JPS588499B2 - Senriyouofukumushashinkankouzairiyou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material having a dyed hydrophilic colloid layer.

The present invention particularly relates to a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a dye that is easily decolorized and removed during photographic processing and a basic polymer.

In silver halide photographic materials, the photographic emulsion layer 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 incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

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, a filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer may be reflected at the interface between the emulsion layer and the support layer, or at the surface of the light-sensitive material opposite to the emulsion layer, and enter the photographic emulsion layer again. In order to prevent blurring of images, that is, halation, between the photographic emulsion layer and the support,
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer.

Such a colored layer is called an antihalation layer.

When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, an antihalation layer may be placed between the layers.

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

These layers to be colored are often composed of hydrophilic colloids, and therefore, for coloring them, a water-soluble dye is usually incorporated into the layer.

The dye used for this purpose must not only have appropriate spectral absorption characteristics depending on the purpose of use, but also satisfy the following conditions.

1) Photochemically inert.

In other words, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.

2) It should not be bleached or dissolved and removed during the photographic processing process, leaving no 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.

For example, British Patent No. 506,385, Special Publication No. 39-22
No. 069, No. 43-13168, JP-A No. 48-851
Oxonol dyes having a pyrazolone nucleus as described in U.S. Pat. No. 3,247,127;
Oxonol dye having a barbituric acid nucleus as described in US Pat. No. 6,53,905, U.S. Pat. No. 2,5
3 3,4 7 2, British Patent 1,2 7 8,6
Other oxonol dyes such as those described in French Patent No. 21, French Patent No. 1,401,588, British Patent No. 584,609, US Patent No. 3,540
, 8 8 7, 3,6 1 5,5 4 6, 3,687,670, French patent 1,3 5 0,31
Benzylidene (or cinnamylidene) pyrazolone dyes as described in U.S. Pat. No. 1, U.S. Pat.
, 6 2 2, 0 8 2, 3, 3 8 4, 4
8 7, 3,6 5 2, 2 8 3, British patent 1,0 7 5,6 5 3, Belgian patent 733,
styryl dyes as described in each specification of No. 124,
British Patent No. 1,075,653 (Tazushi general formula ■), British Patent No. 1,153,341, British Patent No. 1,153,341, British Patent No. 1,153,341, British Patent No. 1,153,341,
8 4,7 3 0, French patent 1,4 0 1,5
8 Merocyanine dye as described in No. 8 (of the general formula ■), U.S. Patent No. 2,8 4 3,4
Cyanine dyes such as those described in British Patent No. 86, No. 3,294,539, and British Patent No. 1,075,653 (only those of general formulas I and 2) are mentioned. It will be done.

Many of the dyes that are decolorized in the photographic processing process are those that are decolorized by sulfites (or acidic sulfites) contained in the processing solution or by alkaline conditions with them (for example, as described in British Patent No. 506,385). )

In conventional photographic processing, the dyes used to color the hydrophilic colloid layer of photosensitive materials include dyes that are decolorized during the development process as described above, and dyes that are completely or only incompletely decolorized during the photographic processing process. All have been used that can be easily eluted and removed from photosensitive materials.

The latter type of dye not only pollutes the living environment by coloring the photographic processing solution or washing water, but also has a negative effect on the shortened processing time that has been used in recent years to streamline photographic processing. It's inappropriate.

The dyes used in photosensitive materials used for such purposes are not only quickly and completely decolored during photographic processing such as development, but also the decolorized product is easily removed during subsequent processing, primarily during water washing. It must be easily eluted from the photosensitive material during the process, and must not cause recoloring on the photosensitive material during those processes, and preferably in the processing solution or washing water.

With conventionally known dyes, photographic processing is accelerated in all aspects, including the speed of decolorization during processes such as development, the rate of elution of decolorized products or undecolorized dyes during washing with water, and the irreversibility of decolorization. Very few are satisfied with their purpose.

On the other hand, if the colored layer is a single filter layer, or if it is an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. It is usually necessary to ensure that the

This is because, otherwise, not only the effect as a filter layer or an antihalation layer will be reduced, but also a harmful spectral effect will be exerted on other layers.

There are several methods for selectively coloring a specific hydrophilic colloid layer. The most frequently used method is to localize the dye in a particular layer by interaction with the dye molecules (considered as charge attraction and hydrophobic bonding).

Mordants include, for example, polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in British Patent No. 685,475, polyvinyl as described in British Patent No. 850,281. Products obtained by reaction of alkyl ketones with aminoguanidine, U.S. Patent 3,4 4 5,2
Polymers derived from 2-methyl-1-vinylimidazole as described in No. 31 are known.

When such polymer mordanting methods are used, when the dyed layer and another hydrocolloid layer come into wet contact, it often occurs that some of the dye diffuses from the former to the latter.

Such diffusion of the 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 as described above is used, residual coloring is particularly likely to occur on the photosensitive material after photographic processing, particularly after 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 remains in the layer containing the mordant. This is thought to be because.

These difficulties depend not only on the chemical structure of the mordant, but also on the chemical structure of the dye.

On the other hand, in order to introduce foglers, color mixing inhibitors, etc., hydrophobic colloids such as fatty acid esters, aromatic carboxylic acid esters, phosphoric acid aryl esters, aromatic ethers, etc. Even when an emulsified dispersion of an organic solvent is contained, coloring tends to remain on the processed photographic material.

This is because when the dye is contained in the layer in which such an emulsified dispersion exists or diffused from another layer, the emulsified dispersion occurs due to the affinity of the hydrophobic part in the dye molecular structure to the hydrophobic organic liquid. This is thought to be because some of the dye is incorporated into the particles or onto their surfaces and remains without being removed during the washing process or other steps.

Among various water-soluble dyes used for dyeing the hydrophilic colloid layer of photographic light-sensitive materials, oxonol dyes having pyrazolone nuclei, typified by the dye described in British Patent No. 506,385, can be used in developing solutions containing sulfites. It has been used as a useful dye because it is irreversibly decolored and has little adverse effect on the photographic properties of photographic emulsions.

However, the oxonol dye is not sufficiently mordanted by the basic polymer as described above, and diffusion of the dye from the layer containing the basic polymer to other layers occurs.

The first object of the present invention is to provide a silver halide photographic light-sensitive material in which a hydrophilic colloid layer is colored with a water-soluble dye that is irreversibly decolored during photographic processing and has no adverse effect on the photographic properties of the photographic emulsion. It is to provide.

A second object of the present invention is to provide a silver halide photographic material having a hydrophilic colloid layer in which only the hydrophilic colloid layer containing a basic polymer is sufficiently selectively dyed with a dye.

A third object of the present invention is that even if any of the hydrophilic colloid layers constituting the photosensitive material contains a basic polymer,
An object of the present invention is to provide a silver halide photographic material containing a dye in a hydrophilic colloid layer that does not leave any residual coloring after photographic processing.

These objects of the present invention are to provide a silver halide photosensitive material in which at least one hydrophilic colloid layer contains a basic polymer, and at least one hydrophilic colloid layer is substituted with an acylamino group having a sulfo group at the 3-position. is,
This is achieved by incorporating an oxonol dye consisting of two pyrazolone nuclei substituted at the 1st position by an aliphatic group or an aromatic group having at least one sulfo group.

Specifically, the dye used in the present invention has the following general formula (I).
It can be shown by

In the formula, X is an aliphatic group (preferably one having 2 to 5 carbon atoms)
; or an aromatic group (which may have a halogen atom, an alkyl group, etc. as a substituent), and Q represents an aliphatic group {for example, an alkyl group having 2 to 6 carbon atoms; a substituent other than a sulfo group (for example, , halogen, alkoxy, etc.) (the alkyl residue preferably has 2 carbon atoms)
~5): aralkyl group, etc.}, or aromatic group {
For example, monocyclic aromatic groups; substituents other than sulfo groups (e.g.
halogen atom, alkoxy, alkyl, aryloxy, etc.), where n is 0, 1
or 2, m represents 1 or 2, M represents a hydrogen atom, a cation such as an alkali metal, alkaline earth metal, ammonia, or an organic base, and L represents a methine chain.

However, oxonol dyes in which Q is an aliphatic group and X is a phenyl group (or may be a substituted phenyl group) are excluded.More preferably, the group represented by MO3S-X has a sulfo group and has 2 to 2 carbon atoms. 4 aliphatic groups (e.g.
■,1-dimethyl-1-sulfomethyl, 2-sulfoethyl, 1,1-dimethyl-2-sulfoethyl, ■,2-dimethyl-2-sulfoethyl, etc.), or a substituted phenyl group having a sulfo group at the 2-position (for example, 2 -sulfophenyl, 4-methyl-2-sulfophenyl, 4-chloro-2-
sulfophenyl, 4-bromo-2-sulfophenyl, etc.), and Q is preferably an alkyl group having 2 to 4 carbon atoms (
For example, ethyl, n-propyl, 2-methylethyl, n
-Butyl); Substituted alkyl group having 2 to 4 carbon atoms substituted with a substituent other than a sulfo group (e.g., 1-chloroethyl, 2-ethoxyethyl, 2-chloro-2-methylpropylene, etc.); Number of carbon atoms 7 to 10 aralkyl groups (e.g. benzyl, phenethyl, etc.); phenyl groups having substituents other than phenyl or sulfo groups (e.g. 2-chlorophenyl, 2-methylphenyl, 2,5-dichlorophenyl, 2-methoxyphenyl); (enyl, 4-phenoxyphenyl, etc.) is preferred; however, when X is a phenyl group (which may be a substituted phenyl group), Q is not an aliphatic group.

M is a hydrogen atom; alkali metals (sodium, potassium, etc.); alkaline earth metals (calcium, barium, etc.); ammonia; organic bases (triethylamine, pyridine, piperidine, morpholine, etc.) cations; A methine group is preferred, =L-(L
=L) The methine group structuring the methine chain represented by n- includes an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, isopropyl, etc.), a phenyl group, a benzyl group, a phenethyl group, or a halogen atom ( For example, chlorine atom, bromine atom, etc.) may be substituted.

The oxonol dye used in the present invention is characterized by having sulfo groups at the 1st and 3rd positions of the pyrazolone nucleus, and exhibits excellent mordanting and decolorizing properties.

Specific examples of the oxonol dyes used in the present invention are listed below.

However, the dyes of the present invention are not limited to these.

The oxonol dye represented by formula (I) has the following formula (n
) and the following formula (■a), (
■b). (■c), (■a) or (■e) and a base (such as triethylamine, pyridine,
It can be synthesized by condensation in the presence of an aliphatic or aromatic tertiary amine such as morpholine.

In the formula, Q, X, n, rn, and M have the same meanings as above, and Z represents a hydrogen atom, an alkyl group, an aralkyl group, a halogen atom, or a phenyl group.

A represents an anion (e.g., chloride, bromide, iodide, perchlorate, methylsulfate, ethylsulfate, p-toluenesulfonate, etc.), R
1 represents a methyl group or an ethyl group.

Typical specific examples of the compound of formula (■a) include malondialdehyde dianyl hydrochloride, glutacondialdehyde dianyl hydrochloride (or its mesomethyl substituted product), diphenylformamidine hydrochloride, etc. .

Further, as a typical example of the compound of formula (■c), 1
, 1,3.3-tetramethoxypropane, 1,1,3.
Examples include 3-tetramethoxy-2-methylpropane.

Furthermore, typical examples of the compounds of formulas (■d) and (■e) include their chlorides.

The synthesis of the dye of the present invention will be specifically explained below by giving some examples.

Synthesis Example 1 (Synthesis of Dye Example 1) 3-(3'-Sulfopropionylamino)-1-(γ-
Sulfopropyl)-5-virazolone 7.0 g, 1,1,
A mixture consisting of 2.4 g of 3,3-tetramethoxypropane, 40 ml of methanol, and 3.0 g of triethylamine was heated under reflux on a water bath for 3 hours.

Next, a methanol solution of 4.0 g of anhydrous potassium acetate 35
ml was added, refluxed for 20 minutes, and then cooled with water.

The precipitated dark red crystals were collected by filtration, washed with ethanol and acetone, and dried to obtain 5.1 g of dark red crystals.

The aqueous solution of this dye exhibited a red color and its maximum absorption wavelength was 405 nm.

Synthesis Example 2 (Synthesis of Dye Example 2) 3-(3'-sulfopropionylamine)-1-phenyl-5-pyrazolone 6.2 g, ethyl orthoformate 2.3
．． 40 ml of 91 methanol and triethylamine2.
A mixture consisting of 5 g was heated under reflux on a water bath for 4 hours.

Next, a methanol solution of 2.0 g of anhydrous potassium acetate 20
ml was added, refluxed for 20 minutes, and then cooled with water.

The precipitated yellow crystals were collected by filtration, washed with methanol and acetone, and dried to obtain 4.8 g of yellow crystals.

An aqueous solution of this dye exhibits a yellow color, and its maximum absorption wavelength is 4.
It was 10 nm.

Synthesis Example 3 (Synthesis of Dye Example 3) 3-(3'-sulfopyropionylamine)-1-(4'
-sulfophenyl)-5-pyrazolone 6.8g, 2,4
-Dinitrobenzenepyridinium hydrochloride 2.4.0 g of 1,1-ethylamine, 10 ml of methanol and N,
A mixture of 30 ml of N-dimethylformamide was added to 10-1
The mixture was stirred at 5°C for 4 hours.

The reaction solution turned blue with the reaction.

After that, 50ml of methanol solution of 4.0g of anhydrous potassium acetate
1 and then 100 ml of isopropanol to precipitate dark blue crystals.

The subblue crystals were collected by filtration, thoroughly washed with isopropanol, and dried to obtain 5.6 g of dark blue crystals.

An aqueous solution of this dye exhibits a blue color, and its maximum absorption wavelength is 6
It was 20 nm.

Synthesis Example 4 (Synthesis of Dye Example 4) 3-(3'-sulfopyropionylamino)-1-(3'
,5'-disulfophenyl)-5-pyrazolone9. 4
A mixture of 2.3 g of malondialdehyde dianyl hydrochloride, 60 ml of methanol, and 4.0 g of triethylamine was heated under reflux on a water bath for 3 hours.

Next, 50 methanol solution of 4.0 g of anhydrous potassium acetate
ml was added and refluxed for 5 minutes to precipitate dark red crystals.

The crystals were collected by filtration, thoroughly washed with ethanol and then acetone, and dried to obtain 7.1 g of the desired dye.

An aqueous solution of this dye exhibits a red color, and its maximum absorption wavelength is 5.
It was 25 nm.

Synthesis Example 5 (Synthesis of Dye Example 8) 3-(2'-sulfobenzamide)-1-(4'-monosulfophenyl)-5-pyrazolone 3.6 g, malondialdehyde dianyl hydrochloride 1.0 g, N, N-dimethylformamide 30ml, triethylamine 3.0g
The mixture was heated to reflux on a water bath for 3 hours.

Then, a methanol solution of 1.0 g of anhydrous potassium acetate
ml was added, refluxed for 5 minutes, and then cooled on ice.

The precipitated dark red crystals were collected by filtration, thoroughly washed with ethanol and then acetone, and dried to obtain 2.0 g of dark red crystals.

An aqueous solution of this dye exhibits a red color, and its maximum absorption wavelength is 5.
It was 24 nm.

Synthesis Example 6 (Synthesis of Dye Example 9) 10.2 g of 3-(2'-sulfobenzamide)-1-(4'-monosulfophenyl)-5-pyrazolone, 2.5 g of glutacondialdehyde dianyl hydrochloride, N,N - A mixture of 40 ml of dimethylformamide, 10 ml of methanol and 6.0 g of triethylamine was heated at 10-15°C for 4 hours.
Stir for hours.

Then, a methanol solution of 4,0 g of anhydrous potassium acetate
ml, stirred for 10 minutes, and then added 2 ml of isopropanol.
When 00 ml was added, dark blue crystals precipitated.

The crystals were collected by filtration, thoroughly washed with isopropanol, and dried to obtain 7.4 g of dark blue crystals.

An aqueous solution of this dye exhibits a blue color, and its maximum absorption wavelength is 6
It was 20 nm.

The pyrazolones represented by the general formula (II), which are the raw materials for the dye used in the present invention, are 3-amino-5-pyrazolones having a sulfo group at the 1-position represented by the general formula (■),
Cyclic sulfonic acid monocarboxylic acid anhydride represented by general formula (IVa or IVb) (hereinafter referred to as mixed acid anhydride)
and organic solvent {organic base (e.g. pyridine, N,N-
It can be synthesized in good yield by reacting in dimethylformamide, etc.), acetic acid, etc.).

In the formula, X, Q, M, and m represent the same symbols as in general formula (I), R, R1, and R2 represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, etc.), and R3 is hydrogen atom, halogen atom (e.g. chlor, brome, etc.)
, and l represents O or 1, respectively.

Specifically, among the above mixed acid anhydrides, general formula (IVa
) are described in "Chemical Abstracts" Vol. 46, p. 2576 (1952) and [But l. Chem. Soc. Jap. ”
41, 1394 (1698) and the aromatic mixed acid anhydride represented by the general formula (IVb) [J. Chem. Soc. (B) J, 45
4 (1971).

The above mixed acid anhydride and the 3-amino-5-pyrazolones represented by the general formula (■) were prepared in U.S. Patent No. 2,694
In the photographic light-sensitive material of the present invention synthesized according to the description in , 718, the dye can be introduced into the hydrophilic colloid layer by a conventional method.

That is, an aqueous solution of a dye at an appropriate concentration may be added to an aqueous solution of a hydrophilic colloid, and this solution may be coated on the support or other layers constituting the photographic material by a known method.

The amount of dye to be added to the hydrophilic colloid aqueous solution may be selected as appropriate depending on the purpose within the solubility range of the dye.

In general, it is practical to use a 0.5 to 3% aqueous solution of the dye so that the dye content per 1 m'' of area on the photosensitive material is 80 to 800 cm.

In the light-sensitive material of the present invention, it is advantageous to add the dye to the coating solution when coating the hydrophilic colloid layer containing the basic polymer, but it is advantageous to add the dye to the coating solution when coating the hydrophilic colloid layer containing the basic polymer. It may be added to any coating solution for the photosensitive layer.

In the latter case, the dye is preferably introduced into a layer as close as possible to the layer containing the basic polymer, preferably into an adjacent layer.

Even if a dye is introduced into a layer that does not contain a basic polymer, the dye will diffuse into the layer where the basic polymer is present and will be concentrated there, causing the layer containing the basic polymer to be selected in the finished photosensitive material. dyed.

The dye may be incorporated in more than one layer.

The hydrophilic colloid layer containing the basic polymer may be single or two or more, and the (or those) layers may be located above the photographic emulsion layer (farthest from the support), or between the plurality of photographic emulsions. It may be located either between the layers, if any, or between the photographic emulsion layer and the support.

The function of the layer selectively dyed by the presence of the basic polymer can be either a filter layer, an antihalation layer, or a layer with other purposes, depending on its location.

The photosensitive material of the present invention contains a basic polymer in at least one hydrophilic colloid layer.

Basic polymers are water-soluble polymers that have basic residues in their main chains or side chains and are compatible with gelatin. Basic hydrophilic polymers commonly used for mordanting can be used.

Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues, such as those described in British Patent No. 685,475;
Copolymers thereof as described in U.S. Pat. No. 2,839,401, British Patent No. 906;
Maleic anhydride copolymers or derivatives thereof as described in British Patent No. 850,283; polymers obtained by the reaction of polyvinyl alkyl ketones and aminoguanidine as described in British Patent No. 850,281;
A polymer having a 2-methylimidazole nucleus in a side chain as described in U.S. Pat. Addition polymer of bisacrylamide and secondary diamine or quaternary salt thereof, British Patent No. 765
, 520 and 766,202, ternary or quaternary polymers containing polyvinylpyridine or polyvinylquinoline, West German Patent Publication No. 1,914,361 and Same 1,9 1
Polymers such as those described in No. 4,362 can be used.

Hydrophilic colloids constituting the photosensitive material of the present invention include:
Not only gelatin (either lime-treated or acid-treated) but also gelatin derivatives such as U.S. Pat.
Gelatin derivatives made by the reaction of gelatin with aromatic sulfonyl chlorides, acid chlorides, acid anhydrides, isocyanates, 1,4-diketones, as described in 4.92s, U.S. Pat. Gelatin derivatives prepared by the reaction of gelatin and trimellitic anhydride described in No. 18,766, Japanese Patent Publication No. 39-55
Gelatin derivatives produced by the reaction of gelatin with an organic acid having an active halogen described in No. 14, 1973-26
Gelatin derivatives by reaction of aromatic glycidyl ether with gelatin as described in US Pat. No. 845, US Pat. No. 3,1
Gelatin derivatives obtained by reacting gelatin with maleimide, maleamic acid, unsaturated aliphatic diamide, etc. described in No. 8 6, 8 4 6, and sulfoalkyl described in British Patent No. 1,0 3 3, 1 8 9 gelatin, U.S. Patent 3,3 1 2,5 5
Polyoxyalkylene derivatives of gelatin described in No. 3; polymer grafted products of gelatin, such as acrylic acid, methacrylic acid, their esters with monohydric or polyhydric alcohols, and also amides, acrylic (or methacrylic) Gelatin made from nitrile, styrene and other vinyl monomers alone or in combination; synthetic hydrophilic polymeric substances such as vinyl alcohol, N-vinylpyrrolidone, hydroxyalkyl (meth)acrylate, (meth)acrylamide, N Homopolymers containing monomers such as substituted (meth)acrylamide or copolymers of these with each other, copolymers of these with (meth)acrylic esters, vinyl acetate, styrene, etc., any of the above with maleic anhydride Acids, copolymers with maleamic acid, etc.; natural hydrophilic polymeric substances other than gelatin, such as casein, agar, alginic acid, polysaccharides, etc., can also be used alone or in combination.

In order to dispose the hydrophilic colloid layer containing a dye or the hydrophilic colloid layer containing a basic polymer in the present invention, dip coating (including those using an air knife in combination),
A variety of coating methods can be used, such as curtain coating or extrusion coating (including, for example, the hopper method described in US Pat. No. 2,681,294).

U.S. Patent No. 2,7 6 1,7 9 1, U.S. Patent No. 2,9 4
It is also possible to use simultaneous coating of two or more layers by the method described in No. 1,898.

The support may be a glass plate made of glasses such as soda glass, potash glass, borosilicate glass, quartz glass, etc.; polyalkyl (meth)acrylate, polystyrene, polyvinyl chloride, partially formalized polyvinyl alcohol, polycarbonate or Films, papers, and baryta-coated papers made of synthetic polymers such as polyesters such as polyethylene terephthalate, polyamides such as nylon, or semi-synthetic polymers such as cellulose nitrate, cellulose acetate, and monocellulose acetate monobutyrate. Any of the transparent or opaque supports used in photographic elements may be used, such as paper coated with alpha-olefin polymers, synthetic paper such as polystyrene, ceramic, metal, and the like.

The dye-containing hydrophilic colloid layer of the present invention includes hydrophilic colloids, dyes, mordants, hardeners, coating aids,
It can contain additives with various functions to improve the quality of photographic materials, such as plasticizers, slipping agents, matting agents, emulsion polymerization latex, antistatic agents, ultraviolet absorbers, and antioxidants. .

These additives are discussed below. In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be hardened by adding a commonly used hardening agent.

Hardening agents include; for example, aldehydes, such as glyoxal as described in US Pat. N
- dimethylol urea, such as dimethylol hydantoin described in British Patent No. 676,628; dioxane derivatives,
For example, dihydroxydioxane described in U.S. Pat. No. 3,380,829, or
713; Compounds having an epoxy group, such as compounds described in U.S. Pat. No. 3,07,394, U.S. Pat. For example, U.S. Pat. No. 3,325,2
2,4-dichloro-6-hydroxy-1 described in No. 87
, 3,5-triazine; mucohalogen acids, such as mucochloric acid and mucobromic acid described in U.S. Pat. 7 2 6, 1 6
Bis(methanesulfonate ester) described in No. 2; sulfonyl compounds, such as bis(benzenesulfonyl chloride) described in U.S. Pat. No. 2,725,295; aziridine compounds, such as Japanese Patent Publication No. 3
3=compounds described in No. 4212 and No. 37-8790;
Divinyl sulfones, such as U.S. Pat.
Compounds such as those described in No. 9,871; compounds with reactive olefinic bonds, such as those described in German Patent No. 872,153;
Divinyl ketones, such as the compounds described in U.S. Pat.
2 5 5,0 0 0, 3,6 3 5,7.1
No. 8, British Patent No. 994,869, West German Patent No. 1,0
Compounds having an acryloyl group as described in US Pat. No. 90,427, etc.; alkylene bismaleimides described in US Pat. No. 2,992,109, etc.; US Pat. No. 3
, 103,437; carbodiimides described in U.S. Pat. No. 3,100,704; isoxazole derivatives, such as U.S. Pat. No. 3,321,313; , 3,5 4
Compound described in No. 3,292; Japanese Patent Publication No. 41-689
Carbamoyl chloride derivatives described in US Pat.
Compounds such as those described in No. 2550; inorganic hardeners such as chromium alum, chromium acetate, zirconium sulfate, and the like can be used alone or in combination.

In the photographic material of the present invention, various known surfactants may be added to the photographic emulsion layer and other hydrophilic colloid layers as coating aids, or for antistatic purposes, improving slipperiness, and other purposes.

For example, sabonin, polyethylene glycol, polyethylene glycol polypropylene glycol condensates as described in U.S. Pat. No. 3,294,540, U.S. Pat. No. 2,240,472 and U.S. Pat.
Nonionic surfactants such as polyalkylene glycol ethers, polyalkylene glycol esters, and polyalkylene glycolamides described in No. 3 1, 7 6 6; for example, alkyl carboxylates, alkyl sulfonates, and alkylbenzene sulfonates. acid salt, alkylnaphthanesulfonate, alkyl sulfate, N-acylated monoN-alkyl taurine described in U.S. Pat. No. 2,739,891, U.S. Pat.
3 5 9, 9 8 0, 2, 4 0 9, 9 3
No. 0, maleopimarate described in US Pat. No. 2,447,750, or US Patent No. 2,823,1
Anionic surfactants such as compounds described in British Patent No. 1,159,825, Japanese Patent Publication No. 40-378, Japanese Patent Publication No. 40-378, No. 48-43924, U.S. Patent No. 3,726
Amphoteric surfactants, such as the compounds described in , 683, may be used.

In the photosensitive material of the present invention, the hydrophilic colloid layer contains a slipping agent, such as U.S. Pat. No. 2,588,756,
Higher alcohol ester of higher fatty acid described in U.S. Patent No. 3,121,060, U.S. Patent No. 3,295,9
Casein described in No. 7 9, British Patent No. 1, 2 6 3
, 7 2 2, British Patent No. 1,313,384, U.S. Pat. No. 3,04 2,
522, 3, 489, 567, etc. may be included.

Dispersions of liquid paraffin and the like can also be used for this purpose.

In the photosensitive materials of the present invention, plasticizers are used in the photographic emulsion layer and other hydrophilic colloid layers, such as glycerin, diols described in U.S. Pat. No. 2,960,404, and U.S. Pat. No. 3,520. , 694, etc. may also be included.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of increasing dimensional stability.

For example, alkyl (meth)acrylates, alkoxy (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl acetate, acrylonitrile, olefinstyrene, etc. alone or in combination;
Alternatively, a polymer containing a combination of these and acrylic acid, α,β-unsaturated dicarboxylic acid, sulfoalkyl acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

As a specific example, U.S. Patent 2,376,00
5, 3,6 0 7, 2 9 0, 3,6 4
5,7 4 0, British Patent 1,1 8 6,6 9
No. 9, No. 1,307,373, U.S. Patent No. 3,06
2,6 7 No. 4, 2,7 3 9,1 3 7, 3,4 1 1,9 1 1, 3,4 8 8
, No. 708, No. 3,635,715, and No. 2,853,457.

In the photosensitive material of the present invention, the hydrophilic colloid layer contains a matting agent, such as silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, and British Patent No. 1. , 1 7 3, 1 8 1; inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; starch described in US Pat. No. 2, 3 2 2, 0 3 7; Belgian patent 625 , No. 451 or British Patent No. 981,19
Starch derivatives described in No. 8, Japanese Patent Publication No. 44-3643
Polyvinyl alcohol as described in Swiss Patent No. 330,
Polystyrene or polymethyl methacrylate as described in No. 158, U.S. Patent No. 3,079,25
Polyacrylonitrile as described in No. 7, U.S. Patent No. 3,0
22, 169, organic particles such as the polycarbonate described in No. 22, 169.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain ultraviolet absorbers such as compounds belonging to benzophenone, benzotriazole, thiazolidine, and the like.

These ultraviolet absorbers may be mordanted into specific layers in the same manner as dyes.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain brighteners such as stilbene, triazine, oxazole, or coumarin, and these may be water-soluble; Insoluble brighteners may also be used in the form of dispersions.

In addition to the water-soluble dye according to the present invention, other water-soluble dyes known so far may be used in the emulsion layer and other hydrophilic colloid layers of the light-sensitive material to the extent that the effects of the present invention are not substantially impaired. It may also contain a sex dye at the same time.

It is advantageous to use a combination of two or more dyes, especially when a single dye does not provide the desired spectral absorption properties.

Examples of dyes that can be used include JP-A-48-
No. 85130, JP-A-49-5125, U.S. Patent No. 3,
No. 247,127, No. 3,6 5 3,9 0 5,
2,5 3 3,4 7 2, 3,3 7 9,
Oxonol dye described in No. 5 3 3, British Patent No. 58
Examples include hemioxonol dyes described in No. 4,609, US Pat. No. 3,687,670, and French Patent No. 1,421,679.

Along with the dyes according to the invention, alkali-soluble pigments such as manganese dioxide, bleachable pigments such as colloidal silver can be included.

In the photosensitive material of the present invention, the hydrophilic colloid layer contains compounds that have the purpose of preventing color fogging in the case of a color photosensitive material or preventing color mixing between layers, such as alkylhydroquinones, dialkylhydroquinones, aryl-substituted hydroquinones, sulfonate, etc. substituted hydroquinones,
A polymer compound having a hydroquinone residue, a catechol derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid, and the like may optionally be included as a dispersion.

Specific series of compounds include British patents 5, 5, 7,
No. 750, No. 557,802; U.S. Patent No. 2, 3
3 6, 3 2 7, 2, 3 6 0, 2 9 0
No. 2,4 0 3,7 2 1, No. 2,7 2
8,6 5 9, 2,7 3 2,3 0 0,
2,7 3 5, 7 6 5, 2,4 1 8,
6 1 3, 2, 6 7 5, 3 1 4, 2
,7 1 0,8 0 1, 2,8 1 6,0
28, No. 2,360,290; French Patent No. 885,982; U.S. Patent No. 2,336,3
2 7, 2,4 0 3, 7 21; British Patent 1
, 1 3 3, 5 0 0; Special Publication No. 13496, Showa 43
No.; U.S. Patent No. 3,457,079; U.S. Patent No. 2,360,290, U.S. Patent No. 2,384,6
There is a compound described in No. 5 No. 8.

To introduce these compounds into the hydrophilic colloid layer,
For example, a method of dispersing in a hydrophilic colloid together with a high boiling point organic solvent such as an aliphatic ester, an aromatic carboxylic acid alkyl ester, an aromatic phosphate ester, an aromatic ether, a method of adding it to a hydrophilic colloid as an alkaline aqueous solution, etc. are used. be able to.

The silver halide photographic emulsion used in the light-sensitive material of the present invention can be prepared by various conventionally known methods so as to have properties suitable for the intended use of the light-sensitive material.

As the silver halide, any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, etc. may be used, and the content ratio of the halogen is not particularly limited.

Protective colloids used during the formation of silver halide precipitates include commonly used gelatin, acylated gelatin such as phthalated gelatin and succinylated gelatin, and grafted gelatin such as acrylamide and hydroxyalkyl (meth)acrylate. Gelatin derivatives such as gelatin; for example, from three monomers: acrylic acid (or methacrylic acid), acrylamide (or methacrylamide), and an amine derivative of any of them (for example, N-(dialkylaminoalkyl)-acrylamide) Synthetic polymers such as copolymers consisting of the following can be used alone or in combination.

A known method can be used to prepare the silver halide emulsion.

For example, C. E. K. “The Theo” by Mees.
ry of the Photographic Pr
3rd ed., 1966
．． MacMiltanCo. , New York
:P. Written by Grafkides” ChimiePhoto
ographique”2nd ed., 1957,
Photocinema Paul Monttl,
Paris: H. Frieser Edition” Die
Grundlagen der Photog
raphische prozesse mit Si
lberh-alogen iden”1 9 6
8, Akademische Verlaggese
I I Schaft, Frankfurt
-am-Main, Vol. 2, pages 609-674 and 735-743, etc., can be used.

Any of the acid method, neutral method, or ammonia method may be used, and the single jet method or double jet method (referred to as twin jet) may be used.
may also be used.

Berichteder Bunsenges
schaft fiir physikalische
Chem-ie, Band 67 (1963),
A so-called controlled double jet method, as described on page 349 et seq., can also be used if necessary.

Such a method is advantageous in obtaining emulsions with extremely narrow grain size distribution.

The shape of the silver halide grains may be cubic, octahedral, tetradecahedral when they coexist, various twin crystals, or a mixture thereof.

The silver halide emulsion may be coarse-grained or fine-grained, and the average value (number average measured by projection method) of the grain diameter or edge length (or equivalent value indicating grain size) is less than 0.2 μm. , 0.2 to 1 μm or more than 11 μm.

The particle size distribution (particle size indicates the meaning as described above) may be narrow or wide.

The silver halide emulsion may or may not be physically ripened.

After the emulsion is precipitated or physically ripened, soluble salts are usually removed, and even if the long-known Nudel water washing method is used, inorganic salts containing polyvalent anions (for example, ammonium sulfate) cannot be removed. , anionic surfactants, polystyrene sulfonic acid and other anionic polymers, or flocculation methods using gelatin derivatives such as aliphatic mono- or aromatic mono-acylated gelatin may also be used.

Silver halide emulsions that are not chemically sensitized (so-called unripened emulsions) can be used, but they may also be chemically sensitized.

As a method of chemical sensitization, the method described by Mees and Graf
ki des 1 or by Frieser (ed.)
The method described in the book and various other known methods can be used.

i.e. sulfur-containing compounds capable of reacting with silver ions, such as thiosulfates, or US Pat.
4 No. 4, No. 2,278,947, 2,4 1 0,
6 8 No. 9, 3, 1 8 9, 4 5 No. 8, 3, 5
No. 01,313, French patent 2,0 5 9,2 4
Sulfur sensitization using compounds such as those described in U.S. Pat. Patent No. 2,5 1 8, 6 9 8,
No. 2,521,925, 2,5 2 1,9 2 6, 2,4 1 9,9 7 3, 2,4 1 9,9
Amines described in No. 7 5, U.S. Patent No. 2,9
iminoaminomethanesulfinic acid described in US Pat. No. 8 3,6 10, silane compounds described in US Pat.
The H. W. W
Reduction sensitization method such as the method of ood; US Patent 2, 3
Gold sensitization method using gold complex salts or gold thiosulfate complexes described in No. 99,083; US Pat. No. 2,444
8,0 6 0, 2,5 4 0,0 8 6,
2,5 6 6,2 4 5, 2,5 6 6,
The sensitization method using salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium described in No. 263 can be used alone or in combination.

The selenium sensitization method described in US Pat. No. 3,297,446 can also be used in place of or in conjunction with the sulfur sensitization method.

The photographic emulsion used in the light-sensitive material of the present invention may be spectrally sensitized to long-wave blue light, green light, red light or infrared light using a sensitizing dye.

As the sensitizing dye, any one belonging to cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

The dye belonging to cyanine may have any heterocyclic ring such as pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, or pyridine as a basic nucleus.

These nuclei have substituents such as alkyl groups, alkylene groups, hydroxyalkyl groups, carboxyalkyl groups, sulfoalkyl groups, aminoalkyl groups, alkoxyalkyl groups, sulfohydroxyalkyl groups, and sulfoalkoxyalkyl groups. You may.

In addition, these nuclei include unsubstituted or halogen atoms, alkyl groups, alkoxy groups, hydroxy groups, cyano groups, carboxy groups, alkoxycarbonyl groups, alkylamino groups, dialkylamino groups, acylamino groups, phenyl groups,
Alternatively, a hydrocarbon ring substituted with a fluoroalkyl group or such a heteroartic ring may be fused.

Cyanine dyes may be symmetrical or asymmetrical, and the methine and polymethine chains may be substituted with alkyl groups, phenyl groups, substituted phenyl groups such as carboxyphenyl groups, isophorone nuclei, or heterocyclic nuclei.

Merocyanine pigment has two basic nuclei as mentioned above and two acidic nuclei.
- Those having an acidic nucleus such as thioxazolidinedione, rhodanine, thiohydantoin, valpituric acid, and thiovalpituric acid can be used.

The acidic nucleus may be substituted with an alkyl group, an alkylene group, a phenyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group, an alkoxyalkyl group, an acylamino group, a heterocyclic nucleus, or the like.

These sensitizing dyes may be used singly or in combination.

A large number of combinations of sensitizing dyes are known for the purpose of supersensitization.

Along with sensitizing dyes, substances that exhibit supersensitizing effects without substantially absorbing visible light, such as U.S. Pat.
, 3 9 No. 0, 3, 5 1 1, 6 6 4 No. 3,
6 1 5, 6 1 3, 3, 6 1 5, 6 3
Compounds having a pyridinylamino group or triazinylamino group as described in Nos. 2, 3, 6 1 5, 6 4 1, etc., aromatic organic acid-formaldehyde condensates described in British Patent No. 1,137,580, Azaindenes or cadmium salts may be included in the emulsion.

In the photographic material of the present invention, the photographic emulsion contains manufacturing steps,
Prevents fogging during storage or development of photosensitive materials,
Alternatively, various compounds may be included for the purpose of stabilizing photographic performance.

That is, azoles such as benztriazole,
Benzthiazolium salts as described in U.S. Pat. No. 2,13 1,0 3 8, U.S. Pat.
Nitroazoles such as nitroindazole, nitrobenztriazole, nitrobenzimidazole as described in British Patent No. 403,789, U.S. Patent No. 2,324,12
Nitroaminobenzimidazole etc. described in No. 3;
Halogen-substituted azoles, such as 5-chlorobenzimidazole, 5-bromoimidazole, or 6-chlorobenzimidazole; mercaptoazoles, such as the mercaptothiazole derivatives described in U.S. Pat. No. 2,824,001 , mercaptobenzthiazole, derivatives described in U.S. Pat. No. 2,697,099, mercaptoimidazole derivatives described in U.S. Pat. No. 3,252,799, mercaptobenzimidazole, U.S. Pat. Mercaptooxadiazole described in No. 491, U.S. Patent No. 1
, 758, 576, phenylmercaptotetrazole described in U.S. Pat. No. 2,403,927, etc.; U.S. Pat.
, 304,962; mercaptotriazines as described in U.S. Patent No. 2,476,536; British Patent No. 3,2226,2
Mercaptotetrazaindene as described in No. 31; thiosalicylic acid as described in U.S. Patent No. 2,377,375; thiobenzoic acid as described in British Patent No. 3,226,231; Sugar mercaptal described in No. 47-8743 and various other mercapto compounds; US Patent No. 3
, 251, 691, triazolothiadiazole described in Japanese Patent Publication No. 17932/1984, and the like can be added.

Also, azaindene compounds, such as tetrazaindenes, such as U.S. Pat.
9 No. 7, Special Publication No. 39-10166, No. 42-10
Compounds described in No. 516, etc.: Bentazaindenes, such as compounds described in U.S. Pat. A nitrogen-containing heteroartic ring compound having an antifogging effect such as urazol described in No. 1 can be added.

Also, benzenesulfinic acid and benzenethiosulfonic acid described in U.S. Pat.
etc. can be added.

Also, U.S. Patent No. 2,691,588, British Patent No. 623,
No. 488, Special Publication No. 43-4941, No. 43-1349
Various chelating agents described in No. 6 can be added.

In the light-sensitive material of the present invention, the photographic emulsion layer or other hydrophilic colloid layer is provided for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, in U.S. Pat.
1,389; ethers, esters, and amides of polyalkylene oxides as described in U.S. Pat. No. 2,708,161;
British Patent No. 1, 1 4 5, 1 8 6, Special Publication No. 1973-
No. 10989, No. 45-15188, No. 46-434
Other polyalkylene oxide derivatives described in US Pat. No. 35, No. 47-8106, and US Pat. No. 47-8742; U.S. Pat.
up to No. 135, or Special Publication No. 45-9019,
The thioether compound described in No. 47-11119,
Thiomorpholinic acid described in Japanese Patent Publication No. 47-28325; Pyrrolidine etc. described in Japanese Patent Publication No. 45-27037; Urethane or urea derivatives described in Japanese Patent Publication No. 40-23465; Imidazole derivatives described in Japanese Patent Publication No. 47-45541 Polymers such as those described in Japanese Patent Publication No. 45-26471; 3-pyrazolidones described in Japanese Patent Publication No. 45-27670 may also be included.

An inorganic or organic mercury compound may be added to the photographic emulsion in the light-sensitive material of the invention for the purpose of sensitization or fog prevention.

For example, the mercury complex salts described in U.S. Pat. No. 2,728,664; the benzthiazole mercury salts described in U.S. Pat. No. 2,728,667;
, 7 2 8, 6 6 3, 2,7 3 2,3
Mercury salt addition compounds described in U.S. Pat. No. 02; for example, U.S. Pat.
The organic mercury compounds described in No. 6 No. 8, etc. can be used in the photographic emulsion of the light-sensitive material of the present invention, which has a particularly small silver halide grain size (or a value equivalent to it) (0.
(less than 4 μm or less than 0.2 μm), as a sensitizer, for example, British Patent No. 1,316,493, British Patent No. 1,317,138
No. 1,317,139, No. 1,317,709, No. 1,297,901, West German Patent Publication No. 2,2 3
Compounds described in No. 5,031 can be added.

In the photographic material of the present invention, the photographic emulsion layer may contain a commonly used non-diffusive color image-forming coupler.

A color image-forming coupler is a compound that reacts with an oxidation product of an aromatic primary amine developing agent to form a dye during photographic development (hereinafter abbreviated as coupler).

The coupler may be either 4-equivalent or 2-equivalent, and may be a colored coupler for color correction or a coupler that releases a development inhibitor.

As yellow-forming couplers, open-chain ketomethylene compounds such as acylaminoacetamide-based compounds are useful; as magenta-forming couplers, pyrazolone-based or cyanoacetyl-based compounds are useful; and as cyan-forming couplers, naphthol-based or phenol-based compounds are useful.

The coupler can be introduced into the photographic emulsion layer using a method commonly used for multicolor light-sensitive materials.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials typically include a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer.

The order of these layers can be arbitrarily selected as necessary.

The usual combination is that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers contain, for example, aromatic diols such as hydroquinone, aminophenols, phenylenediamines, 3-pyrazolidones, ascorbic acid or its derivatives, etc. It may contain the main drug alone or in combination.

The combination of hydroquinone and N-hydroxyalkyl-substituted para-aminophenol derivatives as described in Japanese Patent Publication No. 48-43814 is particularly advantageous.

The developing agent can also be added as a dispersion if it is water-insoluble.

The photographic emulsion layer and other layers in the light-sensitive material of the present invention can be coated by various known coating methods.

Application methods include dip application method, air knife application method,
Roller coating methods, curtain coating methods, and extrusion coating methods are included.

The method described in US Pat. No. 2,681,294 is one advantageous method.

Also, U.S. Patent Nos. 2,761,791 and 3,5
Two or more layers may be applied simultaneously using methods such as those described in No. 26,528.

The photosensitive material of the invention may have an antistatic layer or a conductive layer, such as a vapor-deposited or electrodeposited metal layer, or a layer consisting of an ionic polymer.

Any known method can be used for the photographic processing of the light-sensitive material of the present invention.

A known treatment liquid can be used, and the treatment temperature can be lower than 18°C, from 18°C to 50°C, or higher than 50°C.

Depending on the purpose, the light-sensitive material of the present invention can be subjected to either a development process for forming a silver image (black and white photographic process) or a color photographic process consisting of a development process for forming a dye image.

When subjecting the light-sensitive material of the present invention to black-and-white photographic processing, the developer used may contain known developing agents.

As the developing agent, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-
dimethylhydroquinone, etc.), 3-pyrazolidones (
For example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4
, 4-dimethyl-3-pyradone, 1-phenyl-4-ethyl-3-pyrazolidone, ■-phenyl-5-methyl-
3-pyrazolidone, etc.), aminophenols (e.g.

-aminophenol, p-aminophenol, N-methyl-101 aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (e.g. -(p-hydroxyphenyl)-3-
Aminopyrazoline, l(p-methylaminophenyl)-
3-Aminopyrazoline, l(p-aminophenyl)-3
-aminopyrazoline, l-(p-amino-m-methylphenyl)-3-aminopyrazoline, etc.) can be used alone or in combination.

The developer may also contain preservatives (e.g. sulfites, bisulfites, ascorbic acid, etc.) and alkaline agents (
hydroxides, carbonates, etc.), pH buffering agents (e.g., carbonates, borates, boric acid, acetic acid, citric acid, alkanol-amino, etc.), solubilizing agents (e.g., polyethylene glycols, their esters, alkanol-amino), Such),
Sensitizers (e.g. nonionic surfactants containing polyoxyethylene chains, quaternary ammonium compounds, etc.), surfactants, antifoaming agents, antifoggants (e.g. potassium bromide,
halides such as sodium bromide, nitroindazoles, nitrobenzimidazoles, benztriazoles,
benzthiazole, tetrazoles, thiazoles, etc.), chelating agents (e.g., ethylenediaminotetraacetic acid or its alkali metal salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (e.g., U.S. Pat.
0 4, 0 2 5, Japanese Patent Publication No. 47-45541, etc.), a hardening agent (for example, glutaraldehyde, etc.), an antifoaming agent, etc. can be added.

A so-called "lith type" development process can be applied to the photosensitive material of the present invention.

"Lith-type" development processing is a development process in which dihydroxybenzenes are usually used as a developing agent and a low sulfite ion concentration is used for the photographic reproduction of line images or the halftone dot photographic reproduction of halftone images. Refers to a developing process that is carried out contagiously. (For details, see Mason's [Photographic Processing Chemistry]
966), pages 163-165).

In the light-sensitive material of the present invention, the dye is easily decolorized even at a low sulfite ion concentration, so its advantage is particularly emphasized in the "lith type" development process.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution to perform development.

Such development treatment is often used in combination with silver salt stabilization treatment using thiocyanate as one of the methods for rapid processing of light-sensitive materials, and such treatment is also possible.

In the case of such rapid processing, the effects of the present invention are particularly large.

As the fixer, one having a commonly used composition can be used.

The fixing solution is generally an aqueous solution consisting of a fixing agent, a hardening agent, and others, and its pH is usually 3.8 to 5.0.

As a fixing agent, in addition to thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate, and thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, organic sulfur compounds that can form soluble stable silver complex salts can be used. A fixing agent known in the art can be used.

It is common to add to the fixer a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum, etc., which acts as a hardening agent.

When forming a dye image, conventional methods can be applied.

For example, “Journal of the Soci”
ety of Motion Picture an
d Television Engineers”61
(1953), pp. 667-701, in which a negative silver image is produced by giving an imagewise exposure and developing with a developer containing a black and white developing agent, followed by at least one uniform exposure. (or other suitable fogging treatment) followed by color development to produce a dye-positive image, or a method using a direct positive emulsion to obtain a dye-positive image.

Color developers generally consist of alkaline aqueous solutions containing color developing agents.

The color developing agent is a known primary aromatic amino developer, such as phenylene diamino (for example, N,N-diethylparaphenylene diamino, N-ethyl-N-(β-hydroxyethyl)amino-2-methylaniline, 4-(N monoethyl-N-β-methanesulfonamidoethyl)amino-2-methylaniline, N,N-diethylamino-2-ethoxyaniline, etc.), p-aminophenols (e.g. 4-aminophenol, 2,6-dichloro-4-amino phenol, 2-promo-4-aminophenol, etc.).

The color developer may also contain other customary additives, such as alkali metal sulfites, carbonates, bisulfites, bromides, iodides, alkaline buffers, and the like.

Furthermore, if necessary, dye-forming couplers, competitive couplers,
Anti-capri agents, hardeners, antioxidants, thickeners, etc. may also be added.

According to the present invention, when a photosensitive material has a filter layer, an antihalation layer, or a dyed hydrophilic colloid layer for other purposes, the thickness of those layers can be made extremely thin in order to maintain good resolution. However, it can be made to have an absorption concentration sufficient for the needs.

This is because the dye used in the present invention has high water solubility and good compatibility with gelatin.

The light-sensitive material of the present invention, particularly the dyed layer thereof, is easily and irreversibly decolorized during photographic processing, so that no coloring remains on the light-sensitive material after processing.

In the photographic material of the present invention, the photographic properties of the photographic emulsion layer are not adversely affected by the dye contained in the hydrophilic colloid layer.

In other words, the sensitivity or gradation of the photographic emulsion layer will not be desensitized or softened, and fog will not occur, except for the filter effect of the dye layer itself (when the dye layer is closer to the light source than the emulsion layer). do not have.

This is regardless of the photographic characteristics in the silver halide specific sensitivity wavelength range or the color sensitization range.

In addition, these effects do not appear even after the photosensitive material has been manufactured. In the photosensitive material of the present invention, the dye is dyed only in the layer containing the basic polymer, and the dye is not applied to other layers. Does not spread.

Therefore, an unexpected decrease in the sensitivity or gradation of the photographic emulsion layer due to undesirable spectral absorption effects due to dye diffusion does not occur, resulting in a light-sensitive material with excellent photographic properties, particularly spectral properties.

In particular, black-and-white and color photographic materials having an antihalation layer between the photographic emulsion layer and the support, and a filter layer having at least three photographic emulsion layers and intervening therebetween which may also serve as an antihalation layer. This is extremely advantageous in color photographic materials that have been developed.

That is, when the dye diffuses from the layer to be dyed to the emulsion layer above it (far from the support) or even above it to the hydrophilic colloid layer, the emulsion layer is subjected to a filtering effect by such dyes. , a decrease in sensitivity and a softening of gradation occur for light in the wavelength range that is absorbed by the dye.

In the light-sensitive material of the present invention, there is no such diffusion of the dye, so the reduction in sensitivity to the emulsion layer above the dyed layer (on the side far from the support) can be virtually ignored. In terms of quantity, it does not exceed 0.06.

The configuration and effects of the present invention will be further clarified with reference to Examples below.

Example 1 A solution containing gelatin and having the following composition was prepared.

gelatin 40g water
600cc poly(diethylaminoethyl methacrylate) 60cc (5% aqueous solution) dye
100cc (1% aqueous solution) Hardener*
200cc (4% aqueous solution) Phenoxypolyoxyethylenebutanesulfonic acid 40cc (1% aqueous solution) *2,
Sodium salt of 4-dichloro-6-hydroxy-1,3.5-triazine In the above, the above-mentioned exemplified dyes 1, 2, 3, 4 are used as dyes.
, 5, 7, 8, 9, 10.12 and comparative dyes A, B, C, D, and E having the following structural formulas were prepared.

Each of the prepared solutions was applied onto a cellulose acetate film to a thickness of 4 microns after drying, and dried.

Spectral absorption was measured for this sample.

Furthermore, a liquid having the following composition was applied onto this layer so that the thickness after drying would be 8 microns, and drying was completed in about 20 minutes.

This sample was immersed in warm water at a temperature of 50° C. for 5 minutes while being moved to wash off the discontinued second layer without adding any dye, and then dried for 10 minutes.

Spectral absorption was also measured for this sample.

Let the optical density at the maximum absorption wavelength measured after coating the first layer be a1, and that of the first layer after coating and removing the second layer be a2.

Fixation of Dye to First Layer The P values obtained for the samples using each dye were as shown in Table 1.

Comparative samples using known dyes A-E had a low percentage of dye remaining in the first layer because the dye diffused into the second layer and was removed along with the second layer.

In all samples according to the invention, most of the dye (more than 80%) remained in the first layer without diffusing into the second layer.

Example 2 A silver iodobromide emulsion color-sensitized to red light and containing a cyan color-forming coupler was coated on a subbed cellulose acetate film to a thickness of 5 μm, and a gelatin intermediate layer was applied thereon to a thickness of 1.5 μm. A silver iodobromide emulsion color-sensitized to green light and containing a magenta color-forming coupler was further coated to a thickness of 4 μm.

Divide this film into 5 equal parts, and coat 2 layers of yellow filter on top of each of them using coating liquids with the following 5 compositions.
It was applied to a thickness of μm.

(The absorption density of one layer of the yellow filter at the absorption maximum wavelength is 0.9).

Furthermore, a blue-sensitive silver iodobromide emulsion containing a yellow coloring coupler was coated on this layer to a thickness of 5 μm, and finally a surface protective layer made of gelatin was coated to a thickness of 1 μm.

The completed sample corresponds to a color negative photosensitive material.

These are called 2A to 2E, respectively, corresponding to the type of yellow filter layer.

In Example 2A, Dye B described above was used in place of Dye A described in Example 1.

The amount of solution (10%) added was 80 cc.

2C: In 2A, Exemplary Dye 2 herein was used in place of Dye A described in Example 1.

The amount of solution (10%) added was 80 cc.

A tungsten light source with a color temperature of 5500°K was used for each sample, and Fuji color separation filter sp-1 (maximum transmittance (Tm
ax) = approximately 38%, wavelength of Tmax = approximately 433m μ,
A 1/200 second exposure was applied through a continuous gray wedge with a wavelength of Tmax/2 = approximately 498 mμ), and the following processing was performed.

Each treatment solution used had the following composition.

Color developer Sodium hydroxide 2g Sodium sulfite 2g Potassium bromide
0.4g sodium chloride
1g sand
4g hydroxylamine sulfate
2g ethylenediaminetetraacetic acid tetrasodium 2g
4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sesquisulfate (monohydrate) 4g Add water 1l Bleach solution Ethylenediaminetetraacetic acid ferric complex salt sodium salt 100g bromide Potassium 50g ammonium nitrate
50g boric acid
Add 5g water
1l Fixer Sodium thiosulfate 150g Sodium sulfite 15g Borax
12g glacial acetic acid
15ml potash alum
Add 20g water
1l Stable liquid boric acid 5g Sodium citrate 5g Sodium metaborate tetrahydrate 3g Potassium alum
Add 15g water
A photographic characteristic curve was created for the yellow image on each sample treated with 1 liter, and the exposure amount required to obtain a fog density of 0.1 was determined, and the reciprocal of the exposure amount was taken as the sensitivity value.

The relative sensitivity values and presence or absence of stain obtained for each sample were as follows.

Samples 2A and 2B, which used comparative dyes A and B, respectively, had a filter effect based on the diffusion of the dye from the yellow filter layer to the blue-sensitive emulsion layer, and the sensitivity of the blue-sensitive emulsion layer was significantly higher than that of control sample 2E. I felt desensitized.

Sample 2C according to the present invention showed almost the same sensitivity as control sample 2E, which used colloidal silver in one layer of the yellow filter, and did not exhibit stains like sample 2E.

Example 3 A silver iodobromide emulsion color-sensitized to red light and containing a cyan color-forming coupler was coated to a thickness of 5 μm on a subbed cellulose acetate film.

This film was divided into five equal parts, and one layer of magenta filter was coated thereon as a gelatin intermediate layer to a thickness of 1.5 m[mu] using coating liquids having the compositions shown in 3A to 3E below.

(The absorption density of one layer of the magenta filter at the absorption maximum wavelength is 0.4.

) (Magenta filter single-layer coating liquid) 3B In 3A, the Exemplary Dye 7 was used in place of the Exemplary Dye 2.

The amount of 10% solution added was 40 cc.

Comparative Dye C (see Example 1) was used in place of Exemplary Dye 1 according to the invention in 3C 3A.

The amount of 10% solution added was 40 cc.

3D In 3A, the Comparative Dye D was used in place of Exemplary Dye 1.

The amount of 10% solution added was 40 cc.

3E Gelatin aqueous solution 8% 500cc2,4-
Dichloro-6-hydroxy 1,3,5-triazine Na salt 1% 25 cc Dodecaethylene glycol-4-nonylphenol ether 2% 30 cc On top of this, a 4 μm silver iodobromide emulsion color-sensitized to green light and containing a magenta coloring coupler was added. It was applied to a thickness of .

Further, on this layer, a single layer of the yellow filter shown in Example 1-2E was applied to a thickness of 2 μm.

Furthermore, a blue-sensitive silver iodobromide emulsion containing a yellow color-forming coupler was coated on this layer to a thickness of 5 μm, and finally a surface protective layer made of gelatin was coated to a thickness of 1 μm.

The completed sample corresponds to a color negative photosensitive material.

These are called 3A to 3E corresponding to the types of magenta filters, respectively.

A tungsten light source with a color temperature of 5500°K was used for each sample, and Fuji color separation filter sp-2 (maximum transmittance (Tmax
) = 63%, wavelength of Tmax = 5 3 5 mμTma
x/2 wavelength = 510 mμ) and 1/200 second exposure was applied through a continuous gray wedge, and the following processing was performed.

Each treatment solution used had the following composition.

Color developer Sodium hydroxide 2g Sodium sulfite 2g Potassium bromide
0.4g sodium chloride
1g sand
4g hydroxylamine sulfate
2g ethylenediaminetetraacetic acid tetrasodium 2
g4-amino-3-menal-N-ethyl-N-(β-hydroxyethyl)aniline sesquisulfate (monohydrate) 4g Add water 1l Bleach solution Ethylenediaminetetraacetic acid ferric complex salt sodium salt 100g bromide Potassium 50g ammonium nitrate
50g boric acid
Add 5g water
1l Fixer Sodium thiosulfate 150g Sodium sulfite 15g Borax
12g glacial acetic acid
15ml potash alum
Add 20g water
1l Stable liquid boric acid 5g Sodium citrate 5g Sodium metaborate tetrahydrate 3g Potassium alum
Add 15g water
A photographic characteristic curve was created for the magenta image on each sample treated with 1L, and the exposure amount required to obtain a fog density of 0.1 was determined, and the reciprocal of the exposure amount was determined as the sensitivity value.

The relative sensitivity values and presence or absence of stain obtained for each sample were as follows.

Samples 3C and 3D using Comparative Dyes C and D had a filter effect based on the diffusion of the dye from the magenta filter layer to the green emulsion layer, and the sensitivity of the green emulsion layer was considerably lower than that of control sample 3E. did.

However, Samples 3A and 3B according to the present invention had negligible diffusion of dye into the green-sensitive emulsion layer, and exhibited almost the same sensitivity as Control Sample 3E.

Practical Example 4 Four types of coating liquids having the following compositions were applied to a thickness of 1 μm as an antihalation layer on the base coated cellulose acetate.

A silver iodobromide emulsion sensitized to red light and containing a cyan color-forming coupler is coated on this to a thickness of 5 μm, and a gelatin intermediate layer is coated on top of this to a thickness of 1.5 μm. A silver iodobromide emulsion color-sensitized to green light and containing a magenta color-forming coupler was coated to a thickness of 4 μm.

On top of this layer, a single layer of the yellow filter shown in Example 1-2E was applied to a thickness of 2 μm.

Furthermore, a blue-sensitive silver iodobromide emulsion containing a yellow color-forming coupler was coated thereon to a thickness of 5 .mu.m, and finally a surface protective layer made of gelatin was coated to a thickness of 1 .mu.m.

The completed sample corresponds to a color negative photosensitive material.
These are referred to as 4A to 4D, respectively, corresponding to the type of antihalation layer.

(Coating liquid for antihalation) 4 A Gelatin aqueous solution 10% 500cc poly(
2-diethylaminoethyl methacrylate) 5% 220cc Dye E for comparison 10% 32cc2,4-
Dichloro-6-hydroxy-1,3.5-triazine Na salt 1% 25 cc Dodecaethylene glycol-4-1 nonylphenol ether 2% 30 cc 4B In place of comparative dye E in 4A, exemplified dye 3 of this specification was used.
was used.

The amount of 10% solution added was 32 cc.

Exemplary Dye 9 herein was substituted for Comparative Dye E in 4C 4A.

The amount of 10% solution added was 32 cc.

4 D Gelatin aqueous solution 10% 500cc2,4-
Dichloro-6-hydroxy-1,3.5-triazine Na salt 1% 25cc Dodecaethylene glycol-4-nonylphenol ether 2% 30cc Each sample was treated with Fuji color separation filter Sp-3 (maximum transmission) using a tungsten light source with a color temperature of 5500°K. The following processing was carried out using an exposure rate (Tmax) = approximately 92%, wavelength of Tmax/2 = approximately 600 mμ) and a 1/200 second exposure through a continuous gray wedge.

Process temperature time 1 Color development 37.8℃ 31 minutes 2 2 wash 1 minute 〃 3 Bleach 6 minutes 〃 4 Wash with water for 1 minute 〃 5 fixed arrival 6 minutes 〃 6. Wash with water for 1 minute. 〃 7 stable 1 minute 〃 Each treatment solution used had the following composition.

Color developer Sodium hydroxide 2g Sodium sulfite 2g Potassium bromide
0.4g sodium chloride
1g sand
4g hydroxylamine sulfate
2g ethylenediaminetetraacetic acid tetrasodium
2g 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sesquisulfate (monohydrate) 4g Add water 1l Bleach solution Ethylenediaminetetraacetic acid ferric complex salt sodium salt 100g bromide Potassium 50g ammonium nitrate
50g boric acid
Add 5g water
1l Fixer Sodium thiosulfate 150g Sodium sulfite 15g Borax
12g glacial acetic acid
15ml potash alum
Add 20g water
1l Stable liquid boric acid 5g Sodium citrate 5g Sodium metaborate tetrahydrate 3g Potassium alum
Add 15g water
A photographic characteristic curve was created for the cyan image on each sample treated with 1L, and the exposure amount required to obtain a fog density of 0.1 was determined, and the reciprocal of the exposure amount was taken as the sensitivity value.

The relative sensitivity values and presence or absence of stain obtained for each sample were as follows.

In sample 4A using comparative dye E, the sensitivity of the red-sensitive emulsion layer was significantly reduced compared to control sample 4D due to a filter effect based on the diffusion of the dye from the antihalation layer to the red-sensitive emulsion layer.

Samples 4B and 4C according to the invention showed approximately the same sensitivity as control sample 4D.

Claims (1)

[Scope of Claims] 1. A silver halide photosensitive material containing a dye in at least one hydrophilic colloid layer, which contains a basic polymer in at least one hydrophilic colloid layer and is represented by the following general formula (1): 3 At least one oxonol dye consisting of two vilazolone nuclei substituted with an acylamino group having a sulfo group at the 1st position and an aliphatic group having at least one sulfo group at the 1st position or an aromatic group. A silver halide photographic material comprising: [In the formula, X and Q may be the same or different, each represents an aliphatic group or an aromatic group, M represents a cation, L
is a methine group, n is 0.1 or 2, m is 1 or 2
are shown respectively. However, oxonol dyes in which Q is an aliphatic group and X is a phenyl group are excluded. ]