JPH1069042A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance rapid development processing aptitude and letter characteristics and to reduce dispersion of color developing density due to variation of temperature at the scanning exposure of a photosensitive material with laser beams by color developing the photosensitive material with a processing solution containing a specified tetrahydroquninoline derivative color developing agent. SOLUTION: The silver halide photographic sensitive material has each at least one of silver halide emulsion layers containing a yellow coupler, a magenta coupler, and a cyan coupler and one of silver halide emulsion layers containing silver chloride in an amount of >=95mol%, and it is color developed with the processing solution containing the tetrahydoquninoline derived color developing agent represented by the formula in which each of R1 -R6 is, independently, an H atom or a substituent; R7 is an alkyl or aryl or heterocyclic group; R8 is a sunstituent; and (m) is 0, 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material, and more particularly, to an image forming method in which the performance of laser scanning exposure does not fluctuate with the temperature during exposure.

[0002]

2. Description of the Related Art Color photography, which has become widespread today, has become more and more quickly and easily available due to advances in photosensitive materials themselves and development processing techniques. In the field of color printing, in particular, centralized processing methods at production bases equipped with high-speed printers for mass production called color labs and large-scale processing equipment, and distributed processing using small printer processors called mini labs installed at stores Due to the development of the method, production according to various purposes is performed. In recent years, light-sensitive materials using high silver chloride emulsions and their processing methods have been put to practical use, and the processing speed has become increasingly sophisticated.

[0003] With the speeding up of such processing, characters desired by end users are printed on prints together with images. For example, images and characters are formed on the same print as seen on Fujicolor postcards, and are widely used for New Year's cards. In order to form the characters of an image on the same print, generally, a negative for the character is separately prepared and exposed at the same time as the negative for the image, but this creates an extra negative for the character Therefore, productivity is poor.

With the recent development of computer technology,
It has become relatively easy to combine image information read by a scanner with character image information on a computer. According to this method, it is not necessary to prepare an extra negative for a character image. Therefore, as a method of recording image information synthesized on a computer on a silver halide photosensitive material, image formation by a scanning exposure method has been studied. Examples of the image forming method by the scanning exposure method include, for example, JP-A-61-137149 and JP-B-62-213.
No. 05, JP-A-62-35352 and JP-A-63-1834.
No. 6, JP-A-2-18548, JP-A-2-124567
Nos. 4,619,892 and 4,956,7
No. 02 and WO87 / 04534. Japanese Patent Publication No. 62-21305 discloses a method of performing scanning exposure on a photographic material using a light emitting diode as a light source.
Further, Japanese Patent Application Laid-Open No. 62-35352 discloses a scanning exposure of a high silver chloride photographic material with a laser beam. JP-A-63-18346 discloses a scanning exposure method using a second harmonic obtained by using a semiconductor laser and an SHG element as a light source. In addition, WO8
JP-A-7 / 04534 discloses a technique for shortening the total image forming time by using a photosensitive material containing a high silver chloride emulsion.

[0005]

Among these techniques, it is advantageous to use a laser light as a light source with less scattering and a good linearity, that is, a laser light. The present inventor based on the method described in these patents,
When an image in which an image and a character coexist on a color photographic paper was output by scanning exposure using a laser as a light source, an image could be obtained in a short time without the necessity of preparing a negative for the character. However, when laser light is used as a light source, the variation in color density due to the temperature at the time of exposure increases, and the stability of the finished image is insufficient. Therefore, an object of the present invention is to provide excellent rapid processing property and character quality,
It is an object of the present invention to provide an image forming method in which a variation in color density due to a temperature variation when a silver halide photosensitive material is scanned and exposed by a laser beam is small.

[0006]

The present inventors have made intensive studies and found that the objects of the present invention can be achieved by the following means. (1) In an image forming method in which a silver halide photographic light-sensitive material is scanned and exposed by a laser beam and then subjected to color development processing, the silver halide light-sensitive material is coated on a support with a silver coupler emulsion layer containing a yellow coupler, a magenta coupler. Having at least one silver halide emulsion layer containing at least one silver halide emulsion layer and one silver halide emulsion layer containing a cyan coupler, wherein at least one of the silver halide emulsion layers contains a silver halide emulsion having a silver chloride content of 95 mol% or more. An image forming method, which is a silver color photographic light-sensitive material, wherein said color development processing is carried out with a processing solution containing at least one tetrahydroquinoline-based color developing agent represented by the following general formula (D). .

[0007]

Embedded image

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ may be the same or different and each represents a hydrogen atom or a substituent. However, R ₁ and R ₂ , R ₃ and R ₄ , R ₅
And R ₆ , at least one of which is a substituent. R ₇ is an alkyl group,
Represents an aryl group or a heterocyclic group. R ₈ represents a substituent. m represents an integer of 0 to 3. The color developing agents used in the present invention are described in U.S. Pat. No. 2,196,739 and JP-A-7-28737.
No. 0, and US Pat.
No. 6,739, there is no description of a specific compound corresponding to the color developing agent of the present invention.
Although No. 70 describes a specific compound corresponding to the color developing agent of the present invention, it suppresses performance fluctuation due to temperature during laser scanning exposure of the silver halide color photographic material intended for the present invention. Nothing is directly suggested or even predictable.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

In the general formula (D) used in the present invention,
R in the compound represented₁, R_Two, R _Three, R_Four, R_Five, R
₆, R₇, R₈And m are described in detail below.
R₁, R_Two, R_ThreeAnd R_FourMay be the same or different
And each represents a hydrogen atom or a substituent. More specifically, R
₁, R_Two, R_ThreeAnd R_FourIs a hydrogen atom or a substituent
Examples of the substituent include a halogen atom, an alkyl group,
Reel, heterocyclic, cyano, nitro, hydroxy
A sil group, a carboxyl group, a sulfo group, an alkoxy group,
Reeloxy group, acylamino group, amino group, alkyl
Amino group, anilino group, ureido group, sulfamoylua
Mino group, alkylthio group, arylthio group, alkoxy
Carbonylamino group, sulfonamide group, carbamoyl
Group, sulfamoyl group, sulfonyl group, alkoxycal
Bonyl group, heterocyclic oxy group, azo group, acyloxy
Group, carbamoyloxy group, silyl group, silyloxy
Group, aryloxycarbonylamino group, imide group,
Telocyclic thio group, sulfinyl group, phosphonyl group, aryl
A luoxycarbonyl group and an acyl group. These are al
Kill, alkenyl, alkynyl, aryl,
Droxyl, nitro, cyano, halogen or
Is other oxygen, nitrogen, sulfur or carbon
It may be substituted with a substituent formed by an atom.

Further examples of the substituents of R ₁ , R ₂ , R ₃ and R ₄ are shown below. Examples of the halogen atom include a fluorine atom and a chlorine atom. The alkyl group has 1 to 2 carbon atoms.
5, preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2- Methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, hydroxymethyl, 2-carboxylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2, 3-dihydroxypropyl, 3,4-dihydroxybutyl, methanesulfonamidomethyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobuty , 4-carbamoyl-butyl, 2
-Carbamoyl 1-methylethyl, carbamoylaminomethyl, 4-nitrobutyl, 2- (2-hydroxyethoxy) ethyl, 2- [2- (2-hydroxyethoxy)
Ethoxy] ethyl, 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl, 2- [2-
(2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethoxy] ethyl, 2- (2-methoxyethoxy) ethyl, 2- [2- (2-methoxyethoxy) ethoxy] ethyl, 2- (2- [2- (2-methoxyethoxy) ethoxy] ethoxy) ethyl, 2- [2- (2-
[2- (2-methoxyethoxy) ethoxy] ethoxy)
Ethoxy] ethyl, 2- (2-ethoxyethoxy) ethyl and 2- [2- (2-butoxyethoxy) ethoxy] ethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, such as phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic ring containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. And the kind of element may be one or more, and examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl, and pyrazolyl. The alkoxy group is an alkoxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxy, ethoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, for example, phenoxy, p-methoxyphenoxy, m- (3
-Hydroxypropionamido) phenoxy. The acylamino group is an acylamino group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms.
-Methoxypropionamide, p-nitrobenzoylamide. The alkylamino group has 1 to 1 carbon atoms.
6, preferably an alkylamino group having 1 to 6 carbon atoms, such as dimethylamino, diethylamino and 2-hydroxyethylamino. The anilino group has 6 to 2 carbon atoms.
Examples of the anilino group 4 include anilino, m-nitroanilino, and N-methylanilino. The ureido group is a ureido group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as ureide, methyl ureide, N, N-diethyl ureide and 2-methanesulfonamidoethyl ureide.

The sulfamoylamino group has 0 carbon atoms.
To 16, preferably 0 to 6 carbon atoms, for example, dimethylsulfamoylamino, methylsulfamoylamino, 2-methoxyethylsulfamoylamino. The alkylthio group has 1 to 1 carbon atoms.
16, preferably an alkylthio group having 1 to 6 carbon atoms, for example, methylthio, ethylthio and 2-phenoxyethylthio. The arylthio group is an arylthio group having 6 to 24 carbon atoms, such as phenylthio, 2-carboxyphenylthio, and 4-cyanophenylthio. The alkoxycarbonylamino group has 2 to 2 carbon atoms.
16, preferably an alkoxycarbonylamino group having 2 to 6 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, and 3-methanesulfonylpropoxycarbonylamino. The sulfonamide group is a sulfonamide group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonamide, p-toluenesulfonamide, and 2-methoxyethanesulfonamide. The carbamoyl group is a carbamoyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as carbamoyl, N, N-dimethylcarbamoyl and N-ethylcarbamoyl. The sulfamoyl group has 0 to 1 carbon atoms.
6, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as sulfamoyl, dimethylsulfamoyl and ethylsulfamoyl. The sulfonyl group has 1 carbon atom
To 16, preferably an aliphatic or aromatic sulfonyl group having 1 to 6 carbon atoms, such as methanesulfonyl, ethanesulfonyl and 2-chloroethanesulfonyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl and t-butoxycarbonyl. The heterocyclic oxy group has 1 to 1 carbon atoms.
5 is a 5- or 6-membered saturated or unsaturated heterocyclic oxy group containing at least one oxygen, nitrogen or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element are one. However, the number may be plural, such as 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy and 2-pyridyloxy.

The azo group is an azo group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms.
Hydroxy-4-propanoylphenylazo and 4-sulfophenylazo. The acyloxy group is an acyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group is a carbamoyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy, and N-phenylcarbamoyloxy. The silyl group is a silyl group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyl, isopropyldiethylsilyl,
t-butyldimethylsilyl. The silyloxy group is a silyloxy group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, such as phenoxycarbonylamino, 4-cyanophenoxycarbonylamino, and 2,6-dimethoxyphenoxycarbonylamino. The imide group has 4 to 1 carbon atoms
The imide group 6 is, for example, N-succinimide or N-phthalimide. The heterocyclic thio group has 1 to 5 carbon atoms.
Is a 5- or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom or sulfur atom, having at least one heteroatom and one kind of element constituting the ring. It may be plural, for example, 2-benzothiazolylthio and 2-pyridylthio.

The sulfinyl group has 1 to 16 carbon atoms,
Preferably it is a C1-C6 sulfinyl group, for example, methanesulfinyl, benzenesulfinyl, and ethanesulfinyl. The phosphonyl group has 2 to 1 carbon atoms.
6, preferably a phosphonyl group having 2 to 6 carbon atoms, for example,
Methoxyphosphonyl, ethoxyphosphonyl and phenoxyphosphonyl. The aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl, 2-methylphenoxycarbonyl, and 4-acetamidophenoxycarbonyl. As the acyl group, an acyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetyl, benzoyl,
4-chlorobenzoyl.

R ₅ and R ₆ each represent a hydrogen atom or a substituent. In this case, the substituent represents an alkyl group, an aryl group or a heterocyclic group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . However, R ₅ , R ₆
Is a heterocyclic group, it is bonded to a carbon atom constituting the heterocyclic ring of the heterocyclic group. R ₇ represents an alkyl group, an aryl group or a heterocyclic group. For details, see R ₁ ,
It has the same meaning as that described for R ₂ , R ₃ and R ₄ . However, when R ₇ is an alkyl group, among the carbon atoms in R ₇ , the carbon atom directly bonded to the nitrogen atom in the general formula (D) includes a hydrogen atom and a carbon atom other than the two elements. Are not combined. When R ₇ is a heterocyclic group, the nitrogen atom in the general formula (D) to which R ₇ is bonded is connected to a carbon atom constituting the hetero ring of the heterocyclic group. R ₈ represents a substituent. For details, see R ₁ , R ₂ , R
₃ and is synonymous to those described in R _4. m represents an integer of 0 to 3.

Among the compounds represented by the general formula (D),
Compounds represented by the following formulas (DD-1) and (DD-2) are particularly preferred. General formula (DD-1)

[0018]

Embedded image

Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R
₁₆ may be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each of R ₁₁ and R _12, R ₁₃ and R _14, R ₁₅ and R _16, which is at least one of both substituents. R ₁₇ represents an alkyl group, an aryl group or a heterocyclic group. R ₁₈ represents a hydrogen atom or a substituent.

General formula (DD-2)

[0021]

Embedded image

Wherein R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆
May be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each of R ₂₁ and R _22, R ₂₃ and R _24, R ₂₅ and R _26, at least one of which is both substituents. R ₉ and R ₂₈ represent a hydrogen atom or a substituent, and n represents an integer of 2 to 8.

In the general formula (DD-1), R ₁₁ , R ₁₂ ,
Preferred combinations of R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ will be described below. R ₁₈ is a hydrogen atom, an alkyl group or an alkoxy group, R ₁₇ is an alkyl group, and R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆
Is preferably a combination each of which is a hydrogen atom or an alkyl group. Here, the alkyl group and the alkoxy group include those substituted with another substituent. In this combination,
More preferably, at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ is an alkyl group substituted with a water-soluble group, and further a hydroxyl group, a carboxyl group , A sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group is preferable. Particularly, it is preferably an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group.

As a more preferred combination, R ₁₈ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or
And R ₁₇ is an alkyl group having 1 to 6 carbon atoms, and R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆
Is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this combination, it is more preferable that at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ is an alkyl group substituted with a water-soluble group, and further a hydroxyl group. , A carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group. It is particularly preferable that the alkyl group is substituted with a hydroxyl group, a carboxyl group, a ureido group or a sulfonamide group.

As a more preferred combination, R₁₈Is
An alkyl group having 1 to 6 carbon atoms;₁₇Has 1 to 6 carbon atoms
Is an alkyl group of₁₁, R₁₂, R₁₃, R₁₄, R_FifteenPassing
And R ₁₆Each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
Is preferred. This combination smells
R₁₁, R₁₂, R₁₃, R₁₄, R_Fifteen, R₁₆, R₁₇And R₁₈
Alkyl at least one of which is substituted with a water-soluble group
Group, more preferably a hydroxyl group,
Ruboxyl group, sulfo group, alkoxy group, acylamino
Group, amino group, alkylamino group, ureido group, sulf
Amoylamino group, sulfonamide group, carbamoyl
Group, a sulfamoyl group, or a sulfonyl group
Preferably an alkyl group, especially hydroxyl
Group, carboxyl group, ureido group, sulfonamide group
It is preferably a substituted alkyl group.

In a more preferred combination, R ₁₈ is a methyl group and an isopropyl group, and R ₁₇ has 1 carbon atom.
And R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R
_{A combination in which 15} and R ₁₆ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. In this combination, it is more preferable that at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ is an alkyl group substituted with a water-soluble group, and further a hydroxyl group, a carboxyl group , A sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group is preferable. Particularly, it is preferably an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group.

R in the general formula (DD-2)_{twenty one}, R_{twenty two},
R_{twenty three}, R_{twenty four}, R_{twenty five}, R₂₆, R₉And R ₂₈About below
The preferred combinations are described below. R₂₈Is hydrogen
An atom, an alkyl group or an alkoxy group,₉Is water
A hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}, R_{twenty five}And R₂₆Is water
Combinations which are an atom or an alkyl group are preferred. here
Alkyl, alkoxy, aryl and hetero
Ring groups include those substituted with other substituents. Replace
Groups include hydroxyl, carboxyl, sulfo
Group, alkoxy group, acylamino group, amino group, alkyl
Ruamino group, ureido group, sulfamoylamino group,
Sulfonamide, carbamoyl, sulfamoyl, etc.
Or a sulfonyl group, particularly a hydroxyl group,
Ruboxyl, ureido and sulfonamide groups are preferred
No.

As a more preferred combination, R ₂₈ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or
6 is an alkoxy group, R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ ,
Preferably, R ₂₅ and R ₂₆ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Here, the alkyl group and the alkoxy group include those substituted with another substituent. As a substituent, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group,
Preferred are an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group and a sulfonyl group, and particularly preferred are a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group.

As a more preferred combination, R ₂₈ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₂₁ and R _21
It is preferable that each of ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Here, the alkyl group includes those substituted with another substituent. As the substituent, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group is preferable. Particularly, a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group are preferred.

More preferably, R ₂₈ is a methyl group and an isopropyl group, R ₉ is a hydrogen atom and a methyl group, and R ₂₁ R ₂₂ R ₂₃ R ₂₄ R ₂₅ and R ₂₆ are each a hydrogen atom or a carbon atom. Combinations of 1 to 3 alkyl groups are preferred. Here, the alkyl group includes those substituted with another substituent. As the substituent, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group is preferable. Particularly, a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group are preferred. Next, specific examples of the representative developing agent represented by formula (D) in the invention are shown, but the invention is not limited thereto.

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

The compound represented by the general formula (D) is very unstable when stored as a free amine.
In general, it is preferable to produce and store the salt as a salt of an inorganic acid or an organic acid, and then to form a free amine for the first time when the salt is added to the treatment solution. Examples of the inorganic and organic acids that form a salt of the compound of the formula (D) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-
1,5-disulfonic acid and the like can be mentioned. Among these, a salt of sulfuric acid or p-toluenesulfonic acid is preferable, and salt formation as a salt with sulfuric acid is most preferable. The color developing agent of the present invention is, for example, a journal of the
It can be easily synthesized according to the methods described in American Chemical Society 73, 3100 (1951), JP-A-7-287370, and Japanese Patent Application No. 8-112472.

The color developing agent of the present invention can be used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compounds to be combined are shown below, but are not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 4-amino-3-methyl-N, N-diethylaniline P-3 4-amino-3-methyl-N-ethyl-N-
(3-hydroxypropyl) aniline P-4 4-amino-N-ethyl-N- (2-hydroxyethyl) aniline P-5 4-amino-3-methyl-N-ethyl-N-
(2-hydroxyethyl) aniline P-6 4-amino-3-methyl-N-ethyl-N-
(2-methanesulfonamidoethyl) aniline P-7 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-8 N, N-dimethyl-p-phenylenediamine P-9 4- Amino-3-methyl-N-ethyl-N-
(2-Methoxyethyl) aniline P-10 4-amino-3-methyl-N-ethyl-N-
(4-hydroxybutyl) aniline P-11 4-amino-3-methyl-N-ethyl-N-
(2-butoxyethyl) aniline

Of the above-mentioned p-phenylenediamine derivatives as compounds to be combined, particularly preferred are P-3 and P-phenylenediamine derivatives.
5, P-6 or P-10. In addition, these p
-Phenylenediamine derivative and sulfate, hydrochloride, sulfite, p-toluenesulfonate, nitrate, naphthalene-
It is generally used in salts such as the 1,5-disulfonate. In the present invention, the treatment composition may be in a liquid state or a solid state (for example, a powdery state or a granular state). These compounds can be used in combination of two or more depending on the purpose. The amount of the aromatic primary amine developing agent to be used is preferably from 0.001 mol to 1 liter of the color developer.
0.2 mol, more preferably 0.005 mol to 0.1
Is a mole. The processing method of the color light-sensitive material of the present invention is described in JP-A-62-215272, page 7, upper right column, line 7 to 1
Line 0, 5th line in the upper right column (Showa 62
Includes amendments made to the Procedure Amendment on March 16, 2013. ), JP-A-2-33144, page 39, upper left column, line 4 to
The processing steps and additives described on page 42, upper left column, last line, and EPO355660A2, page 67, line 14 to page 69, line 28 can be preferably used. The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Normally
A temperature of 33 ° C to 38 ° C is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can improve the image quality and improve the stability of the processing solution. it can.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By processing the color negative film and the color paper using the same processing liquid, the cost of the processing machine can be reduced and the processing can be simplified.

Next, the scanning exposure will be described. In the present invention, a high illuminance light source such as a semiconductor laser or a gas laser is used. Also, a semiconductor laser is used to make the system more compact and inexpensive, or a second harmonic generation light source (a semiconductor laser or a combination of a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal) is used. It is preferred to use (SHG). Particularly, in order to design a device that is compact, inexpensive, has a long life, and has high stability, it is preferable to use a semiconductor laser.
It is preferable to use a semiconductor laser as at least one of the exposure light sources. The wavelength of the laser beam in the present invention can be set arbitrarily according to the spectral maximum of the photosensitive material. The exposure time per pixel in the present invention is 1
It is preferably 0 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.
It is preferably at least 10 ^-12 seconds.

When the above-described scanning exposure light source is used, the spectral sensitivity maximum of the photosensitive material of the present invention can be set by the wavelength of the scanning exposure light source used. It is particularly preferable that the spectral sensitivity maximum of the light-sensitive material of the present invention is in the visible region of blue, green, and red in view of handleability of the light-sensitive material and commonality with general light-sensitive materials. A solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser with a nonlinear optical crystal can halve the laser oscillation wavelength, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material is normal blue, green,
It is possible to have it in the three red areas. The maximum color density of the light-sensitive material of the present invention, which has been developed after being scanned and exposed by the laser beam, is not particularly limited, but is preferably 2.0 to 3.0, more preferably,
2.1 to 2.8.

The effective beam diameter can be obtained in exactly the same manner as described in the lower left column on page 4 of JP-A-5-19423. That is, one line segment is exposed to a photosensitive material using a laser beam having an output of 50% of the laser beam intensity sufficient to give the highest color density in the image to be formed, and the color development process is performed. To obtain a linear colored image. The density profile of this color image is measured in the vertical direction of the line using a microdensitometer. The line width of the density D1 / 5 corresponding to 1/5 of the maximum density Dmax of this profile is defined as the effective beam diameter. The effective beam diameter in the scanning exposure of the present invention is 200 μm or less, preferably 10 μm to 180 μm.
m, more preferably 20 μm to 150 μm. The shape of the laser beam in the scanning exposure is not particularly limited. The diameter of the laser beam is 1 / e ² (approximately 13.5
%) (Refer to FIG. 1). In the scanning exposure applied in the present invention, the diameter of the laser beam is not particularly limited as long as it satisfies the range of the effective beam diameter, but is 200 μm or less, preferably 10 μm to 15 μm.
0 μm, more preferably 20 μm to 100 μm.

The scanning pitch in the scanning exposure is defined by the interval of the raster (trajectory of the laser beam). When the laser beam is a circle, it is expressed by the interval of the center of the beam. In the present invention, the effective beam diameter is preferably larger than the image scanning pitch. Specifically, in the following formula, the overlap width between rasters has the relationship of the following formula. L: overlap width, d: effective beam diameter, p: scanning pitch L = d−p According to the above equation, the scanning pitch of the present invention is 0.25 μm to 1
90 μm is preferred, and 2 μm to 80 μm is most preferred. Further, the overlap width between rasters is not particularly limited in the present invention, but is in the range of 5% to 95% of the effective beam diameter, preferably 15% in order to prevent image unevenness and color skipping. ~ 85%, more preferably 20% ~ 80
% Range.

In the laser beam scanning, a photosensitive material is wound around a cylindrical drum, and the main scanning is performed by rotating the photosensitive material at a high speed, and the sub-scanning is performed by gradually moving the light source in the axial direction of the cylinder. The scanning can be performed by so-called drum scanning, but the main scanning is performed by irradiating a laser beam at a high-speed rotating polyhedral mirror surface (polygon mirror), and the sub-scanning is performed by moving the photosensitive material in a direction perpendicular to the main scanning. Is more preferable. The number of surfaces of the polygon mirror is not particularly limited, but is preferably 2 to 36, and particularly preferably 6 to 14. 4000 to 36000 rpm for stable rotation of polygon mirror
Is preferable. By multiplying the number of rotations by the number of mirror surfaces, the number of scanning lines per time can be calculated.

In the present invention, the silver halide emulsion used in the photosensitive emulsion layer is substantially free of silver iodide and has a silver chloride content of 95 mol% or more, which is suitable for rapid processing. Silver halides are preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2% or less. In the present invention, the silver chloride content of the high silver chloride emulsion is 9
8 mol% or more (including 100 mol%) is preferable. Also preferably, it is less than 100 mol%.

In the silver halide grains of the present invention, the periodic table
Group VIII metals, namely osmium, iridium, rhodium
, Platinum, ruthenium, palladium, cobalt, nickel
Metal ions selected from iron and its complex ions
They can be used alone or in combination. And this
These metals may be used in plural types. Use of Group VIII metals
The amount was 1 × 10^-9~ 1 × 10^-2Mo
Preferably 1 × 10 ^-7~ 1 × 10^-3Mole is more preferred
New These metal ions will be described in more detail.
However, the present invention is not limited to these.

The iridium ion-containing compound is a trivalent or tetravalent salt or complex salt, of which a complex salt is preferable.
For example, iridium (III) chloride, iridium (III) bromide, iridium (IV) chloride, sodium hexachloroiridate (III), potassium hexachloroiridate (IV), hexaammineiridium (IV)
Salts, trioxalatoiridium (III) salts, trioxalatoiridium (IV) salts, and the like, and complex salts having halogens, amines, or oxalic acid as a ligand are preferable. The platinum ion-containing compound is a divalent or tetravalent salt or complex salt, of which a complex salt is preferable. For example, chloroplatinic (IV) acid, potassium hexachloroplatinum (IV), potassium tetrachloroplatinum (II), sodium tetrabromoplatinum (II), tetrakis (thiocyanato) platinum (IV), hexaammineplatinum (IV) ) Chloride or the like is used.

The palladium ion-containing compound is usually a divalent or tetravalent salt or complex salt, and a complex salt is particularly preferred. For example, sodium tetrachloropalladium (II), sodium tetrachloropalladium (IV), potassium hexachloropalladium (IV), tetraamminepalladium (II) chloride, tetracyanopalladium (II)
Potassium acid or the like is used. As the nickel ion-containing compound, for example, nickel chloride, nickel bromide, potassium tetrachloronickel (II), hexaamminenickel (II) chloride, sodium tetracyanonickelate (II) and the like are used.

The rhodium ion-containing compound is usually preferably a trivalent salt or complex salt. For example, potassium hexachlororhodate, sodium hexabromorhodate, ammonium hexachlororhodate and the like are used. The iron ion-containing compound is a divalent or trivalent iron ion-containing compound, and is preferably an iron salt or an iron complex salt having water solubility in the concentration range used. Particularly preferred is an iron complex salt which can be easily contained in silver halide grains. For example, ferrous chloride,
Ferric chloride, ferrous hydroxide, ferric hydroxide, ferrous thiocyanate, ferric thiocyanate, iron hexacyano (II)
There are complex salts, hexacyanoiron (III) complex salts, ferrous thiocyanate complex salts and ferric thiocyanate complex salts. Further, a six-coordinate metal complex having at least four cyan ligands as described in European Patent EP 0,336,426A is also preferably used.

The above-mentioned metal ion-providing compound is added to an aqueous gelatin solution, an aqueous halide solution, an aqueous silver salt solution, or another aqueous solution which serves as a dispersion medium at the time of forming silver halide grains. The silver halide grains of the present invention can be contained in the silver halide grains of the present invention by, for example, adding to the silver halide emulsion in the form of the contained silver halide fine grains and dissolving the fine grains. Also,
The metal ions can be contained in the particles before, during, or immediately after the formation of the particles. Can be changed.

In the silver halide grains of the present invention, 50 mol% or more (preferably 70 mol% or more, more preferably 90 mol% or more, even more preferably 100 mol%) of the metal ion providing compound used is halogen. It is preferably localized in the surface layer or surface phase up to 45% or less of the grain volume from the silver halide grain surface. The volume of this surface layer or surface phase is preferably at most 30%, more preferably at most 20%. When the surface layer or surface phase in which the metal ions are localized has a volume as small as possible, it is advantageous for suppressing an increase in internal sensitivity and obtaining high sensitivity. In order to concentrate the metal ion-providing compound in the surface layer or the surface phase of such silver halide grains, for example, after forming the silver halide grains (core) in a portion excluding the surface layer or the surface phase, the surface layer is formed. Alternatively, it can be carried out by supplying a metal ion providing compound in accordance with the addition of a water-soluble silver salt solution and a halide aqueous solution for forming a surface phase.

The silver halide grains of the present invention are preferably provided with a silver bromide-rich phase. The silver bromide-rich phase of the silver halide grains of the present invention has a silver bromide-rich phase near the top of the grains. It is preferable to form at least 10 mol% or more of a localized phase by epitaxial growth with respect to the total silver bromide content therein. In the present invention, the term “near the vertex” preferably refers to a projected cube or a salt (odor) of a normal crystal similar to a cube.
The length of one side of the diameter of a circle having the same area as the area of the silver halide particle, more preferably 1/5, is defined as one side, and the vertex of the particle (intersection of the cubic or the ridge of the normal crystal grain regarded as a cubic)
Is an area of a square having one corner as a corner. The total content of silver bromide in the silver bromide rich phase is preferably at least 10 mol%, but if the silver bromide content is too high, desensitization may occur when pressure is applied to the light-sensitive material, Variations in the composition of the processing solution may impart undesired characteristics to the photographic material, such as a significant change in sensitivity and gradation. Taking these points into consideration, the silver bromide content of the silver bromide-rich phase is preferably in the range of 10 to 60 mol%, most preferably in the range of 20 to 50 mol%. The silver bromide content of the silver bromide-rich phase can be analyzed using an X-ray diffraction method (for example, described in “New Experimental Chemical Account 6, Structural Analysis”, edited by The Chemical Society of Japan). . The silver bromide-rich phase is preferably composed of silver in an amount of 0.1 to 5 mol% of the total silver constituting the silver halide grains of the present invention, and composed of 0.3 to 4 mol% of silver. More preferably, it is performed.

As is generally well known, the step of preparing a silver halide emulsion in the present invention is a step of forming a silver halide grain by reacting a water-soluble silver salt with a water-soluble halide, a desalting step and a chemical ripening step. Consisting of The application of the silver bromide-rich phase in the present invention is preferably prior to the chemical ripening step, more preferably prior to the desalting step, particularly after the formation of the silver halide host grains. It is preferable to be performed. During silver bromide-rich phase preferably contains a Group VIII metal complex ion IrCl ₆ ^2-like. When an iridium compound is contained in the silver bromide rich phase of the silver halide emulsion grains, the rich phase is preferably deposited together with at least 50 mol% of the total iridium added during the preparation of the silver halide grains. More preferably, the rich phase is deposited with at least 80 mol% of the total iridium added, most preferably with the total iridium added. Here, to deposit the rich phase together with iridium means to supply the iridium compound simultaneously with, just before, or immediately after the supply of silver or halogen for forming the rich phase. When a silver bromide-rich phase is formed by mixing silver halide fine grains having a smaller average grain size than the silver halide host grains and having a high silver bromide content and then ripening, the silver bromide content It is preferred that the iridium salt is previously contained in the silver halide fine grains having a high content.

The silver halide grains used in the present invention may have (100) planes, (111) planes, or both on the outer surface. Or a higher order plane may be included, but a cube mainly composed of a (100) plane,
Alternatively, a tetrahedron is preferred. The size of the silver halide grains of the present invention may be within the range usually used,
It is preferable that the average particle size is 0.1 μm to 1.5 μm. The particle size distribution may be polydisperse or monodisperse, but is preferably monodisperse. The particle size variation coefficient representing the degree of monodispersion is preferably 0.2 or less, more preferably 0.15 or less, in the ratio (s / d) of the standard deviation (s) and the average particle size (d) in statistics. preferable. It is also preferable to use a mixture of two or more monodisperse emulsions.

The shape of the silver halide grains may be cubic or 14
Regular like octahedron besides face
Those having a crystal form, those having an irregular crystal form such as a sphere, a plate, or the like, or those having a composite form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, the particles having the regular crystal form are contained in an amount of 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more. In addition to the grains having a regular crystal form, tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, have a projected area of 50% by weight or more of all grains. Emulsions can also be preferably used. The silver chlorobromide emulsion used in the present invention is P.Gl
afkides, Chimie et Phisique Photographique (Paul
Montel, 1967), Photographic by GFDuffin
Emulsion Chemistry (Focal Press, 1966), V.
Making and Coating Photographi by L. Zelikman et al
c It can be prepared using the method described in Emulsion (Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof. May be used. Method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion used in the present invention is
Emulsion grain formation or physical ripening other than Group VIII metal
Introduce various polyvalent metal ion impurities during the formation process
Can be Examples of compounds used include cadmium
Salts or complex salts of um, zinc, lead, copper, thallium, etc.
They can be used in combination. Addition amount of these compounds
Varies widely depending on the purpose, but 1 mole of silver halide
10 for^-9-10 ^-2Molar is preferred. Used in the present invention
Silver halide emulsions are usually chemically and spectrally sensitized.
Is given. For chemical sensitization, unstable sulfur compounds
Precious metals such as sulfur sensitization and gold sensitization represented by the addition of
Use genus sensitization or reduction sensitization alone or in combination
Can be. About compounds used for chemical sensitization
The lower right of page 18 of JP-A-62-215272
Column to those described in the upper right column of page 22 are preferably used.
You.

The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. This is because by performing the gold sensitization, fluctuations in photographic performance when scanning exposure is performed with a laser beam can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates or gold thiosulfates can be used. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 ×, per mol of silver halide.
It is 10 ^-6 to 1 × 10 ^-4 mol. These compounds are added until the chemical sensitization used in the present invention is completed. In the present invention, it is also preferable to combine gold sensitization with other sensitization methods, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound.

In the photographic material according to the present invention, the hydrophilic colloid layer can be decolorized by photographic processing described in EP 0,337,490 A2, pp. 27-76, for the purpose of improving the sharpness of the image. It is preferable to add a dye (especially an oxonol dye) so that the optical reflection density at 680 nm of the photosensitive material is 0.50 or more. In the present invention, instead of the water-soluble dye or in combination with the water-soluble dye, a colored layer that can be decolorized by treatment is used. The colored layer that can be decolorized by the treatment may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below the emulsion layer (on the side of the support) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. Further, it is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. Regarding the optical reflection density of the colored layer, it is preferable that the optical density value at the wavelength having the highest optical density also in the wavelength of the light source color used for scanning exposure is 0.2 or more and 3.0 or less. More preferably, 0.5 or more and 2.5 or less, especially 0.8 or more and 2.0 or less
The following is preferred.

As the silver halide photographic light-sensitive material used in the present invention, other conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. As the transmission type support, a transparent film such as a cellulose nitrate film or polyethylene terephthalate,
-A material in which an information recording layer such as a magnetic layer is provided on a polyester of naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable. Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the optical brightener, preferably a benzoxazole-based,
Coumarin-based and pyrazoline-based fluorescent whitening agents can be used, and benzoxazolylnaphthalene-based and benzooxazolylstilbene-based fluorescent whitening agents are more preferred. The amount used is not particularly limited, but is preferably 1 to 100 mg /
m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight with respect to the resin,
More preferably, the content is 0.001 to 0.5% by weight.

The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface. The above-mentioned reflective support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer or antifoggant of silver halide emulsion, chemical sensitization method (sensitizer) , Spectral sensitization (spectral sensitizer), cyan, magenta,
Table 1 shows yellow couplers and their emulsifying dispersion methods, color image preservability improvers (anti-stain agents and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive materials, coating pH of photosensitive materials, and the like. Patents 2 to 2 can be preferably applied to the present invention.

[0082]

[Table 1]

[0083]

[Table 2]

Examples of cyan, magenta and yellow couplers usable in the present invention include those described in JP-A-62-21.
No. 5272, page 91, upper right column, line 4 to page 121, upper left column 6
Line 3, page 14 upper right column, line 14 to page 18, upper left column last line and page 30, upper right column, line 6 to page 35 lower right column, line 11 of JP-A-2-33144, EP 0355,660A2. Page 4, lines 15 to 27, page 30, line 30 to end of page 28, 4
Page 5, lines 29 to 31, page 47, lines 23 to 63, page 50
The couplers described in the line are also useful. As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.

For processing the light-sensitive material according to the present invention, the method described in JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9; The processing materials and processing methods described on page 17, upper left column, line 17 to page 18, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used. Further, in the image forming method of the present invention, an apparatus for performing exposure and processing from reading of image information is disclosed in
No. 8, pages 5 to 12 and FIGS. 1 and 2 are preferably used. In particular, it is preferable to use an acousto-optic element which is well known in the art for modulating the intensity of a light beam in an image recording unit and which is easily available.

[0086]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 Preparation of Emulsion A solution I was prepared by adding 5.0 g of sodium chloride to 1000 ml of a 4% aqueous solution of lime-processed gelatin, and adding 2.8 ml of N, N-dimethylimidazolidin-2-thione (1% aqueous solution). . An aqueous solution containing 0.06 mol of silver nitrate (solution II) and an aqueous solution containing 0.06 mol of sodium chloride (solution III) were added to this solution I at 53 ° C. with vigorous stirring.
Mixed. Subsequently, an aqueous solution containing 1.07 mol of silver nitrate (solution IV) and an aqueous solution containing 1.07 mol of sodium chloride (solution V) were added and mixed at 58 ° C. with vigorous stirring. Further, an aqueous solution containing 0.29 mol of silver nitrate (solution VI)
And aqueous solution containing sodium chloride 0.29 mol (Solution VII)
Was added and mixed at 53 ° C. with vigorous stirring. Further, potassium ferrocyanide was allowed to coexist in the solution VII, and was contained in the emulsion grains at a concentration of 7.0 × 10 ^-6 mol per mol of silver halide. After keeping the temperature at 53 ° C. for 20 minutes, the temperature was lowered, desalted and washed with water. Further, 130 g of lime-processed gelatin was added, pH and pAg were adjusted, silver bromide fine particles (0.06 μm) were added to form a silver bromide localized phase on the surface of the emulsion grains, and triethylthiourea was added. And blue sensitizing dyes A, B, and C in an amount of 2.6 × 10 ^-4 mol per mol of silver halide.
3 × 10 ⁻⁴ mol and 1.9 × 10 ⁻⁴ mol were added to perform spectral sensitization. Potassium hexachloroiridate (IV) was added to the silver bromide localized layer in an amount of 2.0 × per mole of silver halide.
10 ^-7 mol was contained. The resulting blue-sensitive silver chlorobromide emulsion was designated as B-1.

[0087]

Embedded image

For the blue-sensitive emulsion B-1, the grain size was changed by changing the temperature at the time of grain formation, the amount of metal ions in the solution VII and the silver bromide localized phase was changed. Blue-sensitive emulsion B-2 was prepared by changing the amount of the blue-sensitive sensitizing dye to be the same. For the blue-sensitive emulsion B-1, the grain size is changed by changing the temperature during grain formation, the amount of metal ions in the solution VII and the silver bromide localized phase is changed, and the blue-sensitive sensitizing dye is further changed. Is added, instead of the green photosensitive sensitizing dyes D, E, and F or the red photosensitive sensitizing dye G, thereby obtaining a green photosensitive emulsion G-1,
G-2 and blue-sensitive emulsions R-1 and R-2 were prepared.
R-1 and R-2 each contained 6.0 × 10 ^-4 mol of Compound H per mol of silver halide.

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

Table 3 shows the halogen composition, size, metal ion content and the like of these emulsions.

[0093]

[Table 3]

Preparation of Sample (101) After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied. . The polyethylene laminated layer on the side of Coating photographic constituent layers was contained K-1 and K-2 one by each ^{3mg / m 2, 12mg / m} 2.

[0095]

Embedded image

A photographic constituent layer shown below was applied to prepare a multilayer silver halide color light-sensitive material: Sample (101). Preparation of coating solution for first layer 100.0 g of yellow coupler (ExY), 13.1 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-2)
6.6 g, color image stabilizer (Cpd-3) color image stabilizer
1 g was dissolved in 32.8 g of a solvent (Solv-1) and 50 g of ethyl acetate, and this solution was emulsified and dispersed in 600 ml of a 20% aqueous gelatin solution containing 7.0 g of sodium dodecylbenzenesulfonate to prepare an emulsified dispersion Y. . The emulsified dispersion Y and the blue-sensitive emulsions B-1 and B-2 were mixed and dissolved to prepare a first layer coating solution having the following composition.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-12 and Cpd-
Total amount 13 respectively 25.0 mg / m ^2, was added to a 50.0 mg / m ^2. (Layer Structure) The layer structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [K-1 was added to polyethylene on the first layer side at 3 mg / m ² , K-2
Contains 12 mg / m ² , a white pigment (TiO ₂ : content 18% by weight) and a bluish dye (ultramarine).] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion B-1 0.14 Silver chlorobromide Emulsion B-2 0.14 Gelatin 1.43 Yellow coupler (ExY) 0.61 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.20 Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.10 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.20 Solvent (Solv-3) 0.15 Solvent (Solv-7) 0.12 Third layer (Green-sensitive emulsion layer) Silver chlorobromide emulsion G-1 0.07 Silver chlorobromide emulsion G-2 0.07 Gelatin 1.35 Magenta coupler (ExM) 0.13 Ultraviolet absorber (UV-1) 0.13 Color image stabilizer (Cpd-2) 0.01 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-6) 0.01 Color Image Stabilizer (Cpd-7) 0.09 Color Image Stabilizer (Cpd-8) 0.01 Dye (Cpd-16) 0.0001 solvent (Solv-4) 0.33 solvent (Solv-5) 0.16

Fourth layer (color mixture preventing layer) Gelatin 0.72 Color mixture inhibitor (Cpd-4) 0.07 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.12 Solvent (Solv-7) 0.09 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion R-1 0.10 Silver chlorobromide emulsion R-2 0.10 Gelatin 0.80 Cyan coupler (ExC) 0.28 Ultraviolet absorber (UV-3) 0.20 Color image stabilizer (Cpd) -1) 0.24 color image stabilizer (Cpd-6) 0.01 color image stabilizer (Cpd-8) 0.01 color image stabilizer (Cpd-9) 0.04 color image stabilizer (Cpd-10) 0.01 solvent (Solv-1) 0.01 Solvent (Solv-6) 0.25 Sixth layer (UV absorption layer) Gelatin 0.64 UV absorber (UV-2) 0.39 Color image stabilizer (Cpd-7) 0.05 Solvent (Solv-8) 0.05 Seventh layer (protection layer) ) Gelatin 1.01 Polyvinyl alcohol acrylic Modified copolymer (degree of modification
17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-11) 0.01 The compounds used in this example are shown below.

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

A blue-sensitive emulsion layer, a green-sensitive emulsion layer,
1- (5-methylureidophenylene)
) -5-mercaptotetrazole with halogen
8.0 × 10 per mol of silver halide^-FourMol, 3.5 × 10^-3Mo
, 2.5 × 10^-FourMole was added. And a blue-sensitive emulsion layer
With respect to the green-sensitive emulsion layer, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene is halogenated
1 × 10 per mole of silver halide ^-FourMol, 5 × 10^-FiveMoles
Added.

The following compound was added to the sixth layer as a water-soluble dye for preventing irradiation.

[0111]

Embedded image

The following exposure and processing were performed on the sample (101). The exposure part of the scanning exposure apparatus will be described in detail below. As a light source, a semiconductor laser GaAl
YA using As (transmission wavelength: 808.5 nm) as an excitation light source
473 nm semiconductor laser GaAlA obtained by converting the wavelength of a G solid-state laser (transmission wavelength: 946 nm) with a LiNbO ₃ SHG crystal having an inversion domain structure
s (oscillation wavelength: 808.7 nm) as excitation light source YVO
532 nm obtained by converting the wavelength of a ₄ solid-state laser (transmission wavelength: 1064 nm) using an SHG crystal of LiNbO ₃ having an inversion domain structure, and AlGaInP
(Sending wavelength: 680 nm: Matsushita Densan type No. LN9R
20) was used as B light, G light and R light, respectively. Laser light of each wavelength was modulated using an external modulator to modulate the amount of light, and reflected by a rotating polyhedron, thereby sequentially scanning and exposing the coated sample moving perpendicularly to the scanning direction. The scanning exposure was performed at 300 dpi, and the average exposure time per pixel was 8 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress a change in light quantity due to temperature. Sample at the time of exposure (10
Setting the ambient temperature of 1) to 15 ° C. and 35 ° C. respectively,
After leaving it unexposed for 30 minutes, the light amount of B, G or R light was modulated to perform scanning exposure, and the following processing was further performed.

Processing Step Temperature Time Replenisher * Tank capacity (liter) Color development 38.5 ° C 45 seconds 120ml 17 Bleaching and fixing 30-35 ° C 45 seconds 180ml 17 Rinse (1) 30-35 ° C 20 seconds -10 Rinse (2) 30 to 35 ° C. 20 seconds - 10 rinse (3) 30 to 35 ° C. 20 seconds 200 ml 10 drying 70 to 80 ° C. 60 seconds * the replenishing amount is 3 tank countercurrent to per photosensitive material 1 m ² (rinse (3) → (1) Flow method)

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Sodium triisopropylene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 2.5g 3.0g 1,2-Dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5g 0.5g Triethanolamine 8.0 g 11.0 g Potassium chloride 4.5 g-Potassium bromide 0.02 g-Potassium carbonate 27.0 g 27.0 g Fluorescent brightener (WHITEX 4, manufactured by Sumitomo Chemical) 0.2 g 0.6 g Sodium sulfite 0.1 g 0.1 g Disodium-N , N-bis (sulfonatoethyl) hydroxylamine 8.5 g 11.0 g D- (I) 5.5 g 11.0 g

[0115]

Embedded image

Add water to 1000ml 1000ml pH (25 ° C) 10.0 11.0

Bleach-fix solution (same as tank solution and replenisher) Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 30 g Iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Nitric acid (67 30g Add water to 100ml pH (25 ° C) (with acetic acid and ammonium water) 5.8 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3ppm or less for calcium and magnesium each)

By measuring the color density of the processed sample, sensitometry corresponding to the yellow, cyan and magenta color layers was obtained. In the sensitometry obtained by exposing at 15 ° C., the fogging and the exposure dose and the density giving 1.5 higher density from the fogging were read, and in the sensitometry obtained by exposing at 35 ° C. I read. At 15 ℃ calculated in this way the concentration (D ₁₅ ℃) at 35 ° C. versus concentration (D ₃₅ ° C.) the difference (D ₃₅ ℃ -D ₁₅ ℃) the stability of the color density due to temperature at the time of exposure of the The index was used. The smaller this value is, the smaller the variation in color density is, and the more stable it is. Further, instead of the above scanning exposure, using a sensitometer (FWH type, manufactured by Fuji Film Co., Ltd., color temperature of light source 3200K) through a blue filter, a green filter or a red filter, an exposure amount of 250 CMS and an exposure time of 1 After giving the sensitometric gradation exposure (surface exposure) in seconds, the same processing is performed, and the color density is measured to obtain the sensitometry corresponding to the magenta, cyan, and yellow coloring layers. (D ₃₅ ° C.−D ₁₅ ° C.). The above is Experiment No. 1. Further, D- (I) was changed to D-18, D-25, D- (I) without changing the amount of the color developing agent D- (I) in the processing solution used in Experiment No. 1 or the molar amount contained therein.
D-28, D-30, D-35, D-36, D-38,
D-39, D-40, D-44, D-48, D-69,
D-77, D-78, D-79, D-93 or D-
Experiment Nos. 2 to 20 were carried out in the same manner except that the number was changed to 107. Table 4 shows the results.

[0119]

[Table 4]

As can be seen from Experiment Nos. 1 to 3 in Table 4,
When the color developing agent D- (I) outside the present invention was used, the fluctuation of the color density due to the temperature at the time of laser scanning exposure was larger than the exposure for 1 second, and this fluctuation was caused by increasing the amount of D- (I). Is small, but at the same time the fogging is significantly increased. On the other hand, from Experiments Nos. 4 to 20, it is clear that when the color developing agent of the present invention is used, it is possible to reduce the variation in color density due to the temperature during laser scanning exposure while reducing the fogging.

Example 2 Each emulsion of Sample (101) was optimally prepared by changing the sulfur sensitizer (triethylthiourea) to a gold sensitizer (chloroauric acid) and a sulfur sensitizer (triethylthiourea). A sample (201) was prepared in place of the sulfur-sensitized emulsion. Sample (20
The same effect as in Example 1 was obtained for 1).

[0122]

According to the method of the present invention, the problem which seems to be peculiar to the method of scanning exposure by laser light can be solved. That is, a color image having excellent character quality and little variation in color density could be obtained even by rapid development processing.

[Brief description of the drawings]

FIG. 1 shows the intensity distribution in a cross section perpendicular to the axis of the light beam.
The horizontal axis represents the light beam diameter, and the vertical axis represents the light beam intensity.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03C 7/00 520 G03C 7/00 520

Claims (1)

[Claims] 1. An image forming method in which a silver halide photographic light-sensitive material is scanned and exposed by a laser beam and then subjected to color development processing, wherein the silver halide light-sensitive material is provided on a support with a yellow coupler-containing silver halide emulsion layer, It has at least one silver halide emulsion layer containing a magenta coupler and at least one silver halide emulsion layer containing a cyan coupler, and at least one of the silver halide emulsion layers contains a silver halide emulsion having a silver chloride content of 95 mol% or more. An image forming method, comprising a silver halide color photographic light-sensitive material, wherein the color development processing is performed with a color developer containing at least one tetrahydroquinoline-based color developing agent represented by the following general formula (D). Method. Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different and each represents a hydrogen atom or a substituent; provided that R ₁ , R ₂ , R ₃ and In the group consisting of each combination of R ₄ , R ₅ and R ₆ , at least one of them is a substituent, R ₇ represents an alkyl group, an aryl group or a heterocyclic group, and R ₈ represents a substituent .M represents an integer of 0 to 3.)