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Патент USA US2126337

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“2,126,337
Patented Aug. 9, 1938
. UNITED STATES , PATENT vOFFlCE
PHOTOGRAPHIO 2,126,337
coma-roams COM-'
POUNDS
Leopold D. Mannes, Leopold Godowsky, Jr., and
Willard D. Peterson, Rochester, N. Y., assignors
to Eastman Kodak Company,‘ Rochester, N. Y.,
a corporation of ‘New Jersey
No Drawing. Application October 14,1936,
Serial No. 105,616
15 Claims.
This invention relates to‘ photographic devel
opers and more particularly to compounds which
form dyes by coupling with the developing com
pound‘ on development.
k
,
(Cl. os-l-ss)
plate using are compounds in which Y is a
hydrogen atom and R is a heterocyclic ring:_
'
images by depositing a colored compound in the
development has been described in numerous .
' with the oxidization product of the photographic
developer. In U. S. Patent No. 2,039,730, granted
May 5, 1936, to L. D. Mannes and L. Godowsky,
Jr., there is disclosed the use of hydroxylated
diphenyl compounds for'this purpose.
The use
20 of other types of compounds was also decribed
in application; Serial No. 8,519, of L. D. Mannes
and L. Godowsky, Jr.
~
We have found that certain hydroxy styryl
compounds are useful as coupler compounds in
photographic developers and form colored im
ages on photographic development. The dyes
(In;
'
S/
photographic ‘layer adjacent the silver image on
priorpatents. The present invention relates to
10 a process in which the color-forming compound
is contained preferably in the developing solu
tion, but might also be in the sensitive material,
and forms a dye simultaneously and in situ with
the development of the silver image by coupling
.
N'\
_ The method of forming colored photographic
l-(o-hydroxycinnamenyl) benzothiazole
0H
N
.
2~(o-hydroxycinnamenyl) pyridine
15
CH
C HF'N
\
l Err- S /C—CH=OH '
Z-(o-hydroxycinnamenyl) thiazoline
20
The following compound is one which may
be used in which Y is a hydrogen atom and R
is an aromatic nucleus:
OH
'
v
-
.
25
which we contemplate using consist of hydroxy
styrenes substituted at the end of the chain
opposite to that at which the aromatic nucleus
30 -is attached, with an unsaturated or saturated
30
aromatic nucleus or with a. heterocyclic nucleus.
‘ o-st-yrylphenol
The hydroxyl group will usually be in the posi
In‘the ‘following compounds Y and R together
tion ortho with respect to the conjugated chain
so that the position para with-respect ‘to the represent a heterocyclic ring:
hydroxyl group is left free for coupling with'.
the oxidization product of the‘ developer. In
some cases, however, the coupling may occur in
the position ortho with respect to the hydroxyl
group and in this case the hydroxyl group may
40 occur in the position para with respect to the
conjugated chain.
,
l
The hydroxy styryl compounds which we use
have the following general formula:
t
5-(o-hydroxybenzal)-2-thiohydantoin
45
in which “Y is a hydrogen atom and R is 'a
heterocyclic ring or Y and R. together form a.
1161361.;6576116 ring or an aromatic-ring.
55
The. following compounds which we contem-v
S-phenyl—5-(o;hydroxybenzal)-2:4-thiazo1idione
55
2,126,337
2
The color of dyes formed from compounds hav
In the following compound Y and R together
represent an aromatic ring:
ing substituent groups in the ring may vary ac
cording to the type of substituent group em
'
ployed.
Although we have described our invention with
particular reference to the use of the coupling
compound in the developing solution itself, our
invention is in no way limited to this method.
As ‘an alternative method, the coupler compound
may be incorporated in'the photographic layer 10
before development, or before development and
exposure. It may be adsorbed to the sensitive
?ii-disalicylalcyclo-hexanone
10
These compounds may be substituted in the
aromatic ring with groups including halide, ni
tro, amino, substituted amino, alkyl, aryl, and
carboxyl groups. These groups may be substi
15 tuted in the ring at any position except ,in most
cases the position para with respect to the
silver halide grain or chemically combined with
the sensitive salt; or, in some cases, the silver salt
of the coupler compound itself, without halide. 15
may exhibit light sensitivity and coupling prop
erties on development.
Our compounds may be used vto form colored
hvdroxyl group. In certain cases, however, the
substituted groups may occur both ortho and
para to the hydroxyl group and in this case
20 the coupling with the developer will occur in
photographic images in films, plates, or paper
when gelatin or other suitable colloid is used as 20
the carrier for the silver halide constituting the
sensitive salt. The emulsion treated to form the
the position ortho with respect to the hydroxyl
group.
‘
colored image may be on one or both sides of the
support or in superposed layers on one or both
sides of the support. Where two or more layers
_
As developing agents we contemplate using
aromatic amino compounds which function as
photographic developers. The compounds pre
are used they may be differently sensitized to
ferred for this purpose are para phenylenedi
form natural colored images on development, ac
amine and its substituted derivatives. These de
velopers may be substituted in the amino groups
as well as in the ring with alkyl, ester, or halide
30 groups. The compounds which we prefer to use
are dialkyl para phenylene diamines substituted
cording to the process described in application,
Serial No. 8,516, ?led February 27, 1935 by LID.
Mannes and L Godowsky, Jr.
30
What we claim is:
1. A color-forming photographic
in one amino group, the other amino group re
developer
comprising an aromatic amino developing com
pound containing a primary amino group andan
maining unsubstituted. These compounds are
ordinarily used in the salt form, such as the
35 hydrochloride or sulfate, since these compounds
ortho hydroxy styrene coupler compound con 35
taining a substituent group in.the 5 Position of
are more stable than the amines themselves.
the chain, with which the developing compound
is capable of reacting on development.
2. A color-forming photographic developer
Developing agents which may be used include
diethyi para "phenylenediamine, monomethyl
para phenylcnediamine hydrochloride. and di
comprising an aromatic amino developing com 40
pound containing a primary amino group and a
40 ethyl para phenylenediamine sulfate.
A developing formula which may be used is the
coupler compound having the formula
following:
A
Diethyl para phgnylenediamine hydrochlo
ride
45
rim
gram..-
Sodium sul?te ___________________ __gram__
Sodium
45
1
0.5
carbonate______ __ ______ __grams-_ 20
Waterto
liter-..
1
gram"
1
B
Acetone _____________ __' ____________ __cc.__ 50
where Y—'C—R is a structure selected from the
class consisting of structures wherein Y—C-—R
together represent the atoms necessary to com
Add B to A.
plete anv organic ring selected from the class 0011- .
50 Coupler
.
-
The developing agent and the ‘proportions of
sisting of heterocyclic rings and carbocyclic rings,
the ingredients used in the above formula may,
of course, be varied. Solvents‘ other than acetone,
55
such as alcohols, may also be used.
and structures wherein Y represents a hydrogen
atom and R represents _an organic ring selected
from the class consisting of heterocyclic rings and
'
The colors formed by the compounds of the
aromatic rings.
I present invention on coupling with the oxidization
3. A color-forming photographic developer
product of the developer in general range from
blue to green. ‘The colors of the speci?c dyes
referred to above, as indicated by visual tests,
comprising diethyl paraphenylenediamine hydro
60
chloride and a coupler compound having the for
_
mula
are as follows:
OH
Blue-green. _____ __
1 - (o-hydroxycinnamenyl) -
65
benzothiazole
Blue-green ______ _._ 2 - (0 - hydroxycinnamenyl)
pyridine
-
Blue-green. _____ __ 2 - ( o - hydroxycinnamenyl)
thiazoline
70
Dark
green _____ .._ o-styrylphenol
Yellow-green______ 5-(o-hydroxybenzal) -2-thio
h'ydantoin
Light green_ ____ __ 3 - phenyl-5-(o-hydroxyben
zal) -2 : 4-thiazolidione
-1
Green _________ __ 2:6-disalicylalcyclo-hexanone
where Y—O-—R is a structure selected from the 70
, class consisting of structures wherein Y-C-R
together represent the atoms necessary to com
plete an organic ring selected from the class con
sisting of heterocyclic rings and carbocyclic rings,
and structures wherein Y represents a hydrogen
areassv
atom and R represents an organic ring selected
from the class consisting of heterocyclic rings'and
aromatic rings.
4. A color-forming
photographic
developer
Ga comprising an aromatic amino developing com
pound containing a primary amino group and
2 : t‘-disalicylalcyclohexanone.
5. A color-forming photographic developer
comprising an aromatic amino developing com
10 pound containing a primary amino group and an
ortho hydroxystyrene compound having a het
erocyclic-ring substituent in the ,3 position of
the chain.
sion layer which comprises coupling the develop
ment product of an aromatic amino developing
compound containing a primary amino group
with an ortho hydroxy styrene containing a sub
stituent group in the 5 position of the chain.
13. The method of producing a colored photo
graphic image in a gelatino-silver halide emul
sion layer which comprises coupling the develop
ment product of an aromatic amino developing
compound containing a primary amino group 10
with a compound having the formula‘
‘on
Y
‘
’
ii. A color-forming photographic developer
15 comprising an aromatic amino developing com
R
15
pound containing a primary amino group and i
(o-hydroxycinnamenyl) =benzothiazole.
7. A color-forming photographic developer
comprising diethyl paraphenylenediamine hydro
20 chloride and 2:ii-disaiicylalcyclohexanone.
where Y——C-R ‘is a structure selected from the
class consisting of structures wherein Y-C-R
'
togetherrepresent the atoms necessary to com 20
8. A photographic image comprising a dye plete an organic ring selected from the class con
formed by the coupling oi’ the development prod; sisting of heterocyclic rings and carbocyclic rings,
not of an aromatic amino developing compound
containing a primary amino group with an ortho
25 hydroxy styrene containing a substituent group
and structures wherein Y represents a hydrogen
atom and 13. represents an organic ring selected
from the class consisting of heterocyclic rings and 25
in the c position of the chain.
aromatic rings.
9. A photographic image comprising a dye
formed ‘by the coupling of the oxidation product
it. The method of producing a colored photo
graphic image in a gelatino-silver halide emul
of an aromatic amino developing compound con
sion layer which comprises coupling the develop
30 taining a primary amino group with an crtho
hydroxy styrene containing a substituent group
in the ,3 positionv oi the chain.
i
ii). A photographic image comprising ‘a dye
'
ment product of an aromatic amino developing 30
compound containing a primary amino group
with a compound present in the developer having
the formula
formed by the coupling of the development prod
35 uct oi’ an aromatic amino developing compound
containing a primary amino group with a com
35
pound having the formula
where Y—C--R is a structure selected from the 40
class consisting of structures wherein Y--C-R.
together represent the atoms necessary to com
plete an organic ring selected from the class con
40
4:5
where Y-—C--R is a structure selected from the
class consisting of structures wherein Y-C‘—R
together represent the atoms necessary to com
plete an organic ring selected from the class con
sisting of heterocyclic rings ‘and carhocyclic rings,
and structures wherein Y represents a hydrogen
atom and R represents an organic ring selected
from the class consisting of heterocyciic rings and
aromatic rings.
ii. A photographic image comprising a dye
formed ‘by the coupling of the development prod
55 not of diethyl paraphenylenediamine hydrochlo
sisting of heterocyclic rings and carbocyclic rings,
and structures wherein Y represents a hydrogen
atom and R represents an organic ring selected
from the class consisting of'heterocyclic rings and
aromatic rings.
15. The method of producing a colored photo
graphic‘ image in a gelatino-silver halide emul
sion layer which comprises coupling the develop
ment product of an aromatic amino developing '
compound containing a primary amino group
with a compound present in the emulsion layer
having the‘ formula
55
ride with a compound having the formula '
till
60
where ‘if-C-R is a structure selected fr0m_the
65
where Y—C-R is a structure selected from the
class consisting of structures wherein Y-JC--R
class consisting‘of structures wherein Y-C—R
together represent the atoms necessary to com
plete an organic ring selected from the class con
together represent the atoms necessary to com
plete an organic ring selected from the class con
sisting of heterocyc/lic rings and carhocyciic rings,
and structures wherein Y represents a hydrogen
and structures wherein Y represents a hydrogen
atom and R represents an organic ring selected
‘atom and It represents an organic ring selected
from the class consisting of heterocyclic rings and
aromatic rings.
70 from the class consisting of heterocyclic rings and
aromatic rings.
-
'
12. The method of producing a colored photo
graphic image in a gelatino-silver halide emul
65
sisting of heterocyclic rings and carlpocyclic rings,
.
\
LEOPOLD D. MANN'ES.
LEOPOLD GODOWSKY, JR.
n I‘ a‘ - i' Ii D. PETERSQN.
70'
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