FIELD OF THE INVENTION
[0001] The present invention relates to a method for development processing a photographic
material having a magnetic recording layer and, more particularly, to a processing
method in which a read error of a magnetic information from the magnetic recording
layer of a photographic material after development processing is prevented.
BACKGROUND OF THE INVENTION
[0002] In a silver halide photographic material (hereinafter, referred to as a photographic
material or a film), it has been almost impossible to input various informations of
the time when photographing using a camera (e.g., the date of photographing, the weather,
the enlargement ratio, the number of sheets of printing), except for only being capable
of inputting the date of photographing optically. Further, inputting informations
to a photographic material when printing has been completely impossible, which has
been hindrance to speedup of the processing and reduction in cost.
[0003] It is a very important means to input various informations into a photographic material
for improving and more simplifying the manipulation of a camera in future. As such
a means of inputting informations, a magnetic recording method has been variously
studied because it is capable of arbitrarily inputting and outputting informations
and due to its inexpensiveness.
[0004] It has become feasible to input various informations to a photographic material by
providing a magnetic recording layer in a photographic material which was formerly
difficult, that is, the conditions when developing and printing have become possible
to be inputted in a magnetic recording layer of a photographic material, e.g., the
date of photographing, the weather, the conditions of lighting, the conditions at
the time of photographing such as the reduction/enlargement ratio, etc., the number
of sheets of reprinting, the place to be zoomed, and the messages. Further, a magnetic
recording layer can be applied as a means of input and output signals when a photographic
material is directly outputted to a television/video signals to form images, therefore,
this is a very promising field.
[0005] However, it has been found that, with respect to input and output of informations,
the input and output error due to the space loss, in particular, the output error
which is generated by development processing is a severe problem when handling a photographic
material provided with a magnetic recording layer.
[0006] Major causes of the space loss include the components coated on the side of a photographic
material on which a magnetic recording layer is provided (e.g., magnetic grains and
binder components), dusts adhered on the film during development processing, components
of the processing solution, dirt from the hands adhered on the film, and dust in the
atmosphere. A magnetic output error is generated presumably because they adhere and
accumulate on the surface of a magnetic head while a film is traveling to cause the
space loss between the film and the magnetic head.
[0007] As a method for solving the input and output error attributable to the space loss,
the techniques of inclusion of a lubricating agent in a magnetic recording layer have
been proposed in JP-A-4-73743 and JP-A-4-124659 (the term "JP-A" as used herein refers
to a "published unexamined Japanese patent application"). It is also disclosed in
JP-A-4-73736 and JP-A-6-161033 that this problem can be resolved by the addition of
grains insoluble in a developing solution into a surface layer of the support on which
the magnetic recording layer is provided such that the surface has projections having
an average height of about from 0.1 to 3.0 µm. However, neither of these methods could
provide a sufficient effect with respect to the output reduction of magnetic recording
after development processing.
SUMMARY OF THE INVENTION
[0008] An object of the present invention is to provide a processing method of a photographic
material having a magnetic recording layer in which the magnetic output is not reduced
after processing.
[0009] Other objects and effects of the present invention will be apparent from the following
description.
[0010] The present invention relates to, as a first embodiment, a method for development
processing a silver halide color photographic material comprising a support having
thereon a magnetic recording layer, wherein the conductivity of a final processing
solution of the development processing is 0.1 mS/cm or less.
[0011] The present invention also relates to, as a second embodiment, a method for development
processing a silver halide color photographic material comprising a support having
thereon a magnetic recording layer, wherein the calcium concentration in a final processing
solution of the development processing is 5 mg/ℓ or less.
[0012] The present invention further relates to, as a third embodiment, a method for development
processing a silver halide color photographic material comprising a support having
thereon a magnetic recording layer, wherein the adhered amount of a final processing
solution remained on a surface of the photographic material on which the magnetic
recording layer is provided after development processing is 0.3 ml/m
2 or less.
[0013] In the first embodiment of the present invention, it is preferred that a color developing
solution used in the method for development processing does not contain hydroxylamine,
and it is also preferred that the final processing solution contains 1,2-benzisothiazolin-3-one.
[0014] In the first embodiment of the present invention, it is further preferred that the
adhered amount of the final processing solution remained on a surface of the photographic
material on which the magnetic recording layer is provided after development processing
is 0.3 ml/m
2 or less.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The silver halide color photographic material having a magnetic recording layer of
the present invention is subjected to ordinary color development processing (hereinafter
referred to as only processing) then drying.
[0016] Magnetic recording is generally carried out before processing and reading is carried
out after processing in many cases, and it has been found that adhered materials accumulate
on the surface of the magnetic head during reading of the information after processing
to cause the space loss between the film and the magnetic head, thereby an output
is reduced. As a result of analyzing this phenomenon, the present inventors have found
that the components of the processing solution adhered after processing on the side
of the film on which the magnetic recording layer is provided, in particular, the
ionic component causes the above reduction of the output.
[0017] The method of the present invention comprises conducting any one of reducing the
conductivity of the final processing solution of the development processing to 0.1
mS/cm or less, reducing the calcium concentration in the final processing solution
to 5 mg/ℓ or less, or reducing the adhered amount of the final processing solution
to 0.3 ml/m
2 or less which is remained after development processing on the surface of the silver
halide color photographic material on which the magnetic recording layer is provided.
[0018] Further, it has also been found that the curling characteristics after processing
of the photographic material can be improved by the present invention.
[0019] In the present invention, the term "final processing solution" means a processing
solution just before the drying process, that is, a stabilizing solution or a rinsing
solution, with a stabilizing solution being particularly effective.
[0020] The present invention is conspicuously effective when a processing solution containing
a surfactant is used as the final processing solution.
[0021] A method for reducing the conductivity of the final processing solution to 0.1 mS/cm
or less (first embodiment) is described below.
[0022] A processing solution such as a stabilizing solution and a rinsing solution contains
various compounds for stabilizing images or other purposes. For reducing the conductivity
of the final processing solution, it is effective to reduce ionic compounds in the
chemicals which are added as the components of the final processing solution, and
also it is effective to previously remove ionic compounds from water to which these
chemicals are to be dissolved (hereinafter referred to as preparation water). Further,
it is also effective that washing and stabilizing steps are carried out by a multistage
countercurrent system to reduce the amount of carryover of the previous processing
solution by the photographic material.
[0023] As a method of removing ionic compounds from the preparation water, methods such
as distillation, amphoteric ion exchange and reverse osmosis can be utilized. It is
not preferred to apply these methods to a stabilizing solution or a replenisher thereof,
since the performances of the stabilizing solution (e.g., stabilization of images,
prevention of staining of a film, liquid extraction of a film) are deteriorated by
the removal or reduction of the compounds added in the stabilizing solution.
[0024] Most preferred method of the above is a method of amphoteric ion exchanging the preparation
water previously.
[0025] In the amphoteric ion exchange method, the preparation water is contacted with various
ion exchangers such as an ion exchange resin and an ion exchange membrane with a method
of using an ion exchange resin being most preferred. When using an ion exchange resin
in the amphoteric ion exchange method, an H-type strongly acidic cation exchange resin
and an OH-type strongly basic anion exchange resin are preferably used in admixture.
It is preferred that the preparation water is passed through a column packed with
the mixture of these resins. The passing rate is generally from 1 to 100 times, preferably
from 5 to 50 times, of the volume of resins per hour. As the structure of a resin,
a gel type, a porous type and a support carrying type can be used.
[0026] Specific examples of ion exchange resins include combinations of Amberlite IR-120B
and IRA-400 manufactured by Rohm & Haas and Diaion SK-1B and SA-10A or SA-20A manufactured
by Mitsubishi Kasei Corp. but the present invention is not limited thereto.
[0027] A reverse osmosis equipment for reverse osmosis treating the preparation water is
preferably a low pressure type equipment, for example, about from 2 to 30 kg/cm
2. As a reverse osmosis membrane, a cellulose acetate membrane, an ethyl cellulose-polyacrylic
acid membrane, a polyacrylonitrile membrane, and a polybutylene carbonate membrane
can be used. Specific examples include NTR-959HR, NTR-950UP, NTR-729HF, NTR-7250,
NTR-719HF, NTR-7410, and NTR-7450 manufactured by Nitto Kagaku Kogyo Co., Ltd., UTC-70,
UTC-40HR, SC-3000, SU-700, SU-410, SU-600, SU-200S, and PEC-1000 manufactured by Toray
Industries Inc., BW-30, HR-30, NF-40, NF-40HF, NF-50, and NF-70 manufactured by Film
Tec (Dow) Co., and Permasep B-9, B-10, B-15 and C-1 manufactured by Du Pont, E.I.
de Nemours.
[0028] The conductivity used herein is a value at 25°C and is measured by a commercially
available conductivity meter. As a conductivity meter, for example, CM-40S and CM-60S
manufactured by Toa Denpa Kogyo Co., Ltd. can be used.
[0029] The conductivity of the final processing solution is 0.1 mS/cm or less, preferably
from 0.001 to 0.05 mS/cm, and more preferably from 0.003 to 0.03 mS/cm.
[0030] In the second embodiment of the present invention, the calcium concentration in the
final processing solution is reduced to 5 mg/ℓ or less, preferably 3 mg/ℓ or less.
The calcium concentration may be zero.
[0031] The calcium concentration means the total calcium concentration of the calcium compounds
contained in one liter of the final processing solution and represented as the weight
of calcium.
[0032] When reducing the calcium concentration in the final processing solution, as in the
case of reducing the conductivity described above, it is also effective to reduce
the calcium concentration in the processing chemicals and/or the preparation water
thereof.
[0033] If the concentration of a calcium ion can be reduced, any of the above methods for
reducing the conductivity can be used.
[0034] Other than the above methods, a cation exchange method can be used in which a calcium
ion is exchanged with a monovalent ion such as sodium or potassium.
[0035] Examples of ion exchangers in the cation exchange method include an ion exchange
resin, an ton exchange membrane and zeolite, with an ion exchange resin being most
preferred of these.
[0036] A method of exchanging a calcium ion with an Na ion using a strongly acidic or a
weakly acidic cation exchange resin as the ion exchange resin is preferred.
[0037] A method of using the cation exchange resin may be the same as the case of the above
described amphoteric ion exchange method.
[0038] A method for reducing the adhered amount of the final processing solution to 0.3
ml/m
2 or less which is remained after development processing on the surface of the silver
halide color photographic material on which the magnetic recording layer is provided
(third embodiment) is described below.
[0039] The adhered amount of the remaining final processing solution used herein is the
amount of the components of the final processing solution adhered on the film and
remained after drying, and the remaining amount of the components of the final processing
solution is expressed as the volume of the solution before drying.
[0040] The adhered amount of the remaining final processing solution can be measured by
coating the surface of the film other than the surface having the magnetic recording
layer after processing, extracting the components adhered on a definite area of the
surface having the magnetic recording layer into distilled water at 25°C, and determining
the concentration of the components in the water.
[0041] In general, the compound to be determined is the main component in the final processing
solution but if such a compound cannot be determined, other compounds contained in
the final processing solution may be determined. However, a compound that has a behavior
of specific adsorption or an unstable compound cannot be used for the determination.
In such a case, for the measurement of the adhered amount of the final processing
solution, a definite amount of a compound (e.g., heavy metal ion or a fluorescent
compound) is previously added in the final processing solution as a marker, and the
determination can be conducted by measuring the marker in the solution extracted from
the film after processing.
[0042] Various known methods can be used for reducing the adhered amount of the remaining
final processing solution. Specifically, a method of squeezing the solution with a
rubber blade or air, a method of wiping off the solution adhered with a water absorptive
cloth or polymer, and a method of vibrating the film in the air before drying can
be used.
[0043] When processing is carried out using a hanging type automatic processor, if a processing
solution is pooled at a hanger or a clip part supporting a film, the amount of the
solution adhered that part increases, which causes staining of the film or the reduction
of output when reading magnetic information. Therefore, the structure which does not
pool a processing solution is preferred. Specifically, the contact area of a hanger
with a film is preferably as small as possible and not to provide a closed space between
the hanger and the film.
[0044] Further, when a film is turned up and processed, if the film is dried with keeping
in contact each other in the vicinity of the lower ends, the amount of the solution
adhered that part also increases. Accordingly, the structure in which the clips attached
to the lower ends of the film keep a distance between the films is preferred.
[0045] The adhered amount of the final processing solution which is remained after development
processing on the surface of the silver halide color photographic material on which
the magnetic recording layer is provided is preferably from 0 to 0.2 ml/m
2, particularly preferably from 0 to 0.1 ml/m
2.
[0046] When the final processing solution has the effect of stabilizing images, the solution
is called a stabilizing solution and solutions other than that are called a rinsing
solution.
[0047] The stabilizing solution and the rinsing solution are explained below.
[0048] The stabilizing solution contains image stabilizers, for example, formaldehyde, benzaldehydes
such as m-hydroxybenzaldehyde, bisulfite addition products of formaldehyde, hexamethylenetetramine
and derivatives thereof, hexahydrotriazine and derivatives thereof, dimethylolurea,
N-methylol compounds such as N-methylolpyrazole, organic acids and pH buffers. The
preferred amount added of these compounds is from 0.001 to 0.02 mol per liter of the
stabilizing solution, and the lower the concentration of the free formaldehyde in
the stabilizing solution, the less is the splashing of the formaldehyde gas, which
is preferred. From these points, m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolazoles
such as N-methylolpyrazole disclosed in JP-A-4-270344, and azolylmethylamines such
as N,N'-bis(1,2,4-triazol-1-ylmethyl)piperazine, etc., disclosed in JP-A-4-313753
are preferred as dye image stabilizers. In particular, a combined use of azoles such
as 1,2,4-triazole disclosed in JP-A-4-359249 (corresponding to EP-A-519190) with azolylmethylamine
such as 1,4-bis(1,2,4-triazol-1-ylmethyl)-piperazine, and derivatives thereof is preferred
because the high image stability can be obtained thereby and also which generates
low vapor pressure of the formaldehyde. Further, it is preferred to include various
compounds in the stabilizing solution, if necessary, for example, ammonium compounds
such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al,
a whitening agent, a hardening agent, alkanolamine disclosed in U.S. Patent 4,786,583,
and preservatives which can be generally included in fixing solutions and bleach-fixing
solutions, e.g., sulfinic acid compounds as disclosed in JP-A-1-231051. These compounds
each is generally added in an amount of from 0.01 to 1 g/ℓ, preferably from 0.05 to
0.5 g/ℓ.
[0049] The rinsing solution and the stabilizing solution can contain various surfactants
to prevent the generation of water marks during drying of the processed photographic
materials. Nonionic surfactants are preferably used, and ethylene oxide addition product
of alkylphenol is particularly preferred. Octyl-, nonyl-, dodecyl-, and dinonylphenol
are preferred as the alkylphenol and the addition mol number of the ethylene oxide
is preferably from 8 to 14. Further, it is preferred to use silicone surfactants which
have the high defoaming ability. The surfactant is generally added in an amount of
from 0.001 to 5 g/ℓ, preferably from 0.05 to 0.5 g/ℓ.
[0050] The rinsing solution and the stabilizing solution are preferred to contain various
kinds of chelating agents. Preferred examples of the chelating agents include aminopolycarboxylic
acid, e.g., ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid,
organic phosphonic acid, e.g., 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N'-trimethylenephosphonic
acid, diethylenetriamine-N,N,N',N'-tetramethylenephosphonic acid, and a hydrolysis
product of a maleic anhydride polymer disclosed in EP-A-345172, and the like. The
chelating agent is generally added in an amount of from 0.001 to 5 g/ℓ, preferably
from 0.01 to 0.5 g/ℓ.
[0051] The rinsing solution and the stabilizing solution are preferred to contain 1,2-benzisothiazolin-3-one
from not only stabilization of the processing solution but also capable of obtaining
the effect of preventing the reduction of the magnetic output after processing. The
amount added of this compound is from 0.01 to 0.5 mg, preferably from 0.03 to 0.3
mg, per liter of the processing solution.
[0052] The overflow generated by the replenishment of the above described rinsing solution
and/or stabilizing solution can be reused in other steps such as a desilvering step,
etc.
[0053] A processing method preferably used in the present invention is explained below.
[0054] The processing method may generally be effected by conducting a developing process,
a desilvering process, and a finishing process, in this order.
[0055] The developing process may comprise color developing, or in a reversal process, black-and-white
developing followed by color developing, and optionally a stopping process. The black-and-white
developing may comprise a reversing process (such as reversal exposure and a reversal
bath), a washing process, and a rinsing process.
[0056] The desilvering process may comprise a process, in which a material is processed
with a solution having bleaching ability such as a bleaching solution and a bleach-fixing
solution, and a process, in which a material is processed with a solution having a
fixing ability, such as a fixing solution and a bleach-fixing solution. In the present
invention, both the processes are conducted or only a bleach-fixing process is conducted.
[0057] After the desilvering process, a finishing process such as washing, rinsing or stabilizing
is conducted. Any combination of them may be employed, and in general, washing or
rinsing is conducted and stabilizing is then conducted.
[0058] The material thus processed by the above processes is then dried by a drying process.
[0059] The present invention can be applied to various silver halide color photographic
materials such as color papers coated with a silver chlorobromide emulsion and a silver
bromide emulsion, color autopositive paper, color negative films coated with a silver
iodobromide emulsion, color reversal films and color reversal papers, and in particular,
color negative films are preferred. Among these, color negative films having a magnetic
recording layer on the back surface of the support (opposite surface to the emulsion
layer) are preferred.
[0060] A photographic material having a magnetic recording layer is described below.
[0061] A magnetic recording layer is a layer coated on a support with a water-soluble or
organic solvent based coating solution comprising magnetic grains dispersed in a binder.
Examples of the magnetic grains for use in the present invention include ferromagnetic
iron oxide such as γ-Fe
2O
3, Co-coated γ-Fe
2O
3, Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic
metal, ferromagnetic alloy, hexagonal system Ba ferrite, Sr ferrite, Pb ferrite, and
Ca ferrite. Co-coated ferromagnetic iron oxide such as Co-coated γ-Fe
2O
3 is preferred of them.
[0062] The shape of the grain may be any of an acicular shape, a granular shape, a spherical
shape, a cubic shape, or a plate-like shape. The specific surface area (S
BET) is preferably 20 m
2/g or more, and particularly preferably 30 m
2/g or more. The saturation magnetization (σ
s) of the ferromagnetic substance is preferably from 3.0 × 10
4 to 3.0 × 10
5 A/m and particularly preferably from 4.0 × 10
4 to 2.5 × 10
5 A/m. The ferromagnetic grains may be surface treated with silica and/or alumina or
organic materials. Further, the surface of the magnetic grains may be treated with
a silane coupling agent or a titanium coupling agent as disclosed in JP-A-6-161032.
In addition, the magnetic grains the surfaces of which are covered with inorganic
or organic substance as disclosed in JP-A-4-259911 and JP-A-5-81652 can also be used.
[0063] The binders which can be used for the magnetic grains includes the thermoplastic
resins, thermosetting resins, radiation hardening resins, reactive type resins, acid-,
alkali- or bio-degradable polymers, natural polymers (e.g., cellulose derivatives,
sugar derivatives), and mixtures thereof disclosed in JP-A-4-219569. The above described
resins have a glass transition temperature Tg of from -40°C to 300°C, and a weight
average molecular weight of from 2,000 to 1,000,000. Examples of such binders include
vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate,
cellulose acetate propionate, cellulose acetate butyrate and cellulose tripropionate,
acrylic resins, and polyvinyl acetal resins. Gelatin is also preferably used. Cellulose
diacetate and cellulose triacetate are particularly preferred. The binder can be hardening
treated by adding an epoxy, aziridine or isocyanate crosslinking agent. Examples of
the isocyanate crosslinking agents include isocyanates such as tolylenediisocyanate,
4,4'-diphenylmethanediisocyanate, hexamethylenediisocyanate and xylylenediisocyanate,
reaction products of these isocyanates with polyalcohols (e.g., a reaction product
of 3 mol of tolylenediisocyanate with 1 mol of trimethylolpropane), and polyisocyanate
formed by condensation of these isocyanates, and they are disclosed, e.g., in JP-A-6-59357.
[0064] The above magnetic substances are dispersed in a binder preferably using, as disclosed
in JP-A-6-35092, a kneader, a pin type mill, and an annular type mill, and the combined
use thereof is also preferred. The dispersants disclosed in JP-A-5-88283 and other
known dispersants can be used.
[0065] The thickness of a magnetic recording layer is from 0.1 µm to 10 µm, preferably from
0.2 µm to 5 µm, and more preferably from 0.3 µm to 3 µm. The weight ratio of the magnetic
grains to the binder is preferably from 0.5/100 to 60/100, and more preferably from
1/100 to 30/100. The coating amount of the magnetic grains is from 0.005 to 3 g/m
2, preferably from 0.01 to 2 g/m
2, and more preferably from 0.02 to 0.5 g/m
2.
[0066] The magnetic recording layer for use in the present invention can be provided on
the back surface of the photographic support entirely or in the form of stripes by
coating or printing. Coating of the magnetic recording layer can be carried out by
means of air doctor coating, blade coating, air knife coating, squeeze coating, impregnation
coating, reverse-roll coating, transfer-roll coating, gravure coating, kiss coating,
cast coating, spray coating, dip coating, bar coating, or extrusion coating, and the
coating solution disclosed in JP-A-5-341436 is preferably used.
[0067] A magnetic recording layer may be provided with functions of lubrication improvement,
curling adjustment, antistatic property, adhesion prevention and head abrasion, or
another functional layer having these functions may be provided. At least one kind
or more of the grains of non-spherical inorganic grains having Mohs' hardness of 5
or more are preferably used as abrasives. The composition of the non-spherical inorganic
grain is preferably oxide such as aluminum oxide, chromium oxide, silicon dioxide,
titanium dioxide, etc., carbide such as silicon carbide and titanium carbide, silicon
carbide, etc., and diamond in the form of powder. The surface of these abrasives may
be treated with a silane coupling agent or a titanium coupling agent. These grains
may be added to a magnetic recording layer, or may be overcoated on a magnetic recording
layer (e.g., a protective layer, a lubricating layer). The above described binders
can be used at this time, the same binders as the binder of the magnetic recording
layer are preferably used. Photographic materials having a magnetic recording layer
are disclosed, e.g. , in U.S. Patents 5,336,589, 5,250,404, 5,229,259, 5,215,874 and
European Patent 466130.
[0068] Photographic materials which are processed by the method of the present invention
are preferably photographic materials for photographing, and the support therefor
is preferably a polyester support, details of which are disclosed in Kokai-Giho, Kogi
No. 94-6023 (Hatsumei-Kyokai, March 15, 1994).
[0069] The polyester for use in the present invention comprises diol and aromatic dicarboxylic
acid as essential components. Examples of the aromatic dicarboxylic acids include
2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic
acid, and phthalic acid. Examples of the diols include diethylene glycol, triethylene
glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polyester
include homopolymers such as polyethylene terephthalate, polyethylene naphthalate,
polycyclohexanedimethanol terephthalate and the like. Particularly preferred is a
polyester comprising from 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid.
Particularly preferred above all is polyethylene 2,6-naphthalate. The average molecular
weight of the polyester used in the present invention is generally about 5,000 to
200,000. Tg of the polyester is generally 50°C or more, and preferably 90°C or more.
[0070] The polyester support may be heat treated at 40°C or more and less than Tg, more
preferably at a temperature lower than Tg by 20°C or more and less than Tg, for the
purpose of being reluctant to get curling habit. The heat treatment may be carried
out at constant temperature within this range or may be carried out with cooling.
The heat treatment time is from 0.1 hours to 1,500 hours, preferably from 0.5 hours
to 200 hours. The heat treatment of the support may be carried out in a rolled state
or may be carried out in a web state while transporting.
[0071] The surface of the support may be provided with unevenness (e.g., coating conductive
inorganic fine grains such as SnO
2 or Sb
2O
5) to improve the surface state. Further, it is desired to contrive so as to prevent
transfer of a cut end shape of the rolled support at the core part by providing knurling
at the side edge part and making only the side edge part a little high. The heat treatment
may be carried out at any stage of after formation of the support, after the surface
treatment, after coating of a backing layer (an antistatic agent, a lubricating agent,
etc.), or after undercoating, but preferably conducted after coating of an antistatic
agent.
[0072] An ultraviolet absorbing agent may be incorporated into the polyester support. Further,
light piping can be prevented by incorporating the commercially available dye or pigment
for polyester such as Diaresin manufactured by Mitsubishi Kasei Corp. or Kayaset manufactured
by Nippon Kayaku Co., Ltd. into the support.
[0073] To ensure adhesion of the support and the constitutional layers of the photographic
material for use in the present invention, the surface activation treatment is preferably
carried out, such as a chemical treatment, a mechanical treatment, a corona discharge
treatment, a flame treatment, an ultraviolet treatment, a high frequency treatment,
a glow discharge treatment, an active plasma treatment, a laser treatment, a mixed
acid treatment, and an ozone oxidation treatment, and preferred of these surface treatments
are an ultraviolet irradiation treatment, a flame treatment, a corona discharge treatment,
and a glow discharge treatment.
[0074] An undercoat layer may be a single layer or may be two or more layers. The binder
for an undercoat layer include copolymers with monomers selected from vinyl chloride,
vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid and
maleic anhydride being starting materials, as well as polyethyleneimine, an epoxy
resin, grafted gelatin, nitrocellulose and gelatin. Compounds which swell the support
include resorcin and p-chlorophenol. A gelatin hardening agent for an undercoat layer
include chromium salt (chrome alum), aldehydes (formaldehyde, glutaraldehyde), isocyanates,
active halide compounds (2,4-dichloro-6-hydroxy-s-triazine), epichlorohydrin resins,
and active vinyl sulfone compounds. SiO
2, TiO
2, inorganic fine grains or polymethyl methacrylate copolymer fine grains (0.01 to
10 µm) may be contained as a matting agent.
[0075] Further, antistatic agents are preferably used in the photographic material of the
present invention. Examples of such antistatic agents include polymers containing
carboxylic acid, carboxylate and sulfonate, cationic polymers, and ionic surfactant
compounds.
[0076] The most preferred antistatic agents are fine grains of a crystalline metal oxide
of at least one selected from ZnO, TiO
2, SnO
2, Al
2O
3, In
2O
3, SiO
2, MgO, BaO, MoO
3 and V
2O
5 having a volume resistivity of 10
7Ω·cm or less, more preferably 10
5Ω·cm or less and having a grain size of from 0.001 to 1.0 µm or fine grains of composite
oxides of them (Sb, P, B, In, S, Si, C), and fine grains of a metal oxide in the form
of sol or fine grains of composite oxides of them. The addition amount to the photographic
material is preferably from 5 to 500 mg/m
2 and particularly preferably from 10 to 350 mg/m
2. The ratio of the crystalline oxides or composite oxides thereof to the binder is
preferably from 1/300 to 100/1, and more preferably from 1/100 to 100/5.
[0077] It is preferred for the photographic material of the present invention to have a
lubricating property. The lubricating agent-containing layer is preferably provided
on both of a light-sensitive layer side and a backing layer side. Preferred lubricating
property is a dynamic friction coefficient of from 0.01 to 0.25. Measurement of the
lubricating property is conducted using a stainless steel ball having a diameter of
5 mm at a transporting speed of 60 cm/min (25°C, 60% RH). In this evaluation, when
the opposite material is replaced with the light-sensitive layer surface, almost the
same level of value can be obtained.
[0078] Examples of the lubricating agent which can be used in the present invention include
polyorganosiloxane, higher fatty acid amide, higher fatty acid metal salt, esters
of higher fatty acid and higher alcohol. Examples of the polyorganosiloxane which
can be used in the present invention include polydimethylsiloxane, polydiethylsiloxane,
polystyrylmethylsiloxane, and polymethylphenylsiloxane. The layer to be added is preferably
the outermost layer of emulsion layers or a backing layer. Polydimethylsiloxane or
esters having a long chain alkyl group are particularly preferred.
[0079] Further, the photographic material of the present invention preferably contains a
matting agent. The matting agent may be added to either of an emulsion layer side
or a backing layer side but it is particularly preferably to be added to the outermost
layer of emulsion layers. The matting agent may be either soluble or insoluble in
the processing solution, preferably both types are used in combination. For example,
polymethyl methacrylate, copolymer of methyl methacrylate and methacrylic acid (methyl
methacrylate/methacrylic acid = 9/1 or 5/5 by mol), and polystyrene grains are preferably
used. The average grain size is preferably from 0.8 to 10 µm, and grain size distribution
is preferably narrow, preferably 90% or more of the entire grain number accounts for
from 0.9 to 1.1 times of the average grain size.
[0080] For increasing the matting property, fine grains having a grain size of 0.8 µm or
less are preferably added at the same time. For example, polymethyl methacrylate (0.2
µm), copolymer of methyl methacrylate and methacrylic acid (methyl methacrylate/methacrylic
acid = 9/1 by mol) (0.3 µm), polystyrene grains (0.25 µm), and colloidal silica (0.03
µm) are enumerated.
[0081] The film patrone preferably used in the present invention is described below. The
main material of the patrone for use in the present invention may be metal or synthetic
plastics. Preferred are plastic materials such as polystyrene, polyethylene, polypropylene,
polyphenyl ether, etc.
[0082] Further, the patrone of the present invention may contain various antistatic agents,
and carbon black, metal oxide grains, nonionic, anionic, cationic and betaine based
surfactants or polymers can preferably be used. Such a patrone static prevented is
disclosed in JP-A-1-312537 and JP-A-1-312538. In particular, those having the resistivity
of 10
12Ω or less at 25°C, 25% RH are preferred. Usually, a plastic patrone is produced using
plastics including carbon black or a pigment to impart light shielding. The size of
the patrone may be 135 size of the present as it is, or for a compact size camera,
it is effective that the diameter of the patrone of 25 mm of the present 135 size
may be decreased to 22 mm or less. The capacity of the case of the patrone is 30 cm
3 or less and preferably 25 cm
3 or less. The weight of the plastics used for the patrone and patrone case is preferably
from 5 g to 15 g.
[0083] Further, the patrone may be a type of sending out the film by revolving a spool.
Further, it may be the structure such that the tip of the film is encased in the body
of the patrone and the tip of the film is sent to outside through the port of the
patrone by revolving the axle of the spool in the feeding direction of the film. These
are disclosed in U.S. Patents 4,834,306 and 5,226,613.
[0084] The photographic material after development processing can be encased again in a
patrone. In this case, the patrone to be used may be the same patrone as used before
processing or may be different one.
[0085] The processing solution and the processing method of the present invention are described
further in detail below.
[0086] The compounds disclosed in JP-4-121739, page 9, right upper column, line 1 to page
11, left lower column, line 4 can be used in the color developing solution of the
present invention. In particular, when carrying out rapid processing with the color
developing time being reduced to 2 min 30 sec or less, 2-methyl-4-(N-ethyl-N-(2-hydroxyethyl)amino)aniline,
2-methyl-4-(N-ethyl-N-(3-hydroxypropyl)amino)aniline, and 2-methyl-4-(N-ethyl-N-(4-hydroxybutyl)amino)aniline
are preferably used as a color developing agent.
[0087] These color developing agents are contained in a color developing solution preferably
in an amount of from 0.01 to 0.08 mol/ℓ, more preferably from 0.015 to 0.06 mol/ℓ,
and still more preferably from 0.02 to 0.05 mol/ℓ. In the replenisher of a color developing
solution, from 1.1 to 3 times of these amounts are preferably used.
[0088] In the present invention, hydroxylamine is preferably not contained in a color developing
solution, and N,N-bis(2-sulfoethyl)hydroxylamine is particularly preferably used in
place of hydroxylamine. N,N-bis(2-sulfoethyl)hydroxylamine is preferably added in
the form of an alkali metal salt of sodium, potassium and lithium, and the addition
amount is from 0.001 to 0.1 mol, preferably from 0.01 to 0.05 mol, per liter of the
color developing solution.
[0089] The concentration of sulfite in a color developing solution is preferably from 0.01
to 0.05 mol/ℓ, and the concentration in the replenisher is preferably from 1.3 to
3 times of these amounts.
[0090] The pH of a color developing solution is preferably from 10 to 10.5, and that of
the replenisher is preferably from 10.2 to 10.7.
[0091] Known pH buffers such as carbonate, phosphate, sulfosalicylate, and borate are used
for the adjustment of pH as well as alkali hydroxide such as potassium hydroxide,
sodium hydroxide, and lithium hydroxide. Carbonate is particularly preferred as a
pH buffer.
[0092] The replenishment rate of a color developing solution is preferably from 80 to 1,300
ml per m
2 of the photographic material but, the less, the better, from the viewpoint of the
reduction of environmental pollution, and is generally from 80 to 600 ml, preferably
from 80 to 400 ml.
[0093] The concentration of bromide ion in a color developing solution is generally from
0.01 to 0.06 mol/ℓ but for purposes of preventing the generation of fog and improving
the discrimination while maintaining sensitivity and, further, improving graininess,
it is also preferred to set the concentration from 0.015 to 0.03 mol/ℓ. When the concentration
of bromide ion is defined in such a range, the concentration of bromide ion in the
replenisher can be obtained from the following equation, however, when C is minus,
bromide ion is preferably not contained in the replenisher.
- C:
- The concentration of bromide ion in the replenisher of a color developing solution
(mol/ℓ)
- A:
- The concentration of bromide ion in an objective color developing solution (mol/ℓ)
- W:
- The amount of bromide ion dissolved out from a photographic material into a color
developing solution when m2 of a photographic material is color developed (mol)
- V:
- The replenishment rate of the color developing replenisher per m2 of the photographic material (ℓ)
[0094] The bromide necessary for preparing the above described color developing solution
or color developing replenisher is contained in the color developing solution of the
present invention. Accordingly, bromide may be contained in the color developing solution
of the present invention or may not be contained at all.
[0095] Moreover, when the replenishment rate is reduced or bromide ion is set in a high
concentration, as a method of increasing sensitivity, pyrazolidones such as 1-phenyl-3-pyrazolidone
and 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone, thioether compounds such as
3,6-dithia-1,8-octanediol, sodium thiosulfate and potassium thiosulfate are preferably
used as a development accelerator.
[0096] In the present invention, it is preferred to apply the compounds and the processing
conditions disclosed in JP-A-4-125558, page 4, left lower column, line 16 to page
7, left lower column, line 6 to the processing solution having a bleaching ability.
A bleaching agent having an oxidation reduction potential of 150 mV or more is preferred,
and specific examples thereof disclosed in JP-A-5-72694 and JP-A-5-173312 are preferably
used in the present invention, in particular, 1,3-diaminopropanetetraacetic acid and
the ferric complex salt of the compounds in specific example 1, page 7 of JP-A-5-173312
are preferred.
[0097] In addition, for improving the biodegradability of a bleaching agent, it is preferred
to use the ferric complex salt of the compounds disclosed in JP-A-4-251845, JP-A-4-268552,
EP-A-588289, EP-A-591934, and JP-A-6-208213 as a bleaching agent. The concentration
of these bleaching agents in the processing solution having a bleaching ability is
preferably from 0.05 to 0.3 mol/ℓ, and for reducing the discharge amount to the environment,
the concentration from 0.1 to 0.15 mol/ℓ is preferred. When the solution having a
bleaching ability is a bleaching solution, the amount of bromide is preferably from
0.2 to 1 mol/ℓ, and particularly preferably from 0.3 to 0.8 mol/ℓ.
[0098] The replenisher of the solution having a bleaching ability contains fundamentally
the concentration of each component calculated by the following equation. According
to this, the concentration in the mother solution can be maintained constant.
- CR:
- The concentration of the component in the replenisher
- CT:
- The concentration of the component in the mother solution (processing tank solution)
- CP:
- The concentration of the component consumed during processing
- V1:
- The replenishment rate of the replenisher having a bleaching ability per m2 of the photographic material (ml)
- V2:
- The amount of carryover from the previous tank by a photographic material of m2 (ml)
[0099] In addition, a bleaching solution preferably contains a pH buffer, in particular,
a comparatively odorless dicarboxylic acid such as succinic acid, maleic acid, malonic
acid, glutaric acid, and adipic acid are preferred. It is also preferred to use the
known bleaching accelerators disclosed in JP-A-53-95630,
Research Disclosure (RD), No. 17129, and U.S. Patent 3,893,858.
[0100] A bleaching solution is preferably replenished with a bleaching replenisher in an
amount of from 50 to 1,000 ml per m
2 of the photographic material, more preferably from 80 to 500 ml and most preferably
from 100 to 300 ml. Further, a bleaching solution is preferably conducted aeration.
[0101] The compounds and the processing conditions disclosed in JP-A-4-125558, page 7, left
lower column, line 10 to page 8, right lower column, line 19 can be applied to the
processing solution having a fixing ability.
[0102] In particular, for improving fixing speed and preservability, the compounds represented
by formulae (I) and (II) disclosed in JP-A-6-301169 are preferably added to the processing
solution having a fixing ability alone or in combination. Further, the use of the
sulfinic acid disclosed in JP-A-1-224762 as well as p-toluenesulfinate is preferred
for improving preservability. In the solution having a bleaching ability and the solution
having a fixing ability, ammonium is preferably used as a cation for improving a desilvering
ability but taking the reduction of the environmental pollution into consideration,
ammonium is preferably reduced or, if possible, zero.
[0103] In bleaching, bleach-fixing and fixing processes, it is particularly preferred to
carry out the jet stirring disclosed in JP-A-1-309059.
[0104] The replenishment rate of the replenisher in bleach-fixing process or fixing process
is from 100 to 1,000 ml, preferably from 150 to 700 ml, and particularly preferably
from 200 to 600 ml, per m
2 of the photographic material.
[0105] It is preferred to recover silver by installing various silver recovery devices by
in-line and off-line systems in bleach-fixing and fixing processes. Using an in-line
system, processing can be carried out with a reduced concentration of silver in a
solution, as a result, the replenishment rate can be reduced. Further, it is preferred
to recover silver by an off-line system and reuse the solution after silver recovery
as a replenisher.
[0106] Bleach-fixing process and fixing process may comprise a plurality of processing tanks
and it is preferred to adopt a multistage countercurrent system with each tank being
arranged in cascade piping. From the balance with the size of a processor, in general,
two-tank cascade structure is effective and the proportion of the processing time
in the preceding tank and the succeeding tank is preferably from 0.5/1 to 1/0.5, particularly
preferably from 0.8/1 to 1/0.8.
[0107] From the viewpoint of improving preservability, it is preferred that a free chelating
agent not in the form of a metal complex is contained in a bleach-fixing solution
or a fixing solution, and the biodegradable chelating agent described above with respect
to the bleaching solution is preferably used as such a chelating agent.
[0108] In the processing of the present invention, it is particularly preferred to conduct
the compensation of evaporation disclosed in Kokai-Giho, Kogi No. 94-4992 (Hatsumei-Kyokai).
In particular, the method of compensation based on the informations of the temperature
and humidity of the atmosphere where the processor is installed according to formula-1
on page 2 of the above literature is preferred. The water to be used for the compensation
of evaporation is preferably drawn from the replenisher tank of water washing, and
in this case deionized water is preferably used as the water washing replenisher.
[0109] The film processor disclosed in the above Kokai Giho, page 3, right column, lines
22 to 28 is preferably used in the present invention.
[0110] Preferred processing agents, automatic processors, and specific examples of the evaporation
compensation method for carrying out the present invention are disclosed in the above
Kokai Giho, page 5, right column, line 11 to page 7, right column to the last line.
[0111] The photographic materials disclosed in JP-A-4-125558, page 14, left upper column,
first line to page 18, left lower column, line 11 are preferably used in the present
invention. In particular, silver iodobromide emulsions having an average silver iodide
content of from 3 to 20 mol% is preferably used as a silver halide emulsion, and tabular
grains having an aspect ratio of 5 or more and double structure grains the interior
and exterior parts of which have different halogen compositions are preferred. Further,
the interior and exterior of the grains may comprise a clear layered structure. The
aspect ratio is preferably from 5 to 20 and more preferably from 6 to 12.
[0112] The monodisperse emulsions disclosed in U.S. patents 3,574,628 and 3,655,394 are
also preferred.
[0113] The photographic material for use in the present invention preferably has a layer
containing light-insensitive fine grain silver halide of the average grain size of
from 0.02 to 0.2 µm. The fine grain silver halide is preferably silver bromide containing
from 0.5 to 10 mol% of silver iodide.
[0114] Additives which can be used in the photographic material of the present invention
are disclosed in the following table.
|
Type of Additives |
RD 17643 |
RD 18716 |
RD 307105 |
1. |
Chemical Sensitizers |
page 23 |
page 648, right column |
page 866 |
2. |
Sensitivity Increasing Agents |
― |
page 648, right column |
― |
3. |
Spectral Sensitizers and Supersensitizers |
pages 23-24 |
page 648, right column to page 649, right column |
pages 866-868 |
4. |
Whitening Agents |
page 24 |
page 647, right column |
page 868 |
5. |
Light Absorbing Agents, Filter Dyes, and Ultraviolet Absorbing Agents |
pages 25-26 |
page 649, right column to page 650, left column |
page 873 |
6. |
Binders |
page 26 |
page 651, left column |
pages 873-874 |
7. |
Plasticizers and Lubricants |
page 27 |
page 650, right column |
page 876 |
8. |
Coating Aids and Surfactants |
pages 26-27 |
page 650, right column |
pages 875-876 |
9. |
Antistatic Agents |
page 27 |
page 650, right column |
pages 876-877 |
10. |
Matting Agents |
― |
― |
pages 878-879 |
[0115] Various dye-forming couplers can be used in the photographic material of the present
invention, and the following couplers are particularly preferred.
Yellow Couplers:
[0116] The couplers represented by formulae (I) and (II) disclosed in EP-A-502424; the couplers
represented by formulae (1) and (2) disclosed in EP-A-513496 (in particular, Y-28
on page 18); the couplers represented by formula (I) disclosed in claim 1 of EP-A-568037;
the couplers represented by formula (I), column 1, lines 45 to 55 of U.S. Patent 5,066,576;
the couplers represented by formula (I), column 0008 of JP-A-4-274425; the couplers
disclosed in claim 1 on page 40 of EP-A-498381 (in particular, D-35 on page 18); the
couplers represented by formula (Y) on page 4 of EP-A-447969 (in particular, Y-1 (page
17) and Y-54 (page 41)); and the couplers represented by formulae (II) to (IV), column
7, lines 36 to 58 of U.S. Patent 4,476,219 (in particular, II-17 and II-19 (column
17), and II-24 (column 19)).
Magenta Couplers:
[0117] L-57 (page 11, right lower column), L-68 (page 12, right lower column), and L-77
(page 13, right lower column) of JP-A-3-39737; [A-4]-63 (page 134), and [A-4]-73 to
[A-4]-75 (page 139) of EP 456257; M-4 to M-6 (page 26) and M-7 (page 27) of EP 486965;
M-45 (page 19) of EP-A-571959; (M-1) (page 6) of JP-A-5-204106; and M-22, column 0237
of JP-A-4-362631.
Cyan Couplers:
[0118] CX-1, -3, -4, -5, -11, -12, -14 and -15 (pages 14 to 16) of JP-A-4-204843; C-7 and
-10 (page 35), -34 and -35 (page 37), and (I-1) and (I-17) (pages 42 and 43) of JP-A-4-43345;
and the couplers represented by formula (Ia) or (Ib) disclosed in claim 1 of JP-A-6-67385.
Polymer Couplers:
[0119] P-1 and P-5 (page 11) of JP-A-2-44345.
[0120] The couplers disclosed in U.S. Patent 4,366,237, British Patent 2,125,570, EP-B-96873
and German Patent 3,234,533 are preferred as couplers the colored dyes of which have
an appropriate diffusibility.
[0121] Examples of preferred couplers for correcting the unnecessary absorption of colored
dyes include the yellow colored cyan couplers represented by formulae (CI), (CII),
(CIII) and (CIV) disclosed on page 5 of EP-A-456257 (in particular, YC-86 on page
84); the yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), and EX-7
(page 251) disclosed in EP-A-456257; the magenta colored cyan couplers CC-9 (column
8) and CC-13 (column 10) disclosed in U.S. Patent 4,833,069; the coupler (2) (column
8) of U.S. Patent 4,837,136; and the colorless masking couplers represented by formula
(A) disclosed in claim 1 of WO 92/11575 (in particular, the compounds disclosed on
pages 36 to 45).
[0122] Known materials such as Permalloy or Sendust can be used for the magnetic head having
the function of reading magnetic informations of the film after processing, in particular,
Sendust is preferred.
[0123] Further, for preventing the reduction of output due to the stains adhered to the
magnetic head, it is preferred that before the part of the film which contacts with
the magnetic head (track) passes through the magnetic head, the stains adhered to
the film are removed by making the film contact with a different head or analogues.
[0124] The present invention will be illustrated in more detail with reference to examples
below, but these are not to be construed as limiting the present invention.
EXAMPLE 1
1) Support
[0125] The support which was used in the present invention was prepared as follows.
[0126] 100 weight parts of polyethylene-2,6-naphthalate polymer and 2 weight parts of Tinuvin
P. 326 (product of Ciba Geigy), as an ultraviolet absorbing agent, were dried, then
melted at 300°C, subsequently, extruded through a T-type die, and stretched 3.3 times
in a lengthwise direction at 140°C and then 3.3 times in a width direction at 130°C,
and further thermal fixed for 6 seconds at 250°C and a polyethylene naphthalate (PEN)
film having the thickness of 90 µm was obtained. Further, appropriate amounts of blue
dyes, magenta dyes and yellow dyes were added to this PEN film (I-1, I-4, I-6, I-24,
I-26, I-27 and II-5 disclosed in Kokai-Giho, Kogi No. 94-6023). Further, the film
was wound on to a stainless steel spool having a diameter of 20 cm and provided heat
history at 110°C for 48 hours to obtain a support reluctant to get curling habit.
2) Coating of Undercoat Layer
[0127] After both surfaces of the above support were subjected to corona discharge, UV discharge
and glow discharge treatments, an undercoat solution having the following composition
was coated on each side of the support (10 cc/m
2, using a bar coater): 0.1 g/m
2 of gelatin, 0.01 g/m
2 of sodium α-sulfo-di-2-ethylhexylsuccinate, 0.04 g/m
2 of salicylic acid, 0.2 g/m
2 of p-chlorophenol, 0.012 g/m
2 of (CH
2=CHSO
2CH
2CH
2NHCO)
2CH
2, and 0.02 g/m
2 of polyamideepichlorohydrin polycondensation product. The undercoat layer was provided
on the hotter side at the time of stretching. Drying was conducted at 115°C for 6
min (the temperature of the roller and transporting device of the drying zone was
115°C).
3) Coating of Backing Layer
[0128] On one side of the above support after undercoat layer coating, an antistatic layer,
a magnetic recording layer and a lubricating layer having the following compositions
were coated as backing layers.
3-1) Coating of Antistatic Layer
[0129] 0.2 g/m
2 of a dispersion of fine grain powder of a stannic oxide-antimony oxide composite
having the average grain size of 0.005 µm and specific resistance of 5 Ω·cm (the grain
size of secondary agglomerate: about 0.08 µm), 0.05 g/m
2 of gelatin, 0.02 g/m
2 of (CH
2=CHSO
2CH
2CH
2NHCO)
2CH
2, 0.005 g/m
2 of polyoxyethylene-p-nonylphenol (polymerization degree: 10) and resorcin were coated.
The electric resistance at 25°C, 10% RH was 10
8.1.
3-2) Coating of Magnetic Recording Layer
[0130] 0.06 g/m
2 of cobalt-γ-iron oxide which was coating-treated with 3-polyoxyethylene-propyloxytrimethoxysilane
(polymerization degree: 15) (15 wt%) (specific surface area: 43 m
2/g, major axis: 0.14 µm, minor axis: 0.03 µm, saturation magnetization: 89 emu/g,
Fe
+2/Fe
+3 is 6/94, the surface was surface-treated with 2 wt%, respectively, based on the iron
oxide, of aluminum oxide and silicon oxide), 1.2 g/m
2 of diacetyl cellulose (dispersion of the iron oxide was carried out using an open
kneader and a sand mill), 0.3 g/m
2 of C
2H
5C(CH
2OCONH-C
6H
13(CH
3)NCO)
3 as a hardening agent, with acetone, methyl ethyl ketone and cyclohexanone as solvents,
were coated with a bar coater to obtain a magnetic recording layer having the film
thickness of 1.2 µm. As matting agents, silica grains (0.3 µm) and an aluminum oxide
abrasive (0.15 µm) coating-treated with 3-poly(polymerization degree: 15)oxyethylene-propyloxytrimethoxysilane
(15 wt%) were added each in an amount of 10 mg/m
2. Drying was conducted at 115°C for 6 minutes (the temperature of the roller and transporting
device of the drying zone was 115°C). The increase of the color density of D
B of the magnetic recording layer by X-light (a blue filter) was about 0.1, and saturation
magnetization moment of the magnetic recording layer was 4.2 emu/g, coercive force
was 7.3 × 10
4A/m, and rectangular ratio was 65%.
3-3) Preparation of Lubricating Layer
[0131] Diacetyl cellulose (25 mg/m
2), and a mixture of C
6H
13CH(OH)C
10H
20COOC
40H
81 (Compound a, 6 mg/m
2)/C
50H
101O(CH
2CH
2O)
16H (Compound b, 9 mg/m
2) were coated. This mixture of Compound a/Compound b was dissolved in xylene/propylene
monomethyl ether (1/1, volume ratio) by heating at 105°C, and poured into propylene
monomethyl ether (10 times amount) at room temperature and dispersed, and further
dispersed in acetone (average grain size: 0.01 µm), then added to the coating solution.
4) Coating of Light-Sensitive Layer
[0132] Each layer having the following composition was multilayer coated on the opposite
side of the above obtained backing layer and a color negative film was prepared as
Sample No. 101.
Composition of Light-Sensitive Layer
[0133] The main components for use in each layer are classified as follows:
- ExC:
- Cyan Coupler
- ExM:
- Magenta Coupler
- ExY:
- Yellow Coupler
- ExS:
- Sensitizing Dye
- UV:
- Ultraviolet Absorbing Agent
- HBS:
- High Boiling Point Organic Solvent
- H:
- Hardening Agent for Gelatin
[0134] The numeral corresponding to each component indicates the coated weight in unit of
g/m
2, and the coated weight of silver halide is shown as the calculated weight of silver.
Further, in the case of a sensitizing dye, the coated weight is indicated in unit
of mol per mol of silver halide in the same layer.
First Layer: Antihalation Layer |
Black Colloidal Silver |
0.09 as silver |
Gelatin |
1.60 |
ExM-1 |
0.12 |
ExF-1 |
2.0 × 10-3 |
Solid Dispersion Dye ExF-2 |
0.030 |
Solid Dispersion Dye ExF-3 |
0.040 |
HBS-1 |
0.15 |
HBS-2 |
0.02 |
Second Layer: Interlayer |
Silver Iodobromide Emulsion M |
0.065 as silver |
ExC-2 |
0.04 |
Polyethyl Acrylate Latex |
0.20 |
Gelatin |
1.04 |
Third Layer: Low Sensitivity Red-Sensitive Emulsion Layer |
Silver Iodobromide Emulsion A |
0.25 as silver |
Silver Iodobromide Emulsion B |
0.25 as silver |
ExS-1 |
6.9 × 10-5 |
ExS-2 |
1.8 × 10-5 |
ExS-3 |
3.1 × 10-4 |
ExC-1 |
0.17 |
ExC-3 |
0.030 |
ExC-4 |
0.10 |
ExC-5 |
0.020 |
ExC-6 |
0.010 |
Cpd-2 |
0.025 |
HBS-1 |
0.10 |
Gelatin |
0.87 |
Fourth Layer: Middle Sensitivity Red-Sensitive Emulsion Layer |
Silver Iodobromide Emulsion C |
0.70 as silver |
ExS-1 |
3.5 × 10-4 |
ExS-2 |
1.6 × 10-5 |
ExS-3 |
5.1 × 10-4 |
ExC-1 |
0.13 |
ExC-2 |
0.060 |
ExC-3 |
0.0070 |
ExC-4 |
0.090 |
ExC-5 |
0.015 |
ExC-6 |
0.0070 |
Cpd-2 |
0.023 |
HBS-1 |
0.10 |
Gelatin |
0.75 |
Fifth Layer: High Sensitivity Red-Sensitive Emulsion Layer |
Silver Iodobromide Emulsion D |
1.40 as silver |
ExS-1 |
2.4 × 10-4 |
ExS-2 |
1.0 × 10-4 |
ExS-3 |
3.4 × 10-4 |
ExC-1 |
0.10 |
ExC-3 |
0.045 |
ExC-6 |
0.020 |
ExC-7 |
0.010 |
Cpd-2 |
0.050 |
HBS-1 |
0.22 |
HBS-2 |
0.050 |
Gelatin |
1.10 |
Sixth Layer: Interlayer |
Cpd-1 |
0.090 |
Solid Dispersion Dye ExF-4 |
0.030 |
HBS-1 |
0.050 |
Polyethyl Acrylate Latex |
0.15 |
Gelatin |
1.10 |
Seventh Layer: Low Sensitivity Green-Sensitive Emulsion Layer |
Silver Iodobromide Emulsion E |
0.15 as silver |
Silver Iodobromide Emulsion F |
0.10 as silver |
Silver Iodobromide Emulsion G |
0.10 as silver |
ExS-4 |
3.0 × 10-5 |
ExS-5 |
2.1 × 10-4 |
ExS-6 |
8.0 × 10-4 |
ExM-2 |
0.33 |
ExM-3 |
0.086 |
ExY-1 |
0.015 |
HBS-1 |
0.30 |
HBS-3 |
0.010 |
Gelatin |
0.73 |
Eighth Layer: Middle Sensitivity Green-Sensitive Emulsion Layer |
Silver Iodobromide Emulsion H |
0.80 as silver |
ExS-4 |
3.2 × 10-5 |
ExS-5 |
2.2 × 10-4 |
ExS-6 |
8.4 × 10-4 |
ExC-8 |
0.010 |
ExM-2 |
0.10 |
ExM-3 |
0.025 |
ExY-1 |
0.018 |
ExY-4 |
0.010 |
ExY-5 |
0.040 |
HBS-1 |
0.13 |
HBS-3 |
4.0 × 10-3 |
Gelatin |
0.80 |
Ninth Layer: High Sensitivity Green-Sensitive Emulsion Layer |
Silver Iodobromide Emulsion I |
1.25 as silver |
ExS-4 |
3.7 × 10-5 |
ExS-5 |
8.1 × 10-5 |
ExS-6 |
3.2 × 10-4 |
ExC-1 |
0.010 |
ExM-1 |
0.020 |
ExM-4 |
0.025 |
ExM-5 |
0.040 |
Cpd-3 |
0.040 |
HBS-1 |
0.25 |
Polyethyl Acrylate Latex |
0.15 |
Gelatin |
1.33 |
Tenth Layer: Yellow Filter Layer |
Yellow Colloidal Silver |
0.015 as silver |
Cpd-1 |
0.16 |
Solid Dispersion Dye ExF-5 |
0.060 |
Solid Dispersion Dye ExF-6 |
0.060 |
Oil-Soluble Dye ExF-7 |
0.010 |
HBS-1 |
0.60 |
Gelatin |
0.60 |
Eleventh Layer: Low Sensitivity Blue-Sensitive Emulsion Layer |
Silver Iodobromide Emulsion J |
0.09 as silver |
Silver Iodobromide Emulsion K |
0.09 as silver |
ExS-7 |
8.6 × 10-4 |
ExC-8 |
7.0 × 10-3 |
ExY-1 |
0.050 |
ExY-2 |
0.22 |
ExY-3 |
0.50 |
ExY-4 |
0.020 |
Cpd-2 |
0.10 |
Cpd-3 |
4.0 × 10-3 |
HBS-1 |
0.28 |
Gelatin |
1.20 |
Twelfth Layer: High Sensitivity Blue-Sensitive Emulsion Layer |
Silver Iodobromide Emulsion L |
1.00 as silver |
ExS-7 |
4.0 × 10-4 |
ExY-2 |
0.10 |
ExY-3 |
0.10 |
ExY-4 |
0.010 |
Cpd-2 |
0.10 |
Cpd-3 |
1.0 × 10-3 |
HBS-1 |
0.070 |
Gelatin |
0.70 |
Thirteenth Layer: First Protective Layer |
UV-1 |
0.19 |
UV-2 |
0.075 |
Acid-Processed Gelatin (Ca 150 ppm) |
0.70 |
Fourteenth Layer: Second Protective Layer |
Lime-Processed Gelatin (Ca 1,900 ppm) |
0.048 |
Polymethyl Methacrylate (average grain size: 2.3 µm, 95% or more of grains account
for between 2.1 to 2.5 µm) |
0.05 |
Poly(methyl Methacrylate/Methyl Acrylate = 55/45 in mol ratio) (average grain size:
2.3 µm, 95% or more of the grains account for between 2.1 to 2.4 µm) |
0.07 |
Polymethyl Methacrylate (average grain size: 0.2 µm, 95% or more of grains account
for between 0.10 to 0.30 µm) |
0.22 |
Polydimethylsiloxane (viscosity: 100 cp (25°C)) |
0.12 |
Stearic Acid Cetyl Ester (dispersed to 0.1 µm with sodium dodecylbenzenesulfonate) |
0.03 |
Colloidal Silver (average grain size: 0.05 µm) |
0.01 |
[0135] Further, W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salt, lead salt, gold salt, platinum
salt, palladium salt, iridium salt and rhodium salt were appropriately included in
each layer to improve storage stability, processing properties, pressure resistance,
fungicidal and biocidal properties, antistatic properties and coating properties.
TABLE 1
Emulsion |
Average AgI Content (%) |
Variation Coefficient of the AgI Content among Grains (%) |
Average Grain Size Corresponding to Sphere (µm) |
Variation Coefficient of the Grain Size (%) |
Projected Area Diameter Corresponding to Circle (µm) |
Diameter/Thickness Ratio |
A |
1.7 |
10 |
0.46 |
15 |
0.56 |
5.5 |
B |
3.5 |
15 |
0.57 |
20 |
0.78 |
4.0 |
C |
8.9 |
25 |
0.66 |
25 |
0.87 |
5.8 |
D |
8.9 |
18 |
0.84 |
26 |
1.03 |
3.7 |
E |
1.7 |
10 |
0.46 |
15 |
0.56 |
5.5 |
F |
3.5 |
15 |
0.57 |
20 |
0.78 |
4.0 |
G |
8.8 |
25 |
0.61 |
23 |
0.77 |
4.4 |
H |
8.8 |
25 |
0.61 |
23 |
0.77 |
4.4 |
I |
8.9 |
18 |
0.84 |
26 |
1.03 |
3.7 |
J |
1.7 |
10 |
0.46 |
15 |
0.50 |
4.2 |
K |
8.8 |
18 |
0.64 |
23 |
0.85 |
5.2 |
L |
14.0 |
25 |
1.28 |
26 |
1.46 |
3.5 |
M |
1.0 |
― |
0.07 |
15 |
― |
1 |
[0136] In Table 1:
(1) Emulsions J, K and L were reduction sensitized during preparation of the grains
using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.
(2) Emulsions A to I were gold, sulfur, and selenium sensitized, respectively, in
the presence of the spectral sensitizing dyes which are described at each light-sensitive
layer and sodium thiocyanate according to the examples of JP-A-3-237450.
(3) Low molecular weight gelatin was used in the preparation of the tabular grains
according to the examples of JP-A-1-158426.
(4) In tabular grains, there were observed such dislocation lines as disclosed in
JP-A-3-237450 using a high pressure electron microscope.
(5) Emulsion L comprised double structure grains containing an internal high iodide
core as disclosed in JP-A-60-143331.
Preparation of Dispersion of Organic Solid Dispersion Dye
[0137] ExF-2 shown below was dispersed according to the following method. 21.7 ml of water,
3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonate,
and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization
degree: 10) were put in a pot mill having a capacity of 700 ml, and 5.0 g of Dye ExF-2
and 500 ml of zirconium oxide beads (diameter: 1 mm) were added thereto and the content
was dispersed for 2 hours. The vibrating ball mill which was used was BO type ball
mill manufactured by Chuo Koki. The content was taken out after dispersion and added
to 8 g of a 12.5% aqueous solution of gelatin and the beads were removed by filtration
and the gelatin dispersion of the dye was obtained. The average grain size of fine
grains of the dye was 0.44 µm.
[0139] The thus prepared photographic material was cut to a size of 24 mm in width and 160
cm in length, and two perforations of 2 mm square at an interval of 5.8 mm were provided
0.7 mm inside from one side of the width direction in the length direction of the
photographic material. The sample provided with this set of two perforations at intervals
of 32 mm was prepared and encased in the plastic film cartridge explained in FIG.
1 to FIG. 7 in U.S. Patent 5,296,887.
[0140] This sample was charged in a camera and photographed standard subjects with the optimal
exposure. Subsequently, digital saturation recording of recording wavelength of 50
µm was conducted from the side of the support having the magnetic recording layer
using an audio type magnetic recording head made of Permalloy with head gap of 5 µm,
the number of turns of 50 at a feed rate of 100 mm/sec.
[0141] One hundred and two sheets of the samples thus written with magnetic informations
were continuously processed using the following described automatic processor with
each stabilizing or rinsing solution.
[0142] Processing was carried out using a pendant type automatic processor H4-220S type
manufactured by Noritsu Koki Co., Ltd. The center part of the film was hung on a hanger
with the emulsion surface outside and clips were attached at both ends of the film.
The hanger supported the near sides of the film edges so as not to touch the image
part, and so that the processing solution did not stay at this part. A plastic pole
was fixed between clips of both ends to make an interval of 10 cm to prevent the film
from touching each other.
Processing Step
[0143]
Step |
Processing Time |
Processing Temperature (°C) |
Replenishment Rate* (ml) |
Color Development |
3 min 15 sec |
38 |
400 |
Bleaching |
6 min 30 sec |
38 |
130 |
Washing (1) |
2 min 10 sec |
24 |
countercurrent system from (2) to (1) |
Washing (2) |
2 min 10 sec |
24 |
1,200 |
Fixing |
6 min 30 sec |
38 |
400 |
Washing (3) |
2 min 10 sec |
24 |
countercurrent system from (4) to (3) |
Washing (4) |
2 min 10 sec |
24 |
1,200 |
Stabilization |
1 min 5 sec |
38 |
400 |
Drying |
22 min 20 sec |
45 |
|
* Replenishment rate: per m2 of the photographic material |
[0144] The composition of each processing solution is described below.
Color Developing Solution
[0145]
|
Tank Solution (g) |
Replenisher (g) |
Diethylenetriaminepentaacetic Acid |
3.0 |
3.0 |
Disodium Catechol-3,5-disulfonate |
0.3 |
0.3 |
Sodium Sulfite |
3.9 |
5.5 |
Potassium Carbonate |
39.0 |
39.0 |
Disodium N,N-Bis(2-sulfonatoethyl)hydroxylamine |
8.0 |
10.0 |
Potassium Bromide |
1.3 |
― |
Potassium Iodide |
1.3 mg |
― |
4-Hydroxy-6-methyl-1,3,3a,7-tetraazaindene |
0.05 |
― |
2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline Sulfate |
4.5 |
6.8 |
Water to make |
1.0 ℓ |
1.0 ℓ |
pH (adjusted with potassium hydroxide and sulfuric acid) |
10.05 |
10.23 |
Bleaching Solution
[0146]
|
Tank Solution (g) |
Replenisher (g) |
N-(2-Carboxyphenyl)iminodiacetato Ferrate Pentahydrate |
25.0 |
35.0 |
1,3-Diaminopropanetetraacetic Acid |
2.0 |
3.0 |
Ammonium 1,3-Diaminopropanetetraacetato Ferrate Dihydrate |
25.0 |
35.0 |
Succinic Acid |
60.0 |
85.0 |
Malonic Acid |
7.0 |
10.0 |
Glutaric Acid |
15.0 |
20.0 |
Sodium Bromide |
40.0 |
60.0 |
Sodium Nitrate |
30.0 |
50.0 |
Sodium Hydroxide |
30.0 |
45.0 |
Diethanolamine |
20.0 |
― |
Water to make |
1.0 ℓ |
1.0 ℓ |
pH (adjusted with sodium hydroxide and nitric acid) |
4.2 |
3.8 |
Fixing Solution
[0147]
|
Tank Solution (g) |
Replenisher (g) |
1,3-Diaminopropanetetraacetic Acid |
6.0 |
7.0 |
Ammonium Sulfite |
20.0 |
22.0 |
An Aqueous Solution of Ammonium Thiosulfate (750 g/ℓ) |
270.0 ml |
300.0 ml |
Acetic Acid (90%) |
5.0 |
5.0 |
Water to make |
1.0 ℓ |
1.0 ℓ |
pH (adjusted with aqueous ammonia and acetic acid) |
6.4 |
6.3 |
[0148] The replenisher was in common with the tank solution in stabilizing process and the
following solution was used. When the processing solution does not have the effect
of image stabilization, the rinsing solution is used (unit: gram).
Stabilizing Solution A
[0149]
Polyoxyethylene-p-monononylphenyl Ether (average polymerization degree: 10) |
0.2 |
1,2,4-Triazole |
0.6 |
1,4-Bis(1,2,4-triazol-1-ylmethyl)-piperazine |
0.40 |
1,2-Benzisothiazolin-3-one |
0.10 |
Water to make |
1.0 ℓ |
Rinsing Solution A
[0150]
Polyoxyethylene-p-monononylphenyl Ether (average polymerization degree: 10) |
0.2 |
Water to make |
1.0 ℓ |
Rinsing Solution B
[0152] With respect to each processing solution in stabilizing process, Sample Nos. 4, 6
and 8 were processed with tap water, Sample Nos. 1, 5 and 7 with the following described
amphoteric ion exchange water, Nos. 2 and 3 with the mixed water of amphoteric ion
exchange water and tap water, and No. 9 with the cation exchange water shown below.
Amphoteric Ion Exchange Water
[0153] Tap water was passed through a mixed bed column packed with an H-type strongly acidic
cation exchange resin (Amberlite IR-120B of Rohm & Haas) and an OH-type strongly basic
anion exchange resin (Amberlite IR-400 of Rohm & Haas) and treated so as to reduce
the calcium concentration to 3 mg/ℓ.
Cation Ion Exchange Water
[0154] Tap water was passed through a mixed bed column packed with an Na-type strongly acidic
cation exchange resin (Amberlite IR-120B of Rohm & Haas) and treated so as to reduce
the calcium concentration to 1 mg/ℓ.
[0155] The above photographic materials after processing were measured for the output signal
level of the isolated reproduction wave using a magnetic reproducing head made of
Sendust with head gap of 2.5 µm, the number of turns of 2,000.
[0156] The same magnetic reproducing heads were arranged in series with the intervals of
5 cm and measurement was conducted using the rear head.
[0157] From the above results, the average output level of the first photographic material
was taken as 100, and the average output of the 100th based on the first output was
represented by percentage and shown in Table 1 (magnetic output).
[0158] Further, 101st photographic material after processing was allowed to stand for 5
hours in a room of 20°C, 50% RH with the emulsion surface down, then the length in
the width direction at the center of the film was measured using calipers. In the
case of the film curls, the length is less than 24 mm (curling characteristics).
Criteria of evaluation:
[0159]
- AA:
- 24.0 mm (no curling)
- A:
- 23.8 mm or more
- B:
- 23.5 mm or more and less than 23.8 mm
- C:
- less than 23.5 mm
[0160] The results are also shown in Table 1.
[0161] The adhered amount of each of the final processing solution of the backing layer
side of the 102nd photographic material was measured, all were 1.0 ml/m
2 or more.
[0162] The measured value was obtained by extracting 1,2-benzisothiazolin-3-one adhered
on the backing layer side with distilled water and determined through a liquid chromatography.
[0163] The conductivity of each final processing solution was the value at 25°C measured
with a conductivity meter CM-60S manufactured by Toa Denpa Kogyo Co., Ltd. Further,
the concentration of calcium in the final processing solution was measured according
to the atomic absorption method.
TABLE 2
No. |
Processing Solution in Stabilizing Process |
Conductivity in Final Bath (mS/cm) |
Concentration of Calcium in Final Bath (mg/ℓ) |
Magnetic Output (%) |
Curling Characteristics |
Remarks |
1 |
Stabilizing Solution A |
0.03 |
3 |
98 |
A |
Invention |
2 |
" |
0.05 |
5 |
92 |
A |
Invention |
3 |
" |
0.1 |
8 |
88 |
A |
Invention |
4 |
" |
0.3 |
30 |
30 |
C |
Comparison |
5 |
Rinsing Solution A |
0.01 |
3 |
97 |
B |
Invention |
6 |
" |
0.28 |
30 |
60 |
C |
Comparison |
7 |
Rinsing Solution B |
0.01 |
3 |
95 |
B |
Invention |
8 |
" |
0.28 |
30 |
50 |
C |
Comparison |
9 |
Stabilizing Solution A |
0.3 |
1 |
79 |
A |
Invention |
[0164] As is shown in Table 2, in the processing using comparative final processing solutions,
as Nos. 4, 6 and 8, when reading of the magnetic recording informations of 100 sheets
were conducted continuously, the output of the 100th film was largely reduced.
[0165] On the contrary, in the processing using processing solutions of the present invention,
70% or more of the magnetic recording informations have been secured, and the lower
the conductivity or the lower the calcium concentration, the better was the results
obtained. Further, with respect to curling characteristics, excellent results were
obtained when using the final processing solutions of the present invention.
[0166] After 102 sheets of the above films were processed in each processing, color negative
films 160S manufactured by Fuji Photo Film Co., Ltd. which were exposed with white
light so as to obtain magenta density of 1.5 were processed. The films after processing
were preserved under 60°C, 60% RH conditions for three days, then magenta density
was measured. Nos. 5 to 8 were all discolored to 1.3 or less but densities of Nos.
1 to 4 and No. 9 were all 1.45 or more and image stabilizing effect was sufficient.
EXAMPLE 2
[0167] In processing of No. 4 of Example 1, after coming out from the final processing solution
and before entering drying section, films were subjected to treatment of reducing
the adhered amount of solution on the back surface by blowing dry air (Nos. 11 to
13). In processing of No. 3 of Example 1, the same procedures as in Nos. 11 to 13
were conducted (Nos. 14 to 16). Control of the adhered amount of solution was conducted
by changing the blowing time of dry air.
[0168] Evaluation was carried out in the same manner as in Example 1. As shown in Table
3, magnetic output and curling characteristics were improved by reducing the adhered
amount of the final processing solution. Particularly, extremely superior results
were obtained if the conductivity of the final processing solution was 0.1 mS/cm or
less.
TABLE 3
No. |
Adhered Amount of Final Processing Solution (ml/m2) |
Magnetic Output (%) |
Curling Characteristics |
Remarks |
11 |
0.1 |
93 |
A |
Invention |
12 |
0.2 |
88 |
A |
Invention |
13 |
0.3 |
74 |
B |
Invention |
4 |
1.0 |
30 |
C |
Comparison |
14 |
0.1 |
100 |
AA |
Invention |
15 |
0.2 |
99 |
AA |
Invention |
16 |
0.3 |
97 |
A |
Invention |
3 |
1.0 |
88 |
A |
Invention |
EXAMPLE 3
[0169] The following processing was carried out with samples' prepared in Example 1.
[0170] Each processing was conducted using an automatic processor FP-560B manufactured by
Fuji Photo Film Co., Ltd. according to the following. The processor was modified such
that all of the overflow from the bleaching bath was introduced to the waste solution
tank not to the next bath. FP-560B is loaded with the evaporation compensation means
disclosed in Kokai Giho No. 94-4992, Hatsumei Kyokai.
[0171] The processing step and the composition of each processing solution are shown below.
Processing Step
[0172]
Step |
Processing Time |
Processing Temperature (°C) |
Replenishment Rate* (ml) |
Tank Capacity (liter) |
Color Development |
3 min 5 sec |
37.8 |
400 |
17.2 |
Bleaching |
50 sec |
38.0 |
130 |
5 |
Fixing (1) |
50 sec |
38.0 |
― |
5 |
Fixing (2) |
50 sec |
38.0 |
200 |
5 |
Washing |
30 sec |
38.0 |
400 |
3.5 |
Stabilization (1) |
20 sec |
38.0 |
― |
3 |
Stabilization (2) |
20 sec |
38.0 |
380 |
3 |
Drying |
1 min 30 sec |
60 |
|
|
* Replenishment rate: per m2 of the photographic material |
[0173] Stabilization and fixation were conducted in a countercurrent system from (2) to
(1), and the overflow from the washing tank was all introduced into the fixing tank
(2). Further, the amount of carryover of the developing solution into the bleaching
step, the amount of carryover of the bleaching solution to the fixing step, and the
amount of carryover of the fixing solution to the washing step were 2.5 ml, 2.0 ml
and 2.0 ml per 1.1 meter of 35 mm wide photographic material, respectively. Further,
the crossover time was 6 seconds in each case, and this time is included in the processing
time of the previous step.
[0174] Open areas of the above processor were 100 cm
2 with the color developing solution, 120 cm
2 with the bleaching solution and 100 cm
2 with other processing solutions.
[0175] The composition of each processing solution is described below.
Color Developing Solution
[0176]
|
Tank Solution (g) |
Replenisher (g) |
Diethylenetriaminepentaacetic Acid |
3.0 |
3.0 |
Disodium Catechol-3,5-disulfonate |
0.3 |
0.3 |
Sodium Sulfite |
3.9 |
5.5 |
Potassium Carbonate |
39.0 |
39.0 |
Preservative (shown in Table 4) |
0.03 mol |
0.03 mol |
Potassium Bromide |
1.3 |
― |
Potassium Iodide |
1.3 mg |
― |
4-Hydroxy-6-methyl-1,3,3a,7-tetraazaindene |
0.05 |
― |
2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline Sulfate |
4.5 |
6.5 |
Water to make |
1.0 ℓ |
1.0 ℓ |
pH (adjusted with potassium hydroxide and sulfuric acid) |
10.05 |
10.23 |
Bleaching Solution
[0177]
|
Tank Solution (g) |
Replenisher (g) |
Ammonium 1,3-Diaminopropanetetraacetato Ferrate Monohydrate |
113 |
170 |
Ammonium Bromide |
70 |
105 |
Ammonium Nitrate |
14 |
21 |
Succinic Acid |
40 |
60 |
Maleic Acid |
33 |
50 |
Water to make |
1.0 ℓ |
1.0 ℓ |
pH (adjusted with aqueous ammonia) |
4.6 |
4.0 |
Fixing (1) Tank Solution
[0178] The mixed solution of 5/95 mixture (volume ratio) of the above bleaching tank solution
and the following fixing tank solution (pH: 6.8)
Fixing (2) Tank Solution
[0179]
|
Tank Solution (g) |
Replenisher (g) |
Aqueous Ammonium Thiosulfate Solution (750 g/ℓ) |
240 ml |
727 ml |
Imidazole |
7 |
20 |
Ammonium Methanethiosulfonate |
5 |
15 |
Ammonium Methanesulfinate |
10 |
30 |
Ethylenediaminetetraacetic Acid |
13 |
39 |
Water to make |
1.0 ℓ |
1.0 ℓ |
pH (adjusted with aqueous ammonia and acetic acid) |
7.4 |
7.45 |
Washing Water
[0180] Tap water was passed through a mixed bed column packed with an H-type strongly acidic
cation exchange resin (Amberlite IR-120B of Rohm & Haas) and an OH-type strongly basic
anion exchange resin (Amberlite IR-400 of Rohm & Haas) and treated so as to reduce
the calcium ion and magnesium ion concentrations to 3 mg/ℓ or less, subsequently 20
mg/ℓ of sodium isocyanurate dichloride and 150 mg/ℓ of sodium sulfate were added thereto.
The pH of this washing water was in the range of from 6.5 to 7.5.
Stabilizing Solution
[0181] The same as No. 2 in Example 1.
[0182] Each developing solution was aged in a processor for one week while controlling the
temperature, then processing was carried out.
[0183] The processing in which the preservatives shown in Table 4 were used was evaluated
for magnetic output in the same manner as in Example 1.
TABLE 4
No. |
Preservative for Color Developing Solution |
Magnetic Output |
21 |
Disodium-N,N-bis(2-sulfonatoethyl)hydroxylamine |
98 |
22 |
Diethylhydroxylamine |
94 |
23 |
Monomethylhydroxylamine |
94 |
24 |
Hydroxylaminesulfate |
90 |
[0184] As is understood from Table 4, if hydroxylamine is used in a color developing solution,
magnetic output is deteriorated.
[0185] Further, processing was carried out in the same manner as No. 21 except for removing
1,2-benzisothiazolin-3-one from the stabilizing solution in No. 21. in Table 4 (No.
25) and evaluation of magnetic output was conducted. As a result, the magnetic output
of No. 25 was 85%, from which it was found that the reduction of the output of No.
25 was large compared with No. 21.
[0186] While the invention has been described in detail and with reference to specific examples
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.