JPH07104421A - Direct positive color photographic material, color image formation, and color-proof formation - Google Patents

Abstract

PURPOSE:To obtain a hard image which has high max. concentration and the low min. concentration, by allowing plural specific kinds of compounds to be contained in a blue sensitive layer, green sensitive layer, red sensitive layer, and a nonphotosensitive layer. CONSTITUTION:A blue sensitive layer, green sensitive layere, and a red sensitive layer which contain the inside latent image type silver halide particles which are not previously blurred and color image forming couplers, and the contiguous nonphotosensitive layer are formed on a supporting body, and the hydroquinone group compound represented by the formula I and the compound which liberates the blurring agent or the development accelerating agent represented by the formula II are contained at least in one layer among the above-described layers. In the formula I, each of RQ<1> and RQ<2> is a hydrogen atom, etc., and each of RQ<3>, RQ<4>, and RQ<6> is a hydrogen atom, halogen atom, etc., and RQ<5> represents the aryl group which is joined with RQ<3> through the same group or a connecting group. Further, in the formula II. R<1> is a hydrogen atom, etc., and R<2> is an alkyl group, etc., X is -CO-, etc., and each of R<3> and R<4> is a hydrogen atom, etc., and B is a group which liberates FA (blurring agent), after the separation from a hydroquinone basic nucleus oxidized body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive color photographic light-sensitive material utilizing an internal latent image type silver halide emulsion, a color image forming method using the same, and a color proof making, which makes it possible to directly obtain a positive image. Regarding the method.

[0002]

BACKGROUND OF THE INVENTION Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative films are well known.
As a method for forming a positive image using a conventionally known direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which is not fogged in advance. This method is a method for directly obtaining a positive color image by subjecting a photographic light-sensitive material to image development, surface development after or after fog treatment. The internal latent image type silver halide photographic emulsion which has not been previously fogged is a type of halide having a photosensitive nucleus mainly inside the silver halide grain and a latent image is mainly formed inside the grain upon exposure. A silver photographic light sensitive emulsion. Various techniques have been known so far in this field. For example, US Pat. No. 2,592,250.
Nos. 2466957, 2497875, 25
No. 88982, No. 3317322, No. 3761266
Nos. 3,761,276, 3,796,577 and British Patent Nos. 1,115,363, 1,150,553, 10,
Those described in each specification of No. 11062 are the main ones. The formation mechanism of the direct positive image is explained as follows. That is, when imagewise exposure is performed, a so-called internal latent image is formed on the silver halide, and a fog treatment is then applied to cause a surface desensitizing action due to the internal latent image (that is, the halogen in the exposed portion is affected). Development nuclei (fog nuclei are not generated on the surface of silver halide), development nuclei are selectively generated only on the surface of unexposed silver halide,
Then, a normal surface development process is performed to form a photographic image (positive image) on the unexposed portion. The fog treatment method includes a so-called "optical fog method" for exposing the entire surface of the photosensitive layer and a "chemical fog method" for using a nucleating agent. Direct positive color silver halide photographic light-sensitive materials using internal latent image type silver halide emulsions which have not been previously fogged as described above have been accepted in recent years due to the simplicity of their processing steps, and color copying and color plate-making, It has been used for inspection of printing, preparation of color proof for adjustment, etc.

The working process of the color printed matter includes the steps of color-separating a color original and converting it into a halftone dot image to produce a transmission type halftone dot image. A printing plate is made from the obtained transmission type halftone image, but prior to this, the final printed matter (main printing)
There is a step of inspecting the state, characteristics, etc., and performing necessary calibration (color calibration). As a color proofing method, conventionally, a method of making a printing plate and making a test print has been used. However, in recent years, various color proofs have been produced for the purpose of speeding up the calibration process and reducing costs.
As a method for producing a color proof, a photopolymer, a diazo method, a surprint method using a photoadhesive polymer and the like, and an overlay method are known (for example, US Pat. No. 3,582,327, JP-A-56-50121).
7 and 59-97140). However, all of these methods require superposition and transfer of images, and also require superposition and transfer of a plurality of figures, and the process is complicated and requires a lot of time and cost. .. JP-A-56-104335 discloses that
A method for producing a color proof using a color photographic light-sensitive material has been disclosed, and this method has a great advantage in terms of simplicity of the process and low cost, and is characterized by excellent tone reproducibility. The color proofing method using the above color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a coloring method having a continuous gradation, and a magenta (M) color, cyan (C) color, yellow ( This is a method in which each color of Y) and black (B) is sequentially contact-exposed so that a color negative is printed on a color paper, and then a designated color development processing is performed to obtain a color proof. This method has a feature that the process is simple and easy to automate as compared with the various methods described above. There are several possible silver halide color photographic light-sensitive materials that can be used in such color proofs. Among them, the transmission type black and white halftone image used in the production process of the color printed matter described above is often a positive type especially in Japan and Europe, and therefore, as a silver halide color photographic light-sensitive material for color proofing. Many positive-positive type photosensitive materials are used. Among them, the direct positive type color photographic light-sensitive material, of which the practical application technology has been rapidly advanced in recent years, has been noted as being most suitable for use in color proof because of the ease of processing.

In this application, halftone dot reproducibility and whiteness of a white background are particularly important performances. Therefore, the maximum image density is high and the minimum image density is low for a direct positive color photographic material. In addition, it is required to provide an image with a hard gradation.

In silver halide color photographic light-sensitive materials, it is already known to release a development accelerator or fogging agent from a certain compound during color development processing. JP-A-57-150845, Japanese Patent Application No. 57-161
515, JP-A-59-170840 and JP-A-2-
No. 213838 discloses a compound which releases a fogging agent by a reaction with an oxidized product of a color developing agent, which is said to have a contrast enhancement effect and a development accelerating effect by releasing an imagewise fogging agent. Also disclosed in JP-A-60-107029 is a compound which releases an imagewise fogging agent by a redox reaction with an oxidized form of a developing agent by black and white development using a black and white developing agent such as hydroquinone, methol, 3-pyrazolidone. Has been done,
It is described that it is effective for enhancing the feeling and contrast of a negative emulsion.

Further, JP-A-2-244041 discloses an imagewise release of a quaternary ammonium salt compound by reacting with an oxidized product of a developing agent. However, in each of these methods, the maximum image density increased, but the minimum image density also increased.

On the other hand, as a method effective for suppressing this minimum concentration, it is known to add a hydroquinone derivative, and JP-A-63-80250 and JP-A-4-28595 are known.
5, etc. Furthermore, the combined use of these hydroquinone derivatives with the above-mentioned fogging agent or compound releasing a development accelerator is also described in JP-A-2-8354.
2 is disclosed. However, although these methods can suppress the minimum image density, they have a problem of decreasing the maximum image density.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a direct positive color photographic light-sensitive material having a high maximum density and a low minimum density and a high contrast, a color image forming method using the photographic light-sensitive material, and a color proof. Is to provide a method.

[0009]

Means for Solving the Problems The present inventor has conducted extensive studies in search of a compound suitable for the above purpose, and as a result, is represented by the specific hydroquinone compound represented by the above formula and the above formula, It was found that the intended light-sensitive material can be obtained by using a fogging agent or a compound releasing a development accelerator in combination, and the present invention has been completed.

The present invention comprises a support having thereon a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing an internal latent image type silver halide grain not previously fogged and a color image-forming coupler, and a non-photosensitive layer adjacent thereto. In a direct positive color photographic light-sensitive material having at least one photosensitive layer, at least one of the following blue-sensitive layer, green-sensitive layer, red-sensitive layer and non-light-sensitive layer has the following general formula (HQ1) or (H
Q2):

[0011]

[Chemical 5]

[Wherein R^Q1And R^Q2Are independent
The hydrogen atoms or bonds with oxygen atoms during development processing.
Represents a group that is released to release a hydroxyl group, and R^Q3, R^Q4And
And R^Q6Are each independently a hydrogen atom, halogen atom,
Rufo group, carboxyl group, cyano group, alkyl group, al
Kenyl group, aryl group, acylamino group, sulfonami
Group, alkoxy group, aryloxy group, alkylthio
Group, arylthio group, acyl group, acyloxy group, sulfur
Fonyl group, carbamoyl group, alkoxycarbonyl group,
Sulfamoyl group, ureido group, urethane group or carbonic acid
R represents an ester group^Q5Is the above R^Q3With the group shown by
Represents an aryl group attached through the same group or a linking group.
Forgotten, but above R^Q5Is the above R^Q3Same as the group represented by
When R is^Q3And R^Q4Or R^Q5And R^Q6Are joint
To form a carbocycle or a heterocycle, and the above R^Q3
~ R^Q6At least one of the
Tsu R ^Q3~ R^Q6Is a hydrogen atom and an alkyl group
When at least one of the alkyl groups has 6 or more carbon atoms,
Yes, and R^Q3~ R^Q6Has a total carbon number of 15 or less. ]

[0013]

[Chemical 6]

[Wherein R ^{Q11 to} R ^Q16 are each independently a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a cyano group, an alkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamide group, an alkoxy group. Represents an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acyloxy group, a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group, or a sulfamoyl group, and has the above R ^Q11 and R ^Q12 or R ^Q14 and R
^Q15 may together form a carbocycle or a heterocycle; R ^Q17 and R ^Q18 are each independently a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group, and R ^Q17 and R ^Q18 described above may together form a carbocycle or a heterocycle. ] A direct positive color photographic light-sensitive material comprising at least one hydroquinone compound represented by the formula [1] and at least one compound capable of releasing a fogging agent or a development accelerator represented by the following formula (I).
General formula (I)

[0015]

[Chemical 7]

In the formula, R ¹ represents a hydrogen atom or an alkyl group, R ² represents an alkyl group, an aryl group, a heterocyclic group, an amino group or an alkoxy group, and X represents —CO— or —S.
Represents O ₂ — or —COCO—. R ³ and R ⁴ represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less. B represents a group that releases FA after the separation from the hydroquinone mother nucleic acid product, m is an integer of 0 to 2, and FA represents a fogging agent or a development accelerator residue. A and A'represent a hydrogen atom or a group which can be removed with an alkali. R ² and R ³ may cooperate with each other to form a heterocycle.

In the present invention, the above direct positive color photographic light-sensitive material is subjected to imagewise exposure, and then the following formula (D):

[0018]

[Chemical 8]

[In the formula, R ^D1 represents an alkyl group, and R ^D2
Represents an alkylene group, provided that R ^D1 and R ^D2 may ^combine with each other to form a ring. ] It is a color image forming method characterized by carrying out development processing using a developing agent.

The present invention further provides a cyan plate halftone dot image film, a magenta halftone dot image film, a yellow plate halftone dot image film and a black halftone dot dot obtained by subjecting the above color photographic light-sensitive material to color separation and halftone image conversion. A method for producing a color proof is characterized in that an image film is used for sequential exposure with red light, green light, and blue light, and then color development processing is performed.

Furthermore, the present invention is a color image forming method characterized in that the above direct positive color photographic light-sensitive material is subjected to color development processing after scanning exposure for an exposure time of 10 ^-3 seconds or less per pixel. .

The direct positive color photographic light-sensitive material of the present invention will be described below. The direct positive color photographic light-sensitive material of the present invention comprises, on a support, a light-sensitive layer (a light-sensitive emulsion layer) having three different color sensitivities of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, and these layers. At least one non-photosensitive layer is provided adjacent to the layer. Each light-sensitive layer contains an internal latent image type silver halide grain and a color image-forming coupler (color coupler) which have not been fogged in advance.

The hydroquinone derivative represented by the above formula (HQ1) or (HQ2) will be described.

First, the compound represented by the above general formula (HQ1) will be described in detail. In the above formula (HQ1), examples of the group represented by R ^Q1 and R ^Q2 which releases a hydroxyl group by breaking a bond with an oxygen atom during development processing include an acyl group, an alkoxycarbonyl group, an aminocarbonyl group, or Further, the groups described in JP-A-59-197037 or 59-201057 can be mentioned. Examples of the acyl group include acetyl group, chloroacetyl group, dichloroacetyl group, benzoyl group, 4-cyanobenzoyl group and 4-oxopentanoyl group. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group, a phenoxycarbonyl group and a 4-methoxybenzyloxycarbonyl group. Examples of the aminocarbonyl group include a methylaminocarbonyl group, a 4-nitrophenylaminocarbonyl group, a 2-pyridylaminocarbonyl group, and a 1-imidazolylcarbonyl group.

Further, the group represented by R ^Q1 and R ^Q2, which is released from the hydroxyl group by breaking the bond with the oxygen atom during the development processing, is a linking group which is bonded to R ^Q3 , R ^Q4 and R ^Q6 , or R ^Q5. May combine with to form a 5- to 7-membered ring. As such an _{example, * - COCH 2 CH 2 -} **, * - COCH 2
CH ₂ CH ₂ -**, * -COCH ₂ SCH ₂ -**, *-
_{CONHCH 2 - **, * - COOCH} 2 - **, * - C
_{ONHCH 2 CH 2 - **, *} - CH 2 CH 2 COCH 2 -
_{**, * - COCH 2 O -} **, * - COCONH- *
* Can be mentioned. Here, * is bonded to the oxygen atom of hydroquinone, and ** is R ^Q3 , R ^Q4 and R ^Q6 , or R
^It represents the position of bonding to the hydroquinone skeleton via the linking group that bonds to ^Q5 . R ^Q1 and R ^Q2 are preferably hydrogen atoms.

In the above formula (HQ1), examples of the halogen atom represented by R ^Q3 , R ^Q4 and R ^Q6 include chlorine atom, bromine atom and fluorine atom. R
^The alkyl group represented by ^Q3 , R ^Q4 and R ^Q6 is an alkyl group having 1 to 30 carbon atoms (preferably 1 to 15), for example, methyl, sec-butyl, t-butyl, t-pentyl, t-hexyl. , Cyclohexyl, t-octyl, benzyl and the like. ^Examples of the alkenyl group represented by R ^Q3 , R ^Q4 and R ^Q6 include an allyl group. Examples of the aryl group represented by R ^Q3 , R ^Q4 and R ^Q6 include aryl groups having 6 to 30 carbon atoms (preferably 6 to 15), such as phenyl and p-tolyl. Examples of the acylamino group represented by R ^Q3 , R ^Q4 and R ^Q6 include acylamino groups having 2 to 30 (preferably 2 to 15) carbon atoms, for example, groups such as acetylamino and benzoylamino. The sulfonamide group represented by R ^Q3 , R ^Q4 and R ^Q6 has 1 to 1 carbon atoms.
There may be mentioned 30 (preferably 1 to 15) sulfonamide groups such as methanesulfonamide and benzenesulfonamide groups. Examples of the alkoxy group represented by R ^Q3 , R ^Q4 and R ^Q6 include alkoxy groups having 1 to 30 carbon atoms (preferably 1 to 15), such as methoxy, butoxy, benzyloxy and dodecyloxy groups. it can.

R^Q3, R^Q4And R^Q6Aryloo
The xy group has 6 to 30 carbon atoms (preferably 6 to 1 carbon atoms).
5) Aryloxy groups, eg phenoxy, p-meth
Mention may be made of groups such as xyphenoxy. R^Q3,
R^Q4And R^Q6The alkylthio group represented by is carbon
An alkylthio group of the number 1 to 30 (preferably 1 to 15),
For example, mention groups such as butylthio and decylthio.
You can R^Q3, R^Q4And R^Q6Arylthio
The group has a carbon number of 6 to 30 (preferably 6 to 15)
Arylthio groups such as phenylthio, p-hexyloxy
Mention may be made of groups such as cyphenylthio. R^Q3,
R^Q4And R^Q6The acyl group represented by has 2 to 2 carbon atoms.
30 (preferably 2 to 15) acyl groups such as ace
Name groups such as tyl, benzoyl, hexanoyl
You can R^Q3, R^Q4And R^Q6Acyloxy represented by
The group has a carbon number of 2 to 30 (preferably 2 to 15)
Acyloxy groups such as acetoxy, benzoyloxy
And the like. R^Q3, R^Q4And R^Q6so
The sulfonyl group shown has 1 to 30 carbon atoms (preferably
1 to 15) sulfonyl group, for example, methanesulfur
Examples include groups such as sulfonyl and benzenesulfonyl.
Wear. R^Q3, R^Q4And R^Q6A carbamoyl group represented by
Is substituted with 1 to 30 carbon atoms (preferably 1 to 15)
Carbamoyl group having a group, for example, N, N-diethyl
Examples include groups such as carbamoyl and N-phenylcarbamoyl.
You can get it. R ^Q3, R^Q4And R^Q6Indicated by
The Coxycarbonyl group has 2 to 30 carbon atoms (preferably
2-15) alkoxycarbonyl group, for example,
Lists groups such as toxycarbonyl and butoxycarbonyl
You can

The sulfamoyl group represented by R ^Q3 , R ^Q4 and R ^Q6 is a sulfamoyl group which is unsubstituted or has a substituent having 1 to 30 (preferably 1 to 15) carbon atoms, such as N, N-dipropyls. Examples thereof include groups such as rufamoyl and N-phenylsfamoyl. R ^Q3 , R
^The ureido group represented by ^Q4 and R ^Q6 has 1 to 1 carbon atoms.
Examples of the ureido group having 20 (preferably 1 to 15) substituents include groups such as 3-methylureido, 3-isopropylureido, 3-cyclohexylureido, 3-hexadecylureido and 3-phenylureido. it can. The urethane group represented by R ^Q3 , R ^Q4 and R ^Q6 is a urethane group having 2 to 20 carbon atoms (preferably 2 to 15), for example, methoxycarbonylamino, t-butyloxycarbonylamino, dodecyloxycarbonylamino. And groups such as phenoxycarbonylamino. The carbonic acid ester group represented by R ^Q3 , R ^Q4 and R ^Q6 has 2 to 20 carbon atoms (preferably 2 to 1 carbon atoms).
The carbonic acid ester group of 5), for example, groups such as ethoxycarbonyloxy and phenoxycarbonyloxy can be mentioned. R ^Q5 represents the same group as the group represented by R ^Q3 , or an aryl group bonded via a linking group.

R above^Q3, R^Q4, R^Q5And R^Q6Is a substituent
You may have. As a substituent, R which will be described later is used.^Q8Replaced with
A group that does However, R^Q5Is the above R^Q3
When it represents the same group as the group represented by^Q3And R ^Q4
And R^Q5And R^Q6Are jointly carbocycles or
It may form a prime ring. Also, R^Q5Is the above R^Q3Indicated by
When it represents the same group as the group represented by^Q3, R^Q4, R
^Q5And R^Q6At least one of them is not a hydrogen atom
And above R^Q3, R ^Q4, R^Q5And R^Q6Is a hydrogen atom and
When it is composed of only a rualkyl group, at least the alkyl group
One also has 6 or more carbon atoms, and R^Q3, R^Q4, R^Q5Over
And R^Q6Has a total carbon number of 15 or less (preferably 4 to 1).
3 and more preferably 7 to 13). The above formula (HQ
In 1), R^Q5Is R^Q3The same group as the group shown in
When forgotten, the above R^Q3, R^Q4, R^Q5And R^Q6Is a hydrogen atom,
Halogen atom, alkyl group, aryl group, alkoxy
A group, a cyano group, an acylamino group or an alkylthio group
Are preferred, and more preferably hydrogen atom and alkyl
A group, an alkoxy group or an acylamino group.

In the above formula (HQ1), R ^Q5 is preferably a group represented by the following formula (HQ1-a).

[0031]

[Chemical 9]

[In the formula, R ^Q7 represents a substitutable group on the benzene ring, R ^Q8 represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group or an amino group, and L represents a divalent group. Represents a connecting group, and p represents an integer of 1 to 3, m represents an integer of 0 to 4, provided that m is 2
In the above case, a plurality of R ^Q7 may be the same or different. Examples of the group represented by R ^Q7 that can be substituted on the benzene ring include the same groups as the groups represented by R ^Q3 described above. Among these, a halogen atom, an alkyl group, an aryl group, an acylamino group, a sulfamoyl group, a sulfonamide group, an alkoxy group, an alkylthio group, a ureido group or a urethane group is preferable, and an alkyl group, an alkoxy group, a sulfamoyl group is more preferable. A group or an acylamino group. In the present invention, m is preferably 0 or 1. The total carbon number of R ^Q3 , R ^Q4 and R ^Q6 and R ^Q7 described above is preferably 50 or less, more preferably 35 or less, and particularly preferably 20 or less.

The divalent linking group represented by L above is
An atom or an atomic group containing at least one of C, N, S and O. Specifically, (1) alkylene group (preferably having 1 to 12 carbon atoms, such as methylene, ethylene, trimethylene, etc.), (2) alkenylene group (preferably having 2 to 12 carbon atoms, such as vinylene) , Butylene), (3) alkynylene group (preferably having 2 to 2 carbon atoms).
12, eg ethynylene, butynylene, etc.),
(4) Arylene group (preferably having 6 to 10 carbon atoms, for example, phenylene, naphthylene, etc.), (5) -O
-, (6) -S-, (7) -NH-, (8) -CO-,
And (9) —SO ₂ — (these groups may have a substituent) and the like, or a combination thereof. Specific examples of the above combination include, for example, (1
0) -NHCO-, (11) -OCO-, (12) -N
_{HSO 2 -, (13) -OCO} -NH -, (14) -N
HCO-O-, (15) -NHCO-NH-, (16)
-OCO-O -, (17) -NHSO 2 -NH- and,
(1) a combination of - (4) and (5) to (17) (e.g., -NHCO- (alkylene) -, - NHSO ₂ -
(Alkylene)-, -NHCONH- (alkylene)-
Etc.) can be mentioned. In the present invention, L
Is an alkylene (in _{particular, -CH 2 -), - NHCO-} ,
_{-NHSO 2 -, - NHCONH-, NHSO} 2 NH- and -NHCO- (alkylene) - are preferred, -NHC
O- is particularly preferred. p is preferably 1 to 2, and particularly 1.

The alkyl group represented by R ^Q8 above is
Mention may be made of alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, butyl, isopropyl, t-butyl, cyclohexyl, octyl and hexadecyl.
The alkenyl group represented by R ^Q8 has 2 to 2 carbon atoms.
Mention may be made of 30 alkenyl groups, such as allyl, 2-pentenyl and octadecenyl. Examples of the alkynyl group represented by R ^Q8 include an alkynyl group having 2 to 30 carbon atoms, for example, propargyl.
The aryl group represented by R ^Q8 has 6 to 3 carbon atoms.
Mention may be made of 0 aryl groups, for example phenyl and naphthyl. The heterocyclic group represented by R ^Q8 is a 3- to 12-membered heterocyclic ring containing at least one hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom or selenium. Such examples include pyridyl, triazinyl, uracil, pyrrolyl, thienyl, furanyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyrrolidinyl and morpholinyl. The above R ^Q8 may have a substituent (including atoms). As the substituent, an alkyl group (having 1 to 18 carbon atoms), an alkenyl group (having 2 to 1 carbon atoms)
8), an alkynyl group (having 2 to 18 carbon atoms), an aralkyl group (having 7 to 20 carbon atoms), an aryl group (having 6 to 20 carbon atoms),
Hydroxyl group, alkoxy group (having 1 to 18 carbon atoms), aryloxy group (having 6 to 20 carbon atoms), halogen atom, amino group, alkylthio group (having 1 to 18 carbon atoms), arylthio group (having 6 to 20 carbon atoms), Acyloxy group (C1
~ 18), sulfonyloxy group (C1-18), acylamino group (C1-18), sulfonamide group (C1-18), carboxyl group, alkoxycarbonyl group (C2-18), Aryloxycarbonyl group (7 to 20 carbon atoms), acyl group (1 to 2 carbon atoms)
0), carbamoyl group (having a substituent having 1 to 20 carbon atoms), sulfamoyl group (unsubstituted or having a substituent having 1 to 20 carbon atoms), sulfo group, cyano group, ureido group (having 1 to 20 carbon atoms). Having a substituent), a urethane group (having 2 to 20 carbon atoms), and a carbonic acid ester group (having 2 to 2 carbon atoms).
0) can be mentioned. The above R ^Q8 is preferably an alkyl group (having 1 to 16 carbon atoms (preferably 1 to 10, more preferably 8 to 10)) or an aryl group (phenyl).

Specific examples of the compound represented by the formula (HQ1) are shown below.

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

An example of the synthesis of the compound represented by the above formula (HQ1) is shown below. Synthesis of Compound (HQ1-2) To 100 ml of acetoniryl, 15.3 g of 2,5-dimethoxyaniline and 10.1 g of triethylamine were added, and 37 g of 2-dodecanesulfonamide benzoic acid chloride was further added with stirring under ice cooling. After further reacting at room temperature for 2 hours, 50 ml of water was added, and the precipitated crystals were collected by filtration, washed with water, and dried at 50 ° C. The obtained solid was added to 200 ml of toluene, and aluminum chloride 40 was added.
g was added and reacted at 120 ° C. for 5 hours. The obtained reaction product was added little by little to ice water, followed by extraction with ethyl acetate and washing with water three times, and then the organic layer was concentrated under reduced pressure.
The residue was dissolved in 150 ml of isopropyl alcohol, 500 ml of n-hexane was added, and the precipitated crystals were collected by filtration to obtain 39 g of the desired product (yield 82%).

Next, the compound represented by the following formula (HQ2) will be described in detail. In the general formula (HQ2), the groups represented by R ^{Q11 to} R ^Q16 are the same as the R described above, respectively.
It is the same as the group represented by ^Q3 . R ^Q11 and R ^Q12 and R ^Q14 and R ^Q15 may be combined to form a carbocycle or a heterocycle, and R ^{Q11 to} R ^Q16 are substituted with the substituents described above as the substituents of R ^Q3. It may have been done. R above
^The alkyl group represented by ^Q17 and R ^Q18 is an alkyl group having 1 to 40 carbon atoms, for example, methyl, i-propyl,
Examples include groups such as undecyl and benzyl.
Examples of the aryl group represented by R ^Q17 and R ^Q18 above include
Aryl group having 6 to 40 carbon atoms, for example, phenyl, p-
Mention may be made of groups such as trill. The heterocyclic group represented by R ^Q17 and R ^Q18 has 1 to 40 carbon atoms.
Can be mentioned, for example, a pyridin-2-yl group. In addition, R ^Q17 and R ^Q18 described above may together form a carbocycle or a heterocycle. The above R ^Q17 and R ^Q18 may be further substituted with an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfo group, a carboxyl group, an amide group, a carbamoyl group, or a halogen atom.
Furthermore, compounds of formula (HQ2), the bis-in R ^{Q1 7} and / or R ^Q18 may form (tetrakis body as hydroquinone part). In the above formula (HQ2), R ^{Q1 to} R ^Q16 are preferably hydrogen atoms, halogen atoms, alkyl groups, aryl groups, acylamino groups or alkylthio groups. More preferably, it is a hydrogen atom, an alkyl group or an acylamino group. Also R ^Q17 and R ^Q18
Is preferably a hydrogen atom or an alkyl group, and it is also preferable that R ^Q17 and R ^Q18 together form a carbocycle. More preferably, R ^Q17 is a hydrogen atom and R ^Q18 is a hydrogen atom or an alkyl group. The total carbon number of R ^{Q11 to} R ^Q18 is 60 or less, preferably 5 to 45, more preferably 10 to 30.

Specific examples of the compound represented by the formula (HQ2) are shown below.

[0046]

[Chemical 17]

[0047]

[Chemical 18]

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

The compounds represented by the above formula (HQ1) or (HQ2) may be used alone or in combination of two or more kinds. In addition, the formula (HQ
The compounds represented by 1) and (HQ2) may be used in combination.
The compound represented by the formula (HQ1) or (HQ2) is
Generally 1 × 10 ⁻⁸ mol / m ² to 1 per 1 m ^{2 of the} light-sensitive material
× 10 ^-2 mol / m ² , preferably ^{1x10 -7} mol / m ² ~
It is used in the range of 1 × 10 ⁻³ mol / m ² .

When the hydroquinone compound is introduced into the silver halide emulsion layer, a known method (for example, the method described in US Pat. No. 2,322,027) is used. For example, a method of dissolving in the following solvent and then dispersing in a hydrophilic colloid is used. The following can be mentioned as a solvent that can be used. Phthalic acid alkyl ester (eg, dibutyl phthalate, dioctyl phthalate), phosphoric acid ester (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg, acetyl citric acid) Tributyl), benzoic acid ester (eg, octyl benzoate), alkylamide (eg, diethyllaurylamide), aliphatic ester (eg, dibutoxyethylsuccinate, diethylazelate), trimesic acid ester (eg, trimesin) Tributyl acid), etc.,
Or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
Methyl cellosolve acetate etc.

The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used. In addition, Japanese Patent Publication Sho 51-3985
The dispersion method using a polymer described in JP-A-51-59943 and JP-A-51-59943 can also be used. When the FR compound has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The fogging agent or the development accelerator releasing compound represented by the above formula (I) will be described in detail. In formula (I), R ¹ is a hydrogen atom or an alkyl group (having 1 to 1 carbon atoms).
20. For example, it represents methyl, ethyl, octyl, octadecyl, etc., and R ² is an alkyl group (having 1 to 40 carbon atoms, for example, methyl, octyl, hexadecyl, eicosyl, etc.), an aryl group (having 6 to 40 carbon atoms, for example, phenyl,
Naphthyl, etc.), heterocyclic group (having 2 to 40 carbon atoms. For example, 2
-Pyridyl, 2-furyl, 4-quinolyl, etc.), an amino group (having 0 to 40 carbon atoms, such as diethylamino, dodecylamino, octadecylamino, etc.), or an alkoxy group (having 1 to 40 carbon atoms, such as methoxy, octyloxy, hexade). Siloxy, etc.) and X represents --CO--, --SO _2-, or --COCO--. R ³ and R ⁴ represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less (these substituents include, for example, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, Arylthio group, acylamino group, sulfonamide group, halogen atom, hydroxyl group, amino group and the like). The substituents represented by R ^{1 to} R ⁴ are other substituents such as an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonamide group, a halogen atom, a hydroxyl group and an amino group. It may be substituted with an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or the like. B represents a group that releases FA after the separation from the hydroquinone mother nucleic acid product, m is an integer of 0 to 2, and FA represents a fogging agent or a development accelerator residue. A and A'represent a hydrogen atom or a group which can be removed with an alkali. R ² and R ³ may cooperate with each other to form a heterocycle. Among the compounds of formula (I), the compounds showing particularly excellent effects are those represented by the following formula (II). General formula (II)

[0058]

[Chemical 25]

In formula (II), the definition of the substituent is the same as in formula (I). In formulas (I) and (II), R ¹ preferably represents a hydrogen atom, and R ² preferably represents an alkyl group, an aryl group or an amino group. R ³ and R ⁴ preferably represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or an alkylthio group, and a hydrogen atom is most preferred. In formulas (I) and (II), the group represented by FA represents a so-called fogging agent or development accelerator which acts on silver halide grains during development to generate fog nuclei capable of initiating development.
Examples of FA include a group that acts reductively on silver halide grains during development to produce fog nuclei or a group that acts on silver halide grains to produce silver sulfide nuclei which are fog nuclei that can initiate development. be able to.

A preferred group for FA is a group containing a group having adsorptivity to silver halide grains and can be represented as follows. AD- (L) _m -X AD represents a group having adsorptivity to silver halide, L represents a divalent group, and m represents 0 or 1.
X represents a reducing group or a group capable of acting on silver halide to form silver sulfide. However, when X is the latter, it may also have the function of AD, and in this case, AD- (L) _m- is not always necessary.

The group capable of adsorbing silver halide represented by AD includes a nitrogen-containing heterocycle having a dissociable hydrogen atom (pyrrole, imidazole, pyrazole, triazole, tetrazole, benzimidazole, indazole, benzotriazole, Uracil, tetraazaindene, imidazotetrazole, pyrazolotriazole, pentaazaindene, etc.), at least one nitrogen atom in the ring and other heteroatoms (oxygen, sulfur, selenium, etc.)
A heterocycle having oxazole (thiazole, thiazoline, thiazolidine, thiadiazole, benzothiazole, benzoxazole, benzselenazole, etc.), a heterocycle having a mercapto group (2-mercaptobenzthiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole) , 2-mercaptothiadiazole, 2
-Mercaptooxadiazole, 1-phenyl-5-mercaptotetrazole, etc.), quaternary salt (quaternary salt of tertiary amine, pyridine, quinoline, benzthiazole, benzimidazole, benzoxazole, etc.), thiophenol, alkylthiol Class (Cystine, etc.),> NC
Examples thereof include compounds having a (= S)-partial structure (for example, thiourea, dithiocarbamate, thioamide, rhodanine, thiazolidinethione, thiohydantoin, thiobarbituric acid).

The divalent linking group represented by L in FA is alkylene, alkenylene, phenylene, naphthylene, --O--, --S--, --SO--, --SO _2- , --N = N.
-, Carbonyl, amide, thioamide, sulfonamide, ureido, thioureido, heterocycle and the like. If one of the divalent linking groups forming L is a group capable of being cleaved by the action of a component (eg, hydroxide ion, hydroxylamine, sulfite ion, etc.) in the developer, the fogging effect can be controlled. It can also be deactivated.

The group represented by X is a reducing compound (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, 1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene. , Quaternary salts such as aminoborane, tetrazolium salt, ethylenebispyridinium salt, etc.) or compounds capable of forming silver sulfide during development (eg thiourea, thioamide,
Dithiocarbamate, rhodanine, thiohydantoin,
Examples thereof include compounds having a partial structure of -C (= S) -N <such as thiazolidinethione). Among the groups represented by X, some of the groups capable of forming silver sulfide at the time of development have an adsorptivity for silver halide grains, and can also serve as an adsorptive group AD. Further, particularly preferred FA is the following general formula
It is represented by (III) and (IV). General formula (III)

[0064]

[Chemical formula 26]

General formula (IV)

[0066]

[Chemical 27]

In the formula, R ₈₁ is an acyl group, a carbamoyl group,
An alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a sulfamoyl group, R ₈₂ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ₈₃ represents a halogen atom or an alkoxy group. Represents an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a carbonamido group or a sulfonamide group. m is 0-4
When m is 2 or more, R _{83 s} may be the same or different, and two or more may be bonded to each other to form a condensed ring. L represents the same meaning as described above, that is, represents a divalent linking group, and n represents 0 or 1. Z ₁ represents a non-metal atom group necessary for forming a monocyclic ring or a condensed ring heterocycle, and Z ₂ represents a nonmetallic atom group necessary for forming a monocyclic ring or a condensed ring heterocycle formed with N. Represent.

Examples of the substituent will be described in more detail below.
R ₈₁ is an acyl group (eg formyl, acetyl,
Propionyl, trifluoroacetyl, pyruvoyl),
Carbamoyl group (dimethylcarbamoyl etc.), alkylsulfonyl group (methanesulfonyl etc.), arylsulfonyl group (benzenesulfonyl etc.), alkoxycarbonyl group (methoxycarbonyl etc.), aryloxycarbonyl group (phenoxycarbonyl etc.) or sulfamoyl group (methylsulfur) Famoyl, etc.) and R ₈₂ is a hydrogen atom, an acyl group (trifluoroacetyl etc.), an alkoxycarbonyl group (methoxycarbonyl etc.) or an aryloxycarbonyl group (phenoxycarbonyl etc.)
R ₈₃ is a halogen atom (fluorine, chlorine, etc.), an alkoxy group (methoxy, methoxyethoxy, etc.), an alkyl group (methyl, hydroxymethyl, etc.), an alkenyl group (allyl, etc.), an aryl group (phenyl, etc.), aryl Examples thereof include an oxy group (phenoxy etc.), an alkylthio group (methylthio etc.), an arylthio group (phenylthio etc.), a carbonamide group (acetamide etc.) or a sulfonamide group (methanesulfonamide etc.). Also,
The quaternary salt nucleating agent described in JP-A-64-44940 is also F
Preferred as A.

In the formulas (I) and (II), the group represented by B is a nucleophile (hydroxide ion, when a hydroquinone mother nucleus is oxidized by a developing agent oxidant during development to a quinone body). Sulfite, hydroxylamine, etc.)
^- - (B) are released as _m -FA, further followed represents a divalent group capable of releasing FA, may have a timing adjustment function. When m is 0, it means that FA is directly linked to the hydroquinone mother nucleus, and when m is 2, it represents a combination of two Bs. When B is a divalent linking group having a timing adjusting function, the group represented by B is specifically the same group as the Time group described in JP-A-4-151144, page 5 and thereafter. .

Examples of the alkali-removable groups represented by A and A'in the formulas (I) and (II) are preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group and an imidoyl group, Hydrolyzable groups such as oxazolyl groups and sulfonyl groups, precursor groups of the type utilizing the reverse Michael reaction described in US Pat. No. 4,009,029, US Pat. No. 4,310,6.
Precursor group of the type utilizing an anion generated after the ring opening reaction described in No. 12 as an intramolecular nucleophilic group, US Pat. Nos. 3,674,478, 3,932,480 or 3,993. A precursor group which causes anion transfer of an anion described in US Pat. No. 661 through a conjugated system to thereby cause a cleavage reaction, and a cleavage reaction by electron transfer of a reacted anion after ring opening described in US Pat. No. 4,335,200. Precursor base or US Pat. No. 4,36
Precursor groups utilizing an imidomethyl group described in Nos. 3,865 and 4,410,618 can be mentioned. A,
A'is preferably a hydrogen atom. General formula (I), (I
Specific examples of the compound represented by I) are shown below, but the present invention is not limited thereto.

[0071]

[Chemical 28]

[0072]

[Chemical 29]

[0073]

[Chemical 30]

[0074]

[Chemical 31]

[0075]

[Chemical 32]

[0076]

[Chemical 33]

The compound of the general formula (I) according to the present invention can be synthesized by the following synthesis example or a method analogous thereto. The exemplary compound (I-5) according to the present invention was synthesized by the route shown below.

[0078]

[Chemical 34]

The above route will be specifically described below. Synthesis example 1 (synthesis of c ^* ) a ^* 2.38 g (5 mmol), b ^* 1.55 g (5 mmol)
And 0.1 g of paratoluenesulfonic acid monohydrate were added to 20 ml of chloroform, and the mixture was stirred at room temperature for 1 hour. The reaction system was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and concentrated to obtain 3.6 g of crude crystals of c ^* . The structure was confirmed by NMR and mass spectrum.

Synthesis Example 2 (Synthesis of Exemplified Compound (I-5)) c ^* 1.75 g (2.2 mmol), d ^* 0.68 g (2.
2 mmol) and 0.13 g of imidazole 20 ml of toluene
It was put in a mixed solvent of 2 ml of dimethyl acetamide and and heated with stirring to react for 2 hours under reflux. After cooling, the reaction system was extracted with ethyl acetate, washed with water, concentrated, and purified by column chromatography to exemplify Compound (I-5).
Was obtained. The structure was confirmed by NMR and mass spectrum.

The FR compound described above may be contained in any of the layers constituting the light-sensitive material, but is preferably contained in the silver halide emulsion layer. The addition amount of the FR compound used in the present invention is in the range of 10 ^-9 to 10 ^-1 mol per 1 mol of silver halide contained in the layer containing the FR compound or in the layer adjacent to the FR compound, preferably 10 ^-7 to 10 ^-2 mol range,

When the FR compound is incorporated in the silver halide emulsion layer, a known method (for example, US Pat. No. 232) is used.
The method described in the specification of No. 2027) is used. For example, a method in which the following solvent is dissolved and then dispersed in a hydrophilic colloid is used. The following can be mentioned as a solvent that can be used. Phthalic acid alkyl ester (eg, dibutyl phthalate, dioctyl phthalate), phosphoric acid ester (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg, acetyl citric acid) Tributyl), benzoic acid ester (eg, octyl benzoate), alkylamide (eg, diethyllaurylamide), fatty acid ester (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid ester (eg, trimesic acid) Tributyl) or an organic solvent having a boiling point of about 30 ° C to 150 ° C, for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutane. Ketone, beta-ethoxyethyl acetate, methyl cellosolve acetate.

The above high boiling point organic solvent and low boiling point organic solvent may be mixed and used. In addition, Japanese Patent Publication Sho 51-3985
The dispersion method using a polymer described in JP-A-51-59943 and JP-A-51-59943 can also be used. When the FR compound has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The silver halide emulsion used in the color photographic light-sensitive material of the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the surface of silver halide grains, or a latent image is mainly silver halide grains. Any of the so-called internal latent image type emulsions formed inside may be used. However, as described above, a type (a direct positive color photographic light-sensitive material) of a type having an emulsion layer containing an internal latent image type silver halide grain which is not fogged in advance can be preferably used as the silver halide emulsion layer. The internal latent image type silver halide grains not previously fogged will be described later.

The grains contained in the silver halide emulsion used in the present invention are preferably silver bromide, silver chlorobromide or silver chloride containing substantially no silver iodide. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Further, regarding the halogen composition distribution of silver halide grains, a so-called uniform structure grain having the same composition in any portion of the silver halide grain, a core inside the silver halide grain and a shell (shell) surrounding it. ) (A single layer or a plurality of layers) has a so-called laminated structure having different halogen compositions, or a structure having a non-layered portion having a different halogen composition inside or on the surface (in the case of being on the surface of the particle, edges, corners or There are particles having a structure in which parts of different compositions are bonded on the surface), and these can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. Alternatively, it may be one that positively has a continuous structural change. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide /
A silver chloride ratio can be used. This ratio is
Wide range depending on the purpose, but the silver chloride ratio is 2%
The above is preferable.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of the high silver chloride emulsion is preferably 90 mol% or more,
95% or more is more preferable. In such a high silver chloride emulsion, a structure having a silver bromide localized layer in the inside and / or on the surface of the silver halide grain as described above is preferable. The halogen composition of the localized layer preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. Or it may be on the surface. As one preferable example, there may be mentioned one epitaxially grown at the corner portion of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% can also be preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. The thickness is preferably 1 μm to 2 μm (more preferably 0.2 μm to 1.2 μm). Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities are used in the emulsion layers having substantially the same color sensitivity. The particles can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains contained in the photographic emulsion have a regular crystal form such as a cube, octahedron, dodecahedron or tetradecahedron, spherical,
It is possible to use a material having an irregular crystal shape such as a plate shape, or a material having a composite shape of these. It may also be a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form are contained in an amount of 50% or more, preferably 70% or more, more preferably 90% or more. In addition to these, an emulsion having tabular grains having an average aspect ratio (circular equivalent diameter / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in P. Glaf
Chides "Chimie et Photograph-ique" (Paul Mon
tel, 1967), GF Duffin, "(Photog
raph-ic Emulsion Chemistry "(Focal Press, 1
966), V. L. Zelikman et al, "Making a
nd Coating Photographic Emulsion "(Focal Press, Inc., 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include cadmium, zinc, lead, copper, thallium, salts such as bismuth, or Group VIII elements iron, ruthenium, rhodium, palladium, osmium,
Examples thereof include salts of iridium and platinum, or complex salts. Of these metals, lead, iridium, bismuth and rhodium are preferred. The addition amount of these compounds may vary depending on the purpose, but is 10 ^-9 to 10 ^-2 mol (more preferably 10 ^-7 mol) with respect to the silver halide.
10 to ³ mol) is preferred. For the method of incorporating these metals, see US Pat. Nos. 3,761,276 and 43,954.
No. 78 and JP-A-59-216136.

The silver halide emulsion used in the present invention is
Usually, it is preferable that chemical sensitization and spectral sensitization are performed. Regarding the chemical sensitization method, treatment such as sulfur sensitization typified by unstable sulfur compound addition, noble metal sensitization typified by gold sensitization, reduction sensitization, or selenium sensitization is performed alone or in combination. be able to. As the compound used for the chemical sensitization, those described in JP-A No. 62-215272, page 18, lower right column to page 22, upper right column of the specification are preferably used. In the above chemical sensitization treatment, as described in JP-A-1-197742, in the presence of a mercapto compound, JP-A-1-254946, JP-A-2-69738, and JP-A-2-273735.
Thiosulfinic acid, sulfinic acid, and sulfite may be added as described in the publication. The chemical sensitization method for core particles is described in JP-A-2-199450 and 2-19.
The method described in Japanese Patent No. 9449 can be used. A detailed specific example is given in Research Disclosure No. 17643-III (issued in December 1978)
There is also a patent described on page 23. Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity, that is, a so-called spectral sensitizing dye. Examples of the spectral sensitizing dye include FM Harm
er `` Heterocyclic compounds-Cyanine dyes and rela
ted compounds "(John Wiley & Sons (NewYork, Londo
n) Published by the company, 1964). Specific examples of the compound and the spectral sensitization method are described in JP-A-62-215272, No. 2
Those described on page 2, upper right column to page 38 are preferably used. A detailed specific example is given in Research Disclosure No. There are also patents described on pages 23 to 24 of 17643-IV (issued in December 1978).

The prefogged internal latent image type silver halide emulsion preferably used in the present invention will be described. An internal latent image type silver halide emulsion which has not been fogged in advance is an emulsion in which the surface of silver halide grains is not fogged and which contains a silver halide which mainly forms a latent image inside the grain. Specifically, the silver halide emulsion is fixed on the transparent support in a fixed amount (0.5 to 3 g / m 2).
² ) Apply and expose to light for a fixed time of 0.01 to 10 seconds, and in the following developer (internal type developer),
When developed at 0 ° C. for 5 minutes, the maximum density measured by a usual photographic density measuring method was the same amount of the above coated silver halide emulsion, which was similarly exposed in the following developing solution (surface type developing solution): Those having a density at least 5 times higher than the maximum density obtained when developed at 18 ° C. for 6 minutes are preferable, and those having a density at least 10 times higher are more preferable. Internal type developer Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.8 g KBr 5.0 g KI 0.5 g Water-added 1000 ml Surface type developer Metol 2 .5G L-ascorbic acid _{10.0g NaBO 2 · 4H 2 O 35.0g} KBr 1.0g water to make 1000ml

Specific examples of the internal latent image type silver halide emulsion include, for example, conversion type silver halide emulsions described in US Pat. No. 2,592,250; or US Pat. Nos. 3,761,276, 3,850,637 and 3,923,513. , 4035185 and 43954.
78, 4504570, JP-A-52-
No. 156614, No. 55-127549, No. 53-6
0222, 56-22681, 59-2085
No. 40, No. 60-107641, No. 61-1337.
No. 62-215272, German Patent No. 2332802c2, Research Disclosure No. 23510 (issued in November 1983), page 236; specification of U.S. Pat. No. 4,789,627, further having a silver chloride shell; JP-A-63-10160 relating to silver chlorobromide core-shell emulsions;
No. 63-47766, and Japanese Patent Application No. 1-24
No. 67; Japanese Patent Application Laid-Open No. 63-191145 and Japanese Patent Application Laid-Open No. 1-5214 relating to emulsions doped with metal ions.
Examples thereof include core / shell type silver halide emulsions described in JP-A No. The internal latent image type silver halide grains which have not been fogged in the present invention are preferably core / shell type. The internal latent image type core / shell silver halide emulsion has a core / shell silver halide molar ratio of 20/1 or less and 1/10.
0 or more is particularly preferable.

The photographic emulsion used in the present invention contains an antifoggant or stabilizer for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can For specific examples, see Research Disclosure No.
17643-VI (issued in December 1978) and E.I.
J. Birr, "Stabilization of Photographic Silv
er Halide Emulsion "(Focal Press), 1974.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 30710 mentioned above.
5, VII-C to G.
Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,4
01,752, 4,248,961, Japanese Patent Publication 58-10739, British Patents 1,425,020, 1,476,760, U.S. Patents
3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having a precursor group as a leaving group.
Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
And Patent Nos. 307105 and VII-F, JP-A-57-151944, 57-154234, 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable. RD No.1
The bleaching accelerator releasing couplers described in 1449, 24241 and JP-A-61-201247 are effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grains. The effect is great when it is added to the photosensitive material using.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after separation described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Gelatin is advantageously used as the binder or protective colloid that can be used in the intermediate layer which is the emulsion layer or the non-photosensitive layer of the light-sensitive material of the present invention, but other hydrophilic colloids can also be used. Can be used. In the light-sensitive material of the present invention, an antifoggant or a color mixing inhibitor can also be used. Typical examples of these are JP-A-62-21527.
The compounds described in Japanese Patent Publication No. 2, pages 185 to 193 can be mentioned. Examples of the compound releasing a photographically useful group include JP-A Nos. 63-153540 and 63-259.
No. 555, JP-A Nos. 2-61636 and 2-24.
The compounds described in each publication of No. 4041 and No. 2-308240 are mentioned. In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. Typical examples of the compounds are JP-A-62-215272, 121-
The thing described in page 125 is mentioned. Dyes that prevent irradiation or halation may be used in the light-sensitive material of the present invention (for example, the compounds described in JP-A Nos. 2-85850 and 2-89047) may be used. Solid fine crystal dispersion method may be used.), UV absorber, plasticizer, fluorescent whitening agent, matting agent, air antifoggant, coating aid, film hardening agent, antistatic agent, slipperiness improver, etc. Can be added. Typical examples of these additives are listed in Research Disclosure No. 17643
Items VII to XIII (issued in December 1978) 25 to 2
7 pages, and 18716 (issued in November 1979) 6
47-651.

The color photographic light-sensitive material of the present invention preferably has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on the support. And it is preferable that the non-photosensitive layer is provided adjacent to these layers. The order of each layer of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. Further, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. . It is usual 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 in some cases, the green-sensitive layer contains a yellow coupler and a magenta coupler. It is also possible to use different combinations such as mixed use.
As described above, the light-sensitive material of the present invention is provided with a non-light-sensitive layer in addition to the silver halide emulsion layer. Examples of such a layer include a protective layer, an intermediate layer, a filter layer, an antihalation layer, There are auxiliary layers such as a back layer and a white reflective layer.

The color photographic light-sensitive material of the present invention preferably contains a nucleating agent. The nucleating agent functions as a development accelerator when the color photographic light-sensitive material is a normal color photographic light-sensitive material (for example, a color negative film). Further, in the direct positive color photographic light-sensitive material which is a preferred embodiment of the present invention, the nucleating agent acts during the surface development processing of the internal latent image type silver halide emulsion which has not been fogged in advance to form a direct positive image. Work. It is a substance used when carrying out the so-called "chemical fogging method". The nucleating agent is a silver halide emulsion layer,
Alternatively, it may be contained in any of the adjacent non-photosensitive layers (for example, an intermediate layer, an undercoat layer or a back layer), but it may be halogenated together with the cyan coupler represented by the formula (CaI) or the formula (CbI). It is preferably contained in the silver emulsion layer. Examples of the nucleating agent that can be used in the present invention include, for example, Research Disclosure Magazine,
No. 22534 (January 1983), pp. 50-54, ibid., No. 15162 (November 1976) 76-77
Page, No. 23510 (November 1983) 346
To 352, quaternary heterocyclic compounds, hydrazine compounds and the like. Two or more kinds of these nucleating agents may be used in combination. The nucleating agent used in the present invention is represented by the formula (N- which is described in JP-A-2-90154 or JP-A-3-155543.
I)) quaternary heterocyclic compounds, or JP-A-2-
A hydrazine compound represented by the formula (N-II) described in JP-A-90154 or JP-A-3-95546 is preferable.

Typical nucleating agents represented by the above formulas (NI) and (N-II) are as follows. (N-I-1) 7- (3-cyclohexylmethoxythiocarbonylaminobenzamide) -10-propargyl-1,2,3,3
4-Tetrahydroacridinium trifluoromethanesulfonate (N-I-2) 6- (3-ethoxythiocarbonylaminobenzamido) -1-propargyl-2,3-trimethylenequinolinium trifluoromethanesulfonate (N-I) -3) 6-Ethoxythiocarbonylamino-2-methyl-1-
Propargylquinolinium trifluoromethanesulfonate (N-I-4) 7- [3- (5-mercaptotetrazol-1-yl)
Benzamide] -10-propargyl-1,2,3,4
-Tetrahydroacridinium perchlorate (N-II-1) 1-formyl-2- {4- [3- {3- [3- (5-mercaptotetrazol-1-yl) phenyl] ureido} benzsulfonamide] phenyl } Hydrazine (N-II-2) 1-formyl-2- {4- [3- (5-mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine

In the present invention, it is preferable to use the quaternary heterocyclic compound and the hydrazine compound in combination. In the present invention, the amount of the nucleating agent added varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the developing conditions, and therefore can be varied over a wide range. About 1 x 1 per mole of silver
A range of 0 ^-8 moles to about 1 × 10 ^-2 moles is practically useful, with about 1 × 10 ^-5 moles to about 1 × 10 ⁵ moles per silver mole being preferred.
^-3 mol range. The nucleating agent may be added to the treatment liquid. In particular, it is effective when directly performing the fogging process on the positive color photographic light-sensitive material. In this case, it is preferable to add it to a low pH pre-bath as described in JP-A-58-178350. When the nucleating agent is added to the treatment liquid, the amount used is preferably 10 ^-8 to 10 ^-1 mol per liter of the treatment liquid, and 10 ^-7 to 10 ^-3.
Molar is more preferred.

In the present invention, the direct fog processing of the positive color photographic light-sensitive material is carried out in combination with the "chemical fog method" using the above nucleating agent or separately in the "light fog method".
You may carry out using. The overall exposure in the "light fog method", that is, fog exposure is performed after imagewise exposure, before color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being exposed. Is most preferred. As a light source for fogging exposure,
For example, JP-A-56-137350 and JP-A-58-702.
A light source having a high color rendering property (as close to white as possible) as described in JP-A No. 23 is preferable. The illuminance of light is 0.01-
2000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. The light-sensitive material using a higher-sensitivity emulsion is preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the light exposure by various filters, the distance between the light-sensitive material and the light source, or the angle between the light-sensitive material and the light source. Further, the illuminance of the fogging light can be increased from low illuminance to high illuminance continuously or stepwise. It is preferable to immerse the light-sensitive material in a color developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the permeation of the liquid to the light exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1
Minutes, more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40 seconds.

In the embodiment of the color photographic light-sensitive material of the present invention, in particular, the direct positive color photographic light-sensitive material, when the above nucleating agent is used, a nucleating accelerator for promoting the action of the nucleating agent is used. Is preferred. A nucleating accelerator does not substantially function as a nucleating agent, but accelerates the action of the nucleating agent to increase the maximum density of the direct positive image and / or obtain a certain maximum density of the direct positive image. Means a substance that has the function of accelerating the development time required. In the present invention, the nucleation accelerator described in JP-A-2-89048 can be preferably used. The nucleation accelerator is a silver halide emulsion layer or an adjacent non-photosensitive layer (intermediate layer, protective layer, etc.)
However, it is preferably contained in the silver halide emulsion together with the cyan coupler represented by the formula (CaI) or the formula (CbI) and the nucleating agent. The amount of nucleation accelerator added is 1 per mol of silver halide.
0 ^-6 to 10 ^-2 mol is preferable, and more preferably 10 ^-5.
It is about 10 ^-2 mol. The nucleation accelerator may be contained in the processing solution (that is, the developing solution or its pre-bath). In that case, 10 ^-8 to 10 ^-3 mol per liter of the processing solution is preferable, and more preferable. It is 10 ⁻⁷ to 10 ⁻⁴ mol.

Known photographic additives that can be used in the present invention are described in Research Disclosure No. 1764
3 (Dec. 1978) and No. 3 of the same. 18716 (1
(November 979), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column ~ Supersensitizer, page 649, right column 4, whitening agent 24 Page 5 antifoggant page 24-25 page 649 right column-stabilizer page 650 right column 6 light absorber, page 25 right column page 649 right column-filter dye, page 650 left column ultraviolet absorber 7 anti-stain agent 25 Page right column 8 Dye image stabilizer page 25 9 Hardener 26 page 651 Left column 10 Binder 26 page Same as above

In the color photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are flexible supports generally used for photographic light-sensitive materials such as plastic films, papers, cloths or the like, or rigid such as glass, pottery, metal or the like. Is coated on a support. Useful as the flexible support are films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate, a baryter layer or an α-olefin polymer. Examples include paper coated or laminated with (eg, polyethylene, polypropylene, ethylene / butene copolymer).
The support may be colored with a dye or pigment. For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. Also, if necessary, US Patent No. 2
No. 681294, No. 2761791, No. 3526
Multiple layers may be simultaneously coated by the method described in each specification such as No. 528 and No. 3508947.

Next, a color image forming method using the color photographic light-sensitive material of the present invention will be described. The color image forming method of the present invention forms a color image by subjecting the above color photographic light-sensitive material to image exposure, and then performing development processing with a developer containing a specific color developing agent represented by the formula (D). It is characterized by The development processing method may be a conventionally known method. Various exposure means can be used for exposing the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source.
Natural light (sunlight), incandescent lamp, halogen atom sealed lamp, mercury lamp, fluorescent lamp and flash light source such as strobe or metal burning flash bulb or semiconductor laser,
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. The spectral distribution used for exposure can be adjusted with a color filter as needed. In particular, a high-density beam light such as various lasers such as a gas laser (He-Ne laser, Ar laser, He-Cd laser) and a semiconductor laser is used as a light source, and this is moved relative to the photosensitive material. An exposing means of a so-called scanning exposure method (scanner method) for exposing an image by means of is preferable for exposing the light-sensitive material of the present invention. As a scanning exposure apparatus, for example, a color copying machine AP-5 manufactured by Fuji Photo Film Co., Ltd.
000 can be used.

In the case of exposure by the scanning exposure system, the time for exposing silver halide is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from digital data is generally used, and is called a pixel. Therefore, the exposure time per pixel varies depending on the size of the pixel. The size of this pixel depends on the pixel density.
It is 2000 dpi. In the color photographic light-sensitive material of the present invention, the pixel size is set to 1 pixel when the pixel density is 400 dpi, and the exposure time per pixel is 10 ^-3 seconds or less (preferably 10 ^-6 to 10 ^-4 seconds). ) Is used for scanning exposure.

The color developing agent used in the color image forming method of the present invention is represented by the following formula (D).

[0112]

[Chemical 35]

Examples of the alkyl group represented by R ^D1 include an alkyl group having 1 to 8 carbon atoms.
As such examples, methyl, ethyl, butyl or methoxyethyl are preferred. Examples of the alkylene group represented by R ^D2 include an alkylene group having 2 to 6 carbon atoms. As such an example, ethylene or trimethylene is preferable. Specific examples of the developing agent represented by formula (D) are shown below.

[0114]

[Chemical 36]

In the present invention, the compound represented by the above (D-2) or (D-3) is preferable. The above formula (D)
The amount of the color developing agent represented by is preferably about 0.1 g to about 20 g, and more preferably about 0.5 to about 10 g per liter of the developing solution. An aromatic primary amine type color developing agent other than the above may be used in combination, but if the developing agent represented by the formula (D) is 50
It is preferable that the content is at least mol%. The developing solution used in the color image forming method of the present invention is the same as the conventional color developing solution except that the developing agent is the above specific compound. The development processing method is also the same as the development processing method known per se, except that the above-described developing solution is used. The photographic light-sensitive material after the above color development processing is usually bleached,
A desilvering process consisting of a fixing process is applied, and after the desilvering process,
Generally, washing and / or stabilization treatment is performed. Regarding the above-mentioned series of processing steps, JP-A-3-12
The method described on pages 380 to 381 of Japanese Patent No. 0537 can be preferably used.

The color photographic light-sensitive material of the present invention has various uses, but is suitable for making color prints, color copies and color proofs. The color proof making method of the present invention can use a conventional color proof making method other than using the color photographic light-sensitive material of the present invention as described above. That is, the color proof making method of the present invention is
The color photographic light-sensitive material of the present invention is subjected to color separation and halftone image conversion, using a cyan plate halftone dot image film, an magenta halftone dot image film, a yellow plate halftone dot image film and a black halftone dot image film, This is a method of forming a color image by sequentially exposing with red light, green light and blue light and then performing color development processing as described above. As an apparatus for carrying out such a method, for example, a fine checker 850H manufactured by Fuji Photo Film Co., Ltd. (exposure time: 0.
02-0.3 seconds).

[0117]

【Example】

Example 1 Preparation of Sample 101 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following first to eleventh layers were applied to the front side, and the twelfth to thirteenth layers were applied to the back side to form a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer is Emulsion E described below.
It was made by changing the particle size by changing the temperature according to the manufacturing method of M-1. However, as the emulsion for the 11th layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver …… 0.10 Color Mixing Inhibitor (Cpd-7) …… 0.05 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalents) …… 0.12 Gelatin …… 0.40

Second layer (intermediate layer) Gelatin: 0.40 Dye (Cpd-32): 0.005

Third Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3 equivalents 5.4 × 10 ^{−4 in} total) (average grain size of 0. 40μ, particle size distribution 10%, octahedron) ...... 0.25 gelatin ...... 0.40 cyan coupler (ExC-1, 2, 3 1: 0.6: 0.2) ...... 0.25 anti-fading agent (Cpd-1, 2, 3) 4,30 equivalents) 0.18 Anti-staining agent (Cpd-5, 15 equivalents) 0.003 Coupler dispersion medium (Cpd-6) 0.30 Coupler solvent (Solv-1, 3, 5 etc.) Amount) …… 0.12

Fourth layer (intermediate layer) Gelatin: 0.70 Color mixing inhibitor (Cpd-7): 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalents): 0.16 Polymer latex (Cpd-8): … 0.10

Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4 2.6 × 10 ⁻⁴ ) (average grain size 0.40 μ, grain size distribution 10%). , Octahedron) ・ ・ ・ 0.20 Gelatin ・ ・ ・ 0.70 Magenta coupler (ExM-1, 2 each equivalent) ・ ・ ・ 0.10 Yellow coupler (ExY-1) ・ ・ ・ 0.03 Anti-fading agent (Cpd-9, 26, 30, 31) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) ...... 0.025 Coupler dispersion medium (Cpd-6) ...... 0.05 Coupler solvent (Solv- Equal amount of 4, 6) 0.15

6th layer (intermediate layer) Same as 4th layer

Seventh Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6 each equivalent weight 3.5 × 10 ⁻⁴ ) (average grain size 0.60 μm, Particle size distribution 11%, octahedron) ...... 0.32 Gelatin ...... 0.80 Yellow coupler (ExY-2, 3, 4 each equivalent) ...... 0.30 Anti-fading agent (Cpd-14) ...... 0.10 Anti-fading agent (Cpd-) 30) ...... 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) ...... 0.007 Coupler dispersion medium (Cpd-6) ...... 0.05 Coupler solvent (Solv-2) ...... 0.10

Eighth layer (ultraviolet absorber-containing layer) Gelatin: 0.60 Ultraviolet absorber (Equivalent amount of Cpd-2, 4, 16) 0.40 Color-mixing inhibitor (Equivalent amount of Cpd-7, 17) ...... 0.03 Dispersion medium (Cpd-6) ...... 0.02 UV absorber solvent (Solv-2, 7 each equivalent) ...... 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 10:10: 13:15:20 ratio) …… 0.05

Ninth layer (protective layer) Fine grain silver iodobromide (99 mol% silver bromide, average size 0.05 μ) …… 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) …… 0.01 Polymethylmethacrylate particles (Average particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent ...... 0.05 Gelatin ...... 0.05 Gelatin hardening agent (Equivalent for H-1 and H-2) ...... 0.18

10th Layer (Back Layer) Gelatin ... 2.50 Ultraviolet Absorber (Equivalent for Cpd-2, 4, 16) 0.50 Dye (Equivalent for Cpd-18, 19, 20, 21, 27) ... … 0.06

Eleventh Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardener (H-1 , H-2 equal amount) …… 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and an aqueous solution of silver nitrate containing 3 × 10 ⁻⁸ mol of rhodium bromide and 3 × 10 ⁻⁶ mol of iridium chloride ammonium salt per 1 mol of silver were vigorously stirred in an aqueous gelatin solution. However, the addition was carried out simultaneously at 65 ° C. over 15 minutes to obtain octahedral silver bromide grains having an average grain size of 0.23 μm. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
Was used in an amount of 10 ^-3 % by weight with respect to the silver halide, and Cpd-22, 28 and 29 were used in amounts of 10 ^-2 % by weight as nucleation accelerators.
Furthermore, alkanol XC (Du
Pont) and sodium alkylbenzene sulfonate as coating aids and succinate and Magefac F-
120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the layer containing silver halide and colloidal silver, a stabilizer (Cpd-23,
24 and 25 equivalent amounts) were used. The film thickness of the photosensitive layer side of this sample was 9.0 μm. This sample was designated as sample number 101. The compounds used in the examples are shown below.

[0132]

[Chemical 37]

[0133]

[Chemical 38]

[0134]

[Chemical Formula 39]

[0135]

[Chemical 40]

[0136]

[Chemical 41]

[0137]

[Chemical 42]

[0138]

[Chemical 43]

[0139]

[Chemical 44]

[0140]

[Chemical formula 45]

[0141]

[Chemical formula 46]

[0142]

[Chemical 47]

Solv-1 di (2-ethylhexyl) sebacate Solv-2 trinonyl phosphate Solv-3 di (3-methylhexyl) phthalate Solv-4 tricresyl phosphate Solv-5 dibutylphthalate Solv-6 trioctyl phosphate Solv- 7 Di (2-ethylhexyl) phthalate

H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-
1,3,5-triazine Na salt

ExZK-17- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-
Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate

(Preparation of Samples 102 to 115) In the preparation of Sample 101, the hydroquinone compound shown in Table 1 was added to the third, fifth and seventh layers at 8 × 10 ^-5 mol / m ² and a fogging agent or a development accelerator was released. Corresponding Samples 102 to 115 were prepared in the same manner as Sample 101 except that the compound was added at 5 × 10 ⁻⁶ mol per mol of silver halide. (Evaluation as a color photographic light-sensitive material) Each sample prepared as described above was subjected to wedge exposure, and color development processing was performed using the following processing step 1, and then maximum image density (Dmax) and minimum image were obtained. The density (Dmin) and the gradation of the toes were measured. The gradation of the toe is shown by the average gradation between Dmin +0.2 (optical density) and Dmin +0.5. Among these results, those relating to magenta density are shown in Table 1. From this, it can be seen that the compound of the present invention has a higher Dmax, a lower Dmin, and gives a hard-tone image in the highlight portion, as compared with the comparative compound shown in Table 1 and the following formula. Similar results were obtained for the yellow image and the cyan image.

[0147]

[Table 1]

[0148]

[Chemical 48]

Processing Step 1 [Processing Condition] Processing Time Temperature Color development 135 seconds 38 ° C Bleach fixing 60 seconds 34 ° C Water washing (1) 40 seconds 32 ° C Water washing (2) 40 seconds 32 ° C Drying 30 seconds 80 ° C

Color developer D-sorbit 0.15 g sodium naphthalenesulfonate / 0.15 g formalin condensate nitrilotris (methylenephosphonic acid) 1.8 g pentasodium salt diethylenetriaminepentaacetic acid 0.5 g 1-hydroxyethylidene-1,1-0.15 g diphosphone Acid Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.8 g Hydroxylamine / 1/2 sulfate 4.5 g Triethanolamine 6.5 g 4- [N-ethyl-N- (β-hydroxy 4.2 g Ethyl) amino] aniline sulfate / 1/2 hydrate Potassium carbonate 30.0 g Optical brightener (diaminostilbene type) 1.3 g Water is added to 1000 ml pH (25 ° C) (pH adjusted with KOH or sulfuric acid) 10.35

Bleach-fixing solution Ethylenediaminetetraacetic acid ・ disodium ・ dihydrate 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammoni 55.0 g Ume ・ dihydrate Ammonium thiosulfate (750 g / l) 168 ml sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium sulfate 10.0 g Water was added to 1000 ml pH (25 ° C) (pH adjustment with ammonia water or acetic acid) 6.50

Washing water Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.50

Example 2 Preparation of Sample 201 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following 1st to 14th layers were multilayer-coated and the 15th to 16th layers were coated on the back side to prepare a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the emulsion of the 14th layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver 0.10 Color Mixing Prevention Agent (Cpd-7) 0.05 Gelatin 0.70

Second layer (intermediate layer) gelatin 0.70

Third Layer (Low Sensitivity Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.22 μ, grain size distribution [coefficient of variation] ] 7%, octahedron) 0.06 Silver chlorobromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (5 mol% silver chloride, average grain size 0.42μ, grain size distribution 9) %, Octahedron) 0.08 Gelatin 1.02 Cyan coupler (ExC) 0.21 Anti-fading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.18 Anti-staining agent (Cpd-5) 0.001 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.18

Fourth Layer (Highly Sensitive Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.58 μ, grain size distribution 14%, Octahedral) 0.16 Gelatin 1.05 Cyan coupler (ExC) 0.28 Antifading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.14 Coupler dispersion medium (Cpd-6) 0.02 Coupler solvent (Solv-1, 2, 3) Equivalent) 0.18

Fifth Layer (Intermediate Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.16 Polymer latex (Cpd-8) 0.10

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.25 μ, grain size distribution 8%, octahedron) 0.04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-4) (5 mol% silver chloride, average grain size 0.40μ, grain size distribution 10%, octahedron) 0.06 Gelatin 0.80 Magenta coupler (ExM -1, 2, 3 equivalents) 0.10 Anti-fading agent (equal amounts of Cpd-9, 26, 30) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15

Seventh Layer (High Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.65 μ, grain size distribution 16%, octahedron) 0.10 Gelatin 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) 0.12 Anti-fading agent (equal amounts of Cpd-9, 26, 30) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 at 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15

8th layer (intermediate layer) Same as 5th layer

Ninth layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixing inhibitor (Cpd-7) 0.03 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.10 Polymer latex (Cpd-) 8) 0.07

10th layer (intermediate layer) Same as 5th layer

Eleventh Layer (Low Sensitivity Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.40 μ, grain size distribution 8%, octahedron). 0.07 Silver chlorobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (silver chloride 8 mol%, average grain size 0.60 μ, grain size distribution 11%, octahedron) 0.14 gelatin 0.80 yellow coupler (ExY-1, 2, 3 equivalents) 0.33 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10

Twelfth layer (high-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.85 μ, grain size distribution 18%, octahedron). 0.15 Gelatin 0.60 Yellow coupler (ExY-1, 2, 3 equivalents) 0.32 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) ) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10

13th layer (UV absorbing layer) Gelatin 1.00 UV absorbing agent (Cpd-2, 4, 16 equivalents) 0.50 Color mixing inhibitor (Cpd-7, 17 equivalents) 0.03 Dispersion medium (Cpd-6) 0.02 UV rays Absorbent solvent (Solv-2, 7 equivalents) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 in 10: 10: 13: 15: 20 ratio) 0.05

Fourteenth Layer (Protective Layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.1 μ) 0.03 Polyvinyl alcohol acrylic modified copolymer (molecular weight 50,000) 0.01 Polymethylmethacrylate particles (average particle Size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent 0.05 gelatin 1.80 Gelatin hardening agent (H-1, H-2 equivalent) 0.18

Fifteenth layer (back layer) Gelatin 2.50 Ultraviolet absorber (Cpd-2, 4, 16 equivalents) 0.50 Dye (Cpd-18, 19, 20, 21, 27 equivalents) 0.06

Sixteenth Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent 0.05 gelatin 2.00 Gelatin hardener (H-1, H- 2 equivalents) 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75 ° C. over 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.35μ were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7 µ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
10 for silver halide ^-3% By weight, promoting nucleation
Cpd-22, 28, and 29 each as an agent^-2weight%
Using. Furthermore, alkanol is used as an emulsification dispersion aid in each layer.
XC (Dupont) and Nato alkylbenzene sulfonate
Sulfuric acid as a coating aid and Magefa
cF-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. halogen
As a stabilizer (Cpd-
23, 24, 25) was used. This sample is Sample No. 20
It was set to 1. The compounds used in the examples are shown below.

[0173]

[Chemical 49]

[0174]

[Chemical 50]

[0175]

[Chemical 51]

[0176]

[Chemical 52]

[0177]

[Chemical 53]

[0178]

[Chemical 54]

[0179]

[Chemical 55]

[0180]

[Chemical 56]

[0181]

[Chemical 57]

[0182]

[Chemical 58]

[0183]

[Chemical 59]

[0184]

[Chemical 60]

[0185]

[Chemical formula 61]

(Preparation of Samples 202 to 215) In the preparation of the above-mentioned sample 201,
Sample 201 was prepared in the same manner as above except that 5 × 10 ⁻⁵ mol / m ^{2 of} hydroquinone compound shown in Table 2 and 2 × 10 ⁻² mol of fogging agent or development accelerator releasing compound were added to each layer per mol of silver halide. Corresponding samples 202-215 were made. (Evaluation as a color photographic light-sensitive material) Each sample prepared as described above was subjected to wedge exposure, and color development processing was performed using the following processing step 2. Then, maximum image density (Dmax) and minimum image were obtained. The density (Dmin) and the gradation of the toes were measured. The gradation of the toe is shown by the average gradation between Dmin +0.2 (optical density) and Dmin +0.5. Of these results, those relating to the yellow density are shown in Table 2. From this, it can be seen that the compound of the present invention has a higher Dmax, a lower Dmin, and gives a hard-tone image in the highlight portion, as compared with the comparative compound shown in Table 2 and the following formula. Similar results were obtained for the magenta image and the cyan image.

[Processing Step 2] Using an automatic processor, continuous processing was carried out by the method described below until the cumulative replenishment amount of the color developer replenisher became 3 times the tank volume. Processing process time Temperature Tank capacity Replenishment amount Color development 135 seconds 38 ° C 11 liters 350 ml / m ² Bleach fixing 40 seconds 34 ° C 3 liters 300 ml / m ² Washing with water (1) 40 seconds 32 ° C 3 liters-washing with water (2) 40 Second 32 ℃ 3 liter 350 ml / m ² Dry 30 s 80 ℃ Replenishment method of washing water is to replenish the washing bath (2) with the washing bath (2).
The so-called countercurrent replenishment system was used in which the overflow liquid of (1) was introduced into the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each processing liquid is as follows. [Color developer] [Tank solution] [Replenisher] D-Sorbit 0.15g 0.20g Sodium naphthalenesulfonate / formalin condensate 0.15g 0.20g Nitrilotris (methylenephosphonic acid) pentasodium salt 1.8g 1.8g Diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g diethylene glycol 12.0 ml 16.0 ml benzyl alcohol 13.5 ml 18.0 ml potassium bromide 0.70 g-benzotriazole 0.003 g 0.004 g sodium sulfite 2.4 g 3.2 g disodium -N, N-bis (sulfonate ethyl) hydroxylamine 8.0g 10.6g triethanolamine 6.0g 8.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid 1 water salt 6.0g 8.0g Potassium carbonate 30.0g 25.0g Optical brightener (diaminostilbene type) 1.3g 1.7g Add water 1000ml 1000ml pH (25 ° C) (pH adjusted with KOH or sulfuric acid) 10.30 10.79

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid / 2 sodium / dihydrate 4.0 g Same as tank solution Ethylenediaminetetraacetic acid / Fe (III) / Ammonium / dihydrate 55.0 g Thio Ammonium sulfate (750 g / liter 168 ml sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water was added to 1000 ml pH (25 ° C) (ammonia water) Or adjust the pH with acetic acid) 6.5

[Washing Water] [Both Tank Solution and Replenisher] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

[0191]

[Table 2]

[0192]

[Chemical formula 62]

Example 3 Among the samples used in Example 1 above, Sample 102, Sample 114 and Sample 115 were used, and a plate-making film having a halftone image was used using Fine Checker FC850H manufactured by Fuji Photo Film Co., Ltd. After making them adhere to each other, red exposure (SC-60 filter manufactured by Fuji Photo Film Co., Ltd.) and green exposure (BPB- manufactured by Fuji Photo Film Co., Ltd.)
53 filter), and further blue exposure (BPN45 and SC-42 filter manufactured by Fuji Photo Film Co., Ltd.) were sequentially performed. At that time, a plate-making film for an unimage and a black image was overlapped with each other during red exposure, a plate-making film for a magenta image and a black image was overlapped during green exposure, and a plate-making film for a yellow image and a black image was further overlapped during blue exposure. A color proof was created in this way. The image formation in this case was performed according to the color development processing according to the above-described Example 1. The minimum halftone dot area of the color-proof yellow image obtained as described above is set to 100.
Observed with a double magnifying glass. The color photographic light-sensitive materials (Invention Samples 114 and 115) were able to reproduce up to 2% halftone dot images, but the color photographic light-sensitive material of Comparative Example (Comparative Sample 10).
In 2), halftone dot images of 2% could not be reproduced, and only halftone dot images of 3% or more could be reproduced.

Example 4 As a light source, a helium-neon gas laser (wavelength 63
3 nm and 543 nm) and argon laser (wavelength 4
58 nm), a light beam having a diameter of 80 μm at a pitch of 100 μm is moved perpendicularly to the scanning direction by a scanning exposure of 1.6 m / s, and a sequential scanning exposure (substantial exposure time of about 5 × 10 ^{−5) is performed.} I assembled a device that can. Using this apparatus, the comparative sample 102 and the sample 115 were exposed and then processed using the processing liquid 1 described above, and the reproducibility of the halftone image of the obtained image was evaluated. As a result, the color photographic light-sensitive material of the present invention (Invention sample 115) was able to satisfactorily reproduce up to a 2% halftone dot image, while the color photographic light-sensitive material of Comparative Example (comparative sample 102) was 4% halftone dot. I could only reproduce the image.

[0195]

The direct positive color of the present invention containing the hydroquinone compound represented by the formula (HQ1) or (HQ2) and the compound releasing the fogging agent or the development accelerator represented by the formula (I). By using a photographic light-sensitive material, the maximum image density is high and the minimum image density is low,
In addition, an image with hard gradation can be obtained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 13, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

The alkyl group represented by R ^Q8 above is
Mention may be made of alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, butyl, isopropyl, t-butyl, cyclohexyl, octyl and hexadecyl.
The alkenyl group represented by R ^Q8 has 2 to 2 carbon atoms.
Mention may be made of 30 alkenyl groups, such as allyl, 2-pentenyl and octadecenyl. Examples of the alkynyl group represented by R ^Q8 include an alkynyl group having 2 to 30 carbon atoms, for example, propargyl.
The aryl group represented by R ^Q8 has 6 to 3 carbon atoms.
Mention may be made of 0 aryl groups, for example phenyl and naphthyl. The heterocyclic group represented by R ^Q8 is a 3- to 12-membered heterocyclic ring containing at least one hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom or selenium. Such examples include pyridyl, triazinyl, uracil, pyrrolyl, thienyl, furanyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyrrolidinyl and morpholinyl. The above R ^Q8 is a substituent (including an atom)
May have. As the substituent, an alkyl group (having 1 to 18 carbon atoms), an alkenyl group (having 2 to 18 carbon atoms), an alkynyl group (having 2 to 18 carbon atoms), an aralkyl group (having 7 to 20 carbon atoms), an aryl group (having carbon number). 6-20), hydroxyl group, alkoxy group (C1-18), aryloxy group (C6-20), halogen atom, amino group,
Alkylthio group (having 1 to 18 carbon atoms), arylthio group (having 6 to 20 carbon atoms), acyloxy group (having 1 to 1 carbon atoms)
8), sulfonyloxy group (having 1 to 18 carbon atoms), acylamino group (having 1 to 18 carbon atoms), sulfonamide group (having 1 to 18 carbon atoms), carboxyl group, alkoxycarbonyl group (having 2 to 18 carbon atoms), aryl Oxycarbonyl group (C7-20), acyl group (C1-20), carbamoyl group (having a C1-20 substituent), sulfamoyl group (unsubstituted or C1-20 substituent) ), Sulfo group, cyano group, ureido group (having 1 carbon atom)
To 20 substituents), urethane group (having 2 to 2 carbon atoms)
0), and a carbonic acid ester group (having 2 to 20 carbon atoms). The above R ^Q8 is an alkyl group (having 1 to 1 carbon atoms).
6 (preferably 1 to 10, more preferably 8 to 10))
Alternatively, an aryl group (phenyl) is preferable.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0147

[Correction method] Change

[Correction content]

[0147]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 7/407 G03F 3/10 B

Claims (4)

[Claims] 1. Inside of the support, which is not previously covered
Latent image type silver halide grains and color image forming coupler
A blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing
At least one non-photosensitive layer adjacent to each other
In the direct positive color photographic light-sensitive material obtained by
Blue sensitive layer, green sensitive layer, red sensitive layer and non-photosensitive
Furthermore, the following general formula (HQ1) or (HQ2):[In the formula, R^Q1And R^Q2Are independently hydrogen atoms or
Or the hydroxyl group is broken during the development process because the bond with the oxygen atom is cut.
Represents a group that releases^Q3, R^Q4And R^Q6Is that
Independently, hydrogen atom, halogen atom, sulfo group, carbo
Xyl, cyano, alkyl, alkenyl, ant
Group, acylamino group, sulfonamide group, alkoxy group
Si group, aryloxy group, alkylthio group, aryl group
O group, acyl group, acyloxy group, sulfonyl group, cal
Vamoyl group, alkoxycarbonyl group, sulfamoyl
Group, ureido group, urethane group or carbonic acid ester group
I, R^Q5Is the above R^Q3The same group as the group shown by or
Represents an aryl group attached through a linking group, provided that
Note R^Q5Is the above R^Q3When the group is the same as the group shown in
Note R^Q3And R^Q4Or R^Q5And R^Q6Are jointly carbocycles or
A heterocycle may be formed, and the above R^Q3~ R^Q6Out of
At least one is not a hydrogen atom, and R ^Q3~ R^Q6But
When it is composed of only hydrogen atoms and alkyl groups, the alkyl
At least one of the groups has 6 or more carbon atoms, and R^Q3~
R^Q6Has a total carbon number of 15 or less. ] [Chemical 2][In the formula, R^Q11~ R^Q16Are each independently a hydrogen atom,
Halogen atom, sulfo group, carboxyl group, cyano group,
Alkyl group, alkenyl group, aryl group, acylamino
Group, sulfonamide group, alkoxy group, aryloxy
Group, alkylthio group, arylthio group, acyl group, acyl group
Luoxy group, sulfonyl group, carbamoyl group, alkoxy group
Represents a carbonyl group or a sulfamoyl group,
R^Q11And R^Q12Or R^Q14And R^Q15Jointly carbon
May form a ring or a heterocycle; R^Q17and
R^Q18Are each independently a hydrogen atom, alkyl group, or aryl
Is a R group or a heterocyclic group, and R^Q17And R^Q18Is
Similarly, a carbocycle and a heterocycle may be formed. ]]
At least one compound represented by the following formula (I)
At least one compound of
Direct positive color photographic light-sensitive material. General formula (I):Where R¹Represents a hydrogen atom or an alkyl group, R²Is
Alkyl group, aryl group, heterocyclic group, amino group or
Represents a lucoxy group, X is -CO-, -SO₂-Or
Represents -COCO-. R³, R^FourIs a hydrogen atom or
Substituent constant σ_pRepresents a substituent of 0.3 or less.
B releases FA after leaving the hydroquinone mother nucleic acid product
Wherein m is an integer from 0 to 2 and FA is
Represents a fogging agent or a development accelerator residue. A, A '
Represents a hydrogen atom or a group capable of being removed with an alkali. R
²And R³May cooperate to form a heterocycle. 2. The color photographic light-sensitive material according to claim 1 is imagewise exposed and then represented by the following formula (D): [In the formula, R ^D1 represents an alkyl group and R ^D2 represents an alkylene group, provided that R ^D1 and R ^D2 may be linked to each other to form a ring. ] The color image forming method characterized by performing color development processing using the developing agent represented by these. 3. The cyan photographic halftone dot image film, the magenta halftone dot image film, the yellow halftone dot image film and the black halftone dot obtained by color separation and halftone image conversion of the color photographic light-sensitive material according to claim 1. A method for producing a color proof, characterized in that a point image film is used to sequentially perform exposure with red light, green light, and blue light, and then color development processing is performed. 4. A color image forming method, which comprises subjecting the color photographic light-sensitive material according to claim 1 to scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel, and then performing color development processing.