Field of the Invention
[0001] This invention relates to a solid type black-and-white photographic processing compound
and particularly to a solid type black-and-white processing compound that does not
deteriorate the solubility thereof in storage and the photographic characteristics
thereof.
Background of the Invention
[0002] Heretofore, processing compound for silver halide photographic light sensitive material
use has been used in the forms of a liquid or a powder. In the cases of the liquid
forms, they have been used either in their original condition or after the concentrated
solution thereof supplied in the form of a kit is diluted with water. In the cases
of the powder forms, they have been used after they are dissolved in water.
[0003] In the cases of the liquid compounds, they may easily be dissolved, however, they
have had the following problems, for example. They contain a considerable amount of
water in advance. Therefore, both the volume and weight thereof may become bulky and
heavy and, accordingly, the transportation and storage thereof may cost much money
and the liquid may be in danger of leaking and, further, the characteristics thereof
may be changed in storage.
[0004] In the cases of the powder compounds, on the other hand, the powdered compounds are
superior in compactness to those of the liquid compounds. However, the powdered compounds
are inferior in solubility to those of the liquid compounds. In both cases of the
liquid and powdered compounds, the liquid or powder is made adhered to remain on the
packaging materials after they are used up, so that the environmental pollution problems
may be raised when the waste packaging materials thereof are abandoned.
[0005] For solving the above-mentioned problems, Japanese Patent Publication Open to Public
Inspection (hereinafter referred to as JP OPI Publication) No. 3-39735/1991 proposes
that powdered processing compound is granulated to serve as a fixing compound and
the raw materials thereof are prepared to have a particle size of not larger than
10 µm. As for the concrete examples, a fixing compound for color photographic light
sensitive material use and a black-and-white fixing compound not containing a water-soluble
aluminium compound are each given in the above-mentioned proposal.
[0006] Generally, a water-soluble aluminium compound is used in black-and-white fixing compound
for the purpose of hardening the layers of light sensitive materials. In solid type
fixing compound each containing a water-soluble aluminium compound, there may be some
instances where a hardly soluble substance is produced so that a complete dissolution
cannot be made when it is stored for a long time or under the high temperature and
humidity conditions, though the reasons are not apparent. Particularly when a water-soluble
aluminium compound is so used as to have an average particle size of not larger than
10 µm, it was found that the solubility of the compound is seriously deteriorated
in storage, not only in the cases of the powdered compounds, but also in the case
of the granulated compounds. In the technological specifications disclosed in the
above-given patent publication, it was further found that any practically applicable
solid type processing compound cannot be obtained.
[0007] For the developing compound as well as for the fixing compound, JP OPI Publication
No. 3-109042/1991 proposes that a powdered processing compound is granulated and the
raw materials thereof are prepared to have a particle size of not larger than 10 µm.
As for the concrete examples, a developing compound for color photographic light sensitive
material use is given in the above-mentioned proposal.
[0008] In the developing compound each containing a polyhydroxybenzene, which is used in
black-and-white photography, it was found that a solid type developing compound is
also liable to characteristic deterioration such as the developability deterioration
caused in storage by the oxidation-induced deterioration of a polyhydroxybenzene.
In the case of making use of a developing compound pulverized into a particle size
of not larger than 10 µm, it was also found that the preservability thereof are seriously
deteriorated not only in the case of using a powdered developing compound, but also
in the cases of using a granulated developing compound. In the technological specifications
disclosed in the above-given patent publication, it was further found that any practically
applicable solid type processing compound cannot be obtained.
[0009] In order to solve the above-mentioned problems, it is an object of the invention
to provide a solid type processing compound easy in transportation and storage, excellent
in solubility, capable of eliminating the deteriorations of solubility and photographic
characteristics in storage, and excellent in environmental aptitude.
Summary of the Invention
[0010] The above-mentioned object of the invention can be achieved with the following photographic
processing compounds;
a black-and-white photographic developing compound containing a polyhydroxybenzene,
that is a solid type black-and-white photographic developing compound characterized
in that, among the raw materials thereof, at least the polyhydroxybenzene is prepared
in advance to have an average particle size within the range of 10 to 500 µm; and
a black-and-white photographic fixing compound containing a water-soluble aluminium
compound, that is a solid type black-and-white photographic fixing compound characterized
in that, among the raw materials thereof, at least the aluminium compound is prepared
in advance to have an average particle size within the range of 10 to 500 µm.
[0011] It is preferred that the above-mentioned developing compound is to contain at least
one kind of developing agent selected from the group consisting of a phenidone and
a monomethyl-p-amino-phenol sulfate Metols.
Detailed Description of the Invention
[0012] Now, the invention will be concretely detailed hereunder.
[0013] In the solid type processing compounds applicable to the invention, the expression,
"solid type", means common solid-forms including, for example, a powdered form, a
granulated form and a paste form, and it may also be any mixed forms thereof.
[0014] Next, the methods for dissolving the solid type processing compounds of the invention
are similar to the methods for preparing common liquid compounds , wherein the dissolution
can be carried out either manually or mechanically and the replenishing tanks may
be provided to either the inside of an automatic processor or the outside thereof.
Any methods for supplying a processing compound can be used, provided that each component
of the processing chemical cannot be scattered. The above-mentioned methods include,
for example, a method in which a solid type processing compound is wrapped in a water-soluble
high polymer film and the wrapped compound is added as it is, and another method in
which a processing compound is packed by paper surface-treated with polyethylene or
the like so that any scattering or remaining of powdered compound can be prevented
and the packed compound is added into a tank. Taking the solubility of a processing
compound to water into consideration, the preferable solid types include a granulated
form and a tableted form. However, there are many instances where photographic processing
compounds contain a component hardly soluble to water and, in this instance, a hardly
soluble substance may sometimes be deposited in a processing solution. To avoid this
trouble, it is also allowed to use a method of separately adding a solvent. For preparing
granules or tablets, it is preferable to use a popularly applicable granulating aid
such as water-, alkali- or acid-soluble high polymers. They include, typically, gelatin,
pectin, polyacrylic acid, polyacrylate, polyvinyl alcohol, polyvinyl pyrrolidone,
vinylacetate copolymer, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl
cellulose, methyl cellulose, alginate, gum arabic, gum traga(ca)nth, methylvinyl ether,
maleic anhydride copolymer, polyoxyethylene alkyl ether such as polyoxyethylene ethyl
ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenol ether such as
polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, and a combination
of 1 or 2 kinds of the water-soluble binders selected from the group consisting of
those given in JP Application No. 2-203165/1990.
[0015] For increasing the preservability of processing compounds as a kit, it is allowed
to enclose the processing compounds in two or more packs in the kit.
[0016] The granulation methods applicable to the invention include, for example, a rolling
granulation method, an extruding granulation method, a compressing granulation method,
a pulverizing granulation method, a stirring granulation method, a spray-dry method,
and a dissolving coagulation method. Among these methods, the extruding granulation
method and stirring granulation method are particularly preferable.
[0017] The sizes and configurations of the granules suitably applicable to the invention
are varied to meet the individual objective characteristics. However, in the case
of granules, the granule size in sphere equivalent is to be within the range of the
order of 0.5 mm to 50 mm and, preferably, 1 mm to 15 mm. The configurations of the
granules include, for example, those of the cylindrical, spherical, cubic and rectangular
parallelepipedonal shaped. Among the configurations thereof, the spherical or cylindrical
shaped are preferable.
[0018] The sizes and configurations of the tableted compounds are also varied similarly
to the above-mentioned case to meet the various objective characteristics. However,
the sizes thereof are preferably within the range of the order of 2 mm to 5 cm. When
the solubility is to be increased, it is effective to use a tabular-shaped tablet
having a reduced thickness, a tabular-shaped tablet having a reduced thickness of
the central portion thereof, a doughnut-shaped tablet having a hollowness in the center
and so forth. On the contrary, the sizes thereof may also be made larger for making
a dissolution slowly. The sizes can freely be adjusted.
[0019] For controlling the solubility, it is also allowed to change the surface conditions
(by making the surface flat and smooth or porous, for example).
[0020] It is further allowed to take a plurality of configurations for providing various
solubilities to a plurality of granules or for matching up the solubilities of raw
materials having the different solubilities together. It is still further allowed
to use multilayered granules having the different compositions between the surface
and the inside thereof.
[0021] The polyhydroxybenzene applicable to the invention include, for example, dihydroxybenzenes
(such as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropyl hydroquinone,
methyl hydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethyl hydroquinone, potassium
hydroquinone monosulfonate and sodium hydroquinone monosulfonate), pyrogallol, 3-pyrazolidones
(such as 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl- 4 -dihydroxymethyl-3-pyrazolidone),
aminophenols (such as o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol
and 2,4-diaminophenol), 1-aryl-3-aminopyrazolidones (such as 1-(p-hydroxyphenyl)-3-aminopyrazolidone
and 1-(p-amino-m-methylphenyl)-3-aminopyrazolidone) and the mixtures thereof.
[0022] The color developing agents include, for example, primary aromatic amino developing
agents such as phenylenediamines (e.g., 4-amino-N,N-diethyl aniline, 3-methyl-4-amino-N,N-diethyl
aniline, 4-amino-N,N-diethyl aniline, 4-amino-N-ethyl-N-β-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethyl
aniline, 3-methyl-4-amino-N-ethyl-N-β-methane sulfonamidoethyl aniline and 4-amino-3-methyl-N-ethyl-N-β-methoxyethyl
aniline).
[0023] As for the developing agents applicable to the black-and-white developers to be used
in the invention, it is preferable to use the combination of dihydroxy benzene ring
and a 1-phenyl-3-pyrazolidone, from the viewpoint that the excellent characteristics
can be enjoyed. It is the matter of course to further contain a p-aminophenol type
developing agent therein, besides the above-mentioned developing agents.
[0024] Further besides the above, it is also allowed to use those described in L.F.A. Mason,
"Photographic Processing Chemistry" (Focal Press, 1966) pp.226∼229, JP OPI Publication
No. 48-64933/1973, and so forth. It is preferable to use these developing agents ordinarily
in an amount within the range of 0.01 to 1.2 mols per liter.
[0025] The sulfite preservatives applicable to the invention include, for example, sodium
sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium
metabisulfite and sodium formaldehyde bisulfite. The sulfites may be used in an amount
of not less than 0.2 mols per liter and, preferably, not less than 0.4 mols per liter.
It is also preferable that the upper limit for using the sulfites is up to 2.5 mols
per liter.
[0026] The pH of the developers applicable to the invention is within the range of preferably
9 to 13 and particularly 10 to 12. The alkalizers applicable to control the pH include,
for example, the pH controllers such as sodium hydroxide, potassium hydroxide, sodium
carbonate, potassium carbonate, tertiary sodium phosphate and tertiary potassium phosphate.
[0027] It is also allowed to use a buffer including, for example, boric acid salts (described
in, for example, JP OPI Publication No. 61-28708/1986), saccharose, acetoxime and
5-sulfosalicylic acid (described in, for example, JP OPI Publication No. 60-93439/1985),
phosphates and carbonates.
[0028] Besides the above-given components, the additives applicable thereto include, for
example, a development inhibitor such as sodium bromide, potassium bromide and potassium
iodide; an organic solvent such as ethylene glycol, diethylene glycol, triethylene
glycol, dimethyl formamide, methyl cellosolve, hexylene glycol, ethanol and methanol;
and an antifoggant such as a mercapto type compound, e.g., 1-phenyl-5-mercaptotetrazole
and sodium 2-mercaptobenzimidazole-5-sulfonate, an indazole type compound, e.g., 5-nitroindazole,
and a benztriazole type compound, e.g., 5-methylbenztriazole. If required, it is further
allowed to add a color toner, a surfactant, a defoamer, a water softener and the amino
compounds, each described in JP OPI Publication No. 56-106244/1981.
[0029] In the developers of the invention, it is allowed to use a silver-stain preventive
such as the compounds given in, for example, JP OPI Publication No. 56-24347/1981.
In the developers of the invention, it is allowed to use an amino compound such as
alkanol amine described in JP OPI Publication No. 56-106244/1981.
[0030] It is further allowed to use the amino compounds described in JP OPI Publication
No. 56-106244/1981.
[0031] As for the typical examples of the water-soluble aluminium compounds applicable to
the invention, the halides, phosphates, sulfates and carbonates of aluminium may preferably
be included. The double salts of potassium alum or sodium alum may also be used therein.
They may be preferably added in an amount within the range of 1.0x10⁻² to 0.5x10⁻¹
mols per liter in terms of aluminium ion content.
[0032] The fixing solution prepared of the fixing compound of the invention is to have a
pH within the range of 3.8 to 6.0 and, preferably, 4.2 to 5.5.
[0033] The fixing compound is preferable to contain a thiosulfate. The thiosulfates are
supplied in the solid form. To be more concrete, they are supplied in the form of
the salt of lithium, potassium, sodium, ammonium, and they are used after they are
dissolved. Among them, it is preferable that they are supplied as a sodium salt or
an ammonium salt and then used after they are dissolved. It is further preferable
that a fixing solution can be prepared to have a rapid fixing speed by using them
after they are supplied as an ammonium salt and dissolved. The concentration of the
thiosulfate is within the range of, preferably, 0.1 to 5 mols per liter, further preferably
0.5 to 2 mols per liter and, particularly 0.7 to 1.8 mols per liter.
[0034] The fixing compounds contain a sulfite. When a thiosulfate and the sulfite are dissolved
to be mixed up together in an aqueous solvent, the concentration of such a sulfite
as mentioned above is not more than 0.2 mols per liter and, preferably, not more than
0.1 mols per liter. As for the sulfites, the solid salts of lithium, potassium, sodium
or ammonium may be used. They are used by dissolving them with the above-mentioned
solid thiosulfates.
[0035] It is preferable that the fixing compound contains citric acid, tartaric acid, malic
acid and succinic acid and that citric acid, isocitric acid, malic acid, tartaric
acid, succinic acid or the optical isomers thereof are contained therein as phenylacetic
acids.
[0036] The salts thereof preferably applicable thereto include, for example, the salts of
lithium, potassium, sodium or ammonium such as, typically, potassium citrate, lithium
citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen
tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium
hydrogen tartrate, ammonium potassium tartrate, sodium potassium tartrate, sodium
maliate, ammonium maliate, sodium succinate and ammonium succinate. One or two kinds
of them selected from the above-given salts can be used in combination.
[0037] The further preferable compounds among them include, for example, citric acid, isocitric
acid, malic acid, phenylacetic acid and the salts thereof.
[0038] The above-mentioned citric acid, tartaric acid, malic acid and succinic acid are
supplied in the solid form and they are used after dissolving them in an aqueous solvent.
After they are dissolved in a fixing solution, their content is not less than 0.05
mols per liter and, most preferably, within the range of 0.2 to 0.6 mols per liter.
[0039] The fixing compound is also allowed to contain additives such as various acids, salts,
a chelating agent, a surfactant, a wetting agent and a fixing accelerator.
[0040] The above-mentioned acids include, for example, inorganic acids such as sulfuric
acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic
acid, propionic acid, oxalic acid and malic acid.
[0041] The above-mentioned salts include, for example, the lithium salts, potassium salts,
sodium salts and ammonium salts of the above-given acids.
[0042] The above-mentioned chelating agents include, for example, aminopolycarboxylic acids
such as nitrilotriacetic acid and ehtylenediamine tetraacetic acid, and the salts
thereof.
[0043] The above-mentioned surfactants include, for example, anionic surfactants such as
those of sulfates or sulfonates, nonionic surfactants such as those of the polyethylene
glycol types or the ester types, and amphoteric surfactants such as those described
in JP OPI Publication No. 57-6840/1982 (wherein, the title of the invention is "Fixing
Solution for photographic Use").
[0044] The above-mentioned wetting agents include, for example, alkanol amine and alkylene
glycol.
[0045] The above-mentioned fixing accelerators include, for example, the thiourea derivatives
described in JP Examined Publication Nos. 45-35754/1970, 58-122535/1983 and 58-122536/1983,
alcohol having a triple bond in the molecule thereof, and thioether described in U.S.
Patent No. 4,126,459.
[0046] Among the above-mentioned additives, the acids such as sulfuric acid, boric acid
and aminopolycarboxylic acid and the salts thereof may preferably be used. They may
be added preferably in an amount within the range of 0.5 to 20 g per liter.
[0047] The developing chemicals and/or fixing chemicals of the invention are preferably
prepared of polyhydroxybenzenes and aluminium compounds each having an average particle
size within the range of preferably 10 to 200 µm. They are particularly preferable
to be solid processing chemicals granulated and formed by making use of polyhydroxybenzenes
and aluminium compounds each having an average particle size within the range of,
preferably 10 to 200 µm.
[0048] The silver halide photographic light sensitive materials applicable with the developing
chemicals and/or fixing chemicals of the invention can be prepared in any processes
known in the field of the art.
[0049] The above-mentioned light sensitive materials include, for example, black-and-white
photographic materials such as photographic materials for medical or industrial use,
light sensitive materials for photomechanical process use, microphotographic materials,
X-ray photographic materials, reversal microphotographic materials, computerized phototype-setting
films and paper, negative photographic materials for general picture-taking use and
printing paper. Among them, the light sensitive materials for photomechanical process
use are preferable and photographic light sensitive materials containing hydrazine
derivatives such as those described in JP OPI Publication Nos. 52-18317/1977, 53-95618/1978,
58-173737/1983 and 58-106493/1983 are particularly preferable.
EXAMPLES
[0050] Now, referring to the following examples, the advantages of the invention will be
illustrated concretely.
EXAMPLE 1
[0051] (Preparation of Fixing Chemicals)
[0052] Solid fixing chemicals F-1 through F-12 were each prepared as shown in the following
Table 1. The average particle sizes of each raw material thereof were prepared by
pulverizing the raw materials by a pulverizer or an air-jet mill.
[0053] F-1 through F-6 were each prepared as the samples in the following manner. Every
part of A, B and C of the raw materials was mixed up and the resulting mixtures were
filled up respectively, in the order of A, C and B parts from the top, into the individual
moisture-proof containers each made of a polyethylene/A1/paper having a polyethylene-coated
inside surface. F-6 through F-12 were each prepared as the samples in the following
manner. Water was added in an amount of 12% of the whole amount of the raw materials
into each of parts A, B and C. By making use of the resulting mixtures, the granulated
solids having an average particle size of 5 mm were each prepared in a fluidized-bed
stirring granulation process. After the resulting solids were dried up, each of the
parts was mixed together, and the mixtures were sealed respectively in individual
moisture containers, in the same manner as in the cases of F-1 through F-6.

(Evaluation of Fixing Compounds)
[0054] Fixing compound samples F-1 through F-12 were each allowed to stand as they were,
at 50°C for one day, for a substitutive evaluation supposed for a long term storage.
After that, they were added into water at ordinary temperature with stirring and the
time required to dissolving them up was visually evaluated. The results thereof will
be shown in Table 2 given below.

[0055] It is apparent from the results shown in Table 2 that the solid fixing compounds
of the invention are excellent in solubility and few in solubility deterioration produced
in storage. It is also apparent without any exemplification that the solid fixing
compounds of the invention are less in volume and weight and more advantageous for
transportation and storage, as compared with any concentrated fixing compounds prepared
of the same raw materials as those of the solid fixing compounds of the invention.
Among those of the invention, F-8 through F-11 do not produce any fixing compound
adhesion to any waste packing material containers nor produce any troubles when making
disposals of the waste packing material containers.
EXAMPLE 2
[0056] (Preparation of Light Sensitive Materials for Evaluation)
(Synthesis of Latex Lx)
[0057] A solution was prepared by adding 0.125 Kg of gelatin and 0.05 Kg of ammonium peroxide
into 40 liters of water. Thereto, a mixed solution consisting of (a) 4.51 Kg of n-butyl
acrylate, (b) 5.49 Kg of styrene and (c) 0.1 Kg of acrylic acid was added while stirring
the resulting solution at 80°C and by taking one hour. Thereafter, the resulting mixed
solution was stirred for 1.5 hours and, 1.25 Kg of gelatin and 0.005 Kg of ammonium
peroxide were then added thereto. After stirring the solution for 1.5 hours to complete
the reaction, the remaining monomers were removed by distilling vapor for one hour.
After cooling the temperature down to room temperature, the pH was adjusted to be
6.0 by making use of ammonia. The resulting latex solution was finished to be 50.5
Kg by adding water thereto.
[0058] In the above-described manner, a monodisperse type latex having an average particle
size of 0.25 µm and a Tg of about 0°C could be prepared.
(Preparation of Emulsion A)
[0059] A solution was prepared by adding rhodium hexachloride complex to an aqueous solution
of sodium chloride and potassium bromide so that the amount could be 8x10⁻⁵ mols per
mol of Ag. The resulting solution and a silver sulfate solution were added at the
same time into a gelatin solution while controlling the flow rate. After the resulting
solution was desalted, a cubic system, monodisperse silver chlorobromide emulsion
having an average grain size of 0.13 M and containing 1 mol% of silver bromide could
be prepared.
[0060] The resulting emulsion was sulfur-sensitized in an ordinary method and then added
with 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene as a stabilizer. After that, the following
additives were added thereto, so that emulsion coating solutions E-1 through E-14
were each prepared. Next, emulsion protective layer coating solution P-0, backing
layer coating solution B-0 and backing protective layer coating solution BP-0 were
each so prepared as to have the following compositions.
(Preparation of Emulsion Coating Solutions E-1 to E-14)
[0061]
Compound (a) |
1 mg/m² |
NaOH(0.5N) |
Adjusted pH to be 5.6 |
Compound (b) |
40 mg/m² |
Compound (c) |
30 mg/m² |
Saponin (20%) |
0.5 cc/m² |
Sodium dodecylbenzene sulfonate |
20 mg/m² |
5-methyl benzotriazole |
10 mg/m² |
Compound (d) |
2 mg/m² |
Compound (e) |
10 mg/m² |
Compound (f) |
6 mg/m² |
Latex Lx |
An amount given in Table 1 |
Styrene-maleic acid copolymer, (a thickener) |
90 mg/m² |

(Emulsion Protective Layer Coating Solution P-0)
[0062]

(Backing Layer Coating Solution P-O)
[0063]
Gelatin |
1.0 g/m² |
Compound (j) |
100 mg/m² |
Compound (k) |
18 mg/m² |
Compound (l) |
100 mg/m² |
Saponin (20%) |
0.6 cc/m² |
Latex (m) |
300 mg/m² |
5-nitroindazole |
20 mg/m² |
Styrene-maleic acid copolymer, (a thickener) |
45 mg/m² |
Glyoxal |
4 mg/m² |
Compound (o) |
50 mg/m² |
(Backing Protective Layer Coating Solution BP-O)
[0064]
Gelatin |
0.5 g/m² |
Spherical polymethyl methacrylate (4µ) |
25 mg/m² |
Sodium chloride |
70 mg/m² |
Glyoxal |
22 mg/m² |
Compound (n) |
10 mg/m² |

[0065] A corona-discharge was applied to a 100µ-thick, subbed polyethylene terephthalate
base exemplified in JP OPI Publication No. 59-19941/1984 and, the coating solutions
prepared as described above were each coated with the following compositions over
the corona-discharged base by making use of a roll-fit coating pan and an air-knife.
The drying treatment was carried out for 30 seconds under the parallel flow drying
conditions at 90°C and 25 Kcal (m²·hr·°C) of overall heat-transfer coefficient and
another drying treatment was successively carried out for 90 seconds at 140°C. The
resulting layer thickness after dried was 1 µ and the specific surface resistance
was 1x10⁸Ω at 23°C and 55%RH.

[0066] A mixture of the follwing compounds

[0067] Over one of the base surfaces to which the emulsion is to be coated, an emulsion
layer and an emulsion protective layer were double-coated simultaneously in this order
in a slide-hopper system, while adding a layer hardening solution and keeping the
temperature at 35°C. After passing the resulting layer-coated base through a cool-air
set zone (at 5°C), a backing layer and a backing protective layer were further coated
thereon in the same slide-hopper system while adding a layer hardening solution and
the resulting layer-coated base was set by cool-air (at 5°C). At the point of time
when passing through each of the set zones, the coating solutions indicated satisfactory
setting characteristics. Successively, both sides of the base were dried in a drying
zone under the following drying conditions. After both sides of the base were back-coated,
the coated base was conveyed without touching it at all, except that it was conveyed
by a roller by the time right up to complete the take-up. The coating speed at that
time was 100 m/min.
(Drying Conditions)
[0068] After completing the above-mentioned setting treatments, the coated base was dried
by dry-air at 30°C until the weight ratio of H₂O/gelatin could be 800% and was then
dried by dry-air at 35°C (and at 30%RH) until the above-mentioned ratio could be 80
to 200%. After that, the base was still exposed to the wind and, 30 seconds after
the point of time when the surface temperature became 34°C (it was regarded as the
completion of the drying treatment), it was further dried for one minute by the air
at 48°C and 16%RH. At that time, the drying time was required for 50 seconds from
the start of the drying to the time when the weight ratio of H₂O/Gelatin was 800%,
for 35 seconds from 800% to 200% and for 5 seconds from 200% to the completion of
the drying treatment.
[0069] The resulting light sensitive material was taken up at 23°C and 15%RH and was then
cut apart under the same surrounding conditions.
(Preparation of Developing Chemicals)
[0070] Solid developing compounds D1 through D-14 were each prepared as shown in the following
Table 3. The average particle sizes of the raw materials were adjusted by pulverizing
them by a pulverizer or an air-jet mill.
[0071] D1 through D7 were each prepared as the samples in the following manner. Parts A
and B of the raw materials were independently mixed up and the resulting mixtures
were filled up respectively, in the order of A and B parts from the top, into the
individual moisture-proof containers each made of a polyethylene/A1/paper having a
polyethylene-coated inside surface. D8 through D-14 were each prepared as the samples
in the following manner. Water was added in an amount of 12% of the whole amount of
the raw materials into each of parts A and B. By making use of the resulting mixtures,
the granulated solids having an average particle size of 3 mm were each prepared in
a fluidized-bed stirring granulation process. After the resulting solids were dried
up, each of the parts was mixed together, and the mixtures were sealed respectively
in individual moisture containers in the same manner as in the cases of D1 through
D6.

(Evaluation of Developing Compounds)
[0072] Developing compound samples D1 through D12 were each allowed to stand as they were,
at 50°C for one day, for a substitutive evaluation supposed for a long term storage.
After that, they were added into water at ordinary temperature with stirring and the
time required to dissolving them up was visually evaluated.
[0073] Films subject to evaluation were each exposed to light through a wedge and were then
processed by making use of the above-mentioned developing compounds and fixing compound
CFL-871 (manufactured by Konica Corp.) at 28°C for 30 seconds through automatic processor
GR-27 (manufactured by Konica Corp.), respectively. The sensitivities obtained were
indicated by the reciprocals of the exposure amount for giving a density of 3.5.
[0074] The results thereof will be shown in Table 4.
Table 4
|
Dissolving time (min) |
Specific sensitivity |
|
|
Immediately after preparation |
After 1 day, at 50°C |
Immediately after preparation |
After 1 day, at 50°C |
Remarks |
F-1 |
20 |
21 |
100 |
97 |
Comparison |
F-2 |
7 |
8 |
101 |
97 |
Invention |
F-3 |
4.5 |
5.3 |
101 |
97 |
Invention |
F-4 |
4 |
4.8 |
100 |
98 |
Invention |
F-5 |
3 |
5 |
101 |
97 |
Invention |
F-6 |
3 |
6 |
96 |
76 |
Comparison |
F-7 |
5 |
30 |
94 |
70 |
Comparison |
F-8 |
15 |
16 |
99 |
98 |
Comparison |
F-9 |
6 |
6.5 |
100 |
99 |
Invention |
F-10 |
3.8 |
4.5 |
101 |
99 |
Invention |
F-11 |
3 |
3.5 |
100 |
98 |
Invention |
F-12 |
2 |
2.5 |
101 |
99 |
Invention |
F-13 |
2 |
3 |
95 |
83 |
Comparison |
F-14 |
2 |
4 |
94 |
76 |
Comparison |
[0075] It is apparent from the results shown in Table 4 that the solid developing compounds
of the invention are excellent in solubility and few in sensitivity deterioration
produced in storage. It is also apparent without any exemplification that the solid
developing compounds of the invention are less in volume and weight and more advantageous
for transportation and storage, as compared with any concentrated developing compounds
prepared of the same raw materials as those of the solid developing compounds of the
invention. Among those of the invention, D8 through D11 do not cause any fixing compound
adhesion to any waste packing material containers nor produce any troubles when making
disposals of the waste packing material containers.
[0076] According to the invention, solid processing compounds can be provided to be ready
for transportation and storage, excellent in solubility in storage, free from any
photographic characteristic deterioration and, further, excellent in environmental
aptitude.