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Патент USA US2407210

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Patented Sept. 3, ‘1946
a‘ ‘ e
._
2,407,210
UNITED STATES -. PATENT 'ZOFFlCE‘
‘COLOR COUPLERS
Arnold Weissberger, Charles J. Kibler, and Paul
W. Vittum, Rochester, N. Y., assignors to East
man Kodak Company, Rochester, N. Y., a cor
poration of New Jersey
'
No Drawing. 7 Application April 14‘, 1944,
Serial No. 531,124
17 Claims.
(Cl..95--6)
"
This invention relates to photography, and particularly to color-forming coupler compounds.
tinctorial' power than. dyes produced from cou
3 plers having only the ortho alkoxy substituent in
The formation of' colored photographic images
by coupling the developmentproduct of aromatic
the‘benzoyl'nucleusa A-combination of the al
koxy group- in ‘the ortho-‘pos'itio'n‘in thee-phenyl
‘amino developing ‘agents with color-forming or 5 ring of the benzoyl group, with chlorine in the
Coupling compounds is Well knoWrl- In these
ortho position in the phenyl ring of the aniline
processes the subtractive process of 00101‘ formation is ordinarily used and the image’ dyes are
intended to be of the Complementary primary
colors cyan or blue-green, magenta, and yelloW- 10
The couplers Which produce the cyan dyes are
usually phenols or naphthols, those producing-the
magenta dyes are Ordinarily pyrazolones or oyano
grourx-thefefqre, produces; couplers which‘résult
in the formation of yellow dyes of improved color
or light absorption characteristics and having
high tinctorial strength. The couplers them
selves interfere with: the dye stability to, a cone
siderably diminished degree,
‘
Compounds illustrating our invention are as fol
acetyl compounds, and those producing theyelv-
lows:
low dyes are ordinarily compounds containing a 15 1
methylene group having two carbonyl groups at-
-
'
‘
‘
tached to it. The dyes produced by coupling are
Q .
azomethines; indamines or indophenols, depend:
developer.
‘
‘
.
'
‘
[F
OCHa
ing upon the composition of the coupler and of
the
~
o‘ooneooNn
2‘
CH3
20
'
One ofcompounds,
the disadvantages
encountered
with
coupler
particularly
coupler com-v
‘
Q_COCHQC,ONH
pounds which are incorporated in sensitive emul
sions, is that the residual couplers in the emul-
3
'
0
‘
sion layer interfere with the stability of the dyes 25 ' QOOCHQOQNHONHCOGH'OGQE
formed upon development.
Many coupler-saris
OCH 3
either unstable and subject to discoloration 1‘ '
4.
themselves or interfere with the stability of the
dye formed in the layers in which the couplers
are incorporated.
‘
H3
_oo'oneo0NH<:?
.
CH3l ‘
‘
30
NH
' 'OmfH'OfO-mm
It is, therefore, an object of the present inven-
CH3
tion to provide a novel class of photographic'cou- i ‘ 5'
'pler compounds.
~COOH2CONHONHCOCH-OO-O?ig
A. further objectlis to provide‘
‘
novel couplers which do not interfere with the
stability of the dyes formed from them.
I
I
(‘ma
Other 35 6-
‘
objects will appear from the following descrip-
‘
0001120ONH-ONHG‘O-CH-O-O-OEHU
tion of our invention.
$2115
These objects are accomplished according‘to’
our invention by the use as coupler compounds
7.
45
.
.
—GOOH2CONH—<:>—NHCOCH-O-O-CsHu
1y compounds having the following structure:
OR
. 1
00m
of ortho-alkoxy benzoyl acetanilides, particular- 40
Q-COCHzOONH-R'
' '
003mm)
OCHS
(‘3H3
8- CgooomooNH-Osm-NO-cm
0H3
“ (11m):
where R is an alkyl radical and R’ is .an aromatic
nucleus of the benzene series.
' 7
.
. .
.
While benzoyl acetanilide couplers are well
known, We have found. that benzoyl acetanilide
couplers having an ortho alkoxy substituent. in 50
the
benzoyl nucleus produce improved yellow 001ors upon color development. and interfere with
the stability of the yellow dyes thus formed to a
considerably less degree than the unsubstituted
benzoyl acetanilides. We have also found that a 55
chlorine substituent in the ortho position in the
aniline nucleus produces dyes having a greater
' 9
‘
'
10 “
.
p
l
‘
o0 omooNn
Q
one.
'
Q
01
CH3
I
ooomo ONH
on,
-
o1
2,407,210
4
11.
22.
coomc om:
QooomcoNH-QNHcocmsooom
SOaN-O-CH:
CH:
(13H:
01
CH:
‘The couplers used according to our invention
with the exception of 20 and 22 are prepared by
treating the appropriate amine with the appro
priate o-alkoxybenzoylacetic ester. For exam
ple, the coupler 21 is prepared as follows:
12.
qoocmc
ONH
on.
NHcooH-o-O-cm,
41H’
1
1
ooorno om;
14.
(‘1H1
1
15
-OOCH|CONH
CHI
N-[3-(2"-methoxybenzoy1acetamino)-4-chlorosu1fonyl]-N-(‘y-phenyl
n-propyD-p-toluidme
Oa-NOC]
OCH;
’
C300 cmo oicim+mNCl
ONO
JIHI
1
1
soar-Q0113 —»
CH:
(CHM
20
somn
15- Qcocmcomr
CH:
"CE'
co CHgOONHUSOgN-O-CHH-CQERO 011
(i?zh
1
16. QoocmwNHQmNH-O-O
'
17.
~CH:
A 500 cc. three-necked ?ask ?tted with a stir
rer, an addition funnel used for solids, and a 10"
distilling column, was charged with 29 cc. (32
1
coomoomr
00H.
-
grams, 0.15 mole) of ethyl o-methoxybenzoyl
oaNH-O-cmnc)
'
1
acetate and 60 cc. of bromobenzene. The flask
was immersed in an oil bath maintained at 170
200°, stirring was begun, and 4'? grams (0.11 mole)
1'
18.
Qcoomoomr
CH:
19.
of N-(3-amino-4-chlorobenzenesulfonyl) -N-('y
phenyl-n-propyl) -p-toluidine was added portion
NHsoOcm
1
wise during one hour. Alcohol distills and the
temperature at the head of the distilling column
remains at 75-80” until the reaction is complete.
‘
vCOOHaC ONHQSOaNG-CH:
C
41H:
CH:
'
H:
After a total reaction time of 1.5 hours, the tem
40 perature of the vapors dropped to ca. 60°. ‘The
reaction mixture was cooled and diluted with 350
cc. of petroleum ether. The oil which separated
crystallized when stirred for a short time. The
CH:
Cells
yield of crude product amounted to 65.7 g., M. P.
45 99-101°. It was recrystallized twice from 500 cc.
20.
0 CH:
>
of alcohol; yield, 44 g. (66%), M. P. 119.5-122".
Q0 O-CH-CONHP-SOr \cmcmonro
CH: (In
21.
Molecular weights
1
N/OCF“
cocmoomz? CH!cHICH:-<:>
.
50 Ethyl o-methoxybenzoylacetate _________ __ 222
N-(3-amin0-4-chlorobenzenesulfonyl) -N
('y-phenylpropyl)-p-toluidine ________ __ 414.5
For \
1
CHI
_ .
Product
55
590.5
The appropriate esters and amines are listed
in the following table:
‘
Ester
Coupler
Amine
Ethyl o-methoxybenzoylacetate ___________ -.
Ethyl 2-methoxy-?amethylbeuzoylaoeta
Aniline
num ber
_ _ _ _ _ _
_ _ _ _ _ _ . _ _ _ _ _ _ _ _.
2
li-P-(y-ten-butylphenoxy)propionamido aniline"
Do ___________________________ _.
_ 3- a-E?-ten-butylphenoxy)propionamido aniline“
Ethyl o-propoxybenzoylacetate__._
Ethyl o~methoxybenmylacetate____
Do ........................ _.
1
--___do
Ethyl o-methoxybenzoylacetate._-.
3
4
. 4» c- 4’-ter.-butylphenoxy)propionamido aniline“
_ 4- a-E'Y-ten-amylphenoxy)butyramido]ani1ine__.__
___
_
5
6
4-[a- 4’-ter.-amylphenoxy)propionamidolaniline ______________ __
7
Do ____________________________________ -. N 21(p-arninobenzenesulfonyl)-N-('y-phenyl-n- propyl) -p-tolui-
8
me.
Do
o-Chlomanilinn
____
Ethyl 2-methoxy-5-methylbenzoylacetate
____do
Ethyl o-methoxybenmylacetate ______ __
Do ________________________ _-
4-amino-3-chlorobenzenesulfonmethyl- -toluide____
4-[a-(4’rter.-butylphenoxy)propionami 01-3-ch10r0a
Do.___
Do_-__
Do.__.
Do..-.
N-(4’-aminc-3-chlorobcnzensu1fonyl)-4-ter.amylani1ine_
.
D0 .................................. __
9
_____ _.
10
11
12
4—amino-3~chl0robenzenesu1fonmethyl-p-chlol'oanilide____
_
4»amino~3-chlorobenzenesulfonmethylanilide _________________ __
4-amino~3-chlorobenzenesulfon-p-toluide ________ __
4-(4’-amino-B-chlorobenzeuesulfonamido)diphenyl. . ___
Do.
Do.
___
_
I
13
14
15
16
17
4-(4’toluenesulfonamido)-2'chloroaniline _____________________ __
18
N-(4~amino‘3'chlorobenzenesu1lonyl)-N-(y-phenyl-n-propyl)-
i9
p-toluidine.
‘12,407,210
5
jCoupler '20 is prepared by chlorinating coupler
19 with sulfuryl chloride in chloroform solution.
Coupler 22 is prepared by condensing 4(2’
methoXy-benzoylacetamino) 3-chloroaniline with
acetylthioglycolyl chloride with a suitable con
densing agent such ‘as sodium acetate or quinoline.
Our couplers may be used in processes in which
the coupleris incorporated in the developingsolu
tion such as those described in Mannes and
Godowsky U. S. Patent 2,113,329, granted April 5,
1938, or. Mannes, Godowsky and Wilder U. S.
Patent 2,252,718,.granted- August 19, 1941, or may
“the jiproduction of colored photographic images
'inllayers of gelatin or other water-permeable .col
loidal'carriers, such as albumimcollodion organic
esters of cellulose, or synthetic resins. The car
rier may be supported by a transparentmedium
such as glass,.a cellulose ester or synthetic resin
or a non-transparent re?ecting medium such ‘as
paper or an opaque cellulose ester. The emul
sion may be coated as a single layer on the sup
port or as superposed layers on one or both sides
of the support.
The superposed layers may be
differentially sensitized and the dyes formed
,be incorporated in the sensitive emulsion layer
therein by coupling may be bleached by ‘an oxi
as described in Fisher U. S. Patent 1,055,155,
dizing agent such as chromiclacid to. colorless
Mannes and Godowsky U. S. Patent 2,304,940, 15 soluble compounds. The destruction of the dye
granted December 15, 1942,»and J elley and Vittum
in this way .doesnot destroy thesilver image and
U. S. Patent 2,322,027, granted June 15, 1943.
a silver image may be developed, bleached-and
The following example illustrates a developing
developed to color images in superposed layers
solution containing a coupler according to our
vas described, for example, in Mannes and Go
invention:
20 .dowsky U. S.‘Patent No. 2,113,329.
The examples and compounds set forth in the
A. 2-amino-5-diethylamino toluene HCl
present speci?cation are illustrative only‘and it
7
>
‘
grams__
2
is to be understood that our invention is to be
taken as limited only by the scope of the append-y
1 25 ed claims.
We claim:
1
‘ Sodium sul?te (anhydrous) ____-___do____‘
2
‘Sodium carbonate (anhydrous)___do____ 20
Potassium bromide _____________ __do___’_
Water to _____________________ __liters__
B. Orthomethoxy benzoyl acetanilide
'
.
grams“
Sodium hydroxide (10% solution)___cc__
(For use, B is added to A.)
2
10 30
-
The foregoing example refers to the addition of.
the coupler compound to the developing solution
itself. The coupler may also be added to the
emulsion layer. Inythe case of multilayer coat 35
ings, it is- desirable» to ‘provide means to prevent
diffusion of the coupler and the adjacent layers.
Also dispersing agents may be used for incorpo~
1. A color-forming photographic ‘developer
comprising a primary aromatic amino developing
agent and an o-alkoxybenzoyl-acetanilide cou
plercompo‘und.
"
,
'
,
,
.
i
2. A colorgforming “ photographic developer
comprising a primary aromatic amino developing
agent and a coupler compound having "the fol
lowing probable formula:
I I
'
'
'
‘
.
Q00 ongo ONE-4R’ '
‘
R
rating the'coupler compound in the emulsion and
in certain cases‘the coupler maybe absorbed or 40 where R is an alkylradical and .R’ is an aromatic
adsorbed to the sensitive saltor may be combined
nucleus of the benzene series.
» , 3. A color-forming photographic developer
with the sensitive salt as a chemical combina;
tion. Certain of the-couplercom‘pounds described
comprising a primary aromatic amino develop
ing agent and a coupler compound having the
above such as Nos. 3, 4, 5, 6, '7, 8, 1‘1, .12, .13, .14,
1'7, 19, 20 and 21, are} in themselves non-diffusing
and ‘may be incorporated in the photographic
following probable formula:
Y
' layer without the use of additional agents ‘to pre
vent di?‘usion. These couplers may also be ‘in
corporated in the emulsion layer according to ‘the
OR
methods of Mannes and Godowsky U. S. .Batent 50
2,304,940 and Jelley and Vittum U. S. Patent
where R is an alkyl radical and Y is an acid
2,322,027 referred to above.
amide group.
In the development of exposed photographic
‘ 4. A color-forming photographic developer
silver halide emulsion layers using the couplers
comprising a primary aromatic amino develop
of our invention, any color-forming developer
ing agent and .a coupler compound ‘having the
containing a primary amino ‘group maybe used.
followingprobable formula:
‘
These include developers having two primary
amino groups as well as those having one of the
I
amino groups substituted orhaving substituents
in the ring, such‘as the alkyl phenylene di'amines. 60
These compounds are usually used in the salt
form, such as the hydrochloride or the’ sulfate
which are more stable than the amines them
selves.
The suitable compounds are diethyl-p
phenylenediamine hydrochloride, monomethyl--p
phenylenediamine hydrochloride, dimethyl-p
phenylene-diamine hydrochloride, and Z-arnino
5-diethylaminotoluene hydrochloride. Th'e ,p~
amino phenols and their substitution products
oR
‘
Y
or
where R is an alkyl radical and Y is an .acid
amide group.
.
'
5. A color-forming photographic developer
comprising a primary aromatic amino developing
agent and a coupler compound having .the fol
lowing probable formula:
' ‘
Q00 omoonnQ-soat-iv
may also be used where ‘the amino group is un 70
substituted. All of these developers have an un-'
'0 CH3
substituted amino group which enables the oxida
tion products of the developer to couple with the
.where R’ is an aromatic nucleus of the benzene
color-forming compounds to form a dye image.
series, and X is selected from the class consist
.
Our development process may be employed for
.
I
01
ing of hydrogen, alkyl, and aralkyl groups.
‘
v.
2,407,210
8
7
developing agent in the presence of a coupler
compound having the probable formula:
6. A color-forming ‘photographic developer
‘comprising a primary aromatic amino developing
agent and a coupler compound having the fol
lowing probable formula:
QooomooNHQeomE-R'
Q-o 0 011,0 ONHQ-SOzNH-R
0 H3
'
CH 5
C1
where R’ is an aromatic nucleus of the benzene
series.
01
where R is an aromatic nucleus of the benzene
13. A photographic emulsion for forming col
10
series.
ored images comprising a water-permeable, col
7. The method of producing a yellow photo
loidal carrier containing a sensitive silver halide
graphic image in a gelatino-silver halide emul
and a coupler compound having the probable
sion layer, which comprises exposing said layer
formula:
and developing it with a primary aromatic amino
developing agent in the presence of an o-alkoxy 15
benzoyl-acetanilide couplerv compound.
CFC o omo ONH-R'
8. The method of producing a yellow photo
R
graphic image in a gelatino-silver halide emul—
Where R is an alkyl radical and R’ is an arc
sion layer, which comprises exposing said layer
and developing it with a primary aromatic amino 20 matic nucleus of the benzene series.
14. A photographic emulsion for forming c01
developing agent in the presence of a coupler
ored images comprising a water-permeable, col
compound having the probable formula:
loidal carrier containing a sensitive silver halide
and a coupler compound having the probable for
" QCOCHzCONH-R’
OR
25
mula:
,
Y
where R is an alkyl radical and R’ is an aro
matic nucleus of the benzene series.
9. The method of producing a yellow photo
OR
graphic image in a gelatino-silver halide emulsion 30 where R is an alkyl radical and Y is an acid
layer,.which comprises exposing said layer and
amide group.
developing it with a primary aromatic amino de
15. A photographic emulsion for forming col
veloping agent in the presence of a coupler com
ored images comprising a water-permeable, col
pound having the probable formula:
35 loidal carrier containing a sensitive silver halide
and a coupler compound having the probable for
Y
QCOCIEHCONHU
mula:
Y
R
Q0 0 011,0 ONH—<
Where R is an alkyl radical and Y is an acid 40
amide group.
10. The method of producing a yellow photo
graphic image in a gelatino-silver halide emul
;
1
OR
where R is an alkyl radical and Y is an acid
amide group.
sion layer, which comprises exposing said layer
16. A photographic emulsion for forming col
and developing it with a primary aromatic amino 45 ored images comprising a water-permeable, col
developing agent in the presence of a coupler
loida1 carrier containing a sensitive silver halide
compound having the probable formula:
and a coupler compound having the probable for
mula:
Y
Q0 0 CH2C ONHQ
OR
01
Where R is an alkyl radical and Y is an acid
amide group.
11. The method of producing a yellow photo
graphic image in a gelatino-silver halide emul
sion layer, which comprises exposing said layer
and developing it with a primary aromatic amino
developing agent in the presence of a coupler
compound having the probable formula:
Q00 0113c ONHQ-iIOni-RI
OCH;
Cl
where R’ is an aromatic nucleus of the benzene
series, and X is selected from the class consist
ing of hydrogen, alkyl, and aralkyl groups.
12. The method of producing a yellow photo
graphic image in a gelatino-silver halide emulsion
layer, which comprises exposing said layer and
developing it with a primary aromatic amino
X
50
Q-oo c1120 oNHQsmn-R'
on;
or
where R’ is an aromatic nucleus of the benzene
series, and X is selected from the class consist
ing of hydrogen, alkyl, and aralkyl groups.
1'7. A photographic emulsion for forming col
ored images comprising a water-permeable, col
60 loidal carrier containing a sensitive silver halide
and a coupler compound having the probable for
mula:
QoooniooNn©-somn_nr
OCHa
Cl
where R’ is an aromatic nucleus of the benzene
series.
ARNOLD WEISSBERGER.
CHARLES J. KIBLER.
PAUL W. VI'ITUM.
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