JPH01266536A - Infra-red sensitive silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To easily make the position detection of a photographic sensitive material by incorporating at least one kind of specified compds. in a nonphotosensitive layer contd. in the photosensitive material. CONSTITUTION:At least one kind of the compds. shown by formula I or II is incorporated in the nonphotosensitive layer. In formula I, (n) is a positive integer of 1 or 2, R is alkyl or aryl group, R1 and R2 are each alkyl or aryl group, R3 and R4 are each hydrogen or halogen atom or alkyl or alkoxy group, X(-) is an anion, (m) is a positive integer of 1 or 2, Z is a nonmetal atomic group necessary for forming a 5 or 6 membered heterocyclic ring. In formula II, R' is alkyl group, R'' is hydrogen or halogen atom or alkyl or alkoxy group, X(-) is an anion. Thus, when the photosensitive material reaches to a prescribed position, the prescribed position of the material can be easily detected.

Description

[Detailed description of the invention] ■ Background of the invention Technical field The present invention relates to an infrared-sensitive silver halide photosensitive material.

Prior art and its problems One of the exposure methods for photographic light-sensitive materials is to scan an original image, and then expose the silver halide photographic light-sensitive material based on the image signal to create a negative or positive image corresponding to the image on the original image. An image forming method using a so-called scanner is known. There are various recording apparatuses that utilize image forming methods using one-scanner type, and a semiconductor laser is used as one of the recording light sources of these one-scanner type recording apparatuses.

Semiconductor lasers are small, inexpensive, easy to modulate, and have a long life. Furthermore, since it emits light in the infrared region, a bright safelight can be used, which has the advantage of improving handling efficiency.

The sensitive material used in this semiconductor laser is a photographic material that is spectrally sensitized in the infrared region, and it is made by adding a certain type of cyanine dye to a silver halide photographic emulsion.
It is obtained by spectral sensitization technology that extends the sensitive wavelength range to longer wavelengths. For spectral sensitization in the infrared region, a sensitizing dye that absorbs infrared light is used, and photographic materials are usually spectral sensitized to have maximum sensitivity in the wavelength range of 750 to 850 nm.

When actually forming an image using such a photographic material and a recording device as described above, it is necessary to detect when the photographic material is at a predetermined position. It is preferable to design it as follows. At this time, the detection light must be of a type that does not sensitize the above-mentioned photographic light-sensitive material, and it is usually necessary to use one with a wavelength longer than the above-mentioned infrared region.

Therefore, it would be advantageous if a photographic light-sensitive material could contain a dye that absorbs in the vicinity of the wavelength of such detection light to enable position detection and the like.

In addition, when such dyes are introduced into photographic materials,
Photographic properties, processing properties, coloring and deterioration of processing solutions, image quality, storage stability,
It must not have an adverse effect on physical properties (pressure sensitivity, capri, scratches), etc., and consideration must be given to such points.

II. OBJECTS OF THE INVENTION An object of the present invention is to easily detect the position of a photographic material in a recording device for forming an image;
The object of the present invention is to provide an infrared-sensitive silver halide photosensitive material that has excellent photographic properties and other properties and is also advantageous in terms of production.

111 Disclosure of the invention Such objects are achieved by the invention described below.

That is, the present invention is an infrared-sensitive silver halide photosensitive material characterized by containing at least one compound represented by the following general formula (1) or (n) in a non-photosensitive layer.

General formula (It) (In the above general formula (1), n represents a positive integer of 1 or 2, R represents an alkyl group or an aryl group. R1 and R2 each represent an alkyl group or an aryl group. R3 and R4 each represent a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group. xe represents an anion. m represents a positive integer of 1 or 2. 2 represents a 5- or 6-membered heterocycle. Represents a group of nonmetallic atoms necessary for formation.

In the above general formula (1), R' represents an alkyl group, and RII represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

x'e represents an anion. ) ■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The infrared-sensitive silver halide photosensitive material of the present invention contains at least 1 ff1 or more of the compound represented by the general formula (1) or (II) in the non-photosensitive layer.

In the general formula (I), n represents a positive integer of 1 or 2.

R represents an alkyl group or an aryl group, and these groups may have a substituent.

Specifically, preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, etc.; a hydroxyalkyl group, such as a β-hydroxyethyl group, a γ-hydroxy Propyl group, δ-hydroxybutyl group, etc.; Carboxyalkyl group, such as β-carboxyethyl group, γ-carboxypropyl group, etc.; Sulfoalkyl group, such as β-sulfoethyl group, γ-sulfopropyl group, γ-
Sulfobutyl group, δ-sulfobutyl group, etc.; Sulfatoalkyl group, such as β-sulfatoethyl group, γ-sulfatopropyl group, etc.; Acyloxyalkyl group, such as β-acetoxyethyl group, γ-acetoxypropyl group, γ- Propionyloxypropyl group, etc.; Aralkyl group, such as benzyl group, phenylethyl group, etc.; Aryl group (which may have a substituent), such as phenyl group, tolyl group, chlorophenyl group, sulfophenyl group, carboxy Phenyl group etc.: These are mentioned.

R1 and R2 are respectively. Alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl group, propyl group,
Isopropyl group, butyl group, hexyl group, octyl group,
Dodecyl group ring; alkoxycarbonyl alkyl group, such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, etc.; aryl group (which may have a substituent), such as phenyl group,
m-1p-tolyl group, m%P-alkoxyphenyl group (here, the alkoxy group includes those having 1 to 4 carbon atoms, specifically m-methoxyphenyl group, m-
Ethoxyphenyl group, m-propoxyphenyl group, m-
butoxyphenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-propoxyphenyl group, p-butoxyphenyl group, etc.);

R3 and R4 are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group,
Examples include isopropyl group, butyl group, etc.; halogen atoms, such as chlorine, bromine, etc.; alkoxy groups having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, etc.

xe is an anion, such as chloride ion, bromide ion, iodide ion, thiocyanate ion, sulfamate ion,
Examples include perchlorate ion, p-toluenesulfonate ion, methylsulfonate ion, ethylsulfonate ion, hexafluorophosphate ion, and the like.

m represents a positive integer of 1 or 2, and m is 1 when R represents a carboxyalkyl group or a sulfoalkyl group.

Z represents a nonmetallic atom group necessary to complete a 5- or 6-membered heterocycle, such as a thiazole ring (e.g., thiazole, 4-methyl-thiazole, 4-phenylthiazole, 4-diphenylthiazole, 4- (2-thienylthiazole, etc.), benzothiazole rings (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7
-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, 5-
Phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5.6-Simethoxybenzothiazole, 5
．． 6-thioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.), naphthothiazole rings (e.g., α-naphthothiazole,
β-naphthothiazole, 5-methoxy-β, β-naphthothiazole, 5-ethoxy-β-naphthothiazole, 3
-methoxy-α-naphthothiazole, 7-nodoxy-α
-naphthothiazole, etc.), thionaftino 7', 6', 4,5-thiazole ring (e.g. 4'-methoxythionaftino 7', 6')
, 4,5-thiazole, etc.), oxazole rings (e.g., 4-methyloxazole, 5-methyloxazole,
4-phenyloxazole, 4.5-diphenyloxazole, 4-ethyloxazole, 4.5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazole rings (e.g., benzoxazole,
5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5- ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole ring (e.g., α-naphthoxazole, β-naphthoxazole, etc.), selenazole ring (e.g., 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazole ring (e.g., benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrocarbon benzoselenazole, etc.), naphthoselenazole rings (e.g., α-naphthoselenazole, β-naphthoselenazole, etc.), thiazoline rings (e.g., thiazoline, 4-methylthiazoline, etc.), 2-pyridine rings (e.g., 2- Pyridine, 5-methyl-
2-pyridine, etc.), 4-pyridine ring (e.g., 4-pyridine, 3-methyl-
4-pyridine, etc.), 2-quinoline ring (e.g., 2-quinoline, 3-methyl-
2-quinoline, 5-ethyl-2-quinoline, 6-chloro-2-quinoline, 8-chloro-2-quinoline, 6-medoxy-2-quinoline, 8-ethoxy-2-quinoline, 8
-hydroxy-2-quinoline, etc.), 4-quinoline ring (e.g., 4-quinoline, 6-medoxy-2-quinoline, 8-ethoxy-2-quinoline, 8-hydroxy-2-quinoline, etc.), 1-isoquinoline ring ( For example, 1-isoquinoline, 3.
4-dihydro-1-isoquinoline, etc.), 3-isoquinoline ring (e.g., 3-isoquinoline, etc.), 3.3-dialkylindolenine ring (e.g., 3.3-
dimethylindolenine, 5- or 6-nitro-3,
3-dimethyl- or 5- or 6-diazo3.3
-dimethylindolenine, 3,3.5-trimethylindolenine, 3,3.7-trimethylindolenine, etc.),
Imidazole rings (e.g. imidazole, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkyl-4,5-dimethylimidazole, etc.), benzimidazole rings (e.g. benzimidazole, 1-alkylbenzimidazole, 1 -Aryl-
5,6-cyclopenzimidazole, etc.), naphthoimidazole rings (e.g., 1-alkyl-β-naphthoimidazole, 1-aryl-β-naphthoimidazole, 1-alkyl-5-methoxy-α-naphthoimidazole, etc.), etc.

The compound represented by the above general formula (I) includes a betaine structure and a quaternary salt.

In the above general formula (It), RJ represents an alkyl group (e.g., methyl group, ethyl group, etc.), and R'' represents a hydrogen atom (e.g., chlorine, bromine, etc.), an alkyl group (e.g., methyl group, ethyl group, etc.), or an alkoxy group. (For example, methoxy group, ethoxy group, etc.)

Xe is an anion, such as a halogen ion (chlorine ion, bromide ion, iodide ion, etc.), thiocyanate ion,
It represents sulfamate ion, perchlorate ion, p-toluenesulfonate ion, methylsulfonate ion, ethylsulfonate ion, hexafluorophosphate ion, etc.

Specific examples of the compounds represented by the above general formula (I) or (II) are listed below.

Q E ■
■ C.J.U.
= =0
Q Small engineering school Small engineering school O Nノ
w = 0 = medium = ○. Q:l:l,l ■ - ■ = The compound represented by the above general formula (1) or (II) is disclosed in U.S. Patent No. 3,671,648 or U.S. Pat.
It can be synthesized by the method described in No. 95,854.

The compound in the present invention has a maximum absorption wavelength near 950 nm and has little absorption in the visible region.

Such compounds may be used alone or in combination of two or more.

Such a compound is used by being contained in a non-photosensitive layer other than the emulsion layer in a light-sensitive material. In particular, it is preferable to include it in the back layer.

This is because when the above-mentioned compounds are contained in the emulsion layer, they have undesirable effects such as fogging of silver halide. Therefore, the layer containing the above compound is preferably a non-photosensitive layer that is not adjacent to the emulsion layer. It is most preferable to include the above-mentioned compound in the back layer since it will not have an adverse effect on the emulsion layer.

In addition, when it is contained in the back layer, unlike when it is contained in the non-photosensitive layer on the emulsion layer side, there is no restriction that it must be contained in a layer other than the emulsion layer or a layer adjacent to the emulsion layer, so a new layer may be provided. The thickness of the entire layer of the photosensitive material can be made thinner without the need. Therefore, rapid processing becomes possible.

Furthermore, when forming the back layer before forming the emulsion layer, it can be done in a bright place, which facilitates manufacturing.

The non-photosensitive layer containing such the above-mentioned compound is used by incorporating it into the hydrophilic colloid described below.

It is preferable that the above compound is adsorbed onto a non-photosensitive inorganic salt and contained in the non-photosensitive layer.

Stability is increased by adsorption to a non-photosensitive inorganic salt in this manner.

A non-photosensitive inorganic salt refers to an inorganic salt that dissolves into a processing solution during a development process (for example, a developing process, a fixing process), and specifically refers to a non-photosensitive inorganic salt such as a non-photosensitive silver halide (for example, silver chloride, silver chloride, etc.). silver bromide, silver iodide or mixed crystals thereof), zinc oxide, lead oxide, titanium oxide, copper oxide, tin oxide, cadmium oxide,
Examples include thallium halides (thallium chloride, thallium bromide, thallium iodide), cadmium sulfide, and CdSe.

Among these, non-sensitive silver halide is preferred.

The amount of these inorganic salts is from 0.1 mol to 107 mol, particularly from 10 mol to 105 mol, per mol of the compound according to the invention.

In order to adsorb the compound represented by general formula (I) or (II) to a non-photosensitive inorganic salt and introduce it into the non-photosensitive layer, the compound represented by general formula (1) or (II) must be The content in the layer is about 0.015 to 0.7 g/rn'', preferably about 0.03 to 0.2 g/rn''.

The reason for this content is that if it is less than 0.015 g/rn, the optical density will be too low and the transmission efficiency of the infrared light for detection will be high and it will become undetectable. This is because it remains in the coating film, resulting in residual color, and furthermore, the coloring cannot be kept up with the treatment liquid, resulting in severe discoloration and deterioration of the treatment liquid.

The thickness of the non-photosensitive layer containing the compound represented by general formula (I) or (■1) is 1 to 5-1 in the case of a back layer.
It is preferably about 2 to 4 tones, and in the case of layers on the emulsion layer side (for example, protective layers, etc.), it is 0.5 to 2-1, preferably 0.7 to 1.
．． It may be about 51iI11.

This thickness is required because if the back layer is less than 1 layer, it will be too thin compared to the emulsion layer side, making it impossible to maintain curl balance, and if it exceeds 5JjJI+, the drying process after processing will take a long time. This is because it becomes

Further, in the layer on the emulsion layer side, if the time is less than 0.5 .mu.s, the ability to prevent scratches will be reduced, and if it exceeds 2, the progress of development will be hindered.

As described above, by containing the compound represented by the general formula (1) or (11), the infrared-sensitive silver halide photosensitive material of the present invention is sensitive to detection light having a wavelength longer than the infrared region.

Therefore, it is possible to detect that the photosensitive material has come to a predetermined position in a recording device that forms an image without adversely affecting photographic properties or the like.

The silver halide photographic emulsion spectrally sensitized in the infrared region used in the present invention can be obtained by adding a sensitizing dye having absorption in the infrared region to silver halide grains.

First, a sensitizing dye that absorbs infrared light will be described.

These can be found, for example, in “The Theory” by Mees.
f thePhotographic Process
, 3rd edition'' (published by MacMillan in 1966)
p. 198-p. 201. In this case, it is desirable that the spectral sensitivity, that is, the sensitivity to light in the infrared region, be high, and that the change in sensitivity be small even during storage of the emulsion. For this purpose, many sensitizing dyes have been developed. These include, for example, U.S. Pat.
, 095,854, 2.095,856, 2,955,939, 3,482,978, 3.552.974, 3,573,921 ,
No. 3,582,344, e.g., U.S. Patent No. 2.87.
5,058 and 3,695°888, U.S. Pat. No. 3,457,0
78, thiourea compounds described in U.S. Pat. No. 3,458,318, pyrimidine derivatives described in U.S. Pat. No. 3,615,632, and U.S. Pat. Section 4.01
No. 1,083 describes the use of an azaindene compound to perform infrared sensitization using a desensitizing amount of an infrared sensitizing dye.

Alternatively, tricarbocyanine dyes and/or 4-quinoline nucleus-containing dicarbocyanine dyes described in JP-A-60-80841 are preferably used. Typical infrared sensitizing dyes are shown below, but of course the present invention is not limited thereto.

10 (J I
+rA (1)
Cl21/J
ψL〆)Vノq rAVλ 〜
To OQ C/)
Re=
= Yes
rework
==
=C,)0 :e
:! :φ
= = = Engineering〇-= The amount of these sensitizing dyes added is 5 x 10' mol to 5 x 10-3 mol, preferably txto-a mol to I x 10-3 mol, per 1 mol of silver halide. , particularly preferably from 2.times.10@-6 mol to 5.times.10@-4 mol.

Preferred examples of compounds used to enhance the supersensitizing effect include the following compounds.

4.4'-bis(2,6-di(benzothiazolyl-2-
thio)pyrimidin-4-ylamino)stilbene-2,
2'-disulfonic acid disodium salt, 4,4'-bis[2,6-di(benzothiazolyl-2-
amino)pyrimidin-4-ylaminocostilbene-2
, 2'-disulfonic acid disodium salt, 4,4'-bis[2,6-di(naphthyl-4-oxy)
Pyrimidin-2-ylaminocostilbene-2,2'-
Disulfonic acid disodium salt, 4,4'-bis(2,6-di(naphthyl-4-oxy))
pyrimidin-2-ylamino]bibenzyl-2,2'-
Disulfonic acid disodium salt, 4,4'-bis[2,6-dianilinopyrimidine-4-
ylamino)stilbene-2゜2'-disulfonic acid disodium salt, 4.41-bis(216-di(1-phenyltetrazolyl-5-thio)pyrimidin-4-ylaminocostilbene-2,2'- Disulfonic acid disodium salt, 4,4'-bis[2,6-dianilinopyrimidine-4-
4.4'-bis(2-anilino-6-hydroxypyrimidin-4-ylamino)stilbene-2,21-disulfonic acid disodium salt, 4. 4'-bis(2-chloro-
6-(2-naphthoxy)pyrimidin-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt, 4,4'-bis(2,6-di(2-naphthoxy)pyrimidin-4-ylamino) Stilbene-2,2'-disulfonic acid disodium salt, 4,4'-bis[2,6-diphenoxypyrimidin-4-ylamino]stilbene-2
゜2'-disulfonic acid disodium salt, 4,4'-bis(2,6-cyphenylthiopyrimidin-4-ylamino)stilbene-2゜2'-disulfonic acid disodium salt, these compounds are Approximately o per mole of silver halide
, otg to 5 g.

The ratio (weight ratio) between the above-mentioned infrared sensitizing dye and these compounds is infrared sensitizing dye/these compounds = 1/1-
A range of 1/100 is advantageously used, in particular 172 to 1
A range of 150 is advantageously used.

Next, the silver halide grains used in the present invention include silver chloride,
Any silver halide consisting of chlorine, bromine, or iodide may be used, such as silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide, but especially silver bromide, Silver iodobromide and silver chloroiodobromide are preferred. Silver iodide in silver halide is preferably 0 to 20 mol%, particularly 0 to 10%. Silver chloride in silver halide is preferably at most 20 mol%, and at least 10 mol%. It is more preferable that it is, and it is especially preferable that it is 5 mol% or less.

゛Particularly preferably used silver halide grains are (100
) plane/(111) plane ratio of 1 or more, and can be prepared by various methods. The most common method is to simultaneously add a silver nitrate aqueous solution and an alkali halide aqueous solution while keeping the PAg value at a constant value of 8.10 or less during particle formation (so-called controlled double jet method). The PAg value is preferably 7.80 or less, more preferably 7.60 or less.

When silver halide grain formation is divided into two types, nucleation and its growth, there are no restrictions on the p and Ag values at the time of nucleation, and the pAg is the same as described above.

These emulsions may have coarse grains, fine grains, or mixed grains thereof, but preferably have an average grain size of about 0.05 mm as measured by, for example, the projected area method or the number average method.
Particles of 0.04μ to 1.0μ are preferable, and the size distribution has a coefficient of variation of within 20%, preferably 1.0μ.
It is preferable to use a monodispersed emulsion within %.

The particle shape is preferably cubic, but may be potato-shaped, spherical,
It may have an irregular crystal shape such as a plate shape or a tabular shape with a particle diameter of 5 times or more the particle thickness.

The light-sensitive material used in the present invention does not have to have only one silver halide emulsion layer, but may have two or more layers, and two or more types of emulsions with different grain sizes, sensitivities, etc. may be mixed or used in separate layers.

Further, the emulsion layer is not limited to one side of the support, but may be provided on both sides.

These light-sensitive emulsions may be mixed with a substantially non-light-sensitive emulsion (for example, an internally covered fine grain emulsion), or they may be coated in separate layers.

Furthermore, even if the crystal structure of silver halide grains is internalized, there are also grains with a layered structure in which the inside and outside are different, British Patent No. 635°841, U.S. Patent Nos. 3 and 6, etc.
The particles may be of the so-called conversion type as described in No. 22,318, or may be of the type in which a latent image is mainly formed on the surface or of the internal latent image type in which the latent image is formed inside the particles.

Iridium ions are preferably used in the emulsion of the present invention, and in order to contain iridium ions, a water-soluble iridium compound (for example, hexachloroiridate (III) salt, hexachloroiridate (IV)) is used during emulsion preparation.
This is achieved by adding the acid salt) in the form of an aqueous solution. It may be added in the same aqueous solution form as silver halide for grain formation, it may be added before grain formation, it may be added during grain formation, or it may be added after grain formation until chemical sensitization, but it is particularly preferred. is added during particle formation.

During the formation of silver halide grains, for example, ammonia, rhodanpotash, rhodanammonium, thioether compounds, thione compounds, amine compounds, etc. can be used as silver halide solvents to control grain growth.

In addition to silver halide solvents, compounds that control crystal habit by absorbing onto the grain surface, such as cyanine sensitizing dyes, tetrazaindene compounds, and mercapto compounds, can be used during grain formation.

Various commonly used chemical sensitization methods such as gold sensitization, sulfur sensitization, reduction sensitization, and sensitization using thioether compounds are applied to silver halide photographic emulsions.

Various compounds can be added to the photographic light-sensitive material of the present invention in order to prevent a decrease in sensitivity and the occurrence of capri during the manufacturing process, storage or processing of the light-sensitive material. These compounds include nitrobenzimidazole, ammonium chlorobratinate, 4-hydroxy-6-methyl-1,3°3
A large number of compounds have been known for a long time, including 8.7-titraazaindene, l-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. An example of a compound that can be used is "The Theo" by C.E.
ry of thePhotographic Pro
cess” (3rd edition, 1966) pp. 344-3
The original documents are listed on page 49. For example, U.S. Patent No. 2,131°038 and U.S. Patent No. 2,694.716
Thiazolium salts described in U.S. Patent No. 2, etc.
．． Azaindenes described in US Pat. No. 886,437 and US Pat. No. 2,444,605; US Pat. No. 3.287
, 135; sulfocatechols described in U.S. Patent No. 3,236.652; oximes described in British Patent No. 623,448; U.S. Patent No. 623,448; 2.403.927
No. 3,266.897, No. 3,397,98
Mercaptotetrazoles described in No. 7, etc.
Nitrones, nitroindazoles; U.S. Patent No. 2.83
Polyvalent metal salts (Po1
yvalent metal 5 alts); thiuronium salts (thiuronJum 5 alts) described in U.S. Pat. No. 3,220.839, etc.; U.S. Pat.
Examples include palladium, platinum, and gold salts, which are described in No. 5.

The silver halide photographic light-sensitive material of the present invention contains developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones and phenylenediamines; It is possible to contain a combination of the following. The developing agent is used in the silver halide emulsion layer and/or
Or it can be incorporated into other photographic layers (eg, protective layer, intermediate layer, filter layer, antihalation layer, back layer, etc.). The developing agent may be dissolved in a suitable solvent or as described in US Pat. No. 2,592,368 or French Patent No.
505,778 in the form of a dispersion.

In the present invention, as a matting agent, U.S. Patent No. 2.992
．． No. 101, No. 2.7 of the same, No. 245, No. 4, 14 of the same
Homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid as described in No. 2,894 and No. 4,396.706, organic compounds such as starch, silica, titanium dioxide, sulfuric acid, strontium, barium The particle size that can be used is 1.0 to 10 Jj.
m, particularly preferably 2 to 5 μ.

The surface layer of the photographic light-sensitive material of the present invention may contain silicone compounds described in U.S. Pat. No. 3,489.576, U.S. Pat.
In addition to the colloidal silica described in the publication, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

The hydrophilic colloid in the constituent layers of the photographic material of the present invention includes:
Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be added as plasticizers.

Further, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. Examples of the polymer include a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid, and styrene. -butadiene copolymers, polymers or copolymers consisting of 1,000 yen, which have active methylene groups, can be preferably used.

The photographic emulsions and non-photosensitive woody colloids of the present invention may contain inorganic or organic hardeners, such as aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), and N-methylol compounds (dimethylol urea). , methyloldimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3゜5-triacryloyl-hexahydro-5-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-[
β-(vinylsulfonyl)propionamide], etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. Among them, JP-A-53
-41220, 53-57257, 59-16
Preferred are the active vinyl compounds described in US Pat. No. 2,546 and 60-80,846 and the active halides described in US Pat.

The silver halide photographic material of the present invention may have a light-sensitive silver halide emulsion layer, a back layer, a surface protective layer, an intermediate layer, an antihalation layer, and other non-photosensitive layers.

There may be two or more silver halide emulsion layers, and the sensitivity, gradation, etc. of the two or more silver halide emulsion layers may be different.
Further, one or more silver halide emulsion layers or non-photosensitive layers may be provided on both sides of the support.

The photographic emulsion layer or other wood-philic colloid layer of the light-sensitive material produced using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast). Various surfactants may be included for various purposes such as oxidation, sensitization, etc.

Examples of the surfactant used in the present invention include "Surfactants and Their Applications" by Ryohei Oda et al. (Maki Shoten, 1964);
“New Surfactants” by Hiroshi Horiguchi (Sankyo Publishing ■, 1975)
Or ``Mattachation's Day Targent and E Marzifires.''
Visions, MC Publishing Company 1985) (rMc Cutcheon'sD
etergents &Ea+ulslflers J
(MC Cutcheon Divisions, Mc
Publishing Co., 1985)),
It is described in Japanese Patent Application Laid-Open No. 60-76741, Japanese Patent Application No. 13398/1982, Japanese Patent Application No. 61-16056, Japanese Patent Application No. 61-32462, etc.

As antistatic agents, in particular U.S. Pat. No. 4.201.58
No. 6, JP-A-60-80849, JP-A No. 59-74554
No. 60-249021, Patent Application No. 61-32462
Fluorine-containing surfactants or polymers described in JP-A-60-76742, JP-A-60-80846, JP-A-60-
No. 80848, No. 60-80839, No. 60-767
No. 41, No. 58-208743, Patent Application No. 1988-133
Nonionic surfactants described in No. 98, No. 61-16056, No. 61-32462, etc., or also Japanese Patent Application Laid-Open No. 57-204540, Japanese Patent Application No. 61-32
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in No. 462 can be preferably used.

Examples of inorganic antistatic agents include ammonium, alkali metal, and alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphates, and thiocyanates. Composite oxides prepared by doping conductive tin oxide, zinc oxide, or these metal oxides with antimony or the like, as described in Japanese Patent No. 118242, etc., can be preferably used. Furthermore, various charge transfer complexes, doping compounds for π-conjugated polymers, organometallic compounds, eyebrow compounds, etc. can also be used as antistatic agents, such as TCNQ/
Examples include TTF, polyacetylene, and polypyrrole.
These are Morita et al., Chemical 1 and Kogyo 59 (3), 103-t
t 1 (1985), 1 and (4), 146-152
(1985).

A hydrophilic colloid is used as a protective colloid in the silver halide photographic emulsion layer, intermediate layer, back layer, etc. in the present invention, and gelatin can be used as the hydrophilic colloid. In addition, acylated gelatins such as phthalated gelatin and malonated gelatin, cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; soluble starches such as dextrin; polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid. hydrophilic polymers can be added.

Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

Also, U.S. Patent Nos. 3,411,911 and 3.411.
, No. 912, No. 3.142,568, No. 3.32
No. 5.286, No. 3,547.650, Special Publication No. 1973
-5331, etc., to improve the dimensional stability of photographic materials.
It can be included for purposes such as improving film properties.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a plasticizer, optical brightener, air fog inhibitor, toning agent, etc.

The silver halide photographic material of the present invention can contain color couplers such as cyan couplers, magenta couplers, yellow couplers, and compounds that disperse the couplers. That is, these couplers may contain a compound that develops color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine conductor, an aminophenol derivative, etc.) during color development processing. A non-diffusible coupler having a hydrophobic group called a group is preferable.The coupler may be either 4-equivalent or 2-equivalent to silver ions.
It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

In addition, a color image can also be formed by developing with a color developer containing a diffusible coupler.

The present invention can be applied not only to black and white photographic materials but also to various color photographic materials.

Exposure to obtain photographic images may be carried out using conventional methods: natural light (sunlight), tungsten lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, light emitting diodes, Any of a variety of known light sources including infrared light such as laser light (eg, gas laser, colored laser, YAG laser, semiconductor laser, etc.) can be used. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like.

Exposure times include not only exposure times from 1/1000 seconds that are normally used in cameras, but also exposure times shorter than 1/1000 seconds,
For example, using a xenon flashlight or cathode ray tube,
Exposures of 1/10♂ seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. The photosensitive material of the present invention is particularly suitable for use in scanners using semiconductor lasers.

Any known method can be used for photographic processing of the light-sensitive material produced by applying the present invention. A known treatment liquid can be used. Processing temperature is usually 1
Selected between 8°C and 50°C. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

As the developing agent used in the developer used in the present invention, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is most preferable because it is easy to obtain good performance.
Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone%2.3-dibromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3-
Examples include dichlorohydroquinone, 2.5-dichlorohydroquinone, 2.3-dibromohydroquinone, and 2.5-dimethylhydroquinone, with hydroquinone being particularly preferred.

The developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention is 1-phenyl-4,4-
Examples include dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. ,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.01 mol/1 to 1.2 mol/fL.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.2 mol/A or more, particularly 0.4 mol/A or more, and the upper limit is preferably 2.5 mol/A.

The pH of the developer used in the present invention is preferably in the range of 9 to 13, more preferably 10 to 12.
The range is up to

Alkaline agents used for setting pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

Japanese Patent Application No. 1987-28708 (Borate), Japanese Patent Application No. 1988-
Buffers such as No. 93433 (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethyl formamide, methyl cellosolve, hexylene glycol, ethanol; Organic solvents such as methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-
Mercapto compounds such as sulfonic acid sodium salt, 5-
It may also contain antifoggants such as indazole compounds such as nitroindazole, benztriazole compounds such as 5-methylbenztriazole, and, if necessary, color toners, surfactants, antifoaming agents, water softeners, and other additives. It may also contain amino compounds described in JP-A-56-106244.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, F. A. Mason r Photographic
"Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent No. 2,1
No. 93,015, No. 2,592,364, Japanese Unexamined Patent Publication No. 4
Those described in No. 8-64933 may also be used.

In the present invention, a one-component developer containing the above-mentioned 3-pyrazolidone type developing agent may be used by replenishing the developer. These 3-pyrazolidone compounds are added in an amount of 0.1 g to 30 g, more preferably 0.5 g to 20 g, and still more preferably 1 g to 15 g, in the developer 11.
added. Further, the above-mentioned one-component developer can be used in a concentrated form, and in that case, it is preferable to dilute the developer with water as the photographic material is processed.

The development temperature and time of the development process in the present invention are preferably about 5° C. to about 50° C. and 15 seconds or less, particularly preferably 30° C. to 40° C. and 6 seconds to 15 seconds.

The fixer used in the present invention is an aqueous solution containing thiosulfate and has a pH of 3.8 or more, preferably 4.2 to 5.5. More preferably, the pH is 4.65 to 5.5.

Sodium thiosulfate and ammonium thiosulfate are available as fixing agents, but they contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.The amount of fixing agent used may be changed as appropriate. and generally about 0.1 to about 6 mol/I
It is t.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid, or their derivatives can be used alone or in combination of two or more. These compounds are 0.0 per IJl of fixer
Those containing 0.05 mol or more are effective, especially 0.01 mol/1
~0.03 mol/1 is particularly effective.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution may optionally contain preservatives (e.g. sulfites, bisulfites), pi (1!l) buffering agents (e.g. acetic acid, boric acid).
, a pH adjuster (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-218562.

The fixing temperature and time are preferably 6 seconds to 1 minute at about 0°C to about 50°C, more preferably 6 seconds to 30 seconds at 30°C to 40°C, and still more preferably 6 seconds to 30°C to 40°C. 15
Seconds.

In the present invention, the fixer concentrate may be composed of a single agent if the fixer concentrate is replenished into the automatic processor along with water to dilute the photosensitive material as it is processed.

The fixer stock solution exists stably as a single agent at pH 4,
5 or more, more preferably pH 4.65 or more. 9) If it is less than 14.5, the thiosulfate will decompose and eventually become sulfurized, especially if the fixer is left for a long time before it is actually used. Therefore the pH
In the range of 4.5 or more, less sulfur dioxide gas is generated and the working environment is improved. The upper limit of pH is not so strict, but if it is fixed at too high a pH, the pH of the membrane will deteriorate even after washing with water.
As H increases, membrane swelling increases.

Therefore, since the drying load becomes large, the pH is limited to about 7. In fixing solutions that use aluminum salts to harden films, the pH limit for preventing precipitation of aluminum salts is 5.5.

In the process of the present invention, either the developing solution or the fixing solution may be a so-called working solution that does not require dilution water as described above (that is, it is replenished as an undiluted solution).

The amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1:0 to 8.
The total amount of each of the developer and fixer is preferably 50 ndl to 1500 mR relative to the photosensitive material trn'.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

Any method known in the art can be applied to the water washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water for washing water or stabilizing liquid, not only is it possible to conserve water by reducing the amount of replenishment to less than 31 ml per photosensitive material, but it also eliminates the need for piping for installing an automatic processing machine. Furthermore, it is possible to reduce the number of stock tanks. That is, the solution dilution water and washing water or stabilizing solution for the developer and fixer can be supplied from a common single-layer stock tank, making it possible to further downsize the automatic developing machine.

When water treated with mildew-proofing means is used in combination with washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
-0 to 31. Preferably, water saving treatment of 0 to 11 can be performed.

Here, when the replenishment amount is 0, no replenishment is performed at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservation water" is essentially not refilled. Refers to cases in which a processing method is used.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect can be obtained. The amount of water used for washing is also much smaller compared to conventional methods.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with water treated with anti-mold means, is disclosed in Japanese Patent Application Laid-Open No. 60-235133. As described, it can also be used in a processing solution having fixing ability, which is a processing step before that. This is more preferable because the stock water can be saved and the amount of waste liquid can be reduced.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986-
No. 253807, No. 60-295894, at-6
The method using the antibacterial agent described in No. 3030 and No. 61-51396 can be used.

Furthermore, L, 6, West “Mlater Q
ualityCriteria"Photo, Sc1.
& Eng, Vol. 9 No. fi (1965), M.
l, Beach “Microbiological
Growths in Motion-Picture
Processing”SMPTE Journal
Vol, 85. (1976), Deegan, R.O.
.

”Photo Processing Wash Wa
ter Biocides”J, Imaging Te
ch, Vol, 10. No. 6 (1984) and JP-A Nos. 57-8542, 57-58143, and 58
-105145, 57-132146, 58-
No. 18631, No. 57-97530, No. 57-157
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 244 and the like can also be used in combination.

In addition, in the washing bath, R, T, Reiman, J.
, Image, Tech 10 (8), 242 (
RE is an isothiazoline compound described in 1984).
SEARC) IDISCLO5tlRE Volume 205, Item 20526 (May issue, 1981) Isothiazoline compounds described in Volume 228, Item
22845 (April issue, 1983), the compound described in Japanese Patent Application No. 61-51396, etc. are used as antibacterial agents (Microbioci
It can also be used in combination as de).

Furthermore, specific examples of the anti-piping agent include phenol, 4-chlorophenol, pentachlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2
-(4-thiazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4,4'-trichloro-2'-hydroxy Examples include diphenyl ether.

It is preferable that the water treated with anti-mold measures and stored in a water stock tank be used both as dilution water for the undiluted solution of processing solutions such as the developer-fixer and as washing water, since it takes up less space. Preparation dilution water and washing water (
(or stabilizing liquid) can be stored separately in separate tanks, or only one of them can be taken directly from the tap.

When stored in separate tanks, apply anti-mold measures and
The washing water (or stabilizing bath) can contain various additives.

For example, the chelate stability constant with aluminum ftog
A chelate compound having a K value of 10 or more may be included. These are effective in preventing scuttling in washing water when the fixing solution contains an aluminum compound as a hardening agent.

Specific examples of chelating agents include ethylenediaminetetraacetic acid (J!ogK = 16.1, same hereinafter), cyclohexanediaminetetraacetic acid (17,6), diaminopropanoltetraacetic acid (13,8), diethylenetriaminepentaacetic acid (18, 4), triethylenetetraminehexaacetic acid (1
9,7) etc. and their sodium salts, potassium salts,
There is an ammonium salt, and the amount added is preferably 0.0
1 to 10 g/Il, more preferably 0. 1-5g/I
It is t.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing water droplet unevenness. Surfactants include cationic, anionic,
Either non-ionic type or amphoteric type may be used.

Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho ■.

Various compounds are added to the stabilizing agent for the purpose of stabilizing the image. For example II! Various buffers (e.g. borate, metaborate, boric acid, phosphate, carbonate, potassium hydroxide,
(Used in combination with sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.)
Typical examples include aldehydes such as and formalin. In addition, various additives such as chelating agents, bactericidal agents (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardening agents, etc. may be used. , two or more of the same or different desired compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. as a membrane pt+ adjusting agent for the processor in order to improve image storage stability.

The water washing or stabilization bath temperature and time using the above method are O
6 seconds to 1 minute at ℃ to 50℃ is preferable, but 15℃ to 40℃
more preferably from 6 seconds to 30 seconds, and more preferably from 15°C to 4°C.
Preferably, the temperature is 6 seconds to 15 seconds at 0°C.

The photographic material that has been developed, fixed, and washed is squeezed out of the washing water. That is, it is dried through a squeeze roller method. Drying is carried out at a temperature of about 0°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 100°C.
The time may be 1 minute, but it is more preferably about 5 seconds to 30 seconds at 40°C to 80°C.

In the present invention, the so-called dry-to-dry processing time for development, fixing, washing, and drying is within 3 minutes and 15 seconds, preferably within 100 seconds, and most preferably within 70 seconds.

Here, "dry to day" refers to the time from the moment the leading edge of the photosensitive material to be processed enters the film insertion area of the processor to the moment the leading edge emerges from the processor after being processed. .

(19) Specific effects of the invention According to the invention, the position of a photographic material can be easily detected in a recording apparatus for forming an image. Such a method is applicable and effective to various recording apparatuses, such as image diagnostic apparatuses, and especially scanner-type apparatuses.

In addition, it can be applied to terminals such as computer equipment and printing in general.

It also has good photographic properties, good storage stability, and can withstand rapid processing.

Furthermore, it is advantageous in terms of production, especially in photosensitive materials that are incorporated in the back layer.

(1) Specific Examples of the Invention Below, specific examples of the present invention will be shown and the present invention will be explained in more detail.

Example (1) Preparation of silver halide emulsion After adding an appropriate amount of ammonia to a container heated to 55°C containing gelatin, potassium bromide and water, the p and Ag values in the reaction container were adjusted to 7. A silver nitrate aqueous solution and a potassium bromide aqueous solution were added by a double-jet method while maintaining the concentration of silver nitrate at 60° C. to prepare monodisperse silver bromide emulsion grains having an average grain size of 0.55 μm. In this emulsion grain, 98% of the total number of grains existed within ±40% of the average grain size. After desalting this emulsion, the pH was adjusted to 6.2 and the PAg to 8.6, and then gold/sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to obtain the desired photograph.

The (100) plane/(111) sedimentation ratio of this emulsion was measured by the Kubelkamunk method and was found to be 98/2. This was named Emulsion A.

(2) Preparation of emulsion coating solution Weigh out 1 kg of emulsion A and dissolve it by heating at 40°C.
X10-4M/f) at 70mA, 4-hydroxy-6-
Methyl-1,3゜3a, tutetrazaindene aqueous solution,
An aqueous solution of dodecylbenzenesulfonate as a coating aid and an aqueous solution of polypotassium p-vinylbenzenesulfonate compound as a thickener were added to prepare an emulsion coating solution.

(3) Preparation of coating solution for surface protective layer of photosensitive material layer A 10 wt % gelatin aqueous solution heated to 40°C, a thickener polyethylene sodium sulfonate aqueous solution, and a matting agent polymethyl methacrylate fine particles (average particle size 3. 04), Hardener N.

Added N'-ethylene bis-(vinylsulfonylacetamide), an aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a coating aid, an aqueous polyethylene surfactant solution as an antistatic agent, and an aqueous solution of a fluorine-containing compound with the following structure. A coating solution was prepared.

Ca F 17502 N (C3H7) CH2Co
o and C6F 17502 N (C3H7)
(CH2CH2-0+ts+((4) Preparation of pack coating solution 1 g
thickener polyethylene sodium sulfonate aqueous solution, exemplified compound (I-1), and hardening agent N.

A back coating solution 1 was prepared by adding an aqueous solution of N'-ethylene bis(vinylsulfonylacetamide) and an aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a coating aid.

(5) Preparation of coating solution for the surface protective layer of the back layer A 10 wt% gelatin aqueous solution heated to 40°C, a thickener polyethylene sodium sulfonate aqueous solution, and a matting agent polymethyl methacrylate fine particles (average particle size 3° OP) A coating solution was prepared by adding an aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a coating aid, an aqueous polyethylene surfactant solution as an antistatic agent, and an aqueous solution of the fluorine-containing compound used in the above (3). .

(6) Preparation of coating sample The above-mentioned back coating solution I was coated on one side of a polyethylene terephthalate support together with the back surface protective layer coating solution so that the gelatin coating amount was 4 God. Moreover, exemplified compound (1-1) is 0.14 g/rr? The coating amount was set to . Subsequently, on the opposite side of the support, first, an emulsion coating solution of emulsion A containing a near-infrared sensitizing dye and a surface protective layer coating solution for this were coated at a silver amount of 2.8 g/rr? Sample 101 was obtained.

In back coating liquid 1, AgBr with an average particle size of 0.08μ was used as the exemplified compound (I-1) as a non-photosensitive inorganic salt.
Exemplary compound (1-1) / A g Br using
A so that the ratio is -0, 14g / 0, 75g
A back coating solution 2 was prepared in the same manner except that exemplified compound (1-1) was adsorbed to the gBr emulsion.

In addition, in the back coating liquid 2, the exemplary compound (n - t
) or Exemplary Compound (II-2) were prepared in the same manner except that they were used as back coating liquid 3.4.

Further, back coating liquid 5 was prepared in the same manner as back layer coating liquid 1 except that a compound represented by general formula CI) or (Vl) was used.

Samples 102 and 103 were prepared in the same manner as sample 101 using these back coating liquids 2.3.4.5.
．． 104.105.

In addition, the general formula (
Sample 106.1 was prepared in the same manner except that the compound represented by 1) or (II) was contained in the photosensitive layer either as it was or by adsorbing it to a non-photosensitive inorganic salt.
10f. The coating amount of the compound represented by the general formula (I) or (II) was 101 to 104.10 in samples.
6.107, all were set to 0.14 g/rn'.

These samples 101 to 10 were subjected to image exposure/
The following processes of exposure, development, fixing, washing, and drying were performed using an automatic developing device.

Exposure was performed using a semiconductor laser with a wavelength of 80 nm.
A scanning exposure of 7 seconds was performed.

Development and fixing after exposure were performed using the following developer and fixer. Then, processing including fixing, washing with water, and drying was performed for 70 seconds at a standard developing temperature of 35°C.

Developer Potassium hydroxide 16.98 g Glacial acetic acid 1.8 g Sodium sulfite 60 g Potassium carbonate
5.0g boric acid
3g diethylene glycol 12g diethylenetriaminepentaacetic acid 2.0g 5-methylbenzotriazole 0.6g hydroquinone
25.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.65 g Potassium bromide 2.0 g Add water and t
Finish to ft.

(p) Adjust l to 10.50. ) Fixer Ammonium thiosulfate 140 g Sodium sulfite (anhydrous) 15 g Ethylenediaminetetraacetic acid disodium dihydrate 0.025 g Adjust to pH 5.1 with glacial acetic acid.

Add water to bring the total volume to 1 ft.

In addition, the following tests were conducted.

Test for film position detection using an external diode A photointerrupter (Sharp Photointerrupter GPIA17, manufactured by Sharp Corporation) that incorporates an LED with a maximum emission wavelength around 950 nm, a sensor that receives the light, and the necessary electronic circuits. An unprocessed film sample was inserted between the LED sensor of this photointerrupter in a dark room, and the on-off operation (detecting the presence or absence of film) was performed. We evaluated whether it could be performed stably. A case in which the presence or absence of a film could be detected without error even after repeated tests was indicated as O, and a case in which the presence of a film could not be detected was indicated as × (Table 1).

iKungokosu 1 Each photosensitive material was stored at 50° C. and 68% RH for 5 days, and then developed in the same manner as above.

Table 1 shows the photographic properties and film position detection results before and after forced aging.

Table 1 101 100 0.15 90 0.17
0 (present invention) 102 100 0.15 90 0.17
0 (present invention) 103 Zoo O, 15900, 1f O
(Present invention) 104 100 0.15 90 0.17
0 (present invention) 105 100 0.15 97 0.15
x (comparison) 106 80 0.16 50 0.20
0 (comparison) 107 85 0.17 45 0.21
0 (Comparison) From the above results, it is concluded that the samples of the present invention can be easily and precisely detected in position in the apparatus, have excellent photographic properties even in rapid processing, and have good storage stability. found.

Claims (1)

[Claims] (1) An infrared-sensitive silver halide photosensitive material containing at least one compound represented by the following general formula (I) or (II) in a non-photosensitive layer. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above general formula (I), n represents a positive integer of 1 or 2 . R represents an alkyl group or an aryl group. R_1 and R_2 each represent an alkyl group or an aryl group. R_3 and R_4 each represent a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group. X^■ represents an anion. m represents a positive integer of 1 or 2. Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle. In the above general formula (II), R' represents an alkyl group, and R'' represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X'^■ represents an anion.}