Document 85MZg651vvdBGM1VRQRoOXojm
E. I. DU PONT DE NEMOURS & COMPANY
KREBS PIGMENTS DEPARTMENT 256 YANDERPOOL STREET NEWARK. NEW JERSEY
Library Fila
TIT:; Ss
NEWARK PLANT
PIGMENT COLOR RESEARCH REPORT JACXSOH LABORATORY
FIGMENTS GROUP RESEARCH REPORT
PIGMTS FROM DERIVATIVES OF 2-AMIilO-BEliZOIC ACID (AHTHRANILIC ACID? AHD RELATED INTRRISEDI&TES
Period Covered:
February 3.1947 February 201948,
FILE: DATE:
222,2 3/26/48
N42153 Njea7o
Serial So. 101-48-4 Copy loo *3
1 - Sumerleal File
2 - Research File (222.2)
3 - Library File (222.2)
4 - Dr. JV E* BooWiXsi.
5 ~ Dr. !?, F. Spangoman*, Iswark
6 - Mr;, A* SXe^el/A.A.BrAesolara, iewark
7 - Br. D, B,, iCIXXian, Jackson lab.. Wito.
8 - Sr* A. D,, Reid laager,
*
9 - Mr. Jo 1. 1 iakers
*
"
10 - Mr-o Jo Mo Sinker*
t}
11 - Imperial Chemical Industries, ltd a
12 - " "
K
u (i
13 -
58
18
14 Extra Copy
j a c k s o i ijmmmmi
$mm$s mow r es ear c h r epo b
5?m.E PIGMiS FROM DERIVATIVES OF 2.4i09K~S8i20$C AC3 uifm&Miiic a c id ) m> musm ik t e b k b b ia x e s ...
p e r io d CQFERJSB; February 3, 194? to February 20, 1948. CEftBOE* A-II-C-238
SUBMITTED Sis A* ,D. Bald ingel* APPROVED Bis Do S, Killian
BAKE SUBMITTEDs DATE ISSOEDz
DUP050066906
Investigation was mads of the usefulness as .-dla&o components of a number of Intermediates related structurally to 2~amino teensoic acid (antfaranillc acid), Sam of these'had teen evaluated a number of: years ago and la. view of tha results- than obtained-, further study appeared to be warranted. As a bos is for comp.ariso;nf couplings of sntlaranilic acid to various second components war
used, Improvements In the hake Bad D type pignssit (anthranflic Acid---> Beta Baphthcl) anil In Pigment Scarlet take (aiithruailie Acid H-Salt) Yfere looked for. It was also planned to check
earlier work "which* Indicated that pigment of "fhtdiung1* Rod shads
(Permanent Red 28 Acid BQtO could he obtained from derivatives of anthranilic acid or their isomers.
mmmumsasmsm
Of the intermediates tried, 4chlar2-sm.ino `benzoic acid
appears to be of most Interest., Iho manganese' salt of the coupling
io" BOH was a maroon pigment somewhat lighter' than
(?OB**ii>
BOKj Mr) with much yellower undertone. It m&y have application
in automotive enamels,particularly In metallic finishes .In .which
PUS #143), the K-25X2 formula is attfeetesd,.
k sample <18-14-4) representing the manganese salt of -S-eb-tor2-amino tes.nko.ic acid-^ BOf? was also prepared for evaluation, Bills is a maroon about equal In depth to Ef-533-B {JPCASBA---^ B01) end therefore lighter than tha 4~etelsr derivative, it is of- interest tee cense the interned late cm tee made from, a cheap by-product .of the Chambers Works 6ctelor~2-ait3rotoluene.
A close tinctorial taatch for ^Watchung** Eedj 8$-428*4> was obtained from 2-chlor-!?'-amino teen&ole acid coupled to 801 (Ca 'salt}? provided the color was' flushed into varnish-, fte dried toner wa& weak. fteis interne-late is at present too expensive for considera tion.
P-amlno turnsole acid coupled to SOI? also approximated the . -rfatchungs Rod shade. Ifee higher -cost of this Intermediate compared-' to Rod .3 sold would make its .use uneconomic*
imlnoterepfatte&Xte acid coupled to Bata laphtliol <Ca salt) may tea of interest as ah Intermediate for a .Bake Bod R typo pig ment. Bis product doss not show the sensitivity to drier' eafciteited by Lake Bad R but on the otter -hand hm poorer 1 ightfas tness
DUP050066907
\
2w
msmmj&jmmx
--Tbs lln salt is described above* The Ca mas similar in shads but duller and less lightfabt*
'T^Beta faphthol, The Ba salt showed no advantage over taka Bad J> The product *** somewhat yellower and mealier and exhibited the characteristic sensitivity to metallic drier*
E-Salt Ih the tom of Pigment Scarlet Lakea of RL~211~D type* the products obtained wars hard la texture and weak in tinting strength* Pulps of barium sM strontium toners, tested by paper dyeings, showed no advantage over Pigment Scarlet in strength or in lightfastaass* In the form of paper coatings <brusho.ut) the strontium toner exhibited excellent light resistance*
BOI The manganese salt is a dull maroon of no interest* ^is product is similar to that from the 4chlor isomer*'
--> W 'The Ba salt is a strong clear-tinted yellow possessing very poor lightfes.tneas*
.
' The Ma* salt is discus sad in the Summary* This product'exhibited instability in ths making formula and also in the enamel from it, which turned brown on aging* Development of the color at 80C. instead . of at a boil gave more consistent results* The Ca salt, propped by a rosin&ted formula, is a dark transparent reel possessing excellent baking and bleed resistance*
BOH The Co salt is close to 3hfe.tclmag^ Bod, BT*428~J>, in -shad and if flushed from the filter cake Into varnish is equal in strength* Drying the color re* suited in a hard, weak pigment* Lightfs-stness and bleed properties' were inferior to the ?kfatchung!* colors*'
DUP050066908
Beta Maphthoi, Ba and Ca salts had mors Intens a mas stones , and less bronzy finish than the corresponding anthranilic acid-***#* .BS pigments hut wens weaker due pre sumably to poor texture of the dry color*
--*> PIP The Ba salt is a reddish shade yellow of fair lightfastness* fhe combination is probably too expensive to merit consideration*
B1 Barium end calcium salts slightly weaker- than obtained from.the hasulforated intermediate,,
Otherwise similar*
,,^ap go!
Calcium salt was mak as a dry color with sosnwhat
poorer .strength but more intense ass stone than the
unsulfonatod intermediate*
*:$* H-Salt Barium lake of R1-2XI-I3 type was hard textured and weak in tinting strength*
*& BOS
The calcium salt is considerably yellower in shads than `slatchungsi> Bod Toner, HT-428-D, is slightly worse in ligbtfustness sad definitely inferior in Mood pro perties. Texture of the dried product was good* The higher cost of this intermediate compared to Bed 2B
leid would make its use uneconomic*
*"> PIP --^ .BS *--> BOB
Both Ba and Ca salts are very m&k yellom$ approxi mating Bensidins 'fellow %T~4$9~D in shade. The Ca toner is lighter and stronger than the Be salt and show a definite advantage in lightfestncss over 1T-459-B, its poor tinting strength would be & 'handicap to its pr(motion.
The 2a salt is a weak red of no interest* The Ca salt is superior tlnctorlaXly and although somewhat bluer in tint may he of: interest as a lake Bed type. It appears to be less sensitive to metallic driers than the latter pigment tut ia not as good la lightfasIncss*
The coupled dye mm -completely soluble as' the soda salt and was .not converted to *tfe .metal salts.
DUP050066909
E&phthol* 3*ha product of this combination is an orange somewhat yallovyer then Parra* tone Orange, 12~419<D in shade with excellent lighifastnoss of'fall etrhagta
d?8%Mioe
PSl? A reddish yollow much wcak-iar tb&a the .strong tjpm BssizMlaa fellow, '12*553-$ with about equal lightfastaess,
'Bi&sotisation of this iuterstedicto was effected by ass of aitrosyl sulphuric acM Since' coupling did mt taka plac^ readily In acid solution, neutralisation of the --eacess acid was necessary# As the 5-ehlor derivative is soluble ia - hydrochloric eeid solution, it mj he possible to develop a hotter method for disaotisatioa*
-*f Bate Haphthol.* in orange si.Hr.:' to Orange 02 (BOA- JAA.P) in shade hut considerably weaker* ifio difficult-/- of
die'sotisfe.g am coupling mzf account for the lack of strength and also ths poor llghtfastncoa which eras obtained*
^EtoenyX Bffisthjl fyuagolonse A reddish yellow similar to that from the f-ehlor derivative Mt considerably weaker,.
Ss.2L.lliei:iaii:ilAa,.Mis,
A deep maroon ^igaont. ecnHderebly bluer than Am Bordscu:t lake, ES*'3$*B? aM superior in lightfustacwa* Because of hard texture of tho"dry color, evaluation t o * mads by flushing from'the rater paste*
fhe coMbinatioBs tasted aau the corresponding notebook
references arc listed belows. -
l-|ihayl3*jS0tb.yl*5-PiP,^^o3hh ***a^ Beta l&phthol **P> Beta oscy aaplathoic acid
te^8,
IB 1234
n
libspt, 4
16, 21 . 22
18, 25 36.# 51
DUP050066910
2*ejaino-g4-chl&g bsmolc ac Id
-h ? son **$> 'B*SXfc
.2S*Wk<
"**g* BOH w&H-Salt
ESxplJp 4 '5? Expt422 18, 25, 2? 12 .
IB X236s ExpU 4, 58 " 285 42 ,f 19* 25*27> 31 11 36, 51
m -1260, gxpt.15, 24 , 35, 40, 48 j- 53 ,
IIS 1279V 8*t* 9, 14, 35, 46
~g> BI
IvCpto 4, 56 ffl&pt022* 48
25, 27, 31
2ehlo5Vana lno4~aulfo benzoic sold
BIT
*$> BOH R-Salt
IB 1si23.6 ?s
Exptp 22, 42
Bxpta 19 Bxpt.o 12, 36
Jfcfiffll >,gGQ.a.d.c Acid
IB 1236 , %xpU 2?, 31 IB 1236, Mxpti 53
st
DUP050066911
** & TO
i 33 30 47
Eapt* 50
SOM
5*5i **& B-Salt
IB S^pt* 33 Bn>t 30* 47 SxpS* 50
SB .X2?9?. Expt.. 30
Attached Is the foamXn foy tha preparation of R25>12 (4~chloy-2-a&iao bimaoic aoid-^BOlij, Ita). SJti-a d*ehlor
derivative ms a&de fei .simiXcir^iaamies? asjeepfc that It was
developed at 80C instead pf at boil*
DUP050066912
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DUP050066913
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DUP050066914
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W jfoilO# TO&ertooe .esc! ii;at in
raisiios to sasstO:a&>, 'tho festayla is tesofi an pm^e&vtmn ttf*o$ fw sisalier
piggteKrts m& ii^ormtioa t o o Sstsdaed 9.6 to -sfre^i e? TOrl&Xjr*
Cesii>Xt iiaerli miles of
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fie. to tli* low s0lat3lIi.iT of its hy^tooSdoviM* 5I* effect of a loag^r stirring
perlcfi t o o 4fc*tfJdU
Cmiplisg i.a
papoooaoo of eofiiem oariHmafce prmzmIn m-ddf if the
pB is mieiair^.d sfep ?&* Mfiitioa of osairiio scia lasjr feo '&6* if aoooMiay#
Xs3latlo of if** %& s r t o & 4os&r 'oluor product ifes ufcfcn &&s*:rict
otrol^rt ttira* -."t
'a gs$s&bX to saroifi
with salt .s o '&j v Io b. bp
ad^uotoamt of pf alien soapliag to a'ouut 0,0*
BEJJWi:eSmE. ' \ 3/19/
.CC
DUP050066915