsol Blue &Z and @D, expts. 25 & 27, B.B. 460, pages 102 and 108 respectively. DUP050315843 / StJBKITTSB mi xsmora Bsr* EflafeBB COLOR BESEARCH RBBORT 3sr-/*? HLSgSLLAggBlIS LAKES & TONERS V/ FILE* g3S3~C7~LAJgB& DATE* HAY-1935 nrfRQsgoTioH Samples of 4 chior aniline 2 sulphonlc acid hare been tested for the preparation of Bed loner C3-7779, and a large sample of the latter prepared In the laboratory* Some cooperative work was carried out with the Dyewcrka on the testing of Du Pont R Salt by the Newark coupling and laking procedures. SUMMARY A large sample of 4 chior aniline 2 sulphonlc acid prepared by Jackson Laboratory has been found satisfactory for OS-7779. A pound of this toner was prepared in the laboratory for further evaluation* The pigment is non-bleeding in lacquer and equal to the original CS sample by ruboui test# '4' nr A number of charges of h Salt were tested for the Du Pont Naph thalene Area. The majority of the batches have given Pigment Scarlet HI,-21X-P in the laboratory equal to that obtained from G.D.C* Standard R Salt and standard plant dye# 2000 lbs.* charges 359, 363 and 364* h&ve been recommended for plant manufacture of Pigment Scarlet dye and lake at Hewarle. BXEBRlgglfTAh RESULTS B. Salt - Bxpi. 20, BUB. 460, page 80. 03-7779 - Sxpts. 24 & 29, 3ff.B. 460, page3 98 and 116 respectively. DUP050315844 PIGMENT COLOR RESEARCH REPORT BLUB PIGMENTS gQR LA.C3.U3R - DRIFT IE SHADE QJ&hOeJU. SUBMITTED BY: APPROVED BY (1) OBJECT OP THE INVESTIGATION FILE: MiaO'. LAKES DATS: MAY- 1935 A complaint was received By Krebs from General Motors through the Pariin plant that two shades of blue lacquer, made from Prussian Blue (B-140-D) drifted in shade on aging so badly that it was impossible to use them in the automotive trade. This investigation was under taken to determine the extent of this drift and possible ways cf* pre venting it, (2) Period Covered by Report Newark, N. J. March 11, 1935 to June 6, 1935. (3) Historical Background It has been known for some time that Prussian Blue exhibits a change in shade of tint on aging when applied as a linseed oil ink. 7/hen used for very dark blues either in oil or lacquer this drift in shade is not readily apparent. Two shades of blue in which the ratio of zinc oxide to blue pig ment, is high, were adopted for Chevrolet cars. It was found that various parts of the car sprayed at different times with the same lac quer did not match when the car was assembled. This difficulty proved so serious that these two colors, Brainard 31ue and 5 Purple Blue 23 were withdrawn from use. (4) SUMMARY & CONCLUSIONS The colors in question (Brainard Blue and 5 Purple Blue 23) have been matched by combinations which are essentially non-drifting in shade. The Prussian Blue (3-140-D) which drifts badly, has been re placed by a mixture of the greener LTilori Blue (B-66-D) and Ponso 1 Violet AR both of which, are practically non-drifting. -Approximately 16$ of the vat dye is required. Other conclusions drawn from this investigation are given below: 1. Unbaked Prussian 31ue lacquer panels drift in shade from red to green on aging. This conclusion and the following one are based on Munsell color measurements as discussed in the experimental details, 2. Prussian Blue lacquer drifts in shade in the can from green to red. The degree of change is considerably less than that on the panel. 3. Baking the sprayed panels at 175CF produces the same effect as aging in an accelerated manner. As a result, baked panels show less change on aging than do unbaked ones. Baking sections of the same panel for varying lengths of time shows that drifting is still taking place up to 24 hours. DUP050315845 2. 4. Unbaked panels are still drifting in shade after 2-1/2months aging. 5. Lacquer grinds in 1/2 pint jars are more effective in devel oping full color strength than grinds made in 1/5 gallon jars.. Plant grinds from Parlin fall between the large and small jar grinds in strength. All drift to the same extent. 6. Mixtures of Prussian Blue and Zinc Oxide appear to exhibit the same type of drift as 5 purple Blue 25 and Brainard Blue which are shaded with carbon black and iron oxide red. 7. Incorporating Tomahawk zinc oxide in plant Prussian Blue slur ry producesja^acquer, green and strong vs. standard. The drift in shade is not improved. 3. Substituting Timonox (Antimony Oxide) for sine oxide produces a lacquer, green, bright and weak vs. control. It is somewhat superior in drifting properties. 9. The addition of barium chloride to the Prussian Blue strike throws the shade green. The drift is not improved appreciably. 10. Lacquer grinds made with glass balls show no improvement in drift over grinds made with steel balls. Glass balls do not develop the full strength of the color. 11. Chinese Blue (B-63-D) exhibits less drift than Prussian Blue (B-140-D). Milori Blue (B-66-D) shows the least drift of the iron blues. Its change in shade is very slight. The following vat dyes are essentially non-drifting: Ponsol Blue GZ, Ponsol Blue RCX, Ponsol Dark Blue BOA, Ponsol Navy Blue and Ponsol Yiolet AR, Sulfogene Bril liant Blue 5 GCF exhibits considerable drift in the same direction as that of iron blues. 12. Yat dye pastes emulsified with lacquer plasticizers and ground in lacquer are only slightly stronger than toner samples. Alum ina Hydrate lakes of vat dyes appear very strong when compared with toners brought to the same organic content with zinc oxide lacquer. 13. Vat dye pastes treated with mineral spirits prior to drying exhibit considerable strength as toners when rubbed out in oil aid com pared with a control. These strength differences disappear when the toners are ground into lacquer. Apparently ball milling the lacquer grind develops the strength of even a poor texture pigment. 14. Vat dye pigments made by Dr. Adamson at Carrollville and by Mr. Siegel at Jackson Laboratory, which show strength advantages by rubout, fail to show such advantage in lacquer. 15. The I.C.I. method for dispersing Copper phthalocyanine (drown ing a sulfuric acid solution in boiling water, filtering and ball mill ing the press cake with dibutyl phthalate) fails to show a strength improvement. 16. Treatment of a vat dye with zinc stearate failed to show to advantage. DUP050315846 3 17. Co-precipitating Ponsol Violet AR with blanc fixe from a sulfuric acid solution changed the shade to a blue with no great strength advantage. 18. Other combinations showing very little drift and matching the Prussian Blue shade can be made from (a) Ponsol Blue GZ and Anthraquinone Blue B and (b) Iiilori Blue and Ponsol Blue GZ. (4A) Patent Situation No patent situation is involved so far as is now known. (5) Plans for Puture Work The above findings and samples of dyes will be* submitted to Parlin. (6) EXPERIMENTAL RESULTS (a) Comparison of Lacquer Grinding Methods Lacquer grinds of Prussian Blue (B-140-B) were made as follows: (a) Pigment 2Tinc Oxide Grinding Vehicle #1 Stainless steel balls Thinning Vehicle #1 6.5 g 0.5 g 43.0 g 500.0 g 110.0 g Grind 10 hrs. in 1/2 pt. jar (b) Similar grind in l/3 gal. jar Grinding cycle 36 hrs. Ball ratio 3-1 (c) Plant ground material from Parlin. These blue lacquers were used in making up 5 Purple Blue 23 as follows: Blue lacquer (parlinfs 246-052) 39 g Zinc Oxide white lacquer(Parlin' s 246-009) 235 g Carbon black lacquer Iron Oxide red lacquer Thinner and Brainard Blue ( ( ( It II It 246-020) 246-031) 3601) 14.9 g 13.2 g 300. g Blue lacquer ( Chinese Blue lacquer ( Zinc Oxide white lacquer( Carbon Black lacquer ( Thinner ( It 11 !t t rt 246-052) 246-050) 246-009) 246-020) 3601) 55.5 g 14.2 g 199.8 S 23.8 g 300. g Sprayouts showed the lacquer ground in the small jars to be the strongest and that ground in the large jars the weakest,wi th the plant material being intermediate in strength. Sprayouts of the same lacquers made at later dates showed the older panels to be green vs. the freshly sprayed ones. The difference was noticeable after one day of aging and persisted over a period of we eks. DUP050315847 1% 4 (0/ Effect of Incorporating Zinc Oxide in Pigment-rf'ater Slurry Tomahawk Zinc Oxide was- added to a plant slurry of Prussian 31ue (3-140-D) in amount equivalent to that in Purple Blue lacquer. The pigment was filtered, washed, dried and ground into lacquer. It was green and strong vs. the control but drifted just as badly. (c} Bffect of Barium Salts on Prussian Blue Strike. Three runs were made on Krebs 3-140-D formula dated 2-18-35. a) Control b) Barium chloride added to Yellow Prussiate of Soda and Anm. Sulfate c) " " "" "in place of " These pigments were then ground into lacquer on the regular for mula. The barium effected a change in shade toward the green, but had no effect in reducing drift. (d) Comparison of Drift of Extended Blue Lacquer and Purple Blue Lacquer In order to simplify the testing of pigments for drift in shade, a comparison was made between Prussian 31ue lacquer mixed with zinc oxide lacquer to give a blue tint, and Prussian Blue shaded with black, white and red to give 5 Purple Blue 23. Both lacquers were found to drift to about the same extent. The simpler procedure was adopted for most of the work. (e) Drifting of Various Blue Pigments Drift studies made on lacquer panels from various blue pigments revealed the following: Prussian Blue B-140-D exhibits the most drift of those studied Chinese Blue 3-63-D drifts much less than B-140-3 Milori Blue B-66-D drifts but very slightly, being better than B-63-D Sulfogene 3rilliant Blue 5 GCF lake drifts badly Ponsol Blue GZ lake (3P-121-D) ) Ponsol Blue G-Z toner ) Dark Blue BOA toner *f Blue RCX toner If ITavy Blue toner ft Violet AR toner ) exhibit practically no drift ) ) ) (f) Substitution of Other ,'hites for Zinc Oxide Timonox (Antimony Oxide) which is one of the few whites other than zinc oxide suitable for use in lacquer, was used as an extender for 3-140-D lacquer. The resulting color was much greener in shade than the zinc oxide extended material. The drift was not greatly improved but seemed to be in the opposite direction (fresh panels green)-. (g) Munsell Color Measurements to Determine the Relative Amounts of Drift on the Panel and in the Can. _____ _ The Munsell System is a scheme for identifying a color by matching with a set of permanent standards. Spinning discs of the sample and UP050315848 5 sectors of the standards are compared. While the limitations of the system are definitely recognized, it is sufficiently accurate to give a definite starting point in distinguishing between changes v/hich oc cur on the panel and those which occur in the can. Notations are given on panels when freshly sprayed and after agin.'- six days. Lacquer Sample 29-7 Prussian Blue + white 29-3 Ponsol Blue GZ lake + white 29-9 Chinese Blue + white 29-10 Kilori Blue + white March 27, 1935 Hue Value Chroma 5.68 PB 2.84/8.06 3.45 P3 1.24/7.23 4.59 P3 3.06/11.04 4.55 PB 3.02/10.96 April 3, 1935 Hue Value Chroma 5.29 PB 3.0078766 8.45 PB 1.37/7.06 4.92 PB 3.09/11.28 4.53 PB 3.07/13.12 Comments on Table 29V On aging panel goes green, light, strong (clean) 28- 8 " " " no hue change, si.light, si.weak 29- 9 " " " red, light, strong (clean) 29-10 ** " ,f v.si.green, light, strong (clean) (si.dirty; Visible differences detectable to the eye by this system are noted. 1% in hue = .033 in hue number Ifo in value s? .01 in value number 1% in chroma = .04 in chroma number. Twelve days after the original lacquer was made and sprayed, another sample of 29-7 (Prussian Blue + white) lacquer was made and sprayed. This was compared with fresh sprayings of the original sample. Lunsell notations are given: Original 29-7 lacouer (Made 3-27-35) A - Sprayed 3-27-35 fresh" 5.68 PB 2.84/8.06 3- " 4-9-35 aged in can 12 days 5.79 P3 2.62/8.50 New lacquer on same formula (Made 4-9-35) C - Sprayed 4-9-35 fresh 5.64 PB 2.83/9.32 Comments on table. C should check A which it does rather closely. Since A : 3 are read immediately after spraying, there has been no aging on the panel. The difference between A P 3 represents the drift in the can. The lacquer on aging has gone red, dark and strong but to a much less degree than the aged panel. (h) Comparison of Grinds Using Glass Balls and Steel Balls A l/2 pt. jar grind made with 150 g. glass balls (the capacity of the jar) instead of 500 g. steel balls failed tc show/ proper strength after 48 hours of grinding (compared to 10 hours for the control). No differences in drift were noted. (x) Effect of Baking Panels Conferences with representatives of Parlin disclosed their belief that baking the sprayed panels at high temperature (175'p) for consid- -2 v#r- DUP050315849 rf 6 erable periods of time, stabilized the color so that it would no longer exhibit a drift in shade. YThile this is not a practical solution to the problem it was considered by them as an aid in testing. Three lacquers were sprayed so as to have eight panels of each. The lacquers used contained: (A) Prussian Blue (3-140-D) (B) Milori Blue (B-66-D) (C) Ponsol Blue GZ toner The various panels of each were baked at 175CP as follows: (a) Unbaked (o' 4 hours (b) 1 hour 5 hours c) 2 hours 7 hours d) 3 hours (h) 7 hours at 175CE then 17 hours at 130CF. Visual examination indicated that Hilori Blue and Ponsol Blue GZ changed very little on baking. The Prussian 31ue panels changed con siderably in the direction of aging (greener) cn baking and showed no evidence of coming to an equilibrium under the baking conditions used. In other words, drifting v/as still taking place between (g) and (h) . Kunsell measurements were made on the unbaked and c hour baked panels, both when fresh and when aged 8 days. A (a) unbaked B" " Cn A (f) baked 5 hours 2 * (l w Q B tl May 8, 1935 5.78 PB 2.60/8.38 5.00 P3 2.90/12.18 6.95 P3 2.21/10.91 5.32 P3 2.98/9.60 5.00 P3 2.93/12.12 6.95 PB 3.35/11.11 May 16, 1935 5.35 PB 2.82/10.0 5.00 PB 2.90/12.18 7.17 PB 2.34/11.54 5.32 P3 2.98/9.60 5.00 PB 2.93/12.12 7.00 PB 2.50/10.91 These results indicate that Milori Blue and Ponsol Blue GZ change very little on baking or aging. Prussian Blue apparently changes to approximately the same extent on 5 hours baking as it does on 8 days aging. (5) Attempts to Improve the Strength of Vat Colors in lacquer The following vat dye crude press cakes were obtained from Carrollville and used in the experiments noted below: Ponsol Bark Blue BOA, Ponsol Blue RCX, Ponsol Kavy Blue, Ponsol Violet AH and Ponsol Blue GZ. The pastes were treated as follows: (a) Dried to toners at 140'F. (b) Laked with Alumina Hydrate on Krebs B1--1210 formula) 13/ dye). (c) Colloid milled. Dried at 140'F. (d) Emulsified in colloid mill with dihutyj. phthalate and blown castor oil. Dried. (a), (b) and (c) were ground into lacquer on the regular formula, the pigment of (b) being adjusted to the same aniline content as the DUP050315850 9^ 7 others. (d) was ground into lacquer solvents from which the plasti cizers had been deleted. (The plasticizers are present in the pigment). The emulsion treated dyes showed only very slight improvement in strength over the toners. Colloid milling the toner showed no advan tage. The lakes exhibited considerably more strength than the toners. Since alumina hydrate is not desirable in lacquer, other types of lakes should be tried. All the vat dye pigments were essentially non-drifting. Ponsol Blue RCX paste was thoroughly mixed with Mineral Spirits, colloid milled three times and dried to a toner of excellent texture. Experiments varying the amount of Mineral Spirits from 5 to 5C.':' of the weight of the dry color showed 10% to be optimum. Mujol was somewhat effective when substituted for the volatile Mineral Spirits but was of less interest than the latter. The soft texture pigment obtained, exhibited increased strength of 40-50,'a over the control when rubbed in oil. It was actually strong vs. a lake of the same aniline content, when ball milled into lacquer however this strength difference dis appeared. This is probably due to the fact that wet ball milling of the hard vat dye toner actually grinds sufficiently to develop its strength. Vat dye toner dry ball milled does not show a strength ad vantage in rubout over a control. Mineral Spirits treatment of the other vat dyes used in this work produced in rubouts strength advantages over a control varying with the dye used. A soft texture was obtained in every case. Samples of vat dye toners of improved texture received from Dr, Adamson at Carrollville (C#32626 and C-32627) and of vat dye lakes of improved tinctorial properties in ink, submitted by Mr. Siegel (460-17C. 19A, 19B, 19D) failed to exhibit increased strength over con trols when ground into lacquer. The I.C.I. method for treating copper phthalocyanine was adapted to Ponsol Blue GZ dry toner in the following experiment: 375 g. con. sulfuric acid 3.75 g. Pyridine Iced externally to 0-5cC 37.5 g. Ponsol Blue GZ dried toner added Stirred 45 min. Drowned in 3750 cc boiling water in 5 minutes. Cooled, by stirring, to 70cC. filtered. 'washed acid) Press cake(18-20/* solids; ball milled 2 hrs .) free.) 4 cc Dibutyl Phthalate with) 1000 g. Stainless steel balls Dried at 140CF The resulting color was very jet in masstone but weak vs. control on both rubout and lacquer grind. Colloid milling Ponsol Blue GZ paste with 6% zinc stearate pro duced a pigment when dry which is slightly stronger than the control on rubout but of no greater strength in lacquer. DUP050315851 8 An attempt to co-precipitate Ponsol Violet AR with blanc fixe by dissolving the dye in sulfuric acid and drowning in bariurrf chloride solution, resulted in a pigment of entirely different shade, being a greenish blue. (k) Matching of Prussian Blue and 5 Purple Blue 23 Shades by Mixtures __Exhibiting Much Less Drift.___________________ Lacquers of the following composition are fairly close matches to 5 Purple Blue 23 and are practically non-drifting in shade; 36-A Ponsol Blue GZ lake (BP-121-D) lacquer Milori Blue (B-66-D) lacquer Zinc Oxide white lacquer (246-009) Carbon black lacquer (246-020) Iron Oxide red lacquer (246-031) Thinner 3601 65.8 g 12.15 g 142.0g 14.3 9.3 236.0 38-3-1 Ponsol Blue GZ lake (BP-121-D) lacquer Anthraquinone Blue B lake(3L-79-D) " Zinc Oxide white lacquer (246-009) Carbon black lacquer (246-020) Iron Oxide red lacquer (246-031) Thinner 3601 27.2 g. 10.0 58.3 6.1 2.88 80.0 75-A-l Milori Blue (B-66-D) lacquer Ponsol Violet AH lake lacquer Zinc Oxide white lacquer (246-009) Carbon black lacquer (246-020) Iron Oxide red lacquer (246-031) Thinner 3601 14.6g 22.5 111.0 9.37 6.5 125.0 Matches for Prussian Blue + white which are essentially non drifting have been made as follows: 38-A-l Ponsol Blue GZ lake. (3P-121-D) lacquer Milori Blue (B-66-D) lacquer Zinc Oxide white lacquer (246-009) Carbon black lacquer (246-020) Thinner 3601 33.3 g. 3.55 67.0 1.77 80.0 This combination is equivalent to 55;1 Vat Bye and 45> Iron Blue. 75-A Milori Blue (B-66-D) lacquer 39.0g. Ponsol Violet AR lake lacquer 60.0 Zinc Oxide white lacquer (246-009) 296.0 Carbon black laccuer (246-020) 5.0 Thinner 3601 335.0 This combination is equivalent to 84:\! Iron blue and 16,0! vat dye. Reference - J.L. N.B. 1740- pp. 1-85 inclusive. ajpi# DUP050315852 PIGMENT COLOR RESEARCH REPORT SUBMITTED BY APPROVED BY: PEACOCK BLUE LAKE BL-151-D 2*3./>- c5 9- jrt-/C^. FILE: MIOO. LAISS DATE: MAY - 1935 ^ INTRODUCTION 3emi Works production on this color has been resumed to secwre weak material for shading. Pinal results are available on four of v these batches. SUMMARY & CONCLUSION v*.... The first two of these batches were made on the standard BL-151-D formulation except that the dye was cut considerably in each case (6 pounds and 4 pounds of dye respectively as compared with the standard amount of 9.75 pounds). Both of these batches were weak, vs red and clean versus the BL-151-D standard but the ink was distinctly higher in consistency than the standard ink. To lower the consistency of the ink the next two batches were made cutting the amount of soda ash used in the base 10$. This im proved the body of the ink noticeably, altho it was still not quite as good as the standard ink but resulted in a vs redder and dirtier product than that secured using the standard base. The first two batches have been consumed in a plant mix. All of these batches were made using Alphasurine Special from National Aniline and were dried in the P & S Dryer aijl40*F - 40$ humidity. Production is being continued in the Semi-Works on weak mater ial for shading. Results tabulated in Table I. . .f? ,3a,M 4^ DUP050315853 EXPERIMENTAL DETAILS TABLE I N B 430 Pages 46-49 BATCH DYE TYPE BASE Aart. Lot RUBOUT RESULTS VS - DRYING TIME 3L 151 Std. YIELD Bass* Draw* Str. Tint fist. Lump SW 7019 6# RMOLLL Std.NL.VW. 66 hrs* P2S Dryer 140"40SI SW 7029 # SW 7044 4f SW 7045 4f * Std*NLVW 70 hrs* P2S Dryer 140"- 401& m 10^ cut in 64 hrs. P&S N-3 in base Dryer 140" F V.W* n check SW 40*H 68 hrs* P&S 7044 Dryer 14QF -40 dk It It It str* vs clean 48ff 49^ wk* wk* wk* clean 48ff 46f wk* wk* vs red 48jf 46j? wk. wk* vs red 48jf 46f tit'. DUP050315854 - t pig l r it t c o l o r h br baiic h r bpo r t 3III-FORKS PRODUCTION & SUBMITTED BYs 7?, APPROVED BY: FILE! SR- se DATE: KAY 1935 INTRODUCTION 62 batches of 20 different colors were made. These included 5 batches of RT-265-B. 4 batches of RT-359-D. 7 batches of AT-7S53-D, 6 batches of 3T-122-D, and 11 batches of 4 different rubber colors. s u mma r y RT-242-D, Barium Duo1 - Two batches were made in a trial of the new type TOBF. RT-265-D, Calcium Duol - Five batches were made for production and in a study of types of Rosin. RT-126-P, RT-329-D in pulp form - Two batches were made to obtain mater ial for samples. RT-359-D. Pigment Rubine Toner- Pour batches were made in a study of the formula continued from previous months. RT-399-D. Improved Maroon - Two batches were made completing 3emi-works trial of new intermediates RT-7801-D. Azo sulfite lithol - One batch of the calcium lithol was made in trial of this type of formula. RT-7873-D.j Improved RT-208-D - Seven batches were made in development and standardisation of this product. RI-7853-D, Permanent Red 23 - Three batches were made upon resumption of development work on this color using a new lot of intermediate. RL-7836, Lake Red C for Rubber - Three batches were made in Semi-TOrks standardisation of the formula. EL-7909-D, Permanent Red 23 lake - One batch was prepared by extending CS-7S53 with gloss white base. RS-6857-D, Pigment Rubine Lake - One batch was made for production. BL-151-D. Peacock Blue Lake - Six batches were made for production of shading material. GP-7789-D, Rubber Color - Pour batches were made in development of this product. GL-7854-D. Rubber Color - Three batches were made for standardization of this lake prepared from 3rilliant Blue 3 and I'aphthol Yellow S. GP-7863-D. Rubber Color - One batch was made in completion of the work i on this shade. GL-7906-D, Treated Pigment Green - Five portions of this dry color were prepared from C-7-33-P by various methods of treatment, G-7391-D- Light Fast Uilcri Green - Three part batches were made to test the stability of this shade of green. 3T-122-D. Blue PTA - 3i:: batches were made in development of an improved product. 3kL-6789-D. Treated Black - Two batches were made in a trial of a new type of carbon black. Y-309-D. Excelsior Yellow - One batch was made concluding for the present work on this problem. ~ DUP050315855 *7 2 Bight grinds of pulp color and ten afees of dry color were ztade in the research semi-works for the plant during May 1935* Grinding Charge Batches lbs. Green Toner Pulp CP Yellow Pulp 730-a 739-s 6 2 8 2569 395 29'd4 pulp . Mixing PTA Toners Blue Lake Green Lake CP Yellow CP Green 751-s 751-s 751-s 753-s 755-s 2 2 1 1 4 Iff 419 550 221 500 1718 OTS 'ST'S .. DUP050315856 irt a0 m# S|S Hn H nUlOt^lAc NcK* O.o^*:^,3c2 |J8SS* Hrtrl H H OH HO at g0 HIs #10 BUILDING? PRODUCTION REPORT FOR MAY 1935 3d! MD0^-MirDrr_l(fr3r^O<'i)cN^frH(0cgNmft4*it~|iir43tiN~r(;ci|^{i>Cm4P{;3|0iaO| naRAta 3 Mo . e 3 * g < cCv ot>Oc*NffhOat OM A CO CO N OnuinOifot* nO 'I* a aa NM pDMNH<J|| rttHC0 Bsah 6- os 6a-ai *e"s amo i fl o p - K Mct i^eaint Hmo?__i_So__uh_i N_ ct0po>amanSoaAmt BaaP2 aNaft.o|at0o.*i S`"H C*>Het~H ;c4sGna-itgaEs^aGta-s)Hni|ajia4 fjfl.KH K(4 btt(>S< oiJ na oM at * * & 3 S8?8l88{gfcg8 e iFo* S83S at 3 eCO~ o<o0 oto sMg|: 6 tJ *0 X.Jh a o 3d! toHoqnqqnin MUR^Otj* Aodjel S2HH2H?H8H2H9H9H2Hs0` * ,to am a*m'jo1mm 1 sss OH H H s ""i *5*5 ^3 *??? SSSSigfgSS HH H SSSgSSSSSSg 3|SSSSSSgggs?|g:33gg3 #Hcpr H<m2 *8 (S? a Si H ** h h He cacMoj oi ot ioE HH d. a q QO O QO uo tO tjl t*!l2E;, a* at t H Ft HeFFNF a H ^ " OW MfloQH m? sssa,sass' H NH R Ft 1X3 ^tc ,f-3lKMOiJ Kt-3pi-tiSfJ 4HoP flSKeOf oats I1nHs 4O 4AI sssls s <f aa e*o<Q Ho H H H oCi ft- fr** Rrj?R*N2RSNP`nN`oFN'aN3OoNtQnrnHmM<mOotmj<imCn**tcKePn~cnomaSo N P) tf A A t*o____p__ DUP050315857 SIMMAHY OF #10 BLDO. PRODUCTION REPORT FOR MAY 1955 NO. Batches 2 5 2 4 1 7 3 3 1 1 6 4 3 1 5 3 6 2 1 Code RT 248 D RT 265 D RT 126 P RT 359 D RT 399 D RT 7801 D RL 7873 D RL 7836 0 RT 7853 D R1 7909 D RE 6857 D Bl* 151 P GP 7789 D GL 7854 D GP 7863 D GL 7906 D G 7891 D BT 122 D BKE 6789 T 309 0 Lbs Struck 382 1180 30 210 90 40 390 465 157 50 247 288 240 237 142 21 132 4 39 6304 Lbs Pack* 300 1150 183 94 31 399 481 164 46 2248 77 233 24 134 38 17 137 23 40 % Yield 93.2 97.5 97.1 104.4 102.3 103.4 104.5 92.0 100.0 96.2 97.1 94.5 94.3 81,0 103.7 95.9 102.6 6221 97.6 t DUP050315858 Lot 4103 4104 4105 4108 4109 411? 4118 4124 4080 4092 4120 4088 4089 4122 4126 4096 409? 4110 4111 4099 4100 4114 4124 4098 4086 4087 4101 4102 4106 4107 4112 4113 4115 4116 4119 4090 4091 5. MATERIAL TRANSFERRED DURING Miff 1 935 FROM RESEARCH SMI WORKS Total CR-200 Color Code Lbs. Grout Cost TJnit Cost 1 RT 265 D 241 2 $ 48.91 1 H 232 2 1 ft 231 2 1 ft 204 2 1 n 242 2 1 RT 242 0 147 2 47.05 1 tl 153 2 1 RT 359 D 36 1 133.42 2 GX 312 0 116 2 4.88 3 Y 305 D 3 Y 309 D 219 2 140 2 7.80 8.51 4 G 7194 D 297 2 18.78 4 ft 293 2 4 G 208 D 102 2 10.73 4 G 365 D 46 2 9.65 6 HE 6857 D 2248 2 11.37 8 YO 38 D 527 2 7.60 11 BL 151 D 11 99 11 n 11 n 47 2 43.50 45 2 49 2 47 2 12 RT 399 D 307 1 306.42 12 ft 62 2 304.42 26 RT 126 P 16f 10056 1 299.50 125 RL 407 D 203 n n 203 if RL 408 D 183 n f 185 n RP 7836 D 246 tr ft 293 99 GP 7863 D 225 n ff 231 ft GU 7854 D 241 t ft 225 GP 7789 D 298 1 46.66 1 1 50.70 1 1 77.26 1 1 1 1 57.86 1 1 127.46 127 BT 125 D 221 1 273.84 127 ft 224 DUP050315859 .6 RECAPITULATI ON Colors Transferred from Sami Works in May 1935 Toners Ext. Colors Yellows Greens "RE" Lakes Oranges "RMM Lakes **RPW * "RL" " Maroon Toners PTA Toners PTA " Pulps Total 1486# 116 359 1338 2248 527 466 1293 962 369 445 16i 9625-J# ?f ''Sp niaSSWiS!? DUP050315860 MATERIAL IN PROCESS" AS 0 F jM fj l, 1935 z R ESEARCH SEMI WORKS fflO BLDG*" u a g CM a o co oo cq Minl a fc- in O o in O a CM O O M o a rt rl ^ <n a ea a a Q Niflcnnn T*e O OO n m c m to c m co <n >C >C }M s CM a v w r-4 00 fr- 13 am r* Oinh 0 go ood ro s ss t- 8C*J 6 Q in CM 141 in Q Q CM c m in CM CM fr< S< aa c q oc* 0 PUtn H a0* I SS2 g & fIeSre a o CM Ok HO CQ * a * * DUP050315861