JPS63239443A - Silver halide photographic sensitive material capable of super rapid processing - Google Patents

Abstract

PURPOSE:To improve the sensitivity and the max. density of contrast of the titled material at the time of super rapid processing by applying a coating solution on the surface of a supporting body before the coating solution applied on the another surface of the supporting body is dried. CONSTITUTION:A silver halide photosensitive emulsion layer and a nonphotosensitive layer are mounted on the supporting body 2. The amount of gelatin contd. in the both layers mounted on the one side of said body is 2.00-3.50g/m<2>, and the outermost layer of the supporting body is formed by applying the coating solution having surface tension of 15-26dyn/cm on the surface of said body. And, for example, the coated layer 4 is formed by a coater 1 while being in contact the supporting body 2 with a supporting roller 3, and then, the layer 4 is gelled by cooling it at a cold wind zone 8. Subsequently, the coated layer 11 is formed by applying the coating solution by the coater 1' on the opposite surface of the supporting body 2 at part in which a gas sprayer 3' is not in contact with said body 2, followed by drying it. However, one or more layers of said emulsion layers are formed on at least one surface of the said body 2. And, the titled material is preferably developed for the total processing time of 20-60sec by means of an automatic developer.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a silver halide photographic material.

In particular, it relates to a silver halide photographic material that is free from failure during coating and can be processed extremely quickly.

C. Prior Art In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of silver halide photographic materials to be processed has increased, and there is a demand for further speeding up of the development process, that is, to increase the amount of processing within the same amount of time.

The above-mentioned trend is also observed in the field of X-ray sensitive materials, such as medical X-ray films. In addition, the number of medical examinations has rapidly increased due to the enforcement of regular health examinations, and the number of examination items has increased in order to make the diagnosis more accurate, and the number of X-ray photographs taken has also increased.

On the other hand, it is also necessary to inform the examinee of the diagnosis result as soon as possible.

That is, there is a strong demand for faster development and diagnosis than before. Particularly in angiography photography, intraoperative photography, etc., it is essentially necessary to view the photographs as quickly as possible.

In order to meet the above-mentioned demands of the medical community, it is necessary to promote automation of diagnosis (imaging, transport, etc.) and to process X-ray films more quickly.

However, if ultra-quick processing is performed, (a),? 5 degrees is not sufficient (decrease in sensitivity, contrast, and maximum density), (b)
This causes problems such as insufficient fixing, (c) insufficient washing of the film, and (d) insufficient drying of the film. Insufficient fixing and insufficient water washing cause the color tone to change during film storage, resulting in a decrease in image quality.

One way to solve these problems is to reduce the amount of gelatin. However, when the amount of gelatin is reduced, failures such as coating unevenness and coating streaks are more likely to occur during coating of the silver halide photosensitive material.

In addition, films with less gelatin may be susceptible to rubbing against each other or when the film is rubbed with other substances.
There is a problem in that after the development process, so-called scratch blackening, which has a higher density than other parts, tends to occur.

Although ultra-quick processing is desired as described above, there are still many problems to be solved. In this specification, ultra-quick processing refers to the process of inserting the leading edge of the film into an automatic developing machine, passing through the developer tank, transfer section, fixing tank, transfer section, washing tank, transfer section, and drying section. The total time it takes for the tip to emerge from the drying section (in other words, the total length of the processing line)
m) divided by the line conveyance speed (m/see, ) (s
ec, ) ) refers to a process in which the duration is 20 seconds to 60 seconds. The reason why the time for the transition part should be included here is that it is well known in the industry that even in the transition part, the liquid from the previous process is swollen in the gelatin film, so it is virtually impossible to This is because it can be considered that the processing process is progressing.

Japanese Patent Publication No. 51-47045 describes the importance of the amount of gelatin in rapid processing, and the total processing time including the crossing portion is 60 seconds to 120 seconds. However, this processing time cannot meet the recent demands for ultra-quick processing.

[Purpose of the invention]

The first object of the present invention is that, as mentioned above, the total processing time is 20 minutes.
To provide a silver halide photographic light-sensitive material which solves the above-mentioned problems of the conventional technology and has excellent sensitivity, contrast, maximum density, fixing property, drying property, etc. when ultra-quick processing is performed in seconds to 60 seconds. There is a particular thing.

A second object of the present invention is to provide a halogenated photographic material that has a small amount of gelatin and has fewer failures during coating even if the surface tension of the coating solution is low.

A third object of the present invention is to provide a silver halide photographic material that exhibits little blackening due to scratches even when the amount of gelatin is small.

[Structure and operation of the invention]

The above object consists of a support, a photosensitive silver halide emulsion layer provided on the support, and a non-photosensitive layer provided on the support, and the emulsion layer and the non-photosensitive layer are The amount of gelatin on the provided side is 2.00 g/g to 3.
50 g/cd, and the outermost layer has a surface tension of 15 dy
n/am to 26 dyn/ell, and each of the above layers is formed after coating the coating solution for forming each layer on one side of the support and before drying. This is accomplished by coating the other side of the support with a coating solution for forming each of the layers, gelling it, and drying it to form a layer.

The total processing time for the above-mentioned silver halide photographic light-sensitive material is 2
It is preferable to process with an automatic processor for 0 to 60 seconds.

In the present invention, the term "outermost layer" usually means the outermost layer, but a coating called a supercoat or the like by spraying or coating may be applied on the outermost layer. Moreover, the "outermost layer" as used in the present invention may be a photosensitive layer or a non-photosensitive layer.

Further, in the present invention, a small number of photosensitive silver halide emulsion layers (one layer is formed on at least one surface of the support) and a photosensitive silver halide emulsion layer is formed on at least one surface of the support. Alternatively, a non-photosensitive layer may be formed.

When two or more photosensitive silver halide emulsion layers are formed on at least one surface of the support, a non-photosensitive layer may be provided between these emulsion layers, for example. However, the support must at least have a photosensitive silver halide emulsion layer on both sides, or a photosensitive silver halide emulsion layer on one side and a non-photosensitive silver halide emulsion layer on at least one side. There are layers.

The "amount of gelatin" as used in the present invention is the total amount of gelatin present in the photosensitive layer on the photosensitive side and the non-photosensitive layer, and if the photosensitive layer is present on both sides of the support, This is the amount for one side.

The "photosensitive layer" as used in the present invention refers to a photosensitive layer such as a photosensitive silver halide emulsion layer.

The term "non-photosensitive layer" as used in the present invention refers to non-photosensitive layers such as a subbing layer, an intermediate layer, a protective layer, an anti-halation layer, and a filter layer.

In a preferred embodiment of the present invention, the average grain size of the silver halide grains used in the silver halide emulsion layer is 0.30.
~1.50μm, more preferably 0.40~1.30
Examples include embodiments in which the corner is 0.40 to 1.10 μ, most preferably 0.40 to 1.10 μ.

Another preferred embodiment is a silver halide grain consisting essentially of silver iodobromide and having a multilayer structure, wherein any adjacent 27i (
The difference in average iodine content between the coating layers (or between the inner core and the coating layer) is 10 mol% or more, the average iodine content of the outermost layer is 10 mol% or more, and it has been chemically sensitized. It is to have.

Here, the particles having a multilayer structure are those in which a coating layer made of an arbitrary halogen composition is provided on the outside of the inner core, and this coating layer may be only one layer, or may have two or more layers, for example, three layers.
N, 4 layers may be stacked. Preferably the number of layers is 5 or less.

Silver halide in the inner core and coating layer includes silver bromide,
Silver iodobromide and silver iodide are used, but a small amount of silver chloride may be mixed. Specifically, silver chloride may be contained in an amount of about 10 mol% or less, preferably about 5 mol% or less.

Further, the outermost layer is preferably substantially silver bromide or substantially silver iodobromide (iodine content of 10% or less), and may contain less than several % of chlorine atoms.

The average iodine content of the entire silver halide grains of the present invention is 1
It is preferably 0 mol% or less, more preferably 6 mol% or less.

For example, in X-ray photosensitive materials, iodine may increase problems such as inhibition of development and infectious development, so it is practically preferable to keep the content of iodine below a certain level. In any case, the method of the present invention has the effect of reducing stress fog, but for this reason, the total cord content is preferably 10 mol% or less in the entire particle, and 7 mol%
The following is more preferable, and 5 mol% or less is most preferable.

When the inner core is made of silver iodobromide, it is preferably a homogeneous solid solution phase.

Here, being homogeneous can be more specifically explained as follows.

That is, when performing X-ray diffraction analysis of silver halide grain powder using Cu-Kp X-rays, the half-width of the peak of the surface index [200] of silver iodobromide is Δ2θ = 0.30 (
deg) or less. The conditions for using the diffractometer at this time are that the scanning speed of the goniometer is ω (deg/1lin), and the time constant is r (se
e) When the receiving slit width is r (m+n), ωr/r≦10.

As for the halogen composition of the internal core, the average iodine content is preferably 40 mol% or less, more preferably 0 to 40% by mole.
It is 20 mol%.

Adjacent 2Ji! The difference in silver iodide content between (any two coating layers or coating layer and internal core) is preferably 10 mol% or more, more preferably 20 mol% or more, particularly preferably 25 mol%. That's all.

In addition, the silver iodide content of the coating layer other than the surface coating layer is as follows:
Preferably it is 10 mol% to 100 mol%.

When silver halide grains consist of three or more layers and the coating layer consists of silver iodobromide, it is not necessary that they all be homogeneous, but all layers must be made of homogeneous silver iodobromide. is preferred.

Such a coating layer (or inner core) with high iodine content
In the case of a negative-working silver halide emulsion, it is preferable that it exists below the outermost surface. In the case of a positive silver halide emulsion, it may be present either inside or on the surface.

The silver iodide content of the surface coating layer is preferably 10 mol% or less, more preferably 0 to 5 mol%.

Regarding the iodine content of the inner core and coating layer of silver halide grains used in the practice of the present invention, for example, J.
1. Goldstein, D.
B. Williams rTEM
/X-ray analysis in ATEM” Scanning Electron Microscope (1977), Volume 1 (
IIT Research Institute), No. 65
It can also be determined by the method described on page 1 (March 1977).

When the silver halide grains used in the practice of the present invention are composed of two layers, for example, it is preferable that the inner core has a higher iodine content than the outermost layer, and when the silver halide grains are composed of three layers, the coating other than the outermost layer is preferable. It is preferable that the layer or inner core has a higher iodine content than the outermost layer.

The present invention can be preferably applied to chemically sensitized silver halide grains. This is because unsensitized particles have very low sensitivity and are difficult to cause scratch blackening or pressure desensitization.

The silver halide grains used in the present invention may be positive type or negative type.

In the case of a negative type, it is preferable to perform chemical sensitization so that the degree of chemical sensitization is 60% or more of the optimum sensitivity when taking the sensitivity point of "fog + 0.1" in optical density.

In the case of a positive type, the degree of chemical sensitization is determined by chemically sensitizing the inside of the particle so that the sensitivity point is 60% or more of the maximum sensitivity when taking the sensitivity point of "maximum density - 0,1" in the optical density. It is preferable to apply

The average grain size of the silver halide grains used in the present invention is:
The particle size is defined as the length of the edge when converted into a cube of equal volume, and is expressed as the average value.

In the present invention, the surface tension is 15 dyn/cm ~
The outermost layer is formed using a coating liquid of 26 dyn/crm, but in order to keep the surface tension of the coating liquid used to form the outermost N (usually the uppermost N) within the range of the present invention of 26 dyn/ca or less, An embodiment may be adopted in which at least one type of surfactant is used in the outermost layer. In addition, the layer immediately below the outermost layer may or may not contain a surfactant. The surfactants used in the outermost layer and the layer immediately below it may be the same or different.

The surface tension of the coating liquid used to form the outermost layer is 26 dyn.
/am or less, the lower the better, but in the present invention it is 15 dyn/cta or more. 15dyn
It is practical to set the lower limit to / cm from a specific coating technique, and if it is less than 15 dyn 7 cm, coating becomes difficult.

Examples of the surfactants that can be used in the present invention include saponin, alkylene oxide derivatives,
Examples include nonionic surfactants such as glycidol derivatives, fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Also included are anionic surfactants containing acidic groups such as carboxylic groups, sulfo groups, phosphor groups, sulfuric ester groups, and phosphoric ester groups. Further examples include amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides. Also,
Cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium, and phosphonium or sulfonium salts containing aliphatic or heterocycles. Furthermore, a fluorine-containing surfactant, a fluorine-containing surfactant containing a polyoxyethylene group, etc. can be used.

As an alkylene oxide type surfactant,
1-9610, DT-2648746, Japanese Unexamined Patent Publication No. 1973
-129623, 54-89624, 54-982
35, 5B-203435, 58-208743
, 60-80848, 60-94126, etc.

Examples of fluorine-containing surfactants include Japanese Patent Publication No. 47-93
03, 48-43130, 52-25087, 5
7-1230, JP 49-46733, JP 50-16
525, 50-34233, 5I-32322, 54-14224, 54-111330, 55-5
57762, 56-19042.56-41093,
56-34856, 57-11341, 57-2
9691, 57-64228, 57-146248
, 56-114944, 56-114945, 5
B-196544, 58-200235, 60-1
09548, 57-136534, US-358
9906, same 3775126, same 4292402,
Examples include compounds disclosed in RD-16630 and the like, and compounds exemplified in JP-A-60-164738.

Preferred examples of anionic surfactants that do not contain polyalkylene oxide are shown below in 1-1 to 1-10.

1- I C4H*0-5OJa 1-5 C) I! C00CIIH
I? Na0tS-Ctl-COOCsH+ 11-6
CsH++ CON CHzCHtSOJa
CHtsu1-7 C, HaCON-CHzCOONaCH
5 So, Na? Na0aS CHC00CHzCII CJqtH
s 2 1 CJsO(CtlzCHJ)zoc+
zHzs2-2 -CJsO(C4bCHtO)sC
sFs2 3 C1F+? 0(CHzC)It
O)+oCJq2 4 Cbl'+zO(CH
zCHzO)zocbH+a2-5 CaFlf
fO(C4bCHtO)? CH32-6C1F+? 0(
CHzC)ItO)zocJIsCqF+J(CHzC
HiO) tou CuICI.

2-14 C1F+? 0(CHzCHzO)4゜-C11lIhs2 15 CJ+tO(CH
iCHtO)+. -H2-16C+tFtzO(CHz
CHzO)so-CHsH3 2-19 0H C11F 19CH□CHC[l to (CeHtO
L. CH32-21CaF+t(CI(zclhO+r
(-CIlz-hsOJa2 22 H+ CF2
-)IICHzO+ Ct(zcHz M Cl1z
-hSOJ2 23 CtFISCOO+ CH□
C1(□0→τ÷CH,→]S Oz K2-24
CH3 CsF+tSOzN+CHzCHzO→-gsO3Na
2 25 C4F++CHzCHzO→1SO
s N a2 26 Cs'thC3
F17SOZN+CHzCHzO→1cllzcOON
ato÷CF, →-gctizo÷CHzCHzO→]P
ONl+4N114 CH.

CH.

2 31 CJ7CsF +?
5OzN + CIl□CItO→]H232CJ+3
SOJa 2 33 CsF+tSOJa2 34
C6Fl:Ic0OK2 35 CsF+
, SO+C00K2 36 C11FI? S.O.
□NCHzCOOKJt 2 37 hC(CFz)t C00H2-3
8H-(CFZ)6-COOII2-39 CF
ff-(CFZ)&-COONH42-40H
-(Ch)+. -COOH2-41H-(CFz)6-
CHz-O3OJa2-42 H-(CFri!-C
Hz-OSOJa Beef H (CFz)a CHz OP OHOH 03Na 薯CH.

2-48 8-(CFz)i-CONH-CHt-0
-5O3Na2-54 1l-(CFz), CHz
-0-CHt-CHz-CHz-5O3Na2 55
F+C(CFz)b-Cut OCHz
CHz-CHz 5OJaF,F.

2-57 CJs F2OC-0-CHt CHz-CHi 5OJa
CJs 258 F2O(CPz)t-Coo-CHt-
CTo CHz-5OJa2-59 H-(C
Fz)to-COO-CHg-C1lz-CHz 5
O3Na2-61 F2O(CFz)t-COO
(-CHzCHzO)y CHi2 63 h
C-(CFz)z-CHtO(-CIIzCHzO)s
H265Cz, Hgz CHCOOCHI CF2
03Na C,t+.

2 68 F2O(CF,)? Sow
N CHz CHz-OSOJCJs 2 70 Na0sS CH-COOCHt(
CFzCFt)JCHg C00CJlz(CF2C
Fz) YuHCsF+ySQtNCtfzCI(zOf'
+0H) tzHs CH3 CsF+ qsOtNcHtcHtOP + 0NII
t) zCs l('r CH3 lh CH3 *-C)IzCHJ CH3Cl eHff H+CFz)+oCHzOP1000Na) t2-81
0B C9F I*CHzCHCHzO(-CHiCHzO)
z. -CHff2-82 CaF+tSO□N +
CHzCHtOsnHCH3 Commercially available fluorine-containing surfactants include those commercially available from Daikin Industries, Ltd. under the trade name Unidyne and from 3M (Sumitomo 3M) under the trade name Florado.

Next, specific examples of polyoxyethylene surfactants preferably used in the present invention are shown in 3-1 to 3-44.

3 1 CzHz: +COO+CHgCHzO-)
r-H3-2C,? H,3COO-(-CH,C)1t
O-)rv-H33CsH+tO+CHzCHzO-)
TH3-4Cz□)I4sO+CH□cti□Ohd I
+0 + cozct+go 10T"H O+ CH, CH□0÷T"H 3-14CHgoC+ Jz7CON + CHzCHzO+rrHa+
b=29 3 19 C+zlhsS+CHIC1hO÷
'rrl(Hs cnzcnzo thousand CHzCHtO+r-rH3-30
C4H9332C+J! sO+C
HgCHtO÷D←CHz +r SOJa3 36
CHi CzHt3CON(CHzCHzO+y←CH1÷7−
803Na3-37 C9H190+CHICH
2O÷r−SOJ3 39 C1JssO+C11
zC1(to+rsO+Na341C+zHzsO+C
HzCHzO+rCHzCOONaC+, HssO+C
HtCHzO-)rPONaNa Preferred quaternary ammonium salts include the following compounds 4-1 to 4-20.

cut - cut C1- C1, -CH.

4-15 CH3 and I C,H,, -N-C1l, ・Br- CHt 4-16 C)13 and I C9HI9-N CHzCOO- CH3 4-18c) I:1 YuI CJ+5COC1l□-N-CH, COO-CH3 4-19C11゜ya1 can , , So□NH(CHt) x N C
To I-CH.

OHCl.

Next, particles used in carrying out the present invention will be described. The particles used may have a narrow or broad particle size distribution.

Further, the grain size distribution of silver halide grains in the photographic emulsion is arbitrary, and may be monodisperse.

Here, monodisperse means a dispersion system in which 95% of the particles fall within ±60%, preferably within 40%, of the number average particle size. Here, the number average grain size is the number average diameter of the projected area diameter of silver halide grains.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may have a regular crystal shape such as a tetrahedron or a dodecahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or a composite of these crystal shapes. It can be something that has a shape. It may also consist of a mixture of particles of various crystalline forms.

In addition, for example, a junction type silver halide crystal that combines an oxide crystal such as PbO and a silver halide crystal such as silver chloride, and an epitaxially grown silver halide crystal (
For example, silver chloride, silver iodobromide, silver iodide, etc. are grown epitaxially on silver bromide. ), a hexagonal crystal, a crystal in which a regular hexahedral silver chloride is aligned over a regular octahedral silver iodide, and the like.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area. For details, see JP-A-58-127.
921, No. 58-113927, etc.

In carrying out the present invention, for example, when regular silver halide grains as described above are contained, irregular silver halide grains may be contained.

However, if such grains are present, they generally should not be more than about 50% by weight or grain number; in preferred embodiments, at least about 60 to 70% by weight are regular silver halide grains. Consisting of

In the production of monodispersed emulsions and/or emulsions with regular silver halide grains, supply of silver ions and halide ions is important so that existing crystal grains are not dissolved away as the crystal grains grow, and conversely, new crystal grains are not dissolved away. It is preferable to increase the growth rate continuously or stepwise at a critical growth rate that does not allow generation or growth of grains and supplies sufficient silver halide to grow only existing grains, or within its permissible range. This increasing method is based on the
No. 0, No. 52-16364, JP-A No. 55-14232
It is described in Publication No. 9.

In the practice of the present invention, the silver halide grains used in the silver halide emulsion are, for example, T, H.

James, The Theory of the Photographic Process
e Photo-graphic Process),
4th edition published by Maemilan (1977), P.
Written by Glfkides, Chin+fe et Physi Photographic
(Paul
Monte1 Publishing, 1967), G, F, Duff
in, Photographic Emulsion Chemistry, (Photographic Emulsion
Chemistry) (The Focal Pre
ss, 1966), V, L, Zelikn+a
Net a! Author, Making and Coating Photographic Emulsions
and Coating Photographic
Bmul-sion), (The Focal Pr.
Neutral method, acidic method, ammonia method, forward mixing method, back mixing method, double jet method, Chondrald double jet method,
It can be manufactured by applying a method such as a congersion method or a core/shell method.

Another form of the double jet method is the triple jet method, in which soluble halogen salts of different compositions are added independently (for example, soluble root salt, soluble bromine salt, and soluble iodide salt).
can also be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (
For example, U.S. Pat. No. 3,271,157, U.S. Pat.
74, No. 628, No. 3,704,130, No. 4
．． No. 297,439, No. 4,276.374, etc.), 1,000-ion compounds (e.g., JP-A-53-144.319)
No. 53-82,408, No. 55-77, 73
No. 7), amine compounds (e.g. JP-A-54-100)
．． No. 717, etc.) can be used. Among them, ammonia is preferred.

Two or more types of silver halide emulsions formed separately may be mixed and used.

These silver halide grains or silver halide emulsions contain at least one salt (soluble salt) of iridium, thallium, palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, and tungsten platinum. is preferably contained. Its content is preferably 10-6 to io per mol Ag.
−'Mole.

Particularly preferably, at least one of thallium, palladium, and iridium salts is contained. These may be used alone or in combination, and the addition position (time) is arbitrary. This improves flash exposure characteristics,
It is expected to have effects such as prevention of pressure desensitization, prevention of latent image progression, and sensitization.

In carrying out the present invention, it is preferable to adopt an embodiment in which the mother liquor containing the protective colloid has a pAg of at least 10.5 during particle growth before chemical sensitization as described above. Particularly preferably, an atmosphere with a large excess of 11,5 or more bromine ions is passed through at least once. In this way (111
) By increasing the number of faces and rounding the particles, the effects of the present invention can be further enhanced. (11
1) It is preferable that the ratio of the surface to the total surface area is 5% or more.

In this case, the increase rate of the (111) plane (the increase rate with respect to that before passing through the above pAg atmosphere of 10.5 or more)
is preferably 10% or more, more preferably 10 to 20%.

The outer surface of the silver halide grain is the (111) plane or the (10
0) How to measure whether one side is covered or the ratio thereof is reported by Akira Hirata,
“Bulletin of the Society of Scientific Photography of Japan” m1
3. 5-15 (1963).

During particle growth before chemical sensitization, by once passing through an atmosphere in which the pAg of the mother liquor containing a protective colloid is at least 10.5, it is possible to obtain
1) It can be easily confirmed whether the area has increased by 5% or more.

In this case, the time when the above pAg is set is approximately 2 of the total amount of added silver.
It is preferable to do this after the addition of 1/3 is completed and before the so-called desalting step which is usually carried out before chemical sensitization. This is because it is easy to obtain a monodispersed emulsion with a narrow particle size distribution.

In addition, aging in an atmosphere where pAg is 10°5 or more,
It is preferable to do this for 2 minutes or more.

pAg like ko(7) ;#[11! : Yori, (111
)7m increases by 5% or more and the shape becomes rounded, making it possible to obtain a preferable particle in which the (111) plane accounts for 5% or more of the total surface area of the particle.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which involves gelling gelatin, may be used. A precipitation method (flocculation method) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used. The process of removing soluble salts may be omitted.

The silver halide emulsion may or may not be chemically sensitized.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye. It's okay.

There are various sensitizing dyes used in blue-sensitive silver halide emulsion layers, sensitizing dyes used in green-sensitive silver halide emulsions, and aggravating dyes used in red-sensitive silver halide emulsions. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as formaldehyde condensates of aromatic organic acids ( For example, U.S. Pat.
, 437,510), cadmium salts, azaindene compounds, and aminostilbene compounds substituted with nitrogen-containing heterocyclic groups.

When carrying out the present invention, as a sensitizing dye used for color sensitization, the general formula (
It is preferable to use compounds represented by 1) to [III) (specifically, compound examples (1) to (72) described in the same publication).

The total amount of the compound represented by the formula (I) (II) (II[) described in JP-A-61-80237 used in the present invention is 10 to 6 mol per mole of silver halide.
It can be used in the range of 00■. In particular, 15 to 45
0 mg is preferred.

A plasticizer may be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of increasing flexibility.

Various types of plasticizers can be used, but
Among these, a preferred compound is trimethylolpropane. When using diols or polyols such as trimethylolpropane, the amount used is preferably 0.01 to 100% by weight based on gelatin, more preferably 0.
．． The content is 1 to 100% by weight, particularly preferably 0.1 to 10% by weight.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

For more information, see Stabilization of Photographic Silver Halide Emulsions by E. J. Birr.
photo-graphic 5ilver Halid
e Emulsions), Foca IPress
, 1974, etc.

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

As such a dye, Absorbing and
Filter soybean (Absorbing andf)
i 1 terdyes) is used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and class ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole 33H forms, 3-pyrazolidones, and the like.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

The photographic material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

The silver halide photographic light-sensitive material of the present invention is preferably provided with a protective layer, and this protective layer is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above. Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention, preferably to the SI layer.

Various other additives may be used in the photographic material of the present invention, if necessary. Examples include dyes, development accelerators, fluorescent whitening agents, color antifoggants, and ultraviolet absorbers. Specifically, research disclosure (
RESEARCHDISCLO3URE) No. 176 No. 2
Those described on pages 2 to 31 (RD-17643, 1978) can be used.

The silver halide photographic material of the present invention may also be provided with an antihalation layer, an intermediate layer, a filter layer, etc., if necessary.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers can be embodied by being coated on one or both sides of a flexible support commonly used in photographic light-sensitive materials.

The support may be colored using dyes or pigments, or it may be colorless for the purpose of blocking light.The surfaces of these supports are generally treated with an undercoat to improve adhesion with photographic emulsion layers, etc. .

The surface of the support may be subjected to corona irradiation, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. For details, see Research Disclosure, Vol. 176 P, 25 rs.
The one described in the section ``upportsJ'' is used.

In the photographic light-sensitive material of the present invention, the photosensitive silver halide emulsion layer and the non-photosensitive layer on the support are dried after coating the coating solution for forming each layer on one side of the support. In the meantime, the coating liquids for forming each layer are applied to the other side of the support, gelled, and dried to form layers.

-C In photographic light-sensitive materials, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods, such coating methods include dip coating,
There are roller coating methods, curtain coating methods, extrusion coating methods, and more.
As described in the section of Proeedures J, in the present invention, after applying a coating liquid to one side as described above, the coating liquid is applied to the other side before drying.

As a method of applying a coating liquid to one side of a support in this way and then continuously applying the coating liquid to the other side before drying, Japanese Patent Application Laid-Open No. 57-63163 and Japanese Patent Publication No. 51-3
There is a method described in 8737, 49-17853, etc.

Further, by disposing a coater and a gas ejector at positions substantially facing each other with the continuously running support in between, and ejecting gas from the gas ejector toward the support, the support It is also possible to use a coating device in which the coater applies the coating while supporting the body without contact. Such a device will be described in detail in the description of the embodiments below.

Specifically, the silver halide photographic materials of the present invention include X-ray photosensitive materials, Lith photosensitive materials, black and white photographic photosensitive materials, color negative photosensitive materials, color reversal photosensitive materials, color photographic paper, colloid transfer process, and silver salt photosensitive materials. It can be used in diffusion transfer process, gui transfer process, silver dye bleaching method, printout sensitive material, photosensitive material for heat development, etc.

Exposure to obtain a photographic image may be performed using a conventional method.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclo
sure) No. 176, pages 25-30 (RD-17, 64
Any of the various methods and various treatment liquids as described in 3) can be applied. This photographic processing may be either a photographic processing that forms a silver image (black and white photographic processing) or a photographic processing that forms a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 1
The temperature is selected between 8°C and 50°C, but the temperature may be lower than 18°C or higher than 50°C.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color-forming coupler that can form a color by oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative, an aminophenol derivative, etc.) in a color-forming process. It may also contain compounds.

The product of the campling reaction may also be colorless and include a colorless DIR coupling compound that releases a development inhibitor.

The silver halide photographic material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The silver halide photographic material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer.

When carrying out the present invention, an anti-fading agent can also be used in combination.

〔Example〕

The present invention will be explained below with reference to Examples. Naturally, the invention is not limited to the examples.

Example-1 First, silver iodobromide emulsion E- containing 112.0 mol% iodide
1 was prepared as i11 by sequential mixing using the full ammonia method. The average grain size of this emulsion was 1.10 μm.

This silver iodobromide emulsion E-1 was optimally sensitized with gold and sulfur by adding chloroauric acid, sodium thiosulfate, and ammonium thiocyanate, and 4-hydroxy-6-methyl-1,3
, 3a, stabilized with 7-chitrazaindene.

The above emulsion and a protective layer containing a hardener are coated on one side (represented as the front side) of an undercoated polyester film support using a slide hopper method at a high speed in the order of silver halide emulsion layer and protective 8W layer. 100m/win, multi-layer coating between two layers, gelling and drying, 10.5kg/36
It was wound up with a winding tension of cn. Next, it was applied to the other side (referred to as the back side) under the same conditions as the front side, gelled, and dried to obtain samples No. 1 to No. 30.

These do not belong to the coating according to the present invention because the front side is coated and dried, and then the back side is coated.

Next, according to the present invention, an emulsion layer and a protective layer prepared in the same manner are simultaneously coated in multiple layers on the front side of the undercoated polyester support, and then simultaneously coated in multiple layers on the back side of the undercoated polyester support. At the same time, it was dried to obtain sample Na31-nu51.

These are coated according to the present invention because the back side is coated after the front side is coated and before it dries.

Specifically, in this example, the coating as described above was performed using the coating apparatus shown in FIGS. 1 and 2.

That is, the illustrated coating apparatus is an example of a coating apparatus suitable for coating the silver halide photographic light-sensitive material of the present invention, and includes a coater and a coater at substantially opposite positions across a continuously running support. The coating device is provided with a gas ejector, and performs coating with the coater while supporting the support without contact by ejecting gas from the gas ejector toward the support pair.

In this embodiment, a case in which a sample is coated using this coating device will be described below.

FIG. 1 is a longitudinal cross-sectional view of the coating apparatus, showing a case in which a two-layer coating method using a slide hopper is adopted as the coating method, and the photographic constituent layer coating solution is continuously coated on both sides of the support. FIG. 2 is a longitudinal sectional view showing an example of a gas ejector used in this coating device.

In FIG. 1, the support 2 to be coated is first coated with a support roll 3.
The coating material is applied by a conventionally known method using a coater 1 in direct contact with the material. In order to gel the applied coating layer 4, the support 2 passes through a cold air zone 8. In the cold air zone 8, cold air is applied to the coated surface 4 through a slit plate or a group of small holes 7, and in order to further increase cooling efficiency, a slit plate or a group of small holes 7 is used to blow cold air onto the coated surface 4. It is desirable to bring the roll group 6 installed in the box 5 into contact with each other, and apply suction from the opposite side to increase the contact area with the roll group 6, thereby cooling and gelling the coating layer 4. The support 2 having the gelled coating N4 is then coated on the opposite side with the non-contact support part of the gas ejector 3', with the support 2 sandwiched therebetween and facing the gas ejector 3'. The coating is performed by a coater 1' arranged as follows. Although various forms are possible for the gas ejector 3', a roll type one, which is considered to be the most common form due to ease of manufacture, will be exemplified.

The hollow roll-shaped gas ejector 3' has a plurality of through holes 10 for ejecting gas in a portion of its outer shell corresponding to the non-contact support part, and the gas supplied inside is passed through the through holes. 10 from the outer surface of the roll to the surface of the gelled coating layer 4 to support the coated support 2 in a non-contact state. The wet state of the coated layer or the thickness of the coated layer 6 after drying usually needs to be suppressed to a variation of 1% or less. That is, it is necessary to keep the floating amount as constant as possible. The range of variation that should be allowed for this gap is several microns or less, and at most 10 microns.
It is preferable to keep it below.

As a means of suppressing floating amount fluctuations, when the gas ejector 3' is constructed of a hollow roll having a through hole 10, the diameter d (Fig. 2) of the smallest part of the through hole 10 and the length l (
Fig. 2), pore area ratio (in the non-contact support part, each through hole 1
By appropriately determining the sum of the cross-sectional areas of the narrowest parts of 0 and the outer diameter of the gas jet 3' and the roll outer diameter, the supporting static pressure (
= back pressure) and supply pressure □～□, io ioo.

It is possible to set the amount of floating in the coating liquid contact area to take one value each in the range of 20 to 500μ, thereby suppressing fluctuations in the floating of the flexible support to be coated within the above-mentioned allowable range. can.

Regarding the relationship between support width and gas ejection amount, W2 ・Q≦
Preferably, the size is 5×10′. Here, W is the width of the support (cm), and Q is the gas jet per unit area it (N mj!/min-cm").

Each sample coated as described above had a coated silver amount of 54 .mu./-, and the amount of hardener was adjusted so that the melting time was about 7 minutes. The above melting time refers to the time after a sample (silver halide photographic material) cut into 1cI11 x 2CI11 is immersed in a 175% sodium hydroxide solution kept at 50°C.
This is the time until the emulsion layer begins to dissolve.

Next, the number of coating failures (e.g. coating streaks, coating unevenness, etc.) of the sample obtained as described above was measured, and
It was expressed on a five-point scale of 5 (excellent). Note that 3 to 5 poses no problem, but 1 to 2 is not practical.

In addition, seismic measurements were performed as follows. That is, a sample is sandwiched between two optical wedges whose concentration gradients are mirror-symmetrically aligned, and a light source with a color temperature of 5,400'K is used to simultaneously illuminate the sample from both sides.
/12.5 seconds equal exposure.

The processing was carried out using a roller conveyance type automatic developing machine according to the following steps. Note that the total processing time is 45 seconds.

Processing temperature Processing time insertion 1.2 seconds development + transfer 35℃ 14.6 seconds fixing + transfer 33℃ 8.2 seconds washing + transfer
25℃ 7.2 seconds squeeze 40℃
Dry for 5°7 seconds at 45°C 8.1
Total seconds: 45.0 seconds The developer used was XD-90, and the fixing used was XF (both trade names manufactured by Konishiroku Photo Industry ■).

From the obtained characteristic curve showing the relationship between iogE (logarithm of fi scene) and D (optical density), the exposure amount at the base density of 10 Capri density + 1.0 was determined, and the relative sensitivity was determined.

In addition, drying properties were evaluated as follows. That is, 45 above
Automatic development is performed in seconds, and the sample that has passed through the drying area is comprehensively evaluated for its texture, degree of stickiness with other samples, etc., and is expressed on a five-point scale from 1 (poor) to 5 (excellent). Ta. Note that 3 to 5 poses no problem, but 1 to 2 is not practical. The following results are summarized in Table 1.

In addition, for some samples, the line speed of the above 45-second automatic processor was reduced to 1/2, and the sensitivity of the conventional 90-second processing was determined. As is clear from the results in Table 2 and Table 2, according to the present invention, the coating properties (especially coating properties on the back side) were good, and the sensitivity and drying properties were also excellent. This shows that it is suitable for ultra-rapid processing. In comparison with the conventional 90 second processing, it can be seen that the processing time is reduced to 1/2 while maintaining the sensitivity of the conventional system, and the processing capacity is doubled.

Example-2 Emulsion E-2 was obtained by the method shown below. First, 60℃, p
Ag-8.0, silver iodide 2.0 with an average grain size of 0.3 μI was produced using the double jet method while controlling the pH to 2.0.
A monodisperse cubic emulsion of silver iodobromide emulsion containing mol % was obtained.

An electron micrograph of this emulsion showed that the incidence of twin grains was 1% or less in number. Using this emulsion as a seed crystal, 40℃
The gelatin was added to a solution containing protected gelatin and ammonia added as needed, and the pH was adjusted with glacial acetic acid.

Using this solution as a mother liquid, a 3.2N ammoniacal root ion aqueous solution and a halide aqueous solution were added by a double jet method while controlling the flow rate to sequentially form layers with various silver iodide contents.゛In this case, when forming a layer with a silver iodide content of 30 mol%, pAg is 7.3, p
It was prepared by controlling the temperature to H9.7. In addition, the silver iodide content is 0.
The mole % layer was prepared by controlling the pAg to 9.0 or above 9.0 as shown in FIG. That is, as shown in Figure 1, up to 7% of the silver used in the preparation was formed with 20 mol% or more of silver iodide, and then a layer containing less than 1120 mol% of iodide was prepared according to the pattern shown in Figure 1. . The emulsion thus obtained was a monodisperse silver iodobromide emulsion with an average grain size of 0.85 μm and a total ratio of silver iodide to total silver halide of 2 mol %.

The obtained emulsion E-2 was optimally sensitized with gold and sulfur in the same manner as in Example-1, and 4-hydroxy-6-methyl-1,3
,3a, ? - After stabilization with tetrazaindene, the following sensitizing dye (I) was added at 200% per mole of silver halide.
n+g was added.

Sensitizing dye (I) The above emulsion and a protective layer containing a hardener were coated in the same manner as in Example-1, and a sample was obtained! 1h52 to black 102 were obtained. In addition, the front and back surfaces of samples 53 to 81 were coated and dried separately, and black 82 to 1lh102
is a sample obtained by sequentially coating the front and back sides and drying both sides at the same time.

The obtained samples were evaluated in the same manner as in Example-1, and the results are summarized in Table 3.

As is clear from Table 3, in the present invention, the effect is significant even in systems subjected to color sensitization.
The preparation of E-7 will be described. First, a solution containing 36ON ammoniacal silver nitrate solution, potassium bromide, and 2.0 mol% potassium iodide was heated at 45°C.

It was added to the gelatin solution by a double jet method while maintaining pAg=11.0 and pH=9.0. The addition rate was gradually increased as the particles grew.

The obtained emulsion was an octahedral monodisperse emulsion with an average grain size of 1.05 μm. Further, an ammoniacal silver nitrate solution and a potassium bromide solution were added using the double jet method at pAg=11.0 and pf (=9°0) to form a shell of pure silver bromide.The resulting emulsion had an average grain size. It was an octahedral monodispersed emulsion with a diameter of 1.10 μm.This emulsion was designated as E-3.

Next, the manufacturing method is almost the same as E-3, but the ratio of potassium iodide and potassium bromide is changed, and the core grain size is changed so that the average silver iodide content after the shell is the same, and the same Adjust the addition speed at the initial stage of mixing so that the size of silver iodide is 5 mol%, 10 mol%, 20 mol%, 30 mol%.
An octahedral silver iodobromide emulsion was prepared. The subsequent steps were exactly the same as E-3 to prepare octahedral monodispersed emulsions with an average grain size of 1.10 μm.
It was set to 6°E-7.

The five types of emulsions obtained were chemically sensitized in the same manner as in Example 1, stabilized, and simultaneously coated on both sides.
Samples k103 to N1112 shown in Table 4 were obtained.

These samples were processed for 45 seconds in the same manner as in Example-1, and the sensitivity was determined. In addition, blackening of scratches was measured as follows. That is, after conditioning the sample at 23°C and 55% RH for 4 hours, it was scratched with a sapphire needle with a radius of 0.3 mm at varying loads, and developed to reach the load (g) at which blackening begins.
). That is, the smaller the value, the weaker the blackening of scratches.

The above results are summarized in Table 4. As is clear from Table 4, particles with a difference in iodine content of 10 mol% or more between the core and shell cause blackening due to abrasion as the amount of gelatin is smaller compared to particles with an iodine content of less than 10 mol%. It can be seen that the sensitivity is also excellent.

Example-4 60°C, [)Ag=8.0, PH-2.0 controlled, average particle size 0.28 μm by double jet method
A silver iodobromide monodispersed cubic emulsion containing 2.0 mol % of silver iodide was obtained. Using this emulsion as a seed crystal, it was grown as follows. That is, a solution containing this seed crystal and gelatin was heated at 40°C and p
Ag=8.0, pH-9.5, ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added by double jet method, and silver iodide was added at 5 mol%, 10 mol%,
First coating layers containing 15 mol% and 30 mol% were respectively formed.

Then, for each emulsion, a second coating layer of pure silver bromide was formed in the same manner as E-3 except that the pAg was set to 9.0, and a cubic crystal monodisperse layer of steel with an average grain size of 0.80μ was formed. Core-shell emulsions of silver iodobromide were prepared, and E-8, E-9, and
They were named E-10 and E-11. The average silver iodide content of these emulsions was all 3 mol%.

After chemically sensitizing these emulsions in the same manner as in Example-1, the sensitizing dye (I) shown in Example-2, the sensitizing dye (■) shown below, and the sensitizing dye (III) were added. Both sides were added in multiple layers at the same time in the same manner as in Example-1, and sample light 1 was applied.
13 to N1128 were obtained.

The obtained sample was subjected to scratches and blackening in the same manner as in Example-3.
The sensitivity was determined and the results are shown in Table 5.

Sensitizing dye (IF) C,H.

■ Sensitizing dye (III) As is clear from Table 5, those using grains having a layer in which the difference in silver iodide content between the core and shell is 10 mol% or more are systems to which a sensitizing dye is added. Also, it can be seen that the less gelatin is contained, the less blackening of scratches occurs and the sensitivity is better.

〔Effect of the invention〕

As described above, according to the present invention, the total processing time is from 20 seconds to
Even when ultra-quick processing of 60 seconds is carried out, the problems of the prior art are overcome and silver halide photographic materials excellent in sensitivity, contrast, maximum density, fixing properties, drying properties, etc. can be obtained.

Further, according to the present invention, a silver halide photographic material can be obtained which has a small amount of gelatin and has few failures during coating even if the surface tension of the coating solution is low.

Further, according to the present invention, a silver halide photographic material with little blackening due to scratches can be obtained even if the amount of gelatin is small.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of an example of a coating device that can be used in carrying out the present invention, and illustrates a case in which a two-layer coating method using a slide hopper is adopted as a coating method, and coating is continuously applied to both sides of a support. It is. FIG. 2 is a longitudinal sectional view showing an example of a gas ejector that can be used in carrying out the present invention. FIG. 3 is a diagram showing a 91g control pattern when forming silver halide grains having layers with various silver iodide contents. DESCRIPTION OF SYMBOLS 1... Coater, 2... Support body, 3'... Gas ejector.

Claims (1)

[Scope of Claims] 1. Consisting of a support, a photosensitive silver halide emulsion layer provided on the support, and a non-sensitive layer provided on the support, wherein the emulsion layer and the non-photosensitive silver halide emulsion layer are provided on the support. The amount of gelatin on the side where the sexual layer is provided is 2.00g/m^2 to 3.50g/m^2
The outermost layer has a surface tension of 15 dyn/cm to 26 dy
n/cm, and each of the above layers is formed by applying the coating solution for forming each layer on one side of the support and before drying. A silver halide photographic light-sensitive material, characterized in that the layers are formed by coating the other side of the body with a coating solution for forming each of the layers, gelling it, and drying it. 2. The silver halide photographic material according to claim 1, which is processed in an automatic processor for a total processing time of 20 seconds to 60 seconds.