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Патент USA US3084058

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United States Patent 0 " ICC
3,084,044
Patented Apr. 2, 1963
2
1
I The heterocyclic compounds contemplated for use here
1n have the following general formulae:
3,084,044
NITROGENOUS HETEROCYCLIC CARBOXYAL
KYLMERCAPTO POLYOXYALKYLENE ESTER
PHOTOGRAPHIC SENSITIZER
Fritz Dersch and Millet R. De Angelus, Binghamton,
N.Y., assignors to General Aniline & Film Corpora
tion, New York, N.Y., a corporation of Delaware
N0 Drawing. Filed Dec. 9, 1960, Ser. No. 74,786
19 Claims. (Cl. 96-456)
10
This invention relates to photographic materials.
More particularly, this invention relates to photographic
materials sensitized by means of water soluble hetero
wherein X represents the carbon atoms necessary to com
cyclic compounds in which a heterocyclic nucleus is linked
plete a ?ve-membered heterocyclic nucleus; Y represents
—-S—-, --0—, ---NH--- or —CH=CH— (oxygen, sul
fur, imino or vinylene); Z represents the atoms necessary
to a polyoxyalkylene chain by means of a carboxyalkyl
cercapto group.
It is well known that polyalkylene oxides such as poly
to complete an aromatic nucleus of the benzene or naph
thalene series so that X and Z together form a benzoxa
oxyethylene and polyoxypropylene increase the speed of
silver halide emulsions.
It has also been observed that
condensation products of alkylene oxides with amines,
carboxylic acids, alcohols, amides or phenols (made ac
cording to United States Patents 1,970,578 and 2,213,477)
and dicyclohexylol-dialkyl methane (see United States
20
zole, naphthoxazole, benzothiazole, naphthiazole, ‘benz
imidazole or quinoline nucleus; R1 and R2, which may
be alike or different, are alkylene groups having from 2
to 3 carbon atoms as represented by ethylene and pro
pylene groups; R3 represents hydrogen or an alkyl radical
Patent 2,240,472) have been used as sensitizers. The
polyalkylene oxides or the alkylene oxide condensation 25 having from 6 to 18 carbon atoms, for example, hexyl,
octyl, nonyl, decyl or dodecyl; n is an integer ranging
products should have a molecular weight of at least 300
from 1 to 3 and m is an integer between 5 and 40 so as
and preferably 1,500 to 4,000 or more.
to give this compound a molecular weight of at least 400.
The use of the polyalkylene oxides or alkylene oxide
Examples of compounds within the ambit of this gen
condensation products as sensitizers is limited because of
their tendency to increase the formation of fog during 30 eral formula are:
storage of the photographic ?lm, especially storage at ele
vated temperature and high humidity. The use of con
ventional antifoggants is not su?icient to satisfactorily
eliminate or minimize fog formation in a ?lm coated with
an emulsion containing such products as sensitizers. Spe
cial antifoggants had to be found for use with such emul
sions; and, in this connection, reference is made to United
Ester of 2carhoxymethylmcrcaptobenzothlazole and dodecyl
oxypolycthyleneoxy-ethanol
States Patents 2,704,716, 2,716,062 and 2,728,666.
S
It is an object of this invention to provide a novel sen
40
sitizer for use with a photographic emulsion or with a
/
C~C3H5COO—CzH4O—(C:H4O)mC1sTIn
photographic developer to greatly increase the speed of
the emulsion without materially increasing the fogging
tendency thereof, any tendency to fog being eliminated or
minimized by the use of conventional antifoggants.
Another object of this invention is to provide a photo
graphic ?lm having a layer thereon containing a water
soluble polyoxyethylene ester of Z-carboxyalkylmercapto
Cl
\
N
Ester of 2~carhoxyethylmercapto-d-chlorobenzothlnzole and
‘hexadecylorry-polyethyleneoxy—ethanol
azoles or the terminal alkyl ethers of such esters.
Other objects and advantages of this invention will
appear to those skilled in the art from the detailed descrip
50
tion thereof given below.
We have now discovered that water-soluble polyoxy
alkylene esters of 2—carboxyalkylmercapto-azoles as well
Ester of 0ctadecyloxy-polyethylcneoxy-ethano] and 2-cnrboxy
propylinercapto-5-nitrobenzot11iazole
‘as the terminal alkyl ethers of such esters have a re
markable speed increasing effect on silver halide emul
sions. Surprisingly, these heterocyclic derivatives, unlike
the heretofore used polyoxyalkylenes, do not have the ob
jectionable tendency of increasing the fog of photographic
?lms during storage especially under high temperature
and humidity conditions. ‘fogging of photographic ?lm
Ester of dodecyloxy-polyethyleneoxy-ethnnol and firm-boxy
60
metllylmercupto—5,ddimethylbcnzothiazole
having a coating of a silver halide emulsion and contain
ing the novel sensitizer of our invention may, therefore,
be controlled by the use of the conventional antifoggants
and stabilizers used in the photographic art. Conse
quently, the use of a special type of antifoggant to prevent 65
fogging of an emulsion containing unhalogenated poly
oxyalkylenes such as those disclosed in United States
Patents 2,704,716, 2,716,062 and 2,728,666 becomes un
Ester of liexadecyloxy~polyothyloneoXy-ethunol and 2~cnrboxy
ethylrncrcaptolahdhcnzobcnzotlliazole
necessary.
3,084,044»
3
s
/ \
o- s -oH,o o o_orno mo rno—<o mo memo) roam,
orno-
\ /
N
2~n1ercaptobenzothiazolc, 2—mercapto-S-mcthyl-benzothia
Ester
of dodecyloxy-polyproglyleneoxy-propanol
and 2
carboxymethylmercaptd
~methoxybenzothiazo1e
zole, Z-mercapto-5—methoxy-benzothiazole, 2-mercapto~
NH
4,5 - benzobenzothiazole, Z-mercapto-S-chlorobenzlothia
/
zole, Z-mercapto-S-nitro-bcnzothiazole, 2-mercapto-5,6-di
H
N
Ester of dodecyloxy-polyethyleneoxyethanol and 2-carboxy
methylbcnzothiazole and the various analogues and
homologues thereof.
The increase of effective sensitivity of photographic
silver halide emulsions with the polyoxyalkylene esters
of the 2-carboxyalkylmercapto azoles can be obtained
in a number of ways. They may be added to an under
methylmercuptobenzimidnzole
O
/
coating, to a middle coating, to an \overcoating or to a
C-S —CH:C 0 001120 IIzO-(C H16 H10) mC 1110111011
surface coating prior to the coating operation. If desired,
they may be added during the actual preparation of the
N
emulsion either before or after washing of the emulsion.
The speed of sensitivity increasing agents of our inven
tion may be used in various types of photographic emul
Polyethyleneoxy ester of 2~carboxymethylmercaptooxazole
sions; for example, nonsensitized emulsions, orthochro
matic, panchromatic, and X-ray emulsions. If used with
sensitizing dyes, they may be added to the emulsion be
Ester of dodecyloxy-polyethyleneoxy-ethnnol and 2-carboxy
fore or after the dyes are added. Various silver salts may
be used as a sensitive element; such as, silver bromide,
methylmercaptothiuzoline
H¢C—S
silver iodide, silver chloride or mixed silver halides.
¢C—-SC*H;0O0CIIZCJII1O—(C;IH|O)[11-431mm
OHnC-——N
30
Ester of d0dccyloxy-polyethyleneoxy-ethanol and 2-carboxy~
methylmercaptothiaaolidine
The above compounds are prepared by re?uxing a
2-mercaptoazole with the lower alkyl ester of a chloro
or bromoaliphatic acid such as ethyl bromoacetatc, methyl
These sensitivity increasing agents may be used in emul
sions intended for color photography; for example, emul
sions containing color-forming components. The carrier
in the photographic emulsion may be gelatin or other col
loids such as collodium, albumen, cellulose derivatives,
polyvinyl alcohol or synthetic resins. The emulsion con
chloroacetate, ethyl-,B-bromopropionate, methyl-'y-bnomo
taining our novel sensitizer may be coated on any con
ventional base such as paper, glass, cellulose ester such
as cellulose acetate, cellulose ethers and others.
butyrate and the like in the presence of an acid-binding
agent such as sodium hydroxide, pyridine and the like and
The amounts of sensitivity increasing agents used per
kilogram of emulsion range from 0.15 to 5.0 grams per
then converting the lower alkyl ester of the carboxyalkyl
kilogram of liquid emulsion. When expressed in terms
mercaptoazole thus obtained into the polyoxyalkylene 40 of silver halide, the ‘amounts of sensitivity increasing
ester by heating the azole in the presence of a suitable
solvent diluent such as toluene or xylene with a polyoxy
alkylene or polyoxyalkylene alkyl ether.
agents range from 0.25 to 5.0 grams per mole of silver
halide.
The sensitivity increasing agents of our invention can
also be added to prc-bath solutions or to standard devel
This reaction
is of the ester exchange type so that the lower alcohol
which is used in the starting material is driven off during
the reaction.
oper solutions. These developer solutions contain, in
addition to the speed increasing agent, a developing agent
such as Metol, hydroquinone, 1-phenyl-3-pyrazolidone
In an alternate method, the polyoxyalkylene alkyl ether
is treated with thionyl chloride to replace its terminal hy
(Phcnidone); an alkali such as sodium or potassium car
bonate; a preservative or anti-oxidant such as sodium sul
droxy group by a chloride. The chloride derivative is
then reacted with the alkali metal salt of a carboxyalkyl
mercaptoazole to yield an oxy product.
Examples of polyoxyalkylene ethers which can be used
in the preparation of the hcterocyclic esters include the
?te; and an antifoggant such as potassium bromide. The
amounts of speed increasing agents used range from 0.3
to 6.0 grams per liter of developer solution.
The following speci?c examples are given of the man
ner of producing and using the sensitizers of our inven
tion. It is to ‘be understood, however, that these ex
amples are given by way of illustration and not by way
of limitation.
following:
Example I
(it)
A silver halide emulsion in gelatin containing 4 per
cent silver iodide and 96 percent silver bromide was pre
pared in a conventional manner and brought up to its
Among the azoles suitable as starting materials are the
following: 2-mercaptobenzimidazolc, Z-mercaptoquino
line, 2-mercapto-4-methylquinoline, Z-mercaptobenzoxa
zole, 2 - mercapto - 5 - mcthylbenzoxazole, 2-mercapto-5
methoxy-bcnzoxazole, 2-mercapto-4,5-benzobenzoxazole,
maximum light sensitivity. It was then readied for coat
ing on ?lm base; that is, melted at 40° C. The necessary
coating ?nals were added, such as sensitizing dyes, sta
bilizers and hardeners. A 10 percent aqueous solution
of the above-illustrated ester of 2~carboxymethylmercap
tobenzothiazole and polyoxycthylene lauryl ether was
prepared, and measured amounts of this solution were
added to a sample of the above~described emulsion con
3,084,044
6
5
Example IV
taining about 0.4 mole of silver halide. A sample of the
same emulsion, but not containing the speed increasing
additive, served as a control.
A second control was pre
pared by adding polyoxyethylene lauryl ether to a third
emulsion sample. The so-prepared emulsion samples
were coated on a suitable cellulose ester base and dried.
Samples of these ?lm coatings were then exposed in a
type II-B sensitorneter and developed in a developer of
the following composition:
The procedure was the same as in Example I except
that the reaction product of Z-carboxymethylmercapto
benzothiazole and 8 moles of propylene oxide iodide was
Grams 10 used. The results were similar to those obtained in Ex
Metol (p-methylaminophenol sulfate) _________ __ 1.5
Sodium sul?te, anyhydrous __________________ __ 45.0
ample I.
The compound was prepared by heating under reflux 1
mole of Z-carbethoxymethylmercaptobenzothiazole and 1
Sodium bisul?te ____________________________ __
1.0
Hydroquinone _____________________________ __
3.0
mole of propylene oxide for 1 hour using a small amount
Sodium carbonate, monohydrated _____________ __
6.8
Potassium bromide _________________________ __
.8
of potassium hydroxide. Additional increments of pro
pylene oxide were added while heating and re?uxing con
tinued until a total of 8 moles of propylene oxide had
Water to make 1.0 liter.
The developed ?lms were short-stopped, ?xed and
washed in the conventional manner. The results ob
been consumed.
tamed were as follows:
Example V
GIL-S
\o-sornooo-omemo-(oinornmm-onmi
Fog
Relative
Speed
H:-N/
The procedure was the same as in Example I except
6 Days
that the reaction product of 2~carbethoxymethylmercapto
thiazolidine and polyoxyethylene lauryl ether was used.
After 12’
Oven
Dev.
Test and
6’ Dev.
The results were similar to those obtained in Example I.
Example VI
Quantity of ester of 2-carhoxymethly
mereaptobenzothiazole and polyoxyeth
30
ylcnc lauryl ether:
One kilo of a silver halide emulsion in gelatin con
0 _________________________________ __
0 5 gram _________________ __
10D
150
. 13
. 15
.08
.08
taining 4 percent silver iodide and 96 percent silver bro
1.0 gram __________________________ .,
16D
.20
.09
mide was coated on film base in a manner known to
150
. 28
. 16
Quantity of polyoxyethylene lauryl
the art.
ether added:
1.0 gram __________________________ __
The ester of Z-carboxymethylmercaptobenzothiazole
After the coating was performed, an aqueous
gelatin solution containing 20 grams of gelatin per liter
and 20 milligrams of the heterocyclic polyoxyethylene
derivative of Z-mercaptobenzimidazole of Example I was
coated thereon as an anti-abrasion layer. After drying,
sitiner was prepared as follows: Twenty grams of poly
?lm samples were exposed and processed as described in
oxyethylene lauryl ether (commercially available as Atlas
Example I. The samples described exhibited a relative
40
Powder Company’s Brij-35) and 1.1 grams of Z-Carbeth
speed of 150 with a fog of .18 as compared with a type
oxymethylmercaptobenzothiazole (prepared by the reac
coating of the same emulsion having an anti-abrasion
tion of Z-mercapto-benzothiazole and ethyl bromoacetate)
layer similar to that described above, but lacking the
were added to 50 milliliters of toluene. The mixture was
speed increasing additive and having a speed of 100 and
heated to re?ux for 8 hours, the toluene removed by dis
a fog of .22.
tillation and the residue dried over phosphorus pentoxide
Example VII
in a dessicator. Seventeen grams of a light tan, waxy
Several samples of a conventional photographic ?lm
compound was obtained.
were exposed in a type 1113 sensitometer and then divided
into two groups. One group of samples was developed
Example II
for twelve minutes at 68° F. in a standard Metol-hydro
quinone developer as described in Example I. The other
s
group
of samples was developed for the same length of
/ \
Q—S—-CgH5COO-CH:CH2O—(CHgCHzO)mCmH33 time and at the same temperature as the ?rst group in
and polyoxyethylene lauryl ether which served as a sen
Cl
\
N
The procedure was the same as in Example I except
that the reaction product of polyoxyethylene-hexadecyl
ether and 2~carbethoxyethylmercapto-S-chlorobenzothia
zole was used. The results were similar to those obtained
in Example I.
Example III
a Metol-hydroquinone developer which had been prepared
by adding to 1 liter of the developer described in Ex
ample I, 2 grams of the polyoxyethylene lauryl ether of
2-carboxymethylmercaptobenzothiazole. It was found
that the samples developed in the standard developer had
a relative speed of 100 whereas the samples developed
60 in the developer containing the novel sensitivity increas
ing agent of our invention showed a relative speed of
175 without an increase in fog.
Modifications of the invention will occur to persons
skilled in the art. Thus, it is evident that in lieu of the
ethylene oxide addition products of the examples, any
of the addition products mentioned above may be em
ployed in our invention. In place of the speci?c poly
oxyethylene derivatives used in the reaction with the 2
carboxyalkylrnercapto azoles or their esters for the prepa
The procedure was the same as in Example I except
that there was used the ester of polyoxyethylene lauryl 70 ration of our novel speed sensitizing agents, there may
be used the condensation products of alkylene oxide with
ether and 2-carbethoxymethylrnercaptoquinoline. The re
amines, carboxylic acids, amides or phenols as prepared
results were similar to those of Example I.
according to United States Patent 1,970,578.
The compound was prepared by heating in toluene
We, therefore, do not intend to be limited in the patent
polyoxyethylene lauryl ether and Z-carbethoxymethylmer
75 granted except as necessitated by the appended claims.
captoquinoline.
3,084,044
7
We claim:
wherein R1 and R2 are alkylene groups containing from
1. A photographic material comprising a light-sensitive
2 to 3 carbon atoms; R3 is a member of the group con
emulsion having in contact therewith a water-soluble
sisting of hydrogen and alkyl groups of from 6 to 18
carbon atoms; X represents the carbon atoms necessary
to complete a S-membered heterocyclic nucleus; and Y
represents the atoms necessary to complete a heterocyclic
mononuclear ring and is a member selected from the
group consisting of oxygen, sulfur, imino and ethylene;
nitrogenous heterocyclic carboxyalkylmercapto polyoxy
alkylene ester having a molecular weight of at least 400
to increase the sensitivity thereof.
2. A light-sensitive silver halide emulsion containing
as a sensitizer therefor, a water-soluble heterocyclic poly
oxyalkylene compound selected from the group consist
ing of those having the following general formulae:
Z represents the atoms necessary to complete an aromatic
10 ring system of the benzene and naphthalene series; n
is an integer ranging from 1 to 3 and m is an integer
between 5 and 40.
7. A photographic material comprising a base, a silver
halide emulsion layer and in contact with said emulsion,
a layer containing a compound of the following formula:
S
Y
/
/C-s-oHiGoo-c H1OHiO—(OH=CHg0)mCmHu.
N/
N
wherein m is an integer between 5 and 40.
wherein R1 and R2 are alkylene groups containing from
‘8. A photographic material comprising a base, a silver
2 to 3 carbon atoms; R3 is a member of the group con
halide emulsion layer and, in contact with said emulsion,
a layer containing a compound of the following formula:
sisting of hydrogen and alkyl groups of from 6 to 18
carbon atoms; X represents the carbon atoms necessary
to complete a S-membered heterocyclic nucleus; and Y
s
/
represents the atoms necessary to complete a hetero
cyclic mononuclear ring and ‘is a member selected from
the group consisting of oxygen, sulfur, imino and ethylene;
Cl
Z represents the atoms necessary to complete an aromatic
ring system of the benzene and naphthalene series; 11 is
an integer ranging from 1 to 3 and m is an integer be
tween 5 and 40.
wherein m is an integer between 5 and 40.
‘9. A photographic material comprising a base, a silver
halide emulsion layer and, in contact with said emulsion,
a layer containing a compound of the following formula:
3. A light-sensitive silver halide emulsion containing
as a sensitizer therefor, in a sensitizing amount, a com
pound having the following formula:
8
/
C~S~CII2COO——GIT2GU2O—(CIIzCIIgO)mGi2lI25
\
10. A photographic material comprising a base and a
gelatin silver halide emulsion layer containing in a sensi
tizing amount a compound having the following formulae:
N
wherein In is an integer between 5 and 40.
4. A light-sensitive silver halide emulsion containing
as a sensitizer therefor, in a sensitizing amount, a com
pound having the following formula:
s
/
C—S—CgiI5C00-OII¢OHzO—(OIIgOHiO]mGmH33
Cl—
50
N
wherein m is an integer between 5 and 40.
5. A light-sensitive silver halide emulsion containing
wherein R1 and R2 are alkylene groups containing from
as a sensitizer therefor, in a sensitizing amount, a com
pound having the following formula:
N
Cl U
60
6. A photographic material comprising a base, a layer
of gelatino silver halide emulsion thereon and in contact
with said emulsion a water-soluble ester of a carboxy
alkylmercaptoazole and a polyalkylene oxide said emul
sion having the following general formulae:
N
sisting of hydrogen and alkyl groups of from v6 to 18
carbon atoms; X represents the carbon atoms necessary
to complete a S-membered heterocyclic nucleus; and Y
represents the atoms necessary to complete a heterocyclic
mononuclear ring and is a member selected ‘from the
group consisting of oxygen, sulfur, imino and ethylene;
Z represents the atoms necessary to complete an aromatic
ring system of the benzene and naphthalene series; n is
an integer ranging from 1 to 3 and m is an integer be
tween 5 and 40.
11. A photographic material comprising a base and a
light-sensitive silver halide emulsion layer containing in
1 s
x’
2 to 3 carbon atoms; R, is a member of the group con
%
o_s-(o1~ri),,-co o-n10-(Ri0)m—m
a sensitizing amount a compound having the following
formula:
8
and
Y
wherein m is an integer between 5 and 40.
3,084,044
9
10
16. The process as de?ned in claim 14 wherein said
12. A photographic material comprising a base and a
compound has the following formula:
light-sensitive silver halide emulsion layer containing in
a sensitizing amount a compound having the following
formula:
s
UK
wherein m is an integer between 5 and 40.
17. A photographic developer solution comprising a
wherein m is an integer between 5 and 40.
13. A photographic material comprising a base and a
10 silver halide developing agent, an alkali, an anti-oxidant
and an antifoggant containing as a speed-increasing agent,
a water-soluble heterocyclic polyoxyalkylene compound
light-sensitive silver halide emulsion layer containing in
having the following general formulae:
a sensitizing amount a compound having the following
formula:
s
\
20
14. The process of increasing the sensitivity of a light
sensitive silver halide material comprising a base having
a light-sensitive silver halide emulsion thereon which
comprises exposing said emulsion and developing the
wherein R1 and R2 are alkylene groups containing from
same in the presence of a water-soluble heterocyclic poly
oxyalkylene compound selected from the group consist
ing of those having the following formulae.
2 to 3 carbon atoms; R3 is a member of the group con
sisting of hydrogen and alkyl groups of from 6 to 18
carbon atoms; X represents the carbon atoms necessary
to complete a S-rnembcred heterocyclic nucleus; and Y
30 represents the atoms necessary to complete a heterocyclic
mononuclear ring and is a member selected from the
group consisting of oxygen, sulfur, imino and ethylene;
Z represents the atoms necessary to complete an aro
matic ring system of the benzene and naphthalene series;
n is an integer ranging from 1 to 3 and m is an integer
between 5 and 40.
18. The developer solution as de?ned in claim 17
wherein said compound has the following formula:
wherein R1 and R2 are alkylene groups containing from 40
2 to 3 carbon atoms; R3 is a member of the group con
sisting of hydrogen and alkyl groups of from 6 to 18
carbon atoms; X represents the carbon atoms neces
sary to complete a S-membered heterocyclic nucleus; and
Y represents the atoms necessary to complete a hetero
cyclic mononuclear ring and is a member selected from
wherein m is an integer between 5 and 40.
19. The developer solution as de?ned in claim 17
the group consisting of oxygen, sulfur, imino and ethyl
wherein said compound has the following formula:
ene; Z represents the atoms necessary to complete an aro
S
matic ring system of the benzene and naphthalene series;
n is an integer from 1 to 3 and m is an integer between 50
5 and 4O.
15. The process as de?ned in claim 14 wherein said
compound has the ‘following formula:
/
wherein m is an integer between 5 and 40.
References Cited in the ?le of this patent
UNITED STATES PATENTS
wherein m is an integer between 5 and 40.
60
2,819,965
2,952,539
2,955,037
Murray et al. _________ __ Jan. 14, 1958
Dersch et al. _________ _._ Sept. 13, 1960
Smith ________________ __ Oct. 4, 1960
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