Document X888GjxZ6Q4dJ2Vq957N8m02w
t
,
E. I. DU PONT DE NEMOURS & COMPANY
KREBS PIGMENTS DEPARTMENT
256 VANDERPOOL STREET
NEWARK, NEW JERSEY
Copy No.
/
UBRARY copy
NEWARK PLANT
PIGMENT COLOR RESEARCH REPORT Ksport
Scarlet Lake BE-542S Laboratory Variable Study. *>
November 11, 1943 to May 3, 1944. i Period Covered: * *
FILE: DATE:
222*4 6'*23*44
a<a.s.
* N39981
Copy to*
#1 - numerical File
2 - Research Office
3 - Library File
4 - #10 Building File
5-#6 "
*
6 - imperial Chemical Industries Ltd
7-
8-
9 - Mr. C. H, Rupprecht/I.C.I. File.
Serial Ho. KN-44-34 Copy Ho. /
NEWARK PLABT PIGMENT COLOR RESEARCH REPORT
Final Report
Title: Scarlet Lake RE-542-D Laboratory Variable Study.
Period Covered* November 11, 1943 to May 3, 1944.
DATE ISSUED* 6-23-44
N39981.01
DUP050150269
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anmarait
la earlier exploratory work, reported ia KU-4.2-I66, it was discovered that the mixed barium-aluminum pigment of the dye, 6-chlor~2-amiao-toluene^R-salt, laked on alumina hydrate and barytes, gave aa approximate match to Soarlet Lake RE-85-D. This product, K-1729, was found to be superior to RE-85-D in lightfastness* A few charges of -1729 were made in the semi-works and samples submitted for evaluation to Bewburgh, F&F Department, under the code, RE-542-D. Bewburgh approved the lake as an accept able substitute for the Scarlet 2R type lake BE-85-0.
It was decided to return the formula to the laboratory for detailed study of the variables before carrying out extensive development* this report covers the laboratory work carried out on the formula.
1. The laboratory variable study on K-1729 has been com pleted and a "direct laking" procedure, K-2016, has been developed.
K-2016 differs in several minor details from K-1729 (see formula
and formula notes appended) but principally in elcninating isolation of the dyestuff.
2. Tinctorial comparisons!
K-2016 versus BE-542-0 (K-1729). K-2016 " BS-S5-D
HaafctoBfi Undertone Tint LJW
vs dark s.strong s.strong approx
vs lnt. equal
light, si*strong strong superior
vs yellow
M.T, &
Tint
3* The principal variable for control of undertone and tint hue is the pB for strike. The optimum pB for the dye slurry prior to strike appears to be between 2 and 3* It has been found most feasible to maintain this level by allowing the dye coupling to finish at a pH in the neighborhood of 2-3 and adjusting to the desired pB with acetic acid or caustic soda as required* In general,
a pH below tee optimum level produces slightly lighter yellower
raasstones, yellower and slightly weaker tints* Above the optimum level, slightly darker and bluer masstones, bluer and stronger tints are obtained* The darker, bluer material is superior in lightfastness to the lighter yellower type.
4* Discussion of other process variables will be found in notes attached to the "K" formula at the end of this report.
5. K-2016 was set up using Rational Aniline R-Salt, A change over to Calco intermediate, now available on the plant, gave light masstone and yellow tint material on the formula. The
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3
application of the pH variable eventually produced an
approximate match for the
sample but the lakes are on
the defensive in being somewhat duller and bluer in under
tone and tint*
The filtration of the dye slurry as specified in K-1729 procedure was difficult sod objectionable owing to the slimy gelatinous nature of the dye* It has been found satisfactory to eliminate .the filtration provided pH of the dye slurry is adjusted before laklng, as specified in K-2016.
The amine has been found to dissolve in the hydrochlor ic acid solution at room temperature with agitation* However, upon continued agitation the amine-hydrochloride separates from solution but upon addition of sodium nitrite the soluble diesonlum salt is formed and a clear solution results* The sulfamic add used in K-1729 has been eliminated as probably unnecessary for improvement of tinctorial properties.
Reduction of the R-flalt excess from 10}f to 5% apparently
has no effect tinctorially* The use of caustic soda rather than soda ash in dissolving the R-Salt was desirable because the former resulted in more easily controlled pH.
The substitution of re-slurried #3 LC Alumina Hydrate for freshly prepared base was unsuccessful in several experi ments. a bluer tint pigment was invariably formed which could not be shifted toward the yellow shade necessary to match RE-85-D by application of process variables. Although it was found necessary to wash the freshly precipitated hydrate base required in the formula, aging of this base for as much as 14 days apparently had no detrimental effect.
Employment of the mixed barium-aluminum precipitant used in K-1729 was found unnecessary in K-2016 since the same effect could be obtained by control of pH. However, In one experiment in which Caleo R-Salt was used, a mixture of 18 grama of barium chloride and 0.5 grams of alum for an 0.02$ mol strike was effective in obtaining a desired shift to a yellower hue.
Hotebook 1076 Expts. 1 to 41; Notebook 1097 Expts. 1 to 9.
1. Volume variations 1076-21, 26, 27.
2. Temperature variations 1076-19, 23, 24; 1097-4 3. Alumina Hydrate bases 1076-18, 19, 20, 24, 26.
4. Variations of pH for coupling 1076-19, 20, 21, 36; 1097-7.
5. Variations of pH for strike
232, 34, 35, 38;
6. Coupling variables. 1076-29, 25,. 3$, 5*6, 4(7;* inovT.*! 0
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K*13398
FORMULA SHEET
COLOR CODE
OBJECT "Mwel
DATE
fmtmSm* fter
BASED ON tUlMMtiwp pemt&mm
BATCH SIZE-MOL.S.
BATCH No. OF 4*K" SAMPLE
NAME ff*SflS* MS*
LBCSM*8O.R
MATERIAL
tfjf Sw4#%S 9*U W& * (mP ssi *3sti*d
1S.S
100%*WT. W*f
GAL.
Iff
e. c.
fSff
MANIPULATION
Mists t* *t iff, m *m
K- 3993.4* (Baft)
)
N/ 21 m
%y *!*** Misss*
P" Tw
99JS
tttrfts
*# t# Iv mV Wfffftf m tm
If.5
niNn.mi
Ail MfSAl? (s |Im*m)
SM&r** Ss n too ai mmfrirt 9* 3tY mtfc
tt* Mac* IS stastss r mill.
$lsp Mtetiftfs iflrthjliro^R, tMRMCaSMM St 3BP 2$r*
.-ffilMffe* PMtlttS* SS Mfefff it 8MPMPI 13ftwi mi iffijpgp Hgfl gpggpgg**
s s
SI
> vt Sets IffSf
#a.4SH# Wrnmt
Mff II sff# t
- m m t TfY# Mi
m ft-*M 4i ml* mtt
11*4
AM
m im Ml fS*P nt stir t* ssisi&Mi
te*S*
ts |ft3f atwstss* Cwj** *i ?J*F.
I^MI MMs 4r*ft is t#l*i*t**y t HS*P
tffftp <S *S*wrjr Iff s Amh Iw k * fluffs fffcpRIss ffsst Wm ****** 4Hmm
m ff*l #Mfii&c!t sststlMif p mEMmi
MS
lust Wm ffHMtft stiff BMMUmff^s tstssss* ffwi rntornmt %$ *mj
f
m **m*mMm0 f*Se tuatwr Misti**)
wm mmmwr* *m
Iff
Smbp f iflNlifUi
&&& frit
. fWiSWi W*
m
pi Rr *MU> (j j w * m*m$* ****>
m 9*4* tRI * tlP
Hff Ms mSs s is. Us IJVff eft- tRtf1* Stint* stiff 14 mtm* % ISff W **** Mi *ttm# t as *&*t** mi
Hi lie attta 10 mwrt**. - ftssits
ffNff S8HB Sess mMmm w3JLmM$t agffmts ts Mitts
mo mmm&9*a*tiw t** e ** *ttti east* tfMSss. iMi Iff tteMl S*f *mJ
35 1
PACKAGE GOAL YIELD
LB8. PER
COST GROUP
TYPE COLOR
SIGNATURE
DUP050150272
K*13398
FORMULA" s h e e t
COLOR CODE
OBJECT BASED ON BATCH SIZE-MOLS.
UB* OH CMS.
MATERIAL
m tHyiM *# ilP
18 Siw&at * t#
NAME
BATCH No. OF "K** SAMPLE
109% WT. OAL.
c. c.
MANIPULATION
*gw4* f Awiu tie
dtaraftal Mi
ft lea Mwr t iRttNMMril C46
rt pigA- friimf
3PB mm *mmff*P* ftrlkv l arftM I* 3$ &&
In
IfO im *t IBM***. *ti*t
iff*
fer 15 ........
Slgi fceewt iB CM 44
** t* tspr. t 15-ae
m* * i*r* ftr $
**#* fS {Mental *. JMt)* *H8*P*
sr *% mp t . Fniwi** tvs#*,
***
If
II
fgm tMA# Sigftm salt #f <$*
W&mtim mm
PACKAGE
_JJM. PER
GOAL YIELD **&** 4***
ttW%QST GROUP
TYPE COLOR
**fe3rirsa* {** lT-3?>
SIGNATURE
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Hates te K-2Q16 (Bxnt'}
10 This formula Is revision of RE-542-D (K-l?29) and differs from the latter principally in the following respects*
(a) excess R-Salt is reduced fro 10% to 5j (b) caustic soda replaces soda ash la the coupling* (e) the amine is dissolved in hydrochloric add solution at room
temperature, (d) the coupling is finished in add medium, (e) filtration of the dye is eliminated* (f) the alumina hydrate bass is changed from a 30/lJ to a 30/l3 type, (g) the mixed barium chloride/aluminum sulfate precipitant in r=
placed by all barium chloride.
2* The following variables have boon found to be the most effective in control of tint and undertone hues
uH for strike
It has been found that a dye slurry of pH 2,5 0.2 dll produce the hue of tint end undertone required to approximate those of SH-85-D. Using the national Ailie'R-Sali as specified in'the formula, the pH before strife ran between 2*5 to 2.9. Using Calco R-Salt, however, it has been found necessary te omit acetic acid and adjust pH of the dye prior to strifes with 5 lbs. of' caustic soda per 0.25 mol strikej pH aftar strike is 5-5.5 Sakea~obt&inod by this adjustment have been duller and slightly weaker than those obtained using the national Aniline R-Salt a the formula as written.
Temperature for Strife
Increasing temperature of strike from 77 to 105gave increasingly darker aaestonea, stronger and bluer tints* Above 105F,, however, very dark, dull mssatones and dull tints resulted. The temperature control variable appears to be safe te ue within the limit of 7?e'"100Fo
Increase in temperature for development from the formula level of 167F, to the boll had little effect tinctorially.
Alumina Hydrate Base
Change of type bac to a 30/15 g&vo bluer products which were too far out of line to approximate KB-85-b. The us of roslurried #3 hC Hydrate invariably gave much bluer products than the freehly precipitated 30/13 type base used in the formula. Considerable weakness was obtained in the lakes in which poorly vashet hydrate base was used. In the laboratory it appeared to be necessary to drift? the six waters from the base before use in order to obtain optimum results,
bB for Coipling
` It is pc; dble to oarry out an "all alkaline" coupling ending at pH 0.5. Reductiev of the pH level to 2.3, as iff required for the strike, aay"*b done by the nee of acetic acid. However, it was found difficult in the laboratory to efjust this pH accurately and the tinctorial results were in etnas eases inferior to those obtained using the dy made at a lower pH.
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Quality of ft-Salt
Most of the laboratory work m. don with National Aniline Rialto wor laboratory purgoees, the R-Salt was dried at 140*FC ad analysed for GL E d S-*alts (KCR?P) . Although the Calc R*Sslt used {OU-3771} differed by only +2r from the previous National Aniline materialf and not significantly
in Quantity of free acid present* the resulting lakes on the foraula* m written* were too yellow for consideration, A indicated above* elimination of acetic acid and adjustment with caustic soda brought the'Calc R-Sali lakes in line with those produced fro National Aniline material.
3* Tfc following variables were found to have an indeterminate effect on the tinptorial properties of the lakes
Volumes of the dye slurry prior to strike. avariation had little effect.
Volume for precipitant. ..... a *50% variation had little effect.
Volume of Piaxo and of R-Salt. *50$ variations ted little effect.
Accessory Agents
The substitution of $ mol per cent of (3 acid* Mono acid L or Mue acid t for the R~$a!i produced bluer and stronger tisrhe^ However, those same effect can b obtained by simple formula variation*
Variation of Strike
He improvement were obtained by varying the time for strike* Rover a strike had minor effect on tinctorial properties,
4. Yield
The goal yield of 953 Xb0 *as is" 1 based on the average of five 0o025 mol strikes run in a consistency eerie on the formulae Toluene distilla tion* KCH-123, gave an average of 2.8% moisture in the "IP ample. Brafcender
moisture determinations were somewhat higher* giving a 3c2$ average. The average from toluene distillation was used in calculating the anhydrous yield.
Reference should be mads to X?6~3?
5 Alcohol bleed of the *K" sample is somewhat mors intense than for RK?42~D (F-1729f""but^both arc greater than RH85~Oo
60 Evaluations were c&ri'ivd out by rubout lei in varnish drier, extension Xa3 iw sine oxide.
X-20X6 vs RE-542~B K-201& vs WC-85-0
vg dark light
Undertone strong
Scstrong
&&&strongjv intense strong$ve intense
)!
DUP050150275
The runouts ere ensitiv to higher temperature, turning dark and brews* in masstene, dull in tint upon heating at 140?0 Upon cooling the material apparently return slowly t its original colorc
7* Sulfamic acid has boon omitted from the diasotlgaiion procedure~ Tt was found in the laboratory ttei ex nitrous acid had little effect m color*
80 Approximately 300 grama of laboratory material, 1076"3?8* have been sent to rtK" files a 11 Original Sample"c
>/ >J
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