JPH01265249A - Direct positive type silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the rapid processing of a sensitive material and the sharpness of a color image by incorporating a specified compd. in a cyan coupler, and specifying an amount of silver of an anti-halation layer. CONSTITUTION:One or more kinds of the compd. shown by the formula are incorporated in one or more kinds of the cyan coupler contd. in the sensitive material, and the wt. ratio of silver to gelatin contd. in the antihalation layer is 0.05-0.2. In the formula, R<1> is alkyl or aryl group, R<2> is alkyl or cycloalkyl group, etc., R<3> is hydrogen or halogen atom, etc., Z is hydrogen atom or a group capable of being released by allowing it to react with the oxidant of a color developing agent. And, a positive image is formed by developing the sensitive material with a color developing agent (A) in the presence of a fogging agent. And, it is preferable that the developing solution (A) contains a phosphoric acid compd., and does snot substantially contain hydroxylamine.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a direct positive silver halide color photographic light-sensitive material, which is a direct positive silver halide color photographic material that forms detailed and highly sharp color images and is suitable for rapid processing. This invention relates to silver oxide color photographic materials.

[Background of the invention]

It is well known that positive photographic images can be directly formed using silver halide photographic materials (hereinafter simply referred to as "photosensitive materials") without the need for intermediate processing steps or negative photographic images.

Conventionally known methods for producing positive images using direct positive photosensitive materials can be mainly divided into the following two types.

One type is to obtain a positive image after development by using a silver halide emulsion that has been fogged in advance and destroying the fog nuclei in the exposed area using solarization or the Burschel effect. The other type uses an internal latent image type silver halide emulsion that has not been fogged in advance, and performs surface development after performing a fogging treatment after image exposure, or while performing a fogging treatment.
This is to obtain a positive image.

The internal latent image type silver halide photographic emulsion mentioned above refers to a silver halide photographic emulsion which has photosensitive nuclei mainly inside the silver halide grains and forms a latent image inside the grains upon exposure.

This latter type of method is generally more sensitive than the former type of method and is suitable for applications requiring high sensitivity, and the present invention is particularly concerned with this latter type of method.

Various techniques have been known in this field, such as U.S. Pat. No. 2,592,250;
No. 466.957, No. 2,497,875, No. 2.5
No. 88.982, No. 3,761,266, No. 3,76
No. 1,276, No. 3.796577 and British Patent 1
, No. 151, 363 is the main method.

By using these known methods, it is possible to produce direct positive type photographic materials with relatively low illuminance.

Furthermore, although it cannot be said that a clear explanation has been given regarding the details of the direct positive image formation mechanism, for example, in ``The Theory Op.'' by Mies and James,
The Photographic Process
ory of the Photography
cProcess) J, 3rd edition, p. 161, the process by which a positive image is formed can be understood to some extent by the "desensitizing effect due to an internal latent image."

In other words, fog nuclei are selectively generated only on the surface of unexposed silver halide grains due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide grains by the initial image exposure. It is believed that a photographic image is formed in the unexposed areas by normal development.

As means for selectively generating fog nuclei, there is a method called optical fogging in which the entire surface of the photosensitive layer is exposed to light, and a method called chemical fogging in which fogging is performed using a chemical such as a fogging agent. is known.

Although the optical fogging method described above is convenient in practice, it still has technical problems in order to serve various purposes in a wide range of photographic fields. That is, since the optical power pre-processing method is based on the formation of fog nuclei by photodecomposition of silver halide, the appropriate exposure illuminance and exposure amount vary depending on the type and characteristics of silver halide.

For example, Japanese Patent Publication No. 45-12709 describes a method of uniformly exposing the entire surface with low-intensity light. According to this method, by exposing the entire surface to low-intensity light, high maximum density and low minimum density It is said that it is possible to obtain a good positive image with .

Furthermore, as a result of our studies, we found that in order to obtain a relatively good positive image, it is necessary to perform fog exposure at a relatively low illuminance in a limited range, and that illuminance lower than this is sufficient. Even with exposure, sufficient maximum image density cannot be obtained,
It has also been found that at illuminance higher than the above range, the maximum density decreases and the minimum density increases in proportion to the illuminance, a phenomenon called illuminance failure due to optical fog.

On the other hand, the chemical fog method does not have the above-mentioned drawbacks, and has the advantage of being low in cost and simple in terms of equipment.

Direct positive type silver halide color photographic materials such as those mentioned above, which are expected to continue to be widely used in color copiers and other technical fields that directly obtain positive images from positive images, can produce thin lines depending on the application. reproducibility is not sufficient,
Also, when making copies from halftone printed matter, etc.
Since the color reproducibility is not necessarily sufficient, problems remain in the reproducibility of image information.

Therefore, if an antihalation layer is provided in the light-sensitive material, it is expected that the above-mentioned reproducibility will be improved. According to the findings of the present inventors, providing an antihalation layer is effective in solving the above-mentioned problem, but it is not suitable for rapid processing of the photosensitive material. This causes the inconvenience of not being able to pass through.

In other words, in the antihalation layer to which an antihalation dye is added, the dye is mordant to form the antihalation layer so that the dye does not dissolve during the color development process. If processing of light-sensitive materials containing such materials is accelerated, there is a risk that the dyes may not be sufficiently decolorized in the post-color development process, resulting in dyes remaining in the image; If it is made easier, the dye becomes more likely to be eluted during color development, and as a result, the color development processability changes due to the elution, for example, the action of the fogging agent changes due to the elution, which in turn causes changes in photographic performance. become.

Furthermore, if a method of forming an antihalation layer by adding an inorganic substance such as colloidal silver instead of the antihalation dye is used, the above-mentioned problem does not occur and rapid processing can be achieved, but the stain This not only degrades the contrast of highlight areas but also increases the minimum density of the image.

[Object and Structure of the Invention] The present invention was invented in view of the above-mentioned problems, and is a direct positive silver halide color photographic photosensitive material that forms color images with excellent sharpness and is suitable for rapid processing. For the purpose of providing a material, each silver halide emulsion layer containing a cyan coupler, a magenta coupler, and a yellow coupler is formed on a support, and an antihalation layer containing colloidal silver is formed on the support. A direct positive type silver halide color photograph which has a photographic constituent layer formed between a silver emulsion layer and the support, and which forms a positive image by developing with a color developing solution in the presence of a fogging agent. In the photosensitive material, at least one of the cyan couplers is any one of the compounds represented by the following general formula (1).
The direct positive type silver halide color photographic light-sensitive material is characterized in that the silver/gelatin weight ratio in the antihalation layer is 0.05 to 0.2; 1) [In the formula, R1 represents an alkyl group or an aryl group,
R2 represents an alkyl group, cycloalkyl group, aryl group or heterocyclic group, R3 is a hydrogen atom, a halogen atom,
represents an alkyl group or an alkoxy group, or R
' and Z represents a hydrogen atom or a group capable of leaving by reacting with an oxidized product of an aromatic primary amine color developing agent.

[Detailed description of the invention]

The antihalation layer contained in the direct positive silver halide color photographic light-sensitive material of the present invention is located closer to the support than the silver halide emulsion layer, and its IJH is 4.
The film thickness in this case, which is preferably less than μ, is the thickness of the anti-tursion layer formed on the support, or the anti-halation layer and the auxiliary layer coated on the anti-halation layer. This is the total thickness of the first intermediate layer. As mentioned above, the film thickness is preferably 4 μm or less, and more preferably 3 μm or less and 1 μm or more. When the film thickness is within this range, the increase in minimum density (D, i, . . . ) can be controlled without lowering the gamma-1 (T1) of the shadow portion in the photographic characteristic curve. Therefore, the contrast of the shadow portion can be increased, and the whiteness can be maintained in a good state. A further remarkable effect is that the reproducibility (sharpness) of halftone dots can be significantly improved.

However, when the film thickness exceeds 4μ, T1 decreases and D
Since min shows a tendency to increase, it is not preferable.

On the other hand, when the film thickness is less than 1 μm, the contrast in the shadow area is improved, but coating film formation is slightly hindered.

Next, the support used in the present invention will be described. The support that can be used in the present invention may be any conventionally used support as long as it can support photographic constituent layers such as emulsion layers, and its material can be arbitrarily selected. Among these supports, typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, and polyethylene laminate paper, which have been undercoated as necessary. etc. are included.

In practicing the present invention, reflective supports can be preferably used, such as polyolefin laminated paper. Polyolefin laminated paper with excellent flatness can be obtained, for example, by extrusion coating a molten polyolefin onto a paper substrate to form a water-resistant surface on the paper substrate.

When a reflective support is used in the present invention, it is preferable that its surface has excellent water resistance, and a support with good water resistance can be obtained, for example, by forming a water-resistant surface on a substrate. can.

The water-resistant surface in this case can be formed by coating a substrate, for example a paper substrate, with a hydrophobic resin.

In an embodiment in which such a water-resistant surface is formed, even when the silver halide photographic light-sensitive material is immersed in a bath used for development processing, it is possible to prevent water from forming on the substrate.

Examples of the hydrophobic resin to be coated on the surface of the substrate in the form of a coating layer include polyolefins such as polyethylene, polypropylene, and polybutene, olefins such as ethylene, propylene, and butene, and monomers such as vinyl acetate, vinylidene chloride, and maleic anhydride. (e.g., ethylene 7-hinyl acetate copolymer, propylene-vinylidene chloride copolymer, propylene-maleic anhydride copolymer, etc.), or polystyrene, polyvinyl chloride, polyacrylate, saturated polyester, Examples include homopolymers or copolymers such as polycarbonate, and blends thereof. The thickness of such a hydrophobic resin coating layer is not particularly limited, but is generally 15
The thickness is preferably about 50 μm.

When using polyethylene resin as the above-mentioned hydrophobic resin, there is no particular restriction on its molecular weight as long as extrusion coating is possible, but it is usually molecular weight! ! 20,000~2
00,000 range, and the polyethylene resin in this case may be any of low density, medium density, and high density polyethylene resins, which alone can be
Alternatively, two or more types may be mixed and used.

Further, a fine particle powder having higher heat resistance than the resin described above, for example, a white pigment such as Ba5Oa or Zn0STiOz, can be mixed with the resin, thereby making the support opaque. In this case, a white opaque support with low transmission density can be obtained by mixing a white pigment with the support and extruding it or stretching it to form voids to whiten it, or by bonding the supports together. can.

Furthermore, in the light-sensitive material of the present invention, as an antihalation layer, a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are provided on the side closer to the support than the silver halide emulsion layer. A layer containing a substance that absorbs light corresponding to the gender is formed. This substance does not dissolve into the developing color developer used in developing the photosensitive material. This substance preferably has the effect of preventing halation caused by the support by absorbing the light transmitted through the emulsion layer, and also does not dissolve into the color developing solution during development. Since this substance does not elute, unevenness in the concentration distribution of the substance does not occur, and therefore, it is possible to form an image with high sharpness, thereby making it possible to form an image without uneven development.

As the substance that absorbs light, various inorganic and organic substances having this effect can be used.

As the above-mentioned inorganic substance, for example, a colloidal metal can be used, and as an organic substance, for example, various dyes are bonded to polymers etc. to make them fixed (so-called mondant), so that they do not dissolve into the color developing solution. You can use the .

When using antihalation dyes fixed with a polymer mordant like this, it is not always easy to distribute the dyes uniformly, and if it is difficult to remove the fixed dyes after color development, it is difficult to remove the fixed dyes. Since there will be cases where this is necessary, it is preferable to take measures to address these problems as necessary.

The inorganic compound used in carrying out the present invention is preferably colloidal silver, colloidal silver dispersion, etc.
Colloidal silver is particularly preferred. Since these colloidal metals have good decolorizing properties, they are also effective when the present invention is applied to color photographic materials. The above colloidal silver, for example gray colloidal silver, is prepared by mixing silver nitrate in gelatin with hydroquinone, phenidone, ascorbic acid, pyrogallol,
Alternatively, it can be obtained by reducing the gelatin by keeping it alkaline in the presence of a reducing agent such as dextrin, then neutralizing and cooling it to set the gelatin, and then removing the reducing agent and unnecessary salts by the noodle washing method. When colloidal silver particles are prepared in the presence of an azaindene compound or a mercapto compound during alkaline reduction, a colloidal silver dispersion with uniform particles can be obtained.

Furthermore, each color-sensitive layer of the present invention is formed on the above-mentioned support by a red-sensitive direct positive silver halide emulsion layer containing a cyan coupler, a green-sensitive direct positive silver halide emulsion layer containing a magenta coupler, and a red-sensitive direct positive silver halide emulsion layer containing a magenta coupler. yellow filter layer, according to
and a blue-sensitive direct positive silver halide emulsion layer containing a yellow coupler.

Although the layer order of these layers is arbitrary, for example, they can be formed by coating in the above order from the support side.

Among the couplers contained in each of the above-mentioned color-sensitive layers, yellow dye-forming couplers are of the benzoylacetanilide type, pivaloylacetanilide type, or those in which the carbon atom at the coupling position can be separated during coupling. A 2-color yellow coupler which is fftaed with a split-off group is useful.

Examples of magenta dye-forming couplers include 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indasilone type, or two-equivalent type magenta couplers having a split-off group, among which the following general formula C
Magenta couplers represented by M-I are useful.

In the magenta coupler represented by general formula (M-I) (hereinafter blank) represented by the above general formulas CM-1) according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle. and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl, but in addition to these, halogen Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfonyl Examples include famoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group ring; As the acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylaminocumoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups. etc.; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group, etc.; group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; the heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,
4,5.6-tetrahydrobilanyl-2-oxy group, 1
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1 , 3,5-) lyazole-6 monothio group, etc.; as a siloxy group, a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, etc.; as an imide group, a succinimide group, a 3-heptadecylsuccinimide group, Phthalimide group, glutarimide group, etc. Spiro compound residues include spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
'] hebutan-1-yl, tricyclo[3゜3.1.1
3.7]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy.

Aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino, aryloxy carbonylamino, carboxyl, (R1' is the same as the above R, Z' is the same as the above Z, R2' and Rs' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group), etc. Although various groups may be mentioned, a halogen atom, particularly a chlorine atom is preferred.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

-m Formula (M-I) is more specifically represented by the following general formula (M-11) ~ (M-■]
Represented by

General formula [M-■] General formula (M-1ff) General formula CM-IV) 4 General formula (M-V) General formula (M-Vl) General formula [M-■] General formula (M-11) ~ [M-■] In R1 to R and X have the same meanings as R and X above.

Also, preferred among the -a formulas (M-I) are those represented by the following general formula [M-■].

In the formula, R+, X and Zl have the same meanings as R, X and Z in the general formula (M-I).

Among the magenta couplers represented by the general formulas (M-II) to [M-■], particularly preferred are -
It is a magenta coupler represented by formula a (M-11').

The most preferred substituents R and R1 on the heterocycle are those represented by the following general formula (M-[).

- Formula [M-■) Rs ■ R5゜-〇- In the formula, Rt, R+. and R11 each have the same meaning as R above.

Also, the above Rs, R+. and two of R11, for example R1 and Ro. may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and RI+ may be bonded to the chain ring to form a bridged hydrocarbon compound residue. .

-m formula [:M-IX) is preferable when (ii) at least two of Rs to R1 are an alkyl group, and (ii) one of Rs to R1, for example R1, is a hydrogen atom. This is the case when the other two R1 and R1° combine to form a cycloalkyl together with the root carbon atom.

Further preferred among (i) is the case where two of R9-R1 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, the substituent that the ring formed by Z in the formula (M-1) and the ring formed by Zl in the formula [M-■] may have, and the substituent that the ring formed by Z in the formula [M-■], and the formula CM-
R2-R1 in II) to (M-V[) are preferably represented by the following formula CM-X).

General formula (M-X) -R'-8Q2-R'' In the formula, R- represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the straight chain has one branch or not.

The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one.

Typical specific examples of the compounds according to the present invention are shown below.

Margin below Hs two CHy　　　　　　　-6sHu(t)CH.

rθ Hehe~ In addition to the above typical examples of the compounds according to the present invention, examples of the compounds according to the present invention include Japanese Patent Application No. 61-9791.
Among the compounds described on pages 66 to 122 of the specification, No. 1 to 4, 6.8 to 17.19 to 24.2
6-43.45-59.61-104.106-121
．． Compounds represented by 123 to 162 and 164 to 223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society 4 (Journal of the Ch
e+5icat Society) + Parkin (P
Erkin) I (1977).

2047-2052, U.S. Patent No. 3,725,067,
JP-A No. 59-99437, No. 58-42045, No. 59-162548, No. 59-171956, No. 6
No. 0-33552, No. 6G-43659, No. 60-1
It can be synthesized by referring to No. 72982 and No. 60-190779.

The couplers of the invention typically have IX per mole of silver halide.
It can be used in a range of 10-'' mol to 1 mol, preferably 1 x 10-sum mol to s x to-' mol.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

In addition, as a cyan dye-forming coupler, the following -S formula (
It is also possible to use compounds of the formula PC-II).

General formula (PC-I[) H [In the formula, R1 represents an alkyl group or an aryl group.

R2 represents an alkyl group, cycloalkyl group, aryl group or heterocyclic group, Rx represents a hydrogen atom, a halogen atom,
represents an alkyl group or an alkoxy group, and R3 is R
Z may form a ring in cooperation with 1, and Z represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent] - Formula (PC-II) In the cyan coupler represented by R1, the alkyl group represented by R1 preferably has 1 to 32 carbon atoms, and these may be linear or branched, and include those having a substituent.

The aryl group represented by R1 is preferably a phenyl group, including those having substituents.

The alkyl group represented by R2 preferably has 1 to 32 carbon atoms, and these alkyl groups may be linear or branched, and include those having substituents.

The cycloalkyl group represented by RZ has 3 to 3 carbon atoms.
12 are preferred, and these cycloalkyl groups also include those having substituents.

The aryl group represented by R2 is preferably a phenyl group, including those having substituents.

The heterocyclic group represented by R2 is preferably a 5- to 7-membered one, may have a substituent, and may be fused.

R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but R3 is preferably a hydrogen atom.

Furthermore, the ring formed jointly by R1 and R3 is 5 to 6
A membered ring is preferable, and examples thereof include the following.

The groups represented by Z in the general formula (PC-n) that can be separated by reaction with the oxidized product of the color developing agent include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, and an acylamino group. group, sulfonylamino group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, and imide group (including those each having the position tM l'&), but preferably a halogen atom, an aryloxy group, an alkoxy group It is.

Particularly preferred among the above-mentioned cyan couplers are those represented by the following formula (PC-11-A).

General formula (PC-n-A) H . R.A.
I has the same meaning as RI in the above formula (PC-If). X
A represents a halogen atom, an aryloxy group or an alkoxy group, including those having a substituent.

Typical specific examples of the cyan coupler represented by the general formula (PC-n) are shown below.

(The following is a blank space) Specific examples of the above-mentioned cyan couplers include pages 26 to 35 of the specification of Japanese Patent Application No. 61-21853, and the lower left column of page 7 to the right of page 10 of Japanese Patent Application Laid-open No. 60-225155. It is described in the lower column of JP-A No. 60-222853, page 6, upper left column to page 8, lower right column, and JP-A-59-185335, page 6, lower left column to page 9, upper left column. It contains a 2,5-diacylamino cyan coupler and can be synthesized according to the methods described in these specifications and publications.

The cyan coupler of the present invention is used in the red-sensitive silver halide emulsion layer, and the amount added is preferably 2X10-'' to 8X10-' mole, particularly preferably 1X10I to 5X10-' mole per mole of silver halide. −' molar range.

These dye-forming couplers can be arbitrarily selected, and there are no particular limitations on the method or amount of use.

In addition, in order to prevent fading of dye images due to short wavelength actinic rays, ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, benzophenone compounds, etc. can be used, and in particular, Tinuvin PS, 120
, 320, 326, 327, and 328 (all manufactured by Ciba Geigy) may be used alone or in combination.

(The following is a blank space) The silver halide grains used in the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.The method for producing and growing seed particles may be the same or different. A silver halide emulsion containing the silver halide grains may be prepared by simultaneously mixing halide ions and silver ions, or by mixing one of them in a solution in which the other is present. In addition, while considering the critical growth rate of silver halide crystals, halide ions and silver ions were mixed in p)I, llA in a mixing pot.
It may also be produced by sequentially and simultaneously adding them while controlling the amount of g. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

It is also possible to change the halogen composition of the particles using a conversion method after growth.

The silver halide grains according to the present invention may be composed of at least two types of layers, that is, at least two types of layers having different halogen compositions, and the outermost shell layer is at least a part of the inner core layer. The inner core layer may form a core and the outer shell layer may cover the core as a shell, so-called core/shell structure, or the first layer may cover the second layer. It is also possible to adopt a structure that covers a part of the .

The silver halide grains according to the present invention may be composed of 3 fffi or more layers. For example, silver halide grains may have a three-layer structure consisting of a first layer serving as the core at the center, an inner core layer covering the first layer, and an outer shell layer roughly covering the inner core layer. Hereinafter, in order to simplify the explanation, a particle with a two-layer structure will be taken up, and the first layer located on the outermost side will be assumed to be an outer shell layer, and the second layer adjacent to it will be assumed to be an inner core layer, but the present invention The silver halide grains are not limited to grains having a two-layer structure.

The inner core layer of the silver halide grains according to the present invention preferably contains less silver chloride than the silver chloride contained in the outer shell layer.

The inner core layer preferably consists primarily of silver bromide and may further contain silver chloride and/or silver iodobromide. The silver halide grains forming the inner core layer may have any shape; for example, they may be cubic, octahedral, dodecahedral, tetradecahedral, or a mixture thereof; they may also be spherical, The particles may be tabular particles, irregularly shaped particles, or an appropriate mixture of these particles. In carrying out the present invention, the average particle size and particle size distribution of the silver halide grains constituting the inner core layer can be varied over a wide range depending on the desired photographic performance, but a narrower particle size distribution is more preferable. Specifically, it is preferable that 90% by weight of the silver halide grains constituting the inner core layer is 40% or more away from the average grain diameter, and more preferably, the silver halide grains have diameters that are no more than 30% apart from the average grain diameter.

That is, the silver halide grains constituting the inner core layer are preferably substantially monodisperse.

Here, silver halide grains with a monodisperse inner core layer mean that the weight of silver halide grains included within a grain size range of ±20% around the average grain size T in the silver halide grains constituting the inner core layer. It is 60% or more of the total silver halide weight, preferably 70% or more, particularly preferably 80% or more.

Here, the average particle size T is the frequency n1 of particles having particle size r1
The product n1Xrl' of n1Xrl' and r and 3 means the particle size r1 that is the maximum (3 significant figures, minimum number of digits is 5 to the nearest 4).

In addition, the grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than spherical, the diameter when the projected image is converted into a circular image with the same area. It is.

As a method for producing the monodisperse core emulsion, for example, the double jet method disclosed in Japanese Patent Publication Nos. 411-36890, 48520/1980, and 65521/1980 can be used. . In addition, JP-A-54-1
A premix method described in Japanese Patent No. 58220 and the like can also be used.

The inner core layer preferably has few lattice defects and is disclosed, for example, in US Pat. No. 2,592,250.

Emulsions produced by the conversion method do not pass as an inner core layer. pH and pAg during production by the above double jet method
Particles produced while controlling the lattice defects have fewer lattice defects and are preferable as the inner core layer.

The inner core layer can be produced in the presence of a silver halide solvent. Thioethers shown in U.S. Patent No. 3,574,628, thiourea derivatives shown in JP-A-55-77737, imidazoles shown in JP-A-54-100717, etc. can be used. . In a preferred embodiment of the present invention, ammonia is preferably used as the silver halide solvent.

In the silver halide grains according to the present invention, the outer shell layer preferably covers 50% or more of the surface area of the grains constituting the inner core layer. The outer shell layer can contain silver bromide or silver iodide to the extent that photographic performance is not adversely affected. A portion of the outer shell layer can be converted to silver bromide or silver iodide using an amount of water-soluble bromide or iodide.

The outer shell layer can completely cover the inner core layer or can selectively cover a part of the inner core layer, but preferably covers 50% or more of the surface area of the particles constituting the inner core layer. is preferable, and more preferably completely covers the inner core layer.

As a method for forming the outer shell layer, the above-mentioned double jet method, premix method, etc. can be used. It is also possible to form the inner core layer by mixing fine grains of silver halide with an emulsion containing grains constituting the inner core layer and performing Ostwald ripening.

In practicing the present invention, the inner core layer of the silver halide grains is chemically sensitized, doped with metal ions, or both, or not at all. It may be something.

As the chemical sensitization, sulfur sensitization, gold sensitization, reduction sensitization, noble metal sensitization, and a combination of these sensitization methods can be employed. As the sulfur sensitizer, thiosulfur salts, thioureas, thiazoles, rhodanines, and other compounds can be used. Such methods are described, for example, in US Pat.

The inner core layer of the silver halide grains used in carrying out the present invention is, for example, U.S. Pat.
As described in No. 597,856 and No. 2,642,361, sensitization can be carried out with a water-soluble gold compound or with a reduction sensitizer. Such methods are described, for example, in U.S. Pat.
No. 50, No. 2,518,698, No. 2,983,81
You can refer to the description of No. 0 etc.

Furthermore, noble metal sensitization can also be carried out using noble metal compounds such as platinum, iridium, palladium, and the like. Such methods are described, for example, in U.S. Pat.
8,060 and British Patent No. 618.05-1.

Additionally, the inner core layer of the silver halide grains can be doped with metal ions. To dope the inner core layer with metal ions, the metal ions can be added as water-soluble salts, for example, during any process of forming particles of the inner core layer. Preferred specific examples of metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, osmium, and rhodium. These metal ions preferably range from IX10-3 to IX1 per mole of silver.
It is used at a concentration of 0-' molar. However, the inner core layer of silver halide grains may be one that has not been subjected to the above-mentioned chemical sensitization treatment or metal ion doping. In this case, it is thought that the photosensitive center is formed by forming crystal strain at the interface between the inner core layer and the outer shell layer during the process of covering the particles in the inner core layer with the outer shell layer. U.S. Patent No. 3,935,
Reference can be made to the descriptions in No. 014 and No. 3,957,488.

The silver halide emulsion used in the present invention can be chemically sensitized by a conventional method at any stage of production. Furthermore, the silver halide grains of the present invention can store polyvalent metal ions inside the grains. Preferred specific examples of polyvalent metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, platinum, osmium, and rhodium.

In the silver halide grains according to the present invention, it is preferable that the grain surface is not chemically sensitized, or even if it is sensitized, it is only to a small extent.

In the direct positive silver halide photographic material of the present invention, internal latent image type silver halide grains whose surfaces are not fogged in advance can be used. Here, the meaning that the internal latent image type silver halide grain surface is not fogged in advance means that such an emulsion is coated on a transparent film support at 35 mg Ag/c.
It means that the density obtained when a test piece coated so as to have a density of m' is developed with the following surface developer A at 20° C. for 10 minutes without exposure to light does not exceed 0.6, preferably 0.4.

Surface developer A Metol 2.58℃-Ascorbic acid 10 g NaBO2・4H2
035 g KBr 1 g water added 1 λ Further, the emulsion containing silver halide grains according to the present invention is obtained by exposing a test piece prepared as below and then developing it with internal developer B having the following formulation. It provides sufficient concentration.

Internal developer B Metol 2g Sodium sulfite (
anhydrous) 90 g hydroquinone
8g Soda carbonate (-water salt)
52.5 gKBr
5 gKI O,
12.More specifically, exposing a portion of the specimen to a light intensity scale for a defined period of time up to about 1 second;
When developed with internal developer B for 10 minutes at 20°C, another part of the specimen exposed under the same conditions was developed with surface developer A for 2 minutes.
It exhibits a maximum density that is at least 5 times, preferably at least 10 times, that obtained when developed for 10 minutes at 0°C.

Next, the phosphoric acid compound used in the developer in the processing method of the present invention will be explained.

Any phosphoric acid compound can be used, and typical examples include conductors such as phosphoric acid (orthophosphoric acid), orthophosphoric acid, various polyphosphoric acids, and salts thereof. That is, as a phosphoric acid compound that can be used, the following formula [P-
There are those represented by I, [P-Ill or [P-III].

- Formula [P-1] to'JJ3+a general formula [
P II] A', A', A'nPnO3n-
+-Formula [P -III] To 8, A
", A'PO3 [wherein A'~^7 represents a hydrogen atom, an alkali metal atom or an alkyl group, m and n each represent an integer of 1 to 20,] General formula [P-I], [ P-Ill or [P-111]
Among the phosphoric acid compounds represented by the above, preferred for use in the present invention are compounds represented by any of the following formulas [P-rV] to [P-Xll.

- Formula [P-rV M, P, 02° - Formula [P -
V] ]M, -2P, 10:+n++ In the formula, M represents a hydrogen atom or an alkali metal atom, and m and n each represent an integer of 1 to 20. General formula [P-Vl] ]B1-R21-Z-R
In the 22-COOH formula, E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -R2y+
-0R27-, -R2t-OJvORzt-, RzyZ
Jt-, Z is >N-R27-Be, >N
-Ba, R21 to R27 represent substituted or unsubstituted alkylene groups, and 81 to B6 represent hydrogen, -OH, -CO
OM, -PO3M2; at least one of B1 or R6 represents PO, M; at least one of B2 to Bs represents P03M; M represents a hydrogen atom or an alkali metal atom; P-■] RzaN (C)12PO3M
2) 2 [In the formula, R211 is a lower alkyl group, an aryl group, an aralkyl group, a nitrogen-containing 6-membered ring group (-O as a substituent)
H.

-OP, -COOM), M represents a hydrogen atom or an alkali metal atom; -COOM
.

-poM2), C, -C, are hydrogen atoms, -0f
(,-COOM.

-PQJ2. -Nj2, where j is a hydrogen atom, lower alkyl, hLO)1. -PO3M2, M represents a hydrogen atom or an alkali metal atom, and n and m represent O or 1. ] General formula [P-X Ko OM
R32-O-P-OR33 [wherein, R32+ R33 is a hydrogen atom, an alkali metal,
It represents an alkyl group, alkenyl group, or cyclic alkyl group having 1 to 12 carbon atoms, and M represents a hydrogen atom or an alkali metal atom. [In the formula, R34 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an amino group, a carbon Aryloxy group with number 1 to 24, carbon number 6 to 2
represents the arylamino group and amyloxy group of 4, and Q
I-Q s is 10H1 alkoxy group having 1 to 24 carbon atoms,
Aralkyloxy group, amyloxy group, -0M, (M is a cation), amino group, morpholino group, cyclic amino group,
Indicates an alkylamino group, a sialylamino group, an arylamino group, and an alkyloxy group. ] Representative specific examples of the phosphoric acid compound represented by the above formula are shown below.

(P-1) Na4P4012 (P-2)
Na5P304(P-3) H4P2O7CP-4
))lsPso+.

(['-5) Na4PaOrs (P-6)
)13PO4(P-7) NazPOn
(P-8) 83PO4(P-9) HsPOs (1”IO) PO(OhHs) (OH) x(P
(1) Naz) IPOs (P-12)
(N84POs) r.

(P-131(N)14PGs) s (P-14
) 1(sPsQ+.

(P-44) CP-45
) H2 03H2 H3 H3 2NS 11 Nt12 (P-81) 0 (P-62) 0 (P-85)
, 0) 12N-COO-P-(O
K)2 (P-66) 0 83C-COO-P-(OH)2 (P-70) 0 (P-71) 0 1Naυ υNa The amount of the phosphoric acid compound used is preferably from 3g to 12 developer solutions. 200g, more preferably 5g to 10
It is 0g. Particularly preferably, the amount is 6 g to 50 g. In the present invention, it is preferable to use a developer having a pH of 9.5 to 12.0.

In the processing method of the present invention, a photosensitive material is developed in the presence of a fogging agent.

In the processing method used in the present invention, it is preferable that the color developing solution does not substantially contain hydroxylamine.

By incorporating the compound represented by the following formula [11] into the developer used in the present invention, not only the desired effects of the present invention can be better achieved, but also the fog density in the unexposed areas of the photographic material can be improved. It is preferable to use it in combination with the present invention because it is possible to keep it low.

General formula [! I] In the formula, R2 and R3 each represent an alkyl group or a hydrogen atom. However, both R1 and R2 are not hydrogen atoms at the same time. Further, R1 and R2 may form a ring.

In general formula [II], R+ and R2 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom, but the alkyl groups represented by RI and R2 may be the same or different, and each has 1 to 3 carbon atoms. ++ The alkyl groups of R1 and R2 include those having substituents, and R1 and R2 may be combined to form a ring, for example, a heterocyclic ring such as piperidine or morpholine. Good too.

Specific examples of the hydroxylamine compound represented by the general formula [II] include U.S. Patent No. 3,287,125, U.S. Pat.
No. 4, etc., and particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention are usually used in the form of hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, and non-salt forms.

The concentration of the compound represented by the general formula [II] of the present invention in the color developing solution is usually 0.2 g/j to sog/j! , preferably 0.5 g71 to 30 g/N, more preferably 1 g/I! ~15g/I! It is.

Further, these compounds represented by the formula [■] may be used alone or in combination of two or more.

The direct positive photosensitive material of the present invention preferably contains a compound represented by the following formula [III] in any one of the hydrophilic colloid layers.

This formula [III] is as shown below.

u υi In the general formula [Hl], R,,R2 each represent a hydrogen atom or an alkyl group, and each alkyl group RI
+ The number of carbon atoms in R2 is 5 or less.

-Specifically, the compounds represented by formula [11] are preferably those shown in the following (A) to (H), however, those that can be used in the present invention are particularly limited to these compounds. It's not something you can do.

(Compound Examples) (A) (B) (C) , (D) (E) CF) (G) (H) The amount of this compound added to at least one of the photographic constituent layers is from 0.001 to 0.50 g/m2 is preferable, and more preferably o, oos to 0.20 g/m2.

Each of the above compounds may be used alone, or two or more compounds may be arbitrarily selected and mixed.

Further, as long as the effects of the present invention are not impaired, a quinone bending conductor having 5 or more carbon atoms may be added to the compound represented by the above-mentioned formula [II]. However, in any of these cases, the amount used is preferably in the range of 0.001 No. 50 g/m2 even if it is a mixture.

Silver halide emulsions can be optically sensitized using commonly used sensitizing dyes. Combinations of sensitizing dyes used for supersensitization of internal latent image type silver halide emulsions, negative-working silver halide emulsions, etc. are also useful for the silver halide emulsions of the present invention. Regarding sensitizing dyes, see Research Disclosure.
e) Reference may be made to No. 15182 and No. 17643.

When directly obtaining a positive image using the direct positive photosensitive material of the present invention, image exposure (so-called photography) is carried out in the usual manner.
A positive image can easily be obtained directly by surface development of the photosensitive material (by exposing it to light to form an image). That is, the main process for directly forming a positive image is to subject a photographic material having an internal latent image type silver halide emulsion layer to imagewise exposure and then to a process (hereinafter referred to as fogging treatment) that generates fog nuclei by chemical action. .

surface development is carried out after and/or while carrying out fogging treatment. Here, the fogging treatment can be carried out using a compound that generates fogging nuclei (hereinafter referred to as a fogging agent).

A wide variety of compounds can be used as the fogging agent used in the present invention, and it is sufficient that the fogging agent is present during the development process. (preferably in the silver oxide emulsion layer) or in the developing solution or processing solution prior to development processing.The amount used can be varied over a wide range depending on the purpose. When added to the silver emulsion layer, it is added in an amount of 1 to 1500 mg, preferably 10 to 1,500 mg per mole of silver halide.
It is 1000mg. Further, when added to a processing solution such as a developer, the preferable amount is 0.01 to 5 g/i! , particularly preferably from 0.05 to 1 g/l.

Examples of the fogging agent used in the present invention include US Pat.
563,785, hydrazines described in 2.588.982, or U.S. Pat. No. 3,227.5
Hydrazide or hydrazine compounds described in US Patent No. 52; US Pat.
No. 70, No. 3.719,494, No. 3.734.73
Heterocyclic quaternary nitrogen salt compounds described in U.S. Pat. No. 8 and U.S. Pat. Examples include compounds having groups.

These fogging agents can also be used in combination. For example, Research Disclosure (Research Disclosure)
chDisclosure) No. 1.51 [12 describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent.

As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, and they can also be used in combination.

Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-(4-methylphenyl)hydrazine, 1-acetyl-2-phenylhydrazine, 1-acetyl-12-(4-acetamidophenyl)
hydrazine, 1-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine,
Hydrazine compounds such as 1-methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine, formaldehyde phenylhydrazine; 3-(2-formylethyl)-2-methylbenzothiazolium bromide, 3-(2-formyl ethyl)-2-propylbenzothiazolium bromide, 3-(2-acetylethyl)-2-benzylbenzoselenazolium bromide, 3
-(2-acetylethyl)-2-benzyl-5-phenyl-benzoxacilium bromide, 2-methyl-3
-[3-(phenylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-[3-(p-1
lylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-[3-(p-sulfophenylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-[3-(p-sulfophenylhydrazono)propyl] phenylhydrazono)pentyl]benzothiazolium iodide, 1.
2-dihydro-3-methyl-4-phenylpyrido [2,
1-b] Benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phe and rubylide [2,1-b
] -]5-phenylbenzoxacilium bromide 4.4'-ethylenebis(1,2-dihydro-3-methylpyrido[2,1-b]benzothiazolium bromide), 1.2-dihydro-3- N-substituted quaternary cycloammonium salts such as methyl-4-phenylpyrido[2,1-b]benzoselenazolium bromide; 5-[1-ethylnaphtho(1,2-b)thiazolin-2-ylideneethylidene] -1-(2-phenylcarbazoyl)methyl-
3-(4-sulfamoylphenyl)-2-thiohydantoin, 5-(3-ethyl-2-penzothiazolinylidene)-3-[4-(2-formylhydrazino)phenyl]rhodanine, Examples include 1-[4-(2-formylhydrazino)phenyl]-3-phenylthiourea, 1,3-bis[4-(2-formylhydrazino)phenylcothiourea, and soybean.

After image exposure, the direct positive-type light-sensitive material of the present invention forms a direct positive image by exposing the entire surface to light or developing it in the presence of a fogging agent. Although any development method can be employed for the direct positive photosensitive material according to the present invention, a surface development method is preferable. This surface development processing method means processing with a developer substantially free of silver halide solution.

Developers that can be used in the developer used for developing the direct positive photosensitive material according to the present invention include common silver halide developers, such as polyhydroxybenzenes such as hydroquinone, aminophenols, and 3-pyrazolidone. ascorbic acid and its derivatives, reductones, phenylenediamine, etc., or mixtures thereof.

Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, ascorbic acid, N,N-diethyl-p-phenylenediamine, diethylamino-0-toluidine, 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)aniline, 4-
Examples include amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline. These developers may be included in the emulsion in advance and allowed to act on the silver halide during immersion in a high pH aqueous solution.

The developer used in the present invention may further contain certain antifoggants and development inhibitors, or these developer additives may optionally be incorporated into the constituent layers of the photographic material. 0 Commonly useful antifoggants include benzotriazoles such as 5-methylbenzotriazole, benzimidazoles, benzothiazoles, benzoxazoles, heterocyclic thiones such as 1-phenyl-5-mercaptotetrazole, aromatic Contains group and aliphatic mercapto compounds.

Ru. Further, a development accelerator such as a polyalkylene offside derivative or a quaternary ammonium salt compound can also be contained in the developer.

Even in the case of direct positive-working light-sensitive materials, generally after the silver halide photographic light-sensitive material is developed, a fixing process is performed with a processing solution containing a silver halide solvent to remove unnecessary silver halide, or after development. When a color image is obtained by processing, in order to remove unnecessary silver halide and metallic silver formed by development, a bleach-fixing process is performed using a processing solution containing a silver halide solvent and an oxidizing agent. A bleach-fixing process is usually performed. In order to speed up processing, when a photographic material is used that undergoes direct fixing or bleach-fixing after development without washing with water or stopping with an acid bath, the minimum density of the image can be kept low; Good quality images can be obtained.

Various photographic additives may optionally be added to the emulsion containing silver halide grains according to the present invention.

Other additives used depending on the purpose in the present invention include wetting agents such as dihydroxyalkanes, and film property improvers such as alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid. Suitable are water-dispersible particulate polymeric substances obtained by emulsion polymerization such as copolymers with acrylic acid, styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc.
Coating aids include, for example, saponin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, PO adjusters, antioxidants, antistatic agents, thickeners,
It is optional to use graininess improvers, dyes, mordants, brighteners, development rate regulators, matting agents, and the like.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer and a filter layer, if necessary, to obtain an internal latent image type silver halide photographic light-sensitive material.

It is useful to apply the direct positive-working light-sensitive material according to the present invention to color applications, and in this case, it is preferable to include cyan, magenta, and yellow dye image-forming couplers in the silver halide emulsion. You can use whatever is available.

In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent browning of dye images due to short-wavelength actinic rays, especially Tinuvin PS, 320. It is useful to use Ciba-Geigy 326, Ciba-Geigy 327, and Ciba-Geigy 328 together or in combination.

Any support can be used, but typical supports include polyethylene terephthalate film, polycarbonate film, and
Includes polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, polyethylene laminate paper, etc.

In addition to gelatin, an appropriate gelatin 8 conductor may be used as a protective colloid or binder in the emulsion containing silver halide grains according to the present invention, depending on the purpose. Examples of suitable gelatin derivatives include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

In addition, in the present invention, other hydrophilic binders can be included depending on the purpose, and suitable binders include gelatin, colloidal albumin, agar, gum arabic, dextran, alginic acid, acetyl-containing 19%～
Cellulose derivatives such as cellulose acetate hydrolyzed to 20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinylamino acetate copolymers, polyvinyl Emulsions include alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, boribitriylamine, polyaminoethyl methacrylate, polyethyleneamine, etc. layer or intermediate layer, protective layer,
It can be added to constituent layers of photographic materials such as filter layers and backing layers depending on the purpose, and the hydrophilic binder can further contain suitable plasticizers, lubricants, etc. depending on the purpose.

Further, the constituent layers of the direct positive photosensitive material according to the present invention can be hardened with any suitable hardening agent. Examples of these hardening agents include chromium salts, zirconiums, aldehydes such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners. .

In addition, the photographic light-sensitive material according to the present invention may have a large number of various photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer on a support. is possible.

The following margin [Examples] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples.

<Preparation of emulsion> (1) Preparation of monodisperse silver chlorobromide emulsion EM-1-EM-7 Monodisperse silver chlorobromide emulsion EM-1 was prepared according to the following procedure.

An aqueous solution containing ammonia and silver nitrate, and an aqueous solution containing potassium bromide were added to the aqueous solution containing Osseini gelatin, a silver bromide seed emulsion with an average particle size of 0.11 μm, and ammonia while controlling the temperature at 40°C. Silver bromide core particles having an average particle size of 0.15 μm were formed by simultaneously adding them using a controlled double jet method and at a rate of 70% of the maximum rate at which new silver halide nuclei were not generated.

At that time, the PH and PAg of the emulsion during the above addition were controlled using a potassium bromide aqueous solution and an acetic acid aqueous solution so that cubic-shaped particles could be obtained.

Next, to the emulsion containing the silver bromide core particles, an aqueous solution containing ammonia and silver nitrate, and potassium bromide and sodium chloride (in a molar ratio of KBr:NaC1 = 50
: 50) was added simultaneously using a controlled double jet method at an addition rate of 50% of the maximum addition rate at which no new silver halide nuclei were generated, to obtain grains with an average particle size of 0.225 μm. A shell was formed on the core particles until the core particles were dissolved. At that time, the pH of the emulsion was adjusted during the above addition using an aqueous solution containing potassium bromide and sodium chloride (KBr:NaCf-1:9 in molarization) and an acetic acid solution so as to obtain cubic-shaped particles. and p, Ag was controlled. Next, the emulsion containing the core-shell type silver chlorobromide particles was washed with water to remove water-soluble salts, and then gelatin was added to prepare silver chlorobromide emulsion EM-1.

This emulsion was confirmed to be a monodisperse emulsion containing cubic silver chlorobromide grains of uniform size.

Then, according to the same procedure as above, emulsion EM-2 containing monodisperse silver chlorobromide grains having a silver bromide core grain size, a final average grain size, and a shell halide composition as shown in Table 1 was prepared. ~EM-7 were prepared respectively.

Table 1 (2) Preparation of polydisperse silver chlorobromide emulsion EM-8 Polydisperse silver chlorobromide emulsion EM-8 was prepared according to the following procedure. While controlling the temperature of an aqueous solution containing Osseini gelatin and 0.75 mol of potassium bromide at 60°C, an aqueous solution containing 0.70 mol of silver nitrate was added to this aqueous solution over 40 minutes to form polydispersed silver bromide particles. An emulsion containing the following was prepared. Then, an aqueous solution containing 0.20 mol of sodium chloride and 0.80 mol of potassium bromide and an aqueous solution containing 1.0 mol of silver nitrate were simultaneously added to the emulsion over 20 minutes. The emulsion thus obtained was washed with water to remove water-soluble salts, and then gelatin was added to form silver chlorobromide emulsion EM-8. It was confirmed by an electron microscope that this emulsion was a polydisperse silver chlorobromide emulsion.

<Preparation of Samples> Next, using the above-mentioned silver chlorobromide emulsions EM-1 to EM-7, samples consisting of direct positive type silver chlorobromide color photographic light-sensitive materials were prepared according to the following procedure. did.

First, the following coating solutions were simultaneously coated on a backed support made of polyethylene laminate with a thickness of 110 μm and dried to form an antihalation layer and a first intermediate layer as its auxiliary layer. formed.

1st layer: Antihalation layer (HC) A coating solution prepared by adding a coating aid (S-2) to a gelatin solution containing 5 g of colloidal silver is coated with a coating solution containing 1.5 mg/d of colloidal silver.
It was coated so that the gelatin/gelatin ratio (based on weight, hereinafter the same) was 0.12.

2nd layer: 1st intermediate J! ! (1, LL -1) A coating solution prepared by adding a coating aid (S-2) and a hardening agent (H-3) to a gelatin solution has a gelatin coverage of 7+wg/da.
It was applied so that

On the support on which the antihalation layer and the first intermediate layer were formed in this way, each emulsion consisting of the following formulation was coated, and the following layers 3 (red sensitive layer) to 8 JI (
A sample 1 of the present invention was prepared by forming each layer up to the protective layer).

The values shown in parentheses following each material are the coating amount (
mg/dm”).

Third layer: red-sensitive silver halide emulsion layer (R) the emulsion EM
-1, red-sensitive sensitizing dyes RD-1 and RD-2, cyan couplers CC-1 (2,08) and CC-2 (2,
08), fogging agent FA-1, image stabilizer A
O-3 (2,2), stain inhibitor As-2 (0,15
), solvent 5O-1 (3,3L anti-irradiation dye Al-2 (0,09), inhibitors 5T-1 to 5T-6,
An emulsion prepared by adding gelatin and a coated silver amount of 3
, 28 rag/dIll", weight 3 with gelatin
．． 8 mg/da''.

4th N: Second intermediate 7W (I, L, -2) A gelatin aqueous solution containing a color mixing inhibitor AS-1 (0,55) and a solvent 5o-2 (0,72) was added to a gelatin amount of 7.5B/ dm
” was applied and formed.

5th layer: Green-sensitive silver halide emulsion JiJ (G) The above emulsion EM-2 contains green-sensitive A1 sensitizing dye GD-1, Mazenkkabra-MCI (2,4), fogging agent F-1, image stabilization agent AO-1 (2,2), AO-2 (1,25L stain inhibitor As-1 (0,03), AS-2 (0,19
), solvent 5o-4 (3,15), anti-irradiation dye Al-1 (0,13), inhibitor 5T-1 to 5T-
6 and gelatin and coated with the prepared emulsion.
ft is 3.30 B/dm”, gelatin amount is 13.0
mg/d+a''.

6th N=Yellow filter layer (yc) Yellow colloid produced by oxidation in an alkaline weak reducing agent (weak reducing agent removed by noodle water washing method after neutralization) g! (1,05
) to an aqueous solution containing color mixing inhibitor AS-1 (0,40
), solvent 5O-2 (0,49), polyvinylpyrrolidone (0,47), and gelatin were added and coated to form a gelatin coating amount of 9.2 mg/da+''.

7th layer: blue-sensitive silver halide emulsion layer (B) the above emulsion EM
-3, blue-sensitive sensitizing dye BD-1, capri agent FA-1,
Yellow coupler YC-1 (8,2), image stabilizer AO
-3 (3,0), stain inhibitor AS-1 (0,25)
, AS-2(0,25), solvent 5o-1(5,2),
Inhibitor 5T-1, 5T-2, 5T-4, 5T-5, 5T
-6 and gelatin were added, the silver coating amount was 5.6 mg/d+++" and the gelatin coating amount was 14.3.
mg/dm".

8th layer: Protective layer (PRO) Ultraviolet absorber UV-1 (0,65), UV-2 (1,9
A gelatin aqueous solution prepared by adding solvent 5o-3 (1,0), colloidal silica (0,07), and gelatin to an aqueous solution containing 5) was prepared with a gelatin loading of 7.8 m
g/da''.

Next, the type of silver/gelatin and cyan coupler in the above antihalation layer and the redness Ji (R)
Table 2 was prepared in exactly the same manner as the invention sample 1 above, except that the types of silver chlorobromide emulsions in the green-colored layer (G) and the blue-sensitive layer (B) were changed as shown in Table 2. Samples 2 to 3 of the present invention and Comparative Samples 1 to 7 as shown in Fig. 1 were prepared.

Inventive sample 2 was produced without the first intermediate layer, and comparative sample 2 was produced without the antihalation layer.

Note to Table 2: * in the table indicates that the silver/gelatin ratio and cyan coupler marked with it are outside the scope of the present invention.

D-1 D-2 D-1 D-I A-1 Sl+ c-i c-2 H (C1h)z c-3 shi1 C-1 stl+t(tJ C-1 I o-1 o-2 o -3 H3 H3 5O-4 AS-1 H AS-2 O-1 O-2 O-3 T-I T-2 T-3 T-4 T-5 T-6 0 C, H5 C1h- COO-CHt-C1l-(CL)!-CH
3■ A-1 C0CH=CH! A-2 V-1 し41′l啼(t) UV-2 AI-I AI-2 (Hereafter the margin) Example 1 Each of the above samples was tested with a KS-7 sensitometer (manufactured by Konica Corporation).
After wedge exposure was performed using the following method, development processing was performed according to the following processing method 1.

[Processing method 1]

Processing process Time Temperature color development
2 minutes 30 seconds 33°C bleach fixing
40 seconds Stable at 33°C 20 seconds 3 times Dry at 33°C 30 seconds
60°C to 80'C [Color development - composition of film] Diethylenetriaminepentaacetic acid 2.0g Benzyl alcohol 12.8g Diethylene glycol 3.4g Sodium sulfite 2.0g Sodium bromide
0.5g Hydroxylamine sulfate 2.6g Sodium chloride
3.2g aniline
4.25g potassium carbonate
Add 30.0g water
11p H10.5 (pH was adjusted with potassium hydroxide and sulfuric acid) [Bleach-fix solution composition] Almonium thiosulfate (54wt%) 150c
c Sodium sulfite 15g Glacial acetic acid 8.61g Add water lI! .

pH5,4 The pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stable liquid composition]

1-Hydroxyethylindene-L 1'-diphosphonic acid (60%) 1.6d Bismuth chloride 0.35g Polyvinyl and lolidon 0.25g Aqueous ammonia 2.5m! Nitrilotriacetic acid Na acetate 1.0g Fluorescent brightener (4
,4'-diaminostilbene series) Add 1.0g of water
l-poor pH H7.5 (pH was adjusted with potassium hydroxide or hydrochloric acid.) Blue light (B) and green light (G ) and red light (R
) at gamma-1 (r+) and minimum density (D□7
) was measured and the results are shown in Table 3. Here γ1
The value is the tangent of the angle at which the straight line connecting the densities 0.15 and 0.5 on the characteristic curve intersects the horizontal axis, and indicates the contrast of the image.

Furthermore, dot wedges (150 lines/inch) were set on the sample surfaces of the above-mentioned inventive samples 1 to 3 and comparative samples 1 to 7 to detect blue light (B), green light (G), and red light (R). After decomposing and exposing the sample to each color light and developing it according to the processing method 1, Konica Elia Duck 1000
(manufactured by Konica Corporation) to investigate halftone dot reproducibility, and the results are shown in Table 3.

In addition, the color development time in the processing method 1 is 1 minute and 30 minutes.
Using Processing Method 2, which consists of the same processing steps as Processing Method 1 except for changing the time to seconds, gamma-1, minimum density, and halftone reproducibility were measured in the same manner as above, and these results were also combined. The results are shown in Table 3.

From the results shown in Table 3, in Comparative Samples 1 to 7, processing with a short color development time, that is, processing method 2, resulted in γ3 , D a r n and halftone reproducibility change significantly, whereas in the samples 1 to 3 of the present invention, the changes in the above characteristics are small between processing methods 1 and 2, and therefore the samples of the present invention are suitable for rapid processing. Sample 1 of the present invention forms an image with excellent halftone dot reproducibility, that is, sharpness, and the variation in halftone dot reproducibility between processing methods 1 and 2 is smaller than sample 2 of the present invention. It can be seen that in the present invention, it is preferable to provide an intermediate layer on the antihalation silane layer.

(The following is a blank space) Example 2 Samples 1 to 3 of the present invention were prepared in the same manner as Processing Method 1, except that the bleach-fixing time in Processing Method 1 was changed to 10 seconds, 20 seconds, 30 seconds, and 40 seconds. and Comparative Samples 1 to 7 were developed, and each image obtained as a result was determined to have gamma-1 (r+) and maximum density (D□
X) was measured and the results are shown in Table 4.

From the results shown in Table 4, samples 1 to 3 of the present invention have smaller fluctuations in γ and D m a X than comparative samples 1 to 7 even when the bleach-fixing time is shortened. It can be seen that even in rapid processing, it exhibits good desilvering properties.

Example 3 The present invention was carried out in exactly the same manner as above, except that the magenta coupler and fogging agent used in the green-sensitive layer of the invention samples 1 to 3 and comparative sample 4 were changed as shown in Table 5. Invention Samples 4 to 6 and Comparative Sample 8 were prepared, and after each sample was subjected to a process of passing through an optical wedge, hydroxyl sulfate was extracted from Color Developer 1 used in Processing Method I; and Color Developer I. A color developing solution 2 obtained by excluding the amine; a color developing solution 3 obtained by replacing hydroxylamine sulfate in the color developing solution 1 with 2.4 g of diethylhydroxylamine; a color developing solution 3 obtained by replacing the potassium carbonate in the color developing solution I with phosphoric acid. (85%)
9ml of color developer 4; color developer 5 in which potassium carbonate in color developer 1 is replaced with phosphoric acid (85%) 9d, and hydroxylamine sulfate is excluded; color developer rj, 1; A color development process was performed using a color developer 6 in which potassium carbonate and hydroxylamine sulfate were replaced with phosphoric acid (85%) 9d and diethylhydroxylamine 2.4g, respectively.

Sensimetry was performed on the resulting image to measure the maximum density (D, , ) and minimum density (D, i, ) for each magenta image, and the results are shown in Table 6.

Table 5 From the results shown in Table 6, it is clear that when the color developer contains phosphoric acid and when the color developer does not contain hydroxylamine, the photographic performance is 7N better than when the color developer does not contain phosphoric acid. You can see what you can get.

Example 4 Samples 7 to 10 of the present invention were prepared in the same manner as Sample 1 of the present invention, except that the amount of gelatin applied in the antihalation layer was changed as shown in Table 7 (the silver/gelatin ratio was 0). (fixed at .10).

Table 7 shows that the above-mentioned samples 7 to 10 of the present invention were treated according to the treatment method 1 of Example 1, and were further treated in the same manner using bleach-fix solutions with different pH values of 4.8 and 6.0. ,
Among the images thus obtained, gamma-1 (γl) and minimum density (D, i, .) were measured for the cyan image.

These results are shown in Table 8.

(Hereinafter in the margin) Table 8 From the results shown in Table 8, it is clear that among the present invention samples 8 and 9, which have a preferable amount of gelatin in the antihalation layer, are particularly effective against fluctuations in the pH of the bleach-fix solution. It can be seen that good photographic performance is maintained.

Example 5 The present invention sample 1 and all (
Samples 11 to 14 of the present invention were prepared in the same manner (silver/gelatin ratio was fixed at 0.08).

Table 9 shows that the above-mentioned samples 11 to 14 of the present invention were processed according to the processing methods 1 and 2 of Example 1, and the gamma-1 (γ1), minimum density (D, i,
) and halftone reproducibility were measured and the results are shown in Table 10.

(Left below) From the results shown in Table 10, it can be seen that among the present invention samples 12 and 13, which have a preferable amount of colloidal silver in the antihalation layer, are particularly suitable for rapid processing and have i′# sharpness. It can be seen that a sharp image is formed.

Example 6 The emulsion EM-1 used to form the red-sensitive silver halide emulsion layer in the sample 1 of the present invention was replaced with the emulsion EM-8.
Sample 15 of the present invention was prepared in exactly the same manner as sample 1 of the present invention, except that the sample was changed to, and this sample was treated according to the treatment methods 1 and 2 of Example 1. The measured values of gamma-1 (TI), minimum density, and halftone re-examination of the cyan image obtained as a result were combined with the measured values (obtained in Example 1) of the sample 1 of the present invention, and Shown in the table.

(Left below) Table 11 From the results shown in Table 11, it is clear that silver chlorobromide grains are monodisperse and have a silver chloride content of 30 mol% or more in the shell portion, and that the grains have an average grain strength. (Sample 1 of the present invention, in which the emulsion EM-' 1 having a diameter of 0.3 μm or less was used as the red-sensitive layer, was the sample 1 of the present invention in which the polydisperse silver chlorobromide emulsion EM-8 was used in the red-sensitive layer. It can be clearly seen that it is more suitable for rapid processing than Sample 15 and exhibits superior photographic performance.

〔Effect of the invention〕

As is clear from the above description, the present invention is a direct positive type halogenated color photograph that is suitable for rapid processing, exhibits excellent photographic performance, and forms color images with particularly excellent sharpness. A photosensitive material is provided.

Applicant Konica Co., Ltd. Company Agent Patent Attorney Miki Nakajima 2-person procedural amendment dated May 1, 1999 Director General of the Patent Office Yoshi 1) Moon Yi 1, Indication of Case 1988 Patent Application No. 93181 No. 2, Name of the invention Direct positive silver halide color photographic light-sensitive material 3, Relationship to the case of the person making the amendment Patent applicant address: 1-26-2-4 Nishi-Shinjuku, Shinjuku-ku, Tokyo, Attorney 7; Contents of the amendment - Contents of the amendment - (1) In the specification, the statement in the scope of claims column is attached to the attached sheet (A
).

(2) Specification, page 3, line 4 Where it says "Details", "For more information" I am corrected.

(3) Same, page 11, line 15 It says "film thickness", “II*thickness” I am corrected.

(4) Same, page 16, line 1 It says "Mondante", "Mordaunt" I am corrected.

(5) Same, page 16, line 10 It says "used above", “The above that can be used in combination with colloidal silver” I am corrected.

(6) In the same publication, page 16, lines 11 to 12, the statement "Colloidal silver, etc. is particularly preferred" is corrected to "Colloidal manganese etc. are preferred."

(7) Same, p. 16, 14. to the line It says "Karla", "Color" correct.

(8) Same, page 16, line 15 It says "colloidal silver mentioned above", "Colloidal silver according to the present invention" I am corrected.

(9) In the same publication, page 18, lines 6 to 7, the phrase "magenta couplers, especially those listed below" is corrected to "magenta couplers are useful, but those listed below."

(10) Same, page 18, line 8 It says, "is useful." "is especially preferable." I am corrected.

(11) The description ``The above-mentioned formula CM-1)J according to the present invention in the first line of page 19 of the same publication is deleted.

(12) On page 28, line 15 of the same, the phrase "the following compounds according to the present invention" was replaced with "the following compounds according to the present invention,"
- Expressed by the formula CM-1).”

(13) Ibid., p. 44, lines 1-2: ``The above...
...Specific examples" should be corrected to read, "In addition to the above representative examples, other specific examples of the compound represented by the formula CM-I)."

(14) On page 44, line 16 of the same, the phrase ``The coupler of the present invention is'' is corrected to ``The coupler represented by [-formula CM-1]''.

(15) Same, page 44, line 19 "Also, the coupler of the present invention is" [Also, the coupler represented by the formula CM-1) is I am corrected.

(16) In the same article, page 54, line 7, the phrase ``including cyan couplers, and these'' is corrected to ``including cyan couplers, and these couplers are the above.''

(17) Ibid., p. 89, lines 10 to 11, “
Delete the statement ``Full exposure or''.

Above - Attachment (A) - ``2. Claims (1) Each silver halide emulsion layer containing a cyan coupler, a magenta coupler, and a yellow coupler is formed on a support, and also contains colloidal silver. a photographic constituent layer in which an anti-bulge layer is formed between the silver halide emulsion layer and the support, and a positive image is formed by developing with a color developer in the presence of a fogging agent. In the direct positive silver halide color photographic light-sensitive material, at least one of the cyan couplers comprises any one or two or more compounds represented by the following general formula (I), and in the antihalation layer: Silver/gelatin weight ratio is 0.05
0.2.

- Boatman (I) n [wherein R' represents an alkyl group or an aryl group, R2 represents an alkyl group, cycloalkyl group, aryl group or a heterocyclic group, and R3 represents a hydrogen atom, a halogen atom, an alkyl group or represents an alkoxy group, or forms a ring together with R1, and Z represents a hydrogen atom or a group that can be separated by reacting with an oxidized product of an aromatic primary amine color developing agent] (2) The direct positive silver halide color photographic material according to claim 1, wherein the color developing solution contains a phosphoric acid compound.

(3) The direct positive silver halide color photographic material according to claim (1) or (2), wherein the color developing solution does not substantially contain hydroxylamine. ”

Claims (3)

[Claims] (1) Each silver halide emulsion layer containing a cyan coupler, a magenta coupler, and a yellow coupler is formed on a support, and an antihalation layer containing colloidal silver is formed between the silver halide emulsion layer and the support. It has a photographic constituent layer formed between it and the body,
In a direct positive type silver halide color photographic light-sensitive material which forms a positive image by developing with a color developing solution in the presence of a fogging agent, at least one of the cyan couplers is represented by the following general formula (I). It consists of one or more of the compounds, and the weight ratio of silver/gelatin in the anti-halation layer is 0.05.
The above-mentioned direct positive silver halide color photographic light-sensitive material is characterized in that the general formula (I) is ▲ Numerical formulas, chemical formulas, tables, etc. represents an aryl group, R^2 represents an alkyl group, cycloalkyl group, aryl group or a heterocyclic group, R^3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, or together with R^1; to form a ring, and Z represents a hydrogen atom or a group that can be released by reacting with an oxidized product of an aromatic primary amine color developing agent] (2) The direct positive silver halide color photographic material according to claim (1), wherein the color developing solution contains a phosphoric acid compound. (3) Claim (1) characterized in that the color developing solution does not substantially contain hydroxylamine.
Direct positive silver halide color photographic material according to item (2).