FIELD OF THE INVENTION
[0001] This invention concerns silver halide based color photographic photosensitive materials
and, more precisely, it concerns color photographic photosensitive materials in which
the fading of the dye image which is caused by the fungi which develop when processed
color photographs are stored under conditions of high temperature and humidity is
prevented effectively.
BACKGROUND OF THE INVENTION
[0002] It is known that the image dyes in color photographs are liable to fade as a result
of the presence of fungi, in addition to the usual fading effects due to heat and
light. Photographic photosensitive materials are often stored by being adhered or
sandwiched in an album made from paper or on a mounting board, or by being sandwiched
on Japanese paper with a mounting board on the surface. However, when photographs
are finished for storage in this way the paste used for adhesion and the paper fibers
themselves provide nutrient sources. Fungi grow and proliferate, especially under
conditions of high temperature and humidity, and problems arise with fading of the
image dyes, especially the cyan dyes, as a result of the action of products excreted
by the fungi.
[0003] The fungi themselves can be wiped off the photograph, but the fading cannot be restored
in this way and the quality of the image is permanently degraded. This is a serious
problem.
[0004] Attempts have been made in the past to overcome this problem by using fungicides
(biocides). There are very many fungicides that have been used successfully in many
applications, and they could be used with silver halides. However, none has been found
which has the desired fungicidal effect without having an adverse effect on various
photographic characteristics, or being toxic to humans.
[0005] Known fungicides include those disclosed, for example, in U.S. Patents 2,226,183,
2,762,708, 2,897,081, 3,185,571, 2,663,639, 3,503,746, 3,342,810 and 3,778,276, British
Patents 987,010 and r.065,920, and JP-A-57-157244 (the term "JP-A" as used herein
refers to a "published unexamined Japanese patent application").
[0006] However, virtually all of these fungicides are organic fungicides and they may be
expensive, or liable to oxidization or sublimation. They have the disadvantage that
their effect during the storage of photographic photosensitive materials is poorly
retained.
[0007] It has been indicated in JP-A-61-233743 that a fungicidal effect can be obtained
with little staining and without the occurrence of photostaining by using combinations
of specified fungicides and pyrazoloazole based magenta couplers.
[0008] It has also been proposed that fungi are not likely to grow if the photosensitive
material is made acidic after processing, but such a procedure gives rise to the following
problems in practice.
(1) Use of known organic acids (for example, citric or acetic acids) has the opposite
effect and provides nutrients for fungi, thus promoting the growth of fungi and increasing
the fading.
(2) On acidification to such an extent that fungal growth does not occur, dye fading
is liable to occur as a result of the effect of the acid, and the overall storage
properties of the image are worsened. This effect is especially pronounced when inorganic
acids are used.
[0009] On the basis of the facts outlined above, it has been indicated in JP-A-60-135942,
corresponding to EP 147016 A2, that the problem can be overcome by lowering the pH
of the photosensitive material by immersing the material in an aqueous solution of
an ammonium salt (for example, ammonium sulfate) after processing and releasing the
ammonium ion from the photosensitive material as ammonia.
[0010] However, although good results can be obtained in this way, the situation is the
same as that described earlier once the ammonia has been liberated and dispersed,
and this method does not provide a real solution to the problem.
[0011] A technique is desired by which the fading due to action of material excreted by
fungi can be prevented even when fungi are present.
[0012] It has been proposed that a cyan coupler, high boiling organic solvent and water-insoluble
and organic solvent-soluble polymer are disclosed in WO 88/00723, EP 280238 and JP-A-63-104050,
etc.
SUMMARY OF THE INVENTION
[0013] One object of the present invention is to provide silver halide color photosensitive
materials for color photographs without image deterioration, such as fading, even
on storage under adverse conditions of high temperature and humidity under which fungi
flourish.
[0014] A further object of the invention is to provide silver halide color photosensitive
materials for color photographs in which the cyan image has the proper hue, and which
have good light fastness and little fading due to fungi.
[0015] As a result of various investigations, the inventors have discovered that these and
other objects of the present invention can be achieved by a light-sensitive silver
halide material composed of a support having thereon at least one light-sensitive
silver halide emulsion layer, at least one layer of the light-sensitive silver halide
emulsion layer or an adjacent layer thereof containing an oil droplet dispersion in
a hydrophilic binder, the oil droplets containing the combination of (a) a polymer
insoluble in water and soluble in an organic solvent; (b) a high boiling point organic
solvent having a viscosity at 25. C of at least 500 cp and a boiling point of at least
120° C; and (c) at least one coupler capable of forming a nondiffusible cyan dye by
a coupling reaction with an oxidized form of a product aromatic amine determined agent.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The invention is described in greater detail below.
[0017] A coupler represented by formula (I) is a preferred cyan dye-forming coupler.
wherein Y represents -NHCO- or -CONH-, R, represents a substituted or unsubstituted
aliphatic group, substituted or unsubstituted aromatic group, substituted or unsubstituted
heterocyclic group or a substituted or unsubstituted amino group; X represents hydrogen,
a halogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted
alkoxy group or a substituted or unsubstituted acylamino group; R
2 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted
acylamino group; X and R
2 may be linked to form a 5- to 7-membered ring; and Z, represents hydrogen or a group
which can be eliminated on coupling with the oxidized form of a developing agent,
referred to herein as a "coupling-off group".
[0018] In formula (I), R
i preferably represents a linear or cyclic aliphatic group which preferably has from
1 to 32 carbon atoms (for example, methyl, butyl, pentadecyl, cyclohexyl), an aromatic
group (for example, phenyl, naphthyl), a heterocyclic group, preferably including
a nitrogen atom, (for example, 2-pyridyl, 3-pyridyl, 2-furanyl, 2-oxazolyl) or an
amino group, and these groups are preferably substituted with at least . one substituent
group selected from the alkyl groups, aryl groups, alkyloxy or aryloxy groups (for
example, methoxy, dodecyloxy, methoxyethoxy, phenoxy, 2,4-di-tert-amyl phenoxy, 3-tert-butyl-4-hydroxyphenoxy,
naphthyloxy), carboxyl groups, alkylcarbonyl or arylcarbonyl groups (for example,
acetyl, tetradecanoyl, benzoyl), alkyloxy-carbonyl or aryloxycarbonyl groups (for
example, methoxy-carbonyl, benzyloxycarbonyl, phenoxycarbonyl), acyloxy groups (for
example, acetyl, benzoyloxy, phenylcarbonyloxy), sulfamoyl groups (for example, N-ethylsulfamoyl,
N-octylsulfamoyl), carbamoyl groups (for example, N-ethyl-carbamoyl, N-methyldodecylcarbamoyl),
sulfonamido groups (for example, methanesulfonamido, benzenesulfonamido), acylamino
groups (for example, acetylamino, benzamido, ethoxycarbonylamino, phenylaminocar-
bonylamino), imido groups (for example, succinimido, hydantoinyl, sulfonyl groups
(for example, methanesulfonyl), hydroxyl groups, cyano groups, nitro groups and halogen
atoms.
[0019] The term "aliphatic group" as used herein signifies a linear chain, branched or ring
aliphatic hydrocarbyl group, and this group may be either saturated or unsaturated,
being an alkyl group, an alkenyl group or an alkynyl group.
[0020] R
2 preferably represents an alkyl group which has from 1 to 20 carbon atoms (for example,
methyl, ethyl, butyl, pentadecyl) or an acylamino group (for example, tetradecanoylamino,
benzoylamino, 2-(2,4-di-tert-amylphenoxy)butanamido).
[0021] X represents hydrogen, a halogen atom, aliphatic group, preferably lower alkyl group,
(for example, methyl, propyl, allyl, alkoxy group (for example, methoxy, butoxy) or
acylamino group (for example, acetamido).
[0022] The aforementioned compounds are preferably carbostyryl based cyan couplers in which
R
2 and X are joined together to form a 5-, 6- or 7-membered ring which preferably includes
a nitrogen atom, rather than phenol based cyan couplers, and oxyindole and imidazol-2-one
cyan couplers are especially desirable as condensed couplers of this type.
[0023] Z, represents hydrogen or a coupling-off group and examples of such groups include
halogen atoms (for example, fluorine, chlorine, bromine), alkoxy groups (for example,
ethoxy, dodecyloxy, methoxycar- bamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy),
aryloxy groups (for example, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy),
acyloxy groups (for example, acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy groups
(for example, methanesulfonyloxy, toluenesulfonyloxy), amido groups (for example,
dichloroacetylamino, heptabutyrylamino, methanesulfonylamino, toluenesulfonylamino),
alkoxycar- bonyloxy groups (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy),
aryloxycarbonyloxy groups (for example, phenoxycarbonyloxy), aliphatic or aromatic
thio groups (for example, ethylthio, phenylthio, tetrazolylthio), imido groups (for
example, succinimido, hydantoinyl), N-heterocyclic groups (for example, 1-pyrazolyl,
1-benzotriazolyl), and aromatic azo groups (for example, phenylazo). These leaving
groups may contain photographically useful groups.
[0024] From the viewpoint of hue and antifading characteristics, R
2 is preferably an alkyl group which has from 1 to 15 carbon atoms, and most desirably
from 1 to 4 carbon atoms. Z, is preferably hydrogen or a halogen atom, and most preferably
a halogen atom. Furthermore, X is preferably a halogen atom.
[0025] Specific examples of cyan couplers which can be used in the invention are indicated
below, but the present invention is not to be construed as being limited to these
examples.
[0028] The methods for synthesizing the cyan couplers which can be used in the invention
are described, for example, in Canadian Patent 625,822, U.S. Patents 3,772,002, 4,564,590,
2,895,826, 4,557,999, 4,565,777, 4,124,396, 4,613,564, 4,327,173, 4,564,586 and 4,430,423
and JP-A-61-39045 and JP-A-62-70846.
[0029] The cyan coupler of the present invention is preferably used in an amount of from
1 x 10-
3 to about 1 mol, more preferably from 0.1 to 0.5 mol, per mol of silver halide.
[0030] The color sensitive materials of the present invention may contain yellow couplers
and magenta couplers in addition to cyan couplers.
[0031] The use of the pivaloylacetanilide based couplers disclosed, for example, in U.S.
Patents 4,622,287 and 4,623,616 and the benzoylacetanilide based couplers disclosed,
for example, in U.S. Patents 3,408,194 3,933,501, 4,046,575, 4,133,958 and 4,401,752
as yellow couplers is preferred, and of these the former are more preferred form the
point of view of the fastness of the colored image. Furthermore, these couplers which
have a nitrogen elimination type coupling-off group are most preferred from the viewpoint
of their high activity (good color forming properties).
[0032] Furthermore, the use of 3-anilino-5-pyrazolone based couplers, 3-acylamino-5-pyrazolone
based couplers and pyrazolotriazole based couplers as magenta couplers is preferred.
[0033] From among the pyrazoloazole based couplers, the imidazo[1,2-b]pyrazoles disclosed
in U.S. Patent 4,500,630 are preferred from the viewpoint of their low absorbance
on the yellow side and the light fastness of the colored dye, and the pyrazolo[1,5-b]
[1,2,4]triazoles disclosed in U.S. Patent 4,540,654 are especially preferred.
[0034] Moreover, the use of the pyrazolotriazole couplers in which a branched alkyl group
is bonded directly to the 2-, 3- or 6-position of the pyrazolotriazole ring, such
as those disclosed in JP-A-61-65245, the pyrazoloazole couplers which contain a sulfonamido
group within the molecule, such as those disclosed in JP-A-61-65246, the pyrazoloazole
couplers which have alkoxyphenylsulfonamido ballast groups, such as those disclosed
in JP-A-61-147254, and the pyrazolotriazole couplers which have alkoxy groups or aryloxy
groups in the 6-position, such as those disclosed in European Patent Application (Laid
Open) 226,849, is preferred.
[0035] Specific examples of oil-soluble magenta and yellow couplers which can be used in
the invention are tabulated below, but the present invention is not to be construed
as being limited to these examples.
[0037] The high boiling point organic solvents having a viscosity of at least 500 cp (25
C) and having a boiling point of at least 120° C which can be used in the invention
are described below.
[0038] The high boiling point organic solvents are preferably selected from among the compounds
represented by formulae (II), (III), (IV), (V), (VI), or (VII) indicated below.
wherein W
1, W
2 and W
3, which may be the same or different, each represents a substituted or unsubstituted
alkyl, cycloalkyl, alkenyl, aryl or heterocyclic group; W
4 represents W
1, -O-W
1 or -S-W
i; and n is an integer of 1 to 5, and when n has a value of 2 or more the W
4 groups may be the same or different. Moreover, W, and W
2 in general formula (VI) may be linked to form a condensed ring.
[0039] W
5 represents a substituted or unsubstituted alkyl, cycloalkyl or aryl group, and the
number of carbon atoms in the W
5 group is at least 12. X represents a halogen atom.
[0040] When W
1, W
2, W
3 and W
5 groups have substituent groups, these substituent groups are preferably groups which
have one or two linking groups selected from -
O-, -CON
, -R
8N
(where R
8 represents a 2- to 6-valent phenyl group which is derived from a phenyl group by
removing hydrogen atoms therefrom) and -0-.
[0041] The alkyl groups represented by W
1, W
2, W
3, W
4 and W
s may be linear chain or branched chain alkyl groups. Examples of such groups include
methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl
and eicosyl groups.
[0042] The substituent groups for these alkyl groups may be, for example, halogen atoms,
cycloalkyl groups, aryl groups or ester groups. Examples of such substituted alkyl
groups with halogen (F, Cl, Br) substituents include -C
2HF
4, -CsH
3Fs, -C
9H
3F
16, -C
2H
4Cl, -C
3H
6Cl, -C
3H
5Cl
2, -C
3HsCIBr and -C
3H
5Br
2. Examples of such substituted alkyl groups with cycloalkyl substituent groups include
[0043]
[0044] Examples of such alkyl groups which have aryl substituent groups include
and
[0045] Examples of such substituted alkyl groups with substituents which provide dibasic
esters include
-CH
2CH
2COOC
12H
25, -(CH
2)
4-COOC
10H
21, -(CH
2)
4-COOCH
2(CF
2CF
2)
2H, -(CH
2)
7COOC
4H
9 and -(CH
2)-
8COOR
12H
25. Examples of such substituted alkyl groups with substituents which provide lactic
acid esters include
and
[0046] Examples of such alkyl groups with substituent groups which provide citrate esters
include
[0047] Examples of such substituted alkyl groups which give malate esters include -CH
2CH(OH)COOC
6H
13 and -CH
2CH(OH)COOC
12H
25. Examples of such substituted alkyl groups which provide tartrate esters include
-CH(OH)CH(OH)COOC
s H
17, -CH(OH)CH(OH)COOC,
18H
37, and
and
[0048] Moreover, W, and W
2 in general formula (VI) may include an oxylane, oxolane or oxane ring which forms
a condensed ring.
[0049] The cycloalkyl groups represented by W
1, W
2, W
3, W
4 or W
5 are, for example,
and examples of substituted cycloalkyl groups include
[0051] Examples of alkenyl groups include -C
4H
7, -C
5H
9, -C
6H
11, -C
7H
13, -C
8H
15, -C
10H
19, -C
12H
23 and -C
18H
35, and examples of substituted alkenyl groups include groups such as
-CH = CH-COOC
1 2H
25 and
which have substituent groups such as halogen atoms (F, Cl, Br), -OC
8H
17, -OC
12H
25,
-OCOC
8H
17 and
[0052] The boiling point of high boiling point organic solvents used in the invention is
preferably at least 140° C, and most desirably at least 160° C. The total number of
carbon atoms in the aforementioned groups W
1 to W4. in these compounds is preferably at least 8, these being alkyl groups.
[0053] The term "organic solvent" generally suggests that the material is itself a liquid,
but in the present invention the organic solvents of which the viscosity measured
at 25° C is at least 500 cp include solids, and they are selected from compounds represented
by formulae (II) to (VIII) which preferably have a viscosity of at least 700 cp or
which, most desirably, are solid with a melting point of at least 25 C. Of these compounds,
those represented by formulae (II) and (III) are preferred, and the dialkyl (secondary
and tertiary alkyl or dicycloalkyl esters of phthalic acid or phosphoric acid are
especially desirable. Dicycloalkyl esters of phthalic acid are the most desirable.
The viscosities can be measured using a cone plate type rotary viscometer (Visconisemd,
made by Tokyo Keiki).
[0054] The amounts of the above-mentioned high boiling point organic solvents used can be
varied appropriately according to the type and amount of cyan coupler used, but a
ratio (by weight) of high boiling point solvent to cyan coupler in the range from
0.05 to 20 is preferred.
[0055] The high boiling point solvents of this invention can be used individually or in
the form of mixtures, or they can be used in the form of mixtures with other conventional
high boiling point organic solvents. Examples of such high boiling point organic solvents
include phosphate ester based solvents such as tricresyl phosphate, tri-2-ethylhexyl
phosphate, 7-methyloctyl phosphate and tricyclohexyl phosphate, and phenol based solvents
such as 2,5-di-tert-amylphenol and 2,5-di-sec-amylphenol.
[0057] The preferred polymers for use in silver halide photographic photosensitive materials
of this invention are polymers which have a relative fluorescence yield K value of
at least 0.10 and preferably of at least 0.20. The larger this value more preferred
the polymer.
[0058] The term K value as used herein is the relative fluorescence quantum yield in the
polymer of the compound A of which the structural formula is shown below, this being
a type of dye which is widely used as a fluorescence probe.
Compound A
[0059]
[0060] Here, φa and ob are the fluorescence quantum yields of the compound A in each of
the polymers a and b, and they are determined, for example, using the method described
in Macromolecules, 14, 587 (1981). In practice, the value is obtained by calculation
from oa and φb measured at room temperature using thin polymer films with concentrations
of 0.5 mM of the aforementioned compound. The film is spin coated onto a slide glass
to a thicknesssuch that the optical density at À
max of the absorbance of compound A is from 0.05 to 0.1. Furthermore, in the present
invention, the K values used are those obtained using poly(methyl methacrylate) (number
average molecular weight 20,000) for the above-mentioned polymer b.
[0061] Specific examples of polymers which can be used in the invention are described below,
but the invention is not to be construed as being limited to the use of these examples.
(A) Vinyl Polymers
[0062] Monomers which can be used to form vinyl polymers of this invention include acrylic
acid esters, including methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl
acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate,
amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate,
2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl
acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl
acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl
acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl
acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate,
2-isopropoxy acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate,
2-(2-butoxyethoxy)ethyl acrylate, m-methoxypolyethylene glycol acrylate (number of
mols addition n = 9), 1-bromo-2-methoxyethyl acrylate and 1,1-dichloro-2-ethoxyethyl
acrylate. The monomers indicated below, for example, can also be used.
[0063] Methacrylic acid esters: examples include methyl methacrylate, ethyl methacrylate,
n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate,
sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate,
cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate,
stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate,
2-(3-phenylpropyloxy)ethyl methacrylate, diethylaminophenox- yethyl methacrylate,
furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl
methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl
methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl
methacrylate, 2-ethoxyethyl methacrylate, 2-isopropoxyethyl methacrylate, 2-butoxyethyl
methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy ethyl methacrylate,
2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number
of mols addition n = 6), allyl methacrylate and methacrylic acid dimethylaminoethylmethyl
chloride.
[0064] Vinyl esters: examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl
isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenylacetate,
vinyl benzoate and vinyl salicylate.
[0065] Acrylamides: for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide,
butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
methoxyethyl- acrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide,
diethylacrylamide, p-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetoneacrylamide
and tert-octylacrylamide.
[0066] Methacrylamides: for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide,
propyl- methacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide,
benzyl- methacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethyl-
methacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethyl methacrylamide,
β-cyanoethyl- methacrylamide and N-(2-acetoacetoxyethyl)methacrylamide.
[0067] Olefins: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene.
[0068] Styrenes: for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene,
ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene,
chlorostyrene, dichlorostyrene, bromostyrene and methyl vinylbenzoate.
[0069] Vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether,
methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether.
[0070] Other compounds include, for example, butyl crotonate, hexyl crotonate, dimethyl
itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate,
diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl
vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate,
N-vinyloxazolidone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, methylenemalonitrile
and vinylidene.
[0071] Two or more of the monomers (for example, the above-mentioned monomers) which can
be used in polymers of this invention can be used as comonomers for various purposes
(for example, for improving solubility). Furthermore, monomers which have acid groups,
such as those indicated below, can also be used as comonomers for the adjustment of
solubility provided that the copolymer remains insoluble in water.
[0072] Acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconates,
for example, monomethyl itaconate, monoethyl itaconate and monobutyl itaconate; monoalkyl
maleates, for example, monomethyl maleate, monoethyl maleate and monobutyl maleate;
citraconic acid; styrenesulfonic acid; vinylbenzyl sulfonic acid; vinyl sulfonic acid;
acryloyloxyalkylsulfonic acid, for example, acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic
acid and acryloyloxypropylsulfonic acid; methacryloyloxyalkylsulfonic acids, for example,
methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid and methacryloylox-
ypropylsulfonic acid; acrylamidoalkylsulfonic acids, for example, 2-acrylamido-2-methylethanesulfonic
acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamido-2-methylbutanesulfonic
acid; methacrylamidoalkylsulfonic acids, for example, 2-methacrylamido-2-methylethane
sulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid and 2-methacrylamido-2-methylbutanesulfonic
acid; and the alkali metal (for example, sodium or potassium) or ammonium ion salts
of these acids.
[0073] In cases where a hydrophilic monomer (here, this signifies a monomer which forms
a water-soluble homopolymer) is used as a comonomer with the vinyl monomers indicated
above and other vinyl monomers which can be used in the invention, no particular limitation
is imposed on the proportion of hydrophilic monomer which is included in the copolymer
provided that the copolymer does not.become water-soluble but, normally, such monomers
are used in an amount not exceeding 40 mol%, preferably in an amount not exceeding
20 mol% and, most desirably, in an amount not exceeding 10 mol%. Furthermore, in cases
where the hydrophilic comonomer which is copolymerized with a monomer of this invention
has acid groups, the proportion in the copolymer of the comonomer which has acid groups
is normally not more than 20 mol%, and preferably not more than 10 mol%, while the
absence of copolymers of this type is most desirable from the point of view of the
image storage properties as described earlier.
[0074] The monomers of this invention in the polymer are preferably methacrylate based,
acrylate based and methacrylamide based monomers. The acrylate and methacrylate based
monomers are especially desirable.
(B) Polymers Formed by Condensation and Polyaddition Reactions
[0075] Polyesters formed from polyhydric alcohols and polybasic acids, and polyamides formed
from diamines and dibasic acids and from (o-amino-
M -carboxyiic acids, are generally known as condensation polymers, and polymers such
as the polyurethanes which are formed from diisocyanates and dihydric alcohols are
known as polymers which have been formed by means of a polyaddition reaction.
[0076] Glycols which have an OH-R
i-OH structure (where R
1 is a hydrocarbon chain, especially an aliphatic hydrocarbon chain, which has from
2 to about 12 carbon atoms), or polyalkylene glycols, are effective as polyhydric
alcohols, and acids which have an HOOC-R
2-COOH structure (where R
2 represents a single bond or a hydrocarbon chain which has from 1 to about 12 carbon
atoms) are effective as polybasic acids.
[0077] Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene
glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylol propane, 1,4-butanediol,
isobutylenediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol,
1,13-tridecanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol,
mannitol and sorbitol.
[0078] Examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic
acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid,
decanedicarboxylic acid, undecanedicar- boxylic acid, dodecanedicarboxylic acid, fumaric
acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid,
terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohymelic acid, cyclopentadiene-maleic
anhydride adducts and rosinmaleic anhydride adducts.
[0079] Examples of diamines include hydrazine, methylenediamine, ethylenediamine, trimethylenediamine,
tetramethylenediamine, hexamethylenediamine, dodecylmethylenediamine, 1,4-diaminocyclohexane,
1,4-diaminomethylcyclohexane, o-aminoaniline, p-aminoaniline, 1,4-diaminomethylbenzene
and bis(4-aminophenyl) ether.
[0080] Examples of ω-amino-ω-carboxylic acids include glycine, p-alanine, 3-aminopropanoic
acid, 4-aminobutanoic acid, 5-aminopentanoic acid, 11-aminododecanoic and 4-(4-aminophenyl)butanoic
acid.
[0081] Examples of diisocyanates include ethylenediisocyanate, hexamethylenediisocyanate,
m-phenylenediisocyanate, p-phenylenediisocyanate, p-xylenediisocyanate and 1,5-naphthyldiisocyanate.
(C) Others
[0082] For example, polyesters and polyamides which are obtained by ring opening polymerization:
[0083] In this formula, X represents an -0- group or an -NH- group, and m represents an
integer of value 4 to 7. The -CH
2- groups may be branched.
[0084] Monomers of this type include S-propiolactone,
E-caprolactone, dimethylpropiolactone, a-pyrrolidone, a-piperidone, e-caprolactam and
a-methyl-
E-caprolactam.
[0085] Monomers represented by the general formula indicated below can also be used. ⁅(̵A)̵(̵B)̵⁆
n
[0086] In this formula, A represents a repeating unit which has in the main chain at least
one bond which is an ether bond or an -S0
2- bond. Moreover, B represents a repeating unit which has in the main chain at least
one
bond, ether bond,
bond, -S0
2- bond or ester bond, or a single bond, and this may be the same as, or different
from, A. R represents hydrogen, an alkyl group, aryl group or aralkyl group, and these
groups may be substituted or unsubstituted groups. Moreover, n is an integer of value
at least 5.
[0087] Two or more of the polymers of this invention described above can be used conjointly.
[0088] Among these polymers, the vinyl polymers are preferred as the polymers of this invention,
and the use of acrylic based polymers, especially acrylamide based polymers, is especially
desirable.
[0089] The molecular weights and degrees of polymerization of the polymers of this invention
are not particularly limited, but problems arise with the increased time which is
required to dissolve the polymer in an auxiliary solvent as the molecular weight increases,
and emulsification and dispersion become more difficult because of the higher viscosity.
Coarse particles are formed, and this can result in a worsening of coloring properties,
and problems with coating properties are also liable to arise. The use of a larger
amount of auxiliary solvent and reduction of the solution viscosity to overcome these
problems gives rise to new processing problems. From the point of view of the factors
described above, the viscosity of the polymer is preferably such that the viscosity
on dissolving 30 g of the polymer in 100 cc of the auxiliary solvent which is being
used is less than 5,000 cps, and most desirably such that this solution viscosity
is less than 2,000 cps. Furthermore, the molecular weight of the polymers which can
be used in the invention is preferably less than 150,000 and most desirably less than
100,000.
[0090] In this invention, a "water-insoluble polymer" is a polymer of which the solubility
in 100 g of distilled water is 3 g or less, and preferably 1 g or less.
[0091] The ratio of the polymer of this invention to the auxiliary solvent differs according
to the type of polymer which is being used, and it varies over a wide range depending
on the solubility in the auxiliary solvent, the degree of polymerization, and the
solubility of the coupler. Normally, the amount of auxiliary solvent required to provide
a sufficiently low viscosity such that the solution consisting of at least a coupler,
a high boiling point organic solvent and a polymer in an auxiliary solvent can be
dispersed easily in water or in an aqueous hydrophilic colloid solution is used. The
viscosity of the solution increases as the degree of polymerization of the polymer
increases and so it is difficult to generally define the ratio of polymer to auxiliary
solvent irrespective of the type of polymer, but normally ratios within the range
from 1:1 to 1:50 (by weight) are preferred. The proportion of polymer of this invention
with respect to coupler (by weight) is preferably from 1:20 to 20:1, and most desirably
from 1:10 to 10:1.
[0092] Specific examples of polymers which can be used in the invention are described below,
but the invention is not to be construed as being limited to these examples. Ratios
are by weight.
P- 1) Poly(methyl methacrylate)
P- 2) Poly(ethyl methacrylate)
P- 3) Poly(isopropyl methacrylate)
P- 4) Poly(methyl chloroacrylate
P- 5) Poly(2-tert-butylphenyl acrylate)
P- 6) Poly(4-tert-butylphenyl acrylate)
P- 7) Ethyl methacrylate/n-butyl acrylate copolymer (70/30)
P- 8) Methyl methacrylate/acrylonitrile copolymer (65/35)
P- 9) Methyl methacrylate/styrene copolymer (90/10)
P-10) N-tert-Butylmethacrylamide/methyl methacrylate/acrylic acid copolymer (60/30/10)
P-11) Methyl methacrylate/styrene/vinylsulfonamide copolymer (70/20/10)
P-12) Methyl methacrylate/cyclohexyl methacrylate copolymer (50/50)
P-13) Methyl methacrylate/acrylic acid copolymer (95/5)
P-14) Methyl methacrylate/n-butyl methacrylate copolymer (65/35)'
P-15) Methyl methacrylate/N-vinyl-2-pyrrolidone copolymer (90/10)
P-16) Poly(N-sec-butylacrylamide
P-17) Poly(N-tert-butylacrylamide)
P-18) Cyclohexyl methacrylate/methyl methacrylate copolymer (60/40)
P-19) n-Butyl methacrylate/methyl methacrylate/acrylamide copolymer (20/70/10)
P-20) Diacetoneacrylamide/methyl methacrylate copolymer (20/80)
P-21) N-tert-Butylacrylamide/methyl methacrylate copolymer (40/60)
P-22 Poly(N-n-butylacrylamide)
P-23) tert-Butyl methacrylate/N-tert-butylacrylamide copolymer (50/50)
P-24) tert-Butyl methacrylate/methyl methacrylate copolymer (70/30)
P-25) Poly(N-tert-butylacrylamide)
P-26) N-tert-Butylacrylamide/methyl methacrylate copolymer (60/40)
P-27) Methyl methacrylate/acrylonitrile copolymer (70/30)
P-28) Methyl methacrylate/styrene copolymer (75/25)
P-29) Methyl methacrylate/hexyl methacrylate copolymer (70/30)
P-30) Poly(4-biphenyl acrylate)
P-31) Poly(2-chlorophenyl acrylate)
P-32) Poly(4-chlorophenyl acrylate)
P-33) Poly(pentachlorophenyl acrylate)
P-34) Poly(4-ethoxycarbonylphenyl acrylate)
P-35) Poly(4-methoxycarbonylphenyl acrylate)
P-36) Poly(4-cyanophenyl acrylate)
P-37) Poly(4-methoxyphenyl acrylate)
P-38) Poly(3,5-dimethyladamantyl acrylate)
P-39) Poly(3-dimethylaminophenyl acrylate)
P-40) Poly(2-naphthyl acrylate)
P-41) Poly(phenyl acrylate)
P-42) Poly(N,N-dibutylacrylamide)
P-43) Poly(isohexylacrylamide)
P-44) Poly(isooctylacrylamide)
P-45) Poly(N-methyl-N-phenylacrylamide)
P-46) Poly(adamantyl methacrylate)
P-47) Poly(sec-butyl methacrylate)
P-48) N-tert-Butylacrylamide/acrylic acid copolymer (97/3)
P-49) Poly(2-chloroethyl methacrylate)
P-50) Poly(2-cyanoethyl methacrylate)
P-51) Poly(2-cyanomethylphenyl methacrylate)
P-52) Poly(4-cyanophenyl methacrylate)
P-53) Poly(cyclohexyl methacrylate)
P-54) Poly(2-hydroxypropyl methacrylate)
P-55) Poly(4-methoxycarbonylphenyl methacrylate)
P-56) Poly(3,5-dimethyladamantyl methacrylate)
P-57) Poly(phenyl methacrylate)
P-58) Poly(4-butoxycarbonylphenylmethacrylamide)
P-59) Poly(4-carboxyphenylmethacrylamide)
P-60) Poly(4-ethoxycarbonylphenylmethacrylamide)
P-61) Poly(4-methoxycarbonylphenylmethacrylamide)
P-62) Poly(cyclohexyl chloroacrylate)
P-63) Poly(ethyl chloroacrylate)
P-64) Poly(isobutyl chloroacrylate)
P-65) Poly(isopropyl chloroacrylate)
[0093] Suitable methods for synthesizing the polymer used in the invention are well-known
in the art.
SYNTHESIS EXAMPLE 1
Preparation of Methyl Methacrylate Polymer (P-3)
[0094] Methyl methacrylate (500 g), 0.5 g of poly-(sodium acrylate) and 200 ml of distilled
water were introduced into a 500 ml three-necked flask and the mixture was heated
to 80 C with stirring under a blanket of nitrogen. Dimethyl azobisisobutyrate (500
mg) was added as a polymerization initiator and polymerization started.
[0095] The reaction mixture was cooled after polymerizing for a period of 2 hours, and 48.7
g of Polymer P-3 was obtained by recovering by filtration, and washing with water,
the polymer which had been formed in the form of beads.
SYNTHESIS EXAMPLE 2
Preparation of t-Butylacrylamide Polymer (P-17)
[0096] A mixture of 500 g of t-butylacrylamide and 250 ml of toluene was introduced into
a 500 ml three-necked flask and heated to 80 C with stirring under a blanket of nitrogen.
A toluene solution (10 ml) containing 500 mg of azobisisobutyronitrile was added as
a polymerization initiator and polymerization was started.
[0097] The reaction mixture was cooled after polymerizing for a period of 3 hours, and 47.9
g of Polymer P-17 was obtained on recovering by filtration of the solid which precipitated
out on pouring the mixture into 1 liter of hexane, washing the solid with hexane,
and drying the product by heating under reduced pressure.
[0098] Dispersions of lipophilic fine particles containing coupler, high boiling point coupler
solvent and polymer of this invention can be prepared as indicated below.
[0099] The polymer of this invention, being a linear polymer prepared by a solution polymerization
procedure, an emulsion polymerization procedure or a suspension polymerization procedure,
etc. (without crosslinking), the high boiling point coupler solvent and the coupler
are all dissolved completely in an auxiliary organic solvent and the resulting solution
is dispersed in the form of fine particles in water, or preferably in an aqueous hydrophilic
colloid solution and most desirably in an aqueous gelatin solution, with the aid of
a dispersing agent, using ultrasonics or a colloid mill, for example, and this dispersion
is included in the silver halide emulsion. Alternatively, water or an aqueous hydrophilic
colloid solution such as an aqueous gelatin solution can be added to an auxiliary
organic solvent which contains a dispersion promotor such as a surfactant, the polymer
of this invention, the high boiling point coupler solvent and the coupler and an oil-in-
water dispersion can be formed by phase reversal The auxiliary solvent may be removed
from the dispersion so prepared by distillation, noodle washing or by ultra-filtration,
for example, after which the dispersion may be mixed with a photographic emulsion.
The term "auxiliary solvent" as used herein signifies an organic solvent which is
used at the time of emulsification and dispersion but which is ultimately eliminated
from the photosensitive material during the drying process at the time of coating
or by the methods mentioned above, for example. These solvents are low boiling point
organic solvents or solvents which have some solubility in water and which can be
removed by washing with water. Examples of such auxiliary solvents include the acetates
of lower alcohols, such as ethyl acetate and butyl acetate, ethyl propionate, sec-butyl
alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl
cellosolve acetate, methylcarbitol acetate, methylcarbitol propionate and cyclohexanone.
[0100] Moreover, an organic solvent which is completely miscible with water, such as methyl
alcohol, ethyl alcohol, acetone or tetrahydrofuran, can be used conjointly, as required.
[0101] Furthermore, two or more of these organic solvents can be used conjointly.
[0102] The fine lipophilic particles (oil droplets) are included in a silver halide emulsion
layer or adjacent layers to the silver halide emulsion layer, preferably in a silver
halide emulsion layer.
[0103] The average particle size of the fine lipophilic particles obtained in this way is
preferably from 0.04 µm to 2 u.m, and most preferably from 0.06 u.m to 0.4 u.m. The
particle size of the fine lipophilic particles can be measured using a device such
as the "Nanosizer" made by the British Coal Tar Co.
[0104] Various photographically useful hydrophobic substances can also be included in the
fine lipophilic particles of this invention. Examples of such photographically useful
hydrophobic substances include colored couplers, non-color-forming couplers, developing
agents, developing agent precursors, development inhibitor precursors, ultraviolet
absorbers, development accelerators, gradation controlling agents such as hydroquinones,
dyes, dye-releasing agents, antioxidants, fluorescent whiteners, and antifading agents.
Furthermore, these hydrophobic substances can be used conjointly.
[0105] Furthermore, the compounds of formulae (A) to (C) indicated below improve the color-forming
properties and increase the fading prevention of this invention. Their use is especially
effective as photographically useful hydrophobic substances which are included in
the fine lipophilic particle of this invention which contains coupler, high boiling
point organic solvent and polymer.
wherein A represents a divalent electron-attracting group; R
1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted
aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted
aryloxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted
anilino group, or a substituted or unsubstituted heterocyclic group; and t is an integer
of 1 or 2; R
2 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted
alkoxy group, a hydroxyl group or a halogen atom; and m is 0 or an integer from 1
to 4; Q represents a benzene ring or a . heterocyclic ring which may be condensed
with the phenol ring.
wherein R
3, R
4 and Rs, which may be the same or different, each represents hydrogen, a halogen atom,
a nitro group, a hydroxyl group or a substituted or unsubstituted alkyl, alkoxy, aryl,
aryloxy or acylamino group.
wherein Rs and R
7 each represents hydrogen or a substituted or unsubstituted alkyl group, alkoxy group
or acyl group; X represents -CO- or -COO-; and n is an integer of 1 to 4.
[0107] No particular limitation is imposed on the halogen composition of the silver halide
grains used in the invention, but the use of essentially silver iodide free silver
chlorobromides in which at least 20 mol% (average value) of all the silver halide
in the same silver halide emulsion layer consists of silver chloride is preferred.
Here, the term "essentially silver iodide free" signifies a silver iodide content
of not more than 1 mol%. Further, the use of essentially silver iodide free silver
halides in which at least 80 mol% (average value) of all the silver halide in the
same silver halide emulsion layer consists of silver chloride is more preferred. Most
preferred silver halide consists of from 0 to 1 mol% of silver iodide, 95 mol% or
more of silver chloride and the remainder of silver bromide. Essentially silver iodide
free silver chlorobromides in which at least 95 mol% of all the silver halide in the
same silver halide emulsion layer consists of silver chloride are especially desirable
halogen compositions for the silver halide grains in cases where rapid processing
is envisaged. Furthermore, in cases where such high silver chloride grains are used,
it is preferred that the grains have a local silver bromide phase which has a silver
bromide content of more than 10 mol% but less than 70 mol%. The arrangement of such
a local silver bromide phase is variable, depending on the intended purpose, and it
may be in the interior of the silver halide grains, or in the surface or sub-surface
parts of the silver halide grains, or it may be divided between the interior and surface
or sub-surface regions of the silver halide grains. Furthermore, the local phase may
have a layer-like structure surrounding the silver halide grains internally or at
the surface, or it may have a discontinuous, isolated structure. As an example of
a preferred arrangement, a silver bromide local phase of which the silver bromide
content is at least 10 mol%, and preferably in excess of 20 mol%, is grown locally
on the surface of the silver halide grains (even on the corners).
[0108] The silver bromide content of the local phase is preferably in excess of 20 mol%,
but if the silver bromide content is too high the photosensitive material may be desensitized
when pressure is applied, and undesirable characteristics in the photosensitive material
such as marked variation in speed and gradation due to variations in processing bath
composition arise. In consideration of these points, the silver bromide content of
the local phase is preferably within the range from 20 to 60 mol%, and most desirably
within the range from 30 to 50 mol%. The other silver halide of the local phase is
preferably silver chloride. The silver bromide content of the local phase can be measured,
for example, using the X-ray diffraction method (for example, as described in the
Japanese Chemical Society publication New Experimental Chemistry Series 6, Structural
Analysis, published by Maruzen), or the XPS method (for example, as described in Surface
Analysis--Application of IMA, and Auger Electron and Photoelectron Spectra, published
by Kodansha). The local phase is preferably formed using from 0.1 to 20%, and most
desirably from 0.5 to 7%, of the total amount of silver used to form the silver halide
grains in this invention.
[0109] The boundary between such a local phase and the other phase may be a distinct phase
boundary or the silver halide composition may change gradually to form a short transition
region. The position of the silver bromide local phase can be ascertained by observation
using an electron microscope or by using the method described in European Patent Application
(Laid Open) 273,430.
[0110] Various methods can be employed to form a silver bromide local phase of this type.
For example, a soluble silver salt and a soluble halide can be reacted using a one
sided or simultaneous mixing method to form a local phase. Moreover, the local phase
can be formed using the conversion method, which includes a process in which silver
halide which has already been formed is converted to another silver halide which has
a lower solubility product. Alternatively, a local phase can be formed by adding fine
silver bromide grains and recrystallizing these grains onto the surface of silver
chloride grains.
[0111] These methods have been described, for example, in the specification of European
Patent Application (Laid Open) 273,430.
[0112] The local phase is preferably precipitated along with at least 50% of all the iridium
which is added during the formation of the silver halide grains.
[0113] Here, the term "precipitated together with the iridium" signifies that an iridium
compound is supplied at the same time as the silver and/or halide is being supplied
to form the local phase, or immediately before or immediately after adding the silver
and/or halide.
[0114] The preferred silver halide grains in this invention may have a (100) plane or a
(111) plane for the outer surface, or they may have both of these planes for outer
surfaces, and they may include higher order planes.
[0115] The form of the silver halide grains used in the invention may be a regular crystalline
form, such as cubic, tetradecahedral or octahedral form, an irregular crystalline
form, such as a spherical or tabular form, or a composite form consisting of these
crystalline forms. Mixtures of grains which have various crystalline forms can also
be used, but in such mixtures the presence of at least 50%, preferably at least 70%,
and most desirably at least 90%, of grains which have a regular crystalline form is
desirable.
[0116] The silver halide emulsions used in the invention may be emulsions in which tabular
grains of which the average aspect ratio (length
/thickness ratio) is at least 5, and most desirably at least 8, account for at least
50% of the total projected area of the grains.
[0117] The size of the silver halide grains in this invention may be within the range normally
used, but an average grain size within the range from 0.1 urn to 1.5 /.Lm is preferred.
The grain size distribution may be polydispersed or monodispersed, but monodispersions
are preferred. The particle size distribution which represents the extent of monodispersivity
is preferably such that the statistical variation coefficient (the value S/d obtained
by dividing the standard deviation S by the diameter d in cases where the projected
area is approximately circular) is not more than 20%, and most desirably not more
than 15%.
[0118] Two or more types of tabular grain emulsions and monodispersed emulsions of this
type can be mixed together. In cases in which emulsions are mixed together, at least
one emulsion preferably has a variation coefficient as described above, and the variation
coefficient of the mixed emulsion is preferably within the above range of values.
[0119] Apart from the local phase of the silver halide grains, the substrate may have different
phases for the interior and surface parts or it may consist of a uniform phase.
[0120] Silver halide photographic emulsions which can be used in the invention can be prepared
using the methods described, for example, Chemie et Physique Photographique, by P.
Glafkides, published by Paul Montel, 1967; Photographic Emulsion Chemistry, by G.F.
Duffin, published by Focal Press, 1966; and Making and Coating Photographic. Emulsions,
by V.L. Zelikman et al., published by Focal Press, 1964, etc.
[0121] Silver halide solvents, for example, ammonia, potassium thiocyanate, ammonium thiocyanate,
thioether compounds (for example, those disclosed in U.S. Patents 3,271,157, 3,574,628,
3,704,130, 4,297,439 and 4,276,374), thione compounds (for example, those disclosed
in JP-A-53-144319, JP-A-53-82408 and JP-A-55-77737) and amine compounds (for example,
those disclosed in JP-A-54-100717, can be used to control grain growth during the
formation of the silver halide grains.
[0122] The silver halide grains used in the invention are essentially of the surface latent
image type, and some degree of chemical sensitization of the surface is desirable.
Chemical sensitization can be achieved using sulfur sensitization methods in which
use is made of active gelatin or compounds which contain sulfur which can react with
silver (for example, thiosulfates, thioureas, mercapto compounds and rhodanines),
reduction sensitization methods in which use is made of reducing substances (for example,
stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid and silane
compounds) and precious metal sensitization methods in which use is made of metal
compounds (for example, gold complex salts, and complex salts of metals of group VIII
of the Periodic Table, such as Pt, Ir, Pd, Rh and Fe), and these methods may be used
individually or in combination.
[0123] Details of these methods are disclosed from line 18 of the lower left column on page
12 to line 16 of the lower right column on the same page of the specification of JP-A-62-215272.
[0124] The sensitive materials of this invention typically have a blue-sensitive layer,
a green-sensitive layer and a red-sensitive layer established in this order on a support,
or the order of the layers can be changed appropriately. At least one layer of each
color sensitivity is coated and layers in which spectral sensitization in the prescribed
wavelength region has been provided using sensitizing dyes are preferred.
[0125] The methine dyes such as the cyanine dyes and merocyanine dyes normally used for
photographic purposes can be used as spectrally sensitizing dyes. Examples of these
sensitizing dyes are disclosed at pages 77 to 124 of JP-A-62-215272.
[0126] Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic
acid derivatives can be used, for example, as anti-color-fogging agents in the photosensitive
materials of this invention.
[0127] Various antifading agents can be used in the photosensitive materials of this invention.
Examples of compounds which can be used as organic antifading agents for use with
the cyan, magenta and/or yellow images include hydroquinones, 6-hydroxychromans, 5-hydroxy-coumarans,
spirochromans, p-alkoxyphenols, hindered phenols based on bisphenols, gallic acid
derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester
derivatives of those compounds wherein the phenolic hydroxyl groups have been silylated
or alkylated. Furthermore, metal complexes as typified by (bissalicylaldoximato)nickel
and (bis-N,N-dialkyldithiocarbamato) nickel can also be used for this purpose.
[0128] Examples of organic antifading agents have been disclosed in the specifications of
the patents indicated below.
[0129] Hydroquinone derivatives have been disclosed, for example, in U.S. Patents 2,360,290,
2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944 and 4,430,425,
British Patent 1,363,921 and U.S. Patents 2,710,801 and 2,816,028; 6-hydroxychromans,
5-hydroxycoumarans and spirochromans have been disclosed, for example, in U.S. Patents
3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337, and in JP-A-52-152225; spiroindanes
have been disclosed in U.S. Patent 4,360,589; p-alkoxyphenols have been disclosed,
for example, in U.S. Patent 2,735,765, British Patent 2,066,975, JP-A-59-10539 and
JP-B-57-19765 (the term "JP-B" as used herein refers to an "examined Japanese patent
publication"); hindered phenols have been disclosed, for example, in U.S. Patent 3,700,455,
JP-A-52-72224, U.S. Patent 4,228,235 and JP-B-52-6623; gallic acid derivatives, methylenedioxybenzenes
and aminophenols have been disclosed, for example, in U.S. Patents 3,457,079 and 4,332,886
and JP-B-56-21144, respectively; hindered amines have been disclosed, for example,
in U.S. Patents 3,336,135 and 4,268,593, British Patents 1,326,889, 1,354,313 and
1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846 and JP-A-59-78344; ether and
ester derivatives of phenolic hydroxyl groups have been disclosed, for example, in
U.S. Patents 4,155,765, 4,174,220, 4,254,216 and 4,264,720, JP-A-54-145530, JP-A-
55-6321, JP-A-58-105147, JP-A-59-10539, JP-B-57-37856, U.S. Patent 4,279,990 and JP-B-53-3263;
and metal complexes have been disclosed, for example, in U.S. Patents 4,050,938 and
4,241,155, and in British Patent 2,027,731 (A). These compounds can be used to achieve
the intended purpose by addition to the photosensitive layer after coemulsification
with the coupler in an amount normally ranging from 5 to 100 wt% with respect to the
corresponding color coupler. The introduction of ultraviolet absorbers into the layers
on both sides adjacent to the cyan color forming layer is effective for preventing
deterioration of the cyan dye image due to heat and, more especially, light.
[0130] The spiroindanes and hindered amines are especially desirable among the above-mentioned
antifading agents.
[0131] The use, together with the aforementioned couplers, and especially with the pyrazoloazole
based couplers, of compounds such as those indicated below is preferred in this invention.
[0132] Thus, the use alone or in combination of a compound (A) which bonds chemically with
any aromatic amine based developing agent remaining after color development processing
and produces chemically inactive and essentially colorless compounds and/or a compound
(B) which bonds chemically with any of the oxidized form of the aromatic amine based
developing agent remaining after color development processing and produces chemically
inactive and essentially colorless compounds is desirable for preventing the occurrence
of staining and other side effects due to the reaction of residual color developing
agent or oxidized form of the color developing agent in the film with a coupler and
colored dye formation during storage after processing.
[0133] Compound (A) is preferably a compound which reacts with p-anisidine with a second
order reaction rate constant k
2 (at 80 C in trioctyl phosphate) within the range from 1.0 liter/mol * sec to 1 x
10-5 liter/mol·sec. , If the value of k
2 is larger than this range, the compound itself will be unstable and it may react
with gelatin or water and decompose. If, on the other hand, the value of k
2 is smaller than this range, reaction with the residual aromatic amine based developing
agents is slow and it is not possible to prevent the occurrence of the side reactions
of the residual aromatic amine based developing agents which is the purpose of the
invention. The most desirable compounds (A) of this type are represented by formulae
(Al) or (All):
wherein R, and R
2 each represents an aliphatic group, aromatic group or heterocyclic group; B represents
hydrogen, an aliphatic group, aromatic group, heterocyclic group, acyl group or sulfonyl
group; and Y represents a group which promotes the addition of aromatic amine based
developing agents to the compounds of formula (All); here, R
1 and X, and Y and R
2 or B, may be linked to form a ring structure.
[0134] Substitution reactions and addition reactions are typical of the forms of chemical
bonding with residual aromatic amine based developing agents.
[0135] Typical examples of compounds which can be represented by formulae (Al) and (All)
have been disclosed, for example, in Japanese Patent Application Nos. 62-158342, 62-158643,
62-212258, 62-214681, 62-228034 and 62-279843.
[0136] Ultraviolet absorbers may be included in the hydrophilic colloid layers in the photosensitive
materials of this invention. For example, benzotriazole compounds substituted with
aryl groups (as disclosed, for example, in U.S. Patent 3,533,794), 4-thiazolidone
compounds (as disclosed, for example, in U.S. Patents 3,314,794 and 3,352,681), benzophenone
compounds (as disclosed, for example, in JP-A-46-2784), cinnamic acid ester compounds
(as disclosed, for example, in U.S. Patents 3,705,805 and 3,707,375), butadiene compounds
(as disclosed, for example, in U.S. Patent 4,045,229), and benzoxidol compounds (as
disclosed, for example, in U.S. Patent 3,700,455) can be used for this purpose. Ultraviolet
absorbing couplers (for example, α-naphthol based cyan dye forming couplers) and ultraviolet
absorbing polymers can also be used for this purpose. These ultraviolet absorbing
agents can be mordanted in specified layers.
[0137] Water-soluble dyes may be included as filter dyes or for anti-irradiation or various
other purposes in the hydrophilic colloid layers of photosensitive materials made
using this invention. Dyes of this type include oxonol dyes, hemioxonol dyes, styryl
dyes, merocyanine dyes, cyanine dyes and azo dyes. The oxonol dyes, hemioxonol dyes
and merocyanine dyes are useful among these dyes.
[0138] The use of gelatin is effective as the binding agent or protective colloid which
is used in the emulsion layers of photosensitive materials of this invention, but
other protective colloids can be used, either individually or in combination with
gelatin.
[0139] The gelatin used in the invention may be a lime treated gelatin or an acid treated
gelatin. Details of methods for the preparation of gelatins have been described by
Arthur Weise in The Macromolecular Chemistry of Gelatin (published by Academic Press,
1964).
[0140] Cellulose nitrate films, transparent films of polyethylene terephthalate or reflective
type supports as normally used for photographic materials can be used for the supports
which are used in the present invention. The use of a reflective type support is preferred,
in line with the purpose of the invention.
[0141] The term "reflective support" used in this invention signifies that the reflectance
is high and that the dye image formed in the silver halide emulsion layer is clear,
and such reflective supports include those in which the support is covered with a
hydrophobic resin which contains a dispersion of a light reflecting substance such
as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate, for example,
and those in which hydrophobic resins which contain light reflecting substances are
used for the support itself. For example, use can be made of baryta paper, polyethylene
coated paper, polypropylene based synthetic papers, and transparent supports such
as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate
and cellulose nitrate films, polyamide films, polycarbonate films, polystyrene films
and vinyl chloride resin films on which a reflecting layer has been established or
in which a reflecting substance has been used conjointly, and the supports can be
selected appropriately according to the intended purpose of the resulting material.
[0142] White pigments may be milled thoroughly in the presence of a surfactant as light
reflecting materials and the use of those white pigments of which the surfaces of
the fine pigment particles have been treated with a di-hydric to tetra-hydric alcohol
is preferred.
[0143] The occupied area factor (%) for the area occupied by fine white pigment particles
per specified unit surface area can be obtained most typically by dividing the area
observed into adjoining unit areas measuring 6 u.m x 6 am and measuring the occupied
area factor (%) (R
i) of the fine grains projected in each unit area. The variation factor of the occupied
area factor (%) can be obtained using the ratio s/ R-of the standard deviation s of
R, with respect to the average value of R; ( R). The number of unit areas taken as
subjects for observation is preferably at least six. Hence, the variation coefficient
s/ R-can be obtained from the following expression:
[0144] In this invention, the variation factor of the occupied area factor (%) of the fine
pigment grains is preferably not more than 0.15, and most desirably not more than
0.12. The dispersion of the particles can be said to be "uniform" when the variation
coefficient has a value of not more than 0.08.
[0145] As well as the normal exposure system in which a single surface exposure is made,
scanning exposure methods can be used for exposing the sensitive materials of this
invention. Methods in which a combination of a laser and a wavelength varying element
consisting of a non-linear optical material is used to provide a second harmonic fcr
the light source as disclosed in JP-A-63-113534 are preferred for making such scanning
exposures.
[0146] The conventional color development processing which can be used after exposing the
material in this way is described below.
[0147] The color development baths used for color development processing are preferably
aqueous alkaline solutions which contain primary aromatic amine based color developing
agents as the principal components. Aminophenol based compounds are useful as color
developing agents, but the use of p-phenylenediamine based compounds is preferred.
Typical examples of these compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-p-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline,
and the sulfate, hydrochloride and p-toluenesulfonate salts of these compounds. Two
or more of these compounds can be used conjointly, depending on the intended purpose.
[0148] The color development baths generally contain pH buffers, such as alkali metal carbonates,
borates or phosphates, and development inhibitors or antifogging agents, such as bromides,
iodides, benzimidazoles, benzothiazoles or mercapto compounds. They may also contain,
as required, various preservatives, such as hydroxylamine, diethylhydroxylamine, sulfites,
hydrazines, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine(1,4-diazabicyclo[2,2,2]octane),
organic solvents such as ethylene glycol and diethylene glycol, development accelerators
such as benzyl alcohol, poly(ethylene glycol), quaternary ammonium salts and amines,
dye forming couplers, competitive couplers, fogging agents such as sodium borohydride,
auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents,
various chelating agents, as typified by the aminopolycarboxylic acids, aminopolyphosphonic
acids, alkylphosphonic acids and phosphonocarboxylic acids, typical examples of which
include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic
acid, cyclohexanediaminetetraacetic acid, hydroxyethylimidinoacetic acid, 1-hydroxyethylidene-1,1-diphosphonic
acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N ,N-tetramethylenephosphonic
acid, ethylenediamine di(ohydroxyphenylacetic acid), and salts of these compounds.
[0149] Color development is carried out after a normal black-and-white development in the
case of reversal processing. The known black-and-white developing agents, for example,
dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone,
and aminophenols such as N-methyl-p-aminophenol, can be used individually, or in combinations,
in these black-and-white development baths.
[0150] The pH of these color development baths and black-and-white development baths is
generally within the range from 9 to 12. Furthermore, the replenishment rate of these
development baths depends on the color photo graphic material which is being processed,
but it is generally 3 liters or less per square meter of photo-sensitive material
and it is possible, by reducing the bromide ion concentration in the replenisher,
to use replenishment rates of 500 ml or less per square meter of photosensitive material.
The prevention of loss of liquid by evaporation, and aerial oxidation, by minimizing
the contact area with the air in the processing tank is desirable in cases where the
replenishment rate is low. The replenishment rate can be reduced further by suppressing
the accumulation of bromide ion in the developer.
[0151] The photographic emulsion layers are subjected to a normal bleaching process after
color development. The bleaching process may be carried out at the same time as the
fixing process (in a bleach-fix process) or it may be carried out as a separate process.
Moreover, a bleach-fix process can be carried out after a bleaching process in order
to speed-up processing. Moreover, processing can be carried out in two connected bleach-fix
baths, a fixing process can be carried out before carrying out a bleach-fix process,
or a bleaching process can be carried out after a bleach-fix process, according to
the intended purpose of the processing. Compounds of a multivalent metal, such as
iron(III), cobalt(IIII), chromium(VI) and copper(II), peracids, quinones and nitro
compounds can be used, for example, as bleaching agents. Typical bleaching agents
include ferricyanides; dichromates; organic complex salts of iron(IIII or cobalt(III),
for example, complex salts with aminopolycarboxylic acids, such as ethylenediaminetetraacetic
acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic
acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid,
or citric acid, tartaric acid, malic acid; persulfates; bromates; permanganates and
nitrobenzenes. Of these materials, the use of the aminopolycarboxylic acid iron(III)
complex salts, principally ethylenediaminetetraacetic acid iron(III) complex salts,
and persulfates, is preferred both for rapid processing and the prevention of environmental
pollution. Moreover, the aminopolycarboxylic acid iron(III) complex salts are especially
useful in both bleach baths and bleach-fix baths. The pH of a bleach or bleach-fix
bath in which aminopolycarboxylic acid iron(IIII) complex salts are being used is
normally from 5.5 to 8. Processing can be speeded up by using a bleach-fixing solution
having preferably a pH of 6.0 or less, and more preferably a pH of 5.5 or less.
[0152] Bleach accelerators can be used, as required, in the bleach baths, bleach-fix baths,
or bleach or bleach-fix prebaths. Examples of useful bleach accelerators have been
disclosed in the following specifications: the compounds which have a mercapto group
or a disulfide group disclosed, for example, in U.S. Patent 3,893,858, West German
Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623,
JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426
and Research Disclosure, No. 17129 (July, 1978); the thiazolidine derivatives disclosed
in JP-A-50-140129; the thiourea derivatives disclosed in JP-B-45-8506, JP-A-52-20832,
JP-A-53-32735 and U.S. Patent 3,706,561; the iodides disclosed in West German Patent
1,127,715 and JP-A-58-16235; the polyoxyethylene compounds disclosed in West German
Patents 966,410 and 2,748,430; the polyamine compounds disclosed in JP-B-45-8836;
the other compounds disclosed in JP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727,
JP-A-55-26506 and JP-A-58-163940; and bromide ions. Among these compounds, those which
have a mercapto group or a disulfide group are preferred in view of their large accelerating
effect, and the use of the compounds disclosed in U.S. Patent 3,893,858, West German
Patent 1,290,812 and JP-A-53-95630 is especially preferred.
[0153] Moreover, the use of the compounds disclosed in U.S. Patent 4,552,834 is also preferred.
These bleach accelerators may be added to the sensitive material. These bleach accelerators
are especially effective when bleach-fixing camera color photosensitive materials.
[0154] Thiosulfates, thiocyanates, thioether based compounds, thioureas, and large quantities
of iodides can be used as fixing agents, but thiosulfates are generally used for this
purpose and ammonium thiosulfate, in particular, can be used in the widest range of
applications. Sulfites or bisulfites, or carbonyl-bisulfite addition compounds, are
preferred as preservatives for bleach-fix baths.
[0155] The silver halide color photographic materials of this invention are generally subjected
to water washing and/or stabilizing process after the desilvering process. The amount
of water used in the water washing process can be fixed within a wide range according
to the nature of the photosensitive material (for example, the materials, such as
couplers, which are being used), the application, the wash water temperature, the
number of washing tanks (the number of washing stages), the replenishment system,
i.e., whether a counter flow or a sequential flow system is used, and various other
conditions. The relationship between the amount of water used and the number of water
washing tanks in a multistage counter flow system can be obtained using the method
outlined on pages 248 to 253 of the Journal of the Society of Motion Picture and Television
Engineers, Vol. 64 (May, 1955).
[0156] The amount of wash water can be greatly reduced by using the multistage counter flow
system there described, but bacteria proliferate due to the increased residence tine
of the water in the tanks and problems arise as a result of the sediments which are
formed becoming attached to the photosensitive material. The method in which the calcium
ion and manganese ion concentrations are reduced disclosed in JP-A-62-288838 can be
used very effectively to overcome problems of this sort in the processing of color
photosensitive materials of this invention. Furthermore, the isothiazolone compounds
and thiabendazoles disclosed in JP-A-57-8542, and chlorine based disinfectants such
as chlorinated sodium isocyanurate, and benzotriazoles, and the disinfectants disclosed
in Chemistry of Biocides and Fungicides by Horiguchi, Killing Microorganisms, Biocidal
and Fungicidal Techniques, published by the Health and Hygiene Technical Society,
and in A Dictionary of Biocides and Fungicides, published by the Japanese Biocide
and Fungicide Society, can be used for this purpose.
[0157] The pH of the wash water used in the processing of the photosensitive materials of
the invention is within the range from 4 to 9, and preferably within the range from
5 to 9. The wash water temperature and the washing time can be set variously according
to the nature of the photosensitive material and the application, etc., but, in general,
washing conditions of from 20 seconds to 10 minutes at a temperature of from 15°C
to 45 C, and preferably of from 30 seconds to 5 minutes at a temperature of from 25
C to 40 ° C, are selected. Moreover, the photosensitive materials of this invention
can be processed directly in a stabilizing bath instead of being subjected to a water
wash as described above. The known methods disclosed in JP-A-57-8543, JP-A-58-14834
and JP-A-60-220345 can all be used for this purpose.
[0158] Furthermore, there are cases in which a stabilization process is carried out following
the water washing process, and the stabilizing baths which contain formalin and surfactant
which are used as a final bath for camera color photosensitive materials are an example
of such a process. Various chelating agents and fungicides can be added to these stabilizing
baths.
[0159] The overflow which accompanies replenishment of the above-mentioned wash water and/or
stabilizer can be reused in other processes such as the desilvering process.
[0160] A color developing agent may also be incorporated into the silver halide color photosensitive
materials of this invention in order to simplify and speed-up processing. The use
of various color developing agent precursors is preferred for such incorporation.
For example, the indoaniline based compounds disclosed in U.S. Patent 3,342,597, the
Schiff's base type compounds disclosed in U.S. Patent 3,342,599 and Research Disclosure,
Nos. 14850 and 15159, the aldol compounds disclosed in Research Disclosure, No. 13924,
the metal salt complexes disclosed in U.S. Patent 3,719,492, and the urethane based
compounds disclosed in JP-A-53-135628 can be used for this purpose.
[0161] Various 1-phenyl-3-pyrazolidones can be incorporated, as required, into the silver
halide color photosensitive materials of this invention with a view to accelerating
color development. Typical compounds of this type have been disclosed, for example,
in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
[0162] The various processing baths in this invention are used at a temperature of from
10°C to 50°C. The standard temperature is normally from 33
* C to 38 C, but processing is accelerated and the processing time is shortened at higher
temperatures and, conversely, increased picture quality and improved stability of
the processing baths can be achieved at lower temperatures. Furthermore, processes
using hydrogen peroxide intensification or cobalt intensification as disclosed in
West German Patent 2,226,770 or U.S. Patent 3,674,499 can be carried out in order
to economize on silver in the photosensitive material.
[0163] In order to realize the excellent characteristics of the silver halide photographic
photosensitive materials of this invention, the silver halide color photographic photosensitive
material which has on a single layer reflecting support at least one photo-sensitive
layer which contains silver halide grains and at least one type of coupler which forms
a dye by means of a coupling reaction with the oxidized form of a primary aromatic
amine based color developing agent is preferably processed for a developing time of
not more than 2 minutes 30 seconds in a color development bath which is essentially
benzyl alcohol free and which contains not more than 0.002 mol/liter of bromide ions.
[0164] The term "essentially benzyl alcohol free" as used above signifies that the benzyl
alcohol concentration is less than 2 ml per liter, and preferably less than 0.5 ml
per liter, of color development bath, and most preferably that the color development
bath contains no benzyl alcohol at all.
[0165] The invention is now described in greater detail with reference to the following
specific examples, but the present invention is not to be construed as being limited
thereto. Unless otherwise indicated, all parts, percents and ratios are by weight.
EXAMPLE 1
[0166] The multilayer silver halide photosensitive material Sample 101 having the layer
structure indicated below was prepared on a paper support which had been laminated
on both sides with polyethylene. Moreover, ethyl acetate was used as an auxiliary
solvent together with the high boiling point organic solvent for the coupler solvents
referred to below.
Layer Structure
[0167] The composition of each layer was as indicated below. The values indicate coated
weights (g/m
2). The weights of silver halide emulsions are indicated as weights calculated as silver.
Support
[0168] Polyethylene laminated paper (white pigment (TiO
z) and ultramarine dye were included in the polyethylene on the first layer side).
First Layer: Blue-Sensitive Layer
[0169]
Second Layer: Anti-Color Mixing Layer
[0170]
Third Layer: Green-Sensitive Layer
[0171]
Fourth Layer: Ultraviolet Absorbing Layer
[0172]
Fifth Layer: Red-Sensitive Layer
[0173]
Sixth Layer: Ultraviolet Absorbing Layer
[0174]
Seventh Layer: Protective Layer
[0175]
[0176] In the fifth layer, two kinds of cyan coupler, three kinds of colored image stabilizer,
ultraviolet absorber and polymer for dispersion were dissolved in ethyl acetate and
a mixture of the solution thus obtained and solvent (SV-6) were dispersed to form
an emulsion into an aqueous gelatin solution in the presence of dodecylbenzenesulfonic
acid (surfactant) with a high speed homogenizer. The emulsified dispersion thus obtained
was one containing fine grains. The surfactant was used in an amount of 1/10 (by weight)
the above additives. Then, the emulsified dispersion and silver halide emulsion were
mixed to be used for coating.
[0177] Furthermore, Cpd-11 and Cpd-12 were used as anti-irradiation dyes. Moreover, "Alkanol
XC" (made by the Du Pont Co.), sodium alkylbenzenesulfonate, succinic acid esters
and "Megafac F-120" (made by the Dainippon Ink co.) were used in each layer as emulsification,
dispersion and coating promotors. Cpd-13 and Cpd-14 were used as silver halide stabilizers.
[0178] Furthermore, 1-oxy-3,5-dichloro-s-triazine, sodium salt, was used as a gelatin hardening
agent in each layer, and Cpd-2 was used as a viscosity increasing agent.
[0179] Details of the emulsions used are indicated below.
[0181] Samples 102 to 130 were prepared in the same way as Sample 101 except that the type
of polymer used for dispersion purposes and the type of high boiling point solvent
in the red-sensitive layer of Sample 101 were modified as shown in Table 1.
[0182] The above-mentioned photosensitive materials were subjected to a gray exposure, after
which running tests were carried out using a Fuji Color Paper Processor Model PP600
using the processing operations indicated below until the system had been replenished
to twice the volume of the color developing tank.
[0183] The composition of each of the processing baths was as indicated below.
Color Development Bath
[0184]
Bleach-Fix Bath
[0185]
Rinse Bath
[0186] Deionized water (calcium and magnesium ion concentrations both less than 3 ppm)
[0187] Samples 101 to 130 prepared in this way were subjected to a gray exposure and processed
in the same way as before and the resulting samples were subjected to a fading test
with fungi which was carried out in the way described below.
[0188] Fungi which had grown on a color paper were cultured on a potato dextrose agar medium,
spores were collected and a spore suspension of concentration approximately 1.5 x
10
6 spores/ml was prepared. Next, 0.5 ml of the spore suspension was dripped onto each
sample and the samples were maintained at 28° C under conditions of 95% humidity for
a period of 10 months, during which time fungi developed and propagated, and the extent
of fading of the cyan image in the region in which the fungi had propagated was investigated.
[0189] The results observed for cyan dye fading are shown in Table 2, where a fading factor
of more than about 40% is indicated by x x, a fading factor of at least 10% but less
than 40% is indicated by x, a fading factor of at least 5% but less than 10% is indicated
by o and a fading factor of less than 5% is indicated by
[0190] It is clear from Table 2 that with the samples other than those of this invention,
color changes leading to the formation of red spots appeared in the parts where the
fungi had proliferated on the gray colored parts (tricolor yellow, magenta and cyan),
which is to say that the cyan dye faded in these parts, whereas this phenomenon was
not observed with the samples of this invention. Furthermore, the cyan coloration
was remarkably low immediately after processing with Sample 109 which did not contain
a high boiling point organic solvent and there were problems with the color forming
properties in this case. Thus, by means of this invention the images can be preserved
effectively with no cyan fading even when fungi develop on long term storage. Furthermore,
the cyan images of the samples of this invention had a good hue and good light fastness.
EXAMPLE 2
[0191] Photosensitive material Samples 210 to 230 were prepared in the same way as the photosensitive
material Samples 101 to 130 in Example 1 except that the silver halide emulsions and
magenta couplers were changed as indicated below.
[0192] Thus, Emulsions EM1 and EM2 were replaced by Emulsion EM7, Emulsions EM3 and EM4
were replaced by Emulsion EM8, and Emulsions EM5 and EM6 were replaced by Emulsion
EM9. The emulsions used were as follows:
[0193] Furthermore, the magenta coupler was changed from M-5 in Example 1 to M-2.
[0194] The above-mentioned photosensitive materials were subjected to a gray exposure and
then processed using the following processing operations.
Color Development Bath
[0195]
Bleach Fix Bath
[0196]
Wash Water
[0197] Water which had been treated with an ion exchange resin so that calcium and magnesium
concentrations were both less than 3 ppm was used. (The electrical conductivity at
25 C was 5 as/cm)
[0198] The processed Samples 201 to 230 were subjected to fading tests with fungi in the
same way as in Example 1 and the results obtained were the same as those obtained
in Example 1, confirming that fading due to fungi was effectively prevented in the
samples of this invention irrespective of the type of silver halide emulsion or the
type of development processing used.
EXAMPLE 3
[0199] The multilayer silver halide photosensitive material Sample 301 having the layer
structure indicated below was prepared on a paper support which had been laminated
on both sides with polyethylene.
Layer Structure
[0200] The composition of each layer was as indicated below. The values indicate coated
weights (g/m
2). The weights of silver halide emulsions are indicated as weights calculated as silver.
Support
[0201] Polyethylene laminated paper (white pigment (Ti0
2) and ultramarine dye were included in the polyethylene on the first layer side
First Layer: Blue-Sensitive Layer
[0202]
Second Layer: Anti-Color-Mixing Layer
[0203]
Third Layer: Green-Sensitive Layer
[0204]
Fourth Layer: Ultraviolet Absorbing Layer
[0205]
Fifth Layer: Red-Sensitive Layer
[0206]
Sixth Layer: Ultraviolet Absorbing Layer
[0207]
Seventh Layer: Protective Layer
[0208]
[0209] Furthermore, Cpd-11 and Cpd-12 were used as anti-irradiation dyes at this time. Moreover,
"Alkanol XC" (made by the Du Pont Co.), sodium alkylbenzene-sulfonate, succinic acid
esters and "Megafac F-120" (made by the Dainippon Ink Co.) were used in each layer
as emulsification, dispersion and coating promotors. Cpd-13 and Cpd-14 were used as
silver halide stabilizers.
[0210] Furthermore, 1-oxy-3,5-dichloro-s-triazine, sodium salt, was used as a gelatin hardening
agent in each layer, and Cpd-2 was used as a viscosity increasing agent.
[0211] Details of the emulsions used are indicated below.
[0213] Samples 302 to 330 were prepared in the same way as Sample 301 except that the type
of polymer for dispersion purposes and the type of high boiling point organic solvent
in the red-sensitive layer of Sample 301 were changed as shown in Table 3.
[0214] These samples were subjected to a gray exposure in the same way as in Examples 1
and 2 and then they were procesed using the same processing operations as described
in Example 2, after which fading tests with fungi were carried out in the same way
as in Examples 1 and 2. The results obtained are as shown in Table 4. (The standards
used for evaluation were the same as those used in Example 1.)
[0215] It is clear from Table 4 that there is a marked improvement in respect of cyan fading
due to fungi in the case of this invention. Furthermore, as in Examples 1 and 2, with
Samples 306 and 307 which did not contain any high boiling point organic solvent there
was a pronounced worsening of cyan color formation while with the samples of this
invention the color forming properties were satisfactory and the images could be stored
effectively under adverse conditions without image deterioration even when fungi developed.
[0216] Thus, color photographs which have a good hue (color reproducibility) and good light
fastness, and which exhibit little fading,due to fungi can be obtained by this invention.
[0217] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.