 |
Description  |
|
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a photographic light-sensitive material in which
the use of organic substances which may cause environmental pollution in
the steps of the production and of the development processing is
eliminated and, more particularly, it relates to a photographic
light-sensitive material containing surface active agents having no toxic
physiological action and high biodegradability applied in such a manner
that they exhibit excellent properties as a coating aid and as an aid for
dispersing photographic additives in a light-sensitive silver halide
emulsion.
2. Description of the Prior Art
In the production of a photographic light-sensitive materials, anionic,
nonionic, cationic or amphoteric surface active agents are used as a
coating aid, a dispersing agent, an antistatic agent, a setting agent, an
agent for modifying the physical properties of interfaces, an agent for
modifying the properties of a light-sensitive silver halide such as a
sensitizer or an infectious development accelerator, and further
photographic additives such as sensitizing dyes, antifogging agents,
couplers, ultra-violet absorbants, antioxidants or dyes. Of all of these,
anionic surface active agents are used in great quantities. Since a large
quantity of anionic surface active agents is used also in fields other
than the photographic fields, it is all the more important to develop
improved techniques for overcoming environmental pollution caused by such
surface active agents.
Of the anionic surface active agents used in the production of photographic
light-sensitive materials, those used in the dispersion of photographic
additives in a light-sensitive silver halide emulsion should,
particularly, be selected carefully, regarding their performance such as
their dispersibility relative to the material to be dispersed and their
influence on the essential properties of the additives.
In order to disperse photographic additives, particularly, hydrophobic
couplers and ultraviolet absorbants, the salts of alkylbenzenesulfonic
acids or the salts of alkylnaphthalenesulfonic acids have been used. These
agents are described in, e.g., Japanese Patent Publication Nos. 4293/64
and 4547/71, U.S. Pat. Nos. 2,322,027; 2,360,289; 2,801,170; 2,801,171;
2,852,382; 2,949,360; 3,396,027 and 3,619,195, German Patent Nos.
1,143,707; 2,045,414; 2,043,271 and 2,045,464. However, surface active
agents which have aromatic rings are more or less disadvantageous with
respect to the biodegradability and their effects on physiological action.
Also, saponin has been used, as described in, for instance, British Patent
Nos. 1,098,594; 1,099,415; 1,099,416 and 1,099,417. However, saponin is
unsuitable because of its poor properties for dispersing photographic
additives, its poor adaptability to high-speed coating of a silver halide
emulsion in high concentration in conformity with present techniques, and
insufficient shelf life for the preparation of a dispersion of
photographic additives in high concentration. Furthermore, aliphatic
sulfuric acid esters have been used, as described in, e.g., U.S. Pat. Nos.
2,304,940; 2,311,021; 2,322,027 and 2,533,514. These sulfuric acid esters
tend to be hydrolyzed and, particularly, straight chain alkyl sulfuric
acid esters tend to be inferior to salts of alkylbenzenesulfonic acids in
dispersability when used alone as an anionic surface active agent. Mostly,
they are used together with nonionic surface active agents to correct this
defect, as described in, e.g., German Patent Nos. 1,942,873.
The method of solubilizing photographic additives in an aqueous solution of
anionic surface active agents and then adding the same to a
light-sensitive emulsion is known, as described in, e.g., U.S. Pat. No.
3,822,135. However, no clear descriptions are found in this specification
as to surface active agents of the present invention. In this previously
disclosed method, the salts of alkylbenzenesulfonic acids are also
preferred, but they are not always desirable with respect to physiological
effects and biodegradability.
SUMMARY OF THE INVENTION
This invention provides a method of overcoming these defects.
A first object of this invention is to provide a photographic
light-sensitive material prepared by a process in which substances without
a toxic physiological action are used.
A second object of this invention is to provide a photographic
light-sensitive material prepared by a process using surface active agents
which are highly biodegradable and, thus, do not cause environmental
pollution if discharged during development processing.
A third object of this invention is to provide a method of employing
surface active agents without a toxic physiological action and having high
biodegradability for the coating of a photograhic light-sensitive
emulsion, or the preparation of a dispersion of photographic additives and
the improved addition thereof to an emulsion.
A fourth object of this invention is to provide a dispersion of a coupler,
a hydroquinone derivative or an ultraviolet absorbant, which is
particularly finely dispersed and has excellent stability with time.
These and other objects of the invention will become apparent from the
following description of this invention.
The objects of this invention are accomplished by a photographic
light-sensitive material comprising a support having thereon a hydrophilic
colloid layer containing, in combination, at least two surfaces active
agents selected from the compounds represented by the general formula (I)
##EQU2##
and the general formula (II)
R.sub.3 -- SO.sub.3 M (II)
wherein in the above formulas, R.sub.1 and R.sub.2 each represents an
aliphatic residue in which the sum of the number of carbon atoms contained
in R.sub.1 and R.sub.2 is 8 to 32; R.sub.3 represents an aliphatic residue
having 8 to 20 carbon atoms; and M represents a cation or a cationic group
capable of forming a salt with a sulfonic acid.
DETAILED DESCRIPTION OF THE INVENTION
In the above formulas (I) and (II), R.sub.1, R.sub.2 and R.sub.3 are
preferably an alkyl residue and M is preferably a sodium ion, a potassium
ion, an ammonium ion, etc. Suitable aliphatic hydrocarbon residues include
alkyl groups and alkenyl groups, such as octyl, decyl, dodecyl,
pentadecyl, octadecyl, etc.
The surface active agents represented by the above general formulas (I) and
(II) used in this invention can be synthesized using known process
comprising sulfonation of normal-paraffins. In this process, it is well
known to employ a mixture of compounds with different carbon chain lengths
depending upon the carbon chain length distribution of the composition of
the normal-paraffins used as a starting material, and the conditions for
sulfonation are well known. That is, a mixture of the above secondary
alkane sulfonates of the general formula (I) with different numbers of
carbon atoms in R.sub.1 and R.sub.2 ranging from CH.sub.3 (1 carbon atom)
to C.sub.18 H.sub.37 (18 carbon atoms), or a mixture of the above primary
alkane sulfonates of the general formula (II) with different numbers of
carbon atoms in R.sub.3 ranging from C.sub.8 H.sub.17 (8 carbon atoms) to
C.sub.20 H.sub.41 (20 carbon atoms) can be obtained. Moreover, a mixture
of the secondary alkane sulfonate compounds represented by the general
formula (I) with the primary alkane sulfonate compounds represented by the
general formula (II) can also be obtained.
The production method and the composition of the surface active agents used
in this invention are described in, for instance, European Chemical News,
pp. 3 and 39, December (1966), F. Asinge Paraffine-chemistry and
Technology, Pergamon Press (1967) or Oil Chemistry Vol. 19, p. 458 (1970).
Typical examples of the surface active agents used in this invention
include primary alkane sulfonate such as C.sub.8 -n-alkane solfonate,
C.sub.9 -n-alkane sulfonate, C.sub.10 -n-alkane sulfonate, C.sub.11
-n-alkane sulfonate, C.sub.12 -n-alkane sulfonate, C.sub.13 -n-alkane
sulfonate, C.sub.14 -n-alkane sulfonate, C.sub.15 -n-alkane sulfonate,
C.sub.16 -n-alkane sulfonate, C.sub.17 -n-alkane sulfonate and C.sub.18
-n-alkane sulfonate, the corresponding secondary alkane sulfonates or
mixtures of the above various secondary alkane sulfonates and primary
alkane sulfonates.
Some of the surface active agents corresponding to these compounds are
commercially available such as under the trade name "Hostapur SAS" (made
by Hoechst Co., Ltd.).
The weight distribution of the compounds having a different carbon chain
length is, for example, as follows.
C.sub.13 -n-alkane sulfonate
5%
C.sub.14 -n-alkane sulfonate
16%
C.sub.15 -n-alkane sulfonate
30%
C.sub.16 -n-alkane sulfonate
30%
C.sub.17 -n-alkane sulfonate
15%
C.sub.18 -n-alkane sulfonate
4%
The alkane sulfonates scarcely possess any toxic physiological action and
are highly biodegradable, so they are excellent in controlling
environmental pollution.
A first feature of this invention resides in that the combined use of at
least two surface active agents selected from those of the general
formulas (I) and (II) exhibits a superadditive and advantageous
performance as compared with the individual use of each surface active
agent. For example, when they are used in combination as a dispersing
agent for couplers, an emulsified dispersion with more finely divided
particles and greater stability is obtained. It has been known that when
an anionic surface active agent and a nonionic surface active agent are
used in combination, an excellent emulsified product of a photographic
additive such as a coupler can be obtained as compared with the individual
use of the anionic surface active agent, as described in, e.g., German OLS
No. 1,942,873. However, it is not known hitherto that the combined use of
at least two anionic surface active agents can provide super-additive
effects to provide an emulsified product which is finely divided and
stable with time. A suitable proportion of the surface active agents of
the general formula (I) and/or the general formula (II) is at least about
1% by weight, preferably at least 10% by weight. The surface active agents
according to this invention can be also used together with a nonionic
surface active agent. These nonionic surface active agents include those
containing alkylene oxide units. Suitable examples of nonionic surface
active agents are described in U.S. Pat. No. 3,676,141 and U.S. Pat.
application Ser. No. 283,026, filed Aug. 23, 1972 now U.S. Pat. No.
3,860,425.
A second feature of this invention resides in that the secondary alkane
sulfonate of the general formula (I) exhibits superior performance to that
of the primary alkane sulfonate of the general formula (II) having the
same number of carbon atoms.
A third feature of this invention resides in that the secondary alkane
sulfonate and the primary alkane sulfonate, when mixed and used, exhibit
an even enhanced performance. The aforesaid Hostpur SAS displays very
excellent performance in the emulsification of a photographic additive
such as a coupler, the coating of a light-sensitive colloid layer, and the
preparation of a solution in which a sensitizing dye, an antifogging agent
and a stabilizing agent are solubilized.
The surface active agents of this invention are preferably used as a
dispersing agent for couplers. The couplers used include compounds which
can form color by color development with an aromatic primary amino
developing agent such as phenylenediamine derivatives or aminophenol
derivatives. Examples of couplers are 5-pyrazolone couplers,
cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers,
acylacetamide couplers (such as the benzoylacetanilides and the
pivaloylacetanilides), naphthol couplers and phenol couplers.
More specifically, examples of magenta couplers are 5-pyrazolone couplers,
cyanoacetylcoumarone couplers and indazolone couplers. Particularly useful
couplers are those represented by the following general formula (III).
##EQU3##
In the above formula, R.sub.4 represents an alkyl group selected from
primary, secondary and tertiary alkyl groups (such as methyl, propyl,
n-butyl, t-butyl, hexyl, 2-hydroxyethyl, 2-phenylethyl, pentadecyl, etc.),
an aryl group (such as phenyl, 2,4-di-tert-phenyl, etc.), a heterocyclic
ring (such as quinolinyl, pyridyl, benzofuranyl, oxazolyl, etc.), an amino
group (such as methylamino, diethylamino, phenylamino, tolylamino,
4-(3-sulfobenzamino)anilino, 2-chloro-5-acylaminoanilino,
2-chloro-5-alkoxycarbonylanilino or 2-trifluoromethylphenylamino, etc.), a
carbonamido group (such as alkylcarbonamido such as ethylcarbonamido,
arylcarbonamido, heterocyclic carbonamido such as
benzothiazolylcarbonamido, sulfonamido, alkylsulfonamido, arylsulfonamido
or heterocyclic sulfonamido), a ureido group (such as alkylureido,
arylureido or heterocyclic ureido), an alkoxy group (such as methoxy,
ethoxy, benzyloxy, etc.), an aryloxy group (such as phenoxy, etc.) or the
like, and R.sub.5 represents a hydrogen atom, an aryl group (such as
naphthyl, phenyl, 2,4,6-trichlorophenyl, 2-chloro-4,6-dimethylphenyl,
2,6-dichloro-4-methoxyphenyl, 4-methylphenyl, 4-acylaminophenyl,
4-alkylaminophenyl, 4-trichloromethylphenyl or 3,5-dibromophenyl), a
heterocyclic group (such as benzofuranyl, naphthoxazolyl or quinolinyl),
an alkyl group selected from a primary, secondary or tertiary alkyl group
(such as ethyl or benzyl) or the like. Z.sub.1 represents a hydrogen atom
or a group capable of being split off during color development, for
example, an acyloxy group, an aryloxy group, a halogen atom, a thiocyano
group, a di-substituted amino group, an aryloxycarbonyloxy group, an
alkoxycarbonyloxy group, a benzotriazolyl group, an indazolyl group, an
arylazo group or a heterocyclic azo group. These groups are described in,
e.g., U.S. Pat. Nos. 3,227,550; 3,252,924; 3,311,476 and 3,419,391, U.S.
patent application Ser. No. 461,204, filed Apr. 15, 1974, and 471,639,
filed May 20, 1974. Moreover, Z.sub.1 also includes a residue which
releases a development retarder during the development, for example, an
arylmonothio group (such as a 2-aminophenylthio or
2-hydroxycarbonylphenylthio group), a heterocyclic monothio group (such as
a tetrazolyl, triazinyl, triazolyl, oxazolyl, oxadiazolyl, diazolyl,
thiazyl or thiadiazolyl group), a heterocyclic imido group (such as a
1-benzotriazolyl, 1-indazolyl or 2-benzotriazolyl group) or the like, as
described in, e.g., U.S. Pat. Nos. 3,148,062; 3,227,554; 3,615,506 and
3,701,783.
Examples of yellow couplers are open-chain acylacetamide couplers (such as
a pivaloylacetanilide coupler or a benzoylacetanilide coupler) and
open-chain acylacetonitrile couplers. Particularly useful are those
couplers represented by the following general formula (IV).
##EQU4##
In the above formula, R.sub.6 represents a primary, secondary or tertiary
alkyl group having 1 to 18 carbon atoms (such as t-butyl,
1,1-dimethylpropyl or 1,1-dimethyl-1-methoxyphenoxymethyl), an aryl group
(such as phenyl, alkylphenyl such as 3-methylphenyl, 3-octadecylphenyl,
etc., alkoxyphenyl such as 2-methoxyphenyl, 4-methoxyphenyl, etc.,
halophenyl, 2-halo-5-alkamidophenyl,
2-chloro-5-[.alpha.-(2,4-di-t-amylphenoxy)butyramido]phenyl,
2-methoxy-5-alkylamidophenyl or 2-chloro-5-sulfonamidophenyl), an amino
group (such as anilino, p-methoxyanilino or butylamino group), and R.sub.7
represents aryl group (such as 2-chlorophenyl, 2-halo-5-alkamidophenyl,
2-chloro-5-[.alpha.-(2,4-di-t-amylphenoxy)acetamido]-phenyl,
2-chloro-5-(4-methylphenylsulfonamido)phenyl or
2-methoxy-5-(2,4-di-t-amylphenoxy)acetamidophenyl). Z.sub.2 represents a
hydrogen atom or a group capable of being split off during color
development, for example, a halogen atom, particularly, a fluorine atom,
an acyloxy group, an aryloxy group, an aromatic heterocyclic carbonyl
group, an oxy group, a sulfimido group, an alkylsulfoxy group, an
arylsulfoxy group, a phthalimido group, a dioxoimidazolidinyl group, a
dioxooxazolidinyl group, an indazolyl group, or a dioxothiazolidinyl
group. These groups are described in, for example, U.S. Pat. Nos.
3,227,550; 3,253,924; 3,277,155; 3,265,506; 3,408,194 and 3,415,652;
French Patent No. 1,411,384; British Patent Nos. 994,490; 1,040,710 and
1,118,028; and German OLS Nos. 2,057,941; 2,163,812; 221,346 and
2,219,971. Moreover, Z.sub.2 can represent a residue which releases a
development retarder, for example, an arylmonothio group (such as a
phenylthio or 2-carboxyphenylthio group), a heterocyclic thio group, a
1-benzotriazolyl group or a 1-benzodiazolyl group and, particularly a
residue as described in U.S. patent application Ser. No. 454,525, filed
Mar. 25, 1974.
Examples of cyan couplers are naphthol couplers and phenol couplers.
Particularly, couplers represented by the following general formulas (V)
and (VI) are useful.
##SPC1##
In the above formulas, R.sub.8 represents a substituent generally used for
cyan couplers, for example, a carbamyl group (such as alkylcarbamyl,
arylcarbamyl such as phenylcarbamyl, or heterocyclic carbamyl such as
benzothiazolylcarbamyl), a sulfamyl group (such as alkylsulfamyl,
arylsulfamoyl such as phenylsulfamyl, or heterocyclic sulfamyl), and
alkoxycarbonyl group, an aryloxycarbonyl group, etc. R.sub.9 represents an
alkyl group, an aryl group a heterocyclic group, an amino group (such as
an amino, alkylamino or arylamino group), a carbonamido group (such as
alkylcarbonamido or arylcarbonamido), a sulfonamido group, a sulfamyl
group (such as alkylsulfamyl or arylsulfamyl), a carbamyl group, etc.
R.sub.10, R.sub.11 and R.sub.12 each represents the same groups as defined
for R.sub.9, and also a halogen atom, an alkoxy group, etc. Z.sub.3
represents a hydrogen atom or a group capable of being split off during
color development. Z.sub.3 has the same meanings as defined for Z.sub.2.
Moreover, Z.sub.3 represents a halogen atom such as chlorine, bromine or
iodine atom, a thiocyano group or a group such as indazolyl, cyclic imido
(e.g., maleimido, succinimido, 1,2-dicarboxyimido), acyloxy, aryloxy,
alkoxy, sulfo, arylazo or heterocyclic azo. Examples of these groups are
described in, for instance, U.S. Pat. Nos. 2,423,730; 3,227,550 and
3,311,476; and British Patent Nos. 1,084,480 and 1,165,563.
The couplers used in this invention can also be colored couplers. Colored
couplers are described in, for example, U.S. Pat. Nos. 2,983,608;
3,005,712 and 3,034,892; British Patent Nos. 936,621; 1,269,073; 586,211
and 627,814; and French Patent Nos. 980,372; 1,091,903; 1,257,887;
1,398,308 and 2,015,649.
It is advantageous to render the couplers used in this invention diffusion
resistant. In order to render the couplers diffusion resistant, a group
containing a hydrophobic residue with 8 to 32 carbon atoms is introduced
into the molecule of the coupler. Such a residue is referred to as a
ballast group. The ballast group can be attached to a skeleton structure
of the coupler directly or through, for example, an imino bond, an ether
bond, a carbonamido bond, a sulfonamido bond, a ureido bond, an ester
bond, an imido bond, a carbamoyl bond or a sulfamoyl bond.
Typical examples of ballast groups are those as described in illustrative
examples of couplers used in this invention given hereinafter.
Illustrative examples of ballast groups are given below
I. Alkyl groups and alkenyl groups for example,
--CH.sub.2 --CH(C.sub.2 H.sub.5).sub.2, --C.sub.12 H.sub.25, --C.sub.16
H.sub.33, --C.sub.17 H.sub.33
II. Alkoxyalkyl groups, for example,
--(CH.sub.2).sub.3 --O--(CH.sub.2).sub.7 CH.sub.3,
##EQU5##
as described in Japanese Patent Publication No. 27,563/64.
III. Alkylaryl groups, for example,
##SPC2##
IV. Alkylaryloxyalkyl groups, for example,
##SPC3##
V. Acylamidoalkyl groups, for example,
##EQU6##
as described in U.S. Pat. Nos. 3,333,344 and 3,418,129.
VI. Alkoxyaryl and aryloxyaryl groups, for example,
##SPC4##
VII. Residues having long chain alkyl or alkenyl aliphatic group together
with a carboxyl or sulfo group which provides water solubility, for
example,
##EQU7##
VIII. Alkyl groups substituted with an ester group, for example,
##EQU8##
--CH.sub.2 --CH.sub.2 --COOC.sub.12 H.sub.25 (n)
IX. Alkyl groups substituted with an aryl or heterocyclic group, for
example,
##SPC5##
X. Aryl groups substituted with an aryloxyalkoxycarbonyl group, for
example,
##SPC6##
Illustrative examples of couplers which can be used in this invention are
given below but the invention is not to be interpreted as being limited to
these examples.
Yellow Couplers
1.
.alpha.-{3-[.alpha.-(2,4-Di-tert-amylphenoxy)butyramido]benzoyl}-2-methoxy
acetanilide
2.
.alpha.-Acetoxy-.alpha.-3-[.gamma.-(2,4-di-tert-amylphenoxy)butyramido]-be
nzoyl-2-methoxyacetanilide
3. N-(4-Anisoylacetamidobenzenesulfonyl)-N-benzyl-N-toluidine
4.
.alpha.-(2,4-Dioxo-5,5-dimethyloxazolidinyl)-.alpha.-pivaloyl-2-chloro-5-[
.alpha.-(2,4-di-tert-amylphenoxy)butyramido]acetanilide
5.
.alpha.-(4-Carboxyphenoxy)-.alpha.-pivaloyl-2-chloro-5-{.alpha.-(2,4-di-te
rtamylphenoxy)butyramido}acetanilide
6. .alpha.-(5 or
6-Methyl-1-benztriazolyl)-.alpha.-(N-4-methoxyphenylcarbamoyl-2-methoxy-5-
[.alpha.-(2,4-di-tert-amylphenoxy)-butyramido]acetanilide
7.
.alpha.-Benzoyl-.alpha.-(2-benzothiazolylthio)-4-[N-(.gamma.-phenylpropyl)
-N-(4-tolyl)sulfamyl]acetanilide
8. .alpha.-Pivaloyl-.alpha.-(5 or
6-bromo-1-benztriazolyl)-5-[.alpha.-(2,4-ditert-amylphenoxy)propionamido]-
2-chloro-acetanilide
Magenta Couplers
9.
1-(2,4,6-Trichlorophenyl)-3-[3-(2,4-di-tert-amylphenoxyacetamido)benzamido
]-5pyrazolone
10.
1-(2,4,6-Trichlorophenyl)-3-{3-[.alpha.-(2,4-di-tert-amylphenoxy)-acetamid
o]benzamido}-4-acetoxy-5-pyrazolone
11.
1-(2,4,6-Trichlorophenyl)-3-tridecylamido-4-(4-hydroxyphenyl)-azo-5-pyrazo
lone
12.
1-(2,4,6-Trichlorophenyl)-3-[(3-tridecanoylamino-6-chloro)-anilino]-5-pyra
zolone
13.
1-(2,4,6-Trichlorophenyl)-3-(3-tetradecyloxycarbonyl-6-chloro)anilino-4-(1
-naphthylazo)-5-pyrazolone
14.
1-(2,4-Di-chloro-6-methoxyphenyl)-3-[(3-tridecanoylamino-6-chloro)anilino]
-4-benzyloxycarbonyloxy-5-pyrazolone
15.
1-14-[.gamma.-(2,4-Di-tert-amylphenoxybutyramido)phenyl]-3-piperidinyl-4-(
1-phenyl-5-tetrazolylthio)-5-pyrazolone
16.
1-Benzyl-3-{4-[.alpha.-(2,4-di-tert-amylphenoxy)butyramido]-anilino}-4-(5
or 6-bromo-1-benztriazolyl)-5-pyrazolone
17. 1-[4-{.alpha.-(2,4-Di-tert-amylphenoxy)acetamido}phenyl]-3-ethoxy-4-(5
or 6-bromo-1-benztriazolyl)-5-pyrazolone
Cyan Couplers
18. 1-Hydroxy-N-[.gamma.-(2,4-di-tert-amylphenoxypropyl)]-2-naphthamide
19.
1-Hydroxy-4-[2-(2-hexyldecyloxycarbonyl)phenylazo]-2-[N-(1-naphthyl)]napht
hamide
20.
1-Hydroxy-4-chloro-N-[.alpha.-(2,4di-tert-amylphenoxy)butyl]-2-naphthamide
21.
5-Methyl-4,6-dichloro-2-[.alpha.-(3-n-pentadecylphenoxy)-butyramido]phenol
22. 1-Hydroxy-4-iodo-N-dodecyl-2-naphthamide
23.
5-Methoxy-2-[.alpha.-(3-n-pentadecylphenoxy)butyramido]-4-(1-phenyl-5-tetr
azolylthio)phenol
Non Coloring Coupler
24.
N-{.alpha.-(2,4-Di-tert-amylphenoxy)acetyl}-.omega.-(1-phenyl-5-tetrazolyl
thio)-m-aminoacetophenone
A fading inhibitor for a colored dye image (for example, as described in
U.S. Pat. Nos. 3,764,337 and 3,432,300 and German OLS No. 2,146,668) can
also be dispersed together with the coupler using the surfactant according
to this invention.
The surface active agents of this invention can be applied to the
dispersion of other photographic additives.
An antioxidant which can be used in this invention includes phenol and
hydroquinone derivatives having aliphatic group of 8 or more carbon atoms
or precursors thereof, for example, as described in U.S. Pat. Nos.
2,336,327; 2,728,659; 2,835,579 and 3,700,453.
A filter dye which can be used in this invention includes hydrophobic
oxonol dyes, benzotriazole ultraviolet absorbants and benzophenone
ultraviolet absorbants, for example, as described in U.S. Pat. Nos.
3,253,921; 3,533,794; 3,794,493; 3,785,827 and 3,707,375, etc. Moreover,
as the antioxidant for a colored dye image, the compounds described in
U.S. Pat. Nos. 3,432,300 and 3,764,337 and German OLS No. 2,146,668 are
particularly useful.
Among all, the compounds represented by the following general formulas
(VII), (VIII) and (IX) are preferred.
##SPC7##
In the above formula (VII), R.sub.13 represents a straight or branched
chain alkyl group with 8 to 20 carbon atoms such as n-octyl, tert-octyl,
dodecyl, octadecyl, etc., and R.sub.14 represents a hydrogen atom or a
straight or branched alkyl group with 8 to 20 carbon atoms such as
n-octyl, tert-octyl, dodecyl, octadecyl, etc. A represents a hydrogen atom
or a group capable of being split off by alkali (such as an acyl group
such as an acetyl group or an alkoxycarbonyl group). The benzene ring can
be further substituted with an alkyl group having up to 8 carbon atoms
such as methyl, butyl, octyl, etc., a halogen atom such as chlorine, etc.
or the like.
##SPC8##
In the above formula (VIII), R.sub.15 and R.sub.16 each represents a
hydrogen atom or an alkyl group having up to 5 carbon atoms such as
methyl, ethyl, iso-propyl, n-butyl, sec-butyl, t-butyl, amyl, etc., and
R.sub.17 represents a hydrogen atom, an alkoxy group, e.g., having 1 to 6
carbon atoms such as methoxy, etc., or a halogen atom such as chlorine,
bromine, etc.
##SPC9##
In the above formula A.sub.1 and A.sub.2 is a hydrogen atom or a group
removable with an alkali, such as an alkoxycarbonyl group, an acyl group,
etc., and A.sub.2 can combine with R.sub.18 or Q to form a ring such as an
oxathiol group; P, Q or R.sub.18 each is a hydrogen atom, an alkyl group,
e.g., methyl, ethyl, 1,1,3,3-tetramethylbutyl, n-pentadecyl, an --S--Y
group (wherein Y is an alkyl group, e.g., 2-ethyl-hexyl, n-dodecyl,
n-hexadecyl, n-octadecyl, hydroxycarbonylmethyl, ethoxycarbonylmethyl,
2-hydroxyethyl, etc., or an aryl group, e.g., phenyl, tolyl, etc.), octyl,
tridecyl, allyl, etc., an aryl group, e.g., phenyl, p-tolyl, etc., a
hydroxyl group, a halogen atom, an --S--Z group, an alkoxy group, e.g.,
methoxy, ethoxy, etc., an aryloxy group, an --O--Y group, etc., or a
hetero ring; and Z is a heterocyclic ring which is substantially
photographically inert in a bonded condition and particularly is a
tetrazolyl group, e.g., 1-phenyltetrazolyl, etc., a triazolyl group, e.g.,
4-phenyl-1,2,4-triazole-5-yl, 3-n-pentyl-4-phenyl, 1,2,4-triazole-5-yl,
etc., a thiadiazolyl group, e.g., 2-methylthio-1,3,4-thiadiazole-5-yl,
2-amino-1,3,4-thiadiazole-5-yl, etc., an oxadiazolyl group, e.g.,
2-phenyl-1,3,4-oxadiazole-5-yl, etc., a tetraazaindenyl group, e.g.,
6-methyl-1,3,3a,7-tetraazaindene-4-yl,
6-n-nonyl-1,3,3a,7-tetraazaindene-4-yl, etc., an oxazolyl group, e.g.,
benzooxazole-2-yl, etc., a thiazolyl group, e.g., benzothiazole-2-yl,
etc., etc. In particular, of P, Q and R.sub.18, R.sub.18 can be an --S--Z
group. Preferably, P, Q or R.sub.18 contains a ballast group in its
chemical structure and at least one of P, Q and R.sub.18 is a Y--S--
group.
Suitable high boiling solvents which can be employed include phosphoric
acid esters such as tricresyl phosphate, phthalic acid esters such as
dibutylphthalate, N-di-alkyl substituted alkylamides such as
N,N-diethyllauramide, glycerol esters such as glycerol triacetate, citric
acid esters such as acetyl tri-n-butyl citrate, succinic acid esters such
as tetrahydrofurfuryl succinate or the like. Specific examples are
described in, e.g., U.S. Pat. Nos. 2,322,027; 2,533,514 and 3,287,134,
German Patent No. 1,152,610, British Patent No. 1,272,561, Japanese Patent
Publication No. 21,766/68, U.S. Pat. application Ser. No. 485,655, filed
July 3, 1974.
The high boiling solvent used in this invention can be used together with a
substantially water-insoluble low boiling auxiliary solvent such as methyl
acetate, ethyl acetate and butyl acetate or a water-soluble organic
auxiliary solvent such as methyl isobutyl ketone, .beta.-ethoxyethyl
acetate, methyl carbitol, methyl cellosolve, dipropylene glycol,
dimethylformamide and dioxane. Such solvents are described in, for
example, U.S. Pat. Nos. 2,801,170; 2,801,171; 2,949,360 and 2,835,579. The
auxiliary solvents can be removed by washing with water as described in
U.S. Pat. Nos. 2,801,171; 2,949,360 and 3,396,027; or by volatilizing as
described in U.S. pat. Nos. 2,322,027 and 2,801,171 or German OLS No.
2,045,464.
A solution containing organic photographic additives such as couplers, the
antioxidant and the filter dye dissolved in the high boiling solvent used
in this invention alone or in combination with the auxiliary solvent can
be dispersed in an aqueous solution of a hydrophilic colloid,
particularly, gelatin. Suitable dispersion methods which can be used are
described in, e.g., U.S. Pat. Nos. 2,304,939; 2,322,027; 2,801,170;
2,801,171 and 2,949,360.
The surface active agents of this invention can be also employed in the
preparation of an aqueous solution in which a sensitizing dye, a
stabilizing agent and an antifogging agent are solubilized. For example,
they are particularly useful for the solubilization of substances as
described in U.S. Pat. No. 3,822,135. They are also especially useful for
sensitizing dyes containing, in the dye molecule, an alkylene or
substituted alkylene group with a water-solubilizing group such as a
sulfo, carboxyl or hydroxyl group as described in F.M. Hamer, The Cyanine
Dyes and Related Compounds Vol. 1, Interscience Publishers (1964).
The surface active agents used in this invention can be also employed in
the coating of a silver halide emulsion.
When the above-described dispersion of photographic additives is added to a
silver halide emulsion, the surface active agents of this invention used
for the dispersion of the additives act also as a coating aid.
The silver halide photographic emulsions which can be used in the present
invention include any known silver halide emulsion such as a silver
bromide emulsion, a silver iodobromide emulsion, a silver
chloroiodobromide emulsion, a silver chloride emulsion, and a silver
chlorobromide emulsion or a silver halide emulsion of the so-called
conversion halide type as described in, e.g., U.S. Pat. Nos. 2,592,250 and
3,622,318 and British Patent No. 635,841. The silver halide grains can be
of any size generally used in the photographic art but preferably have a
grain size from about 0.02 to 5 microns, more preferably 0.1 to 2 microns.
Also, examples of the hydrophilic colloid which can be used for the coupler
dispersion and the silver halide photographic emulsion are gelatin; a
gelatin derivative such as acylated gelatin as described in U.S. Pat. No.
2,525,753, etc., graft gelatin as described in U.S. Pat. No. 2,831,767,
etc.; albumin; gum arabic; agar agar; a cellulose derivative such as
acetyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc.;
and a synthetic resin such as polyvinyl alcohol, polyvinyl pyrrolidone,
polyacrylamide, etc.
The silver halide emulsion can be chemically sensitized using active
gelatin or a sulfur compound as described in U.S. Pat. Nos. 1,574,944;
1,623,499; 2,410,689; etc. Also, the emulsion can be sensitized using a
salt of a noble metal such as palladium, gold, ruthenium, rhodium,
platinum, etc., as described in U.S. Pat. Nos. 2,448,060; 2,399,083;
2,642,361; etc. Furthermore, the silver halide emulsion can be sensitized
using a reducing agent such as a stannous salt, as described in U.S. Pat.
No. 2,487,850, and also can be sensitized using a polyalkylene oxide
derivative. Moreover, the silver halide emulsion can be spectrally
sensitized with a cyanine dye or a merocyanine dye, as disclosed in U.S.
Pat. Nos. 2,519,001; 2,666,761; 2,734,900; 2,739,964; 3,481,742; etc.
Typical examples of sensitizing dyes include dyes such as
anhydro-9-methyl-5,5'-dimethyl-3,3'-di-(3-sulfopropyl)benzoselenacarbocyan
ine, 5,5'-dichloro-9-ethyl-di-(2-hydroxyethyl)thiacarbocyanine.bromide or
anhydro-5,5'-diphenyl-9-ethyl-3,3'-di-(2sulfoethyl)benzoxazolocarbocyanine
.hydroxide.
The silver halide emulsion can further contain a stabilizer such as a
mercury compound, an azaindene, etc., as described in U.S. Pat. Nos.
2,886,437; 2,444,605; 2,403,927; 3,266,877; 3,397,987; etc., a plasticizer
such as glycerine as described in C. E. K. Mees and T. H. James The Theory
of Photographic Process, page 53 - 54, The Macmillan Co., New York (1966),
and U.S. Pat. Nos. 2,904,434; 2,940,854; etc., an antifogging agent such
as a mercapto compound or a benzotriazole derivative, a sensitizer such as
an onium derivative, for example, the quaternary ammonium salts as
described in U.S. Pat. Nos. 2,271,623; 2,288,266 and 2,334,864 or the
polyalkylene oxide derivatives as described in U.S. Pat. Nos. 2,708,162;
2,531,832; 2,533,990; 3,210,191 and 3,158,484, etc. In addition, an
anti-irradiation dye can be incorporated in the emulsion. Moreover, a
filter layer, a mordant dyeing layer or a colored layer containing a
hydrophobic dye can be employed as the elements constituting layers of the
color light-sensitive material of this invention.
The photographic light-sensitive material of the present invention
comprises a support having thereon at least one emulsion layer containing
the combination of surface active agents of the present invention.
As the support, examples are a cellulose ester film such as a cellulose
nitrate film, a cellulose acetate film, etc.; a polyester film such as a
polyethylene terephthalate film, etc., a polyvinyl chloride film, a
polystyrene film, a polycarbonate film, a paper, a so-called baryta-coated
paper prepared by coating barium sulfate on a paper support, a laminate
film prepared by coating a cellulose ester, a polyester, a polyvinyl
chloride, a polystyrene, or a polycarbonate on a paper or a baryta-coated
paper, and a synthetic paper. A suitable coating amount of the silver
halide can range from about 4 .times. 10.sup.-.sup.4 to 4 .times.
.sup.-.sup.2, preferably 2 .times. 10.sup.-.sup.3 to 2 .times.
10.sup.-.sup.2, mol/m.sup.2.
The photographic material of the present invention can have in addition to
the above-described silver halide emulsion layers, other layers
conventionally employed for constituting the photographic material, such
as, for instance, a protective layer, a filter layer, an intermediate
layer, an antihalation layer, a subbing layer, a backing layer, a layer
containing an ultraviolet absorber, etc. Also, as the binders for these
layers, the hydrophilic colloid used for the silver halide emulsion layers
can be employed.
Each layer of the photographic material of the present invention can
contain a hardening agent for the hydrophilic colloid. Typical examples of
such hardening agents are aldehyde type compounds such as formaldehyde,
glyoxal, succinaldehyde, glutaraldehyde, 2,3-dihydroxy-1,4-dioxane,
mucochloric acid, dimethylolurea, etc.; active vinylic compounds such as
divinylsulfone, methylene bismaleimide,
5-acetyl-1,3-diacryloyl-1,3,5-hexahydrotriazine,
N,N',N'-triacryloyl-1,3,5-hexahydrotriazine, etc.; active halogen
compounds such as 2,4-dichloro-6-oxytriazine sodium salt,
2,4-dichloro-6-methoxytriazine, sebacic acid bischloromethyl ester,
N,N'-bis(.alpha.-chloroethylcarbamyl)piperazine, etc.; epoxy compounds
such as bis(2,3-epoxypropyl)methylpropyl ammonium para-toluene sulfonate,
1,4-bis(2',3'-epoxypropyloxy)butane,
1,3-diglycidyl-5-(.gamma.-acetoxy-.beta.-oxypropyl)isocyanurate, etc.;
ethyleneiminic compounds such as 2,4,6-triethyleneimino-1,3,5-triazine,
bis-.beta.-ethylene-iminoethyl thioether, etc.; and methane sulfonate
compounds such as 1,2-di(methanesulfonyloxy)ethane,
1,4-di(methanesulfonyloxy)butane, 1,5-di(methanesulfonyloxy)pentane, etc.,
as described in U.S. Pat. Nos. 3,232,764; 3,288,775; 2,732,303; 3,635,718;
3,232,763; 2,732,316; 2,586,168; 3,103,437; 3,017,280; 2,783,611;
2,725,294; 2,725,295; 3,100,704; 2,091,537; 3,321,313; etc.
Further each layer of the photographic material can contain an antistatic
agent as described in U.S. Pat. Nos. 2,739,888; 3,428,456; 3,437,484;
3,457,076; 3,549,375; 3,549,369; 3,551,152; 3,552,972; 3,547,643;
3,564,043; 3,615,531; 3,625,695; 3,655,287; 3,653,906; 3,655,386;
3,686,368; 3,756,828; 3,754,924; etc., an ultraviolet absorber as
described in U.S. Pat. Nos. 2,415,624; 3,052,636; 3,074,971, 3,085,097;
3,067,456; 3,215,536; 2,719,086; 2,537,877; 2,784,087; 2,882,150;
2,875,053; 2,739,971; 3,097,100; 3,060,029; 2,632,701; 2,858,346;
2,748,021; etc., a fluorescent whitening agent as described in U.S. Pat.
Nos. 3,630,738; 3,615,544; 3,586,673; 3,434,837; British Patent Nos.
1,332,475; 1,319,763; 1,333,586; etc., an anti-irradiation dye as
disclosed in U.S. Pat. No. 3,445,231, etc.
In forming black-white silver images or color images, the photographic
light-sensitive material of this invention can be processed using a
developer which can reduce silver halide particles to silver. In the case
of black-white development, a developer containing as a developing agent a
polyhydroxybenzene, an N-alkylaminophenol, a 1-phenyl-3-pyrazolidone or a
mixture thereof can be used. Examples of polyhydroxybenzenes are
hydroquinone, pyrocatechol or pyrogallol, and examples of
N-alkylaminophenols are N-methylaminophenol or N-ethylaminophenol.
Examples of 1-phenyl-3-pyrazolidones are 1-phenyl-3-pyrazolidone or
1-phenyl-4,4-dimethyl-3-pyrazolidone. In subjecting the color photographic
light-sensitive material obtained according to this invention to color
| | |
