JPH0271257A - Silver halide photographic sensitive material having glass base - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material which has high sensitivity to IR light and does not exfoliate at the time of development by allowing at least one of nonphotosensitive layers to exist between a glass base and silver halide emulsion layer and incorporating at least one kind of dyes selected arbitrarily from a dye group consisting of specific dyes therein. CONSTITUTION:This photosensitive material has at least one layer of the silver halide emulsion layers and at least one layer of the nonphotosensitive layers on the glass base. One or more kinds of the silver halide emulsion layers selected arbitrarily from the dye group consisting of a tricarbocyanine dye and 4-quinoline nucleus-contg. dicarbocyanine dye are incorporated therein. One kind of either the tricarbocyanine dye or the 4-quinoline nucleus-contg. dicarbocyanine dye may be used in this case and the selection thereof is arbitrary. These dyes function as an IR sensitizing dye. The photosensitive material which has the high sensitivity to IR light and obviates the exfoliation of the silver halide emulsion layers on the base at the time of development is obtd. in this way.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a photographic material having a silver halide emulsion layer on a glass support, and more specifically, it relates to a photographic material having a silver halide emulsion layer on a glass support. The present invention relates to a photographic light-sensitive material having a silver halide emulsion layer.

[Background of the invention]

Silver halide photographic light-sensitive materials having a glass support have excellent dimensional stability and are used as photomask materials for the manufacture of ICs that require precision, photomask materials for display-related devices, etc. It is widely used for disassembling measurements, phototypesetting, etc.

Conventionally, the method for manufacturing photomasks for manufacturing ICs and display-related photomasks is to reduce and enlarge the original image using a camera, photograph it on film, and develop it.
Furthermore, a technique has been used in which a photomask is obtained by baking and developing a silver halide photographic material (hereinafter referred to as a photographic plate) having a glass support.

In recent years, as a method for producing such photomasks, a method in which an original image is produced by a computer and recorded directly on a photographic plate using an argon laser as a recording light source has become popular. This method has the advantage that a photomask can be obtained without using a film.

On the other hand, the use of semiconductor lasers has become widespread as a recording light source in place of argon lasers. Semiconductor lasers have advantages over argon lasers in that they are more compact, have a longer lifespan, and are cheaper. When exposing with a semiconductor laser, the exposure region is in the infrared region, so a photosensitive material with increased sensitivity in the infrared region is required.

Generally, in order to faithfully reproduce highly accurate images, it is necessary to use glass with excellent dimensional stability as a support.

However, when a silver halide emulsion with properties suitable for semiconductor lasers such as those mentioned above is applied to a glass support, the emulsion layer easily peels off when it comes into contact with other dry plates during the development process, causing pattern images to deteriorate. This had the disadvantage of causing damage.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material that has high sensitivity to infrared light and does not peel off a silver halide emulsion layer on a glass support during development.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive layer on a glass support. one layer is present between the glass support and the silver halide emulsion layer, and comprises a tricarbocyanine dye and a 4-quinoline nucleus-containing dicarbocyanine dye in at least one of the silver halide emulsion layers. This can be achieved by a silver halide photographic material containing at least one dye arbitrarily selected from the group of dyes.

The present invention will be explained in more detail below.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer and at least one non-photosensitive layer on a glass support.

In at least one of the silver halide emulsion layers,
At least one dye arbitrarily selected from the dye group consisting of tricarbocyanine dyes and 4-quinoline nucleus-containing dicarbocyanine dyes is contained.

Preferably, all the silver halide emulsion layers constituting the light-sensitive material of the present invention contain at least one of the above dyes.

This dye will be explained below.

In the present invention, the silver halide emulsion layer contains one or more dyes arbitrarily selected from the dye group consisting of tricarbocyanine dyes and 4-quinoline nucleus-containing dicarbocyanine dyes. In this case tricarbocyanine dye or 4
- Any one of the quinoline nucleus-containing dicarbocyanine dyes may be used, both types may be used in combination, or two or more of them may be used, and the selection thereof is arbitrary. These dyes can function as infrared sensitizing dyes.

Among the above dyes used in the present invention, the following dyes are preferred.

First, in the tricarbocyanine dye used in the present invention,
Particularly useful are the following general formulas (Ia) or (I
b).

General formula (Ia) General formula (Ib) In the formula, R" and R" may each be the same or different, and each represents an alkyl group (preferably having 1 to 8 carbon atoms).
(for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, etc.), substituted alkyl group (
Examples of substituents include carboxyl groups, sulfo groups, cyano groups, halogen atoms (e.g. fluorine atoms, chlorine atoms, bromine atoms, etc.), hydroxy groups, alkoxycarbonyl groups (having 8 or less carbon atoms, e.g. methoxycarbonyl groups, ethoxycarbonyl groups). , hensyloxycarbonyl group, etc.)
, alkoxy groups (having 7 or less carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, hensyloxy, etc.), aryloxy groups (such as phenoxy, p-tolyloxy, etc.), acyloxy groups (having 7 or less carbon atoms), 3 or less, such as an acetyloxy group, a propionyloxy group, etc.), an acyl group (a carbon number of 8 or less, such as an acetyl group, a propionyl group, a benzoyl group, a mesyl group, etc.), a carbamoyl group (such as a carbamoyl group,
N,N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarhamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), ryol group (For example, phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group,
(α-naphthyl group, etc.) (the number of carbon molecules in the alkyl portion is 6 or less). However, two or more of these substituents may be substituted into an alkyl group in combination. ) represents.

R" represents a hydrogen atom, a methyl group, a methoxy group, or an ethoxy group.

RI3 and R14 each represent a hydrogen atom, a lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), a lower alkoxy group (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group, benzyl group .

R15 is a hydrogen atom, a lower alkyl group (for example, a methyl group,
ethyl group, propyl group, etc.), lower alkoxy group (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group, benzene, each substituted or unsubstituted alkyl group (alkyl moiety has 1 to 18 carbon atoms, Preferably 1 to 4 groups, such as methyl group, ethyl group, propyl group, butyl group, benzyl group, phenylethyl group), aryl group (such as phenyl group, naphthyl group, tolyl group, p
-chlorophenyl group, etc.), and Wl and W2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

Dlo represents the atoms necessary to complete a divalent ethylene bond, e.g. ethylene or triethylene, which ethylene bond is replaced by one, two or more suitable groups, e.g. Alkyl groups (e.g. methyl group,
ethyl group, propyl group, isopropyl group, butyl group, etc.), halogen atoms (e.g. chlorine atom, bromine atom, etc.),
Alternatively, it may be substituted with an alkoxy group (having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, etc.).

D'' and D'' each represent a hydrogen atom. However, Dl and Dl2 can also work together to form a divalent ethylene bond having the same meaning as D'' above.

2+0 and Z each represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a thiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6- Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-
Methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methylbenzothiazole, 1-ethyl-5-cyanobenzimidazole, 1 -methyl-5
-Fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole , 1-phenylbenzimidyl'/"-ru,
l-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1
-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnat CI, 1-d) imidazole, etc.)
, pyridine nuclei (for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.). Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used.

X- represents an acid anion.

n represents 1 or 2.

Particularly useful among the 4-quinoline nucleus-containing dicarbocyanine dyes used in the present invention are those having the following general formula % general formula (n) (X++-) n, -+ where R16 and R17 are R11 and R12, respectively. represents the same meaning as

R111 represents the same meaning as R''. However, RIB is preferably a lower alkyl group or a benzyl group.

■ is a hydrogen atom, a lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), an alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, etc.), a halogen atom (
For example, fluorine atoms, chlorine atoms, etc.), substituted alkyl groups (
For example, trifluoromethyl group, carboxymethyl group, etc.)
represents.

z　I　2 represents the same meaning as Z and Zl.

X and 1 represent the same meaning as X.

m, nl, and p each represent 1 or 2.

Specific examples of the above dyes that can be used in the present invention are shown below. However, the present invention is not limited to these sensitizing dyes.

(■ ■-7) ■- (I-19) (I (I (I (■ (■ (■ The above dyes functioning as external sensitizing dyes preferably contain 5X10 - per mole of silver halide.
'mol-5X10-''mol, more preferably lXl0-
6 mol-1X10-' mol, particularly preferably 2X10-'
It is contained in a silver halide photographic emulsion in a proportion of 6 mol-5xto-' mol.

The infrared sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosomal, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution.

Also, ultrasound can be used for dissolution. Further, as a method for adding the above-mentioned infrared sensitizing dye, US Pat.
69,987, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion, Japanese Patent Publication No. 1973-
24185, in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to an emulsion; as described in U.S. Pat. No. 3,822,135. , a method of dissolving a dye in a surfactant and adding the solution into an emulsion; JP-A-51-74624
A method of dissolving a red-shifting compound and adding the solution to an emulsion as described in JP-A No. 1973-
A method such as that described in No. 80826 is used in which a dye is dissolved in a substantially water-free acid and the solution is added to an emulsion. In addition, for addition to emulsions, US Patent No. 2.91
2.343, 3,342,605, 2.9
The methods described in No. 96,287, No. 3,429,835, etc. can also be used.

Furthermore, the infrared sensitizing dyes described above may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but of course they may not be dispersed during any step of the preparation of the silver halide emulsion. Can be done.

The infrared sensitizing dye used in the present invention can be used in combination with other sensitizing dyes. For example, the US patent cylinder 3.7
No. 03.377, No. 2.688,545, No. 3.
397.060, 3.615.635, 3
, 628,964, U.S. Patent No. 1,242,588
No. L293,862, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 43-10773, U.S. Patent No. 3,416,927, Japanese Patent Publication No. 43-4930, U.S. Pat. No. 615,613, No. 3,615,
No. 632, No. 3,617,295, No. 3,635
Sensitizing dyes described in, for example, No. 721, can be used.

Along with sensitizing dyes, substances that exhibit a supersensitizing effect without substantially absorbing visible light, such as U.S. Patent No. 2,933,
No. 390, No. 3,511,664, No. 3,615,6
No. 13, 3,615,632, 3,615,64
Compounds having a pyrimidylamino group or triazinylamino group described in various specifications such as No. 1, aromatic organic acid formaldehyde condensates, azaindenes or cadmium salts described in British Patent No. 1゜137.580. etc. may be included in the emulsion.

The light-sensitive material of the present invention has at least one silver halide emulsion layer and at least one non-photosensitive layer on a glass support, and at least one of the non-photosensitive layers (one layer is a silver halide emulsion layer and a halogen emulsion layer on a glass support). It exists between the silver oxide emulsion layer and the silver oxide emulsion layer.

The non-photosensitive layer (hereinafter referred to as subbing layer) existing between the glass support and the silver halide emulsion layer may have any structure, but is preferably a layer containing a hardening agent. Preferably it is a hydrophilic colloid layer containing a hardening agent.

Hardener materials that can be used in this subbing layer include, for example, aldehydes, such as those described in US Patent Box 1°870, 35
Glyoxal as described in No. 4, U.S. Patent Box 825
．． Geltaraldehyde described in No. 544, etc.;
H-methylol compounds, such as N.

dioxane derivatives such as N-dimethylolhydantoin, such as the dihydroxydioxane described in U.S. Patent No. 3,380,829, or
38713; compounds having an epoxy group, such as U.S. Pat. No. 3,047,394;
No. 3,091,573 specifications, Japanese Patent Publication No. 34-713
Compounds described in Publication No. 3; Compounds having reactive halogens, such as 2,4-dichloro-6-hydroxy-1,35-triazine described in U.S. Pat. No. 3,325,287; Mucohalogen acids; For example, US Patent Box 2,08
Mucochloric acid, mucobromic acid described in No. 0,019, or the above derivatives described in Japanese Patent Publication No. 1872/1987; bis(methanesulfonic acid ester) described in U.S. Patent No. 2,726,162 : Sulfonyl compounds, such as bis(benzenesulfonyl chloride) described in U.S. Pat.
Compounds described in German Patent No. 8790; divinylsulfonic acids, such as those described in US Pat. No. 2,579,871; compounds with reactive olefin bonds, such as those described in German Patent No. Divinyl ketone, such as the compounds described in U.S. Patent Box 3,255,000
No. 3,635,718, British Patent No. 994,86
No. 9, US Pat. No. 2,9, such as compounds having an acryloyl group described in West German Patent No.
Alkylene bismaleimides described in US Pat. No. 92,109, etc.; Isocyanates described in US Patent Box 3,103,437, etc.: US Patent Box 3,100,7
Carboimides described in US Pat. No. 04, etc.; isoxazole derivatives, such as compounds described in US Pat. carbamoyl chloride derivatives of; polymeric hardeners, such as U.S. Patent Box 3,057;
Examples include dialdehyde starch described in Japanese Patent Publication No. 723, or compounds described in Japanese Patent Publication No. 12550/1983; inorganic hardeners such as chromium alum, chromium acetate, and zirconium sulfate. These can be arbitrarily
They can be used alone or in combination.

A compound that accelerates the hardening of gelatin can also be used in combination with the above-mentioned hardening agent. Examples of such curing accelerators include aprotic solvents described in West German Patent Publication No. 2.417.586, hetain type surfactants described in JP-A-5762045, tertiary amines or their salts (
For example, those described in Japanese Patent Application Publication Nos. 56-1043 and 51-9434, West German Patent (Publication) No. 2,138,305, British Patent No. 1,284,305, and British Patent No. 1,269,983) , various inorganic salts and polyhydric alcohols.

As the hydrophilic colloid constituting the undercoat layer and other layers constituting the photosensitive material of the present invention, gelatin (either lime-treated or acid-treated) can be used, but not only gelatin derivatives, For example, US Patent Box 2.
Gelatin derivatives made by the reaction of gelatin with aromatic sulfonyl chlorides, acid chlorides, acid anhydrides, isocyanates, 1,4-diketones, as described in US Pat. No. 614.928, US Pat. Gelatin derivatives prepared by the reaction of gelatin and trimellitic anhydride described in Japanese Patent Publication No. 118,766, 1973
Gelatin derivatives produced by the reaction of gelatin with an organic acid having an active halogen described in Japanese Patent Publication No. 5514,
Gelatin derivatives obtained by reacting aromatic glycidyl ether with gelatin as described in Japanese Patent No. 2-26845, maleimide, maleamic acid, unsaturated aliphatic diamide, etc. and gelatin as described in U.S. Pat. No. 3,186,846. Gelatin derivatives by reaction with British Patent No. 1,03
3. Sulfoalkylated gelatin described in US Pat. No. 3,189, polyoxyalkylene derivatives of gelatin described in US Pat. No. 3,312.553, etc.; Methacrylic acid, their esters with monohydric or polyhydric alcohols, as well as amides, acrylic (or methacrylic) nitrite, styrene and other vinyl monomers, alone or in combination, grafted onto gelatin; synthetic hydrophilic homopolymers containing monomers such as vinyl alcohol, N-vinylpyrrolidone, hydroxyalkyl (meth)acrylate, (meth)acrylamide, N-substituted (meth)acrylamide, etc., or copolymers of these with each other. , copolymers with (meth)acrylic acid esters, vinyl acetate, styrene, etc., copolymers of any of the above with maleic anhydride, maleamic acid, etc.; natural hydrophilic polymer substances other than gelatin, such as casein,
Agar, alginate polysaccharide, etc. can also be used alone or in combination.

The silver halide emulsion of the silver halide emulsion layer in the light-sensitive material of the present invention includes conventional halogenated silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used. Further, there are no restrictions on the grain size and grain size distribution of the silver halide grains, for example, silver chlorobromide or silver chloroiodobromide with a silver halide composition of 50 mol% or less of silver chloride, and a grain size of 0.1 to 1.0
The present invention can be preferably applied to emulsions having a grain size of 0.1 μm or less and a silver iodobromide containing 8 mol % or less of silver iodide.

The glass support used in the present invention is not particularly limited in its glass composition, but soda lime glass, soda lime aluminum glass, and the like are preferable.

Float glass, which is produced by slowly cooling molten glass on a molten tin tank, can also be used.

The light-sensitive material of the present invention has at least one silver halide emulsion layer and at least one non-photosensitive layer on a glass support, and at least one of the non-photosensitive layers comprises the glass support and the silver halide emulsion layer. It exists between layers, and in addition to the core layer, an appropriate layer such as a protective layer can be provided on the emulsion layer, if necessary.

Further, in the light-sensitive material of the present invention, a backing layer containing a light-absorbing dye can be provided on the surface opposite to the silver halide emulsion layer. The light absorbing dye can be selected from any dye, but preferably 680 to 850 nm.
A dye with maximum absorption is good.

Among the dyes contained in such a backing layer, particularly useful dyes are those of the following general formulas (IV-a) and (IV-a).
Examples include dyes represented by b).

General formula (IV-a) General formula (IV-b) In the formula, Y represents a sulfo group or a carboxy group.

R1, R11, R3, R4, R5 and R6 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and Zl and Zl each represent a substituted or unsubstituted benzo-fused ring or naphtho-fused ring. Shows the nonmetallic atomic groups necessary to form. However, R', R2, R3,
R', R', R6, Z' and Z2 represent groups which allow the dye molecule to have at least 3 acid groups. L
represents a substituted or unsubstituted methine group, and Xl represents an anion.

rll represents 2, 3 or 4, and n2 represents 1 or 2.

Specific examples of such dyes are shown below, but are not limited thereto.

6] (CHz)4 SO, θ (CH2)4 to SO3 7] 8] [■ 12] [■ 13] [■ 14] [■ 18] [■ 19] [■ 15] (IV-16) (IV-17) (IV-20) [■ 21] [■ 22] [■ 23] [■ 26] [■ 27] [■ 28] (TV-24) (IV-25) (IV-29) [■ 30] (IV-31) (IL-32) (IV-333 (C11□)4 03e (CH2) a 0J (C!1□).

SO, θ (CHz)i SO, to Can give a sensitive core.

In the silver halide emulsion used in the silver halide photographic material of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, use Research Disclosure.
e) It can be carried out based on the method described in No. 17643.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the art as antifoggants or stabilizers can be added.

The dyes represented by general formulas (IV-a) and (IV-b) can be used in a suitable solvent such as water, alcohol (e.g. methanol, ethanol, propatool, etc.), acetone, etc.
Alternatively, it is preferable to dissolve it in a mixed solvent of these and add it to the backing layer.

Two or more of these dyes can also be used in combination.

The specific amount of dye used varies depending on the purpose, but for boat fishing 10-3 g/m to Ig/m, especially 10-" g/m
The range of 0.5 to 0.5 g/nf is preferable.

In the light-sensitive material of the present invention, the silver halide grains used in the silver halide emulsion layer are
Or, during the growth process, at least one selected from cadmium salts, zinc chlorides, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts (including complex salts) is used. By adding metal ions to the inside of the particles and/or on the surface of the particles, these metal elements can be added to the interior of the particles and/or on the surface of the particles, and by placing them in a suitable reducing atmosphere, the reduction enhancement in the inside of the particles and/or on the surface of the particles can be achieved. The photographic emulsion layer and other hydrophilic colloid layers of the material can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

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

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

The photographic emulsion layer of the light-sensitive material of the present invention may contain polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, and urethane for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also include derivatives, urea derivatives, imidazole derivatives, and the like.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving writing properties, preventing the light-sensitive materials from sticking to each other, and the like.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention may include improved coating properties, antistatic properties, improved slipperiness, emulsion dispersion, prevention of adhesion, and photographic properties (promotion of development, hardening,
Various surfactants can be used for the purpose of improving (sensitization, etc.).

When coating the photosensitive material of the present invention, a thickener may be used to improve coating properties. Also, for things like hardeners, which are so reactive that if added to the coating solution in advance, they will gel before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

For the development of the light-sensitive material of the present invention, any known method can be used, including development using hydroquinone as a developing agent and a Lith developer (infectious developer) having a low concentration of sulfite ions.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 (Preparation of emulsion) Average grain size 0 consisting of 4 mol% silver iodide and 96 mol% silver bromide
．． After chemically sensitizing a 05 μm glue Tubmann type silver halide emulsion (containing 280 μg of hexachloroiridate potassium salt per 1 mole of silver) with sodium periosulfate, the compounds shown in Table 1 were added as sensitizing dyes. , Compound A having the following structure was added as an inhibitor, Compound B having the following structure was added as a development accelerator, and Compound C having the following structure was added as a hardening agent.

(Preparation of subbing liquid) Methanol and chrome bright pan as a hardening agent were added to an aqueous gelatin solution.

(Preparation of backing coating solution) A compound having the structure below was added as a binder to a mixed solvent of methanol and ethanol, and exemplified compound (IV-1) or (IV-14) was added as a light-absorbing dye at 780 nm.
The amount was added to give an optical density of 1.0 at a wavelength of .

(Preparation of sample) The above coating solution was applied to both sides of a glass support (hereinafter referred to as float glass) whose glass surface had been surface-treated with a tinnic chloride solution, and the presence or absence of an undercoat layer, which is a non-photosensitive layer, was measured. The photosensitive material samples Nos. 3 to 7 were prepared by coating as shown in 1.

However, when forming a subbing layer, the emulsion side surface was coated with a subbing liquid on the float glass, dried, and then an emulsion layer was coated on top of the subbing layer.

At that time, the undercoat layer was coated with a gelatin content of 1.0 g/%, the emulsion layer was coated with a gelatin content of 5.0 g/rd, and a silver content of 2.8 g/di.

For comparison, an emulsion layer was coated on a float glass support without a subbing layer, and photosensitive material sample N111. 2 was created.

Compound B lI C0OCzHs Compound C C(C1,SO□CH=CH2)4・3/4NH2(C
H2)2S(hK) The sample thus obtained was heated to 50°C.
Season the film at a relative temperature of 80% for 6 hours, then immerse it in the following developer solution-1 at 20°C for 5 minutes. While the emulsion film is wet, scratch the emulsion film with the tip of tweezers, then scratch the surface with your fingers. was rubbed to evaluate adhesion to glass.

In addition, these samples were wedge exposed using a xenon light source at 1/100,000 second through a Lasoten filter No. 88A (manufactured by Kodasoku), and processed as follows using developer-1 and fixer having the following composition. I did it. The results of measuring this developed sample using a Konica PD-65 (manufactured by Konica Corporation) densitometer were also investigated.

The results are also shown in Table-1.

<Development processing> Development 20℃ 5 minutes Fixing 20℃ 2 minutes Washing with water 20℃ 5 minutes Drying Natural drying <Developer-1> hydroquinone Monomethyl-p-aminophenol sulfate anhydrous sodium sulfite potassium hydroxide potassium bromide The voltage was set to 1000 mA with water.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) Sodium sulfite Sodium acetate trihydrate Borate Sodium citrate Dihydrate acetic acid (90% W/V aqueous solution) (Composition) Pure water (ion exchange water) Sulfuric acid (50% W/V aqueous solution) Aluminum sulfate g g 0g 0g 0.5g 20mj! 7g 6.5g g g 13.6g 7ml 4.7g (Aqueous solution with Aβ203 equivalent content of 8.1% W/W) 26
．． When using 5 g of fixer, the above composition A was dissolved in 500 ml of water in the order of composition A and composition 11 was used.

The pH of this fixer was about 4.3.

Table 3 grade evaluation: O: No problem, Δ: Scratches, ×: Film peeling occurs.

As can be seen from Table 1, the relative sensitivity for obtaining D=2.5 (Sample 1 is 100), the test slopes 3 to 7 of the present invention
has high sensitivity in the infrared region and good adhesion between the emulsion layer and glass.

Example 2 (Preparation of emulsion) Silver bromide 38 mol%, silver chloride 6
A silver halide emulsion of cubic crystal grains having an average grain size of 0.27 μm and a monodispersity of 9 was prepared.

During grain formation, 280 μg of hexachloroiridate potassium salt and 1 mol of silver per mol of silver were added during grain formation.
Contains 0 μg of potassium hexabromorodate salt. After chemical sensitization by adding sodium thiosulfate and chloroauric acid to this emulsion, the compounds shown in Table 2 were added as the sensitizing dye, 1-phenyl-5-mercaptotetrazole as the antifoggant, and 4-hydroxy- as the stabilizer. 6-methyl 1.3.3a, 7-titrazyden, as an inhibitor,
Hydroquinone, potassium bromide, Compound E shown below as a latex polymer, and Compound C described above as a hardening agent were added.

Compound E f (Preparation of subtraction liquid) A subtracting liquid similar to that in Example 1 was prepared.

(Preparation of banking coating liquid) A banking coating solution similar to that in Example 1 was prepared.

(Preparation of sample) The above coating liquid was applied to both sides of a glass support (hereinafter referred to as float glass) whose glass surface had been treated with a tinnic chloride solution, and the photosensitive materials 110 to 14 as shown in Table 2 were coated.
It was created.

In this sample, the emulsion side surface was formed by coating a subbing liquid on float glass, drying it, and then coating the emulsion layer on top of the subbing layer.

In this case, the amount of gelatin in the subbing layer is 1.0 g/rrr, the amount of gelatin in the emulsion layer is 5.0 g/rrf, and the amount of silver is 4. It was applied so that it was Og/ld.

For comparison, photosensitive materials 8 and 9 were prepared by coating an emulsion layer on a float glass support without providing a subbing layer.

The sample thus obtained was processed in exactly the same manner as in Example 1, except that it was developed for 3.5 minutes at 20°C using the following developer-2 as a development processing solution, and evaluated in exactly the same manner. did. The results are shown in Table-2.

(Developer-2) Hydroquinone 20g Potassium sulfite 5g Sodium ethylenediaminetetraacetate 1g Potassium carbonate
35g sodium carbonate
15g potassium bromide
3g5-nitroindazole 4
■Triethylene glycol 30g Jetanolamine 20g Formalin sodium bisulfite adduct 50g Polyethylene glycol (average molecular TL 500) 0.2g 1 with water
β and I)H was adjusted to 10.2 with sodium hydroxide.

As shown in Margin Table 2 below, the sample size 8. does not have a subbing layer.
Sample No. 9 had sufficient sensitivity, but there was a problem with the adhesion between the emulsion layer and the glass. In contrast, the sample barrier 10 of the present invention
It can be seen that Samples No. 1 to 14 have high sensitivity in the infrared region and good adhesion between the emulsion and glass.

〔Effect of the invention〕

According to the present invention, a silver halide photographic material which has high sensitivity to infrared light and whose silver halide emulsion layer on a glass support does not peel off during development can be obtained.

Claims (1)

[Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive layer on a glass support, at least one of the non-photosensitive layers is formed on a glass support. and the silver halide emulsion layer, and in at least one of the silver halide emulsion layers, a dye arbitrarily selected from the group consisting of tricarbocyanine dyes and dicarbocyanine dyes containing a 4-quinoline nucleus. A silver halide photographic material containing at least one kind of dye.