Document wqzGY6n6MJ05pzvyK3Q8Oj66

New Jersey Office Supply Co. Filing Specialists 401 Frelinghuysen Ave., N ew ark, N . J, W:z I N40640 DUP050054584 KfH53-3 KY-816-D -- SIROHG RHODAMBIE Y lys R. F. White 2/61-12/62 M & COMPANY Serial Ho;, PT-KN-&3-3 copy TECHNICAL SECTION - COLORS NEWARK PLANT PIGMENT COLOR PINAL REPORT SUBJECT: HT*8l6-D - STRONG RHODAMINE Y PERIOD COVERED: FEBRUARY I96I - DECEMBER 1962 PILE: 229.1 DUP050054585 PT-KN-63-3 Copy No. / DISTRIBUTION: 1 - Research Numerical Pile 2 - Research Office Pile 3 - E. Gonick/E. N. Kramer 4 - V. H. Chalupski/H. Amoul/Q. C. Pile 5 - W. S. Struve/A. Siegel/Library File 6 - A, A. Brizzolara/R. A. Hageman/T. S. Pile 7 - P. J. Monahan (X Pile) 8 - R. P. White 9 - Extra 10 - Extra TECHNICAL SECTION - COLORS NEWARK PLANT PIGMENT COLOR PINAL REPORT SUBJECT: RT-8l6-D - STRONG RHODAMINE Y PERIOD COVERED: FEBRUARY 1961 - DECEMBER 1962 CHARGE: 5665-924 SUBMITTED BY: R. F. WHITE $ Ci 1*-*-^-- APPROVED BY: R. A. HARMAN DATE: 1/8/63 DATE; /^J ABSTRACT A high strength SMA Rhodaraine Y product, RT-816-D, has been developed, standardized and released to the trade. DUP050054586 TABLE OP CONTENTS; INTRODUCTION SUMMARY & CONCLUSIONS PATENT STATUS DISCUSSION Investigation - Laboratory Semi-Works Manufacture REFERENCES cyvo PAGE 1 1 2 10 DUP050054587 INTRODUCTION Some years ago Newark made a line of Basic Dye pigments (red, blue, violet, green, etc.). Competition in the field was strong, and as a result of low return, most of the line was "obsoleted" or cut to a minimum. However, the blue SMA (BT-264-D, Victoria BO) continued to grow because of its outstanding proper ties . This growth prompted the plant to install new and larger manufacturing equipment. These equipment modifications made possible larger batch sizes and other operating savings and resulted in a more attractive economic picture. In 196I, two competitive Rhodamine pigments offered a serious threat to our remaining RT-612-D (Rhodamine Y) business. The competitives were Uhlich's Rhodamine Y and Coilway*s Rose Toner (R-4572). Of the two, the Collway product was considered better, being stronger and bluer than our offering-. Sales requested the development (product Development Request No. 24-1) of a counteroffering with the strength of the competitive and the good lightfastness of RT-612-D, Because of the improved economics, a study was opened. Shortly after the PDR was issued. Sales surveyed the industry to determine exactly what was desired in a Rhodamine product. It became apparent that the trade was more interested in cost reduction through greater strength and were willing to Sacrifice lightfastness to obtain it. New samples of high strength products were obtained; and the best of these, a Collway FTA Rhodamine Rose Toner (R-4580) obtained at IPI, Elizabeth, was set up as the revised aim of the study. SUMMARY & CONCLUSIONS: 1, A high strength SMA, Rhodamine Y product, BT-816-D, has been developed. This product is slightly stronger (3#), bluer, and more intense in tint with equal lightfastness compared to the best PMA competitive available (Collway*s 4580), It is also slightly superior to the C# in ink mill characteristics, fluid ink uses, printing, solvent and paraffin bleeds, and has better drying characteristics, RT-816-D is about 40# strong, blue and intense versus RT-612-D. 2, Attempts to modify the RT-612-D PTMA formulation to prepare a stronger, bluer product were unsuccessful. However, trials using an imported dye (3G0) yielded a product that was about 25# stronger and blue versus RT-612-D. DUP050054588 -2 3. A survey of plant HP-612-D production showed it to be stable throughout manufacture, and attempts to improve strength by alternate drying methods (spray dry) were unsuccessul. 4. Attempts to prepare a Rhodamine product via an SMA and a PMA route both yielded products equal to the competitive (Coil- way rs 4580) in strength. However, the SMA route consistently gave a better overall product. PATENT? STATUS There is nothing included in this study that is of a patentable nature. DISCUSSION Investigation - Laboratory Initial study was aimed at upgrading RT-612-D to the level of the Coilway and Uhlich products. varnish Drier Rubout Masstone w Strength Tint RT-612-D vs. Coilway's R-4572 dark,blue yel 117*100 yellow,dull Chemical analysis of the competitives showed both to be the PTMA type similar to RT-612-D. Infrared curves showed they contained Rhodamine 5GDN dye with possible trace amounts of Auramine and/or Rhodamine B. Orchem dye analysis confirmed these findings. The following table shows the chemical analysis of these competitives; Sample W lx as% $> Mo 1S1 DPQ RT-612-D, SD-91164 44.23 7.53 1.07 none trace none C#58291, Coilway1s R-4572 40.93 7.50 1.19 none trace none C$58292, Uhlichs Rhodamine Y 37.48 7.05 1.89 none none none DUP050054589 -3- In addition, the Uhlich sample contained a f&ir Amount of an agent that was organic in nature. Based on the above analysis, several laboratory runs were made modifying the RT-612-D process. Some of the modifica tions yielded products that were superior to standard RT-612-D; however, none approached Collwayfs R-4572 in strength, intensity or blueness of tint. Some of these trials and their results are tabulated below. Investigate Higher Dye to Hetro-Poly Ratio All attempts to increase the dye in the standard RT-612-D formula yielded excessively weak products. All strikes except the control showed a very bad bleed during filtration and washing; Indicating that under standard RT-612-D manufactur ing conditions (acidity, heat development, etc.), it was not possible to form a complete and/or stable complex at higher dye ratios. Evaluate Spray Drying & Survey In-Process Strength , Relationships_____________ '' Popular PTMA technology states that RT-612-D loses con siderable strength (il0$6) on pulverization. If true, eliminating the pulverization should increase the strength of RT-612-D by approximately one-half that required to match the competitive. To evaluate this, a sample of washed plant presscake was re-slurried and dried in the Bowen Laboratory Spray Drier. Rubout evaluation of this spray dried material showed that it was equal in strength to the plant tray-dried, pulverized control. These results re-opened the question of the suspected in-process strength loss. To check this, samples were taken from several plant RT-&12-D lots. When compared by rubout, these samples showed no strength loss between plant lump and final grind, and less than 5# total strength loss from vat flushout to finished product. Consequently, no further attempts at alternate means of drying were made. Define Variables Controlling RT-612-D Production To define what factors control the coraplexing of hetro-poly acids and basic dyes, a survey was made of the formulae used in the development of the RT-612-D. These formulae, RT-329-D and RT-357-D, showed that higher strike and development tempera tures were used and that the acid concentration of poly-acid could affect final strength. To evaluate these variables, a 3 X 3 factorial design experiment was set up and a one-half replicate run. The main effects were considered at 3 levels and included; DUP050054590 -4 Strike Temperature Acid Concentration Phosphate Content 120F., l6oF ., 212P. RT-612-D level, -10jg, -20$S -10, RT-612-D level, +105& All other variables were held constant. Statistical analyses of these experiments showed that, at the 6:l8 dye to poly-acid ratio used, the roost important variable was strike and development temperature, Striking at the boil, gave the most strength. Acid concentration also was significant --lowef concentrations giving more strength. The only other significant result was the first order interaction between temperature and acid concentration. Although these pro cess modifications gave additional strength, none of the products approached the competitive in strength, intensity or blueness* Evaluate 3-50 Dye Previous tests and analytical data showed that if more strength were to be gained, the type of basic dye probably would have to be changed. Orehem was contacted (H. Stryker) and the problem reviewed. Their recommendation was that a 3-GO type dye might give us more strength and blueness. A sample of this imported dye, used by Orchem, was obtained and evaluated as a PTMA product on an RT-612-D process. Rubout showed that the 3-GO dye was not the answer However, its strength and blueness coupled with its lower price (approximately $4.6o/lb.) make it interesting enough to carry out further evaluations. Masstone DP Hiding Strength Tint TSC #64-l4c, PTMA ex. 3-GO vs. C#58291, Collway*s R-4572 vs dk,vs yel,int blue trans 90*100 v blue 24 Hour Lightfastness MT DD Tint Equal Better Vs Better DUP050054591 -5 Develop SMA or PMA Product About this time, a Sales review of the Hhodamine pigment situation with the trade indicated that there was con siderable interest In cost reduction through greater product strength. The trade stated they were willing to sacrifice light- fastness to obtain this strength, and they suggested we use Coilway * s R-4580 as target. Studies to prepare a stronger prod uct were directed along two paths. The first was similar to an old SMA formula, RP-651-D, and the second like the current BT-264-D formula. Each route was evaluated as a PMA and an SMA. Evaluation of these lab trials versus the competitive, C$58704, Coilway*s R-4580, gave the following results by varnish drier rubout: Type process MT DD Str. Tint 24 Hr L/F PP Tint SMA RP-651-D(A] PMA RP-651-DU; SMA BT-264-D(l PMA BT-264-d (i ] lt,yel red 95-100 v blue SB ta lt,yel yel 110*100 yellow ta worse It,yel red 97-100 blue SB .wt lt,yel red 102-100 s blue,dull =s worse The two SMA processes above showed that each was some what undesirable from a cost standpoint. The RP-651-D process used hydrochloric acid (N-28-D) and had a high dilution which would restrict the batch size. The BT-264-D process employed a sizeable quantity of acetic acid to aid in solubllzlng the dye. In addition, the precipitation is carried out in a buffered medium and has a relatively high dilution restricting the batch Size. Additional lab trials were made modifying each process in an attempt to improve its manufacturing cost. The trials were: Experiment Type Form Acid Dilution TSC$64-20(E) SMA RP-651-D HOI (G) SMA RP-651-D Mod. H2SO4 (H) SMA RP-65I-D Mod. H2SO4 full full one-half TSC$64-20(A) SMA BT-264-D H2SO4 + HAc full (B) SMA BT-264-D H2SO4 + HAc one-half (C) SMA BT-264-D Mod. H2SO4 full (D) SMA BT-264-D Mod. H2S04 one-half By rubout, these samples gave the following results when compared to C$58704: DUP050054592 6- - Sample Masstone DD Strength Tint 24 Hr. L/F Drawdown Tint TSC#64-20E 0 H A B C D It,yel It,yel lt,yel lt,yel It,yel lt,yel It,yel blue blue blue blue blue blue blue 95=100 93=100 95=100 97=100 102*100 95=100 100*106 v blue v blue v blue v blue v blue v blue v blue cs tet = e* vs better ss vs better vs better vs better S3 vs worse worse *at worse These results show that 20C and 200 (duplicate samples) are the best. The process used included sulfuric acid and high dilution. A comparison of 200 versus 20H, and 20C versus 20D showed a slight advantage for full dilution over double concen tration. Further evaluation of sample 200 and 20H showed them to be equal or slightly better than the C# in lightfastness, ink mill working properties, printing ink, edible fat, paraffin and solvent bleeds, and lithographic break tests, Semi-Works Manufacture Based on these data, a semi-works batch was prepared and evaluated. The batch, coded RT-816-D, lot 10467, handled without incident. Lot 10467 was compared by rubout versus the competitive (C#58704). Lot 10467 was split after drying; the portion identified as 10467 received no treatment, while 10467-1 had 2% DPG added during pulverization. Masstone Drawdown Str. Tint 10467 vs C# v It blue,int 95 blue 10467-1 vs C# v It blue,s int 97 blue 64-20 vs 0# v It blue,s int 95 blue RT-612-D SD vs C# It, dull blue 135 yel 10467-1 vs 10467 vs lt,s int as 102 vs dull 64-20 vs 10467 int 101 vs yel 64-20 vs 10467-1 we It to 98 s int Trans. Finish 24 Hr . L/F Drawdown Tint 10467 vs C# 10467-1 vs C# 64-20 vs C# RT-612-D SD vs C# 10467-1 vs 10467 64-20 vs 10467 64-20 vs 10467-1 opaque opaque opaque vs opaque S3 05 CCS s low s low s low s high S3 S3 S3 B ss .VS better S3 .33 -S3 vs better vs better vs better better .S3 S3 sex DUP050054593 Evaluation showed the semi-works batch equal to the laboratory control (TSC #64-20G), and the DEG treated portion not significantly different from either. However, these products were more opaque in masstone, and had a slightly poorer finish. Consequently, additional laboratory study was opened to further study: Dye to Molybdate Ratio Acid Concentration Development Conditions (Time and Temperature) Shading Effect of Auramine Auramlne - Shading Small amounts of Auramlne in the order of 0.5, 1.0, and 1.5# were used to yellow the product to bring the hue into line with the competitive. The higher amount (1.5$) of Auramine used had little effect on hue of masstone or tint. However, its use resulted in a considerably duller masstone and somewhat weaker product. Dye to Molybdate Ratio Changes in dye ratio gave no improvement in masstone depth or transparency. Acid Concentration Changes in acid concentration in the hetro-poly acid gave no improvement in masstone depth or transparency. Development Conditions Development conditions (time and temperature) have a significant effect on masstone depth and transparency. Rubouts show that lower development temperature (l4oF) gives darker, more transparent masstone, and poorer lightfastness. Medium temperatures (l6oP) give products that approach the competitive in depth and transparency of masstone and have equivalent light- fastness. High temperatures (l8oP) yield products with light, yellow, opaque masstone and slightly better lightfastness. The cross comparison within temperature ranges shows that the longer development times (30 min. vs. 15 min.) yield lighter, yellower, more opaque products. In strength and hue of tint, all the products appear to be insensitive to any of the changes. Tabu lated below are the rubout results of this series versus the competitive (C#58704 - Collway* s R-4580): DUP050054594 8- - Simple 64-27A vs 0# B C D E 64-25E 27B vs 27A 27D vs 27C 25E vs 27E Time/Terap. 15/140P 30/140P 15/160P 30/160*F 15/l80P 30/l80P 30/l4oP 15/140P 30/160P 15/160P 30/180P 15/180P Masstone v dk,dull v dk,dull dk,dull s dk,dull lt,yel It,yel s It yel s It yel s It yel Drawdown blue,int blue,int blue,int blue,int blue,int blue,int Str. 94 94 94 93 94 93 Tint blue,Int blue,int blue,int blue,int blue,int blue,int Sample Time/Temp. Trans. Finish 24 Hr. L/F DD Tint 64-27a v s c # B c D E 64-25E 27B vs 27A 27D vs 27C 25E vs 27E 15/140P 30/l40*P 15/160pP 30/l60P 15/180P 30/180P 30/140P 15/140p 30/160P I5/I6OP 30/180P 15/180P trans trans s trans vs trans opaque v opaque vs opaque 3 opaque opaque less brons less bronz as as less bronz W W vs W vs B vs B vs B sw vs W VS vs B sB Based on these results, a second semi-works batch, lot 10472, was prepared using 30 minutes at l6oF. development. By varnish drier rubout, lot 10472 tested as follows versus the competitive, CollwayVs R-4580 (C#58704). MT DD 24 Hr. L/F STH TINT TRANS DD TINT Lot 10472 vs C#58704 dk blue,int 93*100 blue,int trans vs B * A plant batch, lot 66789, was manufactured on a formula patterned after SW lot 10472. This formula, (A)RT-8l6-D, differed from the current BT-264-D(I) process as follows: DUP050054595 -9- Dye Solution Dye to Poly-Acid Ratio Acid Silicate Strike 'Teinpi Strike Condition Dilution (approx.) % Blanc Fixe # DPG RT-816-D 158-162P water 6:22 Sulfuric-55 moles 4 moles 158-162P 30 min.-158-162*F Unbuffered 10 gal/1 lb. 2,2 0 BT-264-D 170-175P water + 19 moles of acetic acid 6:18 Sulfuric-51 moles 4 moles 183-187P 15 min.-183-187F Buffered 10 gal/1 lb. 2.4 1.0 Results of this batch were satisfactory. Several other plant lots were struck and portions held for a possible standard. These lots were combined t* form PS 96770-1. Firm costs on the process indicated a return of about the same magnitude as BT-264-D (tl4$). Sales has released the product: and to date, it has been well received by the trade. In addition to high strength and acceptable lightfastness, the product has good drying char acteristics, requiring less drier. This results in a distinct reduction in the objectionable odor associated with its use. DUP050054596 -10REPERENCES: TSC #49-50 62-18 64-5, 7, 8, 9, 10, 12, 14, 19, 20, 22 SW 1046? SW 10472-1 & 2 RT-816-D, lot 66789-1 Memorandum: Discussion of Rhodamine Dyes - R.A.H,, 6/l/6l DUP050054597