U.S. patent number RE29,148 [Application Number 05/614,468] was granted by the patent office on 1977-03-08 for color photographic diffusion transfer process.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Atsuaki Arai, Yoshinobu Yoshida.
United States Patent |
RE29,148 |
Yoshida , et al. |
March 8, 1977 |
Color photographic diffusion transfer process
Abstract
A color photographic diffusion transfer process in which a color
photographic material having at least one silver halide emulsion
layer and a layer adjacent to said silver halide emulsion layer,
said layer containing a dye developer, is image-wise exposed,
brought into superposed position with an image-receiving element,
and then treated with an alkaline processing solution to immobilize
the dye developer at the exposed portions of the silver halide
emulsion layer and diffusion-transfer the dye developer at the
nonexposed portions of the silver halide emulsion layer to the
image-receiving element, with the alkali processing being conducted
in the presence of 6,6',7,7'
-tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'-.Iadd.spirochroman.
.Iaddend..[.spirocumarone.].
Inventors: |
Yoshida; Yoshinobu
(Minami-ashigara, JA), Arai; Atsuaki
(Minami-ashigara, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Minami-ashigara, JA)
|
Family
ID: |
26423299 |
Appl.
No.: |
05/614,468 |
Filed: |
September 17, 1975 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
388670 |
Aug 15, 1973 |
03849131 |
Nov 19, 1974 |
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Foreign Application Priority Data
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Aug 17, 1973 [JA] |
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48-82274 |
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Current U.S.
Class: |
430/239; 430/218;
430/435; 430/483 |
Current CPC
Class: |
G03C
8/16 (20130101); G03C 8/36 (20130101) |
Current International
Class: |
G03C
8/36 (20060101); G03C 8/02 (20060101); G03C
8/32 (20060101); G03C 8/16 (20060101); G03C
007/00 (); G03C 005/54 (); G03C 001/40 (); G03C
005/30 () |
Field of
Search: |
;96/3,29D,77,66HD,66R,66.3,95 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Fisher et al., "The condensation of Polyhydric Phenols and Acetone"
Journal of the Am. Chem. Soc. vol. 58, 1936 pp. 820-822. .
Baker et al., "Condensation Products of Phenals and Ketones, Part
III" J. of the Chemical Soc., London, 1939, pp. 195-202..
|
Primary Examiner: Klein; David
Assistant Examiner: Schilling; Richard L.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What is claimed is:
1. A color photographic diffusion transfer process comprising:
imagewise exposing a photographic material having at least one
silver halide emulsion layer and a dye developer present adjacent
to the silver halide in said silver halide emulsion layer and
treating said photographic material in superposed relation with an
image-receiving material with an alkaline processing solution
whereby the dye developer at the exposed portions of the silver
halide emulsion layer is immobilized and the dye developer at the
unexposed portions of the silver halide emulsion layer is
transferred by diffusion to the image-receiving material, said
treatment with said alkaline processing solution being in the
presence of
6,6',7,7'-tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'-.Iadd.spirochroman.
.Iaddend..[.spirocumarone.].
2. The color photographic diffusion transfer process as set forth
in claim 1, in which .[.acid.]. .Iadd.said
.Iaddend.6,6',7,7'-tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2-
.Iadd.spirochroman .Iaddend..[.spirocumarone.]. is present in said
photosensitive material.
3. The color photographic diffusion transfer process as set forth
in claim 1, in which said
6,6',7,7'-tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'-
.Iadd.spirochroman .Iaddend..[.spirocumarone.]. is present in said
alkaline processing solution.
4. The color photographic diffusion transfer process as set forth
in claim 1, in which said
6,6',7,7'-tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'-
.Iadd.spirochroman .Iaddend..[.spirocumarone.]. is present in said
image-receiving element.
5. The color photographic diffusion transfer process as set forth
in claim 1, wherein said photographic material is a multi-layer
photographic material having in order on a support, a red-sensitive
silver halide emulsion layer, a green-sensitive silver halide
emulsion layer, and a blue-sensitive silver halide emulsion layer,
and wherein said 6,6',7,7'
-tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'- .Iadd.spirochroman
.Iaddend..[.spirocumarone.]. is present in one of said silver
halide emulsion layers.
6. The color photographic diffusion transfer process of claim 1,
wherein 6,6',7,7'-tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'-
.Iadd.spirochroman .Iaddend..[.spirocumarone.]. is present at a
level of 0.01-0.5 times on a molar basis of the amount of the
photosensitive silver halide present.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a color photographic diffusion
transfer process and more particularly it relates to an improved
color photographic diffusion transfer process for color
photographic materials containing dye developers.
2. Decription of the Prior Art
Diffusion transfer photographic processes using dye developers or
compounds which are dyes and developers for silver halide have been
reported in many patents including U.S. Pat. No. 2,983,606 and
British Patent No. 804,971. In these processes, as described in the
specifications thereof, an exposed photosensitive silver halide
emulsion layer is developed in the presence of a dye developer,
whereby an imagewise distribution of the unreacted and unoxidized
dye developer is formed as a function of the development. The
unreacted and unoxidized dye developer is mobile in the processing
solution and at least a part of the imagewise distributed dye
developer is transferred to a superposed image-receiving
element.
In a specific embodiment of the above-described diffusion transfer
processes, a photosensitive element having a silver halide emulsion
and a dye developer is exposed and a liquid processing composition
is applied to the photosensitive element by, for instance,
immersing, coating, spraying, etc. Before, during, or after the
application of the aforesaid liquid processing composition, the
photosensitive element is superposed on an image-receiving element
which can be dyed with the dye developer. In a preferred
embodiment, the photosensitive element contains the dye developer
in a layer adjacent to the side of a silver halide emulsion layer
away from the incident light. The silver halide emulsion layer of
the photosensitive element is placed on the image-receiving layer
of the image-receiving element and a liquid processing composition
is spread as a thin layer between the two layers. The liquid
processing composition diffuses into the silver halide emulsion
layer and the dye developer-containing layer to develope the
developable silver halide and the dye developer thus developed the
silver halide is immobilized.
This immobilization is apparently due, at least in part, to the
reduction is mobility or solubility of the oxidation product of the
dye developer as compared with that of the unoxidized dye
developer. The immobilization may be also due, at least in part, to
the localized reduction of alkali concentration as a function of
development.
Since the unreacted dye developer at the nondeveloped areas of the
silver halide emulsion layer is diffusible, an imagewise
distribution of the mobile unoxidized dye developer is formed as a
function of the exposure and development of the silver halide
emulsion. At least a part of the diffusible unoxidized dye
developer thus imagewise distributed is transferred to the
superposed image-receiving layer. This transfer of the unoxidized
dye developer is clearly distinguished from the less mobile
oxidized dye developer and thus a transferred image is formed on
the image-receiving layer.
When a photosensitive element has differently sensitized silver
halide emulsion layers and each silver halide emulsion layer is
associated with each dye developer which has substantially a
complementary color to the main sensitive region of the silver
halide emulsion, that is to say, when a silver halide emulsion
having sensitivity to red light is associated with a cyar dye
developer, a silver halide emulsion having sensitivity to green
light with a magenta dye developer, and a silver halide emulsion
having sensitivity to blue light with a yellow dye developer, each
dye developer is oxidized and immobilized in the developed region
or area of each associated silver halide emulsion layer. The dye
developers in the nondeveloped portions of the silver halide
emulsion layers diffuse and are transferred to the image-receiving
element superposed on the photosensitive element.
Therefore, when large proportions of unoxidized dye developers are
present in the sufficiently exposed negative portions corresponding
to the highlight portions of field or original, they diffuse to an
image-receiving element as the unoxidized dye developers present in
the nonexposed negative portions corresponding to dark portions of
field or original and hence a transferred image having a high
minimum density and indistinct light and darkness is formed.
On the other hand, the typical dye developers as disclosed in the
specifications of U.S. Pat. Nos. 3,255,001,
______________________________________ 2,992,106; 3,297,441;
3,134,762; 3,236,643; 3,134,673; 3,236,645; 3,134,764; 3,134,672;
3,134,765; 3,183,089; 3,135,734; 3,135,604; 3,173,906; 3,222,169;
3,183,000; 3,201,384; 3,246,985; 3,208,991; 3,142,565; 3,218,312;
3,230,086; 3,262,924; 3,275,617; 3,077,402; 3,282,913; 3,141,772;
3,299,041; 3,309,199; 2,983,605; 3,047,386; 3,076,820; 3,173,929;
3,230,083; 3,236,864; 3,239,339; 3,252,969; 3,253,001; 3,288,778;
3,209,016; 3,135,606; 3,076,808; 3,126,280; 3,236,865; 3,135,605;
3,255,205; 3,131,061; 3,347,673; 3,347,672; 3,246,016; 3,245,790;
3,086,005 3,295,973; ______________________________________
3,307,947; 3,230,082; 3,230,085; etc. for instance, such cyan dye
developers as
1,4-bis-(.alpha.-methyl-.beta.-hydroxynonylpropylamino)-5,8-dihydroxyanthr
aquinone, etc., such magenta dye developers as
4-propoxy-2-[p-(.beta.-hydroquinonylethyl)-phenylazo]-1-naphthol,
etc., and such yellow dye developers as
1-phenyl-3-N-n-hexylcarboxyamido-4-[p-2',5'-dihydroxyphenethyl)
phenylazo]-5 -pyrazolone, etc., are weak developing agents for
silver halides even when they are used in a comparatively highly
alkaline state of a pH of about 1.3. Accordingly, when such
conventional dye developers are used, the desired maximum density,
gradation, and sensitivity cannot be obtained. Since the
immobilization of the dye developers occurs as a function of the
development of silver halide emulsion layers, the transferred image
obtained in the diffusion transfer process shows undesirably high
minimum density, low maximum density, and low contrast in the
highlight regions.
This is due, in part, to the fact that the dye developers have weak
development activity as a developing agent for silver halide, to
the fact that the dye developers near silver are not completely
effectively used, and also to other factors.
Furthermore, in a multicolor system it happens that a silver halide
emulsion layer is developed not only by the dye developer having
substantially complementary color to the main sensitive region of
the silver halide emulsion but also by other dye developers
associated with other silver halide emulsion layers. For instance,
a magenta dye developer which is associated with a green-sensitive
silver halide emulsion layer diffuses partially into a
blue-sensitive emulsion layer and a red-sensitive emulsion layer to
initiate development and is immobilized there, which results in
forming a transferred image containing less magenta dye.
In the specifications of Japanese Patent Publication Nos.
4839/1960, 10240/1959, and 2241/1962, the disclosures are that by
adding a colorless auxiliary developer such as
1-phenyl-3-pyrazolidone to a processing composition, the
development of the silver halide is accelerated and the
immobilization of the dye developers in the photosensitive element
is accelerated improving to some extent the above-mentioned
disadvantage. Also, the use of a hydroquinone such as
4'-methylphenyl hydroquinone as an auxiliary developing agent is
described in the specifications of Japanese Patent Publication Nos.
29130/1964 and 13837/1968 and the use of a catechol such as
4-methylcatechol as an auxiliary developing agent is described in
the specification of British Patent No. 1,243,539. However, the
improvements attained by the above-described inventions are not yet
satisfactory and when, in particular, those auxiliary developing
agents are used in multicolor-type multilayer photographic
elements, it is difficult to obtain satisfactory multicolor
transferred images since each dye developer does not cause the
development to the necessary extent and also does not cause the
development so that the dye developer is fixed in the rate
necessary for each specific layer. Still further, it has frequently
been observed that a part of the auxiliary developing agents is
transferred to an image receiving element causing stains of the
color images.
SUMMARY OF THE INVENTION
As the results of various investigations in discovering an improved
color diffusion transfer process without having the above-described
diffulties, the inventors have achieved the process of this
invention. That is to say, according to the present invention,
there is provided a color diffusion transfer process comprising
imagewise exposing a color photographic material having at least
one silver halide emulsion layer and a dye developer disposed
adjacent to the silver halide in the silver halide emulsion layer
and processing the exposed material with an alkaline processing
solution in a superposed relation with an image-receiving material
to immobilize the dye developer at the exposed portions of the
silver halide emulsion layer and transfer by diffusion to the
image-receiving material the dye developer at the unexposed
portions of the silver halide emulsion layer, and conducting the
processing with the alkaline processing solution in the presence of
6,6', 7,7'-tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'
-.Iadd.spirochroman. .Iaddend..[.spirocumarone.].
DETAILED DESCRIPTION OF THE INVENTION
6,6',7,7'-Tetrahydroxy-4,4,4',4'-tetramethyl-bis-2,2'
-.Iadd.spirochroman .Iaddend..[.spirocumarone.]. used in this
invention is a substantially colorless compound and is,
hereinafter, called an "auxiliary developing agent" for the purpose
of distinguishing it from the dye developers. The auxiliary
developing agent can be present in the processing composition or in
the image receiving element but it is preferable that the auxiliary
developing agent be present in the negative photosensitive element
containing the dye developers. In the above preferred case, various
methods can be employed for incorporating the auxiliary developing
agent in a hydrophilic colloid layer of the negative photosensitive
element. For instance, in one embodiment the auxiliary developing
agent used in this invention is dissolved in a substantially
water-insoluble high boiling organic solvent and after finely
dispersing the solution in aqueous solution of a hydrophilic
colloid, the dispersion thus containing the auxiliary developing
agent is coated. In another embodiment the auxiliary developing
agent is dissolved in an alkaline aqueous solution and after mixing
the solution with an aqueous solution of a hydrophilic colloid, the
mixture is coated. In still other embodiment the auxiliary
developing agent is dissolved in a low-boiling organic solvent such
as methanol or ethyl acetate and after mixing the solution with
aqueous solution of a hydrophillic colloid, the mixture is
coated.
The multilayer-type diffusion transfer color photographic material
used in this invention has desirably, as a layer structure, on a
support a red-sensitive emulsion layer, a green-sensitive emulsion
layer and a blue-sensitive emulsion layer in this order and the
emulsion layers have associated therewith a cyan dye developer, a
magenta dye developer and a yellow dye developer, respectively. If
necessary, the color photographic material can have a yellow filter
layer, an antihalation layer, intermediate layers, and a protective
layer.
The silver halide emulsion used in the present invention is a
colloidal dispersion of silver chloride, silver bromide, silver
chlorobromide, silver iodobromide or silver chloroiodobromide or a
mixture thereof. The composition of the halide is selected
depending on the purpose to which the element is to be applied and
treatment conditions of the sensitive material. Particularly, a
silver iodobromide or chloroiodobromide emulsion consisting of 1 -
10 mol percent of iodide, less than 30 mol percent of chloride and
a balance of bromide is preferred. The mean particle size of the
emulsion is usefully within a range of about 0.1 to about 2 microns
and a uniform particle size is desirable depending on the end use
purpose of sensitive material. Particles are of a cubic, an
octahedral or a mixed crystal system. These silver halide emulsion
can be prepared using conventional techniques, for example, as
disclosed in P. Glafkides: Chimie Photographique. Chap. 18-23, 2nd
edition, 1957, Paul Moncle, Paris. For example, a soluble silver
salt such as silver nitrate and a water soluble halide such as
potassium bromide are reacted in a solution of a protective colloid
such as gelatin and the crystal growth accomplished in the presence
of an excess of halide or a solvent for silver halide, such as
ammonia. In this case, a precipitation method such as the single or
double jet method or pAg control double jet method can be used. The
removal of the soluble salts from the emulsion is by washing a
cooled and coagulated emulsion with water, dialysis thereof, or
settlement by adding a precipitating agent such as an anionic
polymer or a surface active agent having sulfon, sulfuric acid
ester or carboxylic group and controlling the pH or by using an
acylated protein such as phthaloyl gelatin as the protective
colloid and controlling the pH. The silver halide emulsion used in
the present invention is desirably sensitized by subjecting the
emulsion to a heat treatment in conjunction with sensitizers
naturally contained in gelatin, a sulfur sensitizer such as sodium
thiosulfate or N,N,N'-trimethyl thiourea, a gold sensitizer such as
thiocyanate or the thiosulfate complex salt of monovalent gold, or
a reducing sensitizer such as stannous chloride or
hexamethylenetetramine (for example, as described in U.S. Pat. Nos.
1,623,499; 2,399,083; 3,297,447; and 3,297,446). Both an emulsion,
by which a latent image is easily formed on the surfaces of
particles, and an emulsion as described in U.S. Pat. Nos. 2,592,550
and 3,206,313 etc., by which a latent image is easily formed in the
interior of the particles, can be used in the present
invention.
The silver halide emulsion used in the present invention can be
stabilized with an additive such as 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene, 5-nitrobenzimidazole,
1-phenyl-5-mercaptotetrazole, 8-chloromercuriquinoline,
benzenesulfinic acid and pyrocatechin. In addition to these
compounds, inorganic compounds such as cadmium and mercury salts,
and the complex salts of platinum group elements, such as the
chlorine complex salt of palladium, are useful for the
stabilization of the sensitive material according to the present
invention. Further, the silver halide emulsion used in the present
invention can contain a sensitizing compound such as polyethylene
oxide compound (for example, as described in U.S. Pat. Nos.
3,046,134; 2,944,900; and 3,294,540).
The silver halide emulsion used in the present invention, if
desired, can have its color sensitivity extended with an optical
sensitizing dye. As useful optical sensitizers, there are mentioned
the cyanines, merocyanines, homopolar cyanines, styryls,
hemicyanines, oxanoles, hemioxanoles and the like. Examples of
these optical sensitizers are decribed in by P. Glafkides, supra
(chap. 35 - 41) and F. M. Hamer: The Cyanine Dyes and Related
Compounds (Interscience). In particular, cyanines, in which the
nitrogen atom in the nucleus is substituted by an aliphatic radical
having a hydroxyl, carboxyl or sulfo group, as described in U.S.
Pat. Nos. 2,503,766; 3,459,553; 3,177,210; 3,384,486; 2,526,632;
2,493,748; 2,912,329 and 3,397,060, are useful in the present
invention.
The dye developer is ordinarily dissolved in a solvent or a solvent
mixture under heating, the solution of the dye developer is added
to an aqueous solution of a hydrophilic colloid such as gelatin and
after passing through a colloid mill suitable number of times, the
mixture is directly coated or is coated after cooling, solidifying,
cutting, washing, and melting. Or, alternatively, the solution of
the dye developer is added to a silver halide emulsion and the
mixture is coated. Preferred examples of the solvents used for the
purpose are described in, for instance, the specifications of
Japanese Patent Publication No. 13,837/1968 and U.S. Pat. No.
2,322,027.
The color developer used in the present invention can be dispensed
using various methods in a hydrophilic colloid as a carrier
corresponding to the type of developer. For example, a compound
such as diffusion dye-releasing coupler having a dissociating group
such as a sulfo or carboxyl group can be dissolved in water or
alkaline aqueous solution and then added to a hydrophilic colloid
solution. Color developers, which are difficult to dissolve in
aqueous medium and easily dissolved in an organic solvent, are
dissolved in an organic solvent, the resulting solution is then
added to a hydrophilic colloid solution and dispersed as fine
particles by agitation. As suitable solvents, there are mentioned
ethyl acetate, tetrahydrofuran, methyl ethyl ketone, cyclohexanone,
.beta.-butoxy-.beta. -ethoxyethyl acetate, dimethyl formamide,
dimethyl sulfoxide, 2-methoxyethanol, tri-n-butyl phthalate and the
like. Among these dispersion solvents, those having a relatively
low vapour pressure can be evaporated off during the drying of the
photographic layer or by the method as described in U.S. Pat. Nos.
2,322,027 and 2,801,171 before coating. Among these dispersion
solvents, those easily soluble in water can be removed by the
washing method as described in U.S. Pat. Nos. 2,949,360 and
3,396,027. To stabilize the dispersion of the color developer and
promote the course of color image formation, it is advantageous to
add a solvent, which is substantially insoluble in water and has a
boiling point above 200.degree. C at normal pressure, together with
the color developer to a sensitive element. As high-boiling
solvents suitable for the puspose, there are mentioned the
triglycerides of higher fatty acids, aliphatic esters such as
dioctyl adipate, phthalic acid esters such as di-n-butyl phthalate,
phosphoric acid esters such as tri-o-cresyl phosphate and
tri-n-hexyl phosphate, amides such as N,N-diethyl lauryl amide,
hydroxy compounds such as 2,4-di-n-amyl phenol and the like.
Further, to stabilize the dispersion of the color developer and
promote the course of color image formation, it is advantageous to
add a solvent-phile polymer together with color developer to the
sensitive element. As solvent-phile polymers suitable for the
purpose, there are mentioned shellac, phenol-formaldehyde
condensates, poly-n-butyl acrylate, the copolymer of n-butyl
acrylate and acrylic acid, the copolymer of n-butyl acrylate,
styrene and methacryl amide, and the like. These polymers can be
dissolved together with the color developer in an organic solvent
and then dispersed in a hydrophilic colloid, or a hydrosol of the
polymer, prepared by emulsion polymerization, can be added to the
hydrophilic colloid dispersion of the color developer. In general,
the dispersion of the color developer can be attained effectively
in the presence of large shearing stress. For example, a high speed
rotating mixer, a colloid mill, a high pressure milk homogenizer,
the high pressure homogenizer disclosed in the British Pat. No.
1,304,264, and a supersonic emulsifier are useful. The dispersion
of the color developer is promoted by using a surface active agent
as an emulsion assistant. As surface active agents, which are
useful for the dispersion of the color developer used in the
present invention, there are mentioned sodium
triisopropylnaphthalenesulfonate, sodium
dinonylnaphthalenesulfonate, sodium p-dodecylbenzenesulfonate,
sodium dioctylsulfosuccinate, sodium cetylsulfate and anionic
surface active agents disclosed in the Japanese Patent Publication
4293/64; as described in U.S. Pat. No. 3,676,141, the combination
of these anionic agents and higher fatty acid esters of
anhydrohexitol shows an especially good emulsifying ability.
Additionally, those disclosed in U.S. Pat. Nos. 3,287,133;
3,384,483; 2,992,104; 3,043,692; 3,044,873; 3,061,453; 3,069,263;
3,069,264; 3,121,011 etc. are suitable.
The specific examples of the dye developers used in this invention
are the compounds described in the specifications of U.S. Pat. Nos.
3,255,001; 3,320,063;
______________________________________ 2,992,106; 3,297,441;
3,134,762; 3,236,643; 3,134,763; 3,134,764; 3,134,672; 3,134,765;
3,183,089; 3,135,734; 3,135,604; 3,173,906; 3,222,169; 3,183,090;
3,201,384; 3,246,955; 3,208,991; 3,142,565; 2,983,605; 3,047,386;
______________________________________
3,076,820; 3,173,929; 3,230,083; etc.
Examples of specifically useful dye developers are
4-[p-(2',5'-dihydroxyphenyl)-phenylazo]-5-acetamido-1-naphthol,
4-[p-(2',5'-dihydroxyphenethyl)-phenylazo]-5-benzamido-1-naphthol,
1-phenyl-3-methyl-4-[p-(2',5'-dihydroxyphenethyl)-phenylazo]
pyrazolone,
2-[p-(2',5'-dihydroxypnenethyl)-phenylazo]-4-acetamido-1-naphthol,
2-[p-(2',5'-dihydroxyphenethyl)-phenylazo]-4-methoxy-1-naphthol,
2-[p-(2',5'-dihydroxyphenethyl)-phenylazo]-4-ethoxy-1-naphthol,
1-phenyl-3-N-n-butyl-carboxyamido-4-[p-(2',5'-dihydroxyphenethyl)-phenylaz
o]- 5-pyrazolone,
phenyl-3-N-n-hexylcarboxyamido-4-[p-(2',5'-dihydroxyphenethyl)-phenylazo]-
5-pyrazolone,
1-phenyl-3-N-cyclohexylcarboxyamido-4-[p-(2',5'-dihydroxyphenethyl)-phenyl
azo]-5-pyrazolone, 1-phenyl-3-amino-4
-(4'-[p-(2",5"-dihydroxyphenethyl)phenylazo]-2',5'-diethoxy(phenylazo)-
5-pyrazolone.
1-acetoxy-2-[p-(.beta.-hydroquinonyl)-phenylazo]-4-methoxynaphthalene,
4-isopropoxy-3-[p-(.beta.-hydroquinonylethyl)-phenylazo]-1-naphthol.
1-acetoxy-2-[p-(.beta.-hydroquinonylethyl)-phenylazo]-4-propoxynaphthalene
, 1,4-bis( 2',5'-dihydroxyanilino)-anthraquinone,
1,5-bis(2',5'-dihydroxyanilino)-4,8-dihydroxyanthraquinone,
1,4-bis[.beta.-(2',5'-dihydroxyphenyl)-isopropylamino]-anthraquinone,
1,4-bis[.beta.-(2',5'-dihydroxyphenyl)-ethylamino]-anthraquinone,
1-chloro-4-[.beta.-(2',5'-dihydroxyphenyl)-ethylamino]-anthraquinone,
N-monobenzoyl-1,4-bis[.beta.-(2',5'-dihydroxyphenyl)-ethylamino]-anthraqui
none,
5,8-dihydroxy-1,4-bis[.beta.-hydroquinonyl-.alpha.-methyl)-ethylamino]-ant
hraquinone, etc.
When one amino nitrogen atom of the cyan dye developer such as, for
instance,
1,4-bis[.beta.-(2',5'-dihydroxyphenyl)-ethylamino]-anthraquinone is
acylated, the color of the cyan dye developer changes into magenta
and when both amino nitrogen atoms of it are acylated, the color
thereof changes into orange-yellow. Similarly, by acylating the
hydroxyl groups of the above-stated dye developers, the colors of
the dye developers can be changed. Thus, the structure or the color
of the dye developer can be changed by a development reaction,
e.g., hydrolysis, that is to say, the color of the dye developer
present in the photosensitive element can be changed when it is
transferred to an image-receiving element. Examples of such
compounds are described in the specifications of U.S. Pat. Nos.
3,307,947; 3,336,287; etc. A leuco compound such as
1-phenyl-3-methyl-4-(2'-methyl-4'-diethylamino)anilino-5-pyrazolone
which does not give light filtering action to the emulsion layer
under the layer containing it, which is immobilized at the
developed portions, which diffuses imagewise from the undeveloped
portions to an image-receiving element, and which is oxidized
therein into a colored image can be also used.
The dye developer is disposed adjacent to the silver halide of a
silver halide emulsion layer in the photosensitive element. That is
to say, the dye developer or dye developers are incorporated in one
or more emulsion layers and are preferably incorporated in silver
halide emulsion layers or hydrophilic organic colloid layers under
the corresponding silver halide emulsion layers. In particular, in
a multilayer-type color photographic element for multicolor
reproduction, it is particularly effective to incorporate the dye
developer in the layer under the silver halide emulsion layer
having the main light-sensitive region which is a complementary
color to the color of the dye developer. However, as described
above, when the developer which does not have a complementary color
but gives the desired color in an image-receiving layer, the dye
developer can be incorporated in the silver halide emulsion layer
which is associated with the dye developer or in the layer adjacent
to the silver halide emulsion layer. Furthermore, in an embodiment
of the association of silver halide with a dye developer, it is
possible that the dye developer in a mixed packet in the colloid
surrounding particles or fine grains containing silver halide
particles. Such a mixed packet system is disclosed in U.S. Pat.
Nos. 2,800,457; 2,800,458; 2,907,682, 3,466,662; and 3,276,869.
As described above, it is preferred that the auxiliary developing
agent be incorporated in a silver halide emulsion layer, a dye
developer-containing layer, an intermediate layer, a protective
layer, etc., of the photosensitive element. It is most preferred
that the auxiliary developing agent be incorporated in one or more
layers of the photosensitive element as a dispersion in an aqueous
solution of an organic colloid such as gelatin as a solution
thereof in a high-boiling organic solvent having a boiling point
higher than about 175.degree. C. Specific examples of these
high-boiling organic solvents are phthalic acid alkyl esters of
which the alkyl group has, preferably, less than 6 carbon atoms,
such as methyl phthalate, ethyl phthalate, propyl phthalate,
n-butyl phthalate, di-n-butyl phthalate, amyl phthalate, isoamyl
phthalate, and dioctyl phthalate, phosphoric acid esters such as
triphenyl phosphate, tricresyl phosphate, and diphenyl
mono-p-tertiary butylphenyl phosphate; alkyl amides, and
acetanilide such as N-n-butylacetanilide and
N-methyl-p-methylacetanilide. The high-boiling solvents may be also
used as mixtures with other solvents having boiling points lower
than these high-boiling solvents by at least 25.degree. C, to aid
the solubility of the auxiliary developer and to permit the films,
such as methyl acetate, ethyl acetate, propyl acetate, butyl
acetate, isopropyl acetate, ethyl propionate, secondary-butyl
alcohol, carbon tetrachloride, chloroform, benzyl alcohol,
2,3-methylcyclohexanone, and 2,4-methylcyclohexanone or solvents
which are more soluble in water than the above-described
high-boiling solvents and have a solubility of at least 2 parts
thereof per 100 parts of water, such as methyl isobutyl ketone,
.beta.-ethoxyethyl acetate, .beta.-butoxy-.beta.-ethoxyethyl
acetate, tetrahydrofurfuryl adipate, diethylene glycol monoacetate,
methoxytriglycol acetate, acetonitrile acetone, acetone alcohol,
ethylene glycol, diethylene glycol, dipropylene glycol,
2,3-methylcyclohexanone, 2,4-methylcyclohexanone, methylene glycol,
monomethyl ether acetate, diethylene glycol monobutyl ether,
cyclohexanone, and triethyl phosphate.
The amount of the auxiliary developing agent used in this invention
depends on the amount and the kind of the dye developers used, the
amount and the kind of silver halide, the layer structure of the
photosensitive element, and the like but the amount thereof is
usually 0.01 - 10 times, more generally 0.1 - 2 times the molar
amount of the dye developer used. Also the amount is suitably 0.01
- 0.5 times the amount of the photosensitive silver halide. The
amount generally used when the auxiliary developing agent is
present in the processing solution is about 2 to 4 times the amount
present when it is used in the photosensitive element. The silver
halide coating amount generally is from about 0.4 to 4 .times.
10.sup..sup.-4 mol/100 cm.sup.2, about 0.3 to 3 mol/100 cm.sup.2
and about 0.3 to 3 mol/100 cm.sup.2 for the red sensitive layer the
green sensitive layer and the blue sensitive layer, respectively,
for a total amount of about 1 to 10 .times. 10.sup..sup.-4 mol/100
cm.sup.2. The amount is, however, not limited to these ranges and
amounts outside these ranges can be used to achieve the objects
desired.
Layers used in the present invention, which are permeable to
treating solutions, such as a silver halide emulsion layer, a layer
containing a color developer, auxiliary layers such as a protective
layer or an intermediate layer, contain a hydrophilic polymer as a
binder. As suitable polymers, there are mentioned gelatin, casein,
gelatin modified with acylating agents etc., gelatin grafted with
vinyl polymer, proteins such as albumin; cellulose derivatives such
as hydroxyethylcellulose, methylcellulose and
carboxymethylcellulose; partial hydrolysates of polyvinyl alcohol
or polyvinyl acetate, high molecular weight nonelectrolytes such as
polyvinyl pyrrolidone or polyacrylamide; polyacrylic acid, the
partial hydrolysate of polyacrylamide, anionic synthetic polymers
such as the copolymer of vinyl methyl ether and maleic acid,
further amphoteric synthetic polymer such as the copolymer of
N-vinyl imidazole acrylic acid and acrylamide or the polyacrylamide
subjected to the Hofmann reaction. These hydrophilic polymers are
used either alone or in as admixtures thereof. Further, these
hydrophilic polymer layers can contain a polymer latex dispersion
of hydrophobic monomer such as an alkyl acrylate or methacrylate
etc. These hydrophilic polymers, above all the polymers having a
functional group such as an amino, hydroxyl and carboxyl group, can
be rendered non-soluble with many kinds of cross-linking agents
without losing the permeability to the treating solution. As
especially useful cross-linking agents, there are mentioned
aldehyde compounds such as formaldehyde, glyoxal, glutaraldehyde,
mucochloric acid or the oligomer or acrolein; aziridines such as
triethylene phosphamide as described in the Japanese Patent
Publication 8790/62; epoxy compounds such as
1,4-bis(2',3'-epoxypropoxy)diethyl ether as described in the
Japanese Patent Publication 7133/59; active halogen compounds such
as the sodium salt of 2-hydroxyl-4,6-dichloro-s-triazine as
described in the U.S. Pat. No. 3,325,287; active olefin compounds
such as hexahydro-1,3,5-triacryltriazine; methylol compounds such
as N-polymethylol urea or hexamethylolmelamine; high molecular
weight substances such as dialdehyde starch or the
3-hydroxyl-5-chloro-s-triazinylated gelatin described in the U.S.
Pat. No. 3,362,827. These hydrophilic polymer layers can contain a
cross-linking promotor such as carbonates or resorcine other than
the cross-linking agent.
An image-receiving element which is dyed by the dye developers from
the negative photosensitive element can be suitably selected. As
the dyeable materials suitable for the image-receiving layer of the
image-receiving element, there are gelatin, polyvinyl pyrrolidone,
poly-4-vinylpyridine, polyvinyl acetate, polyvinyl alcohol,
cellulose acetate, polyvinyl salicylate, partially hydrolyzed
polyvinyl acetate, methyl cellulose, and mixtures of them.
The typical examples of the supports used for the image-receiving
elements and for the photosensitive elements are cellulose nitrate
films, cellulose acetate films, polyvinyl acetal films, polystyrene
films, polyethylene terephthalate films, polyethylene films,
polypropylene films, papers, polyethylene-coated papers, glass,
etc. Also, the multilayer-type negative photosensitive element can
be used as the support for the image-receiving element. The support
can be tranparent or opaque according to the purposes.
It is particularly preferred, as described in the specification of
U.S. Pat. No. 2,584,030, that the image-receiving element be
associated with an acid polymer or an acid compound derivative
which provides an acid material with a definite rate. Such an acid
material is incorporated in the layer under the image-receiving
layer of the image-receiving element. The acid material contributes
to neutralize the alkali in the liquid processing composition on
the image-receiving layer.
The diffusion transfer photographic film unit according to the
present invention preferably possesses a function for neutralizing
alkalis brought from the treating compositions. To provide a high
pH-value, i.e., more than 10, preferably more than 11, sufficient
to promote the course of image formation which comprises the
development of the silver halide emulsion, the formation of the
diffusing color image and the diffusion thereof, the treating
composition contains an alkali. After the substantial completion of
the formation of diffusion transfer image, the pH-value in the film
unit is neutralized to approximately neutral, i.e., below 9,
preferably below 8, to stop practically further image formation and
prevent the change of image tone with the lapse of time. This
results in preventing a color change and discoloration of image,
which are caused at a high concentration of alkali, and
contamination in white areas. For this purpose, it is advantageous
to add a neutralizing layer containing a sufficient amount of an
acid substance to neutralize the alkali in the treating solution up
to the pH-value as described above, i.e., an acid substance in a
surface concentration more than equivalent to the alkali in the
spread treating solution, to the film unit. Preferred acid
substances are those containing an acid group having a pKa value of
less than 9, above all carboxyl or sulfonic acid group, or such a
precursor that can provide such an acid group by hydrolysis. As
specific examples, there are mentioned more preferably higher fatty
acids such as oleic acid, as described in U.S. Pat. No. 2,983,606,
as well as polymers of acrylic, methacrylic or maleic acid, or the
partial esters or anhydrides thereof as described in U.S. Pat. No.
3,362,819. As examples of high molecular acid substances, there are
mentioned copolymers of maleic anhydride and a vinyl monomer such
as ethylene vinyl acetate, vinyl methyl ether etc. and the n-butyl
half-ester, the copolymer of butyl acrylate and acrylic acid,
cellulose acetate, acid phthalate and the like. In addition to
these acid substances, the neutralizing layer can contain polymers
such as cellulose nitrate and polyvinyl acetate, and further
plasticizers as described in U.S. Pat. No. 3,557,237. The
neutralizing layer further can be cured by cross-linking by means
of polyfunctional azilysine compounds and epoxy compounds. The
layer is placed in the image-receiving element and/or sensitive
element. Especially, it is advantageous to place the layer between
the support for the image-receiving element and the image-receiving
layer. As described in the German Laid-open Patent No. 2,038,254,
the acid substance can be encapsulated as microcapsules to join to
the film unit.
The neutralizing layer or acid substance-containing layer used in
the present invention is separated desirably from the treating
solution layer to be spread by means of the neutralization
controlling layer. The neutralization controlling layer serves to
prevent undesirable reduction of the transferred image
concentration due to the too rapid reduction of the pH-value of the
treating solution by the neutralizing layer before the development
of a given silver halide emulsion layer and the formation of the
diffusion transfer image, so that the reduction of the pH-value can
be retarded until after the given development and transfer. In a
preferred embodiment according to the present invention, the
image-receiving member comprises a multi-layer system support
neutralizing layer neutralization controlling layer mordant layer
(image-receiving layer). The neutralization controlling layer
comprises mainly a polymer such as gelatin, polyvinyl alcohol,
polyvinyl propyl ether, polyacrylamide, hydroxypropylmethyl
cellulose, isopropyl cellulose, partial polyvinyl butylal,
partially hydrolyzed polyvinyl acetate, the copolymer of
.beta.-hydroxyethyl methacrylate and ethyl acrylate, and the like.
These polymers are cured usefully by cross-linking by means of
aldehyde compounds such as formaldehyde or N-methylol compounds.
Preferably, the neutralization controlling layer has a thickness of
about 2 - 20 microns.
Furthermore, between the image receiving layer and the acid
material-containing layer can be disposed a spacer layer, as
disclosed in U.S. Pat. Nos. 3,362,819 and 3,362,821, for
controlling the release of the acid material can be disposed. The
image receivng element can further contain a development inhibitor
such as mercaptotetrazole and iodine as disclosed in U.S. Pat. No.
3,265,498.
The image-receiving element used in the pesent invention fixes the
color image-forming substance, such as diffusing dye, being
released with the distribution of image from color developer in
conjunction with silver halide emulsion. When the color
image-forming substance is an anionic material such as a color
developer having a hydroquinonyl group or coupling dye having a
water-soluble acid group, the image-receiving element contains
advantageously a basic polymer or a basic surface active agent. As
basic polymers, those containing tertiary or quaternary nitrogen
atoms are preferred: e.g., poly-4-vinyl pyridine; polymer of
aminoguanidine derivative of vinyl methyl ketone described in U.S.
Pat. No. 2,882,156; poly-4-vinyl-N-benzyl pyridinium p-toluene
sulfonate; poly-3-vinyl-4-methyl-N-n-butyl pyridinium bromide;
styrene/N-3-maleimidopropyl)-N,N-dimethyl-N-(4-phenyl benzyl
ammonium chloride copolymer described in the British Patent No.
1,261,925, poly [N-(2-methacryloylethyl)-N,N-dimethyl-N-benzyl
ammonium chloride], and the like. As basic surface active agents,
those having both onium groupings such as ammonium, sulfonium or
phosphonium and hydrophobic residues such as long chain alkyl
radicals are preferred, e.g., N-lauryl pyridinium bromide, cetyl
trimethyl ammonium bromide, methyl tri-n-lauryl ammonium p-toluene
sulfonate, methylethylcetyl sulfonium iodide, benzidine triphenyl
phosphorium chloride etc. Other than these basic compounds,
compounds of polyvalent metals such as thorium, aluminium or
zirconium have also a fixing action for the anionic color image
forming substance. Advantageously, these compounds are formed in
the form of a film together with a polymer such as gelatin
(preferably, acid-treated gelatin), polyvinyl alcohol,
polyacrylamide, polyvinyl methyl ether, hydroxyethyl cellulose.
N-methoxy methyl polyhexylmethylene adipamide, polyvinyl
pyrrolidone and the like.
Such image receiving materials are described in greater detail in
the specifications of Japanese Patent Publication Nos. 8274/1963,
8449/1963, and 29756/1961 and the specifications of U.S. Pat. Nos.
3,003,872, 3,043,689, 3,065,074, 3,148,061, 3,239,337; 3,353,951
and 3,362,819.
The liquid processing composition for initiating the development of
the exposed portions of the photosensitive element is a strongly
alkaline solution and in general, is a solution having a pH above
12 or containing an OH ion concentration larger than 0.01 N. For
such a purpose a compound capable of providing strong alkalinity,
such as potassium hydroxide, sodium hydroxide, and sodium carbonate
can be used. In the case of applying the alkaline processing
solution to silver halide emulsion layers as a thin and uniform
layer or film by spreading the processing composition or solution,
a film-forming material capable of increasing the viscosity of the
processing composition and forming a comparatively hard and stable
film of the processing composition when the composition is spread
and dried can be added to the alkaline processing composition. When
the material exhibits the faculty of increasing viscosity in the
alkaline processing solution for a long period of time, a
film-forming material which is not substantially influenced in
regard to the reduction in viscosity can be used. Preferred
film-forming materials are water-soluble high molecular weight
polymers inert to the alkaline processing solution, such as
hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyvinyl
alcohol, polyacrylamide and other viscosity increasing agents, as
disclosed in U.S. Pat. Nos. 3,351,465 and 3,362,822, etc.
In the color diffusion transfer process of this invention, it is
preferred to conduct the development in the presence of a
diffusible onium compound. Examples of such onium compounds are
quaternary ammonium compounds, quaternary phosphonium compounds,
and quaternary sulfonium compounds. The specific examples of the
particularly useful onium compounds include 1-benzyl-2-picolinium
bromide, 1-(3-bromopropyl)-2-picolinium-p-toluenesulfonic acid,
1-phenethyl-2-picolinium bromide,
2,4-dimethyl-1-phenethylpyridinium bromide,
.alpha.-picoline-.beta.-naphthoylmethyl bromide,
N,N-diethylpiperidinium bromide, phenethyltrimethyl phosphonium
bromide, dodecyldimethylsulfonium-p-toluenesulfonium, etc.
The onium compound is preferably incorporated in the alkaline
processing composition. It is most preferred that the amount of the
onium compound used be 2 - 15 percent by weight of the total
processing composition. By conducting the development processing in
the presence of the onium compound, the quality of the transferred
images increases greatly. Other examples of the onium compounds and
other examples of the manner of using them are described in the
specifications of U.S. Pat. Nos. 3,411,904 and 3,173,786.
Furthermore, the alkaline processing solution may contain a
development inhibitor such as benzotriazole. The processing
solution can further contain a shading agent such as titanium
dioxide and carbon black. Moreover, the auxiliary developing agent
of this invention can be incorporated in the alkaline processing
solution.
The color photographic diffusion transfer process of this invention
can also be applied to a film unit in which a photo-sensitive
element is combined in a body with an image receiving element. Such
a film unit is described in the specifications of U.S. Pat. Nos.
3,415,644; 3,415,645 and 3,415,646.
It is believed that at least a part of the dye developer will be
oxidized during development and immobilized as the result of the
reaction with the oxidation product of the auxiliary developing
agent. The auxiliary developing agent is oxidized by the
development of the exposed silver halide. The oxidized auxiliary
developing agent is further caused to react with the unoxidized dye
developer to regenerate the auxiliary developing agent for further
reaction with the exposed silver halide. It is further believed
that by using the auxiliary developing agent, at least a part of
the auxiliary developing agent gives, as the result of such a
reaction, a transferred image having improved image density,
improved color separation and less color mixing.
The auxiliary developing agent used in this invention can be
prepared by, for instance, the following manner.
SYNTHESIS EXAMPLE
126 g of hydroxyhydroquinone triacetate was dissolved in a mixture
of 140 cc of glacial acetic acid, 100 cc of concentrated
hydrochloric acid, and 58 g of acetone under heating at above
50.degree. C - 70.degree. C and then the solution was allowed to
stand for 24 hours at room temperature (about 20.degree. -
30.degree. C). Thereby, the reaction product liquid was discolored
from dark red to dark brown and at the same time a red black solid
was precipitated. The solid thus precipitated was recovered by
filtration, washed well with water, and then 76 g of the crude
light-brown crystals was recrystallized from water-acetone mixed
solvent to give the desired product having a melting point of
275.degree. - 277.degree. C with a yield of 65.6 percent.
Elementary analysis:
Found: C 67.70% H 6.81%
Calculated: C 67.74% H 6.50%
Other methods of preparing the auxiliary developing agent are
described in Journal of Chemical Society, 195(1939) and Journal of
American Chemical Society, Vol. 58, 820(1936).
Now, the invention will be explained in greater detail by the
following examples, in which percent is percent by weight unless
otherwise indicated.
EXAMPLE 1
The following layers were coated successively on a cellulose
triacetate support to give Film A.
(film A)
1. yellow Dye Developer Layer:
10 g of a yellow dye developer,
1-phenyl-3-N-n-hexylcarboxyamido-4-[p-(2',5'-dihydroxyphenethyl)-phenylazo
]-5-pyrazolone was dissolved in a mixture of 10 cc of
N-n-butylacetanilide and 25 cc of cyclohexanone and the solution
was dispersed by emulsification in 100 cc of a 10 percent aqueous
gelatin solution containing 8 cc of an 8 percent aqueous solution
of sodium n-dodecylbenzenesulfonate. The emulsion thus prepared was
mixed with 5 cc of a 2 percent aqueous solution of
2-hydroxy-4,6-dichloro-S-triazine sodium salt and further water was
added thereto to make the total volume 300 cc. The mixture was
coated on the support in a dry thickness of 2.0 microns.
2. Photosensitive Silver Halide Emulsion Layer:
A silver iodobromide emulsion (containing 5 mol percent silver
iodide) containing 3.5 .times. 10.sup.-.sup.2 mols of silver and
6.5 g of gelatin per 100 g of emulsion was coated on the dye
developer layer in a dry thickness of 1.5 microns.
3. Protective Layer:
A coating composition of 100 cc of a 5 percent aqueous gelatin
solution containing 2 cc of a 5 percent aqueous solution of sodium
n-dodecylbenzenesulfonate and 5 cc of 2 percent mucochloric acid
was coated on the silver halide emulsion layer in a dry thickness
of 1.5 microns.
(Film B)
The same procedure as was used in the case of producing Film A was
followed except that the photosensitive silver halide emulsion
coating composition contained additionally 20 g of an emulsion
prepared by dissolving 5 g of 1-phenyl-3-pyrazolidone in a mixture
of 10 cc of tri-o-cresyl phosphate and 10 cc of ethyl acetate and
dispersing the solution in 50 cc of a 10 percent aqueous gelatin
solution.
(Film C)
The same procedure as was used in the case of preparing Film B was
followed except that 10.5 g of the auxiliary developing agent of
this invention was used in place of 5 g of 1-phenyl-3-pyrazolidone
in the photosensitive silver halide emulsion coating
composition.
Each of the Films A, B, and C thus prepared was exposed through a
step wedge and treated in superposed relation with the
image-receiving element as shown below with the following
processing composition to conduct the transfer development. The
processing composition was spread between the film and the
image-receiving element in a ratio of 1.8 cc per 100 cm.sup.2 of
the image-receiving element. The composition of the processing
solution used above was as follows:
______________________________________ Processing Composition High
viscous Hydroxyethyl Cellulose* 35 g Sodium Hydroxide 45 g
Benzotriazole 20 g 1-Benzyl-2-picolinium Bromide 20 g Sodium
Thiosulfate 10 g Water to give 100 cc
______________________________________ *NATROSOL TYPE 250 HR made
by HERCULES Co.
Image-Receiving Element:
The image-receiving element used above was prepared by coating on a
baryta-paper a solution of 2 g of poly-4-vinyl-pyridine (mordant)
and 0.1 g of 1-phenyl-5-mercaptotetrazole in 100 g of a 10 percent
aqueous gelatin solution in a dry thickness of 10 microns.
After 1 minute, the photosensitive element was stripped from the
image-receiving element and then the blue filter reflective density
of the yellow image thus transferred to the image-receving element
was measured. The minimum transfer density and the maximum transfer
density are shown in the following table.
______________________________________ Film Minimum Density Maximum
Density ______________________________________ A 0.56 1.46 B 0.35
1.38 C 0.10 1.52 ______________________________________
From the above results it is clear that Film C containing the
auxiliary developing agent of this invention gave an improved
minimum density and maximum density of the transferred image as
compared with those of the other films. Also, the transferred color
image from Film C was less stained as compared with those of the
other films.
EXAMPLE 2
Films D, E, and F were prepared in the following manner:
(Film D)
A multilayer photoelement was prepared by coating on a cellulose
triacetate support the following layers successively.
1. Cyan Dye Developer Layer:
15 g of
1,4-bis-(.alpha.-methyl-.beta.-hydroquinonylpropylamino)-5,8-dihydroxyanth
raquinone was dissolved under heating to 70.degree. C in a mixture
of 25 cc of N,N-diethyllaurylanide, 25 cc of methylcyclohexanone,
and 1 g of sodium dioctyl succinate. The solution was dispersed by
emulsification in 160 cc of a 10 percent aqueous gelatin solution
containing 10 cc of a 5 percent aqueous solution sodium
n-dodecylbenzenesulfonate. After adding water to the emulsion to
make the volume to 500 cc, the mixture was coated on the support in
a dry thickness of 5 microns.
2. Red-sensitive Silver Halide Emulsion Layer:
A red-sensitive silver iodobromide emulsion (containing 1 mol
percent silver iodide) containing 5.5 .times. 10.sup.-.sup.2 mols
of silver and 5.0 g of gelatin per 100 g of emulsion was coated on
the cyan dye developer layer in a dry thickness of 3.5 microns.
3. Intermediate Layer:
100 cc of a 5 percent aqueous gelatin solution containing 1.5 cc of
a 5 percent of aqueous solution of sodium n-dodecylbenzenesulfonate
was coated on the silver halide emulsion layer in a dry thickness
of 1.5 microns.
4. Magenta Dye Developer Layer:
10 g of a magenta dye developer,
4-propoxy-2-[p-(.beta.-hydroxyquinonylethyl)phenylazo]-1-naphthol
was dissolved under heating in a mixture of 20 cc of
N-n-butylacetanilide and 25 cc of methylcyclohexanone and the
solution was dispersed by emulsification in 120 cc of a 10 percent
aqueous gelatin solution containing 8 cc of a 5 percent aqueous
solution of sodium n-dodecylbenzenesulfonate. After adding water to
the emulsion to make the volume to 400 cc the mixture was coated on
the intermediate layer in a dry thickness of 3.5 microns.
5. Green-sensitive Silver Halide Emulsion Layer:
A green-sensitive silver iodobromide emulsion (containing 2 mol
percent silver iodide) containing 4.7 .times. 10.sup.2 mols of
silver and 6.2 g of gelatin per 100 g of emulsion was coated in a
dry thickness of 1.8 microns.
6. Intermediate Layer:
100 cc of a 5 percent aqueous gelatin solution containing 1.5 cc of
a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate
was coated on the silver halide emulsion layer in a dry thickness
of 1.0 micron.
7. Yellow Dye Developer Layer:
10 g of a yellow dye developer,
1-phenyl-3-N-n-hexylcarboxyamido-4-[p-(2',5'-dihydroxyphenethyl)-phenylazo
]-5-pyrazolone was dissolved under heating in a mixture of 10 cc of
N-n-butylacetanilide and 25 cc of cyclohexanone and the solution
was dispersed by emulsification in 100 cc of a 10 percent aqueous
gelatin solution containing 8 cc of a 5 percent aqueous solution of
sodium n-dodecylbenzenesulfonate. Then, after adding to the
emulsion 5 cc of a 2 percent aqueous solution of
2-hydroxy-4,6-dichloro-S-triazine and further water to make the
volume to 300 cc, the mixture was coated in a dry thickness of 1.5
microns.
8. Blue-sensitive Silver Emulsion Layer:
A blue-sensitive silver iodobromide emulsion (containing 7 mol
percent silver iodide) containing 3.5 .times. 10.sup.-.sup.2 mols
and 6.5 g of gelatin per 100 g of emulsion was coated in a dry
thickness of 1.5 microns.
9. Protective Layer:
A 4 percent aqueous gelatin solution containing 2 cc of a 5 percent
aqueous solution of 5 percent sodium n-dodecylbenzenesulfonate and
5 cc of a 2 percent aqueous mucochloric acid solution was coated in
a dry thickness of 1 micron.
(Film E)
The same procedure as was used in the case of preparing Film D was
followed except that 100 cc of the coating composition for the
protective layer of Film D was mixed with 50 g of an emulsion
prepared by dispersing by emulsification in 50 cc of a 10 percent
aqueous gelatin solution a solution of 5 g of
1-phenyl-3-pyrazolidone in a mixture of 10 cc of tri-o-cresyl
phosphate and 10 cc of ethyl acetate and the mixture was coated in
a dry thickness of 1 micron.
(Film F)
The same procedure as was used in the case of preparing Film D was
followed except that 10.5 g of the auxiliary developing agent of
this invention was used in place of 5 g of 1-phenyl-3-pyrazolidone
in the coating composition for the protective layer.
Each of Films D, E. and F prepared was exposed through step wedge
to white light and then was treated in superposed relationship with
the image-receiving element as described in Example 1 with the
processing composition as described in Example 1 to conduct
transfer development for one minute. The processing composition was
spread with a ratio of 1.5 cc per 100 cm.sup.2 of the
image-receiving element. The reflective densities of the color
images thus transferred were measured using red, green, and blue
filters respectively. The minimum transfer density and the maximum
transfer density of each case are shown in the following table.
______________________________________ Film Filter Minimum Density
Maximum Density ______________________________________ D Blue 0.32
1.05 Green 0.42 1.32 Red 0.28 1.03 E Blue 0.23 0.96 Green 0.25 1.25
Red 0.26 0.89 F Blue 0.18 1.15 Green 0.15 1.29 Red 0.17 1.10
______________________________________
From the results shown above it is clear that Film F containing the
auxiliary developing agent of this invention gave improved minimum
density and maximum density.
Each of the films prepared above was exposed in a camera to a
subject and then subjected to transfer development as described in
Example 1. The results showed that in Films D and E, the
distinction of light and darkness was not clear and the contrast
was low, while in Film F, the distinction of light and darkness was
clear and the contrast was good. Also, Film F have a transferred
image showing accurate color reproduction and having less color
mixing and stains.
EXAMPLE 3
Film D prepared as described in Example 2 was exposed through a
step wedge and was treated in superposed relation with the
image-receiving element as shown below with the processing
composition as shown below.
______________________________________ Processing Composition
Auxiliary Developing Agent (shown in the following table) shown in
table Water 100 cc Potassium Hydroxide 11.2 g Carboxymethyl
Cellulose 3.4 g N Benzyl-.alpha.picolinium Bromide 1.5 g
Benzotriazole 1.0 g Titanium Dioxide 50.0 g Composi- Auxiliary
Developing Agent tion (a) None(control) Amount " (b)
1-Phenyl-3-pyrazolidone 1.0 g " (c) 4' Methylphenyl Hydroquinone
1.0 g " (d) 4 Methylcatechol 1.0 g " (e) Compound of This Invention
1.0 g " (f) Compound of This Invention 10.0 g
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Image-Receiving Element:
The image-receiving element was prepared by coating successively on
a transparent support an acid polymer layer of acrylic acid-butyl
acrylate copolymer (1:1 molar ratio; mol. wt. about 50,000) for
controlling the pH of the processing composition, a spacer layer of
polyvinyl alcohol, and a dyeable layer of poly-4-vinylpyridine and
polyvinyl alcohol.
The densities of the transferred images on the image-receiving
element were measured in each case, the results of which are shown
in the following table.
______________________________________ Processing Minimum Maximum
Composition Filter Density Density
______________________________________ (a) Blue 0.35 1.11 Green
0.44 1.25 Red 0.36 1.00 (b) Blue 0.30 1.05 Green 0.39 1.10 Red 0.32
0.98 (c) Blue 0.25 1.21 Green 0.28 1.30 Red 0.20 1.05 (d) Blue 0.28
1.10 Green 0.31 1.20 Red 0.26 0.98 (e) Blue 0.24 1.20 Green 0.25
1.35 Red 0.18 1.11 (f) Blue 0.18 1.20 Green 0.19 1.37 Red 0.18 1.08
______________________________________
As is clear from the above results, in the color images obtained by
the process of this invention, remarkable improvements were
observed with respect to the minimum transferred density and the
maximum transferred density. Also, the transferred color image had
less color stains in the case of employing the processing
composition containing the auxiliary developing agent of this
invention.
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.
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