JPH0414033A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness, film strength, and curl balance by incorporatng a specified amount of hydrophilic colloid or less and a specified amount of solid disperse dye or less in a hydrophilic colloidal layer between a support and an emulsion layer. CONSTITUTION:This pyhotosensitive material is provided between the transpar ent support and the photosensitive layer the hydrophilic colloidal layer(B) containing at least one kind of solid disperse dye(A), such as a compound of formula I, in a coating amount of <= 0.50 g hydrophilic colloid ( gelatin)/m<2> of B in an A/B weight ratio of <= 0.4, and a hydrophilic colloidal layer containing at least one kind of a water-soluble hydrophilic colloid is formed on the reverse side of the support. It is preferred to use a coating amount of the total hydrophilic colloids of <=3.0g/m<2> in the side of the emulsion layer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic material containing a dyed hydrophilic colloid layer, which is photochemically inert and easily decolorized during the photographic processing process. The present invention relates to a silver halogenide photographic light-sensitive material having a hydrophilic colloid layer containing a dye which is eluted and/or a hydrophilic colloid layer.

(Prior Art) In silver halide photographic materials, the photographic emulsion N or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light that should be incident on the photographic emulsion layer, coloring is applied to the light incident surface (exposure surface) side (usually the side far from the support) of the photographic emulsion layer on the photographic light-sensitive material. layers are provided. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, the filter layer may be located between them.

Light that is scattered when passing through or encountering a photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enters the photographic emulsion layer again. Based on this (for the purpose of preventing blurring of the surface image, that is, halation/condensation, between the photographic emulsion layer and the support,
Alternatively, a colored layer is provided on the side of the support opposite to the photographic emulsion layer. Such colored ffII is called an antihalation layer. In the case of a multilayer color photosensitive material, an antihalation layer may be placed between each layer.

Furthermore, in X-ray photosensitive materials, a colored layer is sometimes provided to improve sharpness and serve as a loss-over cut filter to reduce crossover light.

Due to the scattering of light in the photographic emulsion layer (decreased image sharpness (this phenomenon is generally called irradiation))
In order to prevent this, the photographic emulsion layer is also colored.

These materials to be colored often consist of hydrophilic colloids and therefore dyes are usually included in the layer for their coloring. It is necessary for this dye to satisfy the following conditions.

(1) Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. Do not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as reduced sensitivity, latent image regression, or capri.

(3) Although it is decolored during the photographic processing process, it is dissolved and removed and does not leave any harmful coloring on the photographic material after processing.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and a large number of dyes have been proposed.

However, some of these dyes have little effect on the photographic emulsion itself (although they may cause spectrally sensitized emulsions to become spectral sensitized in unnecessary areas or cause sensitizing dyes to be desorbed). It has the disadvantage of causing a decrease in sensitivity, which is thought to be due to a decrease in sensitivity.

On the other hand, when the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion, those layers are selectively colored and the other layers are It is usually required that the shield be substantially free from staining. This is because, if not, the effect of the filter and antihalation layer will not only decrease (but also cause harmful spectral effects on other layers). There are several methods for selectively coloring a water-rupturing colloid layer. One of these methods is to coexist a hydrophilic polymer containing a moiety with a charge opposite to that of the dye ion as a mordant in the hydrophilic colloid layer. Many methods are used to localize dyes in specific layers by interaction with molecules (think of charged attraction and hydrophobic bonding).

However, when using the mordant method, when the dyed layer and another hydrocolloid layer come into wet contact, it often happens that some of the dye diffuses from the #1 layer to the latter. Diffusion of such a dye naturally depends on the chemical structure of the mordant, but also on the chemical structure of the dye used.

Further, when a polymeric mordant is used, residual coloring is particularly likely to occur on the light-sensitive material after photographic processing, especially photographic processing in which processing time is shortened. This is because although the binding force of the mordant to the dye becomes considerably weaker in an alkaline solution such as a developer, some binding force still remains, so the dye or reversible decolorization product is absorbed into the layer containing the mordant. This is thought to be because it remains in the .

Other means for fixing dyes in specific layers in photographic materials are disclosed in JP-A No. 2432-2432 and Ibid. j-/! 63j
O, same! Yo-/j13j1, same! --P27/, number 3-/ri7rihiro 3, number 4J-27131,
No. 441-440127, Yo o Tsuba special Eθθ/!
tO/BI issue, 027bu! It is known to have dyes present in dispersed solid form, as disclosed in International Application Publication No. 4A/2008 and International Publication No. RT7ODA7R≠. According to this method, in a photographic light-sensitive material, in which conventionally all water-soluble dyes are provided on the opposite side of the support to the silver halide emulsion layer, it is possible to immediately adjoin the silver halide emulsion layer without causing any adverse effects as described above. Let me give you Halley/Con prevention effect money, picture jM
There are cases where you can totally improve.

However, providing a new layer as an antihalation layer is not necessarily desirable from the viewpoint of rapid processing, which has been in increasing demand in recent years. As a means to avoid this, reducing the amount of hydrophilic colloid in the solid dispersed dye layer and increasing the ratio of solid dispersed dye to hydrophilic colloid has the disadvantage that the film strength, especially in a wet state during processing, decreases significantly. Furthermore, if the dye layer placed on the opposite side of the support is placed on the side of the entire silver halide emulsion layer, there is a drawback that curl balance cannot necessarily be maintained.

Furthermore, the silver halide light-sensitive material gold film is protected by a safelight that facilitates handling of the tube after being exposed and processed. It is desirable to simultaneously satisfy requirements such as ensuring complete ease of use.

(Problem to be Solved by the Invention!) The first object of the present invention is to provide a silver halide photographic material with excellent sharpness.

A second object of the present invention is to provide a silver halide photographic material with excellent film strength.

Is the third object of the present invention a silver halide photographic material with well-balanced curl? It is to provide.

A further object of the present invention is to provide a halogenated photographic material that is easy to handle under safelight.

(Means for solving the problem) As a result of intensive study by the present inventors, at least one silver halide emulsion layer is provided on the support, and at least one type of silver halide emulsion layer is provided between the support and the silver halide emulsion layer. at least one hydrophilic colloid layer containing a solid disperse dye charge; at least one hydrophilic colloid layer containing at least one water-soluble dye on the opposite side of the support to the silver halide emulsion; In the silver halide photographic material containing the solid disperse dye, the coating process of the hydrophilic colloid in the hydrophilic colloid layer containing the solid disperse dye is O9j.
A silver halide photographic light-sensitive material having an area of 97 m2 or less and a weight ratio of solid disperse dye to hydrophilic colloid of Q,4/- or less.

It has been found that the above object can be achieved by the following method.

The dye used in the present invention is covered by International Patent W○8810479.
Tables ■ to Table X of No. 4, (I) to (■) shown below, and others are used.

General formula (I) General formula (VT) General formula (■) A=C-(CH=CH+□Q General formula (n) General formula (I[I) A=L, -(L2=L3).-A ' General formula (rV) A = (L, -R2)2-, =B General formula (V) (In the formula, A and A' may be the same or different, each represents an acidic nucleus, and B represents a base X and Y may be the same or different, and each represents an electron-withdrawing group.R
represents a hydrogen atom or an alkyl group, R1 and R2 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R1 and R2 may be linked to form a 5- or 6-membered ring.

R5 and R8 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom, and R4 and R5 each represent a hydrogen atom, or R1 and R4 or R2 and R5 are linked to form a 5- or 6-membered ring. Table 1 shows the nonmetallic atomic groups necessary to form t. L, , L, and R3 each represent a methine group.

m represents O or 1, n and q each represent 0.1 or 2, p represents 0 or 1, and when p or 0, R3 represents a hydroxy group or a carboxyl group, and R1 and R5 represent hydrogen represents an atom. B' represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group.

Q represents a heterocyclic group.

However, the compound represented by the general formula (I) or ■) is
Each molecule has at least one dissociable group having a pKa in the range of 4 to 11 in a mixed solution of water and ethanol at a volume ratio of 1:1. ) First, general formula (I) or ■
) will be explained in detail.

The acidic nucleus represented by A or A' is preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbylic acid, thiobarbylic acid, indandione, pyrazolo Represents pyridine or hydroxypyridone.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, henzoxazole, naphthoxazole or pyrrole.

Examples of heterocycles of B' include pyrrole, indole,
Thiophene, furan, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiane,
phenoxazine, indoline, thiazole, pyridine,
These include pyridazine, thianazine, pyran, thiopyran, oxadiazole, henzoquinolidine, thiadiazole, pyrrolothiazole, pyrrolopyridazine, and tetrazole.

The heterocycle represented by Q is preferably a 5-membered heterocycle which may be benzo-fused, more preferably a 5-membered nitrogen-containing heterocycle which may be benzo-fused. Q
Examples of heterocycles include pyrrole, indole, pyrazole, pyrazolopyrimidone, benzindole, and the like.

A group having a dissociable proton with a pKa (acid dissociation constant) in the range of 4 to 11 in a mixed solution with a volume ratio of water and ethanol of 1:1 makes the dye molecule substantially water-insoluble at pH 6 or below. There is no particular restriction on the type and substitution position on the dye molecule as long as it makes the dye molecule substantially water-soluble at pH 8 or above, but preferably a carboxyl group, a sulfamoyl group, a sulfonamide group, A hydroxy group is preferred, and a carboxyl group is more preferred. The dissociative group may be substituted not only directly on the dye molecule, but also via a divalent linking group (eg, alkylene group, phenylene group). Examples of 2(iEr via a linking group include 4-carboxyphenyl, 2-
Methyl-3-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfamoylphenylmoylphenyl, 2-carboxyphenyl , 2.

4,6-1-lyhydroxyphenyl, 3-pensenesulfonamidophenyl, 4-(p-cyamibensenesulfonamito)phenyl, 3-hydroxyphenyl, 2-hydroquinphenyl, 4-hydroxyphenyl, 2-hydroquine -4-carboxyphenyl, 3-methoquino-4-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxydibenzyl, 2-carboxydibenzyl, 3-sulfamoylphenyl, 4-sulfamoylphenyl Examples include huamoylphenyl, 2,5-nsulfamoylphenyl, carboxymethyl, 2-carboxyethyl, 3-galboxypropyl, 4-carboxybutyl, 8-carboxyoctyl, and the like.

R,R. Or the alkyl group represented by R8 has 1 to 1 carbon atoms.
10 alkyl groups are preferred, and examples include groups such as methyl, ethyl, n-propyl, isoamyl, n-octyl and the like.

The alkyl group represented by R1 and R2 is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-brobyl, n
-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferred, and substituents [e.g., halogen atoms such as chlorine bromine, nitro group, cyan group, hydroquine group, carboxy group, alkokyne group (e.g., methquine, ethquine ), alkoxycarbonyl groups (e.g., methquine carbonyl, i-propoxycarbonyl), aryloxy groups (e.g., fenoquine group), phenyl groups, amide groups (e.g., acetylamino, methanesulfonamide), carbamoyl groups (e.g., methyl carbamoyl,
ethylcarbamoyl), sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The aryl group represented by R1 or R2 is preferably a phenyl group or a naphthyl group, and the substituents include the above R
The substituents of the alkyl groups represented by 1 and R2 include the groups and alkyl groups (eg, methyl, ethyl). ].

The acyl group represented by R1 or R2 is preferably an acyl group having 2 to 10 carbon atoms, and includes, for example, acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl, benzoyl, and the like. R1 or R
Examples of the alkylsulfonyl group or arylsulfonyl group represented by 2 include groups such as methanesulfonyl, nitanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, pencenesulfonyl, p-toluenesulfonyl, 〇-carboxybenzenesulfonyl, etc. I can do it.

The alkoxy group represented by R3 or R has 1-1 carbon atoms.
0 alkoxy groups are preferred, and examples include groups such as methquine, nidoxy, n-butoxy, n-octoxy, 2-ethylhexyloquine, isobutquine, and impropoxy. Examples of the halogen atom represented by R3 or R6 include chlorine, bromine, and fluorine.

R. and R, or R2 and R, for example, a julolysine ring can be mentioned.

R. Examples of the 5- or 6-membered ring formed by linking R2 and R2 include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by L, , L2 or L3 may have a substituent (eg methyl, ethyl, cyano, phenyl, chlorine atom, hydroquinpropyl).

The electron-withdrawing groups represented by X or Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, such as acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, ■-oxo-7-taloloheptyl), arylcarbonyl group (arylcarbonyl group that may be substituted, such as benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl)
, alkoxycarbonyl group (an alkoxycarbonyl group that may be substituted, such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxysulfonyl, denruoxy carbonyl, todenoloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butquinethoxycarbonyl, 2-
Methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl, 2-[2(2-chloroethoxy)ethoxy]ethoxycarbonyl), aryloxycarbonyl group (optionally substituted aryloxy is a carbonyl group,
For example, phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-fluorophenoquinecarbonyl, 4-nitrophenoquinecarbonyl, 4-methoxyphenoxycarbonyl, 2,4
-di(t-amyl)phenoxycarbonyl), carbamoyl group (carbamoyl group that may be substituted, such as carbamoyl group ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4
-chlorophenylcarbamoyl, 4-ethquincarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl,
3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-cy(t-amyl)phenylcarbamoyl, 2-chloro-3-(dodecyloxycarbamoyl)phenylcarbamoyl, 3(hexyloxycarbonyl)phenylcarbamoyl) , a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), a sulfamoyl group (a sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl).

Next, specific examples of dyes used in the present invention will be given.

I-6 ■ ■-12 ■ ■-14 ■-15 ■-10 ■-11 ■ ■ ■-18 ■ OOH ShiUUi ■-20 I-21 ■-22 ■-25 ■ CH.

■-26 ■-27 ■-28 ■-34 ■ ■ h OOH H3 ■ ■ ■ ■ I[+-4 ■ ■ II-5 II-6 ■ ■ II[-9 Shii3 Shil'13 ■-10 NH5O□CH.

■ ■ ■ ll-16 ■-17 ■ ■ ■-13 ■-14 ■-15 OOH OOH ■ ■ ■ ■ Ul, ;2M1 ist, +u ■-24 ■ ■ OOH ■ CH.

CI(.

/ '-COOH ■ COCH.

C0CH.

'C0OH ■ 0OH COO)I ■ ■-28 OOH ■-29 CH.

■ ■ ■ CH.

CH.

OOH 0OH CH.

CH.

■-36 ShiHko C2H.

■ C2H.

OOH V-8 ■ C2H.

H3 ■ C2H.

V-12 OOH ■ I7 ■ ■ C2 old ■-15 C2Hi ■ H3 ■ ■ ■ CN , CN NH30□CH3 ■ ■ OOH H3 I-3 CN CN T-5 OOH C00H CH2COOH I-1 C OOH ■ OOH ■ ■ ■ OOH OOH OOH OOH ■-5 COOH The dye used in the present invention is covered by international patent W○8810479.
No. 4, European Patent EPO 274723A1, No. 2
No. 76.566, No. 299,435, JP-A-52-9
No. 2716, No. 55-155350, No. 55-155
No. 351, No. 61-205934, No. 48-6862
No. 3, U.S. Pat. No. 2,527,583, U.S. Pat. No. 3,486,897
No. 3746539, No. 3933798, No. 41
No. 30429, No. 4040841, Patent Application No. 1-508
No. 74, No. 1-103751, No. 1-307363, etc., and can be easily synthesized according to the method.

The present invention is not limited to the dyes shown above.

Due to the insufficient solubility of the solid dispersed dye in the present invention, the dye itself cannot exist in a molecular state in the intended colored layer, and as a solid of a size that is virtually impossible to diffuse in the layer. means the state of existence.

For details on the adjustment method, see International Application Publication (woBIr1017
7ri≠, Europe Press (BP) 0276tjjA/,
Time opening 98 A j / Tough 9 'I J etc. 1i
Although CNr3 is listed, it is preferable to use a method in which the dye is ground in a ball mill and stabilized with a surfactant and gelatin, or a method in which the dye is dissolved in an alkaline solution and then precipitated by lowering the pHt. However, the present invention is not limited to these adjustment methods.

Furthermore, depending on the spectral sensitivity range of the silver halide emulsion and the intended use of the light-sensitive material, it is possible to use a combination of two or more types of solid disperse dyes having different hues.

In addition, if necessary, not only between the support and the silver halide emulsion layer, but also within the silver halide emulsion layer to prevent other problems, such as silver halide emulsion j-
It can also be used as a safelight filter between the light source and the exposure light source, for example, in some cases, during protection.

In the present invention, the hydrophilic colloid used in I#k containing a solid dispersed dye between the support and the silver halide emulsion layer is generally 4 well-known in the field of photosensitive materials, such as gelatin, gelatin derivatives, polyester, etc. Among the materials that can be selected are vinyl alcohol, cellulose, m-powder and a-conductor, polyacrylamide, etc., and gelatin is particularly preferred. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin and the like can be used. Application of hydrophilic colloid in the solid disperse dye layer in the present invention f[o, ojg/m
2 or more and 0.60797m or less, particularly preferably nO, 1097m Di, upper o, log7m2
It is as follows. When the coating amount of water-breaking colloid is increased, layers such as the silver halide emulsion layer necessary to obtain a sufficiently high maximum density after development and the protective layer necessary to obtain film physical properties necessary for handling are removed. The total concentration of hydrophilic colloids contained in the colloid increases, and the suitability for rapid processing is lost.

The dye/hydrophilic colloid ratio (weight ratio) in the solid disperse dye layer is O1≠ or less, preferably 0.3 or less.

Is the total coating amount of hydrophilic colloid on the side of the silver halide emulsion layer the solid disperse dye-containing layer? Including j, preferably less than 0g/m2, preferably less than ji/m2.

In the present invention, since the coating amount of the hydrophilic colloid in the layer containing all the solid disperse dye is 0.5 Ofi/m2 or less, the average particle size is 3 μm or less, preferably 78 m2 or less. Even better is O0! It is less than μm.

The solid dispersion layer may be coated on a support coated with an undercoat, either alone or simultaneously with a silver halide emulsion layer, or as an overlay layer and then as an undercoat layer. Can be applied as part.

When coating as part of an undercoat layer, vinylidene chloride aqueous polymer latex, aqueous vinyl polymer latex, or aqueous polyester is coated and dried at high temperature as the first undercoat layer, and then a thin gelatin Aik is applied as the λ undercoat shield. It can be installed as a third undercoat.

Examples of the undercoat polymer used in the undercoat layer include polyvinyl chloride, vinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, and chlorinated rubber. , vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-imbutylene copolymer, vinyl chloride-
Vinylidene tetrachloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-7゛tadiene copolymer, vinyl chloride-imbrene copolymer , vinyl chloride
Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-dry vinyl terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer Union,
Vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, vinylisochloride/methacrylic acid ester copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride- Halogen-containing synthetic resins such as acrylic ester copolymer, chloroethyl vinyl ether-acrylic ester copolymer, polyvinylidene heptadide, polyethylene, polypropylene, polybutene, poly-
α-olefin copolymer with 3-methylbutene, ethylene-propylene copolymer, ethylene-propylene/
, goohexadiene co-M combination, ethylene-vinyl acetate copolymer, copolybutene-/-propylene, butadiene-
Polyolefins such as acrylonitrile copolymers, blends of these copolymers and halogen-containing resins, acrylic ester-acrylonitrile copolymers, acrylic ester-styrene copolymers, methacrylic ester-acrylonitrile copolymers, Methacrylic acid ester-styrene copolymer, polyalkyl acrylate,
(acrylic acid-butyl acrylate) copolymer, acrylic ester-butanene-styrene copolymer, methacrylic ester-7tazine-styrene copolymer, or d, weight ratio Otsu 7/23/7/3 Methyl methacrylate/ethyl acrylate/2-hydroxyethyl acrylate/methacrylic acid, weight ratio 72//7/7/3 of methyl methacrylate/ethyl acrylate/cohydroxide/
Ethyl acrylate/methacrylic acid, weight ratio 70/20
/7/J methyl methacrylate/ethyl acrylate/2
- Acrylic resins such as hydroxyethyl acrylate/methacrylic acid and methyl methacrylate/butyl acrylate/λ-hydroxyethyl acrylate/methacrylic acid polymers in a weight ratio of 7Q/20/7/3, or polystyrene, styrene, etc. and other monomers (e.g. maleic anhydride, getadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, or.

Polyacetal resin, polyhinyl alcohol, 71 products of these resins, block copolymers, graft copolymers, polyamide fat control, polyvinyl butyral, cellulose derivatives, polyester resins, polyhinyl alcohol 7", C TONOHI' -: Including lumi compounds, other polycarbonate, polyether, and other metal thread polymer compounds, natural rubber, butyl rubber, neorene rubber, styrene-phtadiene copolymer rubber, and other rubbers, or/recon rubber polyurethane, Natural or artificial rubber, polyamide, urethane elastomer, nylon-silicon resin, nitrocellulose-polyamide resin, acrylic thread, methacrylic thread, polyolefin thread, polyamide-based, polyester-based, polyurethane-based, polycarbonate-based, rubber thread, Cellulose resins, aqueous polyesters, blends of these resins, block copolymers, graft copolymers, etc. can also be used in combination.Particularly preferred polymers include styrene-butadiene copolymers and chloride copolymers. It is a vinylidene copolymer.

In order to prevent the deterioration of the dimensionally stable pillars caused by the support absorbing water during the development process in printing sensitive materials, it is desirable to use a hydrophobic polymer as the undercoat, and vinylidene chloride is preferably used.

The most preferred polymer form for the present invention is latex.

In the present invention, a hydrophilic colloid layer containing at least one type of water-soluble dye is formed on the opposite side of the support to the silver halide emulsion layer. Dyes that are decolorized or removed in each group during the treatment process are preferred, and the following dyes are known.
/77.1729, same/, 31/, 1141, same/, 331.7FF, same i, 3rz, 3'yi,
Same/, 1It7, 21 Hiro issue, Same/, 4t33.102
No., Same/, Evening! 3゜5/7+ issue, Tokukai Sho≠J'-16.
/No.30, same≠tar//4t, 4t+20, direction! 0-
/≠7.7 layer No. 2, same jj-/l/, No. 133, same! !
-/4A3.3≠λ issue, same! Tar 3r, 7 Hiroλ, same!
ter///, A4t/, sameyo tar tii, t4to
No., U.S. Patent No. 3.24t7,127, 4tA
Ri, Rit! No. 47.07Ir, No. 5'3J, etc. Oxonol dyes having saletavirazolone cores and barbylic acid groups, U.S. %W + No. 1,633,117λ, No. 3,37Ir, No. 533, UK! #Gth/, 27t.

Other oxonol dyes such as those described in No. 421, British Patent No.! 76, Ari No. 1, same tro, tJi No., same j
Tata, No. 623, 716. No. 07, direction θ7.12
No. 6, same/, 0 hiro, 71 oz, U.S. Patent No. 1. Koj
! , No. 326, JP-A-10-100. // issue, direction j'≠-/it,, 2≠7 issue, UK % total number -, 0/Hiroshi,
γ-dimetine dye described in J Riwo No. 760.03/etc. tl,j,7! Anthraquinone dye described in λ, U.S. Patent No. 2,131,002
No., J, try, rui, Mukai 2. ! 3! .

COx number, UK % liver number l≠, tori number, same/.

No. 210.252, JP-A No. 50-Hiro 0.626, same!
/-j, No. 123, same! /-70, Ri No. 27.

same! ≠−//1. -≠No. 7, Tokko Sho≠♂-3,2ff4
Arylidene dyes described in Japanese Patent Publication No. 21-J, No. 012, No. 1i7+-/
j, jP No. 44, same! Styryl dyes described in British Patent No. 9-21,191, etc., British Patent No. 3, 336. μ, No. 21, Tokukai Sho! 2 pieces, 2j
Triarylmethane dye described in No. o, etc., British Special Edition No. 1.07! , 4 layer No. 3, same/l/j3, 34t/no., same/, 21≠, 730, same/l≠7j, 22f,
Direction/lj≠2゜ Mello-7 aniine dye described in No. 107, etc., U.S. Jihyo No. 3111, 3.2 tada, j
Examples include cyanine dyes described in No. 3P and the like.

Among these, arylidene dyes having a pyrazolone nucleus and oxonol dyes having one pyrazolone nucleus are particularly preferred because they have the property of being decolorized in a developer containing a sulfite.

The water-soluble dye used here has an auxiliary purpose when the antihalation effect in the solid disperse dye layer cannot be sufficiently expressed, or the purpose of safelight safety,
Alternatively, it is used for the purpose of distinguishing front and back, and although there is no particular restriction on absorption characteristics, it is at least 100 m or more, preferably 200 m or more, than the wavelength showing the maximum spectral sensitivity of the silver halide emulsion layer. It is preferable that at least seven types of water-soluble dyes having absorption maxima at positions shifted from each other are included.

The hydrophilic colloid used in the shield containing a water-soluble dye located on the opposite side of the support to the logenated emulsion is similar to that in the solid disperse dye layer described above and is preferably gelatin. . In this case, there is no need to fix the water bath dyeing '#+ at a specific position. The required amount of hydrophilic colloid to be applied is determined from 0 to maintain curl balance (at the same time, from the viewpoint of dimensional stability, it is desirable not to apply too much, preferably Q, !&/m or more, λ).

527 m or less, particularly preferably 0,! fi/
m2 or more, and 0#/m2 or less.

The present invention is preferably applied to rapid processing photosensitive materials, and the processing time until drying is 10 seconds or less, preferably 4 (j
Less than a second is better. In this case, the developing time is 0 seconds or less, preferably 3 seconds to /! Seconds, more preferably 3 seconds to IO seconds.

The silver halide photographic material of the present invention has various uses and is not particularly limited, but it is preferably applied to a black and white silver halide photographic material, more preferably a high contrast silver halide photographic material for photolithography. Needless to say, it can also be applied to micro photography.

The silver halide grains used in the present invention have regular grains such as cubic and octahedral grains. Those with crystalline shapes, as well as those with irregular shapes such as spherical and plate shapes.
gular) 71 crystal form, or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystalline forms, but it is preferred to use regular crystalline forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase. Also, particles that form a latent image on the surface (
For example, it may be a negative-tone emulsion), or it may be an RJ sheet (for example, an internal latent image type emulsion, a pre-fogged direct reversal type emulsion) so as to be formed as a raw material inside the grain. Preferably, the particles are such that a latent image is formed as a pattern on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.05 mm.
A tabular grain emulsion in which grains having a diameter of microns or less, preferably 0.3 microns or less, preferably Bo, T, or more, and an average aspect ratio of 5 or more occupy 0% or more of the total projected area; A monodispersed emulsion with a statistical coefficient of variation (in the distribution expressed by the diameter when approximated to N circles on the projection plane, standard deviation S = i divided by diameter d @ S / d J is less than 0 is preferable) Further, tabular grain emulsions and monodisperse emulsions may be mixed together in amounts of more than 100 ml.

In a preferred embodiment, the average grain size of the silver halide in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly O1! It is preferably less than μ. There are basically no restrictions on the particle size distribution, but it is preferable that it be monodisperse.

The photographic emulsion used in the present invention is P.
, Glafkides), Chimie er Phys Photographic (Chimie er Phys.
ique Ph.

tographique) (published by Ballmontel, 1
967), C.F. Duffin
in), Photographic Emulsion Chemistry (Ph.

tographic Emulsion Chemises
try) (Focal Press, 1966), V.L.
Making an Coating Photographic Emulsion
dCoating Photographic Em
ulsion) (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, U.S. Pat. No. 628, No. 3,704,130, No. 4,297.439, No. 4,276.374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., using various synthetic hydrophilic polymeric materials such as single or copolymers. I can do it.

As for gelatin, in addition to the general-purpose lime-treated ceratin, acid-treated ceratin and the journal of the Japanese Society of Scientific Photography (Bull).

Soc, Sci, Phot, Japan), NCL
16.30 (1966) may be used, or a gelatin hydrolyzate may be used.

In the photosensitive material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or the hack layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-hydroxy-1,3
゜5-triazine and its sodium salt, etc.) and active vinyl compounds (1,3-bis-monylsulfonyl-2-
propatool, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether, or vinyl polymers with vinylsulfonyl groups in their side chains) can quickly harden hydrophilic colloids such as gelatin and produce stable photographs. It is preferable because it gives characteristics. N-
Carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.) and haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) also have a fast curing speed and are excellent. ing.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Nuclei such as thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc., in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine. Nuclei, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, hendithiazole nucleus, naphthothiazole nucleus, henzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
5- to 6-membered heterocyclic nuclei such as a 4-dione nucleus, a thiazolidic 2,4-dione nucleus, a rhodanine nucleus, and a thiobarbyl acid group can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbenzene compounds which are nitrogen-containing heteroartic ring nuclei groups and are substituted (for example, U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635.7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743.510), cadmium salts, asaindene compounds, and the like. U.S. Patent No. 3,615,613,
No. 615,641, No. 3,617,295, No. 3.6
The combinations described in No. 35.721 are particularly useful.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. Namely, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorohenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl 5-mercaptotetrazole), etc.; mercaptopyrimidines: mercaptotriazines; thioketo compounds such as oxadorinthion;
Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1°3.3a
, 7) tetraazaindenes), pentaazaindenes, etc.; adding a number of compounds known as antifoggants or stabilizers such as benzentiosulfonic acid, benzenesulfinic acid, pencenesulfonic acid amide, etc. be able to.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The photographic material prepared using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for various purposes such as anti-irradiation or anti-halation.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The present invention can be applied to multilayer, multicolor photographic materials having at least λ different spectral sensitivities on a support, but black and white photographic materials are preferred. When used as a multilayer natural color photographic material, the support usually has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of arrangement of these skins can be arbitrarily selected as necessary.

A preferred layer arrangement is, from the support side, a red-sensitive layer, an edge-sensitive layer and a blue-sensitive layer in that order, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order.

Any shredded emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity, or a three-layer structure may be used to further improve graininess. A non-light-sensitive layer may be present between one or more emulsion layers having only one color-sensitive gold. A structure may be adopted in which an emulsion J- having a different color sensitivity is inserted between certain emulsion layers having the same color sensitivity. A reflective layer such as a fine-grain halogenated iron may be provided under the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve sensitivity.

A cyan-forming coupler is added to the red g-sensitive emulsion layer, and green-sensitive milk Th1 is added.
Generally, the layer contains a magenta-forming coupler and the blue-sensitive emulsion contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, an infrared-sensitive layer may be combined for use in pseudo color 4-ray or semiconductor laser exposure.

In the uninvented photographic material, the photographic emulsion layer and other r-
C. It is applied to a flexible transparent support such as a plastic film commonly used in photographic materials, or a transparent rigid support such as glass. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose potassium torate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and the like. Preferred is polyethylene terephthalate. The support may be colored using dyes or glazes.

It is preferable that at least one of the constituent layers of the photosensitive material of the present invention has a surface resistivity of IOΩ or less in an atmosphere of λ60C and 2% RH.

That is, it is preferable that the photosensitive material of the present invention has all conductive layers.

As the conductive substance used in the conductive material used in the present invention, a conductive metal oxide, a conductive polymer compound, or the like is used.

Although crystalline metal oxide particles are preferred as the conductive metal oxide used in the present invention, those containing oxygen vacancies and containing a small amount of gold, a foreign atom that forms all of the donors for the metal oxide used. The latter are particularly preferred because they generally have high conductivity, and the latter are particularly preferred because they do not impart turnip IJ i to the silver halide emulsion. Examples of metal oxides include ZnO1Ti02, SnO2, Al2O3
, ■n203, S i 02 , MgOlBaO1M
o O3, v205, etc., or composite oxides thereof are preferable, and ZnO1T i O2 and S n 02 are particularly preferable.

As an example containing a different type of atom, for example, for Zn0K, A
Adding I, In, etc., adding only Sb, Nb, halogen elements, etc. to 5n02, and adding Nb, etc. to TiO2.
Addition of Ta, etc. is effective. The amount of these foreign atoms added is preferably in the range of 0.0/mol% to 30mol%, and particularly preferably in the range of o,Imol-10mol%.

The metal oxide fine particles used in the present invention have a conductivity tW, and have a volume resistivity id of 1070-Cm or less, especially 1
050-cm or less is preferable.

These oxides are described in JP-A-Kokai Sho Tough/Ko 3≠37, TX-i+2ori, and Jza-t16≠7.

Furthermore, Tokko Showaday T23! It is also possible to use a conductive material in which the above gold jIi oxide is attached to other crystalline metal oxide particles or fibrous materials (eg, titanium oxide) as described in the above-mentioned issue.

The available particle size f-I is preferably 10μ or less, but
When it is λμ or less, the stability after dispersion is good and it is easy to use. In addition, in order to minimize light scattering, O0! It is very preferable to use conductive particles of μ or less in size because it is possible to form a transparent photosensitive material.

When the conductive material is acicular or fibrous, the length is preferably 30 μm or less and the diameter is λμ or less, and particularly preferably the length is 2 μm or less and the diameter is 0.5 μm or less. jμ or less, and the length/diameter ratio is 3 or more.

Examples of the conductive metal oxide used in the present invention include polyvinylbenzenesulfonic acid salts, polyvinylbenzyltrimethylammonium chloride, US Pat.
, No. 101, 102, Mukai≠.

//! , 23/issue, same! , /, 21! +, ≠ No. 67,
Same ≠, /37, 2/7 No. 2/7, grade salt water baths US #! f permit number≠, 070. /I number, 0LS2, ff
jQ, No. 747, JP-A/-29t3!2, No. 7/
Polymer latex described in No.-62033 and the like is preferred.

Specific examples of the four utility pole polymer compounds used in the present invention are shown below, but the invention is not necessarily limited thereto.

/ CH3 +CH2-C し0ONa C) (3 CH3 P-g CH2-(,:)i+ 0ONa (-C-CH20 CH3 in the binder for the conductive metal oxide or conductive polymer compound used in the present invention) It is used by dispersing or dissolving it in

The binder is not particularly limited as long as it has film-forming ability, but examples include gelatin,
Proteins such as casein, cellulose compounds such as carboxymethylcellulose, hydroxy7ethylcellulose, acetylcellulose, diacetylcellulose, triacetylcellulose, dextran, agar, alginate,
Saccharides such as starch derivatives, polyvinyl alcohol, polyvinyl acetate, polyacrylic ester, polymethacrylic ester, polystyrene, polyacrylamide, poly-N
-vinylpyrrolidone, polyester, polyvinyl 1i,
Examples include synthetic polymers such as polyacrylic acid.

%, gelatin (lime-treated gelatin, acid-treated gelatin,
Preferred are enzymatically decomposed gelatin, pentatalated gelatin, acetylated gelatin, etc.), acetylcellulose, diacetylcellulose, triacetylcellulose, polyvinyl acetate, polyvinyl alcohol, polybutyl acrylate, polyacrylamide, dextran, and the like.

Conductive metal oxide or conductive IIIt used in invention
In order to use the conductive polymer compound more effectively and lower the resistance of the conductive layer, it is preferable that the volume content of the conductive substance in the conductive layer is high, but in order to ensure that the layer has sufficient strength. Since a binder of at least about j% is required, it is desirable that the volume content of conductive metal oxides or conductive polymers (or arsenic compounds) be in the range of 1 to 1.

The amount of conductive metal oxide WJ or conductive polymer used in the present invention is preferably tL, <, especially 0.1 to λoz per square meter of photographic light-sensitive material.
10g is preferred. The surface resistivity of the conductive layer of the present invention is 26
0C2! %RH in an atmosphere of 10 12 ('') or less, preferably 10 11 Ω or less.

This provides excellent antistatic properties.

In the present invention, a small number of layers are provided as constituent layers of the photographic light-sensitive material. , a pack layer, an intermediate layer, an undercoat layer, etc., but two or more layers can be provided as necessary.

In the present invention, even better antistatic properties can be obtained by using a fluorine-containing surfactant in addition to the above-mentioned conductive substance.

The preferred fluorine-containing surfactant used in the present invention has a fluoro-alkyl group, alkenyl group, or aryl group having a carbon number of μ or more, and has an anionic group (sulfonic acid (salt), sulfuric acid (salt)) as an ionic group. , carboxylic acid (salt),
Phosphoric acid (salt)), cationic group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt,
Examples include surfactants having a phosphoammonium salt) or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group, or rubitan residue).

These fluorine-containing surfactants are disclosed in Japanese Patent Application Publication No. 10722, British Patent No. 1,330.3'jt, U.S. Patent No.
33jlko0/issue, 4(,j≠7゜301', British Special ffW, /,4'/7.P/', Japanese Patent Publication Show!j-/≠
Same as Tata 3! ! -/Pj144≠ issue, British Current Review No. 1
．． ≠32. ≠ No. 02, etc.

Some of these examples are listed below.

F-/CgF1□503K F-, 2 3H7 C8F, to 7802-CH2UOOK -J 3H7 CBF17SO2N+CH2CH2O+7”e CH2
The layer to which the SO3Na-containing fluorine surfactant is added is not particularly limited as long as it is at least one shield of the photographic light-sensitive material, and includes, for example, a surface protective layer, an emulsion layer, an intermediate layer, an undercoat layer, a back #, etc. be able to. Among them, the most preferable place to add it is surface retention! It may be added to either the emulsion layer side or the back layer side, but it is more preferable to add it to both surface protective layers.

When the surface protective layer consists of two or more layers, any of these layers may be used (or it may be used by further overcoating the surface protective layer).

The amount of the fluorine-containing surfactant to be used may be from o, oooi to /g per square meter of the photographic light-sensitive material, more preferably from o, oooi to 0.259, particularly preferably from 0.0003 to 0. It's .7g.

Further, one or more of them may be mixed with the fluorine-containing surfactant.

Next, another antistatic agent can be used in combination with the shield or other layer containing the fluorine-containing surfactant, and by doing so, a more preferable antistatic effect can be obtained.

4. For coating the true emulsion layer and other hydrophilic colloid layers, various known coating techniques such as dip coating, roller coating, curtain coating, and extrusion coating can be used. As necessary, the American Jihyo No. Koztl Kotada issue, the same No.-7 Otsu/7ri No. 7, the same No. 3!2t! Multiple layers may be coated simultaneously by the coating methods described in No. 1 and No. 310t≠7.

Although the present invention can be applied to various color and black-and-white photosensitive materials, black-and-white photographic light-sensitive materials are preferred, and various plate-making films such as lithographic film or scanner film, direct medical and indirect medical use, and industrial use. It can be applied to Xi film, posthumous negative black and white film, COM or normal micro film, etc., and is particularly preferably applied to each type of photolithography film.

When used in various photolithographic films, it is preferable to use a halogenated photolithographic material with high contrast.

In order to increase the contrast, a hydrazine derivative or a tetrathulium compound shown in (1) below can be used.

The human radine derivative used in the present invention is preferably a compound represented by the following formula (1).

-Momonana (AnkLl -N-N-Gt R2 A, A2 In the formula, R1 represents an aliphatic group or an aromatic group, and R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group) , amine group, hydrazino group, carbamoyl group or oxy/carbonyl group, GI H carbonyl group, sulfonyl group, sulfoxy group, O00 II II 11 -)'-4. -c-c- group, thiocarbonyl group or iminomethylene group, AI and A2 are both hydrogen atoms, or 10,000 hydrogen atoms and the other is a substituted or unsubstituted alkylsulfonyl group,
or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In general formula (I), the aliphatic group represented by R1 preferably has carbon atoms/~30, particularly carbon atoms/~30.
20 straight chain, 1 branched, 1 cyclic alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. In addition, this alkyl group is an aryl group,
It may have a substituent such as an alkoxy group, a sulfoquine group, a sulfonamide group, or a carbonamide group.

- The aromatic group represented by R1 in Monka (I) is a monocyclic or monocyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic ring or an aryl group of the A2 ring to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include an inquinoline ring, a penzimitazole ring, a thiazole ring, and a benzothianol ring, among which those containing a benzene ring are preferred.

Particularly preferred as FLl is an aryl group.

The aryl group or unsaturated heterocyclic group of R1 is substituted with Fl
Typical n substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, Aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxinecarbonyl group, aryloquine carbonyl group, acyl group, alkoxy Carbonyl group, aralkyl group, carbonamide group, sulfonamide group, carbonyl group, phosphoric acid amide group, diacylamino group, imide group, A2-NHCN-C- group L2, etc. are mentioned, and preferred substituents include straight chain, A branched and cyclic alkyl group (preferably one with a carbon number of 1 to 0), an aralkyl group (preferably a monocyclic or monocyclic one with an alkyl moiety having 1 to 3 carbon atoms), an alkoxy group (preferably one with a carbon number of 1 to 3), (with carbon number/-10), substituted amide 7 group (preferably substituted with an alkyl group having carbon number/~20)
group), anluamino group (preferably having carbon number λ~30), sulfonamide group (preferably having carbon number λ/~30),
0f), ureido group (preferably carbon number 1 to 3)
0f), phosphoric acid amide group (preferably carbon number/
~30).

- The alkyl group represented by R2 in the pattern hole (1) is preferably an alkyl group having 7 to ≠ carbon atoms, and 1
For example, halogen atom, cyano group, carbonyl group, sulfo group, alkokene group, phenyl group, acyl group, alkoxycarbonyl group, aryloquine carbonyl group, carbamoyl group, alkylsulfo group, arylsulfo group, sulfamoyl group, nitro group, AI having a substituent such as a heteroaromatic ring group, )t, -N- to -01- group
A2 may be used, and these groups may be substituted. Monocyclic or cocyclic aryl groups are preferred,
Examples include benzene rings. This aryl group may be substituted (examples of substituents are the same as for the argyl group).

As the alkoxy group, an alkoxy group having carbon number/~t is preferable, and may be substituted with a halogen atom, an aryl group, or the like.

The aralkyl group is preferably a monocyclic one, and examples of the single substituent include a halogen atom.

As an amine group, an unsubstituted amino group and a carbon number/~10
An alkylamino group and an aryl ε) group are preferred, and may be substituted with an alkyl group, a norogen atom, a cyano group, a nitro group, a carboxyne group, etc.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group or an arylcarbamoyl group having a carbon number of 10 to 10, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxyne group, or the like.

7 carbonyl group r y, number of carbon atoms /~/Q (7)
Flucoquine carbonyl group, aryloquine carbonyl group are preferred, alkyl group, halogen atom, cyan group,
It may be substituted with a nitro group or the like.

Among the groups represented by FL2, when G1 is a carbonyl group, preferred are a hydrogen atom, an argyl group (eg, a methyl group, a trifluoromethyl group).

3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (e.g., 0-hydroxybenzyl group, etc.),
Aryl group (e.g., phenyl group, 3.r-dichlorophenyl group, o-methanesulfonamidophenyl group, ≠-
(methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when Gl is a sulfonyl group, R2 is an alkyl group (e.g., methyl group), an aralkyl group (e.g., 0
-hydroxyphenylmethyl groups), aryl groups (e.g. phenyl groups, etc.) or substituted amino groups (e.g.
7 groups of dimethylamide, etc.) are preferred.

When G1 is a sulfo group, preferred R2 is a cyanobenzyl group, methylthiobenzyl group, etc., and G1 is -P.
- group, R2 is preferably a metquin group, an etquin group, a butquin group, a fenoquine group, or a phenyl group;
In particular, a phenoquine group is preferred.

When G] is N-* or an unsubstituted iminomethylene group,
Preferred R2 is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R2, the substituents listed for R1 can be applied.

As 01 of general formula (11), a carbonyl group is most preferable.

Alternatively, a cyclization reaction may be generated in which the R2iGl -2 part is split from the remaining molecules to generate a complete cyclic structure containing atoms of the Gl 2 part, and specifically, the general formula This can be expressed as (a).

General formula (a R3-Z.

In the formula, Z nucleophilically attacks 01 and GI R3
It is a group that can split the 21 part from the residual molecule, R3 is a hydrogen atom/slit from R2, Zl makes a nucleophilic attack on G, and a cyclic structure can be generated with Gl, Ru3, and Zl. It is something.

In more detail, the zli-Monkana (I) hydrazine compound becomes the next reaction intermediate through oxidation, etc. When formed, it easily undergoes a nucleophilic reaction with G1.

R1-N=N-Gl-R3-ZI R,-N=N is a group that can be split from ThGt, specifically HR4 (R4 is a hydrogen atom,
Alkyl group, aryl group, -cog5, and H-so
2R5, and R5 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), or a functional group that directly reacts with G, such as C0OR (here, O
H, SH, NHR4, -COOH may be temporarily protected to generate these funds by hydrolysis with alkali, etc. -R7 or -C-R6, CR6 (C6, R7 hydrogen atom, alkyl group, alkenyl group,
0 by reacting with nucleophiles such as hydroxyl ions and subsulfuric acid ions, such as aryl groups or heterocyclic groups)
It may be a functional group that is capable of reacting with 1.

Furthermore, the ring formed by G1, R3, and Zl is preferably j-membered or 6-membered.

- Monna (Among those represented by al, preferred are those represented by general formula (b) and (cl).

General formula (bl In the formula, R'b-4L'bt-! Hydrogen atom, alkyl group (
represents an alkenyl group (preferably one having a carbon number of - to /2), an aryl group (preferably one having a carbon number of A-/2), and may be the same or different. Good too. B may have a replacement fund! member circle change 2
Atoms necessary to complete all member rings, m and n are 0 or 7, and (n+mn is 7 or λ).

Formed by B! Examples of the member or t-membered ring include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

Z1μ-monana (synonymous with al).

- Monka (cl Lo3 10N←(ILo"Ro"+Zl p9 In the formula, RC1 and 几C2 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a rogen atom, etc.)
It can be the same or different.

Rc3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents O or /, and q represents /~μ.

1-Lo, Rc, and Ro Hzl bond to each other as long as the structure allows intramolecular nucleophilic attack on CI, and ff
It may be formed at i'.

Rcl and Rc2 are preferably a hydrogen atom, a hydrogen atom, or an alkyl group, and Rc is preferably an alkyl group or an aryl group.

Preferably, q represents /~3, when q is l, p represents O or /, when q is ko, p represents 0 or 7, when q is 3, p represents O or /, and q represents -Also when 3, R61,
几. ′ may be the same or different. Zli-Monka (a)
is synonymous with

A1. A2 is a hydrogen atom, an alkylsulfonyl group having 20 carbon atoms or less, and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group)) The sum of the substituent constants of Met is 10,! The sum of the substituent constants of a phenylsulfonyl group substituted as above), an acyl group (preferably a benzoyl group, or) having carbon z number ao or less, and Met is 10,! benzoyl groups substituted as above, or linear, branched, or cyclic unsubstituted and substituted aliphatic acyl groups (i
The iII substituent includes, for example, a rogen atom, an ether group, a sulfonamide group, a carphonamide group, a hydroxyl group, a carboxyne group, and a sulfonic acid group. )) AI, A2
The hydrogen atom is the most favorable.

- R1 or R2 of the pattern hole (1) may contain a pallast group or a polymer commonly used in immobile photographic additives such as couplers. The palaste group is a group that is relatively inert to photography and has a carbon number of more than 100%. You can choose. In addition, as a polymer, for example, JP-A-100330
The number includes those that have been transferred.

R1 or 1Rzi in the general formula (1) may have a group incorporated therein that enhances the N adsorption to the silver halide grain surface. Examples of such adsorption groups include FF groups made in the United States, such as thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups.

3zaj, /(: # issue, same, 4tt ri, 3da 7th issue, Tokukai Sho! ta/rij, 233, same! ta 200゜237, mukai j ta ioi, o≠! issue , same jter λ0/, 0hiro 6, same jter 20/, 0+L7, sameyo tar 2oi,
o<tr, same jF-20/, 0≠2, JP-A-6/-
/70,733, 6/-270, 74'4', 62-91AI, %i 1977-A7. ! Or issue, same +
x−+”z, the group described in zoi number, t2-1.7.!10 is opened.

In the present invention, the amount of the hydrazine derivative added is preferably from IJ/X/0 mol to XIQ-2 mol per 1 mol of halogenated, particularly in the range of /×10 mol'f (IJ/X/0 mol to 2XIO mol). This is a preferable amount of addition.

Specific examples of the tetrazolium compound used in the present invention are shown below, but the compounds that can be used in the present invention are not necessarily limited to these.

(1) λ-(Benzothiazol-λ-yl)-3-
Phenyl! -dodenru 2H-tetrazolium-bromide α1 αD λ13-nphenyl j-(4L-1-octyloxi/
phenyl)-JH-tetrazolium-chloride 2.3. ! - trino22ru, 2) 1-tetrazolium 2.3. j-tri(p-calhoki/ethylphenyl)-
λH-tetranolium 2-(benzothianol-1-yl)-3-phenyl-
3-
Diphenyl! -Methyl-JH-tetrazolium j-(p-hydroquinophenyl)-t-methyl-phenyl-2H-tetrazolium2.3-diphenyl-terethyl-λH-ftrazoliumλ,3-diphenyl! -n-hekinru λH-tetrazolium! -cyano2.3-diphenyl-2H-telo2t13) trazolium-co-yl-yo-phenyl-
3-(≠-trirun-2H-tetrazolium co(be/)thiazole-coyl)-ter(≠-chlorophenyl)-j-(+-nitro(1e aη gJ σ9 phenyl)-2H-tetra/lium !-Etquincarbonyl-2,3-di(3-nitrophenyl)-2H-tetrazolium!-acetyl-co,3-
di(p-ethoxyphenyl J-,2H-tetrazolium 2, j-diphenyl-j-(p-1lyl)-coH-tetrazolium!, j-diphenyl-3-(p-iodophenyl)-2
H-tetrazolium λ, 3-diphenyl-j-(p-diphenyl)-coH-
Tetrazolium! -(p-70mophenyl)-2-phenyl-3-
(co, 44.j-trichlorophenyl)-λH-tetrazolium ■ 3-(p-hydroquinophenyl I-j-(pnitrophenyl-1-phenyl-λ・Nmetoki/Phenirun-3-
(2-nitoki/phenyl)-2-(≠-methoxy/phenyl)-2H-tetrazolium nj-(4'-dianophenyl)-2,3-diphenyl-2H-tetrazolium c!31-2.3- di(t-methquinphenyl)-yo-
Nidrow-H-naphthoC/, 2-d J-/.

λ,3-Triazolium When the tetrazolium compound used in the present invention is used as a non-diffusible compound, a non-diffusible compound obtained by reacting an anion with a diffusible compound among the above-mentioned exemplified compounds is used.

The tetrazolium compound used in the present invention may be used alone or in combination.

It is preferable to use the tetrazolium compound used in the present invention in a range of 7.per mole of silver halide/×IO-ta×l0-2 mole.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal combustion lamps are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, fluorescent surfaces (CRT, fluorescent screens, etc.), liquid crystals (LCDs) emitted from fluorescent materials excited by electron beams, X-rays, etc.
and lanthanum-doped lead titanium zirconate (PL).
It is also possible to use an exposure means in which a linear or planar light source is combined with a micron Yatter array using gold (ZT), 7 and gold. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

For photographic processing of the light-sensitive material of the present invention, for example, research disclosure can be used.
Any of the known methods and known treatment liquids as described in No. e)/74, pages 21-30 (RD/77≠3) can be applied. This photo processing can be used to form a silver image (black and white photo processing) depending on the purpose.
, or a photographic process that forms a dye image (a color photographic process).The processing temperature is usually chosen between λO0C and jooc.

Known developing crude drugs can be added to the developer used in black-and-white photographic processing. Examples of developing crude drugs include dihydroquine benzenes (e.g. hydroquinone), 3-
Pyrazolidones (e.g. /-phenyl-3-pyrazolidone), aminoenols (e.g. N-methyl-p
-Aminone enol and the like can be used alone or in combination. The developer generally contains other known preservatives,
Contains alkaline agents, pH buffering agents, anti-capri agents, etc., and further contains solubilizing agents, color toning agents, development accelerators (e.g., grade salts, hydrazide/benzyl alcohol), surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners (eg, glutaraldehyde), viscosity-imparting agents, and the like.

As a development accelerator suitable for use in the present invention or as an accelerator for nucleating development, JP-A-3-77676, JP-A-37732, JP-A-37732, Ibid. 3-7.37/33, same t
In addition to the compounds disclosed in O-/4t0311Oq and fAO-/Hori No. 52, various compounds containing N or S atoms are effective.

The developing solution used in the present invention is disclosed in Japanese Patent Application Hei/-Kota Hiroshi lrj
The amino compounds described in the above can be used.

Furthermore, as described in U.S. Jihyohiro, λt, Takota issue, the development speed can be increased and the development time can be shortened by adding amines to the developer.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or anticapri agents such as bromides, iodides, and organic anti-capri agents (particularly preferably nitroindazoles or benzotriazoles). be able to.

If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, and film silver stain preventive agents may be added. (For example, λ-mercabutobenzimitasole sulfonic acids)? May include.

Preferably, thiosulfate, thio7a/chloride salts are used, and water-soluble aluminum salts such as acetic acid and dibasic acids (for example, tartaric acid, citric acid, etc.) or salts thereof may be included if necessary. good.

Examples of thiosulfate include sodium thiosulfate and ammonium thiosulfate, with ammonium thiosulfate being particularly preferred from the viewpoint of a constant N rate. Depending on the amount of fixing agent used, it generally ranges from about O0/l to about J mol/l.

In the present invention, the acidic hardener in the fixing solution includes a water-soluble aluminum salt, a chromium salt, and an ethylenediaminetetraacetic acid complex using a trivalent iron compound as an oxidizing agent. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate, and potassium alum.

Preferred addition amount ij 0, 01 mol - 0, + 2 mol/
1. More preferably 0. OJ~o, or mol/l.

As the aforementioned dibasic acid, tartaric acid or its derivatives, citric acid or its derivatives can be used alone or in combination of two or more kinds. Add fixer/l to these compounds.
Those containing more than 00 moles of Q per are effective, especially o,
Particularly effective is oi mol/l to 0.03 mol/l.

Specifically, tartaric acid, potassium tartrate, sodium tartrate IJ
Potassium hydrogen tartrate, sodium hydrogen tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, potassium aluminum tartrate,
Potassium antimonyl tartrate, sodium antimonyl tartrate, lithium hydrogen tartrate, lithium tartrate, magnesium hydrogen tartrate, potassium boron tartrate, potassium lithium tartrate, etc.

Examples of movable citric acid or its derivatives in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixer may optionally contain a preservative (e.g. sulfite, 1 fk#, salt) and a pHff1 buffer (e.g. acetic acid, boric acid).
, pn adjusters (eg, sulfuric acid), and chelating agents (described above). Here, the p of the developer is added to the pH buffer 4j.
Since H is high, lO~daOg/l, more preferably /l-
About λJ-g/l is used.

The fixing temperature and time are the same as for developing, approximately 20°
(~ Selected from about ro'c, less than 20 seconds, good IL <
flJ seconds to /j seconds.

According to the method of the invention, the developed and fixed photographic material is washed and dried. This is done to almost completely remove silver salts dissolved by washing with water and fixing, and the temperature is about 200C to about zo
0C″cz seconds to 20 seconds is preferable.Drying at about 200C to
The drying time will vary depending on the surrounding conditions, but it usually takes about 100 oz. Seconds to 0 seconds are best.

U.S. Special E No. 3 regarding roller conveyance type automatic processors.
0λ! , No. 77 Specification, No. 3,14tj, No. 7/Specification Homare, etc., and in the present specification, i is referred to as a roller conveyance type processor. A roller conveyance type processor consists of four steps: development, fixing, washing, and drying, and although the method of the present invention does not exclude other steps (for example, stopping power), it is most preferable to follow all of these four steps. .

The developing method of the present invention is particularly suitable for rapid processing using an automatic developing machine. As an automatic developing machine, a roller conveyance type, a belt conveyance type, or any other type can be used. Dry-t according to the invention during processing time.

- Dry for 60 seconds or less, preferably ≠! Adjusted to less than a second.

In the developing solution of the present invention, JP-A-2006-2012 is used as a silver stain preventive agent.
The compound described in ≠3≠7 can be used. As a solubilizing agent added to the developer, JP-A-4/-,! 477
Compounds described in item j can be used. Furthermore, as a pH buffering agent used in the developer,
Compounds described in JP-A No. 62-irt Co., Ltd. Compound * described in No. 6 can be used.

(Examples) Example 1 A first layer of undercoat of the following formulation - (1) and a second undercoat of formulation - (2) were sequentially applied to both sides of a biaxially stretched yl, 100μ polyethylene terephthalate support.

Formulation - ■ Lower layer 1 aqueous dispersion of polyvinylidene chloride/methyl methacrylate/acrylonitrile/methacrylic acid (PO/I////heavy rice ratio)
/! Inguinal area, 2. ≠-Ditalo-t-hydroxy7-ji-triazine 0. :2! Boristile/fine particles (average particle size 3μ) 0. Oration compound - ■ 0.20 Add water and io.

Further, a coating solution containing 70% KOH (770% by weight) and adjusted to pH=g was applied for 2 minutes at 0 degrees C/♂0'C to give a dry film thickness of 022μ.

Compound - ■ Compound - @ Prescription - ■ Undercoat second layer gelatin 7 parts by weight Methyl cellulose 0.0! Compound-■ 0.0coC1zHzsO(UH2CH20)10HOO3 Compound-■ 3.3×10' Vinegar @
0. Cut the water
io.

At this coating and drying temperature/700 Cλ minutes, the amount of gelatin was 0. /6fl/m2.

Compound-■ CH2C/! 1Il11K of the support obtained in this way,
A conductive layer and a backing layer according to the following formulation - (1) and 100% were coated.

Prescription-■ Conductive layer 5102/sb (ri71 weight ratio, average particle size 0.2jμ
) 300m97m2 gelatin
/70 Compound-■ 7 Dodenlebenzenesulfonic acid sodium salt i.

Dihexyl α-sulfosacunnate sodium salt ≠O Polystyrene sulfo/acid sodium salt formulation - ■ Back layer gelatin /, Ifi/m compound - ■
300-7 m2 compound-■
jO compound-of! O Compound - ■ 6 Sodium salt of totenlebenzenesulfonate jO Sodium salt of dibenzyl-α-sulfosacunnate IO /l+2-bis(vinylsulfonylacedo-]nitane 100 Ethyl acrylate latex (average particle size o, orμ) 300 Perfluorooctane sulfonic acid lithium salt 7 Silicon dioxide fine powder particles 3! (Average particle size≠μ, pore diameter/70A, surface area JOOm
27g) Further, the following coating was applied to the opposite side.

Compound - Compound - ■ Compound - ■ 300 g/m2 jOrn9/m2 so■7 rn 2 Emulsion A was prepared by the following method using the following solutions I and II.

■Tatsu, water ≦00xl gelatin/1g pH3.

■Liquid: AgNO32ooi Water 100ml11) Emulsion A
(Br1 mol% particle size 0.20μ uh/, 0X
10 mol 1 mol Ag) fJJA desire: KBr/, 1
19 NaC1769(NH4)3Rhα6≠■ Water 100% Solution 2 and Solution 2 were added to Solution 2 kept at 0C by simultaneous mixing on both sides for 20 minutes while maintaining a constant speed. After removing soluble salts from this emulsion using a conventional method well known in the art, gelatin was added to the emulsion without chemical ripening, and comethyl-≠-hydroquine-1,3, Ja was added as a stabilizer.
, 7-chitraasainden was attached to the blade. The average grain size of this emulsion was 0.20μ, the yield of the emulsion was 1k9, and the amount of gelatin contained was toy'''C.To this emulsion, gold≠×10 mol 17 ru A9 Toguchi Oki was prepared. .

After adding ultraviolet absorber (UV absorber) f100μ/m2, polyethyl acrylate latex was added in a solid content of 30wt to gelatin, and /,3-vinylsulfonyl-λ-propanol was added as a hardening agent. Machining, 2.197m Ag amount on polyethylene terephthalate film, gelatin / , /
The coating was applied to a total area of 197 m2, and the top layer was coated with yellow dye S03 to improve safelight safety, and a protective layer was coated with gelatin at a rate of 0.2.9/m2. A sample /-/ was created.

Furthermore, the compound ■■■ in the puncture layer of the prescription (■) was removed, and samples l-λ~/- were prepared in which the solid dispersion of the dye was completely added to the prescription (■) only in the second undercoat layer on the emulsion side as shown in Table 7. did.

The dye used was a solid dispersion that was dispersed in water together with a surfactant using a ball mill.

The amount of gelatin applied in the second undercoat layer is also listed in Table 1.

Further processing ■ Compounds in the punk layer @f100~/17
12, the compound ■■ was left as is, and the second undercoat layer was made in the same manner as shown in the table /-5, /-5, /
- Fully made.

In the samples /-j and /-4 of the present invention, it was easy to distinguish between the front and the back based on the difference in color in the same way as the comparative sample /-/ in a bright room.

In contrast, the comparison samples l-λ, /-3 had no noticeable difference in color between the front and back surfaces, making it difficult to distinguish between them.

Next, sample /-/~/-6 is attached to (a) a transparent or translucent base (b) snout 1
．． iil original (c) transparent or translucent pasting base (d) i1
4-point original (original made of photosensitive material for photo-reversing) exposed using a Dainippon Screen@P-407 ultra-high-pressure water scissor lamp 0 C-CHM-/oo o with a neutral density filter (ND filter) By adjusting the amount, each sample was exposed to the same number of seconds of exposure, and processed for 3r'ciλ seconds (Dry-t) using the following developing solution Affi and using a Fuji Photo Film ■ reverse automatic developing machine FG-31OPTS.

-Dry approx. 0 seconds) Seven lines of characters [lll1 Quality evaluation was performed. Note that Gft-F/ was used as a fixer.

Extracted character drawing 9! 50% of the halftone dot area is on the photosensitive lamp for return! JOA when properly exposed with a halftone dot area of 0%
It is a very good original drawing that reproduces the m-wide characters. On the other hand, an image *' that can only reproduce characters with a width of ijo μm or more when the same appropriate exposure is given to the image quality of / is an image of poor character quality, and the difference between j and / is official review 11I] A rank of '1'''Cμ to λ was provided. 3 or more is a practical level.

Hydroquinone 4'r, og monomethyl-p-aminophenol//2 sulfate 0. r9 Sodium hydroxide /♂, θ9 Potassium hydroxide
jr, op! -Sulfosalicylic acid
1fj, DJ boric acid
2j, 09 potassium sulfite /10
．． 09 Disodium ethylenediamine tetraltoate 41 i, o9 Potassium bromide j-methylbenztriazole n-butyl-jetanolamine Add water t, ogo o, t, g ir, og / 1 (p) l = / /, 4) As shown in Table 2, the coating sample of the present invention Hto
It is capable of rapid processing in seconds or less, and also exhibits excellent character extraction performance.

Table 2 Sample consideration /-/ Comparative example 1-Co/-3 /-≠ /-1 Present invention/-1 Extracted character image quality Bow 2.5 3, 5 3 +! 3, j 3.5 Scratch strength/≠og/Hiroshi79 Za2g Otsu! Next, the sample /-/~/-1 was completely immersed in the developer solution, and after 20 seconds, a load was applied to the sample with a sapphire needle having a diameter of 011 mm, and the film was scratched to check the film strength. The liquid temperature was 3t0C.

Although the samples of the present invention also have a decrease in membrane strength, samples /-3 and /-3, which have a large dye/gelatin ratio, show a significant decrease in membrane strength, regardless of the measurement volume.

As described above, it is clear that only the samples of the present invention have good cut-out character image quality and excellent front-back discrimination, and also do not cause a fatal decrease in film strength.

Example 2 Comparative sample λ-l The following first layer of undercoat and formulation were applied to both sides of a biaxially stretched floating bed 100μ polyethylene terephthalate support.
The second layer of undercoat (2) was applied in sequence.

Formulation - ■ First layer of undercoat Aqueous dispersion of copolymer of vinylidene chloride/methyl methacrylate/acrylonitrile/methacrylic acid (weight ratio: 0/I/////)
lj parts by weight 1 Hiro-dichloro-6-hydroxy-5-triazine 0.2! Boristilun particles (average particle size 3μ) o, or Compound - ■ 0.20 Add water 100 Furthermore, add 10% by weight of KOH to the blade, and dry the coating solution adjusted to pH -6 @ degree / 1r00Cλ The coating was applied in such a manner that the dry film thickness was Q and μ in 1 minute.

Compound-■ Cl2H2sO(CH2CH20)1oH Compound-■
3. ! ×10' acetic acid
Add 0.2 water to the blade i
o.

This coating solution was coated at a total drying temperature of 700C for 2 minutes so that gelatin violet was 0.10 g/rn2.

Compound ■ HO(-CO(CH2)4CONH(CH2)2N-(
CH2)2-NH-)4 H-HCIH2 C)-10H CHμ Compound-■ Prescription-■ Undercoat second layer gelatin methylcellulose compound-■ 7 parts by weight, Oj, 0+2 Treatment of the support thus obtained On the side of the
A conductive layer of ■, -■ and a backing N were applied.

Prescription 1 ■ Conductive layer 8n02/Sb (R/111 amount ratio, average particle size o, 2
1μ) JOO”S’/m2 gelatin
/70 Compound - ■ 7 Dodecylbenzenesulfonic acid sodium salt 10 Dihexyl-α-sulfosac 7nate sodium salt l/-O Polystyrene sulfonate sodium salt Formula - ■ Back layer gelatin / , 7 g / m2
Compound-@100''97m2 Compound-■ 100 Compound-■ io.

Compound-■ 6 Dodecylbenzene sulfo/acid Sodium salt ≠l Dibenzy-alpha-sulfosac 7-nate sodium salt l, λ-bis(vinyl sulfo) nyl acetamide) ethane ta 0 ethyl acrylate latex (Average particle size 0.02 μn 300 perfluorooctane sulfo Lithium acid salt 6 Silicon dioxide fine powder powder 3j (Average particle size≠μ, pore diameter/70 large, surface area 300m2/g) Furthermore, the following coating was applied to the opposite side.

Compound-■ 100■/m2 Compound-■ Compound-■ 100~/m2 10OIR9/m2 (Preparation of emulsion) K3 I rQ! 6 To(NH4) 3 RhcJs
A mixed aqueous solution of potassium iodide and potassium bromide and an aqueous solution of silver nitrate containing 1. ? -dihydroxy 3.6
- Vigorously stirred into an aqueous gelatin solution containing cythiaoctane and heated at 20C to l! It was added while controlling the pAg to be 7.7 per minute, containing O0j morti of silver iodide, and finally K 3 I rC/! 6 and (NH
4) Monodisperse cubic silver iodobromide containing 10 moles of 3 Rhc16 per mole of silver halide and having an average grain size of 0.27 μm was obtained. Using this silver iodobromide emulsion as a core, under the same precipitation environment as the first precipitation, the pAg of the solution was 7.
Potassium bromide aqueous solution and silver nitrate aqueous solution while controlling so that ≠! In addition, a monodisperse cubic core/Nel iodobromide emulsion (average silver iodide content 0.5 mol %) with an average grain size of O0λtμ was obtained. After washing with water and desalting, this emulsion contains 3 μ of sodium thiosulfate and 3 μ of chloroauric acid per mole of the emulsion. Chemical sensitization treatment was carried out by heating at 71O and 6!0C for 70 minutes, and a ≠-hydroxy-6methyl-/, 3,3a, 7-titrasaindene/% solution was used as a stabilizer.
FzJO■Tobaguchita.

Using this emulsion, a spectral sensitizing dye was added to 3-ethyl-co[3-ethyl-benzothiazolinylidene-methylidene]-s-[3-ethyl-l-methyl-thiazolinylidene-ethylidene)- Rhodanine iodide salt and ≠, ≠′
-bis(dinaphthoki7-pyrimidylamino)stilbe/-2,2-disulfonic acid disodium salt at 20 μm each per mole of silver halide was added as an anti-capri agent/-phenyl-! - Mercaptotetrazole at a ratio of 0119 per mole of silver, polyethyl acrylate latex as a plasticizer and a gelatin binder ratio, and Corbis (vinylsulfonylacetamido)ethane as a hardening agent at a ratio of /10/m2, on the support. silver 3
．． It was coated so that it was λg/m2. gelatin f3/,
It was Ig7m.

On top of this, as a protective layer, gelatin O//m and the following compound ■2/lrOm9/m are used as matte MI with a particle size of 3~
≠μ polymethyl memethacrylate 1,0Tn9/m2,
As an anti-fogging agent, NO IDOKINO//YO0■/m,
Sodium dodecylbenzenesulfonate IJ as a coating aid
A shield containing a fluorine-containing surfactant having the following structural formula (1) and a fluorine-containing surfactant having the following structural formula (2) was simultaneously coated and bound.

■Compared to C8F, 7802NCH2COOK3H7 @ SO3 Sample Coco Next, the dye compound in the back layer of sample λ-/■ Completely removed, and the compound l1l was added between the second undercoat on the emulsion layer side and the emulsion layer.
-100m9 of solid disperse dye dispersed with Jk ball mill
7 m, gelatin 0.2 &/m2 Corbis(vinylsulfonylacetamido)ethane as hardener ~/μO
A sample was prepared by adding a small amount of thickener to the antihalation layer.

Comparative sample λ-3 Dye compound ■■ in the back layer of sample λ-/ was removed, and compound 1-j was added between the second NI undercoat on the emulsion layer side and the emulsion layer.
, Ffl-2 in a volume mill, and Ill.
-j/00 m9/m, (F-Compound I
11-J F/20~/m, gelatin is 0. ! 9
/m, Corbis(vinylsulfonylacetamido)ethane f20~/m as a hardening agent.A dye layer with a small amount of thickener added thereto was installed to prepare sample 2-3.

Remove the dye compound ■ in pack 1 of sample kohiro sample λ-l,
A compound l1 is added between the first base coat on the emulsion j- side and the emulsion layer.
Dispersed in the same manner as 1-1, 1-3100 μ/m2, gelatin 0.6g7m2. A small amount of thickener was added to this, anti-halation, RT-set, and a protective layer of gelatin was added. ! The sample was reduced to fl/m as λ-day.

Sample code~λ-t Sample λ-3-2-4i was prepared in exactly the same manner except that the sample λ-≠ and the dye were changed as shown in Table 3.

Comparative Sample 2-7 Compound (■) was also removed from the back surface of the sample Korg to prepare sample λ-7, which contained no water-soluble dye.

The sample f A 3 j nm thus obtained was wedge-exposed with a He-Ne laser beam having an emission maximum, and a developer LD-7 manufactured by Fuji Photo Film ■ was used. LF-301 (manufactured by Fuji Photo Film Co., Ltd.) was used as a foot dressing, and LF-301 (manufactured by Fuji Photo Film Co., Ltd., processor) "Q-310P"
It was developed for 3t'c and to seconds at 'fS', fixed, washed with water, and dried. Dry-t.

-Dry processing time was about 0 seconds, but it was not completely dry compared to comparative sample λ-2, and its suitability for rapid processing was inferior.

Except for the sharpness of the image, λ-/ is slightly inferior.21~2-
7, the image quality was good with no significant difference observed.

In addition, each sample was placed under the green safelight of a 20W light bulb (Fuji safelight filter waste≠) at a distance of 3 m.
When the safety of Cephrite was examined by developing after standing for a minute, only sample 2-7, which did not contain a water-soluble dye, had a high fog density.

Next, sample λ-/~2-7 was immersed in the same developer, and after 20 seconds, a load was applied to a sapphire needle with a diameter of O1≠mm to check the strength of the scratched film.

The results are shown in the table. Among the comparative samples, Sample 2--Jt'X111, which had a high dye/gelatin ratio, caused a significant decrease in intensity.

As described above, the samples of the present invention had excellent suitability for rapid processing, excellent image quality, excellent film physical properties t-[L, and excellent handling properties.

sample Co/ One λ −Hiroshi one! (comparison) (non-invention) (comparison) Membrane strength 777g /62 ri3 /j.

14t/≠j Example 3 Sample of Example 2 λ-/~Co≠All After exposure in the same manner as in Example 2, using the same developer and fixer as in Example 2, Fuji Photo Film ■Processor manufactured by) 'Q-710
Developed with NH for 10 seconds using J10C. Dry-to-Dr
The processing time for y was about 30 seconds. Although Sample Guco-13 had poor drying, it was as dry as Sample Guco/-1 and was suitable for rapid processing.

Example 4 Sample≠-l On the back side of a support coated with the same undercoat as Sample Co/, on the same conductive layer as Sample-7, the compound of Sample Co/■fjO~/rn except that it was 2 was applied. The same bag/I was applied.

Furthermore, on the opposite side [1-j 601n9/rn
, gelatin 0.3! fl/m2 A small amount of thickener was added to this to make the coating amount of the antihalation layer and the sample λ-/lv emulsion layer 0%. The emulsion layer is the same except for
On top of this is a protective layer of gelatin O0≠? /m2
．． Compound ■-co dispersed in a ball mill according to International Application Publication No. rt7o≠7ri≠ was mixed at 100#/m2. Particle size 3~μμ
polymethyl methacrylate matting agent ftO~/m,
)・Idokimenl! 0rlk? /m2. Dode/rubenzene sulfonic acid sodium salt and Compound 1 were added and applied as a cleaning aid, and sample≠-7 was exploded.

Kawa-3 was applied on a support coated with the same undercoat as S/Blue/.
Solid disperse dye ioo■/m, gelatin O0r, li
' / m anti-nox layer 7 layers, on top of this, gelatin was added to the emulsion layer of sample J-/, and the gelatin total λ
, 0 rfl/m2 except that the emulsion layer was the same, and on top of this was a protective layer of gelatin 0. Ifrji/m
2■-2 Solid disperse dye i3omg/m2. Particle size 3~μμ
601/Mi/
m, No1 Hydroquinone/! 0~/m2 and all coating aids were added to prepare sample≠-2.

Sample Guco is from the U.S. Current Review, riO≠,! This is a comparative sample produced following the example of No. Otsu-j.

When all the exposures were carried out in the same manner as in Example 3, the sample was dried and skewered on a sample plate, but it was not dried on a sample plate, and rapid processing could not be performed.

1. When the sample Goo/, ≠ - was left in an atmosphere of 2!0 C O % RH, the result was 7 rats for the sample ≠ -7, but the emulsion had a large in-plane curl, making it difficult to handle. was there.

(Effects of the invention) According to the present invention, it is possible to obtain sharp and excellent image quality, excellent suitability for rapid processing without deteriorating film strength, and excellent handling properties such as safe light safety and curl size change. Materials are obtained.

AI applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 4゜ Target of correction “Detailed description of the invention” in the specification column 5゜ Contents of correction statement of statement "Detailed description of the invention" Please write down the section below. Correct as described.

In the chemical structural formula on page 29 l-30 2゜ name of invention Silver halide photographic material 3゜ person who makes corrections Relationship with the incident

Claims (6)

[Claims] (1) At least one silver halide emulsion layer on a transparent support, and at least one hydrophilic colloid containing at least one solid disperse dye between the support and the silver halide emulsion layer. A silver halide photographic material comprising at least one hydrophilic colloid layer containing at least one water-soluble dye on the opposite side of the support to the silver halide emulsion layer; A halogenated product characterized in that the coating amount of the hydrophilic colloid in the hydrophilic colloid layer contained is 0.50 g/m^2 or less, and the weight ratio of solid disperse dye to hydrophilic colloid is 0.4 or less. Silver photosensitive material. (2) A photographic processing method characterized in that the silver halide photographic light-sensitive material according to claim 1 is processed for 60 seconds or less. (3) In the silver halide photographic light-sensitive material set forth in claim 1, the total coating amount of hydrophilic colloid on the silver halide emulsion layer side is 3.0 g/m^2 or less. A silver halide photographic material according to Scope 1. (4) The maximum absorption wavelength of the water-soluble dye contained in the hydrophilic colloid layer on the opposite side of the support to the silver halide emulsion layer of the silver halide photographic light-sensitive material in claim 1 2. The silver halide photographic material according to claim 1, wherein the wavelength is at least 10 nm or more away from the maximum sensitivity wavelength of the silver emulsion layer. (5) In the silver halide photographic light-sensitive material according to claim 1, the total coating amount of hydrophilic colloid on the opposite side of the support to the silver halide emulsion layer is 0.5 g/m^2 or more
2.5/m^2, the silver halide photographic light-sensitive material according to claim 1. (6) The silver halide photographic light-sensitive material according to claim 1, characterized in that the silver halide photographic light-sensitive material according to claim 1 has a high contrast.