JPH04340951A - Silver halide photographic sensitive material and developing method for that - Google Patents

Abstract

PURPOSE:To obtain high sensitivity, to improve fogging due to pressure and to enable rapid processing by incorporating colloidal silica into an emulsion layer comprising silver halide which is chemically sensitized with a selenium compd. CONSTITUTION:This photosensitive material has at least one silver halide emulsion layer on a supporting body and at least one protective layer in the upper part of the emulsion layer. At least one emulsion layer contains colloidal silica and silver halide particles sensitized with a selenium sensitizer. As for the silver halide, silver chloride-boride or silver chloride-iodide-bromide containing 0-1mol% silver iodide is preferable, and more preferably, the silver halide has <=0.5mum average particle size. As for the selenium sensitizer, unstable selenium compd. and/or nonstable selenium compd. is added and stirred with the emulsion at high temp. for a certain time. As for the unstable selenium sensitizer, iso- selenocyanates are used. The outermost layer of the protective layer has <=0.35 coefft. of dynamic friction, preferably.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to a silver halide photographic material.
This is related to materials, especially in high-intensity, short-time exposures.
Improved sensitivity and pressure resistance, and excellent suitability for rapid processing.
Regarding silver halide photographic light-sensitive materials and their development processing methods.
It is something to do. [Prior Art] Silver halide photographic materials are generally made of plastic.
Covered with stick film, paper or plastic
A light-sensitive emulsion layer and, if necessary, a support such as paper or glass
Intermediate layer, protective layer, back layer, anti-halation layer depending on
By combining various constituent layers such as antistatic layer and antistatic layer,
It is coated. Silver halide photographic materials are
Photographs of manufacturing processes such as coating, drying, processing, etc.
, handling such as transportation during development processing, printing, projection, etc.
contact parts between various devices and photosensitive materials during printing, or
Contact friction between the photosensitive material such as dust and fiber waste or the surface of the photosensitive material
Contact between photographic materials, such as between the front and back surfaces.
Pressure fog may occur on photosensitive materials due to tactile friction.
Happens often. Improved concentration changes due to pressure
Polymer latex and polyhydric alcohol are used as a means of
Which plasticizer should be added and how should the silver halide emulsion layer be mixed?
How to reduce the silver halide/gelatin ratio and thicken the protective layer
Adding a slip agent or colloidal silica to the protective layer
to relieve the pressure before it reaches the silver halide grains.
There are known methods to do this. British Patent No. 738,618
No. 738,637 refers to heterocyclic cyclic compounds.
No. 738,689 has alkyl esters.
, U.S. Patent No. 2,960,404 describes polyhydric alcohols.
3,121,060, carboxyalkyl
cellulose, and paraffin in JP-A-49-5017.
and carboxylic acid salts, and in Japanese Patent Publication No. 53-28086,
A method using kyl acrylate and an organic acid has been disclosed.
There is. However, the method of adding plasticizers does not improve the mechanical strength of the emulsion layer.
There is a limit to how much it can be used because it reduces the
When the silver/gelatin ratio is decreased, development progress is delayed and
It has drawbacks such as impairing suitability for rapid processing. Also, Hido
Silver halide photographic materials containing radin derivatives are
Droxybenzene compounds were introduced for various purposes and
Patent No. 4,332,108, U.S. Patent No. 4,385,
No. 108, U.S. Patent No. 4,377,634, etc.
JP-A No. 62-21143 describes pressure sensitization.
Techniques to prevent this are described. However, the printing industry
It is strongly desired to improve the efficiency and speed of work.
This speeds up scanning and reduces the processing time of photosensitive materials.
There is a widespread need to shorten the In order to meet these needs in the printing field, we
faster scanning for scanners and plotters
, and increasing the number of lines and narrowing the beam for higher image quality.
In silver halide photographic materials,
is highly sensitive, has excellent stability, and can be processed quickly.
It is hoped that What is meant by rapid development processing here?
Insert the tip of the lum into the automatic developing machine, and then
part, fixing tank, transition part, washing tank, and drying part.
The time it takes for the leading edge of the film to emerge from the drying section is 15 to 60 minutes.
It refers to a process that takes seconds. [0003] In this way, high-sensitivity silver halide photography
Traditionally, selenium sensitizers have been used to obtain materials.
The method of sensitization is disclosed in U.S. Patent Nos. 1,574,944 and 16
No. 02592, No. 1623499, No. 32974
No. 46, No. 3297447, No. 3320069
, Same No. 3408196, Same No. 3408197, Same No.
No. 3442653, No. 3420670, No. 359
1385, French Patent No. 2,693,038, French Patent No. 2
No. 093209, Special Publication No. 52-34491, No. 52-
No. 34492, No. 53-295, No. 57-22090
No., JP-A-59-180536, JP-A No. 59-18533
No. 0, No. 59-181337, No. 59-187338
No. 59-192241, No. 60-150046
, No. 60-151637, No. 61-246738,
Japanese Patent Publication No. 3-4221, Japanese Patent Application No. 1-287380,
No. 1-250950, No. 1-254441, No. 2-3
No. 4090, No. 2-110558, No. 2-13097
No. 6, No. 2-139183, No. 2-229300,
Furthermore, British Patent Nos. 255846 and 861984
and E. H. Spencer et al., Jorna
lof Photographic Science Magazine
, Volume 31, pages 158-169 (1983), etc.
It is shown. This method allows highly sensitive halogenation
A silver photographic material can be obtained, but the pressure
Power fog worsens. By conventionally known means,
Further improvement was required as sufficient effect on pressure fog was not obtained.
was strongly desired. [Problems to be Solved by the Invention] The purpose of the present invention is to
pressure fog caused by contact friction with various materials.
Improved silver halide photographic materials that can be processed quickly
Our goal is to provide the following. [Means for Solving the Problems] These objects of the present invention are
, at least one silver halide emulsion layer on the support, and
a halo having at least one protective layer on top of the emulsion layer;
In the silver-genide photographic light-sensitive material, at least
Silver halide grains sensitized with selenium sensitizer in one layer
and a halo characterized by containing colloidal silica.
This was achieved using silver-genide photographic materials. [0006] The silver halide used in the present invention is, for example, a salt.
Silveride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide
, silver chloroiodobromide, etc. may be used. Smell of the present invention
Among the above silver halides, silver chloroiodobromide, silver chlorobromide
, silver iodobromide are preferred. More preferably silver iodide is 0 to 1
Silver chlorobromide or silver chloroiodobromide containing mol % is advantageously used.
. The average grain size of the silver halide used in the present invention is
Fine particles (for example, 0.7μ or less) are preferable, especially 0.
．． It is preferably 5μ or less. Particle size distribution is basically controlled.
Although there is no limit, monodispersity is preferable. The word here is
Dispersion means that at least 95% of the weight or number of particles is
Is the particle group with a size within ±40% of the average particle size?
It means that it is composed of Halogenation in photographic emulsions
Silver particles have regular shapes such as cubes and octahedrons.
r) It may have a crystalline form, and may also have a spherical or plate-like shape.
It has irregular crystals such as
or a compound of these crystal forms.
There may be. Silver halide grains have uniform interior and surface layers.
It may consist of phases or just phases. By mixing two or more types of silver halide emulsions formed separately.
May be used. Further, the silver halide emulsion layer may be a single layer, or
It may be a multiple layer (two layers, three layers, etc.), or a multiple layer case.
In this case, different silver halide emulsions may be used,
The same one may be used. Halogenation used in the present invention
Silver emulsions contain silver halide grain formation or physical ripening.
Cadmium salts, sulfites, lead salts, thallium salts
, rhodium salt or its complex salt, iridium salt or
A complex salt thereof may also be present. In the present invention,
Water-soluble rhodium salts, typically rhodium chloride,
Dium trichloride, rhodium ammonium chloride
It is preferable to use Furthermore, these complex salts
It can also be used. The above rhodium salt addition time is emulsion
Limited to before the end of the first ripening during production, especially during grain formation.
It is desirable that the amount of addition is 1 per mole of silver.
The preferred range is 1 x 10-8 mol or more and 1 x 10-6 mol or less.
Delicious. Silver halides particularly suitable for use in the present invention
is 10-8 to 10-5 mole of iridium per mole of silver.
It is prepared in the presence of a salt or a complex salt thereof. Above
before the physical ripening of the silver halide emulsion manufacturing process.
Adding the above amount of iridium salt especially during particle formation
is desirable. The iridium salt used here is a water-soluble
Iridium salts or iridium complexes, such as iridium trichloride.
Lydium, iridium tetrachloride, hexachloroiridium
(III) acid potassium, hexachloroiridium (I
V) Potassium acid, hexachloroiridic acid (III)
Ammonium etc. Binding agent or protection for photographic emulsions
As a colloid, it is advantageous to use gelatin.
, other hydrophilic colloids can also be used. Ta
For example, gelatin derivatives, graphs of gelatin and other polymers, etc.
Proteins such as ftopolymers, albumin, and casein;
Roxyethyl cellulose, carboxymethyl cellulose
, cellulose derivatives such as cellulose sulfates, etc.
, sodium alginate, sugar derivatives such as starch derivatives, polyester
Vinyl alcohol, polyvinyl alcohol partial aceter
poly-N-vinylpyrrolidone, polyacrylic acid, poly
Rimethacrylic acid, polyacrylamide, polyvinylimide
Single or copolymer of dazole, polyvinylpyrazole, etc.
It is possible to use a variety of synthetic hydrophilic polymer materials such as
can. The silver halide emulsion used in the present invention is chemically sensitized.
It does not have to be chemically sensitized, but it may be chemically sensitized. Ha
Chemical sensitization methods for silver halide emulsions include sulfur sensitization and reduction.
Original sensitization and noble metal sensitization methods are known, and both of these methods
Both may be used alone or in combination for chemical sensitization.
. Among the precious metal sensitization methods, the gold sensitization method is the representative method.
Compounds, mainly gold complex salts, are used. Precious metals other than gold,
For example, it contains complex salts such as platinum, palladium, and rhodium.
There is no problem. As a sulfur sensitizer, it is included in gelatin.
In addition to sulfur compounds such as
Osulfates, thioureas, thiazoles, rhodanines, etc.
can be used. As a reduction sensitizer, stannous salt
, amines, formamidine sulfinic acid, silane compounds
You can use objects, etc. The selenium sensitizer used in the present invention is
, using selenium compounds disclosed in previously known patents.
can be done. That is, usually unstable selenium compounds
and/or by adding non-labile selenium compounds.
Stir the emulsion for a certain period of time at a temperature, preferably 40°C or higher.
used by Especially as an unstable selenium compound.
Publication No. 44-15748, Special Publication No. 43-13489,
Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-229300
It is preferable to use the compounds described in . concrete
Isoselenocyanates are unstable selenium sensitizers.
(e.g. aliphatic isoselenocyanate such as allyl isoselenocyanate)
selenocyanates), selenoureas, selenoketones
, selenoamides, selenocarboxylic acids (e.g. 2-
selenopropionic acid, 2-selenobutyric acid), selenoester
diacylselenides (e.g., bis(3-chloro
-2,6-dimethoxybenzoyl)selenide), seleno
Phosphates, phosphineselenides, colloidal gold
Examples include genus selenium. Preference for unstable selenium compounds
Although some desirable types have been described above, these are not limited.
stomach. For those skilled in the art, unstable forms as sensitizers for photographic emulsions are known.
Speaking of selenium compounds, as long as selenium is unstable,
The structure of the compound is not very important;
The organic part of the sensitizer molecule carries selenium and makes it unstable.
It has no role other than to exist in the emulsion in a fixed form.
It is generally understood that In the present invention,
Such a broad concept of unstable selenium compounds can be advantageously used.
Ru. As a non-unstable selenium compound used in the present invention
is Special Publication No. 46-4553, Special Publication No. 34492-1977
and the compound described in Japanese Patent Publication No. 52-34491 is used.
It will be done. Examples of non-unstable selenium compounds include selenite.
acid, potassium selenocyanide, selenazole, sele
Quaternary salts of nazoles, diarylselenide, diaryl
Diselenide, dialkyl selenide, dialkyl diselenide
Do, 2-selenazolidinedione, 2-selenoxazoli
Examples include zinthione and derivatives thereof. this
Among these selenium compounds, the following general formula (I
II) and (IV). General formula (III) [Formula 1] In the formula, Z1 and Z2 are each the same
but may also be different, including alkyl groups (e.g. methyl
group, ethyl group, t-butyl group, adamantyl group, t-o
(cutyl group), alkenyl group (e.g. vinyl group, propylene group),
nyl group), aralkyl group (e.g. benzyl group, phenyl group), aralkyl group (e.g. benzyl group, phenyl group),
methyl group), aryl group (e.g. phenyl group, pentaf group), aryl group (e.g. phenyl group,
fluorophenyl group, 4-chlorophenyl group, 3-nitro
phenyl group, 4-octylsulfamoylphenyl group,
α-naphthyl group), heterocyclic group (e.g. pyridyl group,
phenyl group, furyl group, imidazolyl group), -NR1 (
R2), -OR3 or -SR4. R1
, R2, R3 and R4 are the same or different.
alkyl group, aralkyl group, aryl group,
represents a group or a heterocyclic group. Alkyl group, aralkyl group,
Examples of aryl groups or heterocyclic groups are similar to Z1.
can give. However, R1 and R2 are hydrogen atoms or acyl groups
(For example, acetyl group, propanoyl group, benzoyl group
, heptafluorobutanoyl group, difluoroacetyl group
, 4-nitrobenzoyl group, α-naphthoyl group, 4-t
(lifluoromethylbenzoyl group). In general formula (III), preferably Z1 is an alkyl group
, represents an aryl group or -NR1 (R2), and Z2
represents -NR5 (R6). R1, R2, R
5 and R6 may be the same or different.
hydrogen atom, alkyl group, aryl group, or acyl group
represents a group. In general formula (III), more preferably N,N-dial
Kirselenourea, N,N,N'-trialkyl-N'-
Acyl selenourea, tetraalkyl selenourea, N,N
-dialkyl-arylselenoamide, N-alkyl-
Represents N-aryl-arylselenoamide. General formula (IV) ##STR2## In the formula, Z3, Z4 and Z5 are
They may be the same or different, and include aliphatic groups and aromatic groups.
, heterocyclic group, -OR7, -NR8 (R9), -S
R10, -SeR11, X represents a hydrogen atom. R7,
R10 and R11 are an aliphatic group, an aromatic group, a heterocyclic group,
Represents a hydrogen atom or a cation, R8 and R9 are
represents an aliphatic group, aromatic group, heterocyclic group or hydrogen atom,
X represents a halogen atom. In general formula (IV), Z3, Z4, Z5, R
7, R8, R9, R10 and R11
Aliphatic groups include straight chain, branched or cyclic alkyl groups,
Nyl group, alkynyl group, aralkyl group (e.g. methyl
group, ethyl group, n-propyl group, isopropyl group, t-
Butyl group, n-butyl group, n-octyl group, n-decyl group
group, n-hexadecyl group, cyclopentyl group, cyclohexadecyl group,
xyl group, allyl group, 2-butenyl group, 3-pentenyl group
group, propargyl group, 3-pentynyl group, benzyl group,
phenethyl group). In general formula (IV), Z3, Z4, Z5, R
7, R8, R9, R10 and R11
Aromatic groups include monocyclic or condensed aryl groups (e.g.
Nyl group, pentafluorophenyl group, 4-chlorophenyl group
group, 3-sulfophenyl group, α-naphthyl group, 4-methyl
tylphenyl group). In general formula (IV), Z3, Z4, Z5, R
7, R8, R9, R10 and R11
A heterocyclic group consists of a nitrogen atom, an oxygen atom, or a sulfur atom.
Saturated or unsaturated 3- to 10-membered ring containing at least one
heterocyclic groups (e.g., pyridyl, chenyl, furyl)
group, thiazolyl group, imidazolyl group, benzimidazolyl group
Represents a ru group). In general formula (IV), R7, R10 and R11
The cation represented by is an alkali metal atom or an ammonia
The halogen atom represented by
Represents an elementary atom, chlorine atom, bromine atom or iodine atom. In general formula (IV), preferably Z3, Z4 or Z
5 represents an aliphatic group, an aromatic group, or -OR7, and R
7 represents an aliphatic group or an aromatic group. In general formula (IV), more preferably trialkyl phosph
inselenide, triarylphosphine selenide, tri
Alkyl selenophosphate or triaryl seleno
Represents phosphate. Below, general formula (III) and
Specific examples of the compound represented by (IV) are shown below, but the present invention
It is not limited to this. [Formula 3] [Formula 3] [Formula 4] [Formula 4] [Formula 5] [Formula 5] [Formula 6] [Formula 7] [Formula 7] [0020] Regarding the selenium sensitization method, US Pat. No. 15
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297447, No. 99, No. 3297446, No. 3297447, No.
No. 3320069, No. 3408196, No. 34
No. 08197, No. 3442653, No. 34206
No. 70, No. 3591385, French Patent No. 269
No. 3038, No. 2093209, Special Publication No. 52-34
No. 491, No. 52-34492, No. 53-295,
No. 57-22090, JP-A No. 59-180536,
No. 59-185330, No. 59-181337, No. 59-181337, No.
No. 59-187338, No. 59-192241, No. 6
No. 0-150046, No. 60-151637, No. 61
-246738, Japanese Patent Application Publication No. 3-4221, Patent Application No. 1-
No. 287380, No. 1-250950, No. 1-254
No. 441, No. 2-34090, No. 2-110558
, No. 2-130976, No. 2-139183, No. 2
-229300 Furthermore, British Patent No. 255846;
No. 861984 and H. E. Spencer et al.
Author, Journal of Photographic
Science magazine, volume 31, pages 158-169
(1983) and others. These selenium sensitizers can be used in water or methanol.
or a mixture of organic solvents such as alcohol, ethanol, etc.
Dissolution or Japanese Patent Application No. 2-264447, 2-26
It is added at the time of chemical sensitization in the form described in No. 4448. It is preferably added before the start of chemical sensitization. The set used
The selenium sensitizer is not limited to one type, but two or more of the above selenium sensitizers.
The above can be used in combination. unstable selenium compounds
and a non-labile selenium compound may be used in combination. used in the present invention
The amount of selenium sensitizer used depends on the amount of selenium sensitizer used.
activity, type and size of silver halide, ripening temperature and
Preferably, halogenated
It is at least 1×10 −8 mol per mol of silver. more preferable
is 1 x 10-7 mol or more and 1 x 10-5 mol or less
. When using a selenium sensitizer, the temperature of chemical ripening is preferable.
temperature is 45°C or higher. More preferably 50°C or higher, 8
The temperature is below 0°C. pAg and pH are arbitrary. example
The effect of the present invention cannot be obtained in a wide range of pH from 4 to 9.
It will be done. Selenium sensitization is carried out in the presence of a silver halide solvent.
is more effective. Colloidal silica (colloidal silica) used in the present invention
(loidal silica) has an average particle size of 5 mμ to 1000 mμ.
Preferably 5mμ to 500mμ, the main component is silicon dioxide
It contains alumina or sodium aluminate as a minor component.
It may also contain thorium or the like. Also, these colloidal
Silica uses sodium hydroxide and carbon hydroxide as stabilizers.
Inorganic bases such as lithium, lithium hydroxide, ammonia, etc.
Contains organic bases such as tramethylammonium ion.
You can leave it there. Regarding these colloidal silicas,
112732-112, Special Publication No. 57-009051,
It is disclosed in Japanese Patent Publication No. 57-051653. colloid
As a specific example of silica, Nissan Chemical (Tokyo, Japan)
Snowtex 20 (SiO2/Na2O ≧57
), Snowtex 30 (SiO2/Na2O ≧50
), Snowtex C (SiO2/Na2O ≧100
), Snowtex O (SiO2/Na2O ≧500
), etc., and are commercially available under the trade names. Here, (SiO2
/Na2O means silicon dioxide (SiO2) and sodium hydroxide.
The weight ratio of sodium hydroxide is changed to Na2O.
All figures are calculated based on the figures listed in the catalog.
This is the value given. Colloidal silica used in the present invention
The preferred amount is used as a binder for the layer to be added.
dry weight ratio of 0.05 to 1 to gelatin
．． 0, particularly preferably 0.1 to 0.6. What is the dynamic friction coefficient (μk) in the present invention?
Same as friction coefficient test method described in JIS K7125
It can be obtained using the principle of Conditions of 25℃ 60%RH
After setting it under the sapphire needle (e.g. 0 diameter
．． 5 to 5 mm) with a constant load (contact force: Fp Example 5
0 to 200 g) to coat the surface of the silver halide photosensitive material.
Constant speed (e.g. 20-100cm/min)
, measure the tangential force (Fk) at that time, and calculate the following
, calculated using equation 1. ##EQU00001## For example, a surface property measuring machine (H
EIDON-14 type). In the present invention, the coefficient of dynamic friction of the outermost layer is 0.
In order to keep it below 35, it is preferable to use a so-called slip agent.
Delicious. Typical slip agents used in the present invention include:
For example, U.S. Patent No. 3,042,522, British Patent No.
No. 955,061, U.S. Patent No. 3,080,317
, No. 4,004,927, No. 4,047,958,
No. 3,489,567, British Patent No. 1,143,11
Silicone-based slip agent described in No. 8, etc., U.S. Patent Nos. 2 and 4
No. 54,043, No. 2,732,305, No. 2,97
No. 6,148, No. 3,206,311, German Patent No. 1
, No. 284,295, No. 1,284,294, etc.
Higher fatty acid-based, alcohol-based, acid amide-based slip agents, English
National Patent No. 1,263,722, U.S. Patent No. 3,933
, 516, etc., U.S. Patent No. 2,58
No. 8,765, No. 3,121,060, British Patent No. 1
, 198, 387, etc. Ester type, ether type
Sliding agent, U.S. Pat. No. 3,502,473, U.S. Pat. No. 3,04
The taurine-based slip agent described in No. 2,222, the above-mentioned colloid
silica etc. The slip agent of the present invention has the following general formula (
V), general formula (VI), or general formula (VII)
alkylpolysiloxane and a stream in a liquid state at room temperature.
Motive paraffin is preferably used. More preferably one
Adding a polyoxyalkylene chain to the side chain represented by general formula (V)
and an alkylpolysiloxane having the general formula (VI)
The alkylpolysiloxane shown is used. General formula (V) ##STR11## In the formula, R is an aliphatic group {for example, an alkyl group (
Preferably those having 1 to 18 carbon atoms), substituted alkyl groups (e.g.
For example, aralkyl group, alkoxyalkyl group, aryloki group
(such as sialkyl groups) or aryl groups (such as phenylene groups)
nyl group, etc.). R' is a hydrogen atom, an aliphatic group {e.g.
For example, an alkyl group (preferably one having 1 to 12 carbon atoms),
substituted alkyl groups} or aryl groups (such as phenyl groups)
(e.g.). R'' is an alkyl group (e.g. methyl
groups), or alkoxyalkyl groups (e.g.
dimethyl group, etc.). A is divalent aliphatic hydrocarbon
Represents a residue. n is 0 or an integer from 1 to 12, p is 0 to
a number of 50, q is a number of 2 to 50 (preferably 2 to 30),
x is a number from 0 to 100, y is a number from 1 to 50, z is a number from 0 to 10
represents the number 0, and x+y+z is 5 to 250 (preferably
10 to 50). Specific examples of R include methyl
, ethyl, propyl, pentyl, cyclopentyl, cyclopentyl
lohexyl, dimethylpentyl, heptyl, methylhexyl
Cyl, octyl, dodecyl, octadecyl, phenyl
Chil, methylphenylethyl, phenylpropyl, sik
lohexylpropyl, benzyloxypropyl, pheno
xypropyl, ethyloxypropyl, butyloxypropyl
Includes chill, phenyl, etc. The group represented by A is methyl
lene, 1-one-trimethylene, 2-methyl-1-one
-trimethylene, etc. Al denoted by R'
Kill groups include methyl, ethyl, propyl, butyl, a
Mil, hexyl, heptyl, octyl, nonyl, decyl
, dodecyl group. General formula (VI) [Chemical formula 12] [0032] General formula (VI) is the following general formula [VI-1]
Cyclic siloxane having a siloxane unit represented by
and a terminal group represented by the general formula [VI-2]
Includes linear siloxanes. General formula [VI-1] [Chemical formula 13] [Chemical formula 13] [Chemical formula 13] [Chemical formula [VI-2]] [Chemical formula 14] [Chemical formula 14] In the formula, R1 is alkyl having 5 to 20 carbon atoms
, cycloalkyl, alkoxyalkyl group, aryl group
alkyl group, aryloxyalkyl group, glycidyloxy
Represents a sialkyl group. R2 is alkyl having 1 to 20 carbon atoms.
Kyl group, cycloalkyl having 5 to 20 carbon atoms, alkoxy
Alkyl, arylalkyl, aryloxyalkyl
and a glycidyloxyalkyl group. l is also 0
or a number greater than or equal to 1, m is a number greater than or equal to 1, l+m is 1 to 1
Represents the number 000. Preferably l+m is 2 to 500
It is. As a specific example of R1 in the compound represented by general formula (V)
is pentyl, methylpentyl, cyclopentyl, cyclopentyl
lohexyl, dimethylpentyl, heptyl, methylhexyl
Syl, octyl, eicosyl, phenylethyl, methyl
Phenylethyl, phenylpropyl, cyclohexylp
Lopyl, benzyloxypropyl, phenoxypropyl
, tolyloxypropyl, naphthylpropyl, ethyloxypropyl
xypropyl, butyloxyethyl, octadecyloxy
cypropyl, glycidyloxypropyl, glycidyloxypropyl
Examples include xybutyl. General formula (VII) ##STR15## In the formula, R3 is an alkyl group having 1 to 3 carbon atoms,
R4 is an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 2 carbon atoms
Represents an alkoxy group. m is an integer from 0 to 2000
. Next, among the compounds represented by the general formula (V), its substitutes
Typical compound examples are shown below. embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image
Examples of typical compounds are shown below. [Formula 18] [Formula 19] [Formula 19] A compound represented by the general formula (VII)
Among them, typical examples of the compounds are shown below. ##STR20## The present invention includes a compound represented by the following general formula (VIII).
It is more preferable to use an anionic surfactant that
. General formula (VIII) [Image Omitted] [Image Omitted] In the formula, R is a substituted or unsubstituted group having 3 to 30 carbon atoms.
Represents a substituted alkyl group, alkenyl group or aryl group
and R' is a hydrogen group, a substituted or unsubstituted group having 1 to 10 carbon atoms.
represents an alkyl group, alkenyl group or aryl group
. n represents a number from 2 to 6. Also, M is a hydrogen atom, an inorganic or
represents an organic cation. Anion used in the present invention
Specific compound examples of surfactants are shown below. ##STR22## The amount of slip agent applied depends on the amount of binder in the outermost layer.
On the other hand, the weight ratio is 0.01 to 1.0, preferably 0.0
5 to 0.5. Especially 0.01~0.1g/m2
It is preferable that Also, an anion of general formula (VIII)
When using a surfactant, 0.001-0.5g/m2
, especially preferably 0.01 to 0.2 g/m2
. The coefficient of dynamic friction (μk) is 0.35 or less, preferably 0.
．． 35 to 0.10. Next, according to the present invention, pressure resistance can be increased without impairing sensitivity.
Used for the purpose of improving shelf life and storage stability.
It is preferable to use a polyhydroxybenzene compound with
Yes. Polyhydroxybenzene compounds are used as emulsions in sensitive materials.
It may be added to a layer or a layer other than an emulsion layer. The amount added ranges from 10-5 to 1 mol per mol of silver.
The range of 10-3 mol to 10-1 mol is particularly effective.
It is effective. Examples of preferred compounds include the following:
. ##STR23## In the present invention, the protective layer is composed of two or more layers.
It is preferable that Silver halide photosensitive materials are processed under low humidity conditions.
If the hydrophilic colloid layer becomes brittle when stored under
It has the following drawbacks. In order to improve this, glass
Polymer latte with a transition point (hereinafter referred to as Tg) of 20°C or less
It is preferable that the emulsion layer and/or the protective layer include
Delicious. Especially when there are two or more protective layers, the emulsion layer and the outermost layer
Inclusion in the intermediate layer with the film increases the film strength in the developing solution.
, brittle without impairing the adhesion between photosensitive materials under high humidity conditions.
This is preferable in that it improves. In addition, the outermost layer has other slip properties.
Adding colloidal silica to both improves slipperiness.
At the same time, the strength of the dry film is improved and its scratch resistance is further improved.
It is preferable in that it does. Colloidal sugar added to this outermost layer
The amount of binder is 0 in weight ratio to the amount of binder in the outermost layer.
．． 01-1.0, preferably 0.1-0.5. Polymer contained in the protective layer of the present invention
- As for latex, for example, U.S. Patent No. 2,772,1
No. 66, No. 3,325,286, No. 3,411,91
No. 1, No. 3,311,912, No. 3,525,620
Issue, Research Disclosure (Research
Disclosure) Magazine No. 195 19
551 (July 1980) etc.
Acrylic acid ester, methacrylic acid ester, styrene
It is a hydrate of vinyl polymers such as. Tg is below 20℃
A preferred polymer latex is methyl acrylate.
acrylate, ethyl acrylate, butyl acrylate, etc.
Alkyl acrylate homopolymer or alkyl acrylate
Lylate and acrylic acid, N-methylolacrylamide
(preferably a copolymer component such as acrylic acid)
(up to 30% by weight), butadiene homopolymer or
Butadiene and styrene, butoxymethylacrylamide
, copolymers with one or more of acrylic acid, vinylidene chloride
-Methyl acrylate acrylic acid terpolymer etc.
It will be done. The Tg of polymer latex is determined by differential scanning calorimetry.
(DSC) method. With this invention
The preferred range of average particle size of the polymer latex used is
It is 0.005 to 1 μm, especially 0.02 to 0.1 μm. Po
The amount of remar latex added depends on the hydrophilic color of the layer to be added.
5 to 200%, particularly preferably 10 to 100%, based on the weight of the id.
Yes. Next, polymers with Tg of 20% or less in the present invention
Specific examples of latex are shown, but are not limited to these.
There isn't. embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image .
Depending on the pigment, relatively long wavelength blue light, green light, red light, or
or may be spectrally sensitized to infrared light. As a sensitizing dye
, cyanine dye, merocyanine dye, complex dye
Anine dyes, complex merocyanine dyes, holophores
-Lacyanine pigment, styryl pigment, hemicyanine pigment
, using oxonol dyes, hemioxonol dyes, etc.
be able to. Examples of useful sensitizing dyes used in the present invention are
For example, RESEARCH DISCLOSURE
m 17643 Section IV-A (December 1978 p.
．． 23), Item 1831X (August 1979)
Mon p. 437) or in the literature cited.
It is. Particularly suitable for the spectral characteristics of various scanner light sources.
Sensitizing dyes with spectral sensitivity can be advantageously selected.
Ru. For example, for A) argon laser light source, JP-A-60-1
No. 62247, JP-A No. 2-48653, U.S. Patent No. 2,
No. 161,331, the system described in West German Patent No. 936,071
B) Helium-Neon Leather Light
For sources, JP-A-50-62425 and JP-A-54-1
No. 8726, trinuclear shield shown in No. 59-102229
Anine pigments, C) For LED light sources, Special Publication No. 48-
No. 42172, No. 51-9609, No. 55-3981
No. 8, Chiaka described in JP-A No. 62-284343
Rubocyanins, D) Especially for semiconductor laser light sources.
1987-191032, JP 60-80841
Tricarbocyanines described in JP-A-59-19
Zika containing the 4-quinoline nucleus described in No. 2242
Rubocyanins and the like are advantageously selected. below are them
The following are representative compounds of sensitizing dyes. Specific compound examples of A) [Chemical formula 28] Specific compound examples of B) [Chemical formula 29] Specific compound examples of C) General formula (X) [0064] [0065] [In the formula, Y1 and Y2 each represent benzothia
Zole ring, benzoselenazole ring, naphthothiazole ring
, a naphthoselenazole ring, or a complex ring such as a quinoline ring.
Represents a group of nonmetallic atoms necessary to form an elementary ring.
Heterocycles include lower alkyl groups, alkoxy groups, hydroxy
group, aryl group, alkoxycarbonyl group, halogen source
May be replaced by children. R1, R2, each lower grade
Alkyl group, sulfo group, or carboxy group
Represents a rukyl group. R3 represents a lower alkyl group. X1
, represents an anion. n1 and n2 represent 1 or 2
vinegar. m represents 1 or 0, and when it is an inner salt, m = 0.
vinegar. [0066] [Chemical 31] [0067] [Chemical 32] [0068] Specific compounds of D) [Chemical 33] [0070] These sensitizing dyes may be used alone. but
, combinations thereof may be used, and the combination of sensitizing dyes is
In particular, it is often used for the purpose of supersensitization. sensitizing dye
In addition, dyes or dyes that do not themselves have spectral sensitizing effects
is a substance that does not substantially absorb visible light, and is a supersensitized substance.
The emulsion may contain a substance exhibiting the following. useful sensitizing dyes,
Combinations of dyes that exhibit supersensitization and substances that exhibit supersensitization are
Research Disclosure (Research D)
isclosure) Volume 176 17643 (1978
(December issue) Page 23, Section IV, J. Book
The content of the sensitizing dye of the invention is determined by the grain size of the silver halide emulsion,
Halogen composition, method and degree of chemical sensitization, and containing the compound
Relationship between silver halide emulsion and anti-fogging compound
It is desirable to select the optimal amount depending on the type of
The test method for selection is well known to those skilled in the art.
It's ro. Usually preferably 1 per mole of silver halide
0-7 mol to 1x10-2 mol, especially 10-6 mol
It is used in a range of 5×10 −3 mol to 5×10 −3 mol. The photographic light-sensitive material of the present invention has high sensitivity and high contrast.
For the purpose of promotion, JP-A No. 60-140340 and No. 6
Adding the compound described in No. 1-167939
Can be done. These may be used alone or in combination of two or more types.
It may also be used as a set. The photosensitive material of the present invention includes
Prevents fogging during the manufacturing process, storage or photo processing.
, or various compounds for the purpose of stabilizing photographic performance.
can contain substances. In other words, azoles
For example, benzothiazolium salts, nitroindazoles,
Chlorobenzimidazoles, bromobenzimidazole
mercaptothiazoles, mercaptobenzothia
Sols, Mercaptothiadiazoles, Aminotria
Sols, benzothiazoles, nitrobenzotriazo
mercaptopyrimidines; mercaptopyrimidines;
Lyazines; for example, thio-
Keto compounds; azaindenes, such as triazaindenes
compounds, tetraazaindenes (especially 4-hydroxy-substituted
(1,3,3a,7)tetrazaindenes), pentaa
Zaindenes, etc.; benzenethiosulfonic acid, benzene
such as sulfinic acid, benzenesulfonic acid amide, etc.
Many compounds known as antifoggants or stabilizers
You can add things. Among these, preferred
Ino is benzotriazoles (e.g. 5-methyl benzene)
nizotriazole) and nitroindazoles (e.g.
5-nitroindazole). Also, these compounds
A substance may be included in the processing liquid. The photosensitive material of the present invention has antihalation properties.
, dyed to improve safelight safety and to improve front and back discrimination.
It can contain ingredients such as ingredients. For example, U.S. Patent No. 2,2
Pyrazolone oxonol dyes described in No. 74,782;
Diarylua as described in U.S. Patent No. 2,956,879
Zo dye, U.S. Patent No. 3,423,207, U.S. Patent No. 3,3
Styryl dyes and zutadienyl dyes described in No. 84,487
Merosia described in U.S. Patent No. 2,527,583
Nin dye, U.S. Pat. No. 3,486,897;
No. 652,284 and No. 3,718,472
Merocyanine dyes and oxonol dyes, U.S. Patent No. 3,
Enaminohemioxonol dyeing described in No. 976,661
and British Patent No. 584,609, British Patent No. 1,177,
No. 429, JP-A-48-85130, JP-A No. 49-996
No. 20, No. 49-1144220, U.S. Patent No. 2,5
No. 33,472, No. 3,148,187, No. 3,
No. 177,078, No. 3,247,127, No. 3
, No. 540,887, No. 3,575,704, No. 3,575,704, No.
The dyes described in No. 3,653,905 can be used.
Ru. Photographic emulsion and non-photosensitive hydrophilic coating of the present invention
Lloyd contains an inorganic or organic gelatin hardening agent.
can be done. For example, activated vinyl compounds (1,3,5
- triacryloyl-hexahydro-s-triazine,
Bis(vinylsulfonyl)methyl ether, N,N'-
Methylenebis-[β-(vinylsulfonyl)propion
amide], active halogen compounds (2,4-dichloroamide, etc.), active halogen compounds (2,4-dichloro
(6-hydroxy-s-triazine, etc.), mucohalo
Genetic acids (such as mucochloric acid), N-carbamoylpyri
Zinium salts ((1-morpholy, carbonyl-3-pyri
zinio) methanesulfonate, etc.), haloamidinium
Salts (1-(1-chloro-1-pyridinomethylene)pyro
Lysinium, 2-naphthalenesulfonate, etc.) alone
Or they can be used in combination. Among them, Tokukai Sho
53-41220, 53-57257, 59-16
2546, the active vinyl compound described in 60-80846
and the active compound described in U.S. Pat. No. 3,325,287.
Logenides are preferred. The photographic emulsion layer or other layer of the light-sensitive material of the present invention
The hydrophilic colloid layer contains coating aids, antistatic agents, emulsifying and dispersing agents,
Prevention of adhesion and improvement of photographic properties (e.g. development acceleration, contrast enhancement)
Even if it contains various surfactants for various purposes such as
good. For example, saponins (steroids), alkylene
Oxide derivatives (e.g. polyethylene glycol,
Polyethylene glycol/polypropylene glycol condensation
compounds, polyethylene glycol alkyl ethers or
polyethylene glycol alkylaryl ethers,
Polyethylene glycol esters, polyethylene glycol esters
Cole sorbitan esters, polyalkylene glycol
polyalkylamines or amides, silicone polyethylene
(ren oxide adducts), glycidol derivatives (e.g.
For example, alkenyl succinic acid polyglyceride, alkylphenyl
(norpolyglycerides), fatty acid esters of polyhydric alcohols
Nonionic interfaces such as esters and sugar alkyl esters
Activator: alkyl carboxylate, alkyl sulfonic acid
salt, alkylbenzene sulfonate, alkyl naphtha
Rensulfonate, alkyl sulfate, alkyl
Ruphosphate esters, N-acyl-N-alkyltauri
esters, sulfosuccinic acid esters, sulfoalkyl polyesters,
Oxyethylene alkylphenyl ethers, polyoxy
Carbohydrates such as cyethylene alkyl phosphates, etc.
Ruboxy group, sulfo group, phosphor group, sulfate ester group,
Anionic surfactants containing acidic groups such as acid ester groups;
Amino acid salts, aminoalkyl sulfonic acids, aminoal
Kyl sulfate or phosphate esters, alkyl betaines,
Amphoteric surfactants such as amine oxides; alkylamides
salts, aliphatic or aromatic quaternary ammonium salts
, pyridinium, imidazolium, etc.
ammonium salts, and phosphonic compounds containing aliphatic or heterocycles.
cationic surfactants such as aluminum or sulfonium salts.
Can be used. The photographic light-sensitive material of the present invention includes
Silk is added to the emulsion layer and other hydrophilic colloid layers to prevent adhesion.
Lika, magnesium oxide, polymethyl methacrylate, etc.
A matting agent may be included. The photosensitive material of the present invention has improved dimensional stability.
For any purpose, dispersions of water-soluble or sparingly soluble synthetic polymers
can include. For example, alkyl (meth)
rylate, alkoxyalkyl (meth)acrylate,
Glycidyl (meth)acrylate, (meth)acryla
vinyl esters (e.g. vinyl acetate), vinyl esters (e.g. vinyl acetate),
Lilonitrile, olefin, styrene, etc. alone or
is a combination or combination of these with acrylic acid or methacrylic acid.
Acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl
(meth)acrylate, sulfoalkyl (meth)acrylate
Monomer combinations of rylate, styrene sulfonic acid, etc.
A polymer as a component can be used. Feeling of the invention
As a support for optical materials, cellulose triacetate,
Cellulose diacetate, nitrocellulose, polystyrene
Polyurethane, polyethylene terephthalate, etc. can be used;
Most preferably polyethylene terephthalate film.
Delicious. These supports are corona treated using known methods.
If necessary, it may be undercoated by a known method.
may be done. Also, the dimensions may change due to changes in temperature and humidity.
To increase the so-called dimensional stability, polysalt
A waterproof layer containing a vinylidene chloride polymer may be provided. There are development accelerators suitable for use in the present invention.
In addition, as an accelerator for nucleation and infection development, Japanese Patent Application Laid-Open No. 53-77
616, 54-37732, 53-137133,
60-140340, 60-14959, etc.
In addition to the compounds shown, various compounds containing N or S atoms
Compounds are effective. Developing agent used in the developer used in the present invention
There are no special restrictions on this, but it is easy to obtain good halftone dot quality.
It is preferable that dihydroxybenzenes are included, and dihydroxybenzenes are preferably included.
Hydroquinone as a hydroxybenzene developing agent,
Chlorohydroquinone, Bromohydroquinone, Isop
Lopylhydroquinone, methylhydroquinone, 2,3
-dichlorohydroquinone, 2,5-dichlorohydro
Quinone, 2,3-dibromohydroquinone, 2,5-di
Examples include methylhydroquinone, but especially hydroquinone
is preferred. As a preservative for sulfite used in the present invention,
Sodium sulfite, potassium sulfite, lithium sulfite,
Ammonium sulfite, sodium bisulfite, metabisulfite
acid potassium, formaldehyde sodium bisulfite, etc.
There is. Sulfite is 0.25 mol/liter or more, especially
It is preferably 0.4 mol/liter or more. Also, the upper limit is 2.
Preferably up to 5 mol/l, especially up to 1.2
Delicious. [0078] The alkaline agent used for setting the pH is
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Contains pH regulators and buffers such as potassium carbonate. Above mentioned
Additives used in addition to the ingredients include boric acid and borax.
compounds, sodium bromide, potassium bromide, potassium iodide
Development inhibitors such as: ethylene glycol, diethylene
Glycol, triethylene glycol, dimethylform
Amide, methyl cellosolve, hexylene glycol,
Organic solvents such as tanol and methanol: 1-phenyl-
5-mercaptotetrazole, 2-mercaptobenzi
Mercap such as midazole-5-sulfonic acid sodium salt
Indazole such as 5-nitroindazole, 5-nitroindazole, etc.
Bentz compounds such as 5-methylbenztriazole
Antifoggants such as lyazole compounds or black spots (b)
(lack pepper) inhibitor:
Color toner, surfactant, antifoaming agent, water softener as required
hardening agent, JP-A-56-106244, JP-A-61
-267759 and the amino acid described in Japanese Patent Application No. 1-29418.
It may also contain compounds such as Development used in the present invention
The liquid contains JP-A No. 56-24347 as a silver stain preventive agent.
The compound described in JP-A-62-2 as a developing unevenness prevention agent
The compound described in No. 12651, as a solubilizing agent, JP-A No. 6
The compound described in No. 1-267759 can be used.
Ru. The developer used in the present invention contains a buffer and
Boric acid as described in Japanese Patent Application No. 61-28708,
0-93433 (e.g. saccharose),
Oximes (e.g. acetoxime), phenols
(for example, 5-sulfosalicylic acid), etc. are used. The treatment method of the present invention is performed in the presence of polyalkylene oxide.
Can be done with polyalkylene oxide in the developer
In order to contain
0.1-10g/liter of polyethylene glycol
It is preferable to use the range. In addition to the fixing agent, the fixing solution
May contain a water-soluble aluminum compound as a hardening agent.
stomach. Additionally, acetic acid and dibasic acids (e.g. tartaric acid) may be added as needed.
, citric acid or their salts), preferably
Preferably pH 3.8 or higher, more preferably 4.0-6
．． 5. Sodium thiosulfate and thiosulfate are used as fixing agents.
ammonium osulfate, etc., and from the viewpoint of fixing speed,
Ammonium sulfate is particularly preferred. The amount of fixative used is appropriate.
It can be varied as needed, and generally about 0.1 to about 5 mol/liter.
It's a lot. Mainly acts as a hardening agent in the fixer.
Water-soluble aluminum salts are commonly used as hardeners in acidic hardener fixers.
It is a compound known as a chemical agent, such as aluminum chloride.
aluminum, aluminum sulfate, and potassium alum. [0080] As the above-mentioned dibasic acid, tartaric acid or its
derivatives, citric acid or its derivatives alone,
Alternatively, two or more types can be used in combination. these compounds
contains 0.005 mol or more per liter of fixer
is effective, especially 0.01 mol/liter to 0.03 mol
/liter is particularly effective. Specifically, tartaric acid, alcohol
Potassium tartrate, sodium tartrate, potassium tartrate
ammonium tartrate, potassium ammonium tartrate
Um, etc. Citric acid is effective in the present invention.
Examples of its derivatives include citric acid and sodium citrate.
and potassium citrate. The fixer used in the present invention has the following general formula:
It is possible to use the mesoionic compound represented by (I) in combination.
preferable. ##STR34## In the formula, Z is a carbon atom, a nitrogen atom, an oxygen atom
, 5 or 5 composed of sulfur atoms or selenium atoms
Represents a 6-membered ring, and X- is -O-, -S-, or -N
- R (where X is an alkyl group, a cycloalkyl group, a
Lukenyl group, alkynyl group, aralkyl group, aryl group
or a heterocyclic group). Among these, the following
More preferred are compounds represented by general formula (XII). ##STR35## In the formula, R1 and R2 are an alkyl group,
loalkyl group, alkenyl group, alkynyl group, aralkyl group
represents a group, an aryl group, or a heterocyclic group. However, R2
may be a hydrogen atom. Y is -O-, -S-, -
N(R3)-, R3 is an alkyl group, cyclo
Alkyl group, alkenyl group, alkynyl group, aryl group
, heterocyclic group, amino group, acylamino group, sulfona group
Represents a mido group, ureido group or sulfamoylamino group.
Was. R1 and R2, R2 and R3 are each other
may be bonded to form a ring. Compound represented by the above general formula (XII)
will be explained in detail. In the formula, R1 and R2 are substituted
or an unsubstituted alkyl group (e.g. methyl group, ethyl group)
group, n-propyl group, t-butyl group, methoxyethyl group
, methylthioethyl group, dimethylaminoethyl group, mole
holinoethyl group, dimethylaminoethylthioethyl group,
diethylaminoethyl group, aminoethyl group, methylthio
Methyl group, trimethylammonioethyl group, carboxy
Methyl group, carboxyethyl group, carboxypropyl group
, sulfoethyl group, sulfomethyl group, phosphonomethyl group
, phosphonoethyl group, etc.), substituted or unsubstituted
loalkyl groups (e.g. cyclohexyl, cyclopene)
methyl group, 2-methylcyclohexyl group, etc.), substituted
or unsubstituted alkenyl groups (e.g. allyl group, 2-methyl
(ruallyl group, etc.), substituted or unsubstituted alkynyl group
(e.g. propargyl group, etc.), substituted or unsubstituted
Aralkyl groups (e.g. benzyl group, phenethyl group, 4
-methoxybenzyl group, etc.), aryl group (e.g.
Nyl group, naphthyl group, 4-methylphenyl group, 4-metho
xyphenyl group, 4-carboxyphenyl group, 4-sul
fophenyl group, etc.) or substituted or unsubstituted hetero
cyclic groups (e.g. 2-pyridyl group, 3-pyridyl group, 4-pyridyl group)
Pyridyl group, 2-chenyl group, 1-pyrazolyl group, 1-
imidazolyl group, 2-tetrahydrofuryl group, etc.)
Was. [0087] However, R2 may be a hydrogen atom
. R3 is a substituted or unsubstituted alkyl group (for example, methyl
group, ethyl group, n-propyl group, t-butyl group, meth
xyethyl group, methylthioethyl group, dimethylaminoethyl group
thyl group, morpholinoethyl group, dimethylaminoethyl group
Oethyl group, diethylaminoethyl group, aminoethyl group
, methylthiomethyl group, trimethylammonioethyl group
, carboxymethyl group, carboxyethyl group, carboxy
Cypropyl group, sulfoethyl group, sulfomethyl group, phosphor group
honomethyl group, phosphonoethyl group, etc.), substituted or
Unsubstituted cycloalkyl group (e.g. cyclohexyl group,
cyclopentyl group, 2-methylcyclohexyl group, etc.)
, substituted or unsubstituted alkenyl groups (e.g. allyl group)
, 2-methylallyl group, etc.), substituted or unsubstituted atom
ruquinyl group (e.g. propargyl group, etc.), substituted or
is an unsubstituted aralkyl group (e.g. benzyl group, phenyl group)
thyl group, 4-methoxybenzyl group, etc.), aryl group (
For example, phenyl group, naphthyl group, 4-methylphenyl group
, 4-methoxyphenyl group, 4-carboxyphenyl group
, 4-sulfophenyl group, etc.) or substituted or unsubstituted
substituted heterocyclic groups (e.g., 2-pyridyl group, 3-pyridyl group)
group, 4-pyridyl group, 2-chenyl group, 1-pyrazolyte group
group, 1-imidazolyl group, 2-tetrahydrofuryl group
, etc.), [0088] Substituted or unsubstituted amino group (for example, unsubstituted amino group)
Substituted amino group, dimethylamino group, methylamino group, etc.
), acylamino group (e.g. acetylamino group, benzo
ylamino group, methoxypropionylamino group, etc.),
Sulfonamide groups (e.g. methanesulfonamide groups,
4-toluenesulfonamide group, 4-toluenesulfonamide group
group, etc.), ureido group (e.g., unsubstituted ureido group, 3
-methylureido group, etc.), sulfamoylamino group (
For example, unsubstituted sulfamoylamino group, 3-methylsulfamino group,
famoylamino group, etc.). General formula (X
II), preferably Y represents -N(R3)-;
R1 and R3 are substituted or unsubstituted alkyl groups,
substituted or unsubstituted alkenyl group, substituted or unsubstituted
an alkynyl group or a substituted or unsubstituted heterocyclic group
represents. R3 is a hydrogen atom, substituted or unsubstituted atom
Alkyl group, substituted or unsubstituted alkenyl group, also substituted
or unsubstituted alkynyl group or substituted or unsubstituted
A heterocyclic group is preferred. Specific examples of the compounds of the present invention are as follows.
Although an example is shown, the present invention is not limited thereto. ##STR36## The compound of the present invention has a concentration of 1×10-5 mol/liter.
liter to 10 mol/liter, especially 1 x 10-3 mol/liter
Fixer or fixer in the range of liter to 3 mol/liter
Preferably, it is used as a liquid replenisher. Here, process
The halogen composition of the silver halide emulsion in the photosensitive material is iodobromide.
In the case of silver, it is preferable to use 0.5 to 2 mol/liter.
Silver bromide, silver chlorobromide, or high silver chloride emulsions (chloride
silver halide containing 80 mol% or more of silver)
, is preferably used in the range of 0.05 to 1 mol/liter.
Yes. The fixer may further contain a preservative (for example,
sulfates, bisulfites), pH buffers (e.g. acetic acid, borium),
acids), pH adjusters (e.g. ammonia, sulfuric acid), images
Contains preservatives (e.g. potassium iodide) and chelating agents
Can be done. Here, the pH buffer is used because the pH of the developer is high.
10 to 40 g/liter, more preferably 18 to 25
Use approximately g/liter. [0091] Also, add a mold inhibitor (for example, Hori) to the washing water.
Author: “Chemistry of antibacterial and antibacterial protection”, JP-A-62-115154
(compounds listed in this issue), washing accelerators (sulfites, etc.),
It may also contain a rating agent and the like. According to the above method
For example, the developed and fixed photographic material is washed with water and dried. Washing with water almost completely removes silver salts dissolved during fixation.
It is preferably carried out at about 20°C to about 50°C for 10 seconds to 3 minutes.
stomach. Drying is carried out at a temperature of about 40℃ to about 100℃, and the drying time is
can be changed depending on the surrounding conditions, but usually it takes about 5 seconds.
3 minutes and 30 seconds is sufficient. For roller conveyance type automatic developing machine
Regarding US Pat. No. 3,025,779, US Pat.
It is described in the specification of No. 45971 etc., and herein
In other words, it is simply referred to as a roller-conveyed processor.
Ru. Roller-conveyed processors are used for developing, fixing, washing, and
The method of the present invention is also similar to other methods.
Although the process (for example, stop process) is not excluded, these four processes
It is most preferable to follow. The amount of refilling water for washing is 12
00 ml/m2 or less (including 0). washing with water
When the replenishment amount of water (or stabilizing liquid) is 0, the so-called
This refers to a method of washing with stored water. Reduce refill amount
As a method for
3 stages, etc.) are known. Issues that occur when the amount of replenishment of washing water is small
The problem can be effectively treated by combining the following technologies:
performance can be obtained. For the washing bath or stabilization bath, R.
T. Kreiman, J. Image, T
ech. Vol. 10 No. 6242 (1984
) isothiazoline compounds, research data
Scrooger (R.D.) Volume 205, No. 20
Isothiazo described in 526 (May 1981 issue)
Phosphorus Compounds, Volume 228, No. 22845 (1
Isothiazoline compounds described in 983, April issue)
Object, JP-A-61-115154, JP-A-62-209
The compounds described in No. 532, etc. are used as antibacterial agents (Micr
It can also be used in combination as (obiocide). the
Others, "Chemistry of antibacterial and antifungal" by Hiroshi Horiguchi, Sankyo Publishing (1982)
, “Handbook of Antibacterial and Antifungal Technology” Japanese Society of Antibacterial and Antifungal Research,
Hodo (1986), L. E. West “Water”
Quality Criteria ”Photo
Sci & Eng. Vol. 9No. 6 (1
965), M. W. Beach “Microbi
Logical Growth in Motio
n Picture Processing”SMPT
E Journal Vol. 85 (1976), R.
O. Deegan “PhotoProcessin
g Wash Water Biocides”J.
Imaging Tech. Vol. 10 No.
6 (1984).
good. In the method of the present invention, washing with a small amount of washing water
When doing so, use JP-A-63-18350, JP-A-62-28.
Squeeze rollers and cross-overs described in No. 7252, etc.
It is more preferable to provide a bar rack cleaning tank. Furthermore,
The water treated with anti-mildew means in the washing or stabilizing bath of the present invention is used for treatment.
from a water wash or stabilization bath produced by refilling accordingly.
A part or all of the overflow liquid of
No. 5133, described in JP-A No. 63-129343.
The processing liquid that has fixing ability, which is the processing step before
It can also be used for. Furthermore, rinse with a small amount of water.
Prevention of uneven blisters that sometimes occur and/or squeeze roller
The processing agent components that adhere to the film are transferred to the processed film.
Add water-soluble surfactants and antifoaming agents to prevent
may be added. It also prevents contamination caused by dyes eluted from photosensitive materials.
Finally, the dye adsorbent described in JP-A No. 63-163456 was used.
It can also be installed in a washing tank. The developer used in the present invention is
Oxygen and moisture permeability described in JP-A-61-73147
It is preferable to store it in low-quality packaging. Also used in the present invention
The developing solution used is described in JP-A No. 62-91939.
A replenishment system can preferably be used. The silver halide photographic material of the present invention has a high
, Dmax, force reduction processing is performed after image formation.
If the dot area is reduced, the density remains high.
There is. There are no particular restrictions regarding the reducing fluid used in the present invention.
For example, ``The Theory of
the Photographic Process
” pages 738-744 (1954, Macmill
an), “Photo Processing Theory and Practice” by Tetsuo Yano 1
Complete works such as pages 66-169 (1978, Kyoritsu Shuppan)
and JP-A No. 50-27543, No. 52-68429
, No. 55-17123, No. 55-79444, No. 5
No. 7-10140, No. 57-142639, No. 61-
61155, JP 1-282551, JP 2-2
Those described in No. 5846 can be used. That is,
As oxidizing agents, permanganates, persulfates, ferric salts,
Cupric salts, ceric salts, red blood salts, dichromates, etc.
alone or in combination, and if necessary, inorganic substances such as sulfuric acid.
Reduced strength fluid containing acids or alcohols, or red blood salts
Oxidizing agents such as ferric salts of ethylenediaminetetraacetic acid and
Osulfate, rhodan salt, thiourea or their derivatives.
Which silver halide solvent and optionally sulfuric acid etc.
A reducing fluid containing organic acid is used. Typical reducing fluid used in the present invention
An example is the so-called Farmer's reducing fluid, ethylenediamine.
Ferric tetraacetic acid salt, potassium permanganate, ammonium persulfate
Mutual reducing fluid (Kodak R-5) and ceric reducing fluid are listed.
can be lost. The conditions for force reduction treatment are generally 10°C to 40°C,
Especially at a temperature of 15℃ to 30℃ for several seconds to several tens of minutes.
It is preferable that the process can be completed within a few minutes. Manufacture of the present invention
If a photosensitive material for printing plates is used, the reduction force can be sufficiently wide within the range of these conditions.
You can get width. The reducing fluid contains a compound of the invention
Recording is formed in the emulsion layer through the non-photosensitive top layer
Act on the image. Specifically, there are various ways to do it.
For example, by dipping the photosensitive material for plate making into the reducing liquid and stirring the liquid,
Apply the liquid to the surface of the plate-making photosensitive material using a brush, roller, etc.
You can use methods such as The total processing time of the photosensitive material of the present invention is 15 seconds or more.
Excellent rapid development process using an automatic processor in 60 seconds
Demonstrate performance. In the rapid development process of the present invention, development,
The temperature and time for wearing are approximately 25℃ to 50℃ for 25 seconds or more each.
but preferably at 30°C to 40°C for 4 seconds to 15 seconds
It is. In the present invention, the photosensitive material is developed and fixed.
Post-washing or stabilization treatment. Here, the washing process
saves water by using a two- to three-stage countercurrent flushing system.
can be processed. Also, if you wash it with a small amount of water,
It is preferable to install a squeeze roller cleaning tank when
. In addition, the overflow from the washing bath or stabilization bath
Some or all of the information is described in JP-A No. 60-235133.
It can also be used as a fixer, as shown in Kosu
By doing so, the amount of waste liquid is also reduced, which is more preferable. With this invention
The photosensitive material that has been developed, fixed, and washed is squeezed with a squeeze roller.
It is then dried. Drying at 40°C to 80°C for 4 seconds to 30 minutes
It takes place in seconds. The total processing time in the present invention is an automatic
Insert the leading edge of the film into the insertion slot of the imager, then insert it into the developer tank.
, transition section, fixing tank, transition section, washing tank, transition section, drying
After passing through the drying section, the leading edge of the film comes out from the drying outlet.
This is the total time it takes to arrive. Silver halide photosensitive material of the present invention
Emulsion layer and protective layer can be coated without damaging pressure fog.
It is possible to reduce the amount of gelatin used as a binder.
This enables quick processing with a total processing time of 15 to 60 seconds.
development speed, fixing speed, and drying speed.
It can be easily developed. The present invention will be carried out below.
The present invention will be explained specifically by way of examples.
It is not limited to this. [Example] Example 1 (1) Preparation of emulsion I solution Water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
20g sodium chloride
　　　　　　　　　　　　　　　　　　　　　　　　　
20g 1,3-
Dimethylimidazolidine-2-thione
20mg benzene
Sodium sulfonate
6mg
II liquid water
　　　　　　　　　　　　　　　　　　　　　　　　　
400mg silver nitrate
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
100gIII liquid water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml sodium chloride
Umu
30
．． 5g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
14g Hexachloroloy
Potassium lysium(III) acid (0.001
% aqueous solution)
15ml
Ammonium hexabromorodium(III) acid
(0.001% aqueous solution)
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 1.5 ml of I solution kept at 38℃ and pH=4.5.
Mix liquid II and liquid III at the same time for 10 minutes while stirring.
The mixture was added vertically to form 0.16 μm core particles. continue
The following solutions IV and V were added over 10 minutes. moreover
Particle formation was completed by adding 0.15 g of potassium iodide. IV fluid water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml silver nitrate
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
100gV liquid water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml sodium chloride
Umu
30
．． 5g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
14g K4 Fe(C
N)6
1 x 10-5 mol/mol Ag then conventional method
Wash with water by flocculation method according to
, 40 g of gelatin was added. Divide this into two equal parts, and one emulsion (A) has a pH of
= 5.5, pAg = 7.5, and sodium thiosulfate
Add 3.7 mg of aluminum and 6.2 mg of chloroauric acid, and heat at 65°C until the
Chemical sensitization was performed to achieve appropriate sensitivity. The other emulsion (B
) was adjusted to pH = 5.3, pAg = 7.5, and thiosulfate was added.
2.6 mg of sodium chloride, 5.0 mg of chloroauric acid and N,N
- Add 1.0 mg of dimethylselenourea and
4mg of sodium sulfonate, benzenesulfinic acid
Add 1.0 mg of sodium and reach optimum sensitivity at 55°C.
Chemically sensitized as in
Silver iodochlorobromide cubic grain emulsion with an average grain size of 0.20 μm
Prepared. (2) Preparation of coating sample Add 5 x 10-4 moles of sensitizing dye ■ to the emulsions (A) and (B).
1/mol Ag was added for ortho sensitization. In addition, fog
Hydroquinone, 1-phenyl-5-mer as an inhibitor
2.5 g of each captotetrazole per mole of Ag
, 50mg, colloidal silica (Nissan Chemical Snowtech)
C, average particle size 15 μm) was mixed with plasticizer in the amount shown in Table 1.
Polyethyl acrylate latex (0.05μm
) as a hardening agent, 40% by weight based on gelatin, 2-bicarbonate
(vinylsulfonylacetamido)ethane to whole gelatin
Add 30 mg per 1 g of polyethylene terephthalate.
Ag3.0g/m2, gelatin 1.2g on the sheet support
/m2. On top of this the protection of the following composition
The lower layer and the upper protective layer were applied simultaneously. <Protective layer lower layer>
　　　　　　　　　　　　　　　　　　　　　　　　　
Gelatin per m2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.25
g Sodium benzenethiosulfonate
　　　　　　　　　　　　　　　　　　　　　　　　　
4mg 1,5-dihydroxy-2-benza
Ludoxime
25mg polyethyl acrylate latex
　　　　　　　　　　　　　　　　　　　　　　　　　
125mg <protective layer upper layer>
　　　　　　　　　　　　　　　　　　　　　　　　　
Gelachi per m2
hmm
　　　　　　　　　　　　　　　　　　　　　　　　　
0.25g Silica matting agent with an average diameter of 2.5μm
　　　　　　　　　　　　　　　　　　　　　　　　　
50mg compound ■ (slip agent
latin dispersion)
Table-1 Colloidal silica
(Nissan Chemical Snowtex C)
30mg compound-■
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
5mg sodium dodecylbenzenesulfonate
　　　　　　　　　　　　　　　　　　　　　　　　　
22 mg [0099] [0100] Note that the support for the sample used in this example
The body has a back layer and a back protective layer having the following composition. <Back layer> Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0g/m2 Dodecylbenzenesulfate
Sodium phonate
80mg/m2 Compound■
　　　　　　　　　　　　　　　　　　　　　　　　　
70m
g/m2 Compound■
　　　　　　　　　　　　　　　　　　　　　　　　　
70mg/m2 Compound■
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
90mg/m2 1,3-divinylsulfonyl-
2-propanol 6
0mg/m2 <Back protective layer> Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5g/m2 polymethyl methacrylate
Fine particles (average particle size 3.6 μm) 4
0mg/m2 Sodium dodecylbenzenesulfonate
Mu
20mg/m2 Compound (gelatin dispersion of slip agent)
)
100mg/m2 Compound■
　　　　　　　　　　　　　　　　　　　　　　　　　
2mg/m2 [
[Chemical formula 38] [0102] Regarding the sample obtained in this way, the photograph
Evaluations were made of the hardness, scratch fog, and coefficient of dynamic friction. evaluation method
Shown below. (1) Evaluation of photographic properties The obtained sample is filtered through an interference filter with a peak at 488 nm.
- and a continuous concentration wedge with a luminescence time of 10-6 seconds.
Exposure with xenon flash light, Fuji Photo Film Co., Ltd.
) using an automatic processor FG-710NH, as shown below.
The phase of the exposure amount that gives a density of 3.0 when processed under the development processing conditions.
The sensitivity was determined. The developer and fixer are shown below.
A treatment solution with the following composition was used. Development processing conditions Development: 38℃
14.0 seconds fixation
37℃ 9.7 seconds Water
Wash at 26℃
9.0 seconds squeeze
2.4 seconds dry
Drying 55℃ 8.3 seconds
total
43.4 seconds Linear speed
2800mm/min 0103 Developer solution Potassium hydroxide
1
0g/liter 1-hydroxyethylidene-1,1
-Diphosphonic acid 2.6 Bromide
potassium
3.3
〃 5-Methylbenzotriazole
0.08 〃
2-Mercaptobenzimidazole-5-sulfone
acid sodium
0.3
〃 Potassium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
83 Hydroquinone
　　　　　　　　　　　　　　　　　　　　　　　　　
35 〃 4-Hydroxy
dimethyl-4-methyl-1-phenyl-3-pi
lazolidone
1.3 〃 Diechi
lene glycol
30 〃
Adjust pH=10.7 with sodium hydroxide. Fixer ammonium thiosulfate
150g/li
1,4,5-trimethyl-1,2,4-tri
Azolium-3-thiolate
0.25 mol/
liter sodium bisulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
30g/liter ethylenediaminetetraacetic acid disodium
Lium dihydrate 0.025g/liter
Adjust pH to 6.0 with sodium hydroxide. (2) Sapphire with a diameter of 1 mm under pressure fog conditions of 25°C and 60% RH.
After rubbing the surface of the sample with a needle with a continuous load of 0 to 200 g.
, Perform the development process under the development process conditions of 1) above.
The load at which this occurs was determined. (3) Coefficient of dynamic friction (μk) Diameter 1 mm after being left for 1 hour at 25°C and 60%
With sapphire needle, load 100g, speed 60cm/
The dynamic friction coefficient was determined at min. Table of results obtained.
Shown in 1. As is clear from Table 1, the sample of the present invention has a high
It was found that the sensitivity and pressure fog were extremely good.
Karu. [Table 1] Example 2 Sensitizing dye ■ was added to emulsions (A) and (B) of Example-1 at Ag1
Add 100 mg per mole, then supersensitize and stabilize
As an agent, 4,4'-bis(4,6-dinaphthoxy-pi
rimidin-2-ylamino)-stilbendisulfonic acid
・Add 300 mg of disodium salt per mol of Ag,
Panchromatic sensitization. In addition, antifoggants, plasticizers, hardeners,
Add the membrane agent and colloidal silica in the same manner as in Example-1, and
Polymer coated with the first and second undercoat layers of the following composition on both sides.
Ag3.0g/m on ethylene terephthalate support
2. Gelatin was coated at a concentration of 1.2 g/m2. child
The lower and upper protective layers of Example-1 were simultaneously applied on top of the
. <First undercoat layer> Vinylidene chloride/methyl methacrylate/acrylic
Nitrile/methacrylic acid (90/8/1/1
Aqueous dispersion of copolymer (weight ratio)
1
5 parts by weight 2,4-dichloro-6-hydroxy-s-
Triazine 0.25 Polis
Tyrene fine particles (average particle size 3μ)
0.05 Compound-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20
〃 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
100 Additionally, 10% by weight of K
The coating solution was adjusted to pH=6 by adding OH and dried at a temperature of 18.
It was applied for 2 minutes at 0°C so that the dry film thickness was 0.9μ.
. <Second undercoat layer> Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1 part by weight methyl cellulose
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05 〃 Compound
Thing-7
0
．． 02 〃 C12H25O(CH2CH2O)1
0H
0.03 〃 Compound
Thing-8
3.5×10−
3 Acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
10
0〃Dry this coating solution at a drying temperature of 170℃ for 2 minutes.
The coating was applied so that the film thickness was 0.1μ. Note that the support
On the opposite side is a conductive layer with the following composition (surface resistivity: 10% at 25°C)
2×1010Ω) at RH, and applied Example-1 on top of that.
A back layer and a back protective layer similar to those described above were applied. <Conductive layer> SnO2/Sb (9/1 weight ratio, average particle size 0.2
5μ) 300mg/m2
Gelatin (Ca++ content 30ppm)
170
〃 Compound-8
　　　　　　　　　　　　　　　　　　　　　　　　　
7 Dodecylbenze
Sodium sulfonate
10 〃 Dihexyl-α-
Sulfosuccinate sodium salt
40 Sodium polystyrene sulfonate
um salt
9 [0107] [Chemical formula 39] The samples thus obtained were used in Example-1 and
They were evaluated in the same way. (1) Photographicity evaluation is based on interference film.
Change the filter to an interference filter with a peak at 633 nm.
Evaluation was performed in the same manner as in Example-1 except for the following changes. obtained
The results are shown in Table 2. As is clear from Table 2, this
The light sample has high sensitivity and extremely good pressure fog.
It can be seen that it is. [Table 2] Example 3 Sensitizing dye ■ was added to emulsions (A) and (B) of Example-1 at Ag1
Add 80 mg per mole, then supersensitizer and stabilizer
as 4-4'-bis(4,6-dinaphthoxy-pyri)
Midin-2-ylamino)-stilbendisulfonic acid.
Disodium salt and 2,5-dimethyl-3-allyl-ben
300 each of zothiazole iodo salts per mole of Ag.
mg and 450 mg were added and infrared sensitized. In addition, turnip
Examples of anti-oxidants, plasticizers, hardeners, and colloidal silica
- In addition, polyethylene terephthalate support
On top, Ag3.0g/m2, gelatin 1.2g/m2
I applied it to make it look like this. On top of this, there is a lower protective layer with the following composition.
and the upper layer were applied simultaneously. (Lower protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.25g/m2 Compound-9
　　　　　　　　　　　　　　　　　　　　　　　　　
20mg/m
2 Compound-10
　　　　　　　　　　　　　　　　　　　　　　　　　
10 〃 Dodecylbenzenesulfur
sodium phonate
20 〃 Polyethyl acrylate latte
x (0.05μ) 150
(Top protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.25g/m2 polymethyl methacrylate
Fine particles (average particle size 3.4μ) 6
0mg/m2 Colloidal silica (Nissan Chemical Snow
Tex C) table
-3 Compound -■ (gelatin dispersion of slip agent)
　　　　　　　　　　　　　　　　　　　　　　　　　
Table-3 Sodium dodecylbenzenesulfonate
40mg
/m2 Compound-11
　　　　　　　　　　　　　　　　　　　　　　　　　
10 [0111] [Chemical formula 40] Next, on the opposite side, a back layer with the following formulation is applied.
and a protective layer was applied. (Back layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0g/m2 Compound-12
　　　　　　　　　　　　　　　　　　　　　　　　　
34mg/m
2 Compound-13
　　　　　　　　　　　　　　　　　　　　　　　　　
90 〃 Compound-14
　　　　　　　　　　　　　　　　　　　　　　　　　
70〃
Polyethyl acrylate latex (particle size 0.05μ)
400 Dodecylbenzene
Sodium sulfonate
35 〃 1,3-Divinylsulfo
Nyl-2-propanol
50 Sodium polystyrene sulfonate
Mu
20 (Protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5g/m2 polymethyl methacrylate
Fine particles (average particle size 3.4μ)
40mg/m2 Sodium dodecylbenzenesulfonate
Rium
10 Compound-15
　　　　　　　　　　　　　　　　　　　　　　　　　
2 Sodium acetate
Mu
25
[0113] [Chemical formula 41] [0114] The samples obtained in this way were used as Example-1.
They were evaluated in the same way. (1) Photographicity evaluation is based on interference film.
Change the filter to an interference filter with a peak at 780 nm.
Evaluation was performed in the same manner as in Example-1 except for the following changes. obtained
The results are shown in Table 3. As is clear from Table 3, this
The light sample has high sensitivity and extremely good pressure fog.
It can be seen that it is. [Table 3] Example 4 Sample numbers -1 and -7 of Example-1, sample numbers of Example-2
No.-1, -7, Sample No.-1, -7 of Example-3
The four-cut size (254mm x 305mm) is 3200
After 50% blackening exposure with °K tungsten light, Example-1 and
Using the same developer and fixer, use Fuji Photo Film (
Co., Ltd. FG-460A automatic processor (line speed 14)
65mm/min) and process 250 sheets per day.
, under the development conditions shown below and the replenishment amounts shown in Tables 4 and 5.
After two weeks of continuous processing, the photographic properties were evaluated in Example-1.
, -2, -3, and the fixing gap is an unexposed four-section
The size was evaluated based on the transparency when processed. Development conditions Development: 38℃ 14.0
Second fixation 36℃ 13.
Wash with water for 2 seconds 25℃ 12
．． Dry for 8 seconds at 55℃ 1
6.8 seconds total
The results obtained for 56.8 seconds are shown in Tables 4 and 5. As is clear from Tables 4 and 5, the samples of the present invention had a development speed of
There is extremely little delay in speed and fixing speed, and developer and fixing
It is possible to reduce the amount of liquid. In addition, the evaluation score for retention is as follows.
It was as follows. 5: Fully transparent 4: More than 3/4 of the entire area is transparent 3: 〃 2/4 〃2:
〃 1/4 〃1: Fully opaque [Table 4] [Table 5] [Table 5] Example 5 Sensitizing dyes ■ and ■ were added to emulsions (A) and (B) of Example-1.
Add 100mg per mole of Ag, and add other turnips.
Examples of anti-oxidizing agent, colloidal silica, plasticizer, and hardening agent
- In addition, polyethylene terephthalate support
Ag3.0g/m2 and gelatin 1.2g/m2 on top.
It was applied so that it was coated. On top of this, the lower protective layer of Example-1 and
and the upper layer were applied simultaneously. of the subbing layer on the opposite side of the support.
A conductive layer having the following composition was applied on top, and Example-1 and
A similar back layer and back protection layer were applied. <Conductive layer> Compound-16
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g/m2 Compound-17 (aqueous dispersion
)
0.5g/m2 Compound-18
　　　　　　　　　　　　　　　　　　　　　　　　　
300mg/
m2 citric acid
　　　　　　　　　　　　　　　　　　　　　　　　　
40mg/m2 Saponin
　　　　　　　　　　　　　　　　　　　　　　　　　
15
0mg/m2 Lithium nitrate salt
　　　　　　　　　　　　　　　　　　　　　　　　　
50mg/m2 [Chemical formula 42] The sample thus obtained was used in Example-1.
It was evaluated in the same way. Note that (1) Photographicity evaluation is based on interference.
Interference filter with peak at 670nm
Evaluation was carried out in the same manner as in Example-1 except that . Obtained
The results are shown in Table 6. As is clear from Table 6, books
The sample of the invention has high sensitivity and significantly improved pressure fog.
It turns out that it is good. [Table 6]

Claims (5)

[Claims] Claim 1. A silver halide photographic material comprising at least one silver halide emulsion layer on a support and at least one protective layer on top of the emulsion layer, wherein at least one of the emulsion layers contains A silver halide photographic light-sensitive material comprising silver halide grains sensitized with a selenium sensitizer and colloidal silica. 2. The outermost layer of the protective layer has a coefficient of kinetic friction of 0.
．． 2. The silver halide photographic material according to claim 1, wherein the silver halide photosensitive material has a molecular weight of 35 or less. 3. The silver halide photographic material according to claim 1, wherein the silver halide photographic material is processed in an automatic processor for a total processing time of 15 to 60 seconds. [Claim 4] Line speed is 1000mm/mi
Claim 1 characterized in that the processing is carried out using an automatic processing machine of n or more.
and the silver halide photographic material described in 2. 5. A method in which a silver halide photographic light-sensitive material is at least developed, fixed and washed with water using an automatic processor after exposure, and the replenishment amount of the developer and/or fixer is 200 ml or less per 1 m2 of the light-sensitive material. 3. The method for developing a silver halide photographic material according to claim 1, wherein: