JP2003140289A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material with which sufficient sensitivity without irregular density can be obtained even in a treating system with a little replenishing amount of a developing solution. SOLUTION: The silver halide photographic sensitive material having at least one silver halide emulsion layer containing photosensitive silver halide particles and at least one nonphotosensitive hydrophilic colloid layer on a supporting body, is characterized in that the proportion of iodine included in the photosensitive silver halide particles is >0.45 mol% and <=3.5 mol% in average, and the photosensitive material contains a surfactant expressed by general formula (1).

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.
The present invention relates to a silver halide photographic light-sensitive material that can be produced. [0002] 2. Description of the Related Art Photosensitive materials, especially medical X-ray films
Or for industrial X-ray film
Lowering the replenishment amount leads to lowering the amount of waste liquid,
It is greatly highlighted from the viewpoint of environmental issues.
However, with conventional light-sensitive materials, if the replenishment amount is lowered, sufficient sensitivity is achieved.
Degree / gradation cannot be obtained, and a uniform density should be given.
The image was unsuitable for practical use such as density unevenness. others
Enough even in processing systems with a small amount of developer replenishment
Development of a light-sensitive material capable of obtaining high sensitivity was 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
Provided is a silver halide photographic light-sensitive material capable of obtaining high sensitivity.
That is. [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
Can provide a silver halide photographic light-sensitive material and a development processing method thereof.
The following (1), (2), (3),
(4), (5), (6), (7), (8)
It came to complete Ming. That is, the present invention (1) At least one photosensitive layer on the support.
Silver halide emulsion layer containing silver halide grains,
And at least one non-photosensitive hydrophilic colloid layer
In the silver halide photographic light-sensitive material, the photosensitive halogen
The average amount of iodine contained in silver halide grains is 0.45 mol
% To 3.5 mol% or less and the following general formula
It contains a surfactant represented by (1)
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) Surface activity represented by the general formula (1)
The surfactant is a surfactant represented by the following general formula (2)
(1) silver halide photographic light-sensitive material
It is a fee. [0009] [Chemical 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)_fIs charcoal
It represents a perfluoroalkyl group having 2 to 4 prime numbers
In the silver halide photographic light-sensitive material described in (2) above
is there. (4) At least one photosensitive layer on the support.
Silver halide emulsion layer containing silver halide grains,
And at least one non-photosensitive hydrophilic colloid layer
In the silver halide photographic light-sensitive material, the photosensitive halogen
The average amount of iodine contained in silver halide grains is 0.45 mol
% To 3.5 mol% or less and the following general formula
It contains the surfactant represented by (A),
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) Surface activity represented by the general formula (A)
In the sex agent, B is -L_b-SO_ThreeM and L_b
Is a single bond, the halogen described in (4)
This is 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
_b5 is a methylene group.
This is a silver halide photographic light-sensitive material. (7) At least one photosensitive layer on the support.
Silver halide emulsion layer containing silver halide grains,
And at least one non-photosensitive hydrophilic colloid layer
In the silver halide photographic light-sensitive material, the photosensitive halogen
The average amount of iodine contained in silver halide grains is 0.45 mol
% To 3.5 mol% or less and the following general formula
It contains a surfactant represented by (F)
A silver halide photographic light-sensitive material. [0018] [Chemical formula 5] (In the general formula (F), R_fIs perfluoroa
Represents an alkyl group, R_cIs an alkylene group, Z is a surface activity
Anionic group, cationic group,
A group having a tine group or a nonionic polar group is represented. n
Represents an integer of 0 or 1. m represents an integer of 1 to 3. ) (8) In any one of the above (1) to (7)
1m of silver halide photographic material²Per developer
Development under conditions where the replenishment amount is 50 to 350 ml
A development processing method characterized by processing. [0021] 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 amount of iodine contained in the child exceeds 0.45 mol% on average.
3.5 mol% or less, and a specific surface activity described later
It contains a sex agent. Halogenation of the present invention
Silver photographic material is contained in photosensitive silver halide grains.
The average amount of iodine exceeds 0.45 mol% and 3.5 mol
% Or less, and contain a specific surfactant
Even in processing systems with a small amount of developer replenishment,
Sufficient sensitivity without unevenness can be obtained. 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)
Surface active represented by the following general formula (F)
An agent is preferably mentioned. First, it is represented by the general formula (1).
The surfactant will be described. [0024] [Chemical 6] In 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. [0031] [Chemical 7] 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 hydrogen atom of an alkyl group.
Are all fluorine-substituted groups. Perfluoroa
The alkyl group in the alkyl group may be linear or branched.
It may be in the form of a ring or may have a ring structure.
R_fExamples of the perfluoroalkyl group represented by
Trifluoromethyl group, pentafluoroethyl group,
Heptafluoro-n-propyl group, heptafluoroiso
Propyl group, nonafluoro-n-pentyl group, undeca
Fluoro-n-pentyl group, to tridecafluoro-n-
Xyl group, undecafluorocyclohexyl group, etc.
It is done. Among them, perfluoroalkyl having 2 to 4 carbon atoms
Groups (eg pentafluoroethyl, heptafluoro
-N-propyl group, heptafluoroisopropyl group,
Nafluoro-n-butyl group and the like are preferred, and heptaful
Oro-n-propyl group and nonafluoro-n-butyl group
Particularly preferred. In particular, R_fIs a C2-4 full
It preferably represents an oroalkyl group. In 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 and the like 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 [0039] [Chemical 8] [0040] [Chemical 9][0041] Embedded image [0042] Embedded image[0043] Embedded image The fluorine surfactant 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 a number of 13 or less, 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_Four-F₉Group, -C₈H₁₆-C_Four
F₉Group, -C_FourH₈-C₂F_FiveGroup, -C_FourH₈-C_ThreeF₇Group,-
C_FourH ₈-C_FiveF₁₁Group, -C₈H₁₆-C₂F_FiveGroup, -C₂H_Four−
C_FourF₈-H group, -C_FourH₈-C_FourF₈-H group, -C₆H₁₂−
C_FourF₈-H group, -C₆H₁₂-C₂F_Four-H group, -C₈H₁₆−
C₂F_Four-H group, -C₆H₁₂-C_FourF₈-CH_ThreeGroup, -C₂H_Four
-C_ThreeF₇Group, -C₂H_Four-C_FiveF₁₁Group, -C_FourH₈-CF
(CF_Three)₂Group, -CH₂CF_ThreeGroup, -C_FourH_Five-CH (C ₂F
_Five)₂Group, -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 fluorosurfactants, 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. Fluorosurfactants include the following general formula:
Particularly preferred is a surfactant represented by (A).
Yes. [0051] 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. R^l, R², R^ThreeAnd R^FourCarbon number
If the total content is 16 or more, it must be lithium ion
Solubility (especially in water) and antistatic ability or coating uniformity
It is excellent in terms of coexistence. L_bIs a single bond or substituted
Alternatively, it represents an unsubstituted alkylene group. Substituent is R^ThreeAt
Boiled ones are preferred. L_bIs an alkylene group,
The C number is preferably 2 or less. L_bThe
Represents a ren group or a single bond, but a methylene group is particularly preferred.
Yes. 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. [0057] 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,
Is particularly preferred. M represents a cation. Where M is the table
Examples of cations that can be used 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. Hereinafter, the surfactant represented by the general formula (A)
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. [0061] Embedded image [0062] Embedded image[0063] Embedded image [0064] Embedded image[0065] Embedded image[0066] Embedded image[0067] Embedded image [0068] Embedded image[0069] Embedded image Details of the compound represented by formula (F)
Explain. [0071] Embedded image In the general formula (F), R_fIs perfluoroal
Represents a kill group, preferably a perfluoro having 3 to 20 carbon atoms
Represents a loalkyl group. A specific example is C_ThreeF₇-Group, C
_FourF₉-Group, C₆F₁₃-Group, C₈F₁₇-Group, C₁₂F_{twenty five}-Group,
C₁₆F₃₃-Group etc. are mentioned suitably. R_fIs several different
Of a compound having a perfluoroalkyl group having a chain length of
It may be a compound or a single perfluoroalkyl group
It may be a compound having R_fIs several different chains
A mixture of compounds with long perfluoroalkyl groups
At some point, the average chain length of the perfluoroalkyl group
Preferably has 4 to 10 carbon atoms.
9 is particularly preferred. In the general formula (F), R_cRepresents an alkylene group
The The alkylene group has 1 or more carbon atoms, but 2 or more carbon atoms.
Preferably, the upper limit is 20 or less
preferable. Specifically, methylene group, ethylene group, 1,2
-Propylene group, 1,3-propylene group, 1,2-buty
Len group, 1,4-butylene group, 1,6-hexylene group,
A 1,2-octylene group is preferred. In the general formula (F), Z has surface activity.
Anionic group, cationic group, betaine
Represents a group or a group having a nonionic polar group. However, this
If these groups are included, R_cHow to connect with
Not determined. Anions required for surface activity
Examples of functional groups include sulfonic acid groups and their ammonium
Or metal salt, carboxylic acid group and its ammonium or gold
Genus salts, phosphonic acid groups and ammonium or metal salts thereof,
Sulfate ester group and its ammonium or metal salt, phosphorus
Acid ester group and its ammonium or metal salt
Can be mentioned. Cations required for surface activity
Examples of the functional group include trimethyl ammonium ethyl group, tri
Quaternary alkyl amines such as methyl ammonium propyl group
Monium group, dimethylphenylammonium alkyl
Group, aromatic ammonium such as N-methylpyridium group
Groups. These groups have an appropriate counter ion
Specifically, halogen atoms, benzene sulfone
Acid anion, toluenesulfonic acid anion, etc.
Of these, toluenesulfonate anion is preferred. Surface activity
Nonionic polar groups required for
Examples include reoxyalkylene groups and polyhydric alcohol groups.
Preferably, polyethylene glycol, polypropylene
A polyoxyalkylene group such as ethylene glycol. However
These groups are terminated with groups other than hydrogen atoms, such as
It may be a kill group. In the general formula (F), n represents an integer of 0 or 1.
1 is preferable. m represents an integer of 1 to 3
And when Z is not a phosphate group, m = 1 is preferred.
When Z represents a phosphate group, m = 1-3
Or an average value of 1-2.
Good. In the general formula (F), R_fIs preferably charcoal
Perfluoroalkyl group with a prime number of 4 to 16, more preferred
Or a perfluoroalkyl group having 6 to 16 carbon atoms.
Rc is preferably an unsubstituted alkylene having 2 to 16 carbon atoms
More preferably an unsubstituted alkyle having 2 to 8 carbon atoms.
An ethylene group is particularly preferred. Z
R_cWhat is the distance between the group and the group necessary to impart surface activity?
In addition to direct connection, for example, Archile
These groups can be bonded by a chain, arylene, etc.
May have a substituent. These groups are also in the main chain
Or the side chain has an oxy group, thio group, sulfonyl group,
Sid group, sulfonamide group, amide group, amino group, cal
A bonyl group and the like may be contained. Below is the general formula
Specific examples of the surfactant represented by (F) are shown below.
Is not limited to these. [0077] Embedded image [0078] Embedded image[0079] Embedded image[0080] Embedded imageThe compound represented by the general formula (F) is
Telomer-type perfluoroalkyl group-containing surfactant
Commercially available products can be used.
As an example, ZONYL made by DUPONT Co., Ltd.
(R) FSP, FSE, FSJ, NF, TBS, FS-
62, FSA, FSK (more ionic), Zonyl
(R) 9075, FSO, FSN, FS-300, FS
-310 (above nonionic), S-1 manufactured by Asahi Glass Co., Ltd.
11, S-112, S-113, S-121, S-13
1, S-132, S-141, S-145, Daikin
Unidyne DS-101, DS-102 manufactured by Kogyo Co., Ltd.
DS-202, DS-301 (more ionic), DS-
401, DS-403 (more non-ionic)
You can. Of these various compounds, ionic
Surfactants are intended for use, required solubility, etc.
Depending on the ion exchange or neutralization,
Can be used in the form of a counter salt. The specific surfactant described above is, 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. The 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 mentioned above, it is photosensitive in terms of reducing the replenishment amount of the developer.
The average amount of iodine contained in the silver halide grains is 0.4.
It must be more than 5 mol% and 3.5 mol% or less.
is there. This iodine amount is preferably 0.6 moles on average
% To 3.2 mol%, more preferably 0.8 mol%
More than 3.0 mol%. Where photosensitive halogen
The average amount of iodine contained in silver halide grains is the individual feeling.
Y calculated from the halogen composition of light-sensitive silver halide grains
Mean value of the card content. Of photosensitive silver halide
The distribution of halogen composition within the grain may be uniform.
Even if the halogen composition changes on the step
Or continuously changed. Also feeling
The light-sensitive silver halide grains have a core / shell structure.
It is also possible to use photosensitive silver halide grains. As the photosensitive silver halide grain, the 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, JP-A-2-68539 discloses
Page 10, upper right column, line 13 to lower left column, line 16;
-313282 and JP-A-6-110144
The method described in the publication can be used. Silver halide
As a method of chemical sensitization of emulsion, specifically, halogen
Sulfur sensitization method, selenium sensitization method,
Use known methods such as reduction sensitization and gold sensitization
Can be used alone or 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 be. 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
More than 0.5 mmol and less than 4 mmol per silver mole
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, 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 line 1 in the lower right column
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 be. 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, JP-A 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 compound (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
Active vinyl compound described in JP-A-60-80846
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
For example, dialdehyde starch, polyacrylic
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 features in photosensitive 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 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, a super additive is added 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. A developer using these developing agents described above
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. Furthermore, in the present invention
The replenishment amount for development and fixing is photographic photosensitive material lm²Per
50 ml or more and 350 ml or less is preferable, 25 ml or more
More preferably, it is 200 ml or less. 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. Especially for fast processing
The liquid tank roller configuration should increase the fixing speed.
In the case of light-sensitive materials containing sensitizing dyes,
It is more preferred to be an opposed roller for
That's right. By configuring with the opposing roller, the roller
Can be reduced and the processing tank can be made smaller. sand
This makes it possible to make the actual machine more compact. 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 is used.
(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. Further, a hardener may be used for the developer.
Yes. Hardeners are dialdehyde hardeners or their heavy oxides.
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. If necessary, a buffer (for example, charcoal) is used in the developer.
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. Further, in the present invention, a water-soluble bromide salt, a 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. A photosensitive material developed with a developer is usually used.
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
In the case of, means the so-called “Tame water washing method”
To do. As a method of reducing the replenishment amount, it has been suitable for many stages since ancient times.
A flow system (for example, two stages or three stages) is known. The replenishment amount of washing water (or stabilizing solution) is small.
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, contamination 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 5 seconds to 3 minutes 30 seconds.
Yes. The developer of the present invention is processed using an automatic processor.
It is effective in the case. [0137] The following examples illustrate the present invention.
However, the present invention is not limited to these. Example 1 (Preparation of emulsion) -Preparation of silver iodobromide monodisperse high contrast emulsion A- 0.101 g potassium bromide and 5.6 g palatru
4% by weight gelatin containing sodium sulfinic acid
1.4 liters of sodium thiosulfate pentahydrate
9.5 mg, glacial acetic acid 1.8 cc, 25% by weight ammoni
Add 11cc of water and keep it at 70 ° C.
284.2g of silver nitrate by double jet method with stirring
840cc of an aqueous solution containing 200 g of potassium bromide,
840 cc of an aqueous solution containing 1.8 g of potassium iodide
A constant amount was added over 54 minutes. Aged for 3 minutes
Thereafter, 35 cc of an aqueous solution containing 0.35 g of potassium iodide was added.
Added and aged for another 5 minutes. The above reaction solution was flocculated by a conventional method.
Gelatin, thickener, preservative at 40 ° C
Was added and dispersed, and then the pH was adjusted to 5.6 and the pAg to 8.7.
Adjusted. Next, while maintaining this reaction solution at 60 ° C.,
1 × 10 thiosulfonic acid compound T per 1 kg of reaction solution
^-FiveMol / mol Ag added, 4-hydroxy-6-methyl
170 mg of -1,3,3a, 7-tetrazaindene
And after aging for 5 minutes, sensitizing dye A 245 mg, sensitization
215 mg of dye B was added simultaneously and aged for 10 minutes
Later, sodium thiosulfate pentahydrate 5.4 mg, selenium increased
Sensitizer S 0.4mg, Chloroauric acid 3.3mg, Rodankari
44 mg was sequentially added and aged for 100 minutes. Like this
With an average particle size of 0.48 μm and a coefficient of variation of 13%.
A monodispersed monodispersed cubic emulsion A was obtained. Of the obtained emulsion A
The average amount of iodine contained in the silver halide grains is 0.8.
Mol%. [0139] Embedded image -Preparation of silver iodobromide monodisperse high contrast emulsion B- 0.101 g potassium bromide and 5.6 g palatru
4% by weight gelatin containing sodium sulfinic acid
1.4 liters of sodium thiosulfate pentahydrate
9.5 mg, glacial acetic acid 1.8 cc, 25% by weight ammoni
Add 11cc of water and keep it at 70 ° C while stirring vigorously
While stirring, 284.2 g of silver nitrate was obtained by the double jet method.
840 cc of aqueous solution, 200 g of potassium bromide and iodine
840 cc of an aqueous solution containing 1.8 g of potassium halide
A constant amount was added over a minute. After aging for 3 minutes,
Add 35 cc of an aqueous solution containing 0.35 g of potassium iodide
And aged for another 5 minutes. [0141] The above reaction solution was flocculated by a conventional method.
Gelatin, thickener, preservative at 40 ° C
After adding and dispersing, adjust the pH to 5.6 and Ag to 8.7.
I gave it. Next, while maintaining the reaction solution at 60 ° C., the reaction
1 × 1 of the thiosulfonic acid compound T per kg of liquid
0^-FiveMol / mol Ag added, 4-hydroxy-6-methyl
120 mg of ru-1,3,3a, 7-tetrazaindene
After adding and ripening for 5 minutes, 180 mg of the sensitizing dye A
After aging for 10 minutes, sodium thiosulfate
3.8 mg of pentahydrate, 0.3 m of the selenium sensitizer S
g, Chloroauric acid 2.3mg, Rodankari 31mg
And aged for 100 minutes. In this way the average particle support
Monodisperse standing with monodisperse with a noise of 0.62μm and a coefficient of variation of 14%
A rectangular emulsion B was obtained. Silver halide grains of emulsion B obtained
The average iodine amount contained in was 0.8 mol%. (Preparation of coating solution) Each of emulsions A to B
The above composition was added to prepare emulsion layer coating solutions A and B.
Moreover, each layer coating solution was prepared according to the following composition. [0143] -Emulsion layer coating solution composition- ・ Emulsion ・ ・ ・ 1kg (81g gelatin, Ag: 92g) ・ Polymer latex ... 2.9g   (Poly (ethyl acrylate / methacrylic acid) = 97/3, weight ratio) ・ Hardener ... 1.1g   (1,2-bis (vinylsulfonylacetamido) ethane) 2,6-bis (hydroxyamino) -4-diethyl   Amino-1,3,5-triazine 0.04g Dextran (average molecular weight 39,000) ... 10g ・ Foot cut agent 0.34g ・ Potassium p-hydroquinone sulfonate 5.4g ・ Potassium iodide ・ ・ ・ 0.05g ・ Polyethylene oxide compound W ・ ・ ・ 0.12g ・ Mercapto compound M ・ ・ ・ 0.05g ・ Add distilled water to make 1160ml [0144] Embedded image [0145] -Protective layer coating solution composition- ・ Gelatin ・ ・ ・ 1kg ・ C₁₆H₃₃O (CH₂CH₂O)_TenH ・ ・ ・ 27g ・ Surfactant-1 ... 1.4g   (C₈F₁₇SO₂N (C_ThreeH₇) (CH₂CH₂O)_Four(CH₂)_FourSO_ThreeNa) ・ Surfactant-2 ・ ・ ・ 0.92g   (C₈F₁₇SO₂N (C_ThreeH₇) (CH₂CH₂O)₁₅H) ・ Polymethylmethacrylate particles (average particle size 2.5μm) ・ ・ ・ 69g ・ Proxel ・ ・ ・ 0.7g ・ Sodium polyacrylate (average molecular weight 41,000) ・ ・ ・ 19g -Sodium polystyrene sulfonate (average molecular weight 600,000)-10.5g ・ NaOH ・ ・ ・ 3.2g ・ C₈F₁₇C₆H_Four) (OCH₂CH₂)_ThreeSO_ThreeNa ... 16.2g ・ Mercapto compound M2 ・ ・ ・ 1g ・ Compound C: 0.5g ・ Add distilled water for a total volume of 11.1 liters [0146] Embedded image -Antihalation layer coating solution- (1) Preparation of dye dispersion L 2.5 g each of Dye-1 and Oil-I, -II
What was dissolved in 50 cc of dodecylbenzenesulfone
Sodium 1.5g and methacrylic acid p-hydroxybenzoate
90 g of an 8% aqueous gelatin solution containing 0.18 g of water and 60 ° C
And stirred at high speed with a homogenizer. Finish high-speed stirring
After completion, vacuum treatment is performed at 60 ° C using an evaporator, and vinegar
92 wt% of ethyl acid was removed. This makes the average particle size
A dye dispersion L of 0.18 μm was obtained. (2) Preparation of coating solution Adjust the antihalation layer coating solution according to the following composition:
It was. ・ Gelatin ・ ・ ・ 1kg ・ Polymer latex ・ ・ ・ 130g (Poly (ethyl acrylate / methacrylic acid) = 97/3, weight ratio) ・ Phosphoric acid: 1.23 g ・ Snowtex C ... 120g ・ Proxel ・ ・ ・ 0.4g ・ Dye dispersion L ... 190g ・ Dye-2 ・ ・ ・ 18g ・ Dye-3 ・ ・ ・ 12.5g ・ Dye-4 ・ ・ ・ 13g ・ Hardener ... 17.5g   (1,2-bis (vinylsulfonylacetamido) ethane) ・ Add distilled water for a total volume of 13.8 liters [0149] Embedded image [0150] -Back protective layer coating solution composition- ・ Gelatin ・ ・ ・ 1kg ・ C₁₆H₃₃O (CH₂CH₂O)_TenH ・ ・ ・ 33g ・ Surfactant-1 ... 1.4g   (C₈F₁₇SO₂N (C_ThreeH₇) (CH₂CH₂O)_Four(CH₂)_FourSO_ThreeNa) ・ Surfactant-2 ・ ・ ・ 0.92g   (C₈F₁₇SO₂N (C_ThreeH₇) (CH₂CH₂O)₁₅H) ・ Polymethylmethacrylate particles (average particle size 3.7μm) 34g ・ Proxel ・ ・ ・ 0.7g ・ Sodium polyacrylate (average molecular weight 41,000) ・ ・ ・ 75g -Sodium polystyrene sulfonate (average molecular weight 600,000)-10.5g ・ NaOH ... 2.3g ・ C₈F₁₇C₆H_Four) (OCH₂CH₂)_ThreeSO_ThreeNa ... 20g ・ Add distilled water to make 10.7 liters (Production of photosensitive material) -Production of photosensitive material 1- The prepared coating solution is primed by the simultaneous extrusion method.
Coating for protective layer on one side of PET175μm support
And emulsion layer coating solutions A and B were used for coating. The protective layer is the best
Emulsion layer A using emulsion layer coating solution A is on the lower layer.
Emulsion layer B using emulsion layer coating solution B for (upper emulsion layer)
Is the layer structure which is the lowermost layer (lower emulsion layer). In addition,
The amount of gelatin in the protective layer is 0.6 g / m²I made it. Then dry
Thus, a light-sensitive material was prepared. The coating amount of emulsion layer A is milk
The coating silver amount of the agent layer coating liquid A is 1.7 g / m.²And more emulsion
The coating amount of the layer B is 1.7 g / g in the coating silver amount of the emulsion layer coating solution B.
m²It was decided to become. On the opposite side of the photosensitive layer
Anti-dye dye layer coating solution and back protective layer coating solution
The amount of latin applied is 3.0 g / m², 1.27 g / m²In
Apply as antihalation dye layer and
A protective layer was formed. In this way, photosensitive material 1 is produced.
Made. -Preparation of photosensitive materials 2-5- Surfactant-1 for protective layer coating solution and back protective layer coating solution-1
And Surfactant-2, except for changing according to Table 1,
Photosensitive materials 2 to 5 were produced in the same manner as the photosensitive material 1. -Production of photosensitive material 6- Instead of Emulsion A and Emulsion B, respectively,
Emulsion C with an average content of 0.8 mol% changed to 4.0 mol%, and
And an average iodine content of Emulsion B of 0.8 mol% is 4.0 mol%.
Sensitive as in Photosensitive Material 1 except that Emulsion D was changed to
An optical material 6 was produced. -Production of photosensitive materials 7-10- Surfactant-1 for protective layer coating solution and back protective layer coating solution-1
And Surfactant-2, except for changing according to Table 1,
In the same manner as photosensitive material 6, photosensitive materials 7 to 10 were prepared.
It was. (Evaluation) The obtained photosensitive material is as follows.
Evaluation was made as indicated. The results are shown in Table 2. ―Measurement of sensitivity and gradation― The sensitivity of the film is compared with the commercially available UM-Fine screen.
By combining X-ray exposure with the photosensitive material to be measured
Ask. According to the method of changing the amount of X-ray exposure by the distance method
Measurements were taken. This measurement uses the same screen,
Since only the light material is changed, this is the actual breast
Same result as when exposed with Mo target tube for photography
Is obtained. Specifically, 50KVp with three-phase power supply.
X generated from a tungsten target tube operated at
The wire passed through a 3 mm thick aluminum plate
Using. Commercial UM-Fine screen and measurement feeling
Adhering the materials together, Fuji Photo Film Co., Ltd. ECMA
Loaded into a sette. From the X-ray tube, the cassette sky
Arranged so that it becomes a plate, film, screen, X-ray illumination
I went to shoot. The X-ray exposure amount E is changed by the distance method, and lo
Step exposure was performed with a width of gE = 0.15. The exposed film is Fuji Photo Film Co., Ltd.
Company-made automatic processor CEPROS-M and its processing agent CE-
Using DF-1, the following development processing conditions (a) (b)
According to (c), developer temperature 32 ° C. development time 2
Development was performed in 5 seconds (total processing time was 90 seconds). Then the concentration
Irradiation dose required to measure and obtain a fog + 1.0 concentration
The sensitivity of the reciprocal of is 100 for the case of photosensitive material 1.
Shown as a pair. The gradation is fog +0.25 and fog +2.
It was determined by the slope of a straight line connecting zero density points. Further fog +
Uniform across the entire cut-out size with an exposure amount giving a density of 1.0
After exposure and development, density unevenness was evaluated. Comment
The value is evaluated by the following five steps on the obtained image.
I was worth it. 1. Very inferior 2. Inferior 3. usually 4). Good 5). Very good As development processing conditions, the following conditions (a) (b)
(C) Processed.                   Developer replenisher Fixer replenisher   Condition (a) 25ml / 4 cut 25ml / 4 cut (323ml / m²)   Condition (b) 20ml / 4 cut 20ml / 4 cut (258ml / m²)   Condition (c) 15ml / 4 cut 15ml / 4 cut (194ml / m²) [0159] [Table 1] [0160] [Table 2] The evaluation results are shown in Table 2, and the light-sensitive material of the present invention.
2, 3, 4 and 5 have low sensitivity under conditions (b) to (c)
Lower and gradation change is small and density unevenness is good
I understand that. (Example 2) -Production of photosensitive material 11- (Preparation of silver halide emulsion (original emulsion)) In 1 liter of water
And gelatin 21g, NH_FourNO_Three10.7 g, KBr0.
3g, AgNO_Three0.07g was added and kept at 42 ° C.
AgNOL while stirring in the reaction vessel_Three85.7g and N
H_FourNO_ThreeAn aqueous solution containing 0.71 g and an aqueous solution containing KBr
Take 19 minutes and 10 seconds with the control double jet method
Added. 25% by weight after the start of double jet addition
Add 2.4 ml of monia water, and after 0.7 minutes 0.71 g
Neutralized with glacial acetic acid. Then AgNO_Three85.7g and N
H_FourNO_ThreeAn aqueous solution containing 0.71 g and KBr 39.6 g,
KI 1.17g, K_ThreeIrCl₆Water solution containing 0.52mg
The liquid was added over 8 minutes 40 seconds by the double jet method. This
At this stage, the particle diameter corresponding to the sphere is set to 0.21 μm.
Was prepared. After this, the temperature is lowered to 35 ° C.
Soluble salts were removed. Then raise the temperature to 60 ° C and
Add 156g of latin and 5g of 2-phenoxyethanol
The pH was adjusted to 6.70 with NaOH and sulfuric acid. That
1-phenyl-5-mercaptotetrazole 56m
g, sodium thiosulfate 4.79 mg, 4,7-dithia
-1,10-decanediol 124 mg, HAuCl4
Add 9.57mg and 43.4mg potassium thiocyanate
4 minutes later, 4-hydroxy-6-methyl-1,3,3
After adding 0.91 g of a, 7-tetraazaindene
Quenched and solidified to obtain a raw emulsion. T is an emulsion layer / preservation described later.
When the protective layer is applied and the automatic development process described below is performed,
Buri value is 0.15 in optical density (excluding support density)
0.04). Halo of the obtained raw emulsion
The average amount of iodine contained in the silver halide grains is 1.4 mol.
%Met. (Preparation of emulsion coating solution, coating formation of emulsion layer)
2,4-dihydroxybenzal per 1 kg of the original emulsion
Dehydroxime 0.2g, KBr 0.66g, p-Torr
Sodium ensulfinate 3.26 g, 3- (5-
Lucapto-1-tetrazoyl) benzene sulfonate
0.10 g of lithium, 28 mg of lipoic acid, 1,3-dihydro
Xylbenzene 0.8 g, 3,4-dimethylthiazoline
2-thione 82 mg, compound A-1 (21 mg), compound
Product A-2 (6.4 mg), 2,4-dichloro-6-hydride
Roxy-1,3,5-triazine sodium salt 0.60
g was added and water was added to make the total volume 1043 ml. this
First undercoat of styrene-butadiene after biaxial stretching of liquid
(0.3 g / m²) And gelatin (0.1 g / m²Second)
Blue colored polyethylene terephthalate with undercoat
(Thickness: 175 μm) 109 ml / m on the support²Apply
Dried to form an emulsion layer. Particle habit is cubic and spherical
The particle size is 0.21 μm and the coating Ag amount is 7.35.
g / m²The amount of coated gelatin is 12.0 g / m²Met. [0164] Embedded image (Preparation of protective layer coating solution, protective layer coating form)
Adult) Coal-processed gelatin made from beef bone (pH 6.0,
Jelly strength 260g, Ca content 2700ppm) 1kg
Against water 9865ml, methanol 921ml, compound
Product A-3 (29.6 g), PMMA with a particle size of 5.5 μm
Agent (28.8 g), compound A-4 (4.5 g),
Compound A-5 (1.38 g) was added respectively, and phosphoric acid was added.
The pH was adjusted to 5.1. After that, Dainippon Ink Co., Ltd.
209 g of Boncoat DV-759 manufactured by KK
2,4-dichloro-6-hydroxy-1,3,5-tri
Add 3.56g of azine sodium salt,
Gelatin amount is 2.21 g / m²On the emulsion layer to be
And dried to form a protective layer. [0166] Embedded image(Preparation of back layer coating solution, coating of back layer)
Formation) For 1kg of the same type of gelatin as the protective layer,
Xel (product of ICI) 1 g, 4-dichloro-6-hydro
3.5 g of xy-1,3,5-triazine sodium salt,
Snowtex C manufactured by Nissan Chemical Co., Ltd. (20% solution, particle size 10)
m) 0-1514 ml, polymer latex [poly (d
Til acrylate / methacrylic acid) = 97/3] 0-1
Add 500ml and add water to make 9730ml
did. Apply these emulsions to the emulsion layer surface protective layer.
5.2g as gelatin on the back side of the finished single-sided photosensitive material
/ M²Apply and dry to form a back layer
It was. (Preparation of Back Protective Layer Coating Solution, Back Protection
Layer coating formation) Back protective layer coating solution is emulsion layer side protective layer
The same amount as the liquid with a gelatin content of 0.8 g / m²To be
Apply and dry on the back layer to form a back protection layer.
It was. In this way, a photosensitive material 11 was produced. -Production of photosensitive materials 12-16- According to Table 3, compound A-51.38 g of the protective layer coating solution
In the same manner as the photosensitive material 11, except that it is replaced with an equimolar amount.
Thus, photosensitive materials 12 to 13 were produced. -Production of photosensitive materials 17-22- Halo except that KI was changed from 1.17g to 3.35g
In the same way as silver halide emulsion (original emulsion), silver halide grains
Halogen with an average iodine content of 1.4 mol%
A silver halide emulsion was prepared. Using this silver halide emulsion
Except for the photosensitive materials 11-16,
Materials 17-22 were prepared. (Evaluation) The obtained photosensitive material was developed.
The procedure was the same as in Example 1 except that the process was performed as shown below.
And evaluated. However, the relative sensitivity is the following condition of the photosensitive material 11.
Shown in relative value with 100 obtained in (d)
It was. The results are shown in Table 3. ―Development processing― Development processing is performed with an automatic processor in accordance with the following development processing conditions.
Using Fuji Photo Film Co., Ltd. FIP-4000
The processing time was 11 minutes in all steps. Developer is Fuji
Photo film Co., Ltd. Super Doll I23 ° C,
Fixer is Super F · I3 manufactured by Fuji Photo Film Co., Ltd.
The temperature was set to 0 ° C., and the water was washed to 18 ° C. with running water. As development processing conditions, the following conditions (d),
Processed in (e).                   Developer replenisher Fixer replenisher   Condition (d) 50ml / 4 cut 50ml / 4 cut (645ml / m²)   Condition (e) 25ml / 4 cut 25ml / 4 cut (323ml / m²) [0174] [Table 3]From the results shown in Table 3, the photosensitive material 11 of the comparative example is shown.
On the other hand, the light-sensitive materials 12, 13, 14, 15, 16 of the present invention.
Is good with no unevenness of density, and the conditions (e)
Even if the amount of replenisher is reduced, there is little decrease in sensitivity and gradation.
It can be seen that good results can be obtained. (Example 3) Coating of protective layer in Example 1
2 types of surfactants for liquid and back protective layer coating liquid
Example 1 with the exception of FSA-1 and FSA-2
A photosensitive material was prepared and evaluated in the same manner as (Sensitive material 1).
However, all have little sensitivity and gradation change, and density
It was confirmed that there was little unevenness. (Example 4) Coating of protective layer in Example 1
Surfactant and back protective layer coating liquid surfactant FSF-38
(Except for the same mass as the surfactant)
A photosensitive material was prepared and evaluated in the same manner as in Example 1 (Sensitive material 1).
As a result, there is little change in sensitivity and gradation, and density unevenness.
It was confirmed that there were few. (Example 5) Coating of protective layer in Example 2
FSA-1, the surfactant for the liquid and the back protective layer coating liquid,
FSA-2, FSA-9, FSF-18, FSF-2
6 or FSF-38, except that Example 2 (photosensitive
Photosensitive material was prepared and evaluated in the same manner as Material 11).
B) Less uneven density and less change in sensitivity and gradation
It was confirmed. (Example 6) Surfactant and protective layer coating solution
And the type and amount of surfactant in the back protection layer coating solution
Other than changing to the types and addition amounts of surfactants shown in Table 4
In the same manner as in Example 1, photosensitive materials 23 to 32 were prepared,
In the same manner as in Example 1, the conditions (i), (b) and (c) were evaluated.
went. The results are shown in Table 5. [0180] [Table 4] [0181] [Table 5] As is apparent from the results in Table 5, the present invention
The photosensitive materials 24, 25, 26, and 27 satisfy the conditions (A)
(B) In (c), there is little decrease in sensitivity and gradation
There is little change and density unevenness is also good. [0183] 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
To provide a silver halide photographic material capable of obtaining sensitivity.
You can.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Eiichi Okutsu             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. F-term (reference) 2H023 BA02 CD05

Claims (1)

What is claimed is: 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. In the silver halide photographic light-sensitive material having, the average amount of iodine contained in the photosensitive silver halide grains is more than 0.45 mol% and 3.5 mol% or less,
A silver halide photographic light-sensitive material comprising a surfactant represented by the following general formula (1): [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. )