JPH02262645A - Silver halide photographic sensitive material for crt photographing to allow extremely rapid processing - Google Patents

Abstract

PURPOSE:To improve processing stability and to satisfy sensitivity and max. density by adopting the constitution in which the value and gamma value (GC) of the characteristic curve exposed for one second with a CRT attain specific values at the time of subjecting the silver halide photographic sensitive material to a development processing in an extremely short period of time. CONSTITUTION:The silver halide photographic sensitive material having <=3.60[g/m<2>] silver content on a photosensitive emulsion layer side is so constituted that the value [gamma value (GA) of the straight line connecting 0.5 and 1.5 densities/gamma value (GB) of the straight line connecting 1.5 and 2.5 densities] of the characteristic curve obtd. by exposing the above-mentioned material for one second with the CRT of P.45 RMA number at the time of processing the material for <=16 second developing time attains >=0.69 and <=0.88 and the gamma value (GC) of the straight line connecting 1.0 and 2.0 densities in the same characteristic curve attains >=2.4. The prescribed gamma values are attained by controlling the average grain size, grain size distribution, etc., of the emulsions. The extremely rapid processing is enabled in this way and the processing stability is good; in addition, the satisfactory sensitivity and max. density are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material for CRT projection. In particular, C
RTtl! This invention relates to a silver halide photographic material for shadows.

[Background of the invention]

Silver halide photographic materials for CRT photography are used to obtain hard copy films of CR7 images.

Among conventional photosensitive materials for CRTs of this type, no one has been developed that is adaptable to ultra-rapid processing in which the developing time is 16 seconds or less. In the field of photosensitive materials, there is a growing demand for even more rapid processing in all ships, and such ultra-rapid processing suitability has come to be desired for photosensitive materials for CRTs as well.

Photosensitive materials for CRTs are desired to be processed ultra-quickly as described above, and are also required to have small fluctuations in photographic properties with respect to fluctuations in processing conditions.

One possible means for improving rapid processing suitability and processing stability as described in item 2 is to reduce the amount of silver in the photosensitive silver halide. However, if the amount of silver is reduced, for example to 3.60 (g/po) or less, in order to obtain a sufficient maximum concentration, it is necessary to take measures such as making the silver halide grains smaller. When the sensitivity decreases, it is necessary to lengthen the shooting time or increase the brightness of the CRT, resulting in a deterioration in image quality.

Therefore, in the conventional technology, a large amount of silver halide grains with a large grain size (and therefore a low covering power) are used, and the amount of silver used exceeds 3.60 (g/E). Therefore, it was necessary to configure the device to maintain sensitivity and obtain the desired maximum density.As a result, it was not always possible to obtain satisfactory processing stability, and for example, the gamma value varied depending on the processing conditions. In some cases, the range of variation in the image quality became large, fogging deteriorated, and fixing performance deteriorated.

[Purpose of the invention]

The present invention solves the above-mentioned problems of the prior art, enables ultra-rapid processing, has good processing stability, and has satisfactory sensitivity and maximum density. The purpose is to provide photosensitive materials.

[Means for solving problems]

In order to achieve the above object, the present inventor has conducted extensive research, and as a result,
The inventors have discovered that the above-mentioned problems can be solved by a photosensitive material having the following structure, and have arrived at the present invention.

That is, the above-mentioned problem arises in a silver halide photographic light-sensitive material for CRT photography having at least one ortho-spectrally sensitized light-sensitive silver halide emulsion layer on one side of the support. The amount of silver on the photosensitive emulsion layer side of the material is 3.60 (g/rrf) or less, and when the silver halide photographic light-sensitive material is processed with a development time of 16 seconds or less, it is possible to obtain a CRT with an RMA number of P and 45. Gamma 9 (GA) of the straight line connecting densities 0.5 and 1.5 of the characteristic curve exposed for 1 second at
Gamma value (Gm) of the straight line connecting density 1.5 and 2.5)
(It is characterized by a configuration in which i is 0.69 or more and 0.88 or less, and the gamma value (GC) of a straight line connecting densities 1.0 and 2.0 in the characteristic curve is 2.4 or more. This problem could be solved by using silver halide photographic materials for CRT photography.

In the present invention, the characteristic curve is the logarithm fogE of the exposure amount.
A photographic characteristic curve that represents the relationship between the two, with the horizontal axis representing density and the vertical axis representing photographic density.

The gamma value is the slope of a straight line connecting two points on the characteristic curve (tanθ, where θ is the angle between the straight line and the horizontal axis).
In the present invention, each gamma value GA,
The characteristic curve specifying G, GC is a characteristic curve obtained by exposing a silver halide photographic light-sensitive material for 1 second on a CRT with RMA number P and 45. Each gamma value in is under the above-mentioned specific conditions, and the development time here refers to the time from when the sample, which is a photosensitive material, comes into contact with the developer solution surface to when it comes into contact with the fixer solution surface. Each gamma value G A and CIn G c in the characteristic curve referred to in the present invention is particularly determined by the above CRT.
For photosensitive materials exposed for 1 second with Konica automatic processor 5
RX-501 total processing time 45 seconds mode (development time is 1
4.8 seconds), development temperature 35°C using developer XD-3R (starter), fixer XF-3R
These values are obtained when processing is performed at a fixing temperature of 33° C. using Note that the CRT used for exposure is specified by the above-mentioned RMA number, and thereby the phosphor that emits the exposure light and its emission spectrum are specified.

Any mode can be adopted to bring each gamma value into the above range, and by controlling the average grain size, grain size distribution, etc. of the emulsion, the gamma values can be adjusted within the range of the present invention.

A preferred embodiment of the CRTti shadow silver halide photographic light-sensitive material of the present invention is one in which the above-mentioned characteristic curve falls within the following range.

That is, when a photosensitive material is processed using a roller-conveying automatic processor that meets the following processing conditions and the following developer-1, the characteristic curve obtained by exposing for 1 second on a CRT with RMA number P, 45, The gamma value (G, ) of the straight line connecting densities 0.5 and 1.5 is 0.69 or more and 0.88 or less, and the gamma value (G,) of the straight line connecting densities 1.0 and 2.0 in the same characteristic curve is CC) configured to be 2.4 or more
An RTti% shadow silver halide photographic light-sensitive material is preferred.

(Processing conditions) Processing temperature Processing time Development 35°C 14.8 seconds Fixing 34°C 9.2 seconds Washing 33°C 7.2 seconds Drying 45°C 14.6 seconds However, the following developer is used for the above processing. -1
It is.

<Developer-1> Potassium sulfite 60.0 g Hydroquinone 25.0 g 1-phenyl J3-pyrazolidone 1.5 g Boric acid
10.0 g potassium hydroxide
23.0g triethylene glycol 5-methylbenztriazole 5-nitropenzimidazole 1-phenyl-5-mercaptotetrazole glutaraldehyde bisulfite glacial acetic acid Potassium bromide Add water to make 1j2.

The amount of silver on the photosensitive emulsion layer side of the silver halide photographic light-sensitive material of the present invention is 3.60 (g/if) or less, but if the amount of silver exceeds this range, ultra-rapid 45-second processing may be necessary. If the process is
Drying properties tend to deteriorate. The smaller the amount of silver, the better the processability. However, if the amount of silver is too small, it becomes difficult to obtain sensitivity and maximum photographic density, so it is preferable to keep the amount of silver at an appropriate level. The preferred range of silver amount is 1.50 to 3.5
0/I.

17.5 g 0.04 g 0.11 g 0.015 g 8.0 g 16.0 g 4.0 g Furthermore, the silver halide emulsion layer constituting the silver halide photographic light-sensitive material for CRT photography of the present invention, It is preferable to contain silver iodide-containing silver halide grains containing silver iodide in a range of 0.20 mol or more and 3.80 mol or less.

In particular, it is preferable that the photosensitive material has a silver halide emulsion layer containing such silver iodide-containing silver halide grains in an amount of 60% or more of the total silver halide grains.

If the silver iodide content is less than 0.20 mol%, development and fixing progress quickly and processability is good, so it is advantageous in this respect, but it is also advantageous in terms of high sensitivity and covering power. It is necessary to use small silver halide grains with a large grain size in a high silver content, which impairs processability. From this point of view, it is preferable for the silver iodide content to be 0.20 mol% or less. be. Furthermore, if the silver iodide content exceeds 3.80 mol%, there is almost no increase in sensitivity, but processability deteriorates, so there is no point in increasing the silver iodide content. The content is preferably 0.380 mol% or less.

Note that when the silver halide used in the photographic material of the present invention, particularly when the silver halide is a silver halide containing silver iodide, its composition is arbitrary. It may contain a chlorine atom.

The silver iodide-containing silver halide grains are grains of silver iodobromide, silver chloroiodobromide, silver chloroiodide, etc., and among them, silver iodobromide is preferred. The silver iodide content of the silver iodide-containing silver halide grains is further preferably 0.50 mol% or more and 3.00 mol% or less.

In a more preferred embodiment of the present invention, silver iodide is contained in the range of 0.20 mol to 3.80 mol as described above, and the following [I] and/or [II]
Condition (1) Particles must be monodisperse particles that satisfy the following conditions. Particles whose number average particle diameter f and standard deviation S are <0.20.

(II) A tabular grain that satisfies the following conditions. A grain having a ratio of 1:4 to 1:25 between the thickness of the grain and the diameter calculated from the diameter of a circle when the projected area is converted into a circle.

The emulsion layer contains silver iodide-containing silver halide grains corresponding to the following, and it is particularly preferable that the emulsion layer contains such silver halide grains in an amount of 60% or more of the total silver halide grains.

When employing an embodiment using monodisperse particles in the present invention, preferred monodisperse particles include, for example, JP-A No. 59-10
No. 945, No. 59-177535, No. 62-1234
The particles and associated techniques disclosed in No. 45 can be used. In addition, when tabular grains are used, JP-A-58
-113927, 58-113928, 58-
No. 127921, No. 59-105636, No. 60-1
No. 47727, No. 63-138342, No. 63-28
The particles and associated techniques disclosed in No. 4272 and No. 63-305343 can be used.

These silver halide grains have rapid development progress, and can reduce deterioration in sensitivity and contrast in characteristic curves even during rapid processing.

A further preferred embodiment of the present invention is that the dissolution time of the photosensitive silver halide emulsion layer in a sodium hydroxide solution at 50° C. is 18 minutes or more and 130 minutes or less.

If the above-mentioned dissolution time is less than 18 minutes at 50°C, it is advantageous in terms of sensitivity, but the amount of water absorbed increases and the drying load increases, which may cause problems in rapid processing. There is a risk that the performance fluctuation will become large, but if this is longer than 18 minutes, there will be no problem in this regard.
In this sense, it is preferable that the dissolution time is 18 minutes or more.

Further, it is preferable that the dissolution time is 130 minutes or less, since there are no problems such as deterioration of processability or occurrence of uneven development.

Here, the dissolution time of the silver halide emulsion layer in the sodium hydroxide solution is measured under the following conditions.

That is, in a 500-beaker, 1.5% by weight at 50.0°C.
The beaker containing the sodium hydroxide aqueous solution is placed in a constant temperature bath (the water in the beaker is Place the sodium oxide aqueous solution in a constant temperature bath filled with water at a temperature that is stable at a temperature of 50.0°C, usually at a temperature of about 50.2 to 51°C, and keep the temperature constant. Place the sample vertically into a beaker containing sodium hydroxide solution.
Soak in C11 and leave to stand. At this time, the time until the silver halide emulsion layer starts dissolving (the amount of silver halide eluted at this time is usually about 1 to 3%) is measured, and this is defined as the dissolution time.

A further preferred embodiment of the present invention is that the thickness of the photographic constituent layer on the side having the silver halide emulsion layer is 3.9 μm or less.

Here, the photographic constituent layer refers to an undercoat layer (for example, JP-A-5
No. 2-104913, No. 59-18949, No. 59-
19940 and 59-19941), an antihalation layer, a crossover cut layer, a colored layer, an emulsion layer, an intermediate layer, a protective layer, an antistatic layer, etc. , the film thickness is the total thickness of the photographic constituent layers. Measurements are carried out at 23° C. and 55% relative humidity.

It erases local unevenness like a matting agent.

The film thickness can be measured using a film thickness measuring device, but it can also be calculated from the amount and specific gravity of the material coated on the support.

When the film thickness is 3.90 μm or less, there is no problem that the sensitivity and sensitometric characteristics tend to change easily, and there is no deterioration in fixing, washing, and drying properties. A thin film thickness is favorable in terms of processability. However, if the film is too thin, it may cause deterioration of graininess and increase of fog, or the film may lose its stiffness, resulting in deterioration of equipment transportability, so it is preferable to use an appropriate value.

More preferably, the thickness of the photographic constituent layer on the surface coated with the light-sensitive emulsion is 2. ．． The thickness is preferably 50 to 3.70 μm.

It is particularly preferable that the silver halide photographic light-sensitive material for CRT imaging of the present invention has the above-mentioned preferred embodiments.

Particularly preferred embodiments of the photosensitive material of the present invention are as follows. That is, the photosensitive material of the present invention has i on the photosensitive emulsion layer side.
t is 3.60 (g/rrf) or less, and 5 of the emulsion layer
Silver halide having a dissolution time in a sodium hydroxide solution at 0°C of 12 minutes or more and 130 minutes or less, and a thickness of the photographic constituent layer on the side having the emulsion layer of 3.9 μm or less, and which enriches the photosensitive emulsion layer. Monodisperse grains in which 60% or more of the grains have a silver iodide content of 0.30 to 3.80 mol (condition [I])
It is preferable that the grains are composed of silver iodide-containing silver halide grains that are tabular grains (that satisfy condition (n)) or tabular grains (that satisfy condition (n)).

Further, it is preferable to use a vinyl sulfone hardener in the photosensitive material of the present invention, and it is particularly preferable to employ this in combination with the above configuration.

A preferable photosensitive material in the present invention has the above-described preferable structure, and when subjected to the above-described development processing, the characteristic curve G a /G m of 1 second exposure on a CRT with RMA number P and 45 is 0. It is preferable to use a photosensitive material designed so that Ge is 69 or more and 0°88 or less and Ge is 2.4 or more.

The silver halide photographic light-sensitive material for CRT photography of the present invention can be processed by a normal 90-second automatic processing machine and by the recently developed 45
Performance fluctuations due to ultra-quick automatic processing such as second processing,
Fluctuations in performance due to changes in development temperature can be reduced and stable CRT images can be obtained, and this effect is particularly remarkable in the photosensitive material of the preferred embodiment.

When the photosensitive material of the present invention uses a vinyl sulfone hardener alone or in combination with other hardeners,
Performance is stable and high anger can be obtained.

Therefore, it is preferable to use a vinyl sulfone hardener.

Furthermore, particles that meet the above-mentioned conditions [I] and (I[) show little variation in GA, Gm, and Gc and little decrease in sensitivity even in unprecedented ultra-rapid processing with a processing time of 45 seconds. Furthermore, even more stable performance can be obtained by using a vinyl sulfone hardener.

It has a structure that combines the above, and has a hardness of 130 minutes for dissolution time in sodium hydroxide solution at 50°C
The most stable performance is obtained when the thickness of the photosensitive layer on the side having photosensitive silver halide is 3.90 um or less.

In other words, if the degree of hardness is 18 minutes or more for dissolving in sodium hydroxide solution (50°C), the film will be sufficiently hard, so the fluctuations in aA, c, and cc due to treatment will be small, and if it is 130 minutes or less, the desired result will be achieved. GA, Gm, and Gc values are easily obtained, the sensitivity is sufficient, there is no intermittent residual silver after processing, and the storage stability is excellent.

Further, when the dissolution time is 18 minutes or more, the amount of water absorbed by the film can be suppressed and poor drying can be prevented even in ultra-quick processing such as 45-second processing.

In the present invention, by using silver halide grains with appropriate particle sizes and shapes alone or in combination to constitute the photosensitive silver halide emulsion layer, the shape of the characteristic curve of the present invention can be achieved. It is preferable to design it so that

In a preferred embodiment of the present invention, when a monodisperse emulsion with <0.20 is used in the light-sensitive silver halide emulsion layer, high gamma and good linearity in the characteristic curve can be obtained, and also in terms of sensitivity. It's advantageous. Further, even if the processing conditions vary, the variation in the G A/G s value is small, so the effects of the present invention can be made even more pronounced.

Furthermore, when a monodisperse emulsion is used, it is easy to set the G A /G l value and G value within the range of the present invention.

The grain size is determined by the electron micrograph of silver halide grains.
The projected area can be converted into a circle and the diameter can be determined. It can also be obtained by measuring the Stokes diameter using a centrifugal sedimentation liquid phase method. Measurement of particle size distribution can also be similarly obtained from electron micrographs and the like.

Further, the light-sensitive material of the present invention can also have an embodiment containing an emulsion consisting of two or more types of emulsions (preferably both emulsions are monodisperse emulsions) having different average particle sizes.

Next, the silver halide photographic material of the present invention has at least one ortho-spectrally sensitized light-sensitive silver halide emulsion layer on one side of the support.

In the present invention, the photographic constituent layer may be one layer or multiple layers,
Also, even just one emulsion layer is 2F! One or more emulsion layers may be stacked, and at least one emulsion layer to be ortho-spectrally sensitized needs to be present, preferably on the upper side of the emulsion layer (
It is preferable to provide a protective layer on the side opposite to the support. A hydrophilic colloid layer can be provided on the opposite side of the support from the photosensitive silver halide emulsion layer to serve as a backing layer. The backing layer may also be a single layer or a multilayer of two or more layers.

Any ortho-spectral sensitizing dye can be used to ortho-spectrally sensitize the silver halide emulsion layer. For example, the spectral sensitizing dyes listed in the Research Disclosure in the table below can be used.

Preferably, a compound represented by the following formula (1) described on pages 171 to 174 of JP-A-63-178225 is preferably used as the sensitizing dye.

General formula [I] In the formula, Rt and Rz each represent a substituted or unsubstituted alkyl group, Z represents a hydrogen atom, an alkyl group, or an aryl group, and A represents an oxygen atom or N-R2 (R3 is a substituted or unsubstituted alkyl group). represents a substituted alkyl group).

and W, Wr and r are the same or different groups.

X- is an anion, and n is 1 or 2 (however, when forming an inner salt, n=1).

Examples of the substituted alkyl groups for R+ and Rz include vinylalkyl groups, hydroxyalkyl groups, acetoxyalkyl groups, carboxyalkyl groups, and sulfoalkyl groups.

Examples of the anion represented by Xτ include chloride ion, bromide ion, iodide ion, thiocyanate ion, sulfate ion, perchlorate ion, toluenesulfonate ion, and ethylsulfate ion.

When the compound represented by the general formula (1) is used as a sensitizing dye in carrying out the present invention, specifically, for example, the exemplified compound disclosed in JP-A-63-178225 is used as the sensitizing dye. It can be used in any means.

Further, the photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-Open No. 63-259563.
As described in No. 63-264742, it is preferable to add optimal ortho spectral sensitization or dye to relatively increase the green sensitivity.

In carrying out the present invention, the grain shape and structure of the silver halide grains used in the photosensitive silver halide emulsion layer are not limited in any way, but are preferably
154, Japanese Patent Application No. 62-6890 (page 24, line 2 to page 42, line 5) are preferable;
Tabular grains as disclosed in Japanese Patent Nos. 9-105636 and 60-147727 can be used.

As mentioned above, it is preferable to use monodisperse grains as the silver halide grains used, but polydisperse grains such as polydisperse grains or the above-mentioned tabular grains may be used in combination in any proportion. .

As the support used in the present invention, it is preferable to use a flexible support commonly used for photographic materials. Useful flexible supports include cellulose nitrate,
Cellulose acetate, cellulose acetate butyrate, polystyrene,
Films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., paper coated with or laminated with baryta or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymer), etc. . The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light.

The surface of these supports may be subjected to a subbing treatment, as is generally done, to improve adhesion to photographic emulsion layers and the like. The support surface is treated with corona discharge,
Ultraviolet irradiation, flame treatment, etc. may also be applied.

By employing the structure of the present invention, when conventional light-sensitive photosensitive materials for CRTs are subjected to rapid processing, especially ultra-rapid processing with a developing time of 16 seconds or less, not only the sensitivity and gamma decrease, but also the sensitivity and gamma decrease, especially in high density areas. In contrast, the contrast of the photosensitive material of the present invention shows little variation in photographic performance depending on the processing conditions, and thus Even if you shorten the development time and perform ultra-quick processing, the sensitivity, gamma,
Satisfactory contrast was obtained, and the fixing properties, washing properties, and drying properties were also good.

Further, by keeping the gamma G within the range of the present invention, a sharp and good image can be obtained.

In carrying out the present invention, the photosensitive silver halide used in the photosensitive emulsion layer of the photosensitive material can be dispersed in a suitable binder and present in the photographic constituent layer. Various hydrophilic colloids are used as binders,
Typically, gelatin is preferably used. As gelatin, in addition to lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin hydrolysates, oxygen decomposed products, and other gelatin derivatives can be used. Materials made of synthetic polymers such as polyvinyl alcohol can also be used.

The same applies to the hydrophilic colloid used when forming the backing layer.

In the silver halide photographic optical material of the present invention, a hardening agent can be used in any layer thereof.

Hardeners are generally used in conjunction with various other film property improvers as necessary for the purpose of improving the physical properties of coating films containing hydrophilic colloid as a binder.

When using a hardening agent, the amount of water absorption can be adjusted to a desired value by controlling the amount added.

The silver halide photographic material of the present invention uses the vinyl sulfone hardener described below to achieve the effect of the present invention, that is, the effect of reducing fluctuations in photographic properties due to fluctuations in processing conditions. It can be further increased.

Here, the vinyl sulfone hardener is a compound having a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group. Preferably, at least two vinyl groups or groups capable of forming a vinyl group are bonded to the sulfonyl group.
For example, the following general formula (VS-
The compound represented by 13 is preferably used in the light-sensitive material of the present invention.

General formula (VS-r) L-(sow-X).

In the above general formula (vs-H, L is an m-valent linking group, X is -CH=Cut or -GHzGHzY, and Y is a group that can be removed in the HYO form by a base, such as a halogen atom, a sulfonyloxy group , sulfoxy group (
(including salts), tertiary amine residues, etc.

Specific examples of X include -co=cut or -GHzC
Hta etc. are preferred.

m represents an integer from 2 to 10, but when m is 2 or more, multiple 15o! -X may be the same or different from each other.

The m-valent linking group is, for example, an aliphatic hydrocarbon group (e.g., alkylene, alkylidene, alkylidine, etc.),
or a group formed by combining these), an aromatic hydrocarbon group (for example, a group such as arylene or a group formed by combining these), -〇-1NR'- (R' is a hydrogen atom or preferably represents an alkyl group having 1 to 15 carbon atoms), -5--N --CO--50-
It is an m-valent group formed by combining one or more bonds represented by -So□- or -5(h-, etc.), and when it contains two or more NR'-, those R' are bonded to each other. The linking group which may be combined to form a ring further includes those having a substituent such as a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.

Below, representative examples of vinyl sulfone hardeners that can be preferably used in the practice of the present invention VS-I VS-2 VS-3 VS-4 VS-5 VS-8 VS-9 VS-10 VS - 18 V S -19 VS-22 H1C=CHSO1CH*SOgCH-CHxLC-C
HSOx(CHtLSOtC)I-CLHgC-CHS
Ox(CHx)zsOtcH-CHgIItC=CH5
OxCHtOCHxSO*CH=CHtH,C-Cl2
O yo (CL)□0 (CH yo)xsOtcH=CHtH
xC-CHSOiCHzCONHCIhNHCOCHg
SOi CH-Cl rich H, C rich ct+so□CHxCON
H(CI(t)JHCOCHxSO*CHuraCHf11
zc=CHSOICHICONHCH*CHtcHtN
HcOc)ItsoxcH-CHx[(HzC=CII
SOz) zcclItsOz (CHz) gscH
z] zco (HzC=CH5OtCHt) aC VS-15 ) υFuji i Akebonoshi r1g VS-29 VS-36 VS-30 H,CFu CH30I (CI(,), 50□CCHz)
zsO□CH-C1hHxC-1jlsOg (C)I
t) J)l (Cut) JH(cut) zsOz
cH= CH2V S −31 1t tC−CHSO! (CHri go (CL)
JFIONHCCHl) to (CHl) tsOl
cH=CH.

VS-39 VS -40 ■ VS -41 CsH+ffC(C1bS(hC)I-CHz):+S
-48 NH[(C)I5OtCH-CHz]tS-49 CH3C(CH10C1hSO1CI=CH!S-5
0 CCCHzOCHtSOtCH=CHz) aS-51 N[(C)It)zOcHzsOzcH=cHt]sS
-52 CCHz = CH5OzC:Hz) 5ccIIs(h
(CHz) zc1S-53 HzC"CHSOzCH=CHz V S -44 C)Iz(CON)ICHzS(hcH=cHz) z
S-54 H1C=C)ISO2CH2C(CH2SOzCHzC
H1O3O3eNa' )3S-55 CH3SO3 (CHz) tsO□ (CHz) tO5
QzcHxS-46 C[C0(CHz) zs(hcH=cHz] aVS
-56 2C1e Vinylsulfone hardeners that can be used include, for example, German Patent No. 1,100,942 and U.S. Pat.
．． Aromatic compounds as described in No. 490.911 etc., Japanese Patent Publication No. 44-29622, No. 47-25373
Alkyl compounds bonded with hetero atoms as described in Japanese Patent Publication No. 47-24259, etc., Japanese Patent Publication No. 47-87
1,3,5-tris[β-(vinylsulfonyl)-propionyl]-hexahydro as described in JP-A-49-24435, etc.; -8-Triazine or Japanese Patent Publication No. 50-35807, Japanese Patent Publication No. 51-441
It includes alkyl compounds such as those described in JP-A-59-18944, etc., and compounds described in JP-A-59-18944 and the like.

Vinyl sulfone hardeners are soluble in water or organic solvents and generally have a 0.
005-20% by weight, more preferably 0.02-10%
Preferably, it is used in an amount of % by weight.

For addition to the photographic constituent layer, a batch method or an in-line addition method can be adopted.

The layer to which the hardening agent is added is not particularly limited; for example, it may be added to one top layer, one bottom layer, at least one other layer, or all layers. It may also be added to.

- When a vinyl sulfone hardener is used in the photosensitive material of the present invention, a hardener other than the vinyl sulfone hardener may be used in combination. As such a hardening agent, those described in the Research Disclosure shown in the table below can be used.

The photosensitive material of the present invention may contain other arbitrary additives, and these are listed in Research Disclosure 1.
It is described in Vol. 76, Nα 17643 (December 1978) and Vol. 187, Nα 18716 (November 1976), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in preparing the emulsion of the light-sensitive material according to the present invention are also described in the above two Research Disclosures, and the descriptions are shown in the following table.

Further, as processing liquids such as a developing solution and a fixing liquid used in processing the photosensitive material of the present invention, appropriate ones can be used depending on the photosensitive material.

The processing method for the photosensitive material of the present invention is arbitrary, and an appropriate processing method may be used depending on each specific photosensitive material.

Appropriate processing liquids such as a developer and a fixer used in processing the photosensitive material can also be used depending on the photosensitive material.

Preferably, the photosensitive material of the present invention is processed under conditions that correspond to the following formula in view of the balance of developability, fixability, and drying performance.

ffi'-7sX T-50~1240.7<f
<4.0 However, l is the processing length (unit: m) when the silver halide photographic light-sensitive material is processed, and T is the time required for the photosensitive material to pass through the above l (unit: 2 seconds) It is.

Further, the photosensitive material of the present invention is preferably processed in an automatic processor, and in that case, it is particularly preferably processed in a roller conveyance type automatic processor under conditions corresponding to the following formula.

1"-'S x T = 50~1240.7<1
<4.0 However, 1 is the 10th inlet of the roller conveyance type automatic developing machine.
T is the length (unit: m) from the core of the roller to the core of the final roller at the drying outlet, and T is the time (unit: seconds) required for the photosensitive material to pass through the above 1.

When processing using an automatic developing machine, it is preferable to use a roller conveyance type automatic developing machine, but in that case, the total number of conveyance rollers is 0.01-0, which is the processing length divided by the number of rollers. It is preferable that the treatment time is in the range of .04, and the time for each treatment site is preferably in the following range.

Insertion + development + transfer 25-40% Establishment + migration 12-25% Washing + crossing 10-25% Total 100% 〔Example〕 The present invention will be further explained below with reference to Examples.

It goes without saying that the present invention is not limited to the examples.

Example 1 Mameomushiri 1 m Silver iodobromide containing 30 mol% of silver iodide with monodisperse grains of silver iodobromide containing 2.0 mol% of silver iodide having an average grain size of 0.2 μm as cores was grown at pH 9.8 and pAg 7.8, and then equimolar amounts of potassium bromide and silver nitrate were added at pH 8-2 + pAg 9.1 to produce silver iodobromide grains with an average silver iodide content of 2.2 mol. Monodisperse emulsion grains having an average grain size of 0.395 μm were prepared.

The emulsion was desalted to remove excess salts using a conventional flocculation method. That is, the temperature was maintained at 40° C., and an aqueous solution of a formalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to cause aggregation. After removing the supernatant liquid, pure water up to 40° C. was further added, an aqueous magnesium sulfate solution was added again to cause coagulation, and the supernatant liquid was removed.

The particle size dispersibility of the silver halide grains thus obtained was S/F=0.15, and had good monodispersity.

Grain 34'' A polydisperse emulsion was prepared by the direct mixing method as described below.

That is, the above four types of solutions (solutions A to D) were first prepared.

Next, liquids B and C were poured into a reaction vessel for emulsion preparation, and stirred using a propeller type stirrer with a rotational speed of 300 revolutions/minute, and the reaction temperature was maintained at 48°C. Subsequently, the A solution was divided into 1 volume=2 volumes, and 1 volume of the divided solution, 100-volume, was poured into the mixed solution of the B and C solutions over 55 seconds. After continuing stirring for 10 minutes, the remaining 2 volumes of Solution A, 200-mL, were further added over 2 minutes, and stirring was continued for 30 minutes. And liquid A, B
Add liquid D to the mixture of liquid and liquid C to increase the p of the solution in the reaction vessel.
H was adjusted to 6 to stop the reaction. In this way,
Average grain size 0.390μ with average silver iodide content 2.2 mol%
A polydisperse emulsion of m was obtained. The grain size dispersibility of the silver halide grains was a polydispersity of S/F-0.34.

・1・i Silver halide grains ■ and ■ obtained in this way are 1
Add pure water so that the volume per mole is 500 mJ,
Then, the temperature was set at 55°C, and the following spectral sensitizing dyes A and B were added at 20°C.
A total amount of 300 μ/mol of halogenated vA was added in a weight ratio of 0:1, and after 10 minutes 1 liter of ammonium thiocyanate salt! Chemical ripening was started by adding 2.6 x 10-' moles per mole and appropriate amounts of chloroauric acid and hypo.

At this time, the pH was 6.15 and the silver potential was 50 mV.

15 minutes before the end of chemical ripening (70 minutes after the start of chemical ripening), 200 μg of potassium iodide was added per mole of silver.
After 10% (wt/Vol) acetic acid was added to reduce the pH value to 5.6 and keep the pH value for 5 minutes.
After that, potassium hydroxide 0.5% (wt/Vol) solution was added to return the pH to 6.15, and then 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added, and the chemical The aging was completed and a photographic emulsion coating solution was obtained.

The pH after preparing the photographic emulsion coating solution was 6.10, and the silver potential was 81 mV (35° C.).

Using this emulsion coating solution, samples were prepared as follows.

That is, the photographic emulsion layer has a gelatin content of 2.0 [g/
2.8 (g/rrf) ~ 4.2 [:g/rrr)
A protective layer solution was prepared using the additives listed below so that the protective layer had a gelatin content of 1.15 (
g/n'f), and prepare the backing lower layer liquid and upper layer liquid shown below on the back side.
(g/rrf) and used as a sample. Coating is done at 80m/min using two slide hopper type coaters.
glycidyl methacrylate 50wt% at a speed of
A copolymer aqueous dispersion obtained by diluting a copolymer consisting of three monomers, 10-t% methyl acrylate, and 40 wt% butyl methacrylate to a concentration of 10-t%, was applied as an undercoat liquid. It was coated on both sides simultaneously on a 175 μm polyethylene terephthalate film base, and dried in 2 minutes and 20 seconds to obtain a sample.

The obtained sample was captured using a Konica Image Camera M.

After exposing the gray scale for 1 second with M (P, 45 phosphor), Konica automatic processor 5RX-501 (SRX-5
0°l is a 90 second mode, development time 25.5 seconds, fixing time 15.9 seconds, washing time 12.4 seconds, drying time 25.
Equivalent to 2 seconds. ) and the above developer solution-1, fixer solution X
Using F-3R, 45 seconds mode (development temperature 35℃ and 3
2℃) and 90 seconds mode (development temperature 32℃),
Samples 1 to 30 were created.

The 45 second mode corresponds to a developing time of 14.8 seconds, and the 90 second mode corresponds to a developing time of 25.5 seconds.

The dissolution time of all the obtained samples in a sodium hydroxide solution at 50°C was 47 to 51 minutes, and the thickness of the photographic constituent layer on the side having the silver iodobromide emulsion layer was 4.2 (
g/po], it was 3.8 [μm].

The fixing temperature of the automatic developing machine used for processing was 33°C.The washing water was heated at 1.51°C per minute at a temperature of 18°C. We decided to supply it.

For each sample, the highest concentration, GA, G,, G^/cm.

Gc was measured. The results are shown in Table-1.

The sensitivity was expressed as a relative sensitivity, with the reciprocal of the exposure amount giving a blackening density of +1.0 fog for Sample 1 in Table 1 as 100.

The spectral sensitizing dyes used for sample preparation are as follows.

Spectral sensitizing dye B The additives used in the emulsion solution (photosensitive silver halide coating solution) are as follows. The amount added is expressed per mole of silver halide.

1.1-dimethylol-1-bromo- ■-nitromethane 70 ■ t-butyl-catechol 400 ■ Polyvinylpyrrolidone (molecular weight 10.000) Styrene-maleic anhydride copolymer Trimethylolpropane diethylene glycol nitrophenyl-triphenylphosphonium chloride 1.3-hydroxybenzene-4-ammonium sulfonate Sodium 2-mercaptobenzimidazole-5-sulfonate 1.0 g 2.5 g 0 g g 50 ■ g 1.5 ■ Polymethyl methacrylate, area average particle size 3.5 μm Matting agent 1.1g Silicon dioxide particles (matting agent with area average particle size 1.2μm) 0.5g
Ludox AM (colloidal silica from DuPont) 30 g 2.4-dichloro-6-hydroxy-1,3,5-triazine sodium salt aqueous solution 2
% (Hardening agent > 12 methyl formalin 35%
(Hardening agent) 2-component glyoxal aqueous solution 4
0% (hardener) 2.0 m1υi The additives used in the protective layer solution are as follows. The amount added is 11. Shown as a hit amount.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g C+ +Hz
CONH (CHzCHzQ) sH2, OgIn addition to the above-mentioned additives, the following compound (1) was added to the emulsion coating solution according to Example 1 (3) in JP-A No. 61-285445.
According to the method described in 1. Compound (2) dissolved in oil and dispersed in a hydrophilic colloid solution was added in the following amount per mole of silver halide.

(2) Tricresyl phosphate 0.6g
The following liquid was prepared and used for the backing layer.

(Backing N) (Backing lower layer liquid) Coating liquid 1j! 70 g lime-processed gelatin 5 g trimethylolpropane 1.5 g backing dye A
1. Og backing dye B
1. Og glyoxal aqueous solution (4
0%) (hardener) 8m! (Backing upper layer liquid) Lime-treated gelatin 70 g Acid-treated gelatin 5 g Trimethylolpropane 1.5 g Backing dye A per coating liquid if
1.0g backing dye B
1. OgKNO, 0.5g F+qCJ (CHzCHzO)++C■zcHz S
O3Na61g Area average particle size 4. Opm polymethyl methacrylate particles C+ rH*3cONHccHxcHzO) sHl,
1g 1.0g Backing dye A 2% aqueous solution of 2.4-dichloro-6-hydroxy-1,3,5-) riazine sodium salt
20 mZ Backing Dye B Below Margins Below Margins As seen from Table 1, the samples according to the present invention have different gammas of GA, G, with respect to processing temperature and time changes.

It can be seen that the performance is stable with little variation in G and sensitivity. Furthermore, it can be seen that the performance does not easily fluctuate even if the amount of rooting changes during manufacturing.

Furthermore, the sample using the monodisperse emulsion of grains (1) had higher sensitivity, less fluctuation, and more stable performance.

In addition, for samples 1 to 30, residual silver in the fogged areas after processing was examined by dropping an aqueous sodium sulfide solution and checking the degree of coloring.
n? ) It was found that the samples coated above deteriorated significantly and there were concerns about their shelf life.

Example 2 Preparation of particles ■ 5.52% of a 1.5% gelatin solution containing 0.17 mol of potassium bromide was added with 2.52% potassium bromide by the pullet method while stirring at 80° (:5 pH 5.9).
1M and 2.0M of silver nitrate solution were added over 2 minutes. The pBr was maintained at 0.8 (consumed 0.53% of the total silver nitrate used). The potassium bromide solution addition was stopped and the silver nitrate solution continued to be added for 4.6 minutes (consuming 8.6% of the total silver nitrate used).The potassium bromide and silver nitrate solutions were then added simultaneously for 13 minutes. During this time pB
r is maintained at 1.2, and the addition flow rate is 2.
Accelerated to 5 times (4 of total silver nitrate used)
3.6% of the total silver nitrate used), the potassium bromide solution addition was stopped and the silver nitrate solution was added for 1 minute (4% of the total silver nitrate used).
．． 7% was consumed).

A 2.0 molar solution of potassium bromide containing 0.55 molar potassium iodide was added over a period of 13.3 minutes along with the silver nitrate solution. The pBr was maintained at 1.7 during this time and the flow rate was accelerated to 1.5 times the starting rate at completion (consuming 35.9% of the total silver nitrate used). To this emulsion was added 1.5 g of sodium thiocyanate, 1 mol of Ag, and held for 25 minutes. 0.60 mol of potassium iodide solution and silver nitrate were added by double jet method at equal flow rates for approximately 5 minutes until pBr reached 3.0 (consuming approximately 6.6% of the total silver nitrate used). The amount of silver nitrate was approximately 11 moles.

In this way, an emulsion containing tabular silver iodobromide grains with an average grain diameter of 1.62 μm and an aspect ratio of about 16:1 was prepared. This grain accounts for 80% of the total projected area of the silver iodobromide grain.
% or more. However, before desalination, this particle has
The above-mentioned spectral sensitizing dyes A and B were added in a weight ratio of 200:1 in a total amount of 1000 cm per mole of silver halide.

When adding the spectral sensitizing dye, adjust the pH to 7.60, add phenylcarbamylated gelatin after 15 minutes, and adjust the pH with acetic acid.
was allowed to flocculate, and the supernatant was removed.

゛ This f, 1. Chemical ripening was performed in the same manner as in Example 1, and samples were obtained by coating and drying in the same manner using the same emulsion additives and protective layer liquid as in Example 1.

In addition, as a hardening agent for the protective liquid layer, 2, which was used in Example 1,
A sample was prepared in which 4-dichloro-6-hydroxy-1,3゜5-triazine sodium salt, formalin, and glyoxal were removed and a vinyl sulfone hardener shown in Table 2 was used instead. A similar evaluation was conducted. The results are shown in Table 2.

The dissolution time of all the obtained samples in the 50°C sodium hydroxide solution was within the range of 38 to 44 minutes.

As shown in Table 2, it can be seen that the samples according to the present invention have small variations in gamma and sensitivity. In addition, the first
Comparison with the table shows that when a vinyl sulfone hardener is used for samples according to the present invention, gamma and sensitivity are lower than when other hardeners shown in Table 1 are used, even when the amount of silver is changed. It can be seen that there is little change and high sensitivity.

Furthermore, even when the processing time and temperature were changed, the performance of the sample according to the present invention showed little change. The samples according to the present invention in Table 2, which were used with vinyl sulfone-based hardeners, showed particularly little change in performance.

Exemplary compound VS-11 as a vinyl sulfone hardener
113, 25, 28, 29, 32, 33, 38, 40,
Tests Nos. 53, 54, 55, and 56 were also confirmed in the same manner, and the remarkable effects of the present invention were obtained.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material for CRT photography which can be processed extremely rapidly, has good processing stability, and has satisfactory sensitivity and maximum density.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material for CRT photography having at least one ortho-spectrally sensitized light-sensitive silver halide emulsion layer on one side of a support, comprising: The amount of silver on the photosensitive emulsion layer side of the material is 3.60 [g/m^2] or less, and when the silver halide photographic light-sensitive material is processed with a developing time of 16 seconds or less,
RMA number P. Gamma value (G_A) of the straight line connecting densities 0.5 and 1.5 of the characteristic curve exposed for 1 second on a 45 CRT
/ Gamma value of the straight line connecting density 1.5 and 2.5 (G_B)
] value is 0.69 or more and 0.88 or less, and the gamma value (G_
C) is characterized by having a configuration in which C) is 2.4 or more.
Silver halide photographic material for RT photography. 2. In a silver halide photographic light-sensitive material for GRT photography having at least one ortho-spectrally sensitized light-sensitive silver halide emulsion layer on one side of the support, the light-sensitive emulsion layer of the silver halide photographic light-sensitive material The amount of silver on the side is 3.60 [g/m^2] or less, and the silver halide photographic light-sensitive material is processed using a roller conveyance type automatic processor that meets the following processing conditions and the following developer solution-1. In the event that
Gamma value (G_A) of the straight line connecting densities 0.5 and 1.5 of the characteristic curve exposed for 1 second on a CRT with RMA number P: 45
/ Gamma value of the straight line connecting density 1.5 and 2.5 (G_B)
] value is 0.69 or more and 0.88 or less, and the gamma value (G_
C) is characterized by having a configuration in which C) is 2.4 or more.
Silver halide photographic material for RT photography. Processing temperature Processing time Development 35°C 14.8 seconds Fixing 34°C 9.2 seconds Washing 33°C 7.2 seconds Drying 45°C 14.6 seconds <Developer-1> Potassium sulfite 60.0g Hydroquinone 25.0g 1-phenyl -3-Pyrazolidone 1.5g Boric acid 1
0.0g Potassium hydroxide 23.0g Triethylene glycol 17.5g 5-methylbenztriazole 0.04g 5-nitrobenzimidazole 0.11g 1-phenyl-5-mercaptotetrazole 0.015g Glutaraldehyde bisulfite 8.0g Glacial acetic acid 16.0g Potassium Bromide 4.0g Add water to make up to 1L. 3. Silver halide grains that meet the conditions [I] and/or [II] below and contain silver iodide in a range of 0.20 mol to 3.80 mol. It has at least one silver halide emulsion layer containing silver halide grains in an amount of 60% or more of all silver halide grains, and the dissolution time of the silver halide emulsion layer in a sodium hydroxide solution at 50°C is 18 minutes or more. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the photosensitive material has a thickness of 130 minutes or less, and a thickness of the photographic constituent layer on the side having the silver halide emulsion layer is 3.9 μm or less. [I] Particles that are monodisperse particles that satisfy the following conditions, where number average particle diameter @r@ and standard deviation S are S/@r@<0.20. [II] A tabular grain that satisfies the following conditions. A grain that has a ratio of 1:4 to 1:25 between the thickness of the grain and the diameter calculated from the diameter of a circle when the projected area is converted into a circle.