Document Vnr5N4o1K6oB7Nmy4KDvgn0p

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK. NEW JERSEY Serial No. Copy No. 6 ^Period Covered: NEWARK PLANT PIGMENT COLOR RESEARCH REPORT JACKSON LABORATORY PIGMENTS GROUP RESEARCH REPORT MAROON TONER, RT-608~D (4-CBL0RAFIHRANILIC ACID --BON, Hn) SEPTEMBER 13, 1948 to FEBRUARY 10, 1949. FILE: DATE: 2/23/49 222*2 NJ027S N42200 Copy tos 1 i- Numerical File 2 - Research File (222.2) 3- - Library File (222.2) 4 ~ Dr. . J. So Booga, Wiim. 5 ~ Dr. Do Bo Killian, Newark 6 Mr. Ao Siegsl/AoA.Brizzolara, Newark 7 - Dr. Wo So Struve, Jackson Lah. 8 Hr, Ac Do Reidinger, *' " 9 - Mr. J. M, Tinker, " 10 * Mr. J, M. Tinker, *' 11- Extra copy SERIAL NO. XH-49-16 Copy No* 6 10 V JACKSON LABORATORY PIGMENTS GROUP RESEARCH REPORT MAROON TONER, RT~608D (4-CHLORAiTHBAMIlIC ACID BON, Ma) SEPTEMBER 13, 1948 to FEBRUARY 10, 1949 CHARGEi AIX~C~236 (%> < SUBMITTED BY; APPROVED Bis A. B Reidinger W. So'Struve DATE SUBMITTED; 2/10/49 DATE ISSUEDs 2/23/49 DUP050067207 K-2512, the manganese salt of 4^chlor-2araint> benzoic acid (4-chloranthranllic acid) coupled to beta-oxy-naphthoic acid, previously described in KM-484, was found upon exposure (6 months Florida)to exhibit lightfastness and durability on a par with arylide maroon, RT-5?1~1V Its attractive appearance in a metallic finish and its non-bleeding properties aroused considerable interest in the new combination as a possible addition to our line of maroons and it was decided to prepare sufficient sample for evaluation by F&F. Philadelphia and Parlin, The product, was coded ART-608-D and a new formula was written based on the straight thru process for RT~525~D (Mn Red 2B),, Altho this procedure gave a lighter* yellower and also harder product than K-2512, it was considered suitable for costing purposes* This report covers the work done in the study of the processf chiefly of the "isolated dye" procedure K-2512, which was found necessary in order to duplicate the sample originally evaluated,, -fiSJfllABZ' At the outsat it was found that the K-2512 process was sensitive to a number of variables which had not been studied previouslyp Optimum conditions of alkalinity and volume of development, amount of Para soap* and the effect of time and temperature of development were investigated* With this information it was possible to prepare a two pound sample, ICS-197, which altho' not a close match for K-2|?i2 was considered to be satisfactory for submission to Philadelphia,. By rubout and in alkyd enamel, -the new sample was dark, somewhat duller, and yellower than the original product,, Further study of the process did not reveal means of improving the tinctorial properties above the level of KS-X97 and a sample of the same quality in filter cake form was prepared for. evaluation by Pariin* However, since the product exhibited instability of color and of crystal form, it was not submitted* Because of the additional amount of work which appeared to be required' in developing a stable process, the problem was transferred from the Jackson Laboratory group to the Iswark Laboratory* Results of some promise were obtained on a straight thru process based on the K-2512 type of coupling* However., some variations occurred in the products obtained and further study would be required* DUP050067208 ~2 DISCUSSIOM OF RESULTS The following results aoply to the "isolated dye" formula, K-2512, or its modifications Raw materials - The 4-chloranthranilic acid used in the preparation of K-2512 and in part of the work reported heres was prepared by potassium permanganate oxidation of 4- chloro-2-amino toluene by the method referred to in Beilstsin, Subsequently the procedure was modified in accordance with details given in an loCalo reportj H-5246 Based on melting points and nitrite values, all intermediates used were of excellent quality-. Other materials were of the grade used in the Pigments Department Dlazotlzation - Because of the low solubility of 4-ehloranthranilie acid In hydrochloric acid, rate of diazotiaation is relatively slow9 Precipitation of the amine and formation of a considerable amount of diazo-amino compound apparently occurs when the acid is added to the amine-sodium nitripe solution The formation of diazo-amino compound is probably due to local deficiency of acid since on stirring for 30-45 minutes most of it breaks down and dlazotizes An undlazotized residue equiva lent to about 3# of the weight of amine is filtered off before, coupling Use of increased amounts of hydrochloric acid (50% and 100;? more) improved the rate of dlazotlzaflon and reduced the amount of undlazotized material However, the products obtained were weak and duller in tint due possibly to improper balance of the alkalis used in coupling Coupling - A mixture of caustic soda and soda ash as alkalis for coupling appears to be most satisfactory k larger amount of NaOH than In K-25X2 is now used in order to obtain more rapid coupling , Replacement of soda ash with ammonia in one experiment in which it was tried gave a lighter yellow product with harder dry texture Optimum coupling temperature appears to be from 10 to 15C At 25C somewhat lighter, yellower and duller products were obtained When coupled at 58C, weakness, has occurred but mas stones appeared to run more consistently The presence of rosin in the coupling (20 grams per mol charge) did not have a pronounced effect Slight dullness of masstone and tint was noted in a, direct comparison DUP050067209 3~ Ho information, was obtained as to the effect of development of the dye by heating before filtering or of using water in place of salt to wash the dye, or of omitting washing entirely.. * Alkalinity of development appears to be the most important single variable. In all the recent work it was necessary to adjust the pH after adding manganese sulphate to 8.2 - 8.4 to obtain a normal product. Use of a definite amount of JfaOH <18 grams per mol) is preferable to reliance on pH readings as a control. If Insufficient alkali Is used, a light, very dull color results. Use of higher amounts of alkali have relatively slight effects but do give darker pro ducts with yellower tints. Reduction in development volume by 50% resulted in a lighter masstone and bluer dull tints while a two-fold increase had no effect0 Amount of Para soap may be varied from 50% less to 100)? more than the formula amount without much effect but omission results in a duller and weaker product. Amount of manganese sulphate was varied from 116 to 68% of the formula amount without change in tinctorial properties except that at the lowest amount, which is still 12% in excess of theory, a stronger product was obtained. Manganese content of the products varied relatively little and all were lower than anticipated from calculations based on the assumption of one atom Mn per mol of dye 10.96 to 9.88$ by analysis compared to 13$ calculated. ment conditions have been tried* " S'hs following develop Temperature 98 ~ 100C 98 - 100C 98 - lOO^C 90 - 92C 92 - 93G 82 - 83OG ~J0 2-8*4 ' 8.2-8.4 8.2-8.4 8.2-8.4 8.1-8.2 7.8-7*9 30 minutes 10 a (Standard) 2 10 10 10 " She shorter development period, 2 minutes at 98-XOOC instead of 10 minutes, gave similar tinctorial properties and may give better consistency since more rigorous conditions, e.g. 30 minutes at the b.oil,was found to be detrimental to the color. Similarly, develop ment at 9092C had little effect on tinctorial properties compared to the standard procedure. DUP050067210 -4-- The combination of low temperature and low pH resulted in lighter masstonas and more intense tints but did not appear to impart greater stability to the process since off-color was obtained in some instances* Several procedures for adding manganese sulphate were tried* The method of RT>347<0 in which the Ea salt is acidified and the similar process for RT-52I-D.in which the manganese is added in the form of hydrate gave close matches for IS~197 referred to in Summary, although both ware slightly duller in masstone than the control run for the series* Straight Thru Process * The following methods of eliminating isolation of the coupled dye were tried. An RT-52?~D type process in which the fta salt is run into the ilnS04 at ta boil gave a lighter and yellower product than 30-2512. Ligh'tfastnsss and bleed properties were equally good but dry texture was poor* This process was also sensitive to the amount of alkali present during development. A K-2512 type of coupling followed by addition of Para soap and manganese sulphate to the alkaline coupled dye, somewhat as in R.T-55-P (yellow shade Mn Red 2B)? gave promising results on several trials but subsequent study indicated It also was unstable* Somewhat better results were obtained by acidifying the coupling and striking at 5DC in RT-347~D process. Replacement of soda ash with ammonia or additional ftaOH gave inferior products oh the latter formulation* Instability in main form * The instability referred to in the summary was noted when samples of filter cake were composited by reslurrying.in water, the color becoming very dull and changeable in masstone ink. It was not determined if this behavior' is characteristic of the color* However, a sample of filter cake which had been stored for 7 weeks in that form did not show any significant change* S^ERIMMAL-DETAILS! Details will be found in notebooks 1292 and 1320, An index is given of the variations studied. Preparation of samples (ft.B* 1292, Expts0 46, 54 (ft.B, I32O, 4, 16 Raw Materials Tests (ft.B. 1292, Expt. 64 (ft.B, 1320, Expts, .3, 5, 9 Diasotization ft.B, 1320, Expt. 7 DUP050067211 5 Coupling Conditions M.B. 1320, Expt o14 Alkalinity of DevelopmentCr?0 B0 1292, Expto 47 <M.Io 1320, Exptsp 6, 13 Volume of Development I.B. 1292, Expt 53 Amount of Para Soap H.B. 1292, Expt. 49 Amount of Manganese Sulphate H.Bo 1320, Expto 15 Temperature and time of (M,Bo 1292, Expto 48 .development (Mo 1320, Expt. 6, 27 Method of adding Manganese B.Bo 1320, Expto 13 I Straight Thru Process (H0B0 1292, Expto 43 CH0B0 1320, Expt. 20, 22, 23, 26 Composition of pigment codes referred to HT-347-D (Manganese toner of Tobias Acid BT"521"B (coupled to Beta-oxy~naph thole acid. BT-525-B Manganese toner of Permanent Bed 28 RT-55I-B 5ran3.tro~2> amino-anisoIs coupled to ,5IaphthanllM ASD0 A process embodying what is believed to be the optimum conditions is attached* DUP050067212 MRS ttMJPROeCK 0JI.TS 2/8/49 of K-2512 m$m Hatrooa Sene? K- *mmm-- mf&n .*. .o p "sc* aa&spts- JBi^ 1 BMW | *03f$ K/T. 44 fCaustic Soda* 100$ .1 iV5 1 4* ehlor-anthranilio 44 .. ' ! acid 98*99$. I' .1 ci Xc i. j GA2*. aj wo. Add to 300 2500 1 water0 HftKWB4TK83 Shea add Heat to 140l6OF and , , 1 stir 20*30 minutes to dlfsolvf ..T...... 1 (Tests slight on cv nanar) ...... 1 Make to 720 I60QQ I .at 32P with ice a-nd water* | Add 71 1 Sodium nitrite I 1 *as isEt (ca 99$ NaN|>*> 1 mu | Muriatic Acid 1005s j 100f ...... 1 Stir 2*3 minutes , 1 Duaio la with sood as its t ion 1 |Stly 25-35 minutes at 3540F " , Cea 31=45$ HCX solnl) 1 ! . 1 (Tests CR4-5 ICI+ throughout) ,, . . : w .... ,.... ,......... 1i 1 .. |1 1 i Filter thru clarification areas* 1 Collect filtrate- .Add. * 1$ Sulfamic acid f | I | dissolved in % --_ 1 1... ......... . 61 50 I cold water 1 |(Tests KT - or VoSo) 1Counle j 69 Caustic Soda 100$ Rea 50#..... faOH'soiho)] 200 1 MiithosoX"' Aeid B0 69 I 180 !.. . .............................. LAcid to . 1500 water* Then add 'Seat to 130*1400? in 3-5 minutes ; _ 1 j..................................... | .Stil 10*3n minutes t.n ?sr>l'w<ar , r . Dilute to 420 poo"' with cold water* Shea add 160 f.Soda Ash 1' Dlssplred in 75 625 water at 135-140OF 1. I JSake to 720 po6" at 49519f with cold water and ice n "1 1 `1 ; <1 . 16 700 ISalt 1 1 i 1 sea. ma. Couni diazo into BOH solution in 30*40 minutes at 5O-609Fo . , 1 fTasts Diaao. * BQH-fr. wH 9*6-9*81 Stir 30-40 minutes* .1 Filter and wash with 11680 1680 p.4000 cold water .1 i' ' ' | CTesti Filtrate slight on Be) f. -- -csr s o u r . j MSNATORSL DUP050067213 . PAGE #2 mmmMJk mmr COU0ROOUK mrn 2/8/49 Hod1floatton of K-25X2 H.B. 1320-W .. mt s j jawatioM..__sastsss or k 8MHJ& . miMi Isso^Jw. ma* Maroon Toner .. . Ufiuiilii EC. 15 Manganese Sulphate Ls,^.iy..,.5-X(lJ3Jji!?iie-! I Add in 10-12 minutes i I dissolved in ^mrteoi muv'"Tri^ri^0^ 1 Stir 5~1Q minutes I Chests pH -normal 602-605) 18 1 Gadstie Soda 100% l8 ~;sc 50% HaOH ^olruj ......:... [. ......;......................... l ...:...... 1 1. i .... j.. ! 1 1 .1 1 1 1 i 1 i 4I I...................... *1 i- 4i 1 -1.--^- --^ -- 1 . ........... - ^.------- WUfT - 1' tir 5 minutes' -n9....,n.o..maH.9U 2-8 ,4JL 1 W * f-__-i-n OnR.g1 901?__ i r> . AC\~AK ml nntioe___ Hold at 208^?12o F fot ' minutes Quench to l58-"l6oF volume Record oH (normal pH 6,,6-7<>2) Filter^ wash SO,, free Drv at 140OF. Pulverize r 1 I1 I! <8M. YIEUDL- 460 lbs* 11 as is11 * .. . . Ju.XL,^g.idJLrvgga- DUP050067214