JPH07175154A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photosensitive maternal high in sensitivity and contrast even in the case of using a developing solution of pH <=11.2, and small in black spots, and provide its development method. CONSTITUTION:The photosensitive material has at least one kind emulsion comprising silver halide grains containing >=60 mol% silver chloride and a surfactant made of a polyalkyleneoxide block copolymer having at least 2 or more terminal hydrophilic alkylene oxide block units combined through lipophilic alkylene oxide block units having a 4-96 % fraction of the total molecular weight. It is preferred that this emulsion contains a hydrazine derivative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high contrast and less black spot defects.

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this step, a technique by infectious development has been used as a method for reproducing an ultrahigh contrast image. Examples of the lith type silver halide photographic light-sensitive material used for infectious development include those having an average particle size of about 0.2 μm or less, a narrow particle distribution and a well-shaped silver chloride content of at least 50 mol% or more. Silver halide emulsions are commonly used.

Such a lith-type silver halide photographic light-sensitive material can be processed with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type infectious developer to obtain an image with high contrast and high resolution.

However, these lith-type developers have a drawback that they are easily oxidized by air and have extremely poor preservability, so that it is difficult to maintain a constant quality when they are continuously developed. Therefore, as a method for obtaining a high-contrast image rapidly without using such a developing solution, for example, a silver halide photographic light-sensitive material containing a hydrazine derivative as described in JP-A-56-106244 is used. A method of processing with a developer is disclosed. According to the method,
The preservative property of the developer is good, rapid processing is possible, and an ultrahigh contrast image can be easily obtained. However, in this method, in order to exert the high contrast of the hydrazine derivative sufficiently,
Had to be processed with a developer solution having a value of 11.2 or higher.

In a strongly alkaline developing solution having a pH of 11.2 or more, when the developing solution comes in contact with air, the developing agent is significantly oxidized. Although more stable than the lith developer described above, there are many cases in which a super-high contrast image cannot often be obtained due to the oxidation of the developing agent.

[0006] In order to make up for such drawbacks, JP-A-63-29751
No. 1, JP-A-1-179939, the same 1-179940, U.S. Pat.
No. 354 discloses a silver halide photographic light-sensitive material containing a hydrazine derivative capable of increasing the tone even with a developer having a relatively low pH of less than 11.2 and accelerating nucleation.

However, the silver halide photographic light-sensitive material using such a high contrast technique is not excellent in storability over time,
There is a problem that sensitivity fluctuations and softening occur during the raw storability of the film, and further there is a problem that so-called black spots frequently occur in sandy fog-like defects that occur in the unexposed area. Such a phenomenon has a problem that the treatment liquid is replenished with a low replenishment rate and is remarkable when the treatment is performed extremely rapidly.

[0008]

In contrast to the above problems, the object of the present invention is to provide a silver halide light-sensitive material which has high sensitivity and high contrast even with a developing solution having a pH of less than 11.2 and has few black spots. To do.

[0009]

The above-mentioned object of the present invention is to provide a silver halide in which at least one silver halide emulsion is composed of silver halide grains containing 60 mol% or more of silver chloride on a support. In a photographic light-sensitive material, a polyalkylene having at least two or more terminal hydrophilic alkylene oxide block units, which are respectively linked via a lipophilic alkylene oxide block unit accounting for 4 to 96% of the molecular weight in the silver halide grain. A silver halide photographic light-sensitive material characterized by containing an oxide block copolymer surfactant, or a silver halide grain having a molecular weight of 4 to 96.
A silver halide photographic light-sensitive material characterized in that it comprises at least two or more terminal lipophilic alkylene oxide block units, each of which is linked via a hydrophilic alkylene oxide block unit occupying in%.

In a preferred embodiment of the present invention, the above photosensitive silver halide emulsion contains a hydrazine derivative.

The present invention will be specifically described below.

As the hydrazine derivative used in the present invention, a compound represented by the following general formula [H] is used.

[0013]

[Chemical 1]

The general formula [H] will be described in detail below.

In the formula, the aliphatic group represented by A is preferably one having 1 to 30 carbon atoms, and particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group,
Examples thereof include a benzyl group and the like, which further include suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfoxy group,
Sulfonamide group, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [H] is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A in the general formula [H] is preferably a monocyclic or condensed ring heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, for example, a pyrrolidine ring, Examples thereof include an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring.

Particularly preferred as A is an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents are an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms, substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
Group), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxyl group, a phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

Further, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group has 8 carbon atoms.
Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group, an alkylphenoxy group and the like, which are relatively inert to the above photographic properties.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B is specifically an acyl group (eg formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc.), alkylsulfonyl groups (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (eg methanesulfinyl etc.), an arylsulfinyl group (benzenesulfinyl etc.), a carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), an alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.), an aryloxycarbonyl Groups (eg phenoxycarbonyl etc.), sulfamoyl groups (eg dimethylsulfamoyl etc.), sulfinamoyl groups (eg methylsulfur) Finamoyl etc.), an alkoxysulfonyl group (eg methoxysulfonyl etc.), a thioacyl group (eg methylthiocarbonyl etc.), a thiocarbamoyl group (eg methylthiocarbamoyl etc.), an oxalyl group (the general formula [Ha] will be described later) or a heterocyclic group. (Eg, pyridine ring, pyridinium ring, etc.).

B in the general formula [H] represents A ₂ and the nitrogen atom to which they are attached.

[0024]

[Chemical 2]

May be formed.

R ₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.)

Among the hydrazine compounds used in the present invention, particularly preferred are compounds represented by the following general formula [Ha].

[0030]

[Chemical 3]

In the formula, R ₄ represents an aryl group or a heterocyclic group, and R ₅ represents

[0032]

[Chemical 4]

Represents

R ₆ and R ₇ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Alternatively, it represents a heterocyclic oxy group, and R ₆ and R ₇ may form a ring together with an N atom. R ₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. A ₁ and A ₂ represent the same meanings groups as A ₁ and A ₂ in formula (H).

The general formula [Ha] will be described in more detail.

The aryl group represented by R ₄ is preferably a monocyclic ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₄ is preferably a 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, which is a monocyclic ring or a condensed ring. Examples thereof include a ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

Preferred as R ₄ is a substituted or unsubstituted aryl group. Examples of the substituent include those having the same meaning as the substituent of A in the general formula [H].
When the contrast is increased with a developing solution of 1.2 or less, it is preferable to have at least one sulfamide group.

[0039] A ₁ and A _2, A ₁ and A ₂ of the formula H
And a hydrogen atom are the most preferable.

R ₅ is

[0041]

[Chemical 5]

Wherein R ₆ and R ₇ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.),
Alkenyl groups (allyl, butenyl, etc.), alkynyl groups (propargyl, butynyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl) Nyl, quinolidinyl, N, N'-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy , Ethoxy, etc.), alkenyloxy group (allyloxy etc.), alkynyloxy group (propargyloxy etc.), aryloxy group (phenoxy etc.), or heterocyclic oxy group (pyridyloxy etc.), and R ₆ and R ₇ are nitrogen. A ring (piperidine, morpholine, etc.) may be formed together with the atom. R ₈ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.), a heterocycle Group (2,2,
6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl and the like).

Specific examples of the compounds represented by the general formulas [H] and [Ha] are shown below. However, the present invention is not limited to these.

[0044]

[Chemical 6]

[0045]

[Chemical 7]

[0046]

[Chemical 8]

[0047]

[Chemical 9]

[0048]

[Chemical 10]

Specific compounds other than the above are disclosed in
Compound examples H-1 to H-75 described in 4-98239, pages 604 (4) to 607 (7) are mentioned.

The synthetic method of the compound represented by the general formula [H] used in the present invention is described in JP-A Nos. 62-180361 and 62-178246.
No. 63-234245, No. 63-234246, No. 64-90439, JP-A No. 2-37, No. 2-841, No. 2-947, No. 2-120736, No.
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604, 4,994,365, European patent 253,665
No. 333,435, etc. can be referred to.

Next, as the nucleation accelerator, the following general formula [N
Examples thereof include those shown in a] or [Nb].

[0052]

[Chemical 11]

In the general formula [Na], R ₁ , R ₂ , R ₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, a substituted aryl group, an amino group or a substituted amino group. R ₁ ,
A ring can be formed by R ₂ and R ₃ . Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a molecular weight of 300 or more is more preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific compounds include those shown below.

[0055]

[Chemical 12]

[0056]

[Chemical 13]

Specific compounds other than the above are disclosed in JP-A-4-
No. 98239, Compound Examples I-1 to 17 described on page 608 (8),
Compound Examples III-1 described on pages 610 (10) to 626 (26)
-25, IV-1 to 41, V-I-1 to 27, V-II-1 to 30, V
-III-1 to 35, VI-1 to 44, VI-II-1 to 68, VI-III
-1 to 37 can be mentioned.

In the general formula [Nb], Ar represents a substituted or unsubstituted aryl group or a heteroaromatic ring. R represents an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have a preferable diffusion resistant group, the molecular weight is preferably 120 or more, particularly preferably 300 or more.

Specific compounds include those shown below.

[0060]

[Chemical 14]

[0061]

[Chemical 15]

The amount of the compound represented by the general formula [H] and the compound represented by the general formula [Na] or [Nb] used in the present invention is 5 × 10 ^{−7 to} 5 per mol of silver halide, respectively.
It is preferably ^{x10 -1} mol, especially 5 x 10 ^{-6 to} 5 x
It is preferably in the range of 10 ^-2 mol.

In the present invention, the hydrazine derivative and the nucleation accelerator are contained in the silver halide emulsion layer or other hydrophilic colloid layer.

Of the other hydrophilic colloid layers, any layer on the silver halide emulsion layer side is preferable, and a layer adjacent to the silver halide emulsion is more preferable.

The polyalkylene oxide block copolymer surfactant used in the present invention will be described.

Polyalkylene oxide block copolymer surfactants in general, and especially those intended for use in the practice of this invention, are well known and have been widely used for a variety of purposes. . They are generally recognized as falling within the broader category of nonionic surfactants. Molecules that function as surfactants must contain at least one hydrophilic unit and at least one lipophilic unit linked together. For a review of block copolymer surfactants, see IR Schmolka, "A Review of Block Polyme
r Surfactants, J. Am. Oil Chem. Soc., Vol.54, No.3,197
Pages 7,110-116, and AS Davidsohn and BM
ilwidsky, Synthetic Detergents, Johnwiley & Sons,
NY 1987, pages 29-40, especially pages 34-36.

The polyalkylene oxide block copolymer surfactants used in the practice of this invention are briefly illustrated schematically by the following diagram [A] or [B], in the case of [A]: It comprises at least two terminal hydrophilic alkylene oxide block units linked by lipophilic alkylene oxide block units. In the case of [B], it contains at least two terminal lipophilic alkylene oxide block units linked by hydrophilic alkylene oxide block units.

[0068]

[Chemical 16]

In the above formula, LAO represents a linking or terminal lipophilic alkylene oxide block unit in each designation, and HAO represents a linking or terminal hydrophilic alkylene oxide block unit.

In general, each of LAO and HAO contains a single alkylene oxide repeat unit selected to impart the desired hydrophilic or lipophilic character to the block units in which they are included. The hydrophilic-lipophilic balance (HLB) of commercially available surfactants is generally available and can be referred to in selecting a suitable surfactant. Typical HAO
Or LAO is 4 to 4 of the block copolymer based on the total weight.
It is chosen so that 96% is occupied by hydrophilic or lipophilic block units.

Of course, the above block diagram [A] shows at least two terminal hydrophilic block units linked by lipophilic block units, and the block diagram [B] shows at least two terminal parent blocks linked by hydrophilic block units. It is recognized that the polyalkylene oxide block copolymers, each having an oily block unit, are merely one example. In a usual modified structure in which a trivalent amino linking group is sandwiched between one or two polyalkylene oxide chains at the boundary between the LAO block unit and the HAO block unit, three or four terminal lipophilic groups are present. Can bring.

In these simplest possible forms, the polyalkylene oxide block copolymer surfactant is initially [A] with 1,2-propylene glycol.
It is formed by the condensation of 1,2-propylene oxide to form a repeating unit of an oligomer or polymer that acts as a lipophilic block unit, and then the reaction is stopped using ethylene oxide, Add ethylene oxide to each end.
In the case of [B], it is formed by condensation of ethylene glycol and ethylene oxide to form a repeating unit of an oligomer or polymer which acts as a hydrophilic block unit, and then the reaction is terminated with 1,2-propylene oxide. . Propylene oxide is added to each end of the ethylene oxide block unit.

At least 6 1,2-propylene oxide repeat units are required to form a lipophilic block repeat unit. The resulting polyalkylene oxide block copolymer surfactant is [A1] or [B1].

[0074]

[Chemical 17]

Where x is at least 13 and can range up to 490 or more, and y and y'are the lipophilicity required for the ethylene oxide block units to retain surface activity, respectively. It is chosen to maintain the required balance of hydrophilicity. This balance is achieved when x is chosen such that the lipophilic block units make up 4 to 96% by weight of the total block copolymer. Therefore, within the above range for x, y and y'are 1 (preferably 2).
Can range from 320 to 320 or more.

[0076]

[Chemical 18]

Where x and x'are each at least 6 and can range up to 120 or more, and y is the lipophilicity required for the ethylene oxide block units to retain surface activity. It is chosen to maintain the required balance of hydrophilicity. This balance is achieved when y is chosen such that the lipophilic block units make up 4 to 96% by weight of the total block copolymer. Within the above ranges for x and x ', y can range from 2 to 300 or more.

Commercial surfactant manufacturers consider cost in the overwhelming majority of products to provide the lipophilic and hydrophilic block units of nonionic block copolymer surfactants as 1,2. -Propylene oxide and ethylene oxide repeating units are chosen, but it is recognized that they can be replaced by other alkylene oxide repeating units, if desired, and provided so that the intended lipophilicity and hydrophilicity are retained. . For example, the 1,2-propylene oxide repeating unit is represented by the following formula [1].

[0079]

[Chemical 19]

[Wherein R may be represented by a lipophilic group such as a hydrocarbon, eg alkyl having 1 to 10 carbon atoms or aryl having 6 to 10 carbon atoms (eg phenyl or naphthyl). It is just one of the repeating units of the clan.

Similarly, the ethylene oxide repeating unit is represented by the following formula [2]. ]

[0082]

[Chemical 20]

[In the above formula, R ₁ is hydrogen or a hydrophilic group, for example, one or more polar substituents (for example, 1,
It is a hydrocarbon group of a type having two or three or more hydroxyl groups and / or carboxyl groups)] and is only one of the repeating units of the group shown in FIG.

The polyalkylene oxide block copolymer surfactant used in the practice of the present invention can be schematically represented by the following formula [A2] or [B2]. It comprises at least three terminal hydrophilic or lipophilic alkylene oxide block units linked via a lipophilic or hydrophilic alkylene oxide block unit.

[0085]

[Chemical 21]

In the above formula, HAO and LAO represent terminal or linked hydrophilic and lipophilic alkylene oxide block units in each indication, LOL represents a lipophilic alkylene oxide block linking unit, and HOL represents a hydrophilic alkylene oxide block. . z is 2 and z'is 1 or 2.

The polyalkylene oxide block copolymer surfactant used in the practice of the present invention is [A
3] and [B3] can also be adopted.

[0088]

[Chemical formula 22]

In the above formula, HAO represents a hydrophilic alkylene oxide block unit in each designation, LAO represents a lipophilic alkylene oxide block unit in each designation, L represents a linking group such as amine or diamine, and z
Is 2 and z'is 1 or 2.

The linking group L may have any valence. In general, it is preferable to select the linking group that is lipophilic in itself. If z + z 'is equal to 3, then
The linking group must be trivalent. When an amine is used to form the linking unit L, the polyalkylene oxide block copolymer surfactant used in the practice of the present invention may have a form represented by the formulas [A4] and [B4]. it can.

[0091]

[Chemical formula 23]

In the above formula, HAO and LAO are as defined above, and R ¹ , R ² and R ³ are independently a hydrocarbon linking group, preferably a phenylene group or an alkylene having 1 to 10 carbon atoms. Selected from the groups, and a, b and c are independently 0 or 1.

In order to avoid steric hindrance, a
And at least one of b and c (optimally at least two)
Is preferably 1. The hydroxyl-bearing amine (preferably secondary or tertiary amine) involved in the oxyalkylation reaction is a preferred starting material for forming a polyalkylene oxide block copolymer satisfying the formulas [A4] and [B4]. Is.

When z + z 'is equal to 4, the linking group must be tetravalent. Diamines are the preferred tetravalent linking groups. When the linking unit L is formed using a diamine, the polyalkylene oxide block copolymer used in the practice of the present invention has the formula [A5], [B5]
It is also possible to take the form shown in.

[0095]

[Chemical formula 24]

In the above formula, HAO and LAO are as defined above, and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently a hydrocarbon linking group, preferably a phenylene group or a carbon atom. Selected from 1 to 10 alkylene groups, and d, e,
f and g are independently 0 or 1.

Generally, in the case of the formula [A], it is preferable to select LAO so that the LOL lipophilic block unit occupies 4 to 96%, preferably 15 to 95% of the molecular weight of the copolymer. In the case of the formula [B], 4-76%, preferably 5
~ 85% so that HOL hydrophilic block units occupy (H
It is preferable to select AO).

In its simplest possible form, the polyalkylene oxide block copolymer surfactant forms ethylene oxide repeating units to form hydrophilic (HAO) block units and lipophilic (LAO) block units. 1,2-propylene oxide repeating unit for use.
At least 3 propylene oxide repeat units are required to form a lipophilic block repeat unit. When formed in this way, each H-HAO-LAO- group or H-LAO- satisfies the following formulas [A6] and [B6].

[0099]

[Chemical 25]

In the formula [A6], x is at least 3,
Up to 250 or more, and y is selected to maintain the balance of lipophilicity and hydrophilicity necessary for the ethylene oxide block units to retain surface activity. In the formula [B6], y is at least 61, preferably at least 62.
And up to 340 or more, x is a 1,2-propylene oxide block unit. This means that the combined hydrophilic block units are 4 to 4 parts by weight of the total copolymer.
Allows y to be chosen to account for 96 wt% (optimally 10-80 wt%). In this example, the lipophilic alkylene oxide block unit containing the 1,2-propylene oxide repeating unit and the linking moiety is 4 to 96 wt% of the total weight of the copolymer.
(Optimally 20 to 90% by weight). Within the above range,
In the formula [A6], x can range from 3 to 250 or more, and y can range from 1 (preferably 2) to 340 or more. If necessary, other alkylene oxide repeating units can be substituted. For example, the following formula [3]

[0101]

[Chemical formula 26]

Wherein R ₉ is a hydrocarbon, for example a lipophilic group such as alkyl having 1 to 10 carbon atoms or aryl having 6 to 10 carbon atoms such as phenyl or naphthyl. It is only one of a family of possible repeating units.
Similarly, the ethylene oxide repeating unit is represented by formula [4].

[0103]

[Chemical 27]

[In the above formula, R ₁₀ is hydrogen or a hydrophilic group, for example, R ₉ is further substituted with one or more polar groups (for example, 1,
It is a hydrocarbon group of a type having two, three or more hydroxyl groups and / or carboxyl groups)].

The overall molecular weight of the polyalkylene oxide block copolymer surfactant which meets the requirements of the present invention is
It has a molecular weight of more than 1,100, preferably at least 2,000. Generally, any such block copolymer that retains certain surfactant dispersion characteristics can be used. It was confirmed that these surfactants were sufficiently efficiently dissolved or physically dispersed in the reaction vessel. Dispersion of these polyalkylene oxide block copolymers is facilitated by the vigorous stirring commonly used during the preparation of tabular grain emulsions. Generally, a molecular weight of about 6
The use of less than 0,000, preferably less than about 40,000 surfactant is preferred.

The light-sensitive material of the present invention preferably has at least one conductive layer on the support. As a typical method for forming the conductive layer, a water-soluble conductive polymer,
There are a method of forming using a hydrophobic polymer and a curing agent and a method of forming using a metal oxide. For these methods, for example, the methods described in JP-A-3-265842, page (5) to page (15) can be used. In the silver halide emulsion used in the present invention, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride containing 50 mol% of silver chloride are preferably used as the silver halide. Is silver chlorobromide containing 60 mol% or more of silver chloride, silver bromide, or silver chloroiodobromide containing 4 mol% or less of silver iodide.

Moreover, (standard deviation of particle size) / (average value of particle size) × 1
Monodisperse particles having a coefficient of variation represented by 00 of 15% or less are preferable.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention. For example,
The silver halide photographic emulsion and backing layer used in the present invention include various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, and ultraviolet absorbers. , An anti-irradiation dye, a heavy metal, a matting agent and the like can be incorporated by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer of the present invention.

These additives are described in more detail in Research Disclosure (RD) Vol. 176 Item / 7643 (197
December 1988) and Vol. 187, Item / 8716 (November 1979).

[0110]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

(Preparation of Silver Halide Emulsion A) A silver chloroiodobromide emulsion (70 mol% of silver chloride and 0.2 mol% of silver iodide per mol of silver) was prepared by the simultaneous mixing method. K ₂ IrB during this mixing
the r ₆ was added per mole of silver 8.1 × 10 ^-8 mol. The obtained emulsion was an emulsion composed of cubic monodisperse grains (variation coefficient 9%) having an average grain size of 0.20 μm. Denatured gelatin of G-8 described in JP-A-2-280139 was added to desalt. The EAg at 50 ° C after desalting was 1.90 mv.

[0112]

[Chemical 28]

Subsequently, the temperature of the emulsion was adjusted to 60 ° C., and the pH was adjusted to
Was adjusted to 5.58 and EAg was adjusted to 12.3mv.

HAuCl ₄ was added in an amount of 2.2 × 10 ^-5 mol per mol of silver, stirred for 2 minutes, and then S was added in an amount of 2.9 × 10 ^-6 mol per mol of silver, and further stirred for 78 minutes to carry out chemical sensitization. It was After the chemical sensitization was completed, the following compounds were added, and then the temperature was lowered to 40 ° C. to complete the chemical sensitization.

[0115]

[Chemical 29]

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm, the backing surface of which has been subjected to the antistatic treatment described in Example 1 of JP-A-3-92175. In addition, a silver halide emulsion layer having the following formulation (1) had a gelatin content of 2.6 g / m ² and a silver content of 3.3 g / m ² .
by coating so as to be m ^2, and more following formulation (2) of the protective layer was coated so as the amount of gelatin is 1.0 g / m ^2, also the opposite side of the other subbing layer thereon A backing layer was coated according to the following prescription (3) so that the amount of gelatin would be 2.7 g / m ^2, and a protective layer of the following prescription (4) was applied on the backing layer so that the amount of gelatin was 1.0 g / m ² . Sample No. 1 to 18
Got

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.6 g / m ² Silver halide emulsion A Silver amount 3.3 g / m ²

[0118]

[Chemical 30]

[0119]

[Chemical 31]

Formulation (2) (Emulsion protective layer composition) Gelatin 1.0 g / m ² Matting agent: Silica having an average particle size of 3.5 μm 22 mg / m ² Hardener: 1,3-vinylsulfonyl-2-propanol 40 mg / m ²

[0121]

[Chemical 32]

Formulation (3) (Backing layer composition)

[0123]

[Chemical 33]

[0124] Gelatin 2.7 g / m ² Surfactant: Saponin 133 mg / m ² Surfactant: S-1 6.0mg / m ² Colloidal silica 100 mg / m ²

[0125]

[Chemical 34]

Formulation (4) [Composition of backing protective layer] Gelatin 1 g / m ² Matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5.0 μm 50 mg / m ² Hardener: Glyoxal 5 mg / m ²

[0127]

[Chemical 35]

The obtained sample was brought into close contact with a step wedge, exposed to 3200K tungsten light for 5 seconds in the case of ortho photography, and the rapid developing automatic developing machine GR-26SR (Konica) (Manufactured by Co., Ltd.) under the following conditions.

Developer Formulation (per liter) Sodium sulfite 55 g Potassium carbonate 40 g Hydroquinone 24 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (dimesone S) 0.9 g Potassium bromide 5.0 g 5-methylbenzo Triazole 0.13 g 1-Phenyl-5-mercaptotetrazole 0.02 g Boric acid 2.2 g Diethylene glycol 40 g Water and potassium hydroxide are added to make pH 10.5 and 1 liter.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g (Composition B) Pure water (ion Exchanged water) 17 ml Sulfuric acid (50% w / w aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% w / w aqueous solution) 26.5 g When using the fixer, the above composition A and composition in 500 ml of water are used. They were melted in the order of B and finished to 1 liter before use. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Current image 35 ° C 30 seconds Settling 33 ° C 20 seconds Water washing Room temperature 20 seconds Dry 40 ° C 40 seconds (silver halide photographic emulsion B Preparation of -b to Kk) The same procedure as in Emulsion A was performed except that 12% by weight of total silver of the following polyalkylene surfactants b to j was added to the reaction vessel before introducing the silver salt. -B, C-c, D-d, E-
e, F-f, G-g, H-h, I-i, J-j, K-k
Was prepared.

[0132]

[Chemical 36]

The following evaluations were performed using each of the above samples.

(Evaluation of black spots) The sample was observed with a magnifying glass of 100 times, and the one in which no black spots occurred was ranked as the highest rank "5", and the rank "4" was assigned according to the degree of occurrence of black spots. , “3”, “2”, “1” and the ranks were sequentially lowered and evaluated. It should be noted that the ranks "1" and "2" are levels that are not practically preferable. The obtained sample was measured with a Konica Digital Densitometer PDP-65,
The sensitivity at No. 1 density 3.0 is shown as relative sensitivity, and the gamma is displayed by the tangent of density 0.3 and 3.0.

The results of the above examples are shown in Tables 1 and 2.

[0136]

[Table 1]

[0137]

[Table 2]

As is clear from Tables 1 and 2, the sample 8 according to the present invention has a high sensitivity for comparison, has a high contrast, and has little black spots.

[0139]

According to the present invention, it is possible to provide a silver halide light-sensitive material which has high sensitivity and high contrast even with a developer having a pH of less than 11.2, and has less black spots, and a developing method thereof.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material in which at least one silver halide emulsion comprises silver halide grains containing 60 mol% or more of silver chloride on a support.
Polyalkylene oxide block copolymer having at least two or more terminal hydrophilic alkylene oxide block units, each of which is linked via a lipophilic alkylene oxide block unit accounting for 4 to 96% of the molecular weight in the silver halide grain. A silver halide photographic light-sensitive material containing a surfactant. 2. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion comprising silver halide grains containing 60 mol% or more of silver chloride on a support.
It is characterized in that it comprises at least two or more terminal lipophilic alkylene oxide block units connected to each other through a hydrophilic alkylene oxide block unit accounting for 4 to 96% of the molecular weight in the silver halide grain. Silver halide photographic light-sensitive material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein at least one layer of the light-sensitive silver halide emulsion on the support contains a hydrazine derivative.