JPH01252951A - Sheet unit of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the sheet unit which has excellent sensitivity and less generation of a fog, and has less increase of the fog and deterioration of the sensitivity caused by the contact with a wrapping material during preservation by incorporating a specified compd. in the silver halide emulsion layer contd. in the sensitive material. CONSTITUTION:The compd. shown by formula I is incorporated in the silver halide emulsion layer. In the formula, Z1 and Z2 are each a nonmetallic atom. group necessary for forming a benzothiazole nucleus etc., which may be substd., R1 and R2 are each an aliphatic group, A is hydrogen atom., etc., X<-> is an anion, (n) is 1 or 2 [In case that the compd. forms an inner complex salt, (n) is 1]. Thus, the generation of the fog and the deterioration of the sensitivity due to a natural aging or a forced deterioration are lessened, and the deteriora tion of graininess in the emulsion layer does not generate.

Description

[Detailed description of the invention] [Industrial application field]

The present invention is a silver halide photographic light-sensitive material sheet unit 1-
In particular, the present invention relates to a packaging unit for a silver halide photographic light-sensitive material sheet for a laser light source that is spectrally sensitized in the infrared region. More specifically, the present invention relates to a packaging unit that exhibits little increase in fog and decrease in sensitivity due to contact with packaging materials during the use of the photosensitive material, and extremely little density unevenness in intermediate density areas.

[Background of the invention 1. Radiographic images for medical diagnosis are stored as digital values,
Attempts have been made to perform image processing using a computer to make it more suitable for diagnosis and then expose the image to a laser beam to reproduce the image. As lasers for these scanning exposure devices, for example, argon, helium-neon, helium-cadmium, etc. have been put into practical use. However, all of these 17-zers have drawbacks such as short lifespan, large size, and the need for a complicated device to modulate the emission intensity. In response, research into semiconductor lasers has progressed in recent years, leading to increased power and longer lifespans. Semiconductor lasers differ from conventional argon and helium
Compared to neon lasers, it has advantages such as being cheaper, having a longer lifespan, being smaller in size, and allowing direct modulation, eliminating the need for a modulator. However, since the emission wavelength of a semiconductor laser having the above-mentioned characteristics is in the near-infrared region of 750 to 1,500 nah, the recording material must also have a photosensitive region in the near-infrared region. As a method for spectrally sensitizing silver halide to near-infrared light,
For example, The Theory of the Photographic
Process (Th e Th e o r yo
r T b ePboLography Proce
ss) 3rd edition, Macramin (Mae+si l fan
) Publishing (1968), p. 198-2, a method using a long-chain cyanine dye is known. In addition, cost reduction is an important industrial issue, and it is considered that the high cost associated with improving the performance of photographic film itself can be compensated for by cost reduction of photographic film packaging, which is not directly targeted for the purpose of use, and packaging material costs, There is an urgent need to reduce packaging process costs. For example, a photographic film sheet such as an X-ray film or a printing film is gripped one by one with an ink leaf made of folded thin paper, and a predetermined number of the gripped sheets are further sandwiched between U-shaped cardboard sheets. The interleaf packaging form is designed to protect against external impacts and to prevent scratches, RI frictional charging, sticking, and fog caused by sheets and packaging materials. Except for the folded interleaf, a monofilament interleaf is applied one by one only to the surface that contacts the cardboard of the packaging unit, or a monofilament interleaf is not used at all, and it is directly sandwiched between U-shaped cardboard or monofilament 1γ paper. Non-ink leaf packaging is now being adopted. However, if the photosensitive N material spectrally sensitized to the near-infrared region by the method described above is stored in a non-interleaf packaging form in which it comes into direct contact with cardboard, fog increases and sensitivity decreases.
Furthermore, it has been found that when exposed to laser light, graininess such as density unevenness deteriorates in intermediate density areas. It has also been found that these adverse phenomena are related to the material of the cardboard used in the packaging unit, and are particularly severe when valves made from recycled waste paper are used as the papermaking raw material for the 17 paper. However, even when cardboard made from only new valves was used, the above-mentioned adverse phenomenon sometimes occurred. Also, in order to improve sensitivity loss during storage in the shell, the photosensitive material f
The silver ion concentration and hydrogen ion concentration of the photographic emulsion used in 1C may be increased, the inhibitor may be increased to +1!1iJiL, or a combination thereof may be used, but implementation of these conditions increases fog. On the other hand, in order to improve the capri increase, it is necessary to do the opposite of the above, that is, lower the silver ion concentration and hydrogen ion concentration, increase the amount of inhibitor, or even combine these. In other words, it has been difficult to achieve both an increase in fog and a decrease in sensitivity during storage. increased fog due to contact with packaging materials;
There is little decrease in sensitivity, and medium t when exposed to laser light.
It is an object of the present invention to provide a halogen IL silver photographic light-sensitive material sheet unit color-sensitized in the near-infrared region with extremely little density unevenness in m-density areas.

[Structure of the invention]

The above object is achieved by the following configuration. Silver halide photographic light-sensitive material sea!・A unit that is sandwiched by Noah paper made with a new valve!・, wherein at least one silver halide emulsion layer in the silver halide photographic light-sensitive material sheet contains the following general formula [II
A silver halide photographic light-sensitive material sheet unit comprising a compound represented by: General formula [II: benzothiazole nucleus, benzoxazole nucleus,
Represents a group of nonmetallic atoms necessary to form a naphthothiazole nucleus and a naphthoxazole nucleus, and substituents include halogen atoms (e.g., chlorine atoms, bromine atoms, etc.), carbon atoms from 1 to
4 alkyl groups (e.g. methyl group, ethyl group, ■-propyl group, +1-butyl group, L-butyl group, etc.), alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, n-propyloxy etc.) etc. R and R are each a saturated or unsaturated aliphatic group (e.g. methyl group, ethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-force ruboxy 1
0vir group, 4-carboxybutyl group, 52-sulboethyl group, 3-sulfopropyl group, 3-sulbutyl group, 4-
sulbutyl group, vinylmethyl group, benzyl group, phenethyl group, P-sulfophenethyl group, n-propyl group, isopropyl group, n-butyl group, etc.). Z2 represents a 5- or 6-membered carbon atom ring, and in the case of a 5-day ring, the general formula [1] is represented by the general formula [+-al]. General formula [1-al R3 and R4 are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, etc.), a halogen atom (e.g., chlorine atom, bromine atom, etc.), alkoxy groups having 1 to 4 carbon atoms (
For example, it represents a methoxy group, an ethoxy group, a "propyloxy group, etc.", and Rs and Rs each represent an alkyl group having 1 to 12 carbon atoms which may have a substituent (for example, a methyl group, an ethyl group, a propyl group). , isopropyl group, butyl group, hexyl group, octyl group, dodecyl group, etc.)
For example, methoxycarbonylmethyl group, ethoxycarbonylethyl group, etc.), allyl group which may have a substituent (e.g. '
For example, phenyl group, tolyl group, II-tolyl group, ring-tolyl group,
Chlorophenyl group, P-chlorophenyl group, carbon number 1-
s −+ p-alkoxyphenyl group, etc.) having an alkoxy group of 11. is an alkyl group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, dodecyl group, etc.), an allyl group having 6 to 10 carbon atoms, and an allyl group having 1 to 10 carbon atoms. It represents an alkoxycarbonyl group having an alkoxycarbonyl group of 4 (for example, a methoxycarbonyl group, an alkoxycarbonyl group, a propyloxycarbonyl group, etc.). When Z is a 6-membered ring, the formula -a is replaced by the general formula [1-
b]. In the formula, R1 is a hydrogen atom or a methyl group, 11. is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.),
Represents a monocyclic allyl group (eg, phenyl group, tolyl group, etc.). X- is an anion (e.g. chloride ion, bromide ion, iodine ion, perchloric acid, benzenesulfone-1, PI,
luenesulfonate, methylsulfite, ethylsulfane 1=, tetrafluoropouic acid, etc.). n is l or 2 (fllL, n when forming a molecular inner bath)
is 1). Next, specific compounds of formula -a [1] will be illustrated. 12. C11s C1
1s1;1lls v
gl1%C11゜Il x C,lls Ji, 11? The amount of the compound represented by 1L; It's removal [1] is preferably about 0.003 to 3 g per mole of silver halide, particularly preferably about 0.005 to 0.15 H. The sheet unit of the present invention holds, for example, 10 to 100 sheets depending on the type and size of the photographic film, and each of these sheet units is further housed in a light-shielding and moisture-proof sealed bag. , remove excess air and seal. The thickness of the cardboard used in the sheet unit of the present invention varies depending on the number and size of the sheets to be held. That is, a base paper with a thickness of 0.05 to 0.1 mm and a weight of about 50 g / 2 in a dry state D (e.g., 20 ° C., equilibrium conditions with 65% old I) is preferably mixed with casein, starch or l) V The paper is made by combining 1 to 8 sheets using ^ (polyvinyl alcohol) as an adhesive. In the present invention, a new pulp is used for the papermaking base t1 of the cardboard used in the sea I unit, and during the gold dusting,
The new pulp is also used for the papermaking base paper that forms the internal sand layer. In addition, as the new pulp, a white pulp with a low lignin content is preferable. The smoothness of the surface of the cardboard according to the present invention that comes into contact with the photographic film is preferably 10 seconds or more, more preferably 15 seconds or more as specified in JIS-P8119. Note that an upper limit of 40 seconds is sufficient. As a means of increasing the surface smoothness, calendering alone may be sufficient, or 0.5 to 10.0 g of casein, starch, PVA, paraffin, etc., may be added to the paper base paper that forms the surface layer of the cardboard surface that contacts the photographic film sheet. Addition and/or casein, starch, PVA, paraffin on the cardboard surface from 0.5 to 1
A predetermined level of smoothness can be achieved by applying 0.0 g/s' and calendering at a nip pressure of 30 to 200 Kg 7 cm.Furthermore, a synthetic resin (such as benzoguanamine, melamine, etc.) is applied to the surface of the cardboard. It is also possible to apply IRII beads such as polynisder resin, polyfluoroethylene resin, etc. to create a uniform and dense miliary surface.In addition, in the present invention, for the purpose of suppressing fog and preventing static electricity, the moisture content of the cardboard is (preferably ±25 to log/m' with reference to fdan40011/II", and further ±25 to log/m'
23 to 1611/I11' is preferable. still,
The water content is 7 to 3-1%. Yosuisan is lrJ. The paper is then brought to near dryness, and the humidity is adjusted to 20 to 70% at room temperature to reach equilibrium. Further, it is preferable that the 17 paper contains 50 to 100 OB/m2 of water-soluble inorganic salts (e.g., common salt) as an antistatic treatment. ′ In addition, sizing agents are added to the pulp liquid to improve the quality of the paper.
This does not exclude the addition of size fixing agents, water resistance improvers, ta-free additives, wet strength improvers, preservatives, antifoaming agents, etc. necessary for the papermaking process, but water-soluble, vaporizable, etc. It is necessary to check the influence of materials that are permeable. However, on the contrary, papermaking additives that contribute to the improvement of photographic film properties can be used in (W j (+). 20 to m: (40 to 60% in the range of 0°C
It would be better if it was included in the old version 1. In the present invention, a condensate of phenols and aldehydes (novolac resin) can also be added together with the sensitizing dye. Examples of phenolic compounds include phenol, cresol, isopropylphenol,

[-butylphenol, L-aminophenol, hexylphenol, L-ofnalphenol, cyclohexylphenol, 3-methyl-4-chloro-6-tert-butylphenol,
Examples include isobu I7 vircresol, among which phenol, cresol, and L-butylphenol are particularly preferred. Examples of aldehydes include formaldehyde, acetaldehyde, acrolein, crotonaldehyde,
aliphatic and aromatic aldehydes such as furfural;
Includes those having 1 to 6 carbon atoms. Preferably,
Formaldehyde and acetaldehyde. The amount of this condensate used is approximately 0.0 per mole of silver halide.
1 to 2 Fi is preferred, particularly about 0.03 to 1.3 g. The composition of the photosensitive silver halide emulsion used heavily in the present invention may be any of silver chloride, silver arsenate bromine, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, but preferably about 0 It is ^Hurl' with 3 .5 to 10 mol% of 8g+. The photographic emulsion used in the light-sensitive material of the present invention is prepared by an acid method, a neutral method, or an ammonia method. Further, the reaction between the soluble silver salt and the soluble halogen salt may be carried out by any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof, ie, a so-called back mixing method. In addition, the silver halide emulsion can be prepared by adjusting the pH in the reaction vessel by gradually increasing the amount of silver ion solution or halide solution added.
It can be prepared by the so-called controlled double-jet method, which controls the amount and EAg. At the stage of silver halide grain formation or physical ripening, cadmium, palladium 1! , zinc, lead salts, thallium salts,
Iridium I! ! In addition, (Masononugi 1 salt, 17dium salt or its complex salt, iron salt or its j11 salt, etc. may be coexisting.) Furthermore, the silver halide emulsion may be a dispersion emulsion, where: A monodisperse emulsion is one in which σ ≦0.20, where R is the average grain size of silver halide grains and σ is the standard deviation of the grain size. , in the case of spherical silver halide, its diameter is expressed, and in the case of particles of a shape other than spherical, it is expressed as 'F average' based on the diameter when its projected image is converted into a circular image of the same area.In the present invention, halogenated An organic gelatin flocculant is used as a flocculant for desalting and washing with water by the coagulation-sedimentation method of silver emulsion.As an organic gelatin flocculant, a water-soluble polymer compound having a sulfonic acid group or a carboxylic acid group or a relatively molecular weight compound is used. A surfactant with a large
Many are described in No. 22. In particular, polymers such as those shown below as representative examples can be used. comb is the degree of polymerization, and a to d are the composition ratios, and these organic gelatin flocculants have molecular weights in the range of i, ooo to 100,000. Specific examples of these include commercially available products such as Versa TL (Kanebo NNC Co., Ltd.), 5eripl (Monsando, USA), and EMA (Monsando, USA). The organic gelatin flocculant used in the present invention may be used in combination with other flocculants such as sulfate <magnesium tttate, sodium sulfate, etc.). If the amount of the organic gelatin flocculant used in the present invention is too large, resolubility will be lost, and if it remains in the emulsion, it will cause a decrease in sensitivity. Furthermore, if the amount is too small, agglomeration will not occur, so about 3 to 1,511 moles of silver halide are used, particularly preferably about 5 to tog. Further, the pH for coagulation is preferably 7 or less, preferably 3 to 6.5. Some organic gelatin flocculants remain in the emulsion even after desalting and washing with water. If this residual amount is large, it will lead to desensitization of the silver halide emulsion, so it is best to reduce it as much as possible. The remaining amount can be measured by any conventional analytical method, but for example, a small amount of emulsion is dispersed in water and left overnight.
Extract the organic gelatin flocculant. This may be centrifuged, and the organic gelatin flocculant in the supernatant liquid may be quantitatively analyzed by colorimetric analysis or the like. The amount of organic gelatin flocculant remaining in the gelatin may be about 4.5 g or less per mole of silver halide, particularly about 3.5 g or less per mole of silver halide.
It may be within a range of 5g or less. The silver halide hole agent can be chemically sensitized by a known method. Chemical sensitization includes, for example, sulfur sensitization and gold sensitization, and these may be used in combination. The amount of sulfur aggravating agent added varies within a considerable range depending on various conditions, but it is usually lXl0-' to lXl per mol of silver.
The amount of the gold sensitizer added varies over a considerable range depending on various conditions, but is usually about 1X10-' to 1x1O-' mole per mole of silver. In addition, in sulfur/gold sensitization, the proportion of the two varies depending on the aging conditions, etc., but usually the amount of sulfur sensitizer is about 1 to 1000 mol per 1 mol of gold sensitizer. Further, the gold sensitizer may be added at the same time as the sulfur sensitizer, during the sulfur sensitization, or after the sulfur sensitization is completed. These chemical sensitizers are water-soluble sensitizers as aqueous solutions;
Organic solvent-soluble compounds are organic solvents that are easily miscible with water,
For example, it is added as a solution in methanol, ethanol, etc. Further, there are no particular limits to the conditions such as pl+, 9Ag, temperature, etc. during chemical sensitization, but the -11 value is preferably 4 to 9, especially 5 to 8, and the pAg value is 5 to 11, especially 8 to 8. 10
The temperature is preferably maintained at 40 to 90°C, particularly preferably 45 to 75°C. The photographic emulsion used in the present invention may be subjected to the aforementioned sulfur sensitization, gold/sulfur sensitization, reduction sensitization using a reducing substance, lamp metal sensitization using a noble metal compound, or the like. As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed. The structure of the photosensitive material $1 of the present invention can take various forms. For example, the silver halide emulsion layer can be formed on both sides of the support or only on one side. moreover,
Auxiliary layers such as protective layers, antihalation layers, etc. can be provided at appropriate locations. Furthermore, when an emulsion layer is formed on only one side, a layer made of hydrophilic colloid such as gelatin can be formed as a backing layer on the opposite side. Incidentally, the backing layer may contain various dyes for the purpose of making it easier to distinguish between the front and back sides. The preferable layer structure of the photosensitive material ゛↑4 of the present invention is as follows:
A silver halide emulsion layer is formed on only one side of the support, and a backing layer containing a suitable dye is formed on the other side. In the present invention, photosensitive silver halide and the like are dispersed in a suitable binder and present in the photographic constituent layers. Various hydrophilic colloids are used as the binder, and gelatin is typically used. The gelatin used in the present invention is not particularly limited as long as it is a normal gelatin such as alkaline gelatin, acidic gelatin, desalted gelatin, or low calcium gelatin. In addition, in order to improve the physical properties of the coating film using the above-mentioned hydrophilic colloid as a binder, it is preferable to use various film property improving agents, such as a hardening agent, as necessary. Examples of photographic additives other than additives include gelatin plasticizers, surfactants, ultraviolet absorbers, antistain agents, pH regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, and mordants; A brightener, a development speed Fl adjuster, a matting agent, a silver halide developer described below, and the like can be used within the range that does not impair the effects of the present invention. Incidentally, the matting agent may be polydispersed or monodispersed. The following various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. Namely, azoles, nitroindazoles, triazoles, benzotriazoles, benzimidazoles, mercapto compounds (e.g., peterocyclic mercapto compounds, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidals, mercap!
・Pyridines), thioketo-1-hyde compounds, azaindenes,
Various compounds known in the art as stabilizers can be added, such as mercaptoazaindenes, benzenethiosulfonic acids, benzenesulfinic acids, and the like. An example of a compound that can be used is the book by Kay Mies [The Theory of the Four Hegelough Processes].
(K, Hees, “TI+e Tl+'eory or
Ll+e gate+oLogrBbic I'rocess
”) 3rd edition, 1966, citing the original documents. For more detailed examples of these and how to use them, see, for example, U.S. Pat.
, No. 947 and No. 4,021.248. The antifoggants or stabilizers particularly preferably used in the present invention include the following general formulas [11], [111], [IV
], [Vl, and nitrone monohyalone compounds. In the formula, 1 (, represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, a substituent) an acyl group which may have a Z ta group, a carboxymethyl group which may have a Z ta group, a -C00M group or -SO,
H group (H is hydrogen atom, alkali metal atom or ammonium group) -RI2+R13+R14 represents -COON group or -503H group, n+ +nt is an integer from 1 to 3, n represents 1 or 2 -14+n% does not represent 0 or 1, and 114 + +l s cannot both be O. When 11゜n is 2 or 3, RIl and R1* may be the same or different. [V] In the formula, Z represents, together with C=N, an atomic group necessary to form a 5 or 6@ heterocycle consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and this heterocycle may be combined. Examples of these include a tetrazole ring, a triazole ring, an imidazole ring, a thiadiazole ring, an oxadiazole ring, an oxazole ring, a benzthiazole ring, a benzimidazole ring, a benzoxazole ring, a purine ring,
There are azaindene rings, tos/tetou/pentapyridine rings, and pyridine rings. Further, these heterocycles may be substituted with an alkyl group, an alkoxy group, an amino group, a nitro group, a halogen atom, a carbamoyl group, an alkylthio group, a mercapto group, or the like. Among these, preferred are compounds in which Z forms a tetrazole ring, triazole ring, thiadiazole ring, benzimidazole ring, or benzthiazole ring together with C=N, and most preferred are compounds in which Z forms a thiadiazole ring together with C=N. It is a compound that Further, in the formula, H represents a hydrogen atom, -Nl+, a group, or an alkali metal atom. Among the compounds represented by the general formulas [11], [1111, [IV], and [V], one specific example preferably used in the present invention is:
This is described on pages 65 to 74 of Japanese Patent Application No. 61405272. Next, the compound represented by the following - Clothing cost [■a] is preferably used in the present invention. General formula [%? a] -i formula [VIal, 2 represents a phosphorus atom or a nitrogen atom, R, , 11,, R, and R1 each represent a substituted or unsubstituted alkyl group, aryl group, or aralkyl group, provided that R ,, R2, I' (and at least one of R4 is an aryl group or aralkyl group having an electron-withdrawing substituent. X- represents an acid anion. General formula [■a ] Among the compounds represented by formula LVIb, 2 is phosphorus represents an atom or a nitrogen atom, and R,', R,', R,' and R1' each represent i!
! substituted or non-directly negative alkyl group having 1 to 6 carbon atoms, phenyl group, tolyl group, xylyl group, biphenyl group,
naphthyl group, anthryl group, or -(C11)d() (d:1-6
). Here, the substituents include -CI+, -011, -CN
, -802, a halogen atom, a carbonyl group, a carboxyl group, a sulfonyl group, a quaternary amino group, etc., and the number of IfA groups is 1 to 2. However, R,', R,', R
2' and 1 (at least one of 4' is an aryl group having an electron-withdrawing substituent such as a cyano group, a halogen atom, a carbonyl group, a carboxyl group, a sulfonyl group, a quaternary amino group) Or it is an aralkyl group.
・X- is an acid anion, e.g. 0r-CI-, I-, C10
,-. The old ko does not represent -. The compound represented by -maximum [■al or [■b] above can be synthesized by the method described in US Pat. No. 3,951,661. Among the compounds represented by Ichiganshiki [■al, LVI bJ, specific examples preferably used in the present invention include
It is described on pages 78 to 82 of the specification of No. 205272. There are also various nitrone compounds that can be used as antifoggants or stabilizers. For example, Journal of the Chemical Society (Journal or Ll+e C1+emi
eal 5ociety) No. 1, pages 824-825 (
19:J8) The following Yokomichi formula t'/i described in
A nitrone compound represented by J or [■j or 21
- Inorganic acid salts or organic acid salts of nitrone compounds can be used, specifically, for example, chlorate salts of the above-mentioned nitrone compounds,
Mention may be made of bromates, perchlorates, hydrosulfides, acetates, and the like. Yokomichi style [■] Others, JP-A-60-122936, JP-A-60-117
The following compounds shown in No. 240 can be used. Furthermore, compounds represented by the maximum [D] below can also be used. One-component formula [8] In the formula, X represents a sulfur atom or =N-R, 4, R21
+R22+ R25+ R24 represents a hydrogen atom, each substituted or non-Zta alkyl group, aryl group, or heterocycle, provided that, if 1 (, 4 is a hydrogen atom, R2
1~IN2° represents something other than a hydrogen atom, and 116
．． and Lx, R22 and R23, and R23 and R24 may be bonded to each other to form a ring. -ffi formula Substituted branched alkyl groups (in-10vir group, isobutyl group, 2-ethylhexyl group, butyl group, etc.), substituted or unsubstituted cycloalkyl groups (cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), substituted or unsubstituted cycloalkyl groups (cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.) The substituted aryl group refers to a substituted or unsubstituted phenyl group, naphthyl group, etc., and the substituted or unsubstituted heterocyclic group refers to a substituted or unsubstituted 3-pyridyl group, 2-furyl group, 2-furyl group, etc. Represents a benzothiazolyl group, etc. Here, the substituents for I (z + , 1t22, R2) and R24 include a halogen atom, a nitro group, a cyan group, an alkoxy group, a carbamoyl group, a sulfamoyl group, a carboxy group, an alkoxycarbonyl group, a sulfo group, an amide group, Sulfonamide group, hydroxyl group, sulfonyl group, sulfinyl group, sulfenyl group, mercapto group,
Examples include an amino group, a ureido group, an aminocarbonyloxy group, an alkoxycarbonylamino group, an aryl group, and a heterocycle, and one or more of them may be present. Furthermore, L+ and R22, R22 and R22 and R2
4 may be bonded to each other to form, for example, a 50-ring or 6-ring hat ring. -a Among the compounds represented by the formula [B], specific examples preferably used in the present invention are those described on pages 88 to 91 of the specification of Japanese Patent Application No. 61-205272. The photographic emulsion used in the present invention is subjected to rapid development at high PL+ and high temperature 8! Kasa photo ii! In order to suppress the deterioration of the image quality of the J image and also improve the graininess, it is particularly preferable to contain a compound represented by the following -maximum [■]. As described in JP-A-58-158631, the amount added is preferably 0.001 to 20 g, preferably 0.01 to 1 mg, per 1 g of binder. - Maximum [■] In the above formula, ^' and C' each represent a group of nonmetallic atoms necessary to form a heterocycle with S and N, and X- ha anions (e.g. CI-, [lr- , CZO-, C11z
SOz-, etc.). To further explain the -a formula [■], ' and/or B' are a group of nonmetallic atoms necessary to form a heterocycle of the compound represented by -a [■], and n is a 2 Or not represent 3. ) is preferable. Among the compounds represented by the general formula [■], specific examples preferably used in the present invention are those described on page 131 of the specification of Japanese Patent Application No. 61-205272. Supports used in the light-sensitive material of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyester film, polyamide film, polypropylene film, polycarbonate, etc. Typical examples include polyethylene terephthalate, polystyrene film, etc., and polyethylene terephthalate colored blue to the same extent as in medical radiography is preferably used. Although any known method can be used for the development of the photosensitive material of the present invention, high-temperature, short-time processing using an automatic processor is suitable, and development for medical radiography is particularly suitable. A combination of hydronones and 3-pyrazolidones, or a combination of hydroquinones and aminephenols is preferably used as a developing agent in a developer for medical radiographic processing. Further, preferable developing conditions are 30 to 40°C for 10 to 40 seconds. As the fixing solution, an aqueous solution containing a thiosulfate and a water-soluble aluminum compound and having a pH of 3.5 to 5 is preferably used. Example 11 (1) Preparation of cardboard samples Seventeen paper samples of the following three types were produced. (a) 5 sheets of base paper with a thickness of O, 1 mm from the new valve
Combine the sheets and make 400g thick paper. This was added with 400 mg/m2i of common salt to form a cardboard sample of the present invention. (11> Under the paper-making conditions of (a), all 17 papers were made using waste paper recycling valves. (c) Under the paper-making conditions of (a), new pulp is used for the base paper in the front and back sand layers, and for the base paper in the inner sand layer] ■1 Raw pulp (130 g of 2N silver halide emulsion, 12.5H, l-phenyl-5-mercaptodetrazole 30B and 15 g of gelatin were added to Solution 11 at 40"C for 112 minutes. 1 ml containing 1 mol of ammoniacal silver nitrate was added in 1 min,
One minute after the addition, acetic acid was added to bring the pH to 6.0. Thereafter, an aqueous solution of 7I; lumalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to coagulate and precipitate the emulsion. Remove the supernatant! 140℃ hot water 21
After stirring for 10 minutes, an aqueous solution of magnesium oxide was added again to coagulate the emulsion, the supernatant was removed, and 300 seconds of a 5% gelatin solution was added, followed by stirring at 55° C. for 30 minutes to obtain an emulsion. This emulsion was a polydisperse emulsion with an average diameter of 0.30 μm. Next, this emulsion was added with ThioloQ per 11 moles of halogenated ff.
M storium 5mg, ammonium thiocyanate 20m
After adding 3 mg of gold chloride and aging at 60°C for 100 minutes, 4-hydroxy-6-methyl-1,3,3a,7
- Stabilized by adding 1.0 g of chitrazaindene. Furthermore, a sensitizing dye of general formula [1] in Table 1 and a comparative dye were added. (3) Preparation of coating sample A copolymer obtained by diluting a copolymer consisting of three monomers: 50 wL% glycidyl methacrylate, 1-+0 wt% methyl acrylate, and 40 wL% butyl methacrylate to a concentration of 10 wt%. Subtract aqueous dispersion 1
On one side of the polyethylene terephthalate base coated as pi, 400 g of gelatin, 1.2 g of polymethyl methacrylate, 〇g of dodecylbenzenesulfonate, 20 g of the following antihalation dye, and glyoxal were added. A backing layer solution consisting of gelatin, a matting agent, thorium dodecylbenzenesulfonate, and glyoxal (A!tt Jl solution) was coated together to prepare a backed support. The amount of gelatin applied to the backing layer and the protective layer is 2.5 g/m" and 2.0 g/m', respectively. [Antihalation dye 1] 1.0 g of a formalin condensate of phenol and trimena per 1 mole of the above silver halide. 9 g of 11-propane, 30 g of nitrophenyl triphenylphosphonium chloride, ammonium 1,3-dihydroxybenzene-4-sulfonate 18. Sodium 2-mercaptobenzimidazole-5-sulfonate 10111+, 2-
Mercaptobenzothiazole nc. II*Oc11ic11(011)C11.8(
1 g of CIliCOOII), 1 g of 1,1-dimethylol-1-bromo-1-nitromethane, etc. were added. Additionally, the following compound was added as a protective layer additive. That is, O3Na CwF+*-0(CIl□C11 20) l*CII per 1g of gelatin
gCII zOH 2ggCsF
,,s□,to
3aB Sodium Chloride
A matting agent 7+B consisting of 50 mg of polymethylmethacrylate-1 with an average particle size of 5 μm and 70 g of colloidal silica with an average particle size of 0.013 μm were added. Furthermore, 2 ml of hardening agent and formalin (35%),
1.51 glyoxal aqueous solution (40%) was added. (4) Sample evaluation method: Cut the obtained sample into 15 cm square pieces, tightly fit and sandwich them with 17 sheets of paper in the combination shown in Table 1, and form a test sheet unit. A storage test was carried out by putting the bag in a humidity-controlled bag with R1+ for 2 hours and sealing it in a light-shielding moisture-proof seal bag. Preservability test 1: Naturally left for 3 days 2: Naturally left for 6 months 3: Forced aging at 55°C for 3 days The trial clothes obtained in this way were cut to a 3.5cm stirrup width, and exposed to 820nm using a xenon flash light source. The wedge image was printed in 10-5 seconds through an interference filter. Furthermore, it was processed using an automatic original imager for X-ray manufactured by Konica Corporation (trade name: Konica X-ray automatic original imager X-500). The processing liquid is an X-ray automatic imager Kawahara imager liquid manufactured by Konica Corporation (
The image processing was carried out using a fixer (trade name: XD90) and a fixer (trade name: XF) at an original image solution temperature of 35°C. Fog and sensitivity were evaluated for each sample after the original image. still,
Regarding the sensitivity, the reciprocal of the exposure required to give a density of fog+1.0 is expressed as a relative value, with sample 1 being 100. Further, fog is shown as a value after subtracting the base density. Next, a sample (8 inches x 10 inches) that had been subjected to the same storage test as above was exposed to a semiconductor laser beam (820 nm).
), one pixel (1/9.1 millionth per 100 μI12
The entire surface is exposed so that the density after the original image is 0.7 by adjusting the light amount in seconds, and the automatic original image il for Konica Corporation's X-ray! (
The product was processed using a Konica X-Ray automatic original machine (trade name: X~500). The processing liquid is an X-ray automatic original imager (Kawahara image) manufactured by Konica Corporation.
(Product name: New XD-90> and fixer (Product name: N
ew XF) 71? The test was carried out at an original CLI temperature of 35°C. After the original image, each sample was visually judged for density unevenness and graininess. ■, Good, 2. Graininess is a little bad, but there is no problem in practical use, 3
1. There is a problem with poor graininess; 4. Very poor graininess 5. Very uneven and poor graininess. Comparative dye-1 Comparative color A-2 Table 1 shows that the samples of the present invention exhibit very little fogging and sensitivity loss due to natural standing or forced deterioration, and there is no deterioration in graininess. [Example 2] Example N in place of sensitizing dye 7 in No. 1 of Example 1
o, 1.2. :1,4,5,6,31,32,33,3
Samples similar to those in Example 1 were prepared using sensitizing dyes No. 4, 35, and 36. Thereafter, the same treatment as in Example 1 was performed, and the results were the same. Patent applicant Konica Corporation,. iI enter

Claims (1)

[Claims] A unit comprising a silver halide photographic light-sensitive material sheet sandwiched between cardboard made from a new pulp,
A silver halide photographic light-sensitive material sheet unit, characterized in that at least one silver halide emulsion layer in the silver halide photographic light-sensitive material sheet contains a compound represented by the following general formula [I]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ Represents a group of nonmetallic atoms necessary to form an oxazole nucleus. Z_2 represents a 5- or 6-membered carbon atom ring. R_1 and R_2 represent a saturated or unsaturated aliphatic group. A is a ▲ mathematical formula, chemical formula , tables, etc. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. represents an alkyl group, allyl group, or alkoxycarbonyl group which may have represents 1).)