WO2004010218A1

WO2004010218A1 - Silver halide photosensitive material and method of forming image

Info

Publication number: WO2004010218A1
Application number: PCT/JP2002/007312
Authority: WO
Inventors: Toyoki Nishijima; Motoi Nishimura
Original assignee: Konica Minolta Photo Imaging, Inc.
Priority date: 2002-07-18
Filing date: 2002-07-18
Publication date: 2004-01-29
Also published as: CN1639636A

Abstract

A silver halide photosensitive material which can give an image giving an excellent stereoscopic feeling and having improved evenness even when the paper pulp amount is small. The silver halide photosensitive material is characterized in that it comprises: a photographic printing paper substrate comprising a paper base and a water-resistant resin coating layer formed on each side of the base; and at least one silver halide emulsion layer formed on the substrate, and that the amount of the paper base is 110 to 154 g/m2 and the at least one silver halide emulsion layer contains a compound represented by the following general formula (1). General formula (1)

Description

Description Silver halide photographic light-sensitive material and image forming method

Technical field

The present invention relates to a silver halide photographic light-sensitive material and an image forming method thereof, and more particularly, to a silver halide photographic light-sensitive material and an image forming method which are low-mass, inexpensive, and have little deterioration in image characteristics. Background art

Silver halide photographic light-sensitive materials (hereinafter, also referred to as light-sensitive materials) are widely used because of their excellent gradation and high sensitivity. When a silver halide photographic material is exposed and developed to form an image, it is often exposed to analog light through a negative film image as a method of exposure. Cases of digital digital exposure are increasing.

On the other hand, as a support for photographic paper, which is a silver halide photographic light-sensitive material for printing, a photographic paper support having a water-resistant resin-coated layer provided on both sides of a paper substrate is generally used. However, in this support, pulp and paper fibers are used in the middle part, and this pulp and paper fiber causes a large increase in price and consumes forest resources. However, if the weight of paper is simply reduced, the visual density of the image becomes faint when the image is observed as a reflection image, and as a result, the three-dimensional effect and the sharpness of the image are lost. I got it. It has also been found that this tendency is particularly likely to occur when an image is formed after light beam scanning exposure. Further, when a character image is lying on the surface of the paper support opposite to the surface on which the silver halide emulsion layer is coated, there is a disadvantage that image unevenness is likely to occur when the image is observed.

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material which has a small paper mass and a high visual sense of the image.

A second object of the present invention is to provide a silver halide photographic light-sensitive material capable of visually observing an excellent image and having less image unevenness.

A third object of the present invention is to provide a method for forming an image of a silver halide photographic light-sensitive material capable of forming an image excellent in light beam scanning exposure with a small amount of paper. Disclosure of the invention

The above object of the present invention is achieved by each of the following constitutions.

(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a photographic printing paper support having a water-resistant resin coating layer on both sides of a paper substrate, A mass of 110 to 154 g / m ² , and at least one layer containing a silver halide emulsion contains a compound represented by the following general formula (1). Silver halide photographic light-sensitive material. General formula (1)

[Wherein, R _A represents an alkyl group, R _B represents a halogen atom or an alkoxyl group, and R _c represents one COOR _{D 1} , one COR _D2 COOR _D or -NHCOR _D2 S〇 ₂ R _D one N (R _D3 ) S 0 ₂ R _D1 or one S 0 ₂ N (R _D3 ) R _D1 . R _{D 1} represents a monovalent organic group, R _D2 represents an alkylene group, R _D3 represents a § alkyl group, Ararukiru group or a hydrogen atom. Y _A represents a monovalent organic group, n represents 0 or 1, R _E and R _F is each represents a hydrogen atom or an alkyl group. ]

(2) A silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a photographic printing paper support having a water-resistant resin-coated layer on both sides of a paper substrate. A halogen having a weight of 110 to 154 gZm ² and at least one silver halide emulsion-containing layer containing a compound represented by the following general formula (2): Silver photographic material. General formula (2)

[Wherein, represents an alkyl group, a cycloalkyl group or an aryl group; Represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group, and R ₃ represents a group that can be substituted on a benzene ring. n represents 0 or 1. Represents a group capable of reacting with the oxidized form of the developing agent during coupling and leaving, and represents an organic group. ]

(3) The silver halide photographic material as described in (1) or (2), wherein the total mass of gelatin is not more than 6.2 gZm ² .

(4) Any one of (1) to (3), wherein a character image is laid on the surface of the photographic printing paper support opposite to the surface having the silver halide photographic emulsion-containing layer. Or the silver halide photographic light-sensitive material according to item 1.

(5) An image forming method, which comprises subjecting the silver halide photographic material according to any one of (1) to (4) to beam light scanning exposure and then forming an image.

BEST MODE FOR CARRYING OUT THE INVENTION

The present inventors have conducted intensive studies in view of the above problems, and as a result, as a photographic printing paper support having a water-resistant resin coating layer on both surfaces of a paper substrate, the mass of the paper substrate portion is within a specific range, and It has been found that the use of the yellow coupler of the present invention makes it possible to realize a silver halide photographic light-sensitive material having a high stereoscopic effect of an image and little image unevenness, thereby leading to the present invention.

Hereinafter, details of the present invention will be described.

Usually, the support used for photographic paper of silver halide photographic light-sensitive material is provided with a water-resistant resin coating layer on both sides of a paper substrate, and the water-resistant resin coated on the base paper surface is 240 to 340 ° C. From the resins that can be melt extruded at Used. Examples of such a resin include polyolefin resins such as polypropylene (PP), low density polyethylene resin (LDPE), high density polyethylene (HDPE), and linear low density polyethylene (LLDPE), alone or mixed. Then, it is used by laminating. In the present invention, the mass of the pulp fibers contained in the paper substrate is 110 to 154 gZm ² , preferably 120 to 154 g / m ² , more preferably 130 to 150 g / m ² . ~ 1 is a 48 g / m ^2.

At least one layer of the water-resistant resin coating layer on the side to which the silver halide emulsion is to be applied should contain an inorganic pigment such as titanium dioxide, a proofing agent, a fluorescent whitening agent, etc. from the viewpoint of improving image quality. Is preferred. The form of titanium dioxide may be anatase type or rutile type, but it is preferable to use rutile type in order to further exert the effects of the present invention.

In the present invention, it is preferable that a character image is placed on the side of the support opposite to the silver halide photographic emulsion-containing layer. This is printed with a photographic paper manufacturer's logo, etc., and is printed between the paper base and the backside coating resin.

Next, the yellow color coupler represented by the general formula (1) according to the present invention will be described.

In the general formula (1), examples of the alkyl group represented by R _A include a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, a monopropyl group, a t-butyl group, a dodecyl group, —Hexylnonyl, cyclopropyl, cyclohexyl, adamantyl and the like.

These alkyl groups may be further substituted, for example, a halogen atom (a chlorine atom, a bromine atom, etc.), an aryl group (for example, Group, ρ-t-octylphenyl group, etc.), alkoxyl group (eg, methoxy group, etc.), aryloxy group (eg, 2,4-d-pentylphenyloxy group, etc.), sulfonyl group (eg, methanesulfonyl group, etc.) ), An acyl group (eg, an acetyl group, a benzoyl group, etc.), a sulfonylamino group (eg, a dodecanesulfonylamino group, etc.), a hydroxyl group and the like.

_RA is preferably a branched alkyl group, and particularly preferably a t-butyl group. Examples of the alkoxyl group represented by R _B include a straight-chain or branched alkoxyl group such as methoxy, ethoxy, 1-methylethyloxy, t-butyloxy, dodecyloxy, and 11-hexyloxy. And a oxy group. Of these, a methoxy group is preferred.

The halogen atom represented by R _B, for example, a chlorine atom, a bromine atom, can be exemplified full Tsu atom, a chlorine atom is preferable.

One C_〇_OR _D physician one represented by R _c COOR _{D 2} COOR _D physician one NHCOR _D ₂ S0 ₂ R _D have _{_{-N (R D3) S 0 2}} R D 1 or one S 0 ₂ N (R _D3) In R _{D1, the} monovalent organic group represented by R _D1 is preferably a group having a function as a diffusion-resistant group. For example, a linear or branched alkyl group having 10 or more carbon atoms (eg, For example, a dodecyl group, an octadecyl group or the like or an aryl group (a 2,4-dipentylphenyl group or the like) is preferable, and a linear or branched alkyl group having 14 or more carbon atoms is more preferable. The alkylene group represented by R _D2, for example, up propylene group, a trimethylene group are preferable. The alkyl group represented by R _D3 is preferably a straight-chain or branched alkyl group, for example, a methyl group, an ethyl group, an i-propyl group, and the like, and the aralkyl group is, for example, a benzyl group. Can be. As R _c , one C〇OR _D1 group is preferable. Examples of the alkyl group represented by R _E and R _F include a linear or branched alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, i-propyl, butyl, and hexyl. And a methyl group.

Examples of the monovalent organic group represented by Y _A include an alkyl group (for example, an ethyl group, an i-propyl group, a t-butyl group, etc.), an alkoxyl group (for example, a methoxy group, etc.), and an aryloxy group. Group (eg, phenyloxy group, etc.), acyloxy group (eg, methylcarbonyloxy group, benzoyloxy group, etc.), acylamino group (eg, acetoamide group, phenylcarponylamino group, etc.), carbamoyl group (eg, For example, N-methylcarbamoyl group, N-phenylcarbamoyl group, etc., alkylsulfonylamino group (eg, ethylsulfonylamino group, etc.), arylsulfonylamino group (eg, phenylsulfonylamyl group) Amino group), sulfamoyl group (eg, N-propylsulfamoyl group, N-phenylsulfamoyl group, etc.), Imido groups (for example, succinic acid imido group, glutanoleimide group, etc.).

The yellow color coupler represented by the general formula (1) can be synthesized by a conventionally known method. Further, as long as two or more compounds represented by the general formula (1) are used, or the coupler represented by the general formula (1) is used in combination with other couplers as long as the effects of the present invention are not impaired. Is also good.

In the present invention, the coating amount of yellow color couplers silver halide photographic light-sensitive material is ^{0. 5 0 X 1 0- 3} ~1. 1 0 X 1 0- 3 mol Zm ² is it is favorable preferred, particularly preferably ^{0. 6 0 X 1 0- 3} ~ 1. 0 0 X 1 0- 3 mol Zm ² is preferred. The coating amount of the coupler as used herein means the total amount of the yellow color coupler, not the content of only the compound represented by the general formula (1). No.

Among the compounds represented by the general formula (1), preferred compounds are those in which R _c has an ester linking group.

Specific examples of the compound represented by the general formula (1) include compounds I-1 described in paragraphs (0 04 7) to (0048) of JP-A-10-142756. -1-23 are exemplified.

Next, the compound represented by the general formula (2) according to the present invention will be described. In the general formula (2), examples of the alkyl group represented by R include groups such as methyl, ethyl, i-propyl, t-butyl, and dodecyl. The alkyl group represented by these includes those further having a substituent, and examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group, and a hydroxyl group. Can be

Examples of the cycloalkyl group represented by include cyclopropyl, cyclohexyl, and the like, and an organic hydrocarbon residue in which two or more cycloalkyls are condensed (for example, adamantyl and the like). The cycloalkyl group represented by R i includes those having a substituent, and examples of the substituent include those similar to those exemplified above as the substituent of the alkyl group represented by R. No. Examples of the aryl group represented by the formula include a fuunyl group, and the aryl group includes those having a substituent. Examples of the substituent include the same substituents as those exemplified above and the alkyl group as the substituent of the alkyl group represented by the formula: Is preferably a branched alkyl group.

As the alkyl group, cycloalkyl group and aryl group represented by R ₂ , And groups each having a substituent. Examples of the substituent include the same as those exemplified above in the above. Examples of the acryl group include, for example, acetyl, propionyl, butyryl, hexanoyl, benzoyl and the like, and the acryl group includes those having a substituent. R ₂ is preferably an alkyl group or an aryl group, more preferably an alkyl group, and most preferably a lower alkyl group having 5 or less carbon atoms. Examples of the group that can be substituted on the benzene ring represented by R ₃ include a halogen atom (eg, chlorine), an alkyl group (eg, ethyl, i-propyl, t-butyl), and an alkoxy group (eg, methyl). Toloxy), aryloxy group (for example, phenyloxy), acyloxy group (for example, acetyloxy, benzoyloxy, etc.), acylylamino group (for example, acetoamide, benzamide, etc.), and dylbamoyl group (for example, N-methylcarbamoyl, N— Alkylcarbamoyl, etc.) alkylsulfonamide group (eg, ethylsulfonamide), arylsulfonamide group (eg, fuelsulfonamide), sulfamoyl group (eg, N-propylsulfamoyl, N— Pheninolesolev) and imido groups (e.g. Imid, dartal imid, etc.).

The organic group represented by is preferably a group represented by the following general formula (Y-2).

General formula (Y-2)

-(J) _P -R ₄

In the formula, R ₄ represents an organic group containing one linking group having a carbonyl or sulfonyl unit. p represents 0 or 1.

In the above, the group having a carbonyl unit includes an ester group, an amide Groups, canolebamoinole groups, ureido groups, urethane groups, and the like. Examples of the group having a sulfoninole unit include a sulfonyl group, a sulfonylamino group, a sulfamoyl group, and an aminosulfonylamino group.

J represents one N (R ₅ ) CO— or one CON (R ₅ ) one, and R ₅ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

The alkyl group represented by R _5, methyl, Echiru, i one propyl, t - heptyl, dodecyl and the like. Examples of the aryl group represented by R ₅ include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by R ₅ include a pyridyl group.

Each group represented by these R ₅ include those having a substituent. Examples of the substituent include, but are not limited to, a halogen atom (eg, chlorine), an alkyl group (eg, ethyl group, t_butyl group, etc.), and an aryl group (eg, Phenyl, p-methoxyphenyl, naphthyl, etc.), alkoxy (eg, ethoxy, benzyloxy, etc.), aryloxy (eg, phenoxy, etc.), alkylthio (eg, ethylthio, etc.) An arylsulfonyl group (eg, phenylsulfonyl, etc.), an alkylsulfonyl group (eg, β-hydroxyxylsolephoninole), an arylsulfur group (eg, phenylsulfonyl, etc.), an acylamino group (eg, For example, alkylcarboelamino groups such as acetate, arylcarbonylamino groups such as benzamide), Moyl group (for example, alkyl benzomoyl group such as Ν-methylcarbamoyl, aryl rubamoyl group such as Ν-phenylcarbamoyl), and acyl group (for example, alkylcarbonyl group such as acetyl, and arylcarbonyl group such as benzoyl) ), Sulfonamide groups (eg, methyl sulfonamide, etc.) Phenylene sulphonamide, phenylsulfonamide, etc./sulfamoyl group (eg, N-methylsulfamoyl, phanolequillsnorefamoyl group, N-phen) (An arylsulfamoyl group such as Ninoresnofamoinole), a hydroxyyl group, a cyano group and the like.

Examples of the group which is released during the force coupling reaction with the oxidized form of the developing agent represented by X include, for example, a group represented by the following general formula (Y-3) or (Y_4), and is particularly preferable. Is a group represented by the general formula (Υ-4).

General formula (Υ-3)

~ OR ₆

—In the general formula (Y-3), R ₆ represents an aryl group or a heterocyclic group including those having a substituent. General formula (Y— 4)

In the above general formula (Y-4), represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring with a nitrogen atom. As the non-metallic atomic group, for example, a substituted or unsubstituted methylene, methine, = C = 0, one NR _A (R _A has the same meaning as the R _5), one N =, one O-, one S- , One S 0 ₂ — and the like.

The yellow coupler represented by the general formula (2) may form a bis form by bonding at R ₃ or R ₃ . Specific examples of the yellow coupler represented by the general formula (2) according to the present invention include Y described in paragraphs (0045) to (004 9) of JP-A-6-102637. — Compounds represented by 1 to Y-20 can be exemplified. Next, scanning exposure using a light beam according to the present invention will be described.

The scanning exposure using the light beam according to the present invention includes linear exposure using a light beam (a raster exposure: main scan) and relative movement of the photosensitive material in a direction perpendicular to the linear exposure direction (sub-scanning). ) Is generally performed. For example, a photosensitive material is fixed to the outer or inner periphery of a cylindrical drum, and the main scanning is performed by rotating the drum while irradiating a light beam, and at the same time, the light source is perpendicular to the rotation direction of the drum. A method of performing sub-scanning by moving (drum method) or irradiating a rotated polygon mirror with a light beam to scan the reflected beam horizontally (main scanning) in the direction of rotation of the polygon mirror, The sub-running method is carried out by transporting the polygon perpendicular to the rotation direction of the polygon (polygon method). In addition, when using an exposure apparatus in which light sources are arranged in an array beyond the width of the photosensitive material to be exposed, it is possible to regard the portion corresponding to main scanning as being replaced by an array light source. Can be considered.

The types of light sources that can be used in the present invention include a light emitting diode (LED), a gas laser, a semiconductor laser (LD), a solid laser using an LD or an LD as an excitation light source, and a second harmonic change element (so-called SHG). Any known light source such as a combination of (element) and can be used.

In the present invention, the total amount of gelatin contained in the silver halide photographic light-sensitive material, 6. ² gZm 2 but less preferred, more preferably 5. 7 gZm ² below is there.

Constituent elements other than those described above that can be used in the silver halide photographic light-sensitive material of the present invention, for example, silver halide photographic emulsions, emulsion additives, sensitization methods, anti-capri agents, stabilizers, anti-irradiation dyes, fluorescent brightening Agents, yellow couplers, magenta couplers, cyan couplers, spectral sensitizing dyes, emulsifying dispersion methods, surfactants, anti-turbidity agents, binders, hardeners, lubricants and matting agents, supports, bluing agents, The reddish agent, coating method, exposure method, color developing agent, processing method, development processing device, processing agent, etc. are described in JP-A No. 11-3477615, page 9, left, second line, page 9. Each of the compounds and methods described in paragraph No. 0106 of paragraph 17 of page 04 to the left, 17th line, page 14 to page 14 can be used.

Next, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto.

Hereinafter, the present invention will be described specifically with reference to Examples, but embodiments of the present invention are not limited thereto.

Example 1

(Preparation of sample 101)

A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support having “TEST” printed on the back surface. However, on the side to be coated with the silver halide emulsion-containing layer, the reflective support was made by laminating molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass. Was prepared. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further provided thereon to prepare Sample 101, which is a silver halide photographic material. H-1 and H as hardeners -2, F was used as a preservative

[Configuration of Sample 101]

Layer 7 (protective layer) [g Zm ^2]

1.00

D B P 0. 002 D I D P 0. 002 Silicon dioxide 0.003 6th layer (UV absorbing layer)

0.40

AI-1 0.01 UV absorber (UV-1) 0.084 UV absorber (UV-2) 0.027 UV absorber (UV-3) 0.114 Sting inhibitor (HQ-5 ) 0.04 PVP 0.03 5th layer (red-sensitive layer)

30 Red-sensitive silver chlorobromide emulsion (Em_R) 0.21 Cyan coupler (C-1) 0.25 Cyan coupler (C-2) 0.08 Dye image stabilizer (ST-1) 0. 1 0 Sting inhibitor (HQ-1) 0.004 DBP 0.10 D〇 P 0.20 4th layer (UV absorbing layer)

0.94 UV absorber (UV-1) 0.196 UV absorber (UV-2) 0.06 3 UV absorber (UV-3) 0.266 AI-1 0.02 Sting inhibitor (HQ-5) 0.10 3rd layer (green sensitive layer)

30

AI-2 0 1 Green-sensitive silver chlorobromide emulsion (Em-G) 0 14 Magenta coupler (M-1) 0 20 Dye image stabilizer (ST-3) 0 20 Dye image stabilizer (ST — 4) 0 1 7 DIDP 0 1 3 DBP 0 1 3 Second layer (middle layer)

1 20

AI-3 0 01 Sting inhibitor (HQ—2) 0 0 3 Sting inhibitor (HQ—3) 0 0 3 Sting inhibitor (HQ—4) 0 0 5 Sting inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Fluorescent brightener (W-1) 0.10 1st layer (blue-sensitive layer)

20 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.26 Yellow coupler (γ_1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Sting inhibitor (HQ-1) 0.01 Dye image stabilizer (ST-5) 0.10 Image stabilizer A 0.15 DNP 0.05

DBP 0.15 Support: Polyethylene laminated paper (contains a trace amount of colorant) The amount of each silver halide emulsion added is expressed in terms of silver. The details of each additive used in Example 1 are shown below.

DB P: dibutino phthalate

DNP: dinoel phthalate

DOP: Dioctinolephthalate

D I D P: di-i-decino phthalate

PVP: Polyvininolepyrrolidone H: Tetrakis (vinylsulfonylmethyl) methane

H-2: 2,4-dichloro-6-hydroxy s-triazine 'sodium

HQ—: 25-di-t-otatinolenodidroquinone

HQ-2: 25—Gee sec-Doacylnody Droquinone

HQ-3: 25-zy sec-tetradecylhydroquinone

HQ-4: 2 sec-dodecinole-5-sec-tetradecinolenodidroquinone

HQ-5: 2,5-di [(1 dimethyl-41-hexynoleoxycanolephonyl) petitnole] Hydroquinone

Image stabilizer A: P-t-octylphenol

C-1

7312

18

C-2

ST— 1

ST— 2

ST— 3

0 ₂ S IM- \ -OC ₁₃ H ₂₇ (i)

ST— 4

ST— 5

UV-1

UV-2

UV-3

AI-1

AI-2

AI-3

W-1

O

,. +

CI s CH ₃

(50%) (46%) (4%) molar ratio (Preparation of blue-sensitive silver halide emulsion)

The following (Solution A) and (Solution B) were added simultaneously in 1 liter of a 2% aqueous gelatin solution kept at 40 ° C over 30 minutes while controlling pAg = 7.3 and pH = 3.0. Further, the following (Solution C) and (Solution D) were simultaneously added over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(A liquid)

Sodium chloride 3.42 g Potassium bromide 0.0 3 g 200 ml with water

(B liquid)

Silver nitrate 10 g Add water 200 ml

(C solution)

Sodium chloride 02.7 g

K, I r C 1 4 X 1 0— ⁸

_{_{K 4 F e (CN) 6}} 2 X 1 0- 5

Potassium bromide 1.0 g 600 ml with water (D solution)

After adding 300 g of silver nitrate and adding 600 ml of water, desalting was carried out using a 5 ° / ₀ aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to average. A monodispersed cubic emulsion EMP-1 having a grain size of 0.71 m, a variation coefficient of the grain size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained. Next, the average particle size was 0.64 μηι and the particle size was the same as EMP-1 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A monodisperse cubic emulsion EMP-1B having a distribution coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above EMP-1 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimal chemical sensation for EMP-1B, The obtained EMP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Chio sodium sulfate 0. 8mg / ^ A g X chloroauric acid 0. 5 mg / ^ Ag X Stabilizer: S TAB- 1 3 X 1 0- 4 Monore / mol A g X Stabilizer: S TAB- 2 3 X 1 0 ⁴ Monore / mol A g X stabilizer: S tAB- 3 3 X 1 0- 4 Monore / Monore A g X增感dye: BS- 1 4 X 1 0 ⁴ Monore / mol A g X sensitizing dye : BS- 2 1 X 1 0- ⁴ mol / mol a g X preparation of green-sensitive Ha port Gen halide emulsion]

Same as EMP-1 except for changing the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D). 08, a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5% was obtained. Next, in the same manner as in EMP-1, except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed, the average particle diameter was 0.50 μπι. A monodisperse cubic emulsion {—2} having a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained. For the above ΕΜΡ-2, the following compounds were optimally chemically sensitized at 55 ° C. Similarly, after optimal chemical sensitization of EMP-2B, the sensitized EMP-2 and EMP-2B were mixed at a silver ratio of 1: 1 to obtain a green-sensitive silver halide. An emulsion (Em-G) was obtained.

Chio sodium sulfate 1.511187 mol _§ chloroauric acid 1. 0 mg / mol A g X Stabilizer: ST AB- 1 3 X 1 0- 4 mol / mol A g X Stabilizers: S TAB- 2 3 X 1 0- 4 mol Z moles A g X Stabilizer: S TAB- 3 3 X 1 0- 4 mol Z moles A g X sensitizing dyes: GS- 1 4 X 1 0- ⁴ mol / mol A g X

(Preparation of red-sensitive silver halide emulsion)

Except for changing the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D), the average particle diameter is 0.40 μπι, and the coefficient of variation is 0.0 as in EMP-1. 8. A monodisperse cubic emulsion II-3 having a silver chloride content of 99.5% was obtained. In addition, a monodisperse cubic emulsion EMP-3B having an average particle size of 0.38 / m, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above EMP-3 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimal chemical sensitization of EMP-3B, the sensitized EMP-3 and EMP-3B are mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion ( Em—R).

Sodium thiosulfate .8mg / monole A g Chloroauric acid 2.0 mg g X Stabilizer S TAB— 13 X 10-4 g x Stabilizer: S TAB— 23 X 0-4

g X Stabilizer: S TAB— 33 X 0— ⁴ g X Sensitive dye: RS—11 X 0—4 g Sensitive dye: RS — 21 X 0—4 gx S TAB—1: 1—ί 3-acetamidophenyl) 5-mercaptotetazolone

S TAB-2: 1-Fenil 5-5-Mercaptote Tolazole S TAB— 3 (4-ethoxyphenyl) 1 5-mercaptote tolazol

Also, the red-sensitive emulsion, SS- 1 was per mol of silver halide 2. 0 X 1 0 one ³ moles added.

Details of each additive used in the preparation of each color-sensitive emulsion are shown below.

The sample thus prepared is referred to as Sample 101.

(Preparation of samples 102 to 113)

In the preparation of Sample 101, Sample 102 was prepared in the same manner except that the basis weight of the paper pulp used for the support and the type of the yellow coupler added to the first layer were changed to the combinations shown in the following table. ~ 1 13 were prepared.

(Preparation of sample 114)

In the preparation of Sample 11 above, Sample 114 was prepared in the same manner except that the amount of gelatin used in all layers was reduced at the same ratio, and the total amount of gelatin was changed to 6.0 g Zm ² .

Details of each sample prepared as described above are shown in the table below.

Sample No. Paper pulp of the support 1st layer Remarks Basis weight (gZm ² ) Yellow Ippiki v_ γ — 1 ¾Χ.17 ■

1 0 9 1 fi 0 V—— 1 ϋ ¾ί. I 'J

V— 1 human 1 j * ■ ± Υ— 9 | 'J

Λ A J

1 Q V—J

T O R 1 0 0 V— 9 · Η_ι¾ 17 'J

1 0 9 1 6 0 Y— 3 Comparative example

1 1 0 1 5 3 Y— 3 The present invention

1 1 1 14 7 Y— 3 The present invention

1 1 2 1 3 5 Y- 3 The present invention

1 1 3 100 Y— 3 Comparative example

1 1 4 1 3 5 Y-3 The present invention The details of Y-2 and Y-3, which are yellow force blurs used for producing the above sample, are shown below.

(Evaluation of each sample)

Each sample prepared in this manner was subjected to printing and development of a portrayal image by scanning exposure as described below. Scanning exposure uses a semiconductor laser (oscillation wavelength of 650 nm), a He-Ne gas laser (oscillation wavelength of 544 nm), and an Ar gas laser (oscillation wavelength of 458 nm) as light sources. The laser beam is reflected by the polygon while modulating the light intensity by the AOM, and the main scanning is performed on each sample. At the same time, the photosensitive material is transported in the direction perpendicular to the main scanning direction, and the sub scanning is performed. (4) A portrait image was output after exposure. At this time, it was confirmed using a beam monitor that the beam diameter was 100 μm for each of the BGRs.

Next, each of the samples exposed by the above method was subjected to a developing process in the following developing process to produce a color print of a portrait image.

Processing Step Processing temperature Time Replenishment amount Color development 3 8.0 ± 0.3 ° C 4 5 seconds 80ml / ² Bleach-fix 35.0 ± 0.5 ° C 4 5 seconds 1 20 ml Zm ² Stabilization 3 0-34 ° C 60 seconds 1 50 ml l Zm ² Drying 60-80 ° C 30 seconds

The composition of the developing solution is shown below.

[Color developer tank solution and replenisher] Tank solution Replenisher Pure water 800 ml 800 ml l Triethylenediamine 2 g 3 g Dethylene glycol monophosphate 10 g 10 g 0.1 g of power bromide

3.5 g of potassium chloride

Potassium sulphite 0.25 g 0.5 g

N-Ethyl mono-N- (j3-methanesulfonamidoethyl) -13 Methinolee 4-aminoaminophosphoric acid sulfate 6.0 g 10.0 g

N, N-Jetylhydroxylamine 6.8 g 60 g Triethanolamine 100. Og 100 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 20 g Optical brightener (4, 4'-diamino Stilbene disulfonic acid derivative)

2.0 g 25 g Potassium carbonate 30 g 30 g Add water to bring the total volume to 1 liter. Adjust the tank solution to pH = 100 and the replenisher to H = 10.60.

(Bleach-fixer tank solution and replenisher)

Diethylenetriaminepentaacetic acid ferric ammonium dihydrate 6 5 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml

2-Amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the whole volume 1 liter, Carbonated lime or ice Adjust pH = 5.0 with acetic acid.

(Stabilizing solution tank solution and replenisher solution)

o—Feninolefuenore 1.0 g

5-Chloro-2-methyl-4-1-isothiazoline-3-one 0.0 2 g 2-Methyl-4-isothiazoline_3-on 0.02 g Diethylene glycol cornole 1.0 g Optical brightener (Tinopearl SFP) 2. 0 g

1-Hydroxyshethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate 7 hydrate 0.2 g

PVP 1.0 g ammonia water (ammonium hydroxide 25% aqueous solution) 2.5 g Utrilotriacetic acid trisodium salt 1.5 g Add water to make 1 liter, PH == with sulfuric acid or ammonia water Adjust to 7.5.

The portrait image of each sample prepared as described above was visually observed by 10 observers, and the evaluation of image stereoscopic effect and image unevenness resistance was evaluated in 1 ° steps according to the following criteria. The average score was calculated. [Evaluation of image stereoscopic effect]

1: The contrast between the person and the background is low, and the image looks flat.

5: Shading of the person and background is recognized, and a slight three-dimensional feeling and sharpness are recognized.

10: Sharp difference between person and background is clear, and clear and three-dimensional

[Evaluation of image unevenness resistance]

1: The back-printed characters are clearly recognized in the image when observed from the image side.

5: When viewed from the image side, when the print is seen through, the back-printed characters are recognized.

10: No back-printed characters are observed when observed from the image side

In each of the above-mentioned evaluation ranks, the ranks other than the above, 2 to 4 and 6 to 9 were set by dividing them equally based on the ranks of 1, 5, and 10, respectively.

Furthermore, the paper pulp basis weights of the supports used in the preparation of the above samples were ranked, and the paper consumption rank was determined. This is an index determining the economics of each sample (cost), paper pulp basis weight of 1 6 0 § 111 ² below the 〇, the 1 6 0 ~ 1 8 0 g Zm less than ² X, 1 8 0 gZm ² or more was determined to be XX.

The evaluation results obtained above are shown in the table below. Sample number Paper consumption Image stereoscopic effect Image unevenness resistance Remarks

1 0 1 XX 6 5 5.9 Comparative example 1 02 X 6 4 5 8 Comparative example 1 03 〇 6 5 8 Comparative example 1 04 X 7 6 5 9 Comparative example 1 05 〇 7 6 5 9 Invention 1 06 〇 7 5 5 8 Invention 1 07 〇 7 4 5 Invention 1 108 〇 4 3 Comparative Example 1 09 X 7 2 5 7 Comparative Example 1 1 0 〇 7 2 5 7 Invention 1 1 1 〇 7 0 5 4 Invention 1 1 2 〇 7 0 5 0 Invention 1 1 3 〇 4 0 2 9 Comparative Example 1 14 〇 7 2 5 Invention Example 2

In Example 1, running processing was performed according to process name C PK—2—J 1 using NPS—868 J manufactured by Koyuka Corporation as an automatic processor and E CO JET—P as a processing chemical. As a result of evaluating each property in the same manner as in Example 1, it was confirmed that the sample of the present invention was superior to the comparative sample in image stereoscopic effect and image unevenness resistance. Industrial potential

As described above, the silver halide photographic light-sensitive material according to the present invention can realize an image having an excellent three-dimensional image and improved image unevenness resistance even with a small amount of paper pulp.

Claims

The scope of the claims

1. A silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a photographic printing paper support having a water-resistant resin coating layer on both sides of a paper substrate, wherein the mass of the paper substrate is A halogen content of 110 to 154 g / m ² , wherein at least one of the silver halide emulsion-containing layers contains a compound represented by the following general formula (1): Silver photographic material. General formula (1)

Wherein R _A represents an alkyl group, R _B represents a halogen atom or an alkoxyl group, and R _c represents one COOR _D or one COOR _D2 COOR _D1 or one NHCOR _D2 S〇 ₂ R _D or -N (R _D3) S_〇 ₂ R _{D 1} or one _{_{S 0 2 N (R D 3}} ) represent the R _D1. R _D1 represents a monovalent organic group, R _D2 represents an alkylene group, and R _D3 represents an aralkyl group, an aralkyl group or a hydrogen atom. Y _A represents a monovalent organic group, n represents 0 or 1, R _E and R _F is each represents a hydrogen atom or an alkyl group. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a photographic printing paper support having a water-resistant resin coating layer on both sides of a paper substrate, wherein the mass of the paper substrate is Is 110 to 154 g / m ² , and A silver halide photographic material, characterized in that at least one layer containing a silver halide emulsion contains a compound represented by the following general formula (2). General formula

(2)

[In the formula, represents an alkyl group, a cycloalkyl group or an aryl group, R ₂ represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group, and R ₃ represents a group that can be substituted on a benzene ring. n represents 0 or 1. Represents a group capable of reacting with the oxidized form of the developing agent during coupling and leaving, and represents an organic group. ]

3. The silver halide photographic material according to claim 1, wherein the total mass of gelatin is 6.2 g Zm ² or less.

4. The character image is laid on the surface of the photographic printing paper support opposite to the surface having the silver halide photographic emulsion-containing layer, wherein a character image is laid on the support. Item 4. The silver halide photographic material according to any one of items 3.

5. An image forming method, comprising: subjecting the silver halide photosensitive material according to any one of claims 1 to 4 to light beam scanning exposure and forming an image.