JPH01200248A - Packaging unit for silver halide photographic sensitive material for laser light source - Google Patents

Abstract

PURPOSE:To enable packaging which is not deteriorated with age by sandwiching a photosensitive material contg. specific compds. with thick paper made from prescribed raw materials for paper making. CONSTITUTION:The package which obviates fogging and sensitivity degrading upon lapse of time and prevents degradation of a granular characteristic to an unequal density state is obtd. when the silver halide photographic sensitive material contg. >=1 kinds of the compds. expressed by general formula I is sandwiched and packed by the thick paper formed from the raw materials of novel pulp for paper making with casein, starch or polyvinyl alcohol as an adhesive agent. In formula I, Z1, Z2: an atom group for forming 5-, 6-mem bered nitrogen-contained heterocycles, R1, R2: an aliphat. group, Q1, Q2: an atom group for forming rings of 4-, 5-thiazolidinone, etc., L3, L2: a methine group, the substd. methine group expressed by formula II, X: a mineral acid or org. acid anion, (m), (n): 0-3 integer on the range of, In formula II, R3: a methyl group, ethyl group, ethoxy group or aryl group.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material for a laser light source, and particularly targets a spectrally sensitized silver halide photographic light-sensitive material (sheet) for a red-emitting laser. packaging unit.

More specifically, the present invention relates to a packaging unit that does not cause oral fogging or decrease in sensitivity due to contact between the photosensitive material and the packaging material, and has very little deterioration of graininess such as density unevenness in intermediate density areas.

[Background of the Invention] Silver halide photographic materials (hereinafter referred to as photographic films or photosensitive materials for negatives and positives) have been developed in accordance with user requirements in terms of sensitivity, fog, sharpness, graininess, etc. The level of performance has been raised by harmonizing mutually contradictory characteristics, but the technology as a whole is based on gold sensitization of photographic emulsions and thinning of the constituent layers of photographic films.

In addition, reducing manufacturing costs is an important industrial issue, and it may be possible to amortize the soaring cost due to improved performance of photographic film by reducing the cost of packaging for photographic film, which is not directly targeted for the purpose of use. , 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 held by an interleaf made of folded thin paper, and a predetermined number of the held sheets are further sandwiched between U-shaped cardboard sheets. The above-mentioned folded interleaf is used as a packaging unit, and is designed to protect from external impacts and to prevent scratches, frictional electrification, sticking, and fogging caused by mutual scratches or between sheets and packaging materials. Except for this, a non-interleaf packaging form was adopted in which a monolayer interleaf was applied one sheet at a time only to the surface of the packaging unit that contacted the cardboard.

However, the sensitivity of photographic film has increased from the level at which it can be protected by non-interleaving, and the sensitivity has increased even further, and thinned photographic films that have been made highly sensitive with chemical sensitization, especially chemical sensitization including gold sensitization, are required to meet the external conditions. According to research conducted by the present inventors, it has been found that properties have even deteriorated due to the cardboard material used in the packaging unit.

On the other hand, attempts have been made to capture radiation images for medical diagnosis as digital values, perform image processing using a computer to make them more suitable for diagnosis, and then expose the image to a laser beam to reproduce the image.

In particular, argon, helium-neon, helium-cadmium, and the like are in practical use as lasers for these scanning exposure devices.

In particular, for photographic materials for helium-neon laser light sources, those optically sensitized in the red region around 632.8 nm are preferred. Further, it is preferable that the photosensitive material can be handled under a safelight as bright as possible.

For safelight, a yellow-green-blue safelight filter that transmits light in the wavelength range of about 450 to 560 nm can be used, but as a photosensitive material, a sensitizing dye with low sensitivity in the 460 to 560 nm region, so-called green-deficiency dye, is used. A dye with excellent properties is desired. Does the sensitizing dye represented by the general formula [I] satisfy these conditions? The photosensitive material containing this dye is not suitable for the material of the cardboard used in the packaging unit, especially waste paper as the raw material for making the cardboard. The research conducted by the present inventors has revealed that contact with recycled cardboard can cause dullness or desensitization after storage.

Furthermore, it was found that when exposed to helium-neon laser, deterioration of graininess due to density unevenness due to the material of the cardboard was observed in intermediate density areas.

[Object of the Invention] Therefore, the object of the present invention is to prevent the occurrence of fogging and deterioration of sensitivity over time due to contact between the photosensitive material and the packaging material, and to prevent
It is an object of the present invention to provide a packaging unit in which deterioration of graininess such as density unevenness in Jie parts is extremely small.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a packaging unit in which a gold-sensitized silver halide photographic material (sheet) is sandwiched between cardboard sheets, in which the silver halide photographic material has the following general formula [I
This is achieved by a silver halide photographic light-sensitive material packaging unit for a laser light source, which contains at least one of the compounds represented by the following formula and is characterized in that it is a raw material for making cardboard or a new pulp.

General Formula [I] In the formula, zl and z2 each represent an atomic group necessary to form a 5-membered ring and/or a 6-membered nitrogen-containing heterocycle.

n and R2 each represent a hydration or an unsaturated aliphatic group.

Q and Q2 are 4-thiazolidinone, 4-oxanelidinone, 4-imidazolidinone, 5-thiazolidinone, 5-
Oxacylidinone or 5-imidazolidinone ring where R3 represents a methyl group, ethyl group, ethoxy group or aryl group. ) represents.

X represents a cupric acid or an organic acid anion.

+11. n represents an integer of 0 to 3.

The present invention will be explained in detail below.

The packaging unit of the present invention is capable of holding 10 to 100 sheets of photographic film depending on the type and size of the photographic film, and these packaging units are further placed in light-shielding and moisture-proof sealed bags for a predetermined number of sheets. , remove excess air and seal.

The thickness of the cardboard used in the packaging unit of the present invention is optimally selected according to the number and size of the photographic film sheets to be held.

That is, in a dry state (for example, 2 fl "C155'A111
Thickness 0.05-0. ]m
The paper is made by combining 1 to 8 sheets of base paper with a basis weight of about 50 g/rn', preferably using casein, V powder, or PVA (polyvinyl alcohol) as an adhesive.

In the present invention, new pulp is used as the raw material for making the cardboard used in the packaging unit, and new pulp is also used for the combined base paper that becomes the internal sand layer during the combining.

Preferably, it is white with a low lignin content.

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 determined by the method specified in JIS-P8119. An upper limit of 40 seconds is sufficient.

As a means to increase the smoothness of the surface, calendering alone may be used, or 0.5 to 10. Add 0g, and/
Or apply casein, V powder, PVA, halafin at 0.5 to 10.0g/rn'l on the surface of cardboard, and
A predetermined level of smoothness can be achieved by calendering at a nip pressure of 200 kg/c+a.

Furthermore, the surface of the cardboard is coated with synthetic resin (e.g. benzoguanamine,
It is also possible to apply fine beads of resin such as melamine, polyester, or polyfluoroethylene to create a uniformly dense miliary grain surface.

In addition, in the present invention, for the purpose of suppressing fogging and preventing static electricity, the water content of the cardboard is preferably 25 to 10 g/rrf based on a tsubo 1 of 40 Dg/rd, and more preferably 23
It is preferable that the moisture content (wt
%) is 7 to 3 wt%.

The moisture content is adjusted by once drying the cardboard and then allowing it to reach equilibrium by selecting a humidity of 20 to 70% RH at room temperature.

Furthermore, as an antistatic treatment, water-soluble inorganic salts (
For example, it is preferable to contain 50 to 11,000 a1/rn' of salt.

In addition, sizing agents are added to pulp liquid to improve paper quality.
This does not exclude the addition of size fixing agents, water resistance improvers, inorganic additives, wet strength improvers, preservatives, antifoaming agents, etc. necessary for the papermaking process, but it does not exclude the addition of water-soluble, vaporizable, etc. ,
For substances with permeability, it is necessary to check the influence. However, on the contrary, papermaking additives that contribute to preserving the properties of photographic films can be utilized in a very extreme manner.

The temperature and humidity for packaging and enclosing cardboard together with photographic film sheets is generally in the range of 208C to 30'C and 4o%RH to 60%RH.
%RH.

Next, general formula [I] will be explained.

In the formula, L and Z2 represent atomic groups necessary to form a 5-membered ring and a 6-membered nitrogen-containing heterocycle, respectively, and examples of the heterocycle include a thiazole ring, a benzothiazole ring, a naphthothiazole ring, and a selenazole ring. , represents a group of nonmetallic atoms necessary to form a benzoselenazole ring, a naphthoselenazole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, an imidazole ring, a benzimidazole ring, or a nitrogen-containing heterocycle of quinoline, and a substituent Examples include halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-
propyl group, n-butyl group, t-butyl group, etc.), alkoxy groups having 1 to 4 carbon atoms (for example, methoxyl group, hexyl group, n-propyloxy group, etc.).

R1 and R2 each represent 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-carboxypropyl group, 4-carboxymethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfomethyl group, 4
-sulfomethyl group, vinylmethyl group, pencil group, phenethyl group, p-sulfophenethyl group, n-propyl group,
Isopropyl group, n-methyl group, phenylethyl group, p
-sulfophenylethyl group, etc.).

Q, and Q, (combination) are 4-thiazolidinone rings, 5
-thiazolidinone ring, 4-imitazolidinone ring, 5-imitazolidinone ring or 4-oxazolidinone ring, 5-
Represents the atomic group necessary to form an oxazolidinone ring.

The substituent of the thiazolidinone ring, imidazolidinone ring or oxazolidinone ring includes an alkyl group having 4 to 4 carbon atoms (for example, a methyl group, an ethyl group, a 2-hydroxyethyl group, a (,2-methoxyethyl group, a 2- Acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, (propyl group, isopropyl group, pencil group, phenylethyl group, p-sulfophenyl group, etc.), aryl group (e.g. phenyl group, 2-carboxyethyl group, 2-carboxyethyl group, etc.) "°) 5 groups, etc.) 7゛A6・□3L, L2, L3 represent a methine group or substituted methine!ti (=C-). R3 is a methyl group, ethyl group, ethoxy group, aryl group (e.g. phenyl group, p-chlorophenyl group, p-methylphenyl group), and may be substituted.

X represents a mineral acid or an organic acid anion (eg, chloride ion, bromide ion, iodine ion, perchloric acid, benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, etc.).

Specifically, the following dyes may be mentioned.

cao, 9 (+ -1O) (1-u) (+-12) (l-13) (+-13) (+-16) l 1 eCalls
Cals Br I-5, I in the above specific examples
-6, I-7, I-8 and I-9 are particularly preferred dyes.

The amount of these dyes used is 990.0 mol of silver halide.
03g to 0.5g is preferable, especially 0.01g to 0.01g.
A range of 3g is preferred.

In the present invention, an aldehyde condensate of phenols (novolak resin) can also be added together with the sensitizing dye.

Examples of phenolic compounds include phenol, cresol, isopropylphenol, t-methylphenol, aminophenol, hexylphenol, t-octylphenol, cyclohexylphenol, 3-methyl-4-chloro-rotarjarifthylphenol,
Examples include isopropyl cresol, among which phenol, cresol, and t-methylphenol 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, acetaldehyde 1-.

The amount of this condensate used is 0.01 per mole of silver halide.
g to 2 g is preferred, and 4v is preferably 0.03 g to 1.3 g.

The composition of the photosensitive silver halide emulsion used in the present invention is preferably AgBr+ containing 0.5 mol% or more of Agl, more preferably AgBr1 containing 0.5 mol% or more and 10 mol% or less of Agl. .

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-sided mixing method, simultaneous mixing method, or a combination thereof. A so-called back mixing method may also be used.

In addition, surface latent image type silver halide emulsions may be prepared by the so-called controlled double-chet method, in which the pH and EAg in the reaction vessel are controlled by gradually increasing the amount of silver ion solution or halide solution added. I'll come.

At the stage of silver halide I'L formation or physical ripening, cadmium, palladium salts, zinc, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or their 261, etc. are allowed to coexist. You can.

Furthermore, the one-surface latent image type silver halide emulsion may be a monodisperse emulsion. Here, the term "monodisperse emulsion" refers to an emulsion in which the following formula is satisfied: =≦0.20, where r is the average grain size of silver halide grains and σ is its standard deviation.

In the present specification, the average grain size refers to the diameter in the case of spherical silver halide, and in the case of grains having a shape other than spherical, it is the average based on the diameter when the projected image is converted to a circular image of the same area. .

The surface latent image type silver halide emulsion can be chemically sensitized by a known method. The chemical sensitization of the present invention is gold sensitization, but sulfur sensitization may also be used in combination.

The amount of gold sensitizer added varies over a considerable range depending on various conditions, and is usually between lX10-9 and lx per mole of silver.
It is about 10-2 mol.

Also, for gold/sulfur sensitization, the blending ratio of both is 7! ! The amount of sulfur sensitizer is usually about 1 to 1000 mol per 1 mol of gold sensitizer, although it varies depending on the formation conditions. Further, the gold sensitizer may be added in the same manner as the sulfur sensitizer, during the sulfur sensitization, or after the sulfur sensitization is completed.

These chemical sensitizers are water-soluble compounds in the form of an aqueous solution;
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.

There are no particular restrictions on the conditions such as pH, pAg, temperature, etc. during chemical sensitization, but the pH value is preferably 4 to 9, especially 5 to 8, and the p to g value is preferably 5 to 8, especially 8 to 10. It is preferable to keep it. Also, the temperature is ζ, 40 to 90°C1
In particular, 45 to 75°C is preferred.

In addition to gold sensitization and gold/sulfur sensitization described above, the photographic emulsion used in the present invention may also be subjected to reduction sensitization using reducing substances, noble metal sensitization using precious metal compounds, etc. I'll come.

As the photosensitive emulsion, the above emulsion may be used in China, Germany,
Two or more types of emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers may also be used, including 3a,7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

The structure of the light-sensitive material of the present invention can take various forms; for example, silver halide emulsion layers can be formed on both sides of the support, or only on one side. moreover,
Auxiliary layers such as protective layers and antihalation layers may be provided at appropriate locations. Further, when an emulsion layer is formed on only one side, a layer made of a wood-philic colloid such as gelatin can be formed as a halakink layer on the opposite side. In addition, various dyes may be contained in the para-kink layer for reasons such as making it easier to distinguish between the front and back sides.

A preferable layer structure of the light-sensitive material of the present invention is one in which a silver halide emulsion layer is formed on only one side of the support, and a halakink layer containing a suitable dye is formed on the back 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 can be used as binders.
Typically, gelatin is preferably used. Further, in order to improve the physical properties of the coating 11λ using the wood-philic colloid as a binder, it is preferable to use various film property improvers, such as hardeners, as necessary.

Coating compositions containing hydrophilic colloid as a binder include:
If necessary, photographic additives other than the hardening agent may be used, such as gelatin plasticizers, surfactants, ultraviolet absorbers, antistain agents, p11 regulators, antioxidants, antistatic agents,
Thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, silver halide developers, etc. may be used within the range that does not impair the effects of the present invention.

Note that the matting agent may be polybranched or monodisperse.

The following various compounds may 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.

That is, azoles, nitroindazoles, triazoles, benzotriazoles, benzimidazoles:
Mercapto compounds (e.g. heterocyclic mercapto compounds, mercaptothiazoles, mercaptohelizothiazoles, mercaptobenzimidazoles, mercaptopyridines): thioketo compounds niazaindenes: mercaptoazaindenes: benzenethiosulfonic acids: benzenesulfinic acid di Various compounds known in the art as stabilizers can be added, such as.

An example of a compound that can be used is "The Theory Off the Photographic Process J" by K. Mies.
K, Mces, The Theory of the1
'photographic Process'') 3rd edition,
It was written in 1965, citing the original documents.

For more detailed examples of these and how to use them, see, for example, U.S. Pat.
82, No. 947, and No. 1,021,248.

The antifoggants or stabilizers particularly preferably used in the present invention include the following general formulas [II], [■, [T]
There are compounds represented by [V], [V], and nitrone compounds.

[Yuko [Eng.] R (OH)R4(011)R3 In the formula, +RI+ is a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent The group is an alkoxy group which may have a substituent, an acyl group which may have a substituent, a carboxymethyl group which may have a substituent, -(:00M group or -3
03M group (M represents a hydrogen atom, an alkali metal atom or an ammonium group), R1□+ R13+ R
l4 represents -COOM group or -3O,M group, nl
+n2 represents an integer from 1 to 3, R3 represents 1 or 2,
n4+n5 represents 0 or 1, provided that n:l and n are never both 0. When nl+12 is 2 or 3, RIl+RI3 may be the same or different.

[V] In the formula Machi-1111, 2 represents, together with C=N, an atomic group necessary to form a 5- or 6-membered heterocycle consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. .

Moreover, this heterocycle may be bonded. Examples of these include, for example, a tetrazole ring, a trianol ring, an imidazole ring, a thiadiazole ring, an oxadiazole ring,
These include an oxazole ring, a benzthiazole ring, a benzimidazole ring, a benzoxazole ring, a purine ring, an azaindene ring, a tri-teru-pentapyridine ring, and a pyridine ring.

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 that form a tetrazole ring, triazole ring, thiadiazole ring, benzimidazole ring, or benzthiazole ring with Z or C=N, and most preferred are compounds that form a thiadiazole ring with Z or C=N. It is a compound that Also, the middle of the formula is a hydrogen atom, −
Nl+ represents a group or an alkali metal atom.

- Formation Among the compounds represented by [11], [I11], [17], and [V], specific examples preferably used in the present invention are:
It is described on pages 65 to 74 of Tokushō No. 61-205272.

Next, the compound represented by the following formula [VIa] can be preferably used in the present invention.

-Formation [VIa] In the general formula [VIa], 2 represents a phosphorus atom or a nitrogen atom, and R1, R2, R3 and R4 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group. However, at least one of R11R2, R3 and R4
One is an aryl group or an aralkyl group having an electron-withdrawing substituent. X- represents an acid anion.

Among the compounds represented by the general formula [VIa] used in the present invention, compounds particularly advantageously used in the present invention are preferably those represented by the following formula [VIb].

General formula [VTb] In the general formula [VTb], 2 represents a phosphorus atom or a nitrogen atom, and R,', R2'', R,' and R4' are each substituted or unsubstituted carbon atoms having 1 to 6 carbon atoms. alkyl group,
It is a phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthryl group, or -(CH□)d-() (d: an integer of 1 to 6).

Here, the substituents include -Cll:+, -0ff,
Examples include -CN, -No□, a halogen atom, a carbonyl group, a carboxyl group, a sulfonyl group, a quaternary amino group, and the number of substituents is 1 to 2. However, R,”, R2
', L= and R4', at least one of which is an electron-withdrawing substituent such as a nitro group, a cyano group, a halogen atom,
A carbonyl group, a carboxyl group, a sulfonyl group, a quaternary amino group or an aralkyl group. X- is an acid anion such as Br-, C1-.

1-, C or 04-, BF, -.

The compound represented by the above general formula [VIa] or [VIb] can be synthesized by the method described in US Pat. No. 1,951,661.

Among the compounds represented by the general formulas [VTa] and [VIb], specific examples preferably used in the present invention are
It is described on pages 78 to 82 of the specification of No. 205272.

There are also a variety of nitrone compounds that can be used as anti-fog agents or stabilizers.

For example, Journal of Chemical Society (
Journal of the Chemical 5
ociety) No. 1, pages 824-825 (1938)
The following structural formula [VI] or [■] described in
A nitrone compound or an inorganic acid salt or an organic acid salt of a nitrone compound can be used. Specifically, for example, a chlorate, bromate, perchlorate, or hydrosulfide of the above-mentioned nitrone compound can be used. Alternatively, acetate and the like can be mentioned.

Structural formula [■ Structural formula [■] Others: JP-A-60-122936, JP-A No. 60-117
The following compounds shown in No. 240 can also be used.

Furthermore, compounds shown in the following formula [B] can also be used.

General formula [B] In the formula, X represents a sulfur atom or "N-R24, and R2
+ + R22+ R2:l+ R24 represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocycle. However, in the case of R24 or a hydrogen atom,
R21 to R2z represent something other than a hydrogen atom. Also,
R2□ and R22+ R2□ and R23 and R2:l and R
24 may be bonded to each other to form a ring.

In the general formula [B], a substituted or unsubstituted alkyl group refers to a substituted or unsubstituted linear alkyl group (methyl group, ethyl group, n-octyl group, etc.), a substituted or unsubstituted branched alkyl group (isopropyl group, isophthyl group,
(2-ethylhexyl group, t-butyl group, etc.), substituted or unsubstituted cycloalkyl group (cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), substituted or
The 111ζ-substituted aryl group represents a substituted or unsubstituted phenyl group, naphthyl group, or the like. Substituted or unsubstituted heterocycle refers to substituted or unsubstituted 3-pyridyl group, 2-
Represents a furyl group, a 2-benzothiazolyl group, etc.

Here, the substituents in R2□, R22, R2:l and R24 include a halogen atom, a nitro group, a cyano group,
Alkoxy group, carbamoyl group, sulfamoyl group, carboxy group, alkoxycarbonyl group, sulfo group, amide group, sulfonamido group, hydroxy group, sulfonyl group, sulfinyl group, sulfenyl group, mercapto group, amino group, ureido group, aminocarbonyl Examples include an oxy group, an alkoxycarbonylamino group, an aryl group, and a heterocycle, and one or more of them may be present.

R2+ and R22+, R22 and R23, and R23 and R24 may be bonded to each other to form a ring, for example, a 5-membered ring or a 6-membered ring.

Among the compounds represented by the general 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 has a high pl! , suppresses deterioration of image quality of photographic images such as rapid processing at high temperatures,
In addition, in order to improve the graininess, it is particularly preferable to contain a compound represented by the following formula [■].

The amount added is 0.001 to 2 mg per 1 g of binder, as described in JP-A-58-158631.
Preferably 0. O1 to 1 mg is desirable.

-Formation [■] N [In the above general formula, A' and B' each represent a group of nonmetallic atoms necessary to form a heterocycle with S and N, and Br-.

CH:1SO3-, etc.). ] General format ■] is further explained. -Formation [■ Non-metallic atomic group 8' and/or B' or -H:1I) n[ However, R5□ represents a hydrogen atom or a lower alkyl group, and n represents 2 or 3. ] is preferred.

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.

Examples of the support used in the photosensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, polyester film such as polyethylene terephthalate, polyamide film, polypropylene film, and polycarbonate. Films, polystyrene films, etc. are typically included, and polyethylene terephthalate colored to the same extent as in medical radiography is preferably used.

For development of the uninvented light-sensitive material, any known method may be used, or high-temperature, short-time processing using an automatic processor is suitable, and development processing for medical radiography is particularly suitable. In the developing solution for medical radiographic processing, a combination of hydroquinones and 3=pyrazolidones, or a combination of hydroquinones and aminophenols is preferably used as a developing agent. Further, preferable treatment conditions are 30 to 40°C and 10 to 40 seconds.

As the fixing solution, an aqueous solution of p114 to 5 containing a thiosulfate and a water-soluble aluminum compound is preferably used.

In the present invention, it is preferable to use an organic gelatin flocculant as the flocculant used for desalting and washing with water by a coagulation sedimentation method of the silver halide emulsion. As an organic gelatin flocculant,
It is a water-soluble polymer compound having a sulfonic acid group or a carboxylic acid group, or a surfactant with a relatively large molecular weight, and is widely described in JP-A-58-140322. Particularly representative examples include the following polymers.

No, I N
o, 2NO,3 c: d = 1:1 (molar ratio) NO64 NO,6 n = 2~b In is the degree of polymerization, and a~d are the composition ratios, and these organic gelatin flocculants have a molecular weight of 1,000~ 100,000 range.

It is also available as a commercial product, such as Versa
TL (manufactured by Kanebo NNC), 5cripl
There are commercially available products such as (manufactured by Monsando, USA) and HMA (manufactured by Monsando, USA).

The organic gelatin flocculant preferably used in the present invention may be used in combination with other flocculants such as sulfates (magnesium sulfate, sodium sulfate, etc.).

If the amount of the organic gelatin flocculant preferably 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. Further, if the amount is too small, clumps will not occur, so it is preferable to use 3 to 15 g, particularly preferably 5 to 10 g, per mole of silver halide.

In addition, the pl+ to be coagulated is 7 or less, preferably 3 to 6.5.
Good.

The gelatin used in the present invention may be any gelatin normally used in silver halide emulsions (for example, alkaline method gelatin, acid method gelatin, desalted gelatin, low calcium gelatin, etc.), and in short, gelatin coagulated with an organoceratin flocculant. There is no particular limitation if there is.

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 keep it as small as possible.

The remaining amount can be measured by a conventional analytical method. For example, a small amount of emulsion is dispersed in water and left overnight to extract the organic gelatin flocculant. This may be centrifuged and the organic gelatin flocculant in the supernatant liquid may be quantitatively analyzed using liquid chromatography or the like.

The amount of organic gelatin flocculant remaining in gelatin is preferably 4.5 g or less per mole of silver halide, particularly 1.5 g to 3 g.
．． As long as it's within the 5g range.

A matting agent may be used in the present invention, and the matting agent may be a polymeric matting agent or an inorganic matting agent. Further, the shape of the matting agent may be arbitrary, but when it has an emulsion layer on only one side, it is preferable that the matting agents 1 to 1 on the emulsion layer side have a flat plate shape. The average grain size of the matting agent on the emulsion layer side is preferably 1.5 times or less the thickness of the emulsion layer plus the protective film layer.

[Effects of the Invention] According to the present invention, there is provided a packaging unit that does not cause oral fogging or decrease in sensitivity due to contact between the photosensitive material and the packaging material, and has very little deterioration of graininess due to density unevenness in the intermediate density area. can be provided.

The photosensitive material of the present invention is exposed to a laser beam, and a 1ie-Ne laser is particularly preferred in terms of performance stability and durability.

[Example] Hereinafter, the present invention will be further explained by examples, and the present invention is not limited by the examples.

Example 1 (1) Preparation of cardboard sample The following three types of cardboard samples were created.

(a) 5 sheets of base paper with a thickness of 0.1 mm made from a new pulp raw material
The sheets are made of thick paper with a thickness of 400 g/m'. This was made to contain 400 mg/m' of common salt to form a cardboard sample of the present invention.

(b) Cardboard made entirely from recycled waste paper pulp under the papermaking conditions of (a).

(C) Cardboard using new pulp for the base paper of the front and back sand layers and recycled pulp for the base paper of the internal sand layer under the papermaking conditions of (a).

(2) Preparation of silver halide emulsion KBr 130g, NiI 2.5g, 1-phenyl-5
- 30 mg of mercaptotetrazole and 15 g of gelatin
A solution containing 0.5 mol of ammoniacal silver nitrate, SOOmU, was added over 1 minute to a solution containing 1 volume of ammonia at 40°C while stirring, and 2 minutes after the addition, acetic acid was added to bring the pl+ to 6.0. did. After another minute, 500a of solution containing 0.5 mol of silver nitrate
After stirring for 15 minutes, an aqueous solution of formalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to coagulate the emulsion. After removing the supernatant,
Add warm water 21 at 40°C and stir for 10 minutes, then add an aqueous solution of magnesium sulfate again to coagulate the emulsion.After removing the supernatant, add 300ml of 5% gelatin solution and stir at 55°C for 30 minutes to form an emulsion. Had made. This emulsion has an average grain size of 0
．． It was 40p.m.

A small amount of this emulsion was dispersed in water, left overnight, and the supernatant liquid was collected using a centrifuge. When sodium naphthalene sulfonate remaining in the emulsion was analyzed, it was found that the amount was 3.0 g per mole of silver halide. Wata.

Next, 5 mg of sodium thiosulfate, 20B of ammonium thiocyanate, and 3 mg of chloroauric acid were added to this emulsion, and 1.0 g of a formalin condensate of phenol was added to obtain the general formula [I
] or the following ratio 1 sensitizing dye was added as shown in Table 1, and the mixture was chemically aged for 100 minutes at [lO"C. Thereafter, 4-hydroxy-6-methyl-1,:I
, 3a,7-chitrazaindene (1.0 g) was added for stabilization.

Comparative Sensitizing Dye (3) Preparation of Coated Sample A backing layer solution consisting of 400 g of gelatin, 2 g of polymethyl methacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following antihalation dye, and glyoxal was prepared, and glycidyl methacrylate) 50wt%, methyl acrylate 10wt%
A polyethylene terephthalate-based product coated with an aqueous copolymer dispersion obtained by diluting a copolymer consisting of three types of polymers containing 40 wt% of butyl methacrylate to a concentration of 10 wt% as a subbing liquid. A backing support prepared by coating gelatin, a matting agent, glyoxal, and sodium tesilhensensulfone on one side with a layer solution was used. Paint &
The amount of +i is 2.5 g/m' and 2.0 g/rn' in terms of the amount of gelatin applied to the X-pulling layer and the protective layer, respectively.

[Antihalation dye] 5o-Ha 5OJa As an emulsion layer additive, 15% of 1,2.6-hexandriol as a polyhydric alcohol per mol of silver halide.
g, nitrophenyl-triphenylphosphonium chloride 50 mg, 1,3-dihydroxybenzene-4-sulfonate ammonium Ig, 2-mercaptobenzothiazole-5-sulfonate sodium 1
0mg, 2-mercaptobenzothiazole 10mg
, H 1,1-dimethylol-1-from-1-nitromethane OB, etc. were added.

In addition, as a protective layer additive, the following compound was added per gelatin Ig (:++2(:00((:+12)9C113G1G1
lC00(CH2)2CII(C)13)27SO,N
a C9F+9- o+cl12cl12o ) +oCI
12CIlzO! I 2mgC6FI? 503K
3 mg sodium chloride, 5 mg, 1 g of a matting agent 7Il made of polymethyl methacrylate with an average particle size of 5 pm, and 0 mg of colloidal silica cuff with an average particle size of 0.013 gm were added.

Furthermore, as a hardening agent, a 2% aqueous solution of 2,4-dichloro-6-hydroxyl(1.3.5-)-riazine sodium salt was added.
10+mQ, formalin (35%) 2m! 1.5 ral of L and glyoxal aqueous solution (40%) were added, respectively.

(4) Sample evaluation method The obtained sample was cut into 15 crn' pieces, combined as shown in Table 1, and tightly pressed and sandwiched with cardboard to form a desl-packaging unit.
The packaging unit was moistened with 238C 147% chlorine and placed in a light-shielding/moisture-proof seal bag, sealed, and subjected to an integrity test.

: Integrity test: 1. Leaving for 3 days (finish characteristics - standard characteristics) 2. Leaving for 1 month 3. Forced aging at 55°C for 3 days The sample thus obtained was cut into 3.5 cm width.
1 pixel (100I) using 1le-Ne laser beam
LII+2) The film was exposed to light while changing the amount of light at 9.1 millionth of a second, and processed using an X-ray automatic processor manufactured by Konica Corporation (trade name: Konica X-ray automatic processor KX-500).

The processing was carried out using a developer for an X-ray automatic processor (trade name: XD-90) and a fixer (trade name: XF) manufactured by Konica Corporation at a developer temperature of 35°C.

Fog and sensitivity of each sample after development were evaluated. Regarding the sensitivity, the exposure amount required to give a density of fog +1.0 is expressed as a relative value with sample 1 set as 100. For Kafuri, the base concentration was subtracted (+/i).

Next, the remaining sample piece was fully exposed to light using an l1c-Nc laser beam, adjusting the light intensity at 1/100,000th of a second per pixel (100μl112) so that the degree of e after development was 0.7. The film was processed using an X-ray automatic developing machine (trade name: Coconica X-ray automatic developing machine KX-500) manufactured by Coconica Co., Ltd. The processing liquid is manufactured by Konica Corporation and is a developer for X-ray automatic processing machines (product name:
XD-90) and fixing residue (trade name: xF) at a developer temperature of 35°C.

For each sample after development, the degree of deterioration in density unevenness and graininess was visually determined.

1 is not at all, 2 is a slight deterioration of graininess, 3 is a slight deterioration of graininess, 4 is poor graininess, and 5 is a poor evaluation of very unevenness.

From Table 1, it can be seen that in the present invention, the occurrence of fogging and the decrease in sensitivity are extremely small, and there is no deterioration in graininess even after being left alone for one month or due to forced deterioration.

In addition, the sensitizing dyes of sample No. 3 were used as I-8, I-9, l-
As a result of conducting a similar experiment by changing to No. 17, the effect of the present invention was obtained.

Example 2 The sample from Example 1 was processed using the developer and roller conveyance automatic developing machine used in Example 1 of Japanese Patent Application No. 62-54221.
As a result of automatic development processing at 5°C for 45 seconds, the effect of the present invention was obtained.

Patent applicant Nobuaki Sakaguchi, agent of Konica Co., Ltd., patent attorney

Claims (1)

[Scope of Claims] A packaging unit in which a gold-sensitized silver halide photographic light-sensitive material is sandwiched between cardboard, wherein the silver halide photographic light-sensitive material contains at least one compound represented by the following general formula [I]. 1. A packaging unit for a silver halide photographic material for a laser light source, characterized in that the raw material for making the cardboard is a new pulp. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_1 and Z_2 are 5-membered rings and/or 6-membered rings, respectively.
Represents a group of atoms necessary to form a membered nitrogen-containing heterocycle. R_1 and R_2 each represent a saturated or unsaturated aliphatic group. Q_1 and Q_2 are 4-thiazolidinone, 4-oxazolidinone, 4-imidazolidinone, 5-thiazolidinone,
Represents an atomic group necessary to form 5-oxazolidinone or 5-imidazolidinone ring R_3.
| L_1, L_2 and L_3 represent a methine group or a substituted methine group (=C-, where R_3 represents a methyl group, ethyl group, ethoxy group or aryl group). X represents a mineral acid or organic acid anion. m and n represent integers of 0 to 3.