JP2003131334A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material which ensures such satisfactory sensitivity as to cause no unevenness in density and can rapidly be processed even in a processing system in which a developing solution is replenished by a small amount and to provide a processing method for the material. SOLUTION: In the silver halide photographic sensitive material having on the base at least one silver halide emulsion layer containing photosensitive silver halide grains and at least one non-photosensitive hydrophilic colloidal layer, the amount of iodine contained in the photosensitive silver halide grains is 0-0.45 mol% on the average and a surfactant of formula (1) is contained.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a silver halide photograph.
Photosensitive material (hereinafter also referred to simply as photosensitive material) and its development process
Related to the processing method, especially reducing the replenishment amount of the developer.
Photosensitive material excellent in rapid processing suitability and its present
The present invention relates to an image processing method. [0002] 2. Description of the Related Art Photosensitive materials, especially medical X-ray films
Reducing the replenishment amount of developer in
From the viewpoint of environmental problems.
Is up. In addition, there is a strong desire for faster development processing.
It is rare. However, with conventional photosensitive materials, the replenishment amount is lowered
If rapid processing is performed, sufficient sensitivity and gradation cannot be obtained.
Furthermore, the image that should originally give a uniform density causes density unevenness.
Etc. It was not practical. Therefore, it can be processed quickly and developed.
Sufficient sensitivity even in processing systems with low liquid replenishment
The development of photosensitive materials that can be obtained has been awaited. [0003] [Problems to be solved by the present invention]
To solve various problems and achieve the following objectives:
The title. That is, the first object of the present invention is to replenish the developer.
Even with a small amount of processing system, there is no uneven density
Silver halide photographic light-sensitive material capable of obtaining high sensitivity, and its
It is to provide a development processing method. Furthermore, the present invention
The second purpose is a small amount of developer replenishment and quick processing.
Possible silver halide photographic light-sensitive material and development method thereof
Is to provide the law. [0004] [Means for Solving the Problem]
As a result of intensive studies to solve the problem,
Both have one silver halide emulsion layer and at least one insensitive layer
Silver halide photographic light-sensitive material having a light-sensitive hydrophilic colloid layer.
In the material, the iodine contained in the photosensitive silver halide grains
Use a specific surfactant at the same time
Excellent halogeno with the desired effect
Found that silver halide photographic light-sensitive materials can be provided.
<1>, <2>, <3>, <4>, <5>, <6>, <
The present invention has been completed by 7>. That is, the present invention
Is <1> A feeling of at least one layer on the support.
A silver halide emulsion layer containing light-sensitive silver halide grains;
And at least one non-photosensitive hydrophilic colloid layer
In the silver halide photographic light-sensitive material, the photosensitive halo
Average amount of iodine contained in silver halide grains is 0 mol% or more
0.45 mol% or less and represented by the following general formula (1)
Halogen characterized by containing a surfactant
It is a silver halide photographic light-sensitive material. [0006] [Chemical 2] (In the general formula (1), R is substituted or unsubstituted.
Represents a substituted alkyl group. R_afIs perfluoroalkylene
Represents a group. W represents a hydrogen atom or a fluorine atom. L_aIs
Substituted or unsubstituted alkylene group, substituted or unsubstituted
A substituted alkyleneoxy group or a divalent combination thereof
Represents a group. One of A and B represents a hydrogen atom and the other is
-L_b-SO_ThreeM is represented. M represents a cation. L_bIs
A single bond or a substituted or unsubstituted alkylene group
The ) <2> Interface represented by the general formula (1)
The activator is a surfactant represented by the following general formula (2)
The silver halide photographic feeling as described in <1>
It is a light material. [0009] [Chemical Formula 3] (In the general formula (2), R¹Is more than 6 carbon atoms
Represents a substituted or unsubstituted alkyl group. However, R¹
Is not an alkyl group substituted with a fluorine atom
Yes. R_fRepresents a perfluoroalkyl group having 6 or less carbon atoms
The X¹And X²Represents one hydrogen atom and the other is SO
_ThreeM is represented. M represents a cation. n is an integer of 1 or more
Represent. ) <3> R in the general formula (2)_fBut
It represents a perfluoroalkyl group having 2 to 4 carbon atoms.
The silver halide photographic light-sensitive material according to <2>
The <4> At least one layer of feeling on the support.
A silver halide emulsion layer containing light-sensitive silver halide grains;
And at least one non-photosensitive hydrophilic colloid layer
In the silver halide photographic light-sensitive material, the photosensitive halo
Average amount of iodine contained in silver halide grains is 0 mol% or more
0.45 mol% or less and represented by the following general formula (A)
Halogen characterized by containing a surfactant
It is a silver halide photographic light-sensitive material. [0013] [Formula 4] (In the general formula (A), R¹And R²Each
Al fluoride containing 2 or more carbon atoms and 13 or less fluorine atoms
Represents a kill group, R^ThreeAnd R^FourAre hydrogen atoms or
Represents a kill group. One of A and B is a hydrogen atom,
-L_b-SO_ThreeM represents a hydrogen atom or a cation.
Represents. L_bIs a single bond or substituted or unsubstituted
Represents a xylene group. ) <5> Interface represented by the general formula (A)
In the active agent, B is -L_b-SO_ThreeM and L
_bIs a single bond, the halo as described in <4>
A silver halide photographic light-sensitive material. <6> Interface represented by the general formula (A)
In the active agent, B is -L_b-SO_ThreeM and L
_bIs a methylene group, described in <4>
It is a silver halide photographic light-sensitive material. <7> The method according to any one of <1> to <6>
A silver halide photographic light-sensitive material having S × T ≦ 1000 (here
S is the replenishment amount of developer per 4 sheets of photosensitive material (ml
/ 4), T is the processing time of Dry to Dry
(Seconds). ) Under the conditions indicated by
This is a characteristic development processing method. [0018] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method and an implementation of the present invention.
The embodiment will be described in detail. In the present specification, “to”.
Is the lower and upper limit values that are listed before and after
Indicates the range to include. The silver halide photographic light-sensitive material of the present invention has a support.
On the support, at least one layer of photosensitive silver halide grains
Including silver halide emulsion layer and at least one non-light-sensitive layer
A hydrophilic colloid layer, and photosensitive silver halide grains
The average amount of iodine contained in the child is 0 mol% or more and 0.45
Not more than mol% and containing a specific surfactant described later.
It is characterized by having. Silver halide photographic feeling of the present invention
The light material is iodine contained in photosensitive silver halide grains.
The amount is on average from 0 mol% to 0.45 mol%, and
Replenishment amount of developer by containing a specific surfactant
Even with a low processing system, there is sufficient density uniformity
Sensitivity is obtained. In addition, the amount of developer replenishment is small,
Can be processed quickly. A specific surfactant will be described. Specific interface
As an activator (fluorine compound), the following general formula (1)
The surfactants represented, and those with 2 or more carbon atoms
Has two or more fluorinated alkyl groups with 13 or less nitrogen atoms
Less anionic and nonionic hydrophilic groups
A surfactant having either one (hereinafter simply referred to as a fluorine-based interface)
(Referred to as an activator). First, the general formula
The surfactant represented by (1) will be described. [0021] [Chemical formula 5] In the general formula (1), R is substituted or unsubstituted.
Represents an alkyl group. Substituted or unsubstituted represented by R
The alkyl group of is linear or branched.
May also have a ring structure. As the substituent
Can be any substituent, but alkenyl groups, aryls
Group, alkoxy group, halogen atom (preferably C
l), carboxylic acid ester group, carbonamido group, cal
The bamoyl group, oxycarbonyl group, phosphate ester group, etc.
preferable. R preferably has no fluorine as a substituent
An unsubstituted alkyl group is more preferable. R is carbon number
Is preferably 2 or more, more preferably 4 or more,
6 or more are more preferable. In the general formula (1), R_afIs perfluoroal
Represents a xylene group. Where a perfluoroalkylene group and
Is a group in which all hydrogen atoms of the alkylene group are substituted with fluorine.
Say. The perfluoroalkylene group is linear.
Or may be branched and have a cyclic structure.
It may be. R_afPreferably has 10 or less carbon atoms.
More preferably, it is 8 or less. In the general formula (1), W represents a hydrogen atom or a fluorine atom.
Although it represents an elemental atom, it is preferably a fluorine atom. In the general formula (1), L_aIs replaced or absent
Substituted alkylene group, substituted or unsubstituted alkylene
Lists oxy groups or divalent groups formed by combining these.
The Examples of the substituent include those similar to the substituent in R.
It is. L_aPreferably has 4 or less carbon atoms.
Further, it is preferably an unsubstituted alkylene. In general formula (1), one of A and B is hydrogen.
Atom, the other one_bOne SO_ThreeM is represented. M is Kachio
Represents Examples of the cation represented by M include al
Potassium metal ions (lithium ions, sodium ions,
Potassium ions), alkaline earth metal ions (barium)
Muon, calcium ion, etc.), ammonium ion
Etc. are preferably exemplified. Of these, more preferred
Is lithium ion, sodium ion, potassium ion
Or ammonium ion, more preferably Lithium
Um, sodium or potassium ions
The total number of carbon atoms of the surfactant represented by the general formula (1)
Select appropriately according to the degree of branching of the substituent or alkyl group
be able to. In particular, R, L_aAnd R_afTotal carbon number of
If it is 16 or more, the solubility should be lithium ion
(Especially for water) and antistatic ability or coating uniformity
Excellent in terms of L_bIs a single bond or substitution or
An unsubstituted alkylene group is represented. Substituent is substitution in R
The thing similar to group is mentioned. L_bIs an alkylene group
The number of C is preferably 2 or less, and is unsubstituted.
More preferably, it is a methylene group.
L_bIs most preferably a single bond. The surfactant represented by the general formula (1) is
R, R_af, L_a, A, and B in each preferred mode
It is more preferable to combine them together. In addition, general
As the surfactant represented by the formula (1), the following general formula
Particularly preferred is the surfactant represented by (2).
Yes. [0028] [Chemical 6] In the general formula (2), R¹Has a total carbon number of 6 or more
Represents a substituted or unsubstituted alkyl group. However, R¹Is
It is not an alkyl group substituted with a fluorine atom.
R¹The substituted or unsubstituted alkyl group represented by
Whether it is a chain or a branched chain,
You may have. Examples of the substituent include alkenyl.
Group, aryl group, alkoxy group, halogen other than fluorine
Atoms, carboxylic acid ester groups, carbonamido groups. Cal
The bamoyl group, oxycarbonyl group, phosphate ester group, etc.
Can be mentioned. In the general formula (2), R^lThe substitution represented by
Alternatively, the unsubstituted alkyl group has a total carbon number of 6 to 24.
Is preferred. Preferred is an unsubstituted alkyl group having 6 to 24 carbon atoms.
Preferred examples include n-hexyl group, n-heptyl group,
n-octyl group, tert-octyl group, 2-ethyl
Xyl, n-nonyl, 1,1,3-trimethylhexyl
Sil Tomb, n-decyl group, n-dodecyl group, cetyl group, f
Xadecyl group, 2-hexyldecyl group, octadecyl group
Group, eicosyl group, 2-octyldodecyl group, docosyl
Group, tetracosyl group, 2-decyltetradecyl group, tri
Cosyl group, cyclohexyl group, cycloheptyl group, etc.
I can get lost. In addition, the total carbon number including the carbon of the substituent is 6 to
Preferred examples of 24 substituted alkyl groups include 2-hexene.
Senyl group, oleyl group, linoleyl group, linolenyl group,
Benzyl group, β-phenethyl group, 2-methoxyethyl
Group, 4-phenylbutyl group, 4-acetoxyethyl group,
6-phenoxyhexyl group, 12-phenyldodecyl
Group, 18-phenyloctadecyl group, 12- (p-chloro
Rophenyl) dodecyl group, 2- (diphenyl phosphate) ethyl
And the like. In the general formula (2), R¹The substitution represented by
Alternatively, the unsubstituted alkyl group has a total carbon number of 6-18.
Those are more preferred. C6-C18 unsubstituted alkyl
Preferred examples of the group include n-hexyl group and cyclohexyl group.
Sil group, n-heptyl group, n-octyl group, 2-ethyl
To hexyl group, n-nonyl group, 1,1,3-trimethyl
Xyl group, n-decyl group, n-dodecyl group, cetyl group,
Hexadecyl group, 2-hexyldecyl group, octadecyl group
Group, 4-tert-butylcyclohexyl group, etc.
It is. Moreover, the total carbon number including the carbon number of a substituent is 6-18.
As a preferable example of the substituted alkyl group, phenethyl
Group, 6-phenoxyhexyl group, 12-phenyldodecyl
Group, oleyl group, linoleyl group, linolenyl group, etc.
I can get lost. Above all, R¹N-hexyl group,
Chlohexyl group, n-heptyl group, n-octyl tomb, 2
-Ethylhexyl group, n-nonyl group, 1,1,3-tri
Methylhexyl group, n-decyl group, n-dodecyl group, ce
Til, hexadecyl, 2-hexyldecyl, oct
Tadecyl group, oleyl group, linoleyl group, linolenyl group
Are preferably mentioned and are linear, cyclic or branched having 8 to 16 carbon atoms.
Particularly preferred are branched unsubstituted alkyl groups. In the general formula (2), R_fIs a carbon number of 6 or less.
-Represents a fluoroalkyl group. Where perfluoroa
An alkyl group is a fluorine-substituted all hydrogen atom in an alkyl group.
Group. Al in the perfluoroalkyl group
The kill group may be linear or branched.
Further, it may have a ring structure. R_fRepresented by
Examples of perfluoroalkyl groups include trifluoro.
Lomethyl group, pentafluoroethyl group, heptafluoro group
-N-propyl group, heptafluoroisopropyl group,
Nafluoro-n-pentyl group, undecafluoro-n-
Pentyl group, tridecafluoro-n-hexyl group, un
Examples include a decafluorocyclohexyl group. Inside
Are also perfluoroalkyl groups having 2 to 4 carbon atoms (for example,
Pentafluoroethyl group, heptafluoro-n-propiyl
Group, heptafluoroisopropyl group, nonafluoro-
n-butyl group, etc.) are preferred, and heptafluoro-n-propyl
Lopyl group and nonafluoro-n-butyl group are particularly preferred
Yes. In particular, R_fIs a C 2-4 perfluoroalkyl
It is preferable to represent a group. In the general formula (2), n represents an integer of 1 or more.
The Preferably it is an integer of 1 to 4, particularly preferably 1.
Or 2. N and R_fAs a combination of n
= 1 if R_fIs heptafluoro-n-propyl group
Or a nonafluoro-n-butyl group, and when n = 2, R
_fIs more preferably a nonafluoro-n-butyl group.
Good. In general formula (2), X^lAnd X²One is water
Elementary atom, the other is SO_ThreeM represents a cation.
Represent. Here, as the cation represented by M, for example,
Alkali metal ions (lithium ions, sodium ions
, Potassium ions, etc.), alkaline earth metal ions (
(Lium ion, calcium ion, etc.), ammonium ion
ON etc. are preferably exemplified. Especially preferred among these
Or lithium ion, sodium ion, potassium ion
Or ammonium ion. Hereinafter, the surfactant represented by the general formula (1)
Preferred specific examples of the surfactant represented by the general formula (2)
Examples are illustrated below, but the present invention is limited by the following specific examples.
There are no restrictions. In the following, for convenience
Above, X in general formula (2)^lIs SO_ThreeM and X²But
Examples of compounds that are hydrogen atoms are shown below.
X^lIs a hydrogen atom and X²Is SO_ThreeM
These compounds are also specific examples of the fluorine compound of the present invention.
Take as an example. In the structure notation of the following exemplified compounds
Unless otherwise specified, alkyl groups and perfluoroalloalkyls
The group means a straight chain structure. In addition, abbreviations in structure notation
Of these, groups with 2EH and 2BO symbols are respectively
It represents the group shown below. 2EH = 2-ethylhexyl 2BO = 2-butyllocyl [0036] [Chemical 7] [0037] [Chemical 8][0038] [Chemical 9] [0039] Embedded image[0040] Embedded image The fluorosurfactant will be described. F
The fluorine-based surfactant has 2 or more carbon atoms and fluorine atoms
Having two or more fluorinated alkyl groups having 13 or fewer, and
At least one of anionic and nonionic hydrophilic groups
This fluorosurfactant has the above-mentioned fluoride fluoride
2 or more kill groups and an anionic hydrophilic group or nonionic parent
As long as you have one of the water groups,
There may be. In the fluorosurfactant, fluorinated al
Specific examples of the kill group include, for example, —C₂F_FiveGroup, -C_Three
F₇Group, -C_FourF₉Group, -C_FiveF₁₁Group, -CH₂-C_FourF
₉Group, -C _FourF₈-H group, -C₂H_Four-C_FourF₉Group, -C_FourH₈
-C_FourF₉Group, -C₆H₁₂-C_FourF₉Group, -C₈H₁₆-C_FourF₉
Group, -C_FourH₈-C₂F_FiveGroup, -C_FourH₈-C_ThreeF₇Group, -C_Four
H₈-C_FiveF₁₁Group, -C₈H₁₆-C₂F_FiveGroup, -C₂H_Four-C_Four
F₈-H group, -C_FourH₈-C_FourF₈-H group, -C₆H₁₂-C_Four
F₈-H group, -C₆H₁₂-C₂F_Four-H group, -C₈H₁₆-C₂
F_Four-H group, -C₆H₁₂-C_FourF₈-CH_ThreeGroup, -C₂H_Four−
C_ThreeF₇Group, -C₂H_Four-C_FiveF₁₁Group, -C_FourH₈-CF (C
F_Three)₂Group, -CH₂CF_ThreeGroup, -C_FourH_Five-CH (C ₂F_Five)₂
Group, -C_FourH₈-CH (CF_Three)₂Group, -C_FourH₈-C (C
F_Three)_ThreePreferred examples include a group. In the fluorosurfactant, fluorinated al
The kill group has 13 or fewer fluorine atoms, preferably
In the range of 3-11, more preferably in the range of 5-9.
The The number of carbon atoms is 2 or more, preferably 4
-16, more preferably 5-12, still more preferably 6.
To 10. In the fluorosurfactant, fluorinated al
The kill group is preferably represented by the following general formula (FA1).
A fluorinated alkyl group. Formula (FA1) -L_a-R_af-W In general formula (FA1), L_aIs a substituted or unsubstituted
Rulylene group, substituted or unsubstituted alkyleneoxy
Represents a group or a divalent group formed by a combination thereof. Previous
As the substituent, any group may be used.
Group, aryl group, alkoxy group, halogen atom (preferably
Cl), carboxylic acid ester group, carbonamide
Group, carbamoyl group, oxycarbonyl group, phosphoric acid ester
Ter groups are preferred. L_aHas a carbon number of 8 or less.
Preferably, 4 or less is more preferable. Unsubstituted alkyl
Len is preferred. R_afIs a C1-C6 perf
Represents a fluoroalkylene group, preferably having 1 to 5 carbon atoms.
More preferably, it is a perfluorinated alkylate having 2 to 4 carbon atoms.
Group. Here, the perfluoroalkylene group is al
All hydrogen atoms of the xylene group are replaced with fluorine atoms.
An alkylene group. Perfluoroalkylene
The group may be linear or branched.
It may have an annular structure. W is hydrogen atom, fluorine
Represents an atom or an alkyl group, preferably a hydrogen atom or
A nitrogen atom, more preferably a fluorine atom. In the fluorosurfactant, anionic
The hydrophilic group is an acidic group having a pKa of 7 or less, or an
A lithium metal salt or an ammonium salt is preferred.
Specifically, sulfo group, carboxyl group, phosphonic acid
Group, carbamoylsulfamoyl group, sulfamoyls
Rufamoyl group, acylsulfamoyl group and these
Examples include salts. Of these, preferably sulfo
Group, carboxyl group, phosphonic acid group and salts thereof,
More preferred are a sulfo group and salts thereof. Salt form
The cationic species to be formed include lithium, sodium, and potassium.
Lithium, cesium, ammonium, tetramethylammo
Ni, Tetrabutylammonium, Methylpyridinium
But lithium, sodium
, Potassium and ammonium. Nonionic properties in fluorosurfactants
Examples of the hydrophilic group include a hydroxyl group and a polyalkyleneoxy group.
Of these, a polyalkyleneoxy group is preferred. Polyalkyle
Noxy group and the above anionic hydrophilic group in the same molecule
Which may sometimes have, and in the present invention a preferred structure
It is. In addition, anionic compounds and nonionic compounds
It is particularly preferable to use the product in combination for effective use. Fluorine surfactants include the following general formula
Particularly preferred is a surfactant represented by (A).
Yes. [0048] Embedded image In the general formula (A), R^lAnd R²Each
Vertically, the number of carbon atoms is 2 or more and the number of fluorine atoms is 13 or less.
Represents an alkyl group, R^ThreeAnd R^FourAre water independently
Represents a primary atom or a substituted or unsubstituted alkyl group. In the general formula (A), R¹And R²Represented by
Specific examples of alkyl halide groups include the same groups as described above.
The preferred structure is also represented by the general formula (FA1).
A fluorinated alkyl group. Also preferred in it
The structure is the same as that mentioned for the fluorinated alkyl group.
It is. In the general formula (A), R^ThreeAnd R^FourThe position represented by
A substituted or unsubstituted alkyl group may be linear or branched.
It may be a chain or may have a cyclic structure. Previous
As the substituent, any substituent may be used.
Group, aryl group, alkoxy group, halogen atom (preferably
Cl), carboxylic acid ester group, carbonamide
Group, carbamoyl group, oxycarbonyl group, phosphate ester
And the like. In general formula (A), one of A and B is hydrogen.
Atom is already -L_b-SO_ThreeM represents M
Represents Here, examples of the cation represented by M include
Eh alkali metal ions (lithium ions, sodium
Ions, potassium ions, etc.), alkaline earth metal ions
(Barium ion, calcium ion, etc.), Ammonius
Preferred examples include muon and the like. More of these
Preferably lithium ion, sodium ion, potash
Muon or ammonium ion, more preferred
Or lithium ion, sodium ion or potassium ion
The total charcoal of the surfactant represented by the general formula (A)
Appropriately depending on prime number, substituents, degree of alkyl group branching, etc.
You can choose. In general formula (A), R^l, R², R
^ThreeAnd R^FourIf the total carbon content is 16 or more,
ON to be soluble (especially for water) and antistatic
Performance and coating uniformity. L_bIs
A single bond or a substituted or unsubstituted alkylene group is represented.
Substituent is R^ThreeThose mentioned above are preferred. L_bIs alkylene
When it is a group, the C number is preferably 2 or less. Ma
L_bIs preferably a single bond, a methylene group
Most preferably. The surfactant represented by the general formula (A) is
R¹~ R^Four, A, and B
It is more preferable to combine them. Furthermore, the general formula
The surfactant represented by (A) is represented by the following general formula (B).
Particularly preferred is a surfactant. [0054] Embedded image In the general formula (B), R¹And R²Each
A fluorinated alkyl group represented by the general formula (FA1)
The preferred range is also the same. In the general formula (B), X is -L_b-SO_ThreeTable M
And L_bRepresents a methylene group or a single bond,
A ren group is preferred. M represents a cation. Where M
Examples of the cation represented include alkali metal ions.
(Lithium ion, sodium ion, potassium ion
Etc.), alkaline earth metal ions (barium ions, cal
Cium ion etc.), ammonium ion etc. are preferred examples
Indicated. Of these, lithium ion is particularly preferred.
, Sodium ion, potassium ion or ammonia
Muion. The surfactant represented by the general formula (A) is as follows.
Specific examples of (surfactant represented by formula (B)) are as follows:
The present invention is limited by the following specific examples.
It is not limited. In the structure notation of the following exemplified compounds
Unless otherwise noted, alkyl groups, perfluoroalalkyl
The ru group means a straight chain structure. [0058] Embedded image [0059] Embedded image[0060] Embedded image [0061] Embedded image[0062] Embedded image[0063] Embedded image[0064] Embedded image [0065] Embedded image[0066] Embedded image The specific surfactants described above are, for example,
For example, combining general esterification and sulfonation reactions
It can be easily synthesized. Only one specific surfactant is used.
Also, two or more of them may be used in combination. Certain surfactants are sensitive
It may be added to any layer in the optical material. Specific surfactant
For example, a photosensitive layer (emulsion layer),
Intermediate layer, surface protective layer, back layer, back surface protective layer, etc.
Even among these, it is used as a surface protective layer and a back surface protective layer.
It is particularly preferable to use them. Amount of specific surfactant used
Is 0.1 to 200 m on each of the front and back surfaces of the photosensitive material
g / m²Is preferable, and more preferably 0.5 to 5
0 mg / m²More preferably 1-30 mg / m²Range of
It is a circle. Photosensitive silver halide grains will be described.
The Photosensitive silver halide grains are silver chloride, silver chlorobromide, odor
Silver halide, silver iodobromide, silver iodochlorobromide can be used
However, as described above, the replenishment amount of the developer is reduced, and more rapid processing is performed.
From the viewpoint of rationality, yaw contained in photosensitive silver halide grains
The average amount is 0 mol% or more and 0.45 mol% or less.
This iodine amount is preferably 0.05 mol% or less on average.
0.40 mol% or less, more preferably 0.10 mol
% Or more and 0.30 mol% or less. Where photosensitive halo
The “average” of iodine contained in silver halide grains
Obtained from the halogen composition of the photosensitive silver halide grains of
Means the average iodine content. Photosensitive halogenation
The distribution of the halogen composition within the silver grains is uniform.
Even if the halogen composition changes on the step
It may be good or continuously changed. Also,
The photosensitive silver halide grains have a core / shell structure.
Photosensitive silver halide grains having them can also be used. As photosensitive silver halide grains, British special
No. 635,841, U.S. Pat. No. 3,622.
So-called halo as described in 318
Gen conversion (conversion) particles are also preferred.
It is. The halogen conversion method is usually halogen conversion.
Smaller solubility product with silver than the halogen composition of the previous grain surface
This is done by adding an aqueous halogen solution. example
For example, potassium bromide for silver chloride and silver chlorobromide tabular grains
And / or potassium iodide aqueous solution is added.
Add a potassium iodide aqueous solution to the silver bromide plate.
Version. Concentration of these added aqueous solutions
Is preferably thin, more preferably 30% or less
Is preferably 10% or less. Furthermore, halogen before halogen conversion
Conversion halo at a rate of 1 mol% or less per minute per mole of silver halide
It is preferable to add a gen solution. In addition, halogen changes
Of the sensitizing dye and / or the silver halide adsorbing substance
Some or all of them may be present, converted halogen water
Instead of solution, silver bromide, silver iodobromide, silver iodide halogen
Silver halide fine particles may be added. The size of these particles
The thickness is usually 0.2 μm or less, preferably 0. lμm or less
Below, particularly preferably 0.05 μm or less
That's right. The halogen conversion method that can be used in the present invention is described above.
The method is not limited to this method.
Can be used together. Methods for forming photosensitive silver halide grains are known in the art.
Well known in the world, for example, JP-A-2-68539.
Publication, U.S. Pat. No. 3,700,458, and
Research Disclosure 170th June 1978
By using the method described in No. 29, etc.
Can be made. The silver halide photographic light-sensitive material of the present invention has a support.
Silver halide containing photosensitive silver halide grains on the support
Emulsion layer (photosensitive layer), for example, intermediate layer, surface protective layer,
Layer, back surface protective layer, antihalation layer,
At least one non-photosensitive hydrophilic colloid such as a luter layer
Other emulsion sensitizing methods
And various additives are not particularly limited.
2-68539 and the like are preferably used.
You can. Hereinafter, the silver halide photographic light-sensitive material of the present invention
For suitable forms of emulsion sensitization and various additives
I will explain. (1) Chemical sensitization method As a chemical sensitization method
Is disclosed in JP-A-2-68539, page 10, upper right column, line 13
From the left to the bottom left column, line 16, JP-A-5-313282
And the method described in JP-A-6-110144.
Can be used. Chemical sensitization of silver halide emulsions
Specifically, the existence of a silver halide adsorbing substance
Sulfur sensitization method, selenium sensitization method, reduction sensitization method, gold sensitization
Known methods such as the
Are used in combination. Among the noble metal sensitization methods, the gold sensitization method is a typical example.
Gold compounds, mainly gold complex salts. Other than gold
Complex of noble metals such as platinum, palladium, iridium
It may contain salt. Specific examples are U.S. Pat.
No. 448,060, British Patent 618,061
It is described in the booklet. As a sulfur sensitizer, Zera
In addition to sulfur compounds contained in tin, various sulfur compounds
Products such as thiosulfates, thioureas, thiazoles,
Rhodanines and the like can be used. Specific examples are US
No. 1,574,944, No. 2,278,947
No. 2,410,689, No. 2,72
8,668 specification, 5,501,313 specification,
It is described in the specification of 8,656,955.
The As a selenium sensitizer, JP-A-6-11014.
No. 4 publication. Sulfur sensitization with thiosulfate
And, the combined use of selenium sensitization and gold sensitization is useful. Reduction increase
Sensitive agents include primary tin salts, amines, formamine dis
Rufido acid, a silane compound, or the like can be used. (2) Antifoggant and stabilizer As an antifoggant / stabilizer that can be used in the present invention
JP-A-2-68539, page 10, lower left column 17
From line 11 to page 11, upper left column, line 7 and from page 3, lower left column 2
From the line, those described in the lower left column of page 4 can be used. Specifically, azoles (for example, benzothi
Azolium salts, nitroimidazoles, nitrobenzii
Midazoles, chlorobenzimidazoles, chromobe
Benzimidazoles, nitroindazoles, benzoto
Lyazoles, aminotriazoles, etc.); mercap
Compounds (for example, mercaptotheazoles, mercapto
Tobendithiazoles, mercaptobenzimidazoles
, Mercaptothiadiazoles, mercaptotetrazo
, Mercaptopyrimidi, mercaptotriazi
Thiokets such as oxadrine thione
Azaindenes (eg triazaindene)
, Tetraazaindenes (especially 4-hydroxy substituted)
(1,3,3a, 7) tetraazaindenes), penta
Azaindenes); benzenethiosulfonic acid, ben
Such as zensulfinic acid, benzenesulfonic acid amide, etc.
Add compounds known as antifoggants or stabilizers
Can. In particular, JP-A-60-76743, 6
Nitron described in Japanese Patent No. 0-87322 and induction thereof
And mercapto described in JP-A-60-80839
A compound described in JP-A-57-164735
Borocyclic compounds and complex salts of heterocyclic compounds and acids (for example, 1
-Phenyl-5-mercaptotetrazole)
It can be used well. Furthermore, purines or nucleic acids, or special
JP-A-61-36213, JP-A-59-90844
It is also possible to use the polymer compounds described in
Yes. Especially, azaindenes, purines, and nucleic acids
Can be preferably used. Addition of these compounds
The amount is 0.5 to 5.0 millimoles per mole of silver halide.
And preferably 0.5 to 3.0 mmol. (3) Color tone improver As a color tone improving agent usable in the present invention, JP-A-62-2
No. 276539, page 2, lower left column, line 7 to page 10
Lower left column, line 20, and JP-A-3-94249
Listed on page 6, lower left column, line 15 to page 11, upper right column, line 19
Can be mentioned. Specifically, silver halide photographic milk
The silver halide photographic emulsion layer has a covering power of 60 or more.
And / or in other layers, maximum between 520-560 nm
Maximum between dye having absorption wavelength and 570-700nm
The dye having the absorption wavelength is transmitted through the end-exposed area after development processing.
The increase in optical density due to the concentration of dyes is 0.03 or less.
Can be included. The covering power of the silver halide photographic emulsion layer is 60 or more.
Typical emulsions to be used are tabular emulsions and fine-grain milks.
An agent etc. can be mentioned. In particular, silver halide copying
Tabular halogen in which the true emulsion has a grain thickness of 0.4 μm or less
Silver iodide grains or high iodine surface sensitivity
Between an emulsified emulsion and a fine grained emulsion
When mixed emulsion is used, the effect of color tone improvement is great. In the present invention
As a usable dye, 520 to 560 nm is preferable.
Or dyes having a maximum absorption wavelength between 530 and 555 nm.
570-700nm, preferably 580-650n
In combination with a dye having a maximum absorption wavelength during m. very
Large absorption wavelength means that the dye is present in the photosensitive material.
It means the maximum absorption wavelength. Examples of the dye used in the present invention include
Anthraquinone dyes, azo dyes, azomethine dyes,
Indian aniline dye, oxonol dye, carbocani
Dyes, styryl dyes, triphenylmethane dyes, etc.
One having a predetermined maximum wavelength is selected from among them. developing
Stability to processing, light fastness, desensitization, fog,
Considering the impact on photographic performance such as
Quinone dyes, azo dyes, azomethine dyes, and indoor
Preferred among the niline dyes are used. Like
The compounds are listed on page 3, left of JP-A-62-276539.
It is written in the upper column from the 5th line to the upper left column on the 9th page.
The Such dyes are emulsion layers and other hydrophilic colloids.
Layer (intermediate layer, protective layer, antihalation layer, filter)
Can be dispersed in various known ways.
Specifically, Japanese Patent Laid-Open No. 62-276539 No. 9
Listed on page 14 from upper left column line 14 to page 10, lower left column line 20
Has been. (4) Spectral sensitizing dye Spectral sensitizing dyes that can be used in the present invention include
No. 2-68539, page 4, lower right column, line 4
Those described in the lower right column on page 8 can be mentioned. concrete
Includes cyanine dyes, merocyanine dyes, complex
Socyanin dye, complex merocyanine dye,
Ropollananine dye, styryl dye, hemicyanine color
Element, oxonol dye, hemioxonol dye, etc.
Can be. Useful sensitizing dyes used in the present invention are
For example, US Pat. No. 3,522,052 and US Pat.
17,197 specification, 3,713,828 specification
, No. 3615,643, No. 3,615,63
No. 2, No. 3,617,293, No. 3,6
28,964 specification, 3,703,377 specification
, No. 3,666,480, No. 3,667,9
No. 60, No. 3,679,428, No. 3,
No. 672,897, No. 3,769,026
, No. 3,556,800, No. 3,615,6
No.13 current book, 3,613,638 specification, 3,
615,635 specification, 3,705,809 specification
, No. 3,632,349, No. 3,677,7
No. 65, No. 3,770,449, No. 3,
770,440 specification, 3,769,025 specification
, No. 3,745,014, No. 3,713,8
No. 26, No. 8,567,458, No. 3,
625,698 specification, 2,526,632 specification
No. 2,503,776, JP-A-48-76.
No. 525, Belgian Patent No. 691,807
It is described in. Addition amount of sensitizing dye is halogenated
0.5 mmol or more and less than 4 mmol per 1 mol of silver, good
Preferably 0.5 mmol or more and less than 1.5 mmol
Yes. Specific examples of the sensitizing dye include JP-A-2-68539.
II-1 to 5 described on pages 5 to 8
II-47 is mentioned. (5) Surfactant and antistatic agent Surfactant / antistatic agent that can be used in the present invention
For example, JP-A-2-68539, page 11, upper left column 1
From the fourth line to the upper left column on page 12
It is done. Specific examples of the surfactant include, for example, saponin.
(Steroidal), alkylene oxide derivatives (eg
Polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensate, polyethylene glycol
Alkyl ethers or polyethylene glycols
Rukyryl ethers, silicone polyethylene
Oxide compounds), sugar alkyl esters, etc.
Nonionic surfactants; alkyl sulfonates, al
Kill benzene sulfonate, alkyl naphthalene sulphate
Phonates, alkyl sulfates, N-acyl-N
-Alkyl taurines, sulfosuccinates,
Rufoalkyl polyoxyethylene alkyl phenyl agent
Anionic surfactants such as tellurides; alkyl betaines
, Amphoteric surfactants such as alkyl sulfobetaines;
Aliphatic or aromatic quaternary ammonium salts, Viridi
Cationic surface activity such as nium salts and imidazolium salts
A sex agent can be used. Of these, saponin and dodecylbenzenesulfur
Phosphonic acid sodium salt, di-2-ethylhexyl α-sulfoscoha
Sodium succinate, p-octylphenoxyethoxyethane
Sulfonate sodium salt, dodecyl sulfate sodium salt, triisopropyl
Lunaphthalenesulfonic acid Na salt, N-methyl-oleoi
Anions such as rutaurine Na salt, dodecyltrimethyl
Ammonium chloride, N-oleoyl-N ',
N ', N'-trimethylammoniodiaminopropane
Cations such as romide, dodecyl pyridium chloride
N-dodecyl-N, N-dimenal carboxy betai
N-oleyl-N, N-dimethylsulfobutyl beta
Betaine such as in, poly (average degree of polymerization n-10) Oki
Siethylene cetyl ether, poly (n = 25) oxye
Tylene p-nonylphenol ether, bis (1-poly
(N = 15) oxyethylene-oxy-2,4-di-t
-Especially preferred nonions such as benzylphenyl) ethane.
Can be used. Specific examples of the antistatic agent are disclosed in JP-A-60.
-80848, 61-121144,
Japanese Unexamined Patent Publication No. 62-172343, Japanese Unexamined Patent Publication No. 62-1734
Nonionic surfactants and alk
Metal nitrate, conductive tin oxide, zinc oxide, pentaacid iodide
Vanadium or composites doped with antimony or the like
An oxide can be preferably used. (6) Matting agent, slip agent, plasticizer Matting agent, slip agent, plasticizer that can be used in the present invention
As for the upper left column on page 12 of JP-A-2-68539.
From line 10 to the upper right column 10th line, and page 14, lower left
Examples from column 10 line to column 1 on the lower right
The Specifically, US Pat.
No. 101, No. 2701245, No. 414
As described in the specifications of Nos. 2894 and 4396706
Homopolymer or methyl of polymethyl methacrylate
Copolymer of dimethacrylate and methacrylic acid, den
Organic compounds such as Pung, silica, titanium dioxide, sulfuric acid,
Using fine particles of inorganic compounds such as strontium barium
Can. The particle size is 1.0-10μ
m, particularly 2 to 5 μm. Copy of the present invention
In the surface layer of the true photosensitive material, US Pat.
Nos. 489,576 and 4,047,958
Silicone compounds described in Japanese Patent Publication No. 56-2313
In addition to the colloidal silica described in publication No. 9, paraffin
Using wax, higher fatty acid esters, den powder derivatives, etc.
Can be. The hydrophilicity of the silver halide photographic light-sensitive material of the present invention
For the colloidal layer, trimethylolpropane, pentane
Diol, butanediol, ethylene glycol, grease
By using polyols such as serine as plasticizers
Yes. The emulsion of the silver halide photographic material of the present invention
The layer contains polymers and emulsions to improve pressure characteristics.
A plasticizer can be included. For example, British Patent No.
No. 738,618 discloses a heterocyclic compound,
No. 8,637 describes alkyl phthalate, 73
No. 8,639 describes alkyl esters, US patents
No. 2,960,404 describes polyhydric alcohols,
No. 3,121,060 discloses a carboxyl alkyl.
Cellulose is disclosed in Japanese Patent Application Laid-Open No. 49-5017.
Fin and carboxylate salt, JP-B 53-28086
The report includes methods using alkyl acrylates and organic acids.
It is disclosed that these methods can be used in the present invention.
You can. (7) Hydrophilic colloid The emulsion layer, intermediate layer and silver halide photographic light-sensitive material of the present invention.
Binders or protective rollers that can be used for the surface protective layer
As an id, it is advantageous to use gelatin, but
Other hydrophilic colloids can also be used. The present invention
As a hydrophilic colloid that can be used in
No. 2-68539, page 12, upper right column, line 11 from left
Those listed in the lower column, line 16. For example, gelatin derivatives, gelatin and other high
Such as graft polymers with molecules, albumin, casein, etc.
Protein; hydroxyethyl cellulose, carboxymethyl
Cells such as cellulose and cellulose sulfates
Loose derivatives, sodium alginate, dextran, starch
Derivatives and other sugar derivatives; polyvinyl alcohol, polyvinyl chloride
Nyl alcohol partial acetal (poly-N-vinyl pyro
Redone, polyacrylic acid, polymethacrylic acid, polyacrylic acid
Rilamide, polyvinyl imidazole, polyvinyl pyra
Various synthetic hydrophilic properties such as sol and other single or copolymers
Can be used. As gelatin
In addition to lime-treated gelatin, acid-treated gelatin and enzyme-treated gelatin
Latin may be used, as well as gelatin hydrolyzate and
Enzymatic degradation products can also be used. Among these, Zera
Dextran and poly having an average molecular weight of 100,000 or less
It is preferable to use reacrylamide in combination. JP-A-6
No. 3-68887, Japanese Patent Laid-Open No. 63-149641
The method described in the report is also effective in the present invention. (8) Hardener Photographic emulsion and non-photosensitive hydrophilic colloid used in the present invention
May contain an inorganic or organic hardener. Used in the present invention
A hardening agent that can be used is disclosed in JP-A-2-68539.
Report page 12, lower left column, line 17 to page 13, upper right column, line 6
The thing of description is mentioned. Specifically, for example, chromium
Salt (chrome alum, chromium acetate, etc.), aldehydes
(Formaldehyde, glyoxal, darthal al
Dehydride, etc.), N-methylol compound (dimethyloluria)
Elemental, methyloldimethyl and dantoin), dioxa
Derivatives (such as 2,3-dihydroxydioxane), active
Vinyl compounds (1,3,5-triacryloyl-hex
Sahydro-s-triazine, bis (vinylsulfonyl)
Methyl ether, N, N'-methylenebis- (β- (bi
Nylsulfonyl) propionamide)), active halo
Compound (2,4-dichloro-6-hydroxy-s-
Triazines), mucohalogen acids (mucochloric acid,
Mucofenoxycyclolic acid, etc.) isoxazoles, di
Aldehyde starch, 2-chloro-6-hydroxytria
Use dinylated gelatin etc. alone or in combination
Can do. Of these, JP-A-53-41221,
No. 53-57257, No. 59-162546
No. 60-80846, the active vinyl compound
And described in US Pat. No. 3,325,287.
Active halides are preferred. In the present invention, a polymer hardener is also used as the hardener.
It can be used effectively. The height used in the present invention
Examples of the hardener include dialdehyde starch and polyacrylic starch.
Rain, described in US Pat. No. 3,396,029
A polymer having an aldehyde group such as an acrolein copolymer.
Remer described in US Pat. No. 3,623,878
Polymer having epoxy group of US Pat. No. 3,36
No. 2,827, Research Disclosure Magazine
17333 (1978) and the like
Polymer having triazine group, JP-A 56-6684
Poly having active ester groups described in No. 1 publication
Mer, JP 56-142524, US Patent No.
No. 4,161,407, JP 54-65033 A
No., Research Disclosure 16725
(1978) and the like, there is an active vinyl group
Or a polymer having a group as a precursor thereof.
Have an active vinyl group or a precursor group
Among these, preferred are polymers, and among them, JP-A 56-14252.
With long spacers as described in the No. 4 publication
The active vinyl group or its precursor group is
Polymers that are attached to the polymer backbone are particularly preferred.
Yes. Hydrophilic roller in the silver halide photographic light-sensitive material of the present invention
The id layer has a swelling ratio in water of 300 with these hardeners.
% Or less, especially 230% or less.
It is preferable. (9) Support As a support used in the present invention, JP-A-2-68539 is disclosed.
Gazette page 13 upper right column line 7 to line 20
Can be mentioned. Specifically, polyethylene as the support
Terephthalate film or cellulose triacetate film
Is preferred. The support is hydrophilic and has good adhesion to the colloid layer.
To raise the surface, the surface is treated with corona discharge or
Glow discharge treatment or ultraviolet irradiation treatment is preferred.
Or styrene butadiene latex,
Provide a primer layer made of vinylidene chloride latex
It is also possible to provide a gelatin layer on top of it.
Yes. Organic solvent containing polyethylene swelling agent and gelatin
An undercoat layer using may be provided. These primer layers are on the surface
By applying the treatment, the adhesion with the hydrophilic colloid layer is further increased.
It can also be improved. (10) Crossover cut method In the present invention, the upper right of page 4 of JP-A-2-264944
From the 20th line to the upper right column on page 14
A sovercut method can be applied. Cross
-In the industry, bar light can significantly reduce sharpness.
This is a well-known fact. The crossover light of photographic photosensitive material
As a means to make it 12% or less, US patents
No. 4,130,429, JP-A 61-11635
Matches the emission wavelength of the X-ray fluorescent screen in No. 4 publication
A method to absorb light of a certain wavelength using a sensitizing dye or dye
It is shown. Further, US Pat. No. 4,800,150
The booklet contains a dye between the support and the emulsion layer in the form of a microcrystalline dispersion.
The crossover light is less than 10%
Techniques for doing this are disclosed. JP-A-63-3
No. 05345 discloses a cationic polymer latex.
The anion is a technology that fixes the dye to a specific layer using
Furthermore, JP-A-1-16631 discloses a dye fixing layer.
A technique for forming an undercoat layer of a support is disclosed. The present invention
Any of these methods can be used for the photosensitive material of
However, it is preferable that the colored layer with a dye is an undercoat layer.
Preferably, the dye is described in JP-A-1-16631.
In particular, the dyes are fixed in US Pat.
Form of fine crystal dispersion described in the specification of 803,150
It is desirable to be fixed to the undercoat layer. In the present invention
These methods can be appropriately combined.
Examples of the dye that can be preferably used in the present invention include
Kaihei 2-264944, page 4, lower left column to page 9, right
Those listed in the upper column are listed. Also as a mordant layer
Is disclosed in JP-A-2-264944, page 9, lower right column.
14 The ones listed in the upper right column can be used. (11) Dye / Mordant Examples of the dyes and mordants that can be used in the present invention include
No. 2-68539, page 13, lower left column, line 1
14th page, lower left column, line 9, and Japanese Patent Laid-Open No. 3-24537
From the lower left column on page 14 to the lower right column on page 16
Can be mentioned. Namely, the silver halide photographic light-sensitive material of the present invention
Is intended to absorb light in a specific wavelength range,
And filter layer
To control the spectral composition of light to be incident on the photographic emulsion layer
For the purpose of coloring photographic emulsion layers or other layers with dyes
May be. Both like direct medical X-ray film
For surface film, the purpose is crossover cut
A layer to be formed may be provided under the emulsion layer. Such dyes
Are described in, for example, British Patent 506,385,
No. 177,429, No. 1,311,884
, No. 1,338,799, No. 1,385,3
No. 71, No. 1,467,214, No. 1,
Nos. 433,102 and 1,553,516
, JP-A-48-85130, 49-1144.
No. 20, No. 52-117123, No. 55-1
No. 61233, No. 59-111640, Japanese Patent
Sho 39-22069, No. 43-13168
US Pat. No. 3,247,127, Q3, 4
69,985 specification, 4,078,933 specification
Has virazolone acid or barbituric acid nucleus
Oxonol dye, US Pat. No. 2,533,472
No. 3,379,533, British Patent No.
Other options described in the specification of No. 1,278,621, etc.
Xonol dye, British Patent 575,691,
680,631 specification, 599,623 specification
, No. 786,907, No. 907,125
No. 1,045,609, U.S. Pat.
No. 255,326, JP 39-2111048
Azo dyes described in JP-A-50-10011
No. 6, No. 54-118247, British Patent No.
2,014,598 specification, 750,031 specification
Azomethine dyes described in US Pat. No. 2,86.
Anthraquinone dyes described in US Pat. No. 5,752;
U.S. Pat. No. 2,538,009, 2,681
8,541 specification, 2,538,008 specification,
British Patent No. 584,609, No. 1,210,2
No. 52, JP-A-50-40625, 51
No. 3623, No. 51-10927, No. 54
-118247, JP-B 48-3286,
Ariden dyeing described in JP-A-59-37303
Fee, Japanese Patent Publication No. 28-3082, 44-16594
No. 59, No. 59-28898, etc.
Ril dyes, British Patent 446,583, ibid.
335,422, JP-A-59-228250
Triarylmethane dyes described in publications, UK patents
No. 1,075,653, No. 1,153,341
No. 1,284,730, No. 1,47
No. 5,228, No. 1,542,807, etc.
Merocyanine dyes described in US Pat. No. 2,843
3,486, 3,294,539, etc.
And cyanine dyes described in 1). When using the dye, the anionic dye is
Special characteristics in light-sensitive materials using polymers with thione sites
It is an effective technique to mordante a fixed layer. This place
In this case, the dye is irreversibly decolored in the development-fixing-water washing process.
It is preferable to use one. Has a cation site
The layer mordanting the dye using the polymer in the emulsion layer
Even on the interfacial protective layer, the opposite side to the emulsion layer and the support
Is preferably between the emulsion layer and the support, particularly
Purpose of crossover cut of double-sided medical X-ray film
For this purpose, it is ideal to mordante into the primer layer.
As a coating aid for the undercoat layer, polyethylene oxide
Nonionic surfactant has polymer with cationic sites
Can be preferably used in combination. As a polymer providing a cationic site
Is preferably an anion converting polymer. Anion conversion poly
As mers, various known quaternary ammonium salts (or
Sufonium salt) polymer can be used. Quaternary ammonium salt
(Or phosphonium salt) polymer is a mordant polymer or
In the following publications widely as antistatic agent polymers
Are known. That is, JP-A-59-166940,
US Pat. No. 3,958,995, JP 55-1
No. 42339, JP 54-1226027 A,
JP-A-54-155835, JP-A-53-303
28 and JP-A-54-92274.
Water-dispersed latex; US Pat. No. 2,548,564
No. 3,148,061, No. 3,75
Polyvinylpyridinium described in US Pat. No. 6,814
Salt; water-soluble as described in US Pat. No. 3,709,690
Quaternary ammonium salt polymer; US Pat. No. 3,898,
The water-insoluble quaternary ammonium salt described in No. 088
Rimmer and so on. But from the desired layer to another layer or
Moves into the processing solution and has an unfavorable effect on photography.
Therefore, Japanese Patent Laid-Open No. 1-166031 and Japanese Patent Laid-Open No.
No. 1-2016655, Japanese Patent Laid-Open No. 1-307738
It is desirable to apply the method described in the report. Other special
No. 16 from the left lower column of page 14 of the Kaihei 3-24537 gazette.
The techniques described in the bottom page can also be used. (12) Polyhydroxybenzenes As polyhydroxybenzenes that can be used in the present invention
From the upper left column on page 11 of JP-A-3-39948
12th page, lower left column, described in EP Patent No. 452772A
Listed. Specifically, JP-A-8-399.
No. 48, page 11, left upper column of the general formula (III)
Compound, its specific compound, page 11, lower left column of the same publication
To (III) -1 to 25 described in the lower left column of page 12.
Compound may be mentioned. These polyhydroxybenzene compounds
The amount of product added is 5 × 1 per mole of silver halide.
0^-1Less than the mole, preferably silver halide 1
L × 10 per mole^-1To 5 × 10^-3The amount of mole added
The (13) Development processing method As a method for developing a silver halide photographic material of the present invention.
For example, JP-A-2-103037, page 16, upper right column 7
From line 19, page 19, lower left column, line 15, JP-A-2-115
No. 837, page 3, lower right column, line 5 to page 6, upper column 1
0th line, and JP-A-2000-112078 No. 34
The method described on page 42, left column, line 42 to page 35, left column, line 2
Can be adopted. The present invention is for processing a photographic light-sensitive material of the present invention.
Conventionally, the silver halide photographic photosensitive for medical use
Hydroquinone used in material processing systems
Representative polyhydroxybenzene compounds and Asco
Ruvic acid or ersorbic acid (ascorbic acid
Diastereomers) and their lithium salts, sodium
Alkali metal salts such as humic salts and potassium salts are preferably used
It is done. In the present invention, super processing is carried out together with a developing agent.
It is preferable to use an auxiliary developing agent exhibiting a composition. Super
As an auxiliary developing agent showing additivity, 1-phenyl-3-
There is an auxiliary development business for pyrazolidones. 1-phenyl-3
-Pyrazolidones as auxiliary developing agents are 1-phenyl-
3-pyrazolidone, 1-phenyl-4,4-dimethyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hy
Droxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, 1-p-a
Minophenol-4,4-dimethyl-3-pyrazolide
1-p-tolyl-4,4-dimethyl-3-pyrazoli
Don, 1-p-tolyl-4-methyl-4-hydroxyme
Til-3-pyrazolidone and the like. Of the developer using these developing agents.
The pH is preferably 7 or more and less than 11, more preferably pH 8
More preferably, it is 10.5 or less. 1 developer of these
The sulfite ion concentration in the kettle is 0.01 mol or less.
The upper limit is 0.6 mol or less. In addition, the silver halide photographic light-sensitive material of the present invention.
As a method of processing Dry to Dry
The interval is preferably from 20 seconds to 200 seconds, and from 25 seconds to 1
More preferably, it is 50 seconds or less. In addition, each of development and fixing
Replenishment amount is photographic photosensitive material lm²More than 5ml per 300m
l or less is preferable, and 25 ml or more and 200 ml or less is more preferable.
Is preferred. Silver halide photographic light-sensitive material / processing of the present invention
Development process of 70 seconds or less with Dry to Dry in the system
When processing, prevent uneven development unique to rapid processing
For this reason, it is described in JP-A-63-151943
The rubber roller is a roller at the developing tank outlet.
To the application, or the time-opening of Shokai Sho 53-151944
The developer agitation in the developer tank as described in
For the discharge flow rate to be 10 m / min or more,
It is described in Japanese Patent Application No. 61-315537
Thus, at least during development processing, stir more intensely than during standby.
More preferably. Furthermore, the rapid processing as in the present invention.
For this reason, the configuration of the rollers in the fixer tank should be
Photosensitive materials that increase the speed of wearing and contain sensitizing dyes
Then, in order to speed up the elution of the dye,
More preferably. Consist of opposed rollers
Can reduce the number of rollers and reduce the processing tank.
Can be small. In other words, make your own machine more compact
It becomes possible. The developer contains a compound known as a developer component.
Can be added. For example, it is not covered with developer
An inhibitor can be used. As an antifoggant,
Indazole, benzimidazole, benzotria
Zole or mercaptoazole antifoggants
Misalignment can also be used. Specifically, 5-nitroindazo
5-p-nitrobenzoylaminoindazole, 1
-Methyl-5-nitroindazole, 6-nitroindazole
Sol, 9-methyl-5-nitroindazole, 5-ni
Trobenzimidazole, 2-isopropyl-5-nitrate
Robenzimidazole, 5-nitrobenzotriazol
4- (2-mercapto-1,3,4-thiadiazo
Ru-2-yl-thio) sodium butanesulfonate, 5
-Amino-1,3,4-thiadiazole-2-thiol
Etc. In the present invention, a fog having a nitro group
Inhibitors are particularly preferred. Among the above antifoggants
Are 5-nitroindazole, 5-nitrobenzimidazole
Sol and 5-nitrobenzotriazole are preferred,
6,5-nitroindazole is preferred from the viewpoint of safety
That's right. The amount of antifoggant used is usually per liter of developer.
0.02 to 3 mmol, preferably 0.1 to 2 mmol
It is a rimole. In the present invention, a preservative is added to the developer.
Is preferred. Preservatives include sulfites, bisulfites,
Metabisulfite, etc., specifically sodium sulfite
Sodium bisulfite, sodium metabisulfite,
Potassium sulfate, potassium bisulfite, potassium metabisulfite
And ammonium sulfite are used. In the present invention, various organic or inorganic substances are used in the developer.
Chelating agents can be used. With inorganic chelating agents
For example, sodium tetrapolyphosphate, hexametasili
Sodium acid salt or the like can be used. Organic chelate
Agents mainly include organic carboxylic acids and aminopolycarboxylic acids
Using acid, organic phosphonic acid, aminophosphonic acid
it can. Organic carboxylic acids include acrylic acid and shu
Acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Norric acid, succinic koji, atellanic acid, sebacic acid,
Nandicarbon, decanedicarboxylic acid, undecanedi
Carboxylic acid, maleic acid, itaconic acid, malic acid, que
Examples include acid and tartaric acid. Further, aminopolycarboxylic acids include i.
Minodiacetic acid, nitrilotriacetic acid, nitrilotripropion
Acid, ethylenediamine monohydroxyethyl triacetic acid,
Tylenediamine tetraacetic acid, triethylenetriamine pentaacetic acid
Acid, triethyltetramine hexaacetic acid, glycol ether
Diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1,
2-Diaminopropanetetraacetic acid, and its name
5632, 55-67747, 57-1026
Compounds described in No. 24 and JP-B 53-40900
Can be mentioned. As organic phosphonic acid, the United States
Patent Nos. 3,214,454 and 3,794,591
And West German Patent Publication No. 2,227,639, etc.
Hydroxyalkylidene diphosphonic acid and research diss
Known compounds such as closure 18170
Yes. As aminophosphonic acid, aminotris
(Methylenephosphonic acid), ethylenediaminetetramethyl
Lenphosphonic acid is known, but other research
No. 18170, Japanese Patent Laid-Open No. 57-2065
No. 54, No. 54-81125, No. 55-29
883 and 56-97347, etc.
A compound can be mentioned. Organic phosphonic carboxylic acid
For example, JP-A-52-102726 and 53-
No. 42730, No. 54-121127, No. 5
5-4024, 55-4025, 55
-126241 gazette, 55-65955 gazette, ibid.
No. 55-85956 and Research Disclosure
And the compounds described in No. 18170.
These chelating agents are alkali metal salts and ammonium salts.
It may be used in the form of Chelating agent per liter of developer
Preferably l × 10^-9~ 1x10^-1Mole, especially 1 x 10
^-Five~ 2x10^-2Used in the molar range. In addition, a hardening agent may be used for the developer.
Yes. As a hardener, dialdehyde hardener or its heavy oxide
Sulfate adducts are preferably used.
Glutaraldehyde or this bisulfite adduct
and so on. As additives used in addition to the above components
Is sodium bromide, potassium bromide, potassium iodide, etc.
Development inhibitors of ethylene glycol, diethylene glycol
, Triethylene glycol, dimethylformamide
, Methyl cellosolve, hexylene glycol, etano
Organic solvent such as methanol and methanol: 1-phenyl-5-
Mercaptotetrazole, 2-mercaptobenzimid
Mercapto series such as sodium sol-5-sulfonate
Indazole-based compounds, 5-nitroindazole, etc.
Compound, Benztria such as 5-methylbenztriazole
It may contain an antifoggant such as a sol compound, R
search Disclosure Vol. 176, N
o. 17643, Section XXI (December issue, 1978)
Development accelerators described in the above and further toning agents,
A surfactant, an antifoaming agent, a hard water softening agent, and the like may be included. In development processing, silver stains are prevented in the developer.
Agents, for example, compounds described in JP-A-56-24347
Can be used. As the developer, JP-A-56-1
Alkanolamines and the like described in Japanese Patent No. 06244
Mino compounds can be used. In addition, L. F. A
  “Photographic Processing Ke” by Mason
Mistry, published by Focal Press (1966)
Pp. 226-229, U.S. Pat. No. 2,193,015
No. 2,592,362, JP-A-48-6
Those described in Japanese Patent No. 4938 may be used. In the developer, if necessary, a buffer (for example, charcoal) is used.
Acid salt, boric acid, borate), alkali agent (eg, hydroxylated)
Products, carbonates), solubilizers (eg polyethylene glycol)
And esters thereof), pH regulators (eg acetic acid)
Organic acids), development accelerators (eg, US Pat. No. 2,648).
No. 604, No. 3171247, Shoko
Various pyrimidines described in Japanese Patent No. 44-9503
And other cationic compounds phenosafra
Cationic pigments such as nin, thallium borate and potassium nitrate
Neutral salt such as lithium, Japanese Examined Patent Publication No. 44-9304,
U.S. Pat. Nos. 2,533,990 and 2,253,183
No. 2, No. 2950970, No. 257
Polyethylene glycol described in No. 7127, etc.
Nonionic compounds such as its derivatives, polythioethers
, Japanese Patent Publication No. 44-9509, Belgian Patent No. 68
2862), other than the above
Auxiliary developing agent (eg p-aminophenol), interface
Activator, eluent silver colloid dispersant (eg mercap
Compound) and the like. These successes
The developer consists of one or more types of drug parts
Is done. That is, from several powders and / or liquids
Become. In the present invention, a water-soluble bromide salt, water-soluble
A liquid agent solution in which iodide salt and silver halide solvent are dissolved together.
You can add the necessary amount to a normal developer.
Yes. Developer is used as replenisher for automatic processor processing
In other cases, it consists of an acid and a water-soluble halide.
A development initiator may be used. This development initiator includes acid and water.
In addition to soluble halides, JP-A-57-63530
Use of the thioether compound described in 1
From the point of improving the balance between sensitivity and gradation
Yes. Development processing temperature and time are interrelated and the total processing
Although it is determined in relation to time, it is usually about 20 ° C to 50 ° C.
10 seconds to 3 minutes. The photosensitive material developed with a developer is usually
Next, a fixing process is performed. Fixer is thiosulfate and if necessary
Hardeners (water-soluble aluminum salts, etc.) and liquids (tartar)
Acid, citric acid, gluconic acid, boric acid or their salts
An aqueous solution containing a pH of about 3.8 to
7.0 (20 ° C.). In the present invention, between development and fixing.
In general, an automatic processor
The stopping step is omitted. Therefore, the developer is the fixer.
The pH of the fixing solution may rise. Obedience
Therefore, when using an aluminum compound in the fixer,
In order to keep the reactivity of the fixing solution high, the pH of the fixing solution is about 3.
It is desirable to adjust to 8-5 (20 degreeC). Fixing agents are ammonium thiosulfate and thiosulfuric acid.
Containing essential thiosulfate ions such as sodium
In terms of fixing speed, ammonium thiosulfate is particularly
preferable. The amount of fixing agent can be changed as appropriate,
0.1 to 5 mol / 1. Hardener mainly in fixer
Aqueous solution aluminum salt that acts as an acid dura
A compound known as a fixer hardener, for example
Aluminum chloride, aluminum sulfate, potash alum
There is. The amount of this compound used is usually 10^-3~ 2x10
^-1Mol / 1 (in terms of aluminum). The amount of acid or its salt used in the fixing solution is usually
0.005 mol / 1 to 0.05 mol / 1. Fixer
If necessary, preservatives (eg, durarate, bisulfite)
Salt), pH buffering agent (for example, boric acid, borate), Kiree
And the like (as described above). Fixing
The temperature and time can be changed as appropriate, but usually about 20 ° C to 50 ° C.
10 seconds to 3 minutes is preferable. The developed and fixed light-sensitive material is washed with water (or cheaply).
) And dried. Washing is a silver melted by fixing
About 20 ° C, sufficient to remove salt almost completely
It is preferably 10 seconds to 3 minutes at -50 ° C. Flushing water (or stable
The replenishment amount of the liquid is 1200 ml / m²Below (including 0)
It may be. Replenishment amount of washing water (or stabilizing solution) is 0
Means the so-called warm water washing method.
The As a method of reducing the replenishment amount, multi-stage countercurrent has been used since ancient times.
A system (for example, two stages or three stages) is known. Low replenishment amount of washing water (or stabilizing solution)
If the problem occurs when you combine the following technologies
As a result, better processing performance can be obtained. Flushing water (also
Is a stabilizing solution). T.A. “J.Im” by Kreimmn
age Tech, "Volume 10, No. 6, p.242 (1
984), Research Disclosure 20526, ibid.
Isothiazoline-based compounds described in 22845
, JP-A 61-115154, 62-209
Antibacterial agents (M
can be used as icbiocide)
The Other "Bacterial and antibacterial chemistry" by Hiroguchi Higuchi, Sankyo Publishing
(Showa 57), "Anti-bacterial control technology handbook" Japan
Japan Society for Bacteria Control, Hakuhodo (1986), L. E. We
St person “Water Quality Criteri
a "(Photo. Sci, Eng, Vol. 9, No.
6 (1965), M.M. W. Beach, “Microb
iolical Growths in Moti
on Picture Processing "(SM
PTE Journal Vol. 85, (197
6), R.I. O. “Photo Proc” by Deegan
essingWash Water Biocide
s "(J. Imaging Tech 10, No. 6)
(1984) may be used.
Good. Treat with a small amount of washing water (or stabilizing solution)
Sometimes described in JP-A-62-287252
Cleaning of squeeze rollers or crossover rollers
It is preferable to provide a tank. In addition, flush water (or stabilization
Liquid) is replenished according to the treatment.
Overflow from washing (or stabilization) bath caused by
Part or all of the flow liquid is disclosed in JP-A-60-235133.
It is described in the gazette, 63-129343 gazette
It can be used to replenish the fixer, which is the previous processing step.
You can. Further processing with a small amount of washing water (or stabilizing solution)
Water bubbles and / or squeeze
The processed component adhering to the roller is transferred to the film.
Add water-soluble surfactant and antifoaming agent to prevent
May be. In addition, stains caused by dyes eluted from the photosensitive material.
In order to prevent dyeing, JP-A-63-163456
The dye adsorbent described in 1) may be installed in a washing tank. Dry
Performed at about 40 ° C to 100 ° C for a period of time
Therefore, it will be changed as appropriate, but it should be applied from about 5 seconds to 3 minutes and 30 seconds.
Yes. The developer of the present invention is processed using an automatic processor.
It is effective in the case. In particular, the silver halide photographic light-sensitive material of the present invention.
Is S × T ≦ 1000 (where S is one piece of photosensitive material)
Expresses the replenishment amount per developer (ml / 4 cut), T is D
This represents the processing time (seconds) of ryto Dry. )
It is preferable that the development processing be performed under the conditions (the present invention).
Image processing method). To develop under these conditions
More preferably, the reduction in the amount of developer replenishment and the rapid processing are the same.
Sometimes can be achieved. [0123] The following examples illustrate the present invention.
However, the present invention is not limited to these. (Example 1) (Preparation of silver halide emulsion T-11) Odor in 1 liter of water
6 g of potassium halide and 7 g of gelatin were added and kept at 55 ° C.
While stirring into the container, 37 ml of silver nitrate aqueous solution (silver nitrate
4.00 g) and an aqueous solution 38 containing potassium bromide 5.9 g
ml was added in 37 seconds by double jet method. One
After adding 18.6 g of gelatin, the temperature was raised to 70 ° C.
89ml of silver nitrate aqueous solution (9.8g of silver nitrate)
Added. Here, 7ml of 25% aqueous ammonia solution
After physical aging at the same temperature for 10 minutes
6.5 ml of 100% acetic acid solution was added. Then glass
An aqueous solution of 153 g of silver acid and an aqueous solution of potassium bromide
While maintaining 8.5, control double jet method 3
Added over 5 minutes. Next, using an aqueous silver nitrate solution, pBr
After adjusting to 2.8, 2 mol / L potassium thiocyanate
15 ml of um solution was added. At the same temperature for 5 minutes
After physical aging, the temperature was lowered to 35 ° C. Average projected area
Diameter 1.10 μm, thickness 0.165 μm, diameter variation
Monodispersed pure silver bromide tabular grains having a number of 18.5% were obtained. this
Thereafter, soluble salts were removed by a sedimentation method. Again to 40 ° C
1. Increase the temperature and 30g of gelatin together with phenoxyethanol
35g and polystyrene sulfonate sodium as thickener
0.8g of sodium hydroxide and silver nitrate solution
The pH was adjusted to 5.90 and pAg 8.25. This emulsion
Chemical sensitization while maintaining the temperature at 56 ° C with stirring
It was. However, the AgI fine particles are each single before and during chemical sensitization.
0.05 mol% per 1 mol of dispersed pure silver bromide tabular grains
Minutes were added. First, add 0.043 mg of thiourea dioxide.
And held for 22 minutes for reduction sensitization. Next
4-hydroxy-6-methyl-1,3,3a, 7-
20 mg of tetrazaindene and 400 mg of sensitizing dye A
Added. Add 0.83g of calcium chloride
It was. Subsequently, sodium thiosulfate 1.5 as a sensitizer
mg, selenium sensitizer B 2.2 mg, chloroauric acid 2.6 m
g and 90 mg of potassium thiocyanate were added and 40 minutes later
Cooled to 35 ° C. Thus flat silver halide milk
Agent T-1 was prepared. Obtained silver halide emulsion T-1
The average amount of iodine contained in each silver halide grain was 0.
It was 1 mol%. (Preparation of silver halide emulsion T-2) AgI
The amount of fine particles added is 0.5 mol before and during chemical sensitization.
Silver halide emulsion T
A silver halide emulsion T-2 was prepared in the same manner. Halo
Yaw contained in silver halide grains of silver halide emulsion T-2
The average amount of the catalyst was 1.0 mol%. [0125] Embedded image (Preparation of coated sample) ―Preparation of emulsion layer coating solution― Coating solution with the following chemicals added per mole of silver halide
An emulsion layer coating solution was prepared. -Silver halide emulsion (described in Tables 2 and 3) ・ Gelatin (including Gel in emulsion) 65.6g ・ 9g of trimethylolpropane Dextran (average molecular weight 39,000) 18.5g -Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8g Hardener: 1,2-bis (vinylsulfonylacetamide) ethane swelling ratio is 23 Adjust the addition amount to 0% [0127] Embedded image -Preparation of coating solution for surface protective layer- Coating solution for surface protective layer so that each component has the following coating amount
Was made.   Contents of coating solution for surface protective layer ・ Gelatin 0.966g / m² ・ Sodium polyacrylate (average molecular weight: 400,000) 0.023 g / m² 4-hydroxy-methyl           -1,3,3a, 7-tetrazaindene 0.015 g / m² ・ Polymethyl methacrylate (average particle size 3.7 μm) 0.087 g / m² Proxel (adjusted to pH 7.4 with NaOH) 0.0005 g / m² ・ Surfactant (described in Tables 2 and 3) [0129] Embedded image(Preparation of undercoat support) (1) Preparation of dye D-1 for undercoat layer The following dyes are described in JP-A-68-197943
Ball milled by the method. [0131] Embedded image 434 ml of water and Triton X-200
6.7 mass% aqueous solution 79 of surfactant (TX-200)
1 ml was placed in a 2 liter ball mill. Dye 20
g was added to this solution. Zirconium oxide (ZrO)
400 ml of beads (2 mm diameter) was added and the contents were kept for 4 days.
Grinded for a while. After this, 12.5% by weight gelatin 160g
Was added. After degassing, filter the ZrO beads
Removed. Observation of the resulting dye dispersion revealed pulverization
The particle size of the dye was applied to a diameter of 0.05 to 1.15 μm.
With an average particle size of 0.37 μm.
there were. Furthermore, it is 0.9 by performing centrifugation operation.
Dye particles having a size of μm or more were removed. Thus the dye
Dispersion D-1 was obtained. (2) Preparation of support Biaxially stretched thick 183μm polyethylene terephthal
Corona discharge treatment is applied to the rate film, and the following composition
A coating amount of the first undercoating liquid consisting of 5.1 ml / m ²Become
Apply with a wire bar rotor to 175 ° C
And dried for 1 minute. Next, apply the first primer on the opposite side in the same way.
A layer was provided. The polyethylene terephthalate used
What contains 0.04% by mass of a dye having the following structure
Using. [0134] Embedded image [0135] -Composition of the first primer solution- ・ Butadiene-styrene copolymer latex solution (Solid content 40% butadiene / styrene weight ratio = 31/69) 79 ml * In the latex solution, a surfactant with the following structure is contained in the latex as an emulsion dispersion. It is contained by 0.4% by mass with respect to the revolving part. 2,4-dichloro-6-hydroxy           20.5 ml of 4% by weight solution of -s-triazine sodium salt ・ Distilled water 900.5m1 [0136] Embedded image Furthermore, the first lower side of both surfaces of the support is as follows.
Apply a second primer solution with the following composition on the coating layer.
One side and the wire bar on both sides
-Apply and dry at 150 ° C by coater method
An undercoat layer was formed. . [0138] -Composition of second undercoat layer- ・ Gelatin 160mg / m² Dye dispersion D-1 (26 mg / m as dye solid component)²) ・ Matting agent 2.5mg / m²   (Polymethyl methacrylate having an average particle size of 2.5 μm) [0139] Embedded image(Preparation of photosensitive material) The above prepared undercoat
The emulsion layer coating solution and the surface protective layer coating solution are the same on the carrier.
Emulsion layer and surface protective layer coated on both sides by time extrusion method
And photosensitive material samples Nos. 1 to 19 were obtained. Na
The amount of coated silver per side is 1.75 g / m.²It was. (Evaluation of photographic performance) Sample of photosensitive material obtained
X Ray Orthoss made by Fuji Photo Film Co., Ltd.
0.05 second exposure from both sides using clean HR-4
The sensitivity was evaluated. Automatic machine used in this experiment
Is Fuji Photo Film Co., Ltd.
The process is as shown in Table 1 below.
It is. [0142] [Table 1] The treatment liquid is as follows. -Preparation of each concentrate- <Developer> (Parts A) ・ 270g potassium hydroxide ・ Potassium sulfite 1125g ・ 450g sodium carbonate ・ 75 g of boric acid ・ Diethylene glycol 150g ・ Diethylenetriaminepentaacetic acid 30g 1- (N, N-diethylamino) ethyl                   -5-mercaptotetrazole 1.5g ・ Hydroquinone 405g 4-hydroxymethyl-4-methyl                   -1-phenyl-3-pyrazolidone 30 g ・ Water 4500m1 [0144] (Part agent B) ・ Tetraethylene glycol 750g ・ 3,3'-dithiobishydrocinnamic acid 3g ・ 75 g of glacial acetic acid ・ 4.5g Nitroindazole 4.5g ・ 67.5 g of 1-phenyl-3-pyrazolidone ・ 1000m1 with water        [0145] (Parts C) ・ Glutaraldehyde (50 mass / mass%) 150 g ・ Potassium bromide 15g ・ Potassium metabisulfite 120g ・ 750m1 with water [0146] <Fixing solution> ・ Ammonium thiosulfate (70 mass / volume%) 3000 ml ・ Ethylenediaminetetraacetic acid ・ disodium ・ dihydrate 0.45g ・ Sodium sulfite 225g ・ Boric acid 60g 1- (N, N-dimethylamino) -ethyl                     -5-mercaptotetrazole 15g ・ 48g tartaric acid -Glacial acetic acid 675g ・ Sodium hydroxide 225g ・ Sulfuric acid (18 mol / L) 58.5 g ・ Aluminum sulfate 150g -Add water 6000m1 ・ PH 4.68 (Preparation of processing solution) The developer concentrated solution is placed in a container.
Each part agent was filled. This container is part agent A, B
And C partial containers are connected together by the container itself
It is what. The above fixer concentrate is of the same type.
The vessel was filled. First, acetic acid is used as a starter in the developing tank.
300m aqueous solution containing 54g and potassium bromide 55.5g
1 was added. Invert the above processing solution container and
On the drilling blade of the processing liquid stock tank mounted on the side
Forcibly, tear the cap sealing film, and each treatment in the container
The agent was filled into a stock tank. Lower each of these treatments
In the proportion of the
The pump installed in was activated and filled. Here
The replenishment solution shown below was used to replenish the image and fixing. The replenisher is as follows. (Developer) ・ Part agent A 60m1 ・ Parts B 13.4ml ・ Parts C 10ml ・ 116.6 ml of water ・ PH 10.50 (Fixing solution) ・ Concentrate 80ml ・ Water 120m1 ・ PH 4.62 The washing tank was filled with tap water. Here, the amount of replenishment was changed as follows.
Fee No. A running process was carried out by pressing at 4. sample
No. The blackening rate of 4 was 35%.                   Developer replenisher Fixer replenisher     Condition (I) 25m1 / four cuts 25m1 / four cuts     Conditions (b) 18m1 / four cuts 18ml / four cuts     Condition (c) 12m1 / four cuts 12m1 / four cuts The developing / fixing solution has reached a sufficient equilibrium state.
And the exposed photosensitive material sample No. 1-19 above
Photographic properties (sensitivity, floor) after developing under conditions (a) to (c)
Tone). Here, sensitivity is processed for each sample.
Condition (A) is set to 100, and the optical density of fog + 1.0 is set.
Expressed as the reciprocal of the exposure ratio required to give
Every time). The gradation is fog +0.25 and fog +2.0.
Indicated by inclination. In addition, fog + 1.0 exposure and 4 cuts
The entire surface of the noise is uniformly exposed and exposed under the conditions (a) to (c) above.
Image processing was performed and density unevenness was evaluated. Evaluation is obtained
The obtained image is evaluated by the following five stages by visual inspection.
It was. These results are shown in Table 2. 1. Very inferior 2. Inferior 3. usually 4). Good 5, very good [0153] [Table 2][0154] Embedded image From the results shown in Table 2, the photosensitive material sample N of the present invention was obtained.
o. 4-No. 11 is sensitivity in conditions (b) to (c)
Little decrease, high contrast, and good density unevenness
It is understood that (Example 2) Photosensitive material sample No. 1-19
Parts agent C prepared by removing glutaraldehyde
The development process was performed in the same manner as in Example 1 except that
As a result, similar results were obtained. Example 3 Photosensitive material sample no. 1-19
Change the developer, fixer and replenishment as follows:
In the same manner as in Example 1 except that the development conditions were further changed.
Then, development processing was performed and photographic performance was evaluated. However,
The treatment time was 45 seconds. The results are shown in Table 3. [0158] -Developer- (Parts A) ・ Potassium hydroxide 28.0g ・ Potassium sulfite 75.0g ・ Diethylenetriaminepentaacetic acid 2.0g ・ Sodium carbonate 30.0g ・ Hydroquinone 18.0g 1- (Diethylamino) -ethyl                 -5-mercaptotetrazole 0.1 g ・ Potassium bromide 1.0g ・ 300ml with water [0159] (Part agent B) ・ Triethylene glycol 6.0g ・ 0.3g Nitroindazole ・ Acetic acid 40.0g ・ 1-Phenyl-3-pyrazolidone 3.5g ・ 0.2 g of 3,3'-dithiobishydrocinnamic acid ・ 50m1 with water 1 liter of working solution by adding water (adjusted to pH10.30) [0160] Replenisher ratio ・ Part agent A 300m1 ・ Parts B 50m1 ・ Water 650m1 COD about 50,000 in this state [0161] -Fixer- ・ Parts A ・ Sodium thiosulfate 96.4g ・ Disodium ethylenediaminetetraacetate dihydrate 0.025g ・ Sodium metabisulfite 22.0g ・ 500m1 with water Adjust pH to 5.0 with NaOH [0162] Replenishment ratio ・ Part A 500ml ・ Water 500m1 COD of about 40,000 in this state [0163] [0164] [Table 3] From the results of Table 3, the same as in Examples 1 and 2,
Sample No. of the invention. 4-No. 11 is sensitivity, gradation and density
It is understood that it is effective against unevenness. Example 4 (Preparation of silver halide emulsion T-3) Gelatin in 1 liter of water
Dissolve 40 g of tin and add bromide to a container heated to 55 ° C.
After adding 3 g of lithium and 60 mg of the following compound [I],
200 g of glass while maintaining the pAg value in the reaction container at 7.0
1000 ml of an aqueous solution containing acid silver and hexachloroylid
Potassium um (III) in a molar ratio of silver to 10^-7Mol /
Aqueous solution 1 of 140 g of potassium bromide containing only 1 mol of silver
Add 080 ml to the average grain
Cubic monodispersed silver bromide grains with a child size of 0.20 / μm
Prepared. After desalting the emulsion, 71 g of gelatin was added.
Yes, sodium thiosulfate according to pH 6.0 and pAg 8.5
3 mg of lithium, 4 mg of chloroauric acid and 4-hydroxy-6-
0.2 g of methyl-1,3,3a, 7-tetrazaindene
And silver halide emulsion T chemically sensitized at 60 ° C
-3 was prepared. Halogenation of silver halide emulsion T-3
The average amount of iodine contained in the silver particles was 0 mol%.
It was. [0167] Embedded image (Preparation of emulsion coating solution) Silver halide emulsion T
-3 weight of 850g was heated to 40 ° C,
Additives were added according to the formulation shown to prepare an emulsion coating solution. [0169] -Emulsion coating solution formulation- A. Emulsion T-3 850g B. Spectral sensitizing dye [II] 1.2 × 10^-FourMole C. [XVI] 0.8 × 10 for supersensitizer^-3Mole D. Preservative good agent [VI] 1 × 10^-3Mole E. Polyacrylamide (molecular weight 40,000) 7.5g What. 1.6 g of trimethylolpropane 卜. Polystyrene sulfonate Na 2.4g H. Poly (ethyl acrylate / methacrylic acid) latex 16g Li. 1.2 g of N, N'-ethylenebis- (vinylsulfonacetamide) [0170] Embedded image (Preparation of dye emulsified dispersion) Infrared semiconductor laser
As an antihalation dye for laser light, JP-A-2-2-2
Color tone adjustment using Compound 8 described on page 4 of No. 074
As a dye for use, described on page 3 of JP-A-8-231738
Dye No. listed 4, weigh 10kg each and individually
In addition, 12 liters of tricresyl phosphate, acetate
It was dissolved at 55 ° C. in a solvent consisting of 85 liters of chill. This
This is called an oil-based solution. On the other hand, anionic surface activity
1.35 kg of agent (W-1 below) 9.3% gelatin water
It melt | dissolved in the solution 270ml at 45 degreeC. This is an aqueous solution
Called. Put the oil and water solution into a dispersion kettle
In the dispersion kettle while controlling the temperature to be kept at 40 ° C
High-speed rotating propeller 1 for dispersion is rotated at 6500 times / minute
The pressure in the dispersion kettle from 760mmHg for 60 minutes
Over time, the pressure is gradually reduced to 100 mmHg, and then 20
Dispersion was continued for 1 minute under the same conditions. The following dispersion was added to the obtained dispersion.
Additive (a) 8 g and phenoxyethanol in methanol 3
Add 1.2 liter of 5% solution and water to finish 240 kg
After cooling, it was cooled and solidified. [0172] Embedded imageThe area average particle size of the obtained dispersion was all
It was in the range of 0.08 to 0,10 μm. Obtained
Each emulsified dispersion (antihalation dye emulsified fraction)
Dust) AH-8, (color tone adjusting dye emulsified dispersion) S-6 and
To do. (Preparation of back layer coating solution) Container at 40 ° C
Heat and apply back layer with additives as shown below
Liquid. ―Back layer coating solution formulation― A. 80g gelatin B. Antihalation dye emulsified dispersion AH-8 42g C. Color tone adjusting dye emulsified dispersion S-6 1.0 g D. Polystyrene sulfonate 0.6g 15g poly (ethyl acrylate / methacrylic acid) latex What. N, N'-ethylenebis- (vinylsulfonacetamide) 5.0 g (Preparation of coating solution for back surface protective layer) Container
Warm to 40 ° C and add additives with the formulation shown below.
A cloth liquid was used. [0176] -Back surface protective layer coating solution formulation- A. 80g gelatin B. Polystyrene sulfonate 0.3g C. N, N'-ethylenebis- (vinylsulfonacetamide) 1.7 g two. 4 g of polymethyl methacrylate fine particles (average particle size: 4.0 μm) E. 3.6 g of sodium t-octylphenoxyethoxyethanesulfonate What. NaOH (1mo1 / L) 6m1 卜. Polyacrylic acid soda 2g H. C₁₆H₃₃O- (CH₂CH₂O)_Ten-H 3.6 g Li. 130 ml of methanol Nu. Surfactant (described in Table 5) (Preparation of photosensitive material) The above back layer coating solution
Back layer surface protective layer coating solution lg / m²With transparency
Gelatin total on the side of the polyethylene terephthalate support
Application amount is 3.5g / m²It applied so that it might become. to this
Next, on the opposite side of the support, the above emulsion coating solution and surface protection
The coating Ag amount is 2.5 g / m.²And surface protection
The gelatin coating amount of the layer is 1 g / m²Photosensitive material No. 20
~ 22 were made. The hardener N, N'-ethylene vinyl
S- (Vinylsulfone acetamide) amount is the total gelatin amount
To 2.6% by mass. (Method of Sensitometry) Preparation in this way
Photosensitive material sample No. 20 to 22 at 25 ° C relative humidity 6
Leave at 10% temperature and humidity for 10 days, then 25.7 × 3
It cut | judged to 6.4 cm size. Fuji Photo Film for each sample
780nm infrared semiconductor laser for FCR7000
-It exposed with the scanner (CR-LP414 type). Self
The dynamic development process is performed on the gear head of the self-existing part of CR-LP414.
The belt was replaced and the conveyance speed was doubled. CR-LP414 type double speed remodeling machine is photosensitive
From the moment the tip of the material is inserted into the automatic machine, it is processed.
The time until the moment the tip comes out of the self-machine
The loose “Dry to Dry” is 33.4 seconds. same
The detailed specifications of the modified machine are shown below. The developing machine and fixing solution are commercially available Fuji Photo Film.
Each developer and fixer of CE-DF / 1 kit manufactured by KK
After adding water to prepare 15 liters, develop
Fuji RD- manufactured by Fuji Photo Film Co., Ltd.
III starter with 300ml added
Using. Developer temperature is 35 ℃ ± 0.2 ℃, fixing temperature is 3
The temperature was adjusted to 2 ° C. ± 0.2 ° C. (Anti-halation dye drying section roller rolling
Evaluation of copying failure) Photosensitive material sample No. 20 to 22 in Table 4
After each continuous treatment under treatment conditions AG
Contamination of the drying section roller with anti-blocking dye, transfer to photosensitive material
The occurrence of failure to be copied was evaluated. At the same time, evaluation of density unevenness
The price was also done. Concentration unevenness is evaluated with each sample
Evaluate by performing uniform exposure at an output of yellow +1.0
It was. Evaluation was carried out by visual evaluation of the following five stages. result
Is shown in Table 5. 1. Very inferior 2. Inferior 3. usually 4). Good 5). Very good [0182] [Table 4] [0183] [Table 5] [0184] Embedded image As is apparent from the results in Table 5, the present invention
Photosensitive material sample No. 22 is antihalation dye drying
There is little transfer to the part roller, and there is little density unevenness
Understood. Example 5 As a surfactant for the surface protective layer
FSA-1, -2, and -9 in total 12 mg / m
²Photosensitive material sample N in Example 1 except that
o. Photosensitive material samples were prepared and evaluated in the same manner as in 4-11.
However, there is little decrease in sensitivity under the conditions (i) to (c).
And high contrast and good density unevenness
It was confirmed. Similarly, as a surfactant for the surface protective layer,
FSA-1, -2, and -9 in total 12 mg / m²The
The photosensitive material sample No. in Example 4 was used except that it was used. 2
Photosensitive material samples were prepared and evaluated in the same manner as described in 2.
B) Transfer of antihalation dye to the drying section roller
It was confirmed that there was little density unevenness. (Example 6) Surfactant seed for surface protective layer
Types and addition amounts of surfactants shown in Table 6
In the same manner as in Example 1 except that the photosensitive material 101 is changed to
To 119, and conditions (ii) in the same manner as in Example 1.
(B) (c) was evaluated. The results are shown in Table 6. [0188] [Table 6] As is apparent from the results in Table 6, the present invention
The photosensitive materials 104 to 111 satisfy the conditions (A), (B), and (C).
In this case, there is little decrease in sensitivity and little change in gradation,
Further, it is understood that the density unevenness is also good. Example 7 Photosensitive material prepared in Example 6
For 101-119, conditions were the same as in Example 3.
(D) (e) (e) was evaluated. The results are shown in Table 7.
Show [0191] [Table 7] As is apparent from the results in Table 7, the present invention
The photosensitive materials 104 to 111 satisfy the conditions (d) (e) (f)
In this case, there is little decrease in sensitivity and little change in gradation,
Further, it is understood that the density unevenness is also good. [0193] As described above, according to the present invention, the replenishment amount of the developer
Even with a low processing system, there is sufficient density uniformity
Silver halide photography that provides sensitivity and enables rapid processing at the same time
Photosensitive material and development processing method thereof can be provided
The

Claims (1)

1. A silver halide emulsion layer containing at least one photosensitive silver halide grain and at least one non-photosensitive hydrophilic colloid layer on a support. A silver halide photographic light-sensitive material having an average amount of iodine contained in the light-sensitive silver halide grains of 0 to 0.45 mol% and represented by the following general formula (1): A silver halide photographic light-sensitive material comprising an agent. [Chemical 1] (In general formula (1), R represents a substituted or unsubstituted alkyl group. R _af represents a perfluoroalkylene group. W
Represents a hydrogen atom or a fluorine atom. La represents _a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group obtained by combining these. A
And B each represents a hydrogen atom, and the other represents -L _b -SO _3.
M is represented. M represents a cation. L _b represents a single bond or a substituted or unsubstituted alkylene group. )