JP3117589B2 - Silver halide photographic material and color image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and in particular, has no residual color due to rapid processing, has excellent sharpness, and generates fog even when pressure is applied to the light-sensitive material before processing. Silver halide photographic light-sensitive material having a small particle size.

[0002]

2. Description of the Related Art In recent years, various electronic image forming means have been developed, and the image quality has been compared with that of silver halide photographic materials. As the comparison has been made, the high image quality and simplicity of silver halide photographic light-sensitive materials have been reviewed. Therefore, use of the silver halide color photographic light-sensitive material not only as a photographic print material but also as a hard copy material for electronic images has been studied. Under these circumstances, in order to further enhance the characteristics of silver halide photographic light-sensitive materials, sharpness and color reproducibility are improved to achieve higher image quality, and further, processing is simplified by improving processing time and processing method. Research on providing quickness and the like has been actively conducted. With respect to the simplification of processing, the development of a simple and rapid developing system represented by a minilab system has made it possible to supply extremely high-quality printed photographs relatively easily in a short time and at low cost. Further, by using a silver halide emulsion having a high silver chloride content, the processing time has been greatly reduced and the processing fluctuation has been improved.

Various methods have conventionally been known as means for improving the sharpness of a silver halide photographic light-sensitive material having a reflective support. The methods include: 1) prevention of irradiation by using a water-soluble dye. 2) Prevention of halation by colloidal silver, mordant dyes, solid particulate dyes and the like.
3) Increasing the filling ratio of white pigment in the laminate resin on the paper support.

It has been disclosed in JP-A-3-156452 and the like that sharpness can be greatly improved by increasing the content of a white pigment in a water-resistant resin coating layer on the photosensitive layer coating side on a reflective support. I have. Further, JP-A-4-256948 and the like disclose a reflective support having two or more polyolefin layers having different white pigment contents. It has been found that with these configurations, the amount of white pigment used can be reduced while maintaining sharpness, which is advantageous in terms of cost. EP 0507489 (A1) discloses a reflective support in which polyester is used instead of polyolefin as a water-resistant resin for forming a coating layer, and a mixed composition of polyester and white pigment is laminated. The lamination of the mixed composition of polyester and white pigment shows that it is possible to further increase the content of white pigment as compared with the case of using polyolefin, and it is a very effective means of improving sharpness. I understand. However, when a pressure such as scratching is applied to a photosensitive material using a support in which the content of the white pigment in the water-resistant resin coating layer is further increased, fogging is likely to occur at the location where the pressure is applied. There has occurred. Furthermore, it has been found that this problem is greater in silver halide emulsion grains having a very high silver chloride content.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high silver chloride photographic light-sensitive material capable of rapidly and inexpensively providing a high-quality photograph, which has excellent sharpness and high sensitivity. It is an object of the present invention to provide an image forming method which provides a photographic light-sensitive material free from fogging or the like even when pressure is applied to a mold photosensitive material, and further uses the material to quickly provide a high-quality photograph.

[0006]

The above object of the present invention is as follows.
The following silver halide photographic material and the image forming method
Achieved.  (1) At least one layer of photosensitive halogen on a reflective support
Silver halide photographic light-sensitive material having a layer containing silver halide emulsion grains
The water-resistant resin coating on the photosensitive layer coating side of the reflective support
2 g / m of white pigment in the covering layer^TwoContained
At least in the photosensitive layer is represented by the following general formula (I)
At least oneCompoundIs a single molecule or dimer molecule
Silver halide photographic light-sensitive material containing in a dispersed state
material.

[0007]

[0008] (2) the substituent R ₁ one general formula (I), R _2, R
₃ and R ₄ have no dissociable group
(1) The silver halide photographic material as described in (1) above . (3) the substituents R ₁ one general formula (I), R _2, R ₃ and R ₄ are a hydrogen atom, an alkyl _{group, -COOR 5, -CONR 6 R 7} , -CONHR 8, -NR 9
COR ₁₀ , -NR ₁₁ R ₁₂ , -CN, OR ₁₃ , -NR ₁₄ CONR ₁₅ R ₁₆ (R _{5 to} R ₁₆
Represents an alkyl group which may be substituted with a hydrogen atom or a substituent having no dissociable group, and R ₆ , R ₇ or R ₁₁ , R
₁₂ or R ₁₅ and R ₁₆ may form a ring. ) Wherein R ₃ and R ₄ are both alkoxy
It is not a carbonyl group. ) Characterized in that it is a (2) The silver halide photographic material according to claim. (4) compounds of general formula (I), the general formula characterized in that it is a compound represented by (II) (1) halogen <br/> down halide photographic material according to claim.

[0009]

[0010] (5) substituents R ₁ one general formula (II), R _6, R
Item ₇ is characterized in that it does not have a dissociable group.
Silver halide photographic light-sensitive material of the mounting.

(6 ) In the reflective support, the water-resistant resin coating layer on the photosensitive layer coating side has a white pigment content (% by weight) different from that of the photosensitive support.
(1), (2), (3), a reflective support comprising a water-resistant resin coating layer having at least one layer and a substrate .
(4) The silver halide photographic material as described in (5) . (7) At least one layer of photosensitive halogen on a reflective support
Silver halide photographic light-sensitive material having a layer containing silver halide emulsion grains
The water-resistant resin coating on the photosensitive layer coating side of the reflective support
The covering layer contains ² g / m ² or more of a white pigment ,
The reflective support has a white water-resistant resin coating layer on the photosensitive layer coating side.
Water resistant resin of two or more layers with different pigment content (% by weight)
A reflective support consisting of a coating layer and a substrate, and among two or more water-resistant resin coating layers having different white pigment contents , the white pigment content of the water-resistant resin coating layer closest to the substrate (% by weight) ) Is the white pigment content (% by weight) of at least one water-resistant resin coating layer on the side opposite to the substrate with respect to this layer
Rather lower than, further the following general formula in at least a photosensitive layer
Converting at least one compound represented by (XI) into a single molecule or
Features and to Ruha b <br/> Gen halide photographic light-sensitive material to include in a molecular dispersion state of the dimer. (8) of the white color pigment content of different two or more layers of water-resistant resin coating layer, and wherein the white pigment content of the nearest water-resistant resin coating layer on the photosensitive layer (wt%) is the highest Do
(6) The silver halide photographic material as described in (6) above . (9 ) The reflective support has at least three water-resistant resin coating layers having different white pigment contents, and the water-resistant resin coating layer closest to the photosensitive layer of the multilayer water-resistant resin layer and the water resistance closest to the substrate. (6) wherein the content (% by weight) of the white pigment in the intermediate layer with the conductive resin coating layer is the highest.
The silver halide photographic light-sensitive material according to the above item . (10 ) The white pigment in the water-resistant resin coating layer of the reflective support is titanium oxide, and the weight ratio of the resin of the water-resistant resin coating layer having the highest white pigment content (% by weight) to the white pigment is 1
Any one of (6) to (9), wherein the content of the white pigment is 0/90 (titanium oxide / resin) or more.
6. The silver halide photographic light-sensitive material according to item 1 .

(11 ) A composition in which the water-resistant resin coating layer on the side of the reflective support on which the photosensitive layer is coated is a mixture of titanium oxide and a resin composed mainly of polyester synthesized from a dicarboxylic acid and a diol by condensation polymerization. a layer, and wherein the weight ratio of the titanium oxide and the resin is 10/90 content of (titanium oxide / resin) or titanium oxide
The silver halide photographic light-sensitive material according to the item (1), (2), (3), (4) or (5) . (12 ) The polyester as described in (11 ), wherein the polyester of the reflective support is a polyester containing polyethylene terephthalate as a main component.
The silver halide photographic light-sensitive material.

[0013] (13) at least a photosensitive silver halide emulsion layer on the reflective support is a yellow, magenta or with any of coupler coloring in cyan, each containing color sensitivities different silver halide emulsion grains to each other It consists three kinds of light-sensitive parental aqueous colloidal layer, and wherein the photosensitive hydrophilic colloid layer each silver content of 95 mol% or more silver halide emulsion grains chloride in are contained
The silver halide color photographic light-sensitive material according to any one of (1) to (12) . (14) (13) to a silver halide photographic material as claimed in claim, the color image forming method in which the support body is characterized in that printing through a color negative film made of polyethylene terephthalate or polyethylene naphthalate. (15 ) A color image, wherein the silver halide color photographic light-sensitive material according to the item ( 13) is exposed by a scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds, followed by color development. Forming method.

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The general formulas (I) and (XI) will be described in detail. In the general formula (I) or (XI) , (R ₁ +
The total of the atomic weight of at least one of R ₃ ) and (R ₂ + R ₄ ) needs to be 160 or less, and it is preferable that both of them are 160 or less. n is particularly preferably 1. The substituents R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, an alkyl group, -COOR ₅ , -CONR ₆ R ₇ , -CONHR ₈ , -NR ₉ COR
₁₀ , -NR ₁₁ R ₁₂ , -CN, OR ₁₃ , -NR ₁₄ CONR ₁₅ R ₁₆ (R _{5 to} R ₁₆ represent a hydrogen atom or an optionally substituted alkyl group, and R ₆ , R ₇
Alternatively, R ₁₁ and R ₁₂ or R ₁₅ and R ₁₆ may form a ring. ) Is preferred. However, the general formula
In the compound (I), R ₃ and R ₄ are both alkoxy.
As described above, it is not a carbonyl group.
You. More preferably, the substituents R ₁ , R ₂ , R ₃ and R ₄ do not have a dissociative group. The dissociable group which these substituents do not have is a dissociable group which substantially dissociates in water at 25 ° C. and has a pKa of 12 or less. Specific examples of such a dissociable group include a sulfonic acid group, a carboxyl group, and a phosphate group. Further, R ₁ , R ₂
Is more preferably a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, and a propyl group, and may have a substituent. Such a substituent is preferably a substituent having an unshared electron pair such as a hydroxyl group, an ether group, an ester group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, and a cyano group. Particularly, a hydroxyl group and an ether group are preferable.

The alkali metal represented by M is Li, Na,
K and Cs are preferred. When the substituent R ₃ and / or R ₄ is an alkyl group, a preferable alkyl group is a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, and a methyl group and an ethyl group are particularly preferable.
When the substituent R ₃ and / or R ₄ is represented by —COOR ₅ ,
The alkyl group of R ₅ is a methyl group, an ethyl group, a propyl group,
A lower alkyl group such as a butyl group is preferred, and a methyl group and an ethyl group are particularly preferred.

Substituent R_ThreeAnd / or R_FourBut -CONR₆R₇so
When represented, R₆And R₇Is a hydrogen atom or an alkyl group
But at least one is preferably an alkyl group.
Good. As the alkyl group, a methyl group, an ethyl group
Group, propyl group, etc., which may have a substituent.
No. As the substituent, a hydroxyl group or an ether group is preferable. or
R ₆And R₇May be connected to each other to form a ring. That
The morpholine ring is particularly preferred as the ring formed in this case.
No. Substituent R_ThreeAnd / or R_FourBut -CONHR₈Represented by
R₈Is an alkyl group, the alkyl group may be R₆
And R₇Is synonymous with Substituent R_ThreeAnd / or R_FourIs -N
R₉COR₁₀When represented by R₉, R_Ten, Is a hydrogen atom
It may be an alkyl group. Alkyl groups include methyl and d.
A tyl group and a propyl group are preferred, and a methyl group is particularly preferred.
Good. Further, it may have a substituent. Water as a substituent
Acid groups and ether groups are preferred.

The substituent R_ThreeAnd / or R_FourIs -NR₁₁R₁₂Ma
Or -OR₁₃When represented by R ₁₁, R₁₂, R₁₃Is water
It may be an elemental atom or an alkyl group. As an alkyl group,
Til, ethyl, propyl and the like are preferred, and substituents
May be provided. As a substituent, a hydroxyl group or an ether group is
preferable. Also R₁₁And R₁₂To form a ring
Is also good. Substituent R_ThreeAnd / or R_FourIs -NR₁₄CONR₁₅R₁₆
When represented by R₁₄, R₁₅, R₁₆Is a hydrogen atom
It may be a kill group. Methyl group, ethyl group as alkyl group
Group, propyl group and the like are preferable, and methyl group is particularly preferable.
No. Further, it may have a substituent. Hydroxyl group as a substituent
And ether groups are preferred.

As the substituents R ₃ and R ₄ ,
R ₆ R ₇ is particularly preferred. The dye in the present invention needs to exist in a coating film in a molecular dispersion state such as a single molecule or a dimer. The molecular dispersion state is represented by the general formula (I) or
Indicates that the compound represented by (XI) is uniformly dispersed in the emulsion layer and other hydrophilic colloid layers.
Even if it is magnified 10,000 times, substantially no solid is detected. Next, specific examples of the compound used in the present invention will be shown, but the present invention is not limited to these specific examples.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

[0023]

[Table 5]

[0024]

[Table 6]

[0025]

[Table 7]

[0026]

[Table 8]

[0027]

[Table 9]

[0028]

[Table 10]

[0029]

[Table 11]

[0030]

[Table 12]

[0031]

[Table 13]

[0032]

[Table 14]

The compound of the present invention can be molecularly dispersed in a photosensitive layer or a non-photosensitive layer by various known methods. A method in which the compound is directly dispersed in the photosensitive layer or the non-photosensitive layer, or a suitable solvent (for example, methyl alcohol, ethyl alcohol, propyl alcohol,
Methyl cellosolve, halogenated alcohol, acetone, water, pyridine, etc. described in JP-A-48-9715, and U.S. Pat. No. 3,756,830, or a mixed solvent thereof and the like, and a method of adding in the form of a solution. There is. When the compound of the present invention is added to either the photosensitive layer or the non-photosensitive layer, it diffuses almost uniformly throughout the light-sensitive material constituting layer upon application. The amount of the compound of the present invention is not particularly limited, but may be 0.1 mg /
It is preferably used in the range of m ² ~200mg / m ^2, particularly preferably from ^{1mg / m 2 ~100mg / m 2} .

Hereinafter, the reflective support of the present invention will be described in detail. In the reflective support of the present invention, it is necessary that the water-resistant resin coating layer on the photosensitive layer coating side of the reflective support contains a white pigment of 2 g / m ² or more. This content is 2 g / m ²
If the amount is smaller, the sharpness is greatly deteriorated, and the object of the present invention cannot be achieved. The content of the white pigment was 3.0 g.
/ M ² or more, more preferably 4.0 g / m ² or more. There is no particular upper limit, but from the viewpoint of cost, 30
g / m ² or less is preferred.

Examples of white pigments mixed and dispersed in the water-resistant resin include inorganic oxides such as titanium dioxide, barium sulfate, lithopone, aluminum oxide, calcium carbonate, silicon oxide, antimony trioxide, titanium phosphate, zinc oxide, lead white, and zirconium oxide. Examples include pigments and organic fine powders such as polystyrene and styrene-divinylbenzene copolymer. Among these pigments, the use of titanium dioxide is particularly effective. Titanium dioxide may be either a rutile type or an anatase type, but anatase type is preferred when whiteness is prioritized, and rutile type is preferred when sharpness is prioritized. Anatase type and rutile type may be blended and used in consideration of both whiteness and sharpness. Further, when the water-resistant resin layer is composed of multiple layers, some layers have anatase type,
It is also preferable to use a rutile type for the other layers. Further, these titanium dioxides may be produced by any of a sulfate method and a chloride method.
Specific product names include KA-10 and KA-
20, A-220 manufactured by Ishihara Sangyo, and the like.

The titanium dioxide used is generally one whose surface has been surface-treated with an inorganic substance such as aluminum hydroxide or silicon hydroxide, polyhydric alcohol, polyhydric amine, in order to suppress the activity of titanium dioxide and prevent yellowing. It is preferable to use one that has been surface-treated with an organic substance such as metal soap, alkyl titanate, or polysiloxane, and one that has been surface-treated with an inorganic or organic treating agent. When used, the amount of the surface treatment substance is 0.2 wt% to 2.0 wt% for an inorganic substance and 0.1 wt% to 1.
0 wt% is preferred. The average particle size of the titanium dioxide used is preferably 0.1 to 0.8 μm. When it is less than 0.1 μm, it is difficult to uniformly mix and disperse the resin, which is not preferable. When the thickness exceeds 0.8 μm, sufficient whiteness cannot be obtained, and projections are formed on the coated surface, which adversely affects the image quality.

In the present invention, it is preferable that the fine white pigment particles are uniformly dispersed in the reflective layer without forming an aggregate of the particles, and the size of the distribution is determined by the occupied area ratio of the fine particles projected to a unit area. (%) (Ri). The coefficient of variation of the occupied area ratio (%) is
The ratio s / of the standard deviation s of Ri to the average value (R) of Ri
It can be obtained by R. In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the white pigment is 0.1.
It is preferably 5 or less, more preferably 0.12 or less. Especially 0.08
The following is preferred.

The water-resistant resin of the reflective support used in the present invention is defined as having a water absorption (% by weight) of 0.5 or less, preferably 0.1% or less.
1 or less resin, for example, polyolefin such as polyethylene, polypropylene, polyethylene polymer, vinyl polymer and its copolymer (polystyrene, polyacrylate and its copolymer), and polyester (polyethylene terephthalate, polyethylene isophthalate, etc.)
And its copolymers. Particularly preferred are polyethylene and polyester. As the polyethylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and a blend of these polyethylenes can be used. The melt flow rate (hereinafter abbreviated as MFR) of these polyethylene resins before processing is shown in Table 1 of JISK7210.
1.2 g / 10 min to 12 g /
A range of 10 minutes is preferred. The MFR of the polyolefin resin before processing refers to the MFR of the resin before kneading a bluing agent and a white pigment.

As the polyester, a polyester synthesized by condensation polymerization from a dicarboxylic acid and a diol is preferable, and preferable dicarboxylic acids include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Preferred diols include ethylene glycol, butylene glycol, neopentyl glycol, triethylene glycol, butanediol, hexylene glycol, bisphenol A ethylene oxide adduct (2,2-bis (4- (2-hydroxyethyloxy)
Phenyl) propane), 1,4-dihydroxymethylcyclohexane and the like. Various polyesters obtained by condensation polymerization of these dicarboxylic acids alone or in mixtures with diols alone or in mixtures can be used. Among them, at least one of the dicarboxylic acids is preferably terephthalic acid. In addition, a mixture of terephthalic acid and isophthalic acid (molar ratio: 9: 1 to 2: 8) or a mixture of terephthalic acid and naphthalenedicarboxylic acid (molar ratio of 9: 1 to 2: 8) is also preferably used. As the diol, it is preferable to use ethylene glycol or a mixed diol containing ethylene glycol. The molecular weight of these polymers is preferably from 30,000 to 50,000.

It is also preferable to use a mixture of a plurality of polyesters having different compositions. Further, mixtures of these polyesters with other resins can also be preferably used. Other resins to be mixed include polyethylene, polyolefins such as polypropylene, polyethylene glycol, polyoxymethylene, polyethers such as polyoxypropylene, polyester-based polyurethane, polyether polyurethane, polycarbonate,
It can be widely selected as long as it is a resin extrudable at 270 to 350 ° C. such as polystyrene. These resins may be used alone or in combination of two or more. For example, 90% by weight of polyethylene terephthalate may be mixed with 6% by weight of polyethylene and 4% by weight of polypropylene. The mixing ratio of polyester and other resin varies depending on the type of resin to be mixed, but for polyolefins, the weight ratio of polyester / other resin = 1.
00/0 to 80/20 is appropriate. If it exceeds this range, the physical properties of the mixed resin are sharply reduced. In the case of resin other than polyolefin, polyester / other resin = 1 by weight ratio
It can be mixed in the range of 00/0 to 50/50.

The mixing ratio of the water-resistant resin to the white pigment is 98/2 to 30/70 (water-resistant resin / white pigment) by weight, preferably 95/5 to 50/50, particularly preferably 90/10. 60/40. 2% by weight of white pigment
If it is less than 70%, the contribution to the whiteness is insufficient. If it exceeds 70% by weight, the surface smoothness of the photographic support is insufficient, and a photographic support having excellent gloss is obtained. Can not. These water-resistant resin layers are 2 to 200
It is preferably coated on the substrate with a thickness of μm, more preferably 5 to 80 μm. If the thickness is more than 200 μm, the brittleness of the resin will be emphasized, causing problems such as cracking. If the thickness is less than 2 μm, the waterproofness, which is the original purpose of the coating, is impaired, and the whiteness and the surface smoothness cannot be simultaneously satisfied, and the physical properties become too soft, which is not preferable. The thickness of the resin or resin composition coated on the surface of the substrate other than the photosensitive layer application surface is 5 to 100.
μm is preferred, and more preferably 10 to 50 μm. If the thickness exceeds this range, the brittleness of the resin is emphasized, and problems such as cracking occur in physical properties. If the ratio is less than the above range, the waterproof property which is the original purpose of the coating is impaired and the physical properties are too soft, which is not preferable.

In the reflective support used in the present invention, the water-resistant resin coating layer on the photosensitive layer coating side may be a reflective support comprising two or more water-resistant resin coating layers having different white pigment contents. It may be more preferable from the viewpoints of cost, suitability for production of the support, and the like. In this case, among the water-resistant resin coating layers having different white pigment contents, the content of the white pigment of the water-resistant resin coating layer closest to the substrate is at least one of the water-resistant resin coating layers above the layer. It is preferably lower than the content of the white pigment. In a further preferred embodiment,
Among the water-resistant resin coating layers having different white pigment contents, a reflective support having the highest white pigment content of the water-resistant resin coating layer closest to the photosensitive layer, or a reflective resin having at least three reflective supports. Reflection having the highest white pigment content in any layer between the water-resistant resin coating layer closest to the photosensitive layer of the multilayer water-resistant resin layer and the water-resistant resin coating layer closest to the substrate. A support.

The content of the white pigment in each layer in the multilayer water-resistant resin layer is from 0% by weight to 70% by weight, preferably 0% by weight.
-50% by weight, more preferably 0-40% by weight. The content of the layer having the highest white pigment content in the multilayer water-resistant resin layer is 9% by weight to 70% by weight, preferably 15% by weight to 50% by weight, more preferably 20% by weight to 40% by weight. It is. If the white pigment content of the layer having the highest white pigment content is less than 9% by weight, the sharpness of the image is low, and if it exceeds 70% by weight, the melt-extruded film is cracked. The thickness of each layer of the multilayer water-resistant resin layer is preferably 0.5 μm to 50 μm. For example, 2
In the case of a multilayer water-resistant resin layer having a layer configuration, the thickness of each layer is 0.5
The thickness is preferably from 50 μm to 50 μm, and the combined total film thickness is preferably in the above range (2 to 200 μm).
In the case of a three-layer structure, the thickness of the uppermost layer is 0.5 μm to 10 μm.
m, the thickness of the intermediate layer is preferably 5 μm to 50 μm, and the thickness of the lower layer (the layer closest to the base) is preferably 0.5 to 10 μm. When the film thickness of the uppermost layer and the lowermost layer is 0.5 μm or less, the effect of the highly-filled white pigment in the intermediate layer is likely to cause die lip streaks. On the other hand, when the thickness of the uppermost layer, the lowermost layer, particularly the uppermost layer is 10 μm or more, the sharpness and the sharpness tend to be reduced.

The mixture of the water-resistant resin and the white pigment includes a metal salt of a higher fatty acid, ethyl higher fatty acid, amide higher fatty acid,
Using a higher fatty acid or the like as a dispersing aid, the resin is kneaded into the resin by a kneader such as a two-roll, three-roll, kneader, or Banbury mixer. The amount of the dispersing aid is generally about 0.5% by weight to 10% by weight based on the white pigment. An antioxidant can be contained in the resin layer, and the content is suitably 50 to 1000 ppm based on the resin.

It is preferred that the water-resistant resin layer contains a bluing agent. As the bluing agent, generally known ultramarine blue, cobalt blue, cobalt oxide phosphate, quinacridone pigments and the like and a mixture thereof are used.
The particle size of the bluing agent is not particularly limited, but the particle size of a commercially available bluing agent is usually about 0.3 μm to 10 μm.
When the water-resistant resin layer of the reflective support used in the present invention has a multilayer structure, the content of the bluing agent in the water-resistant resin layer, the content in the water-resistant resin layer of the uppermost layer, the content of the lower layer It is preferable to make the above. The preferred content of bluing agent is 0.2% to 0.5% by weight in the uppermost layer and 0 to 0.45% by weight in the lower layer. The bluing agent is kneaded into the water-resistant resin by a kneader such as a two-roll, three-roll, kneader, and Banbury mixer. At this time, a white pigment can be kneaded together,
In order to help disperse the bluing agent, a dispersing aid such as a low molecular weight water-resistant resin, a metal salt of a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, or a higher fatty acid can be used.

The method for forming the water-resistant resin layer in the present invention includes paper as a running substrate, base paper such as synthetic paper, polyester film such as polyethylene terephthalate and polybutylene terephthalate, cellulose triacetate film, polystyrene film and polypropylene film. Pellets containing the white pigment and / or bluing agent melted by heating and melted on a plastic film such as a polyolefin film, etc. and, if necessary, diluted with a heat-resistant resin and melted. Or a method such as a lamination method using a multi-layer extrusion die of a foot block type, a multi-manifold type, or a multi-slot type. The shape of the multilayer extrusion die is generally a T die, a coat hanger die, or the like, and is not particularly limited. The exit temperature at the time of hot melt extrusion of water resistant resin is usually 270 ° C.
To 350 ° C, particularly preferably 300 ° C to 330 ° C. Further, it is preferable to perform an activation treatment such as a corona discharge treatment, a flame treatment, and a glow discharge treatment on the substrate before coating the resin on the substrate.

The surface of the uppermost layer of the water-resistant resin layer on the side on which the emulsion is coated can be provided with a glossy surface, or a fine surface, matte surface or silk surface described in JP-A-55-26507. The back surface can be provided with a matte surface or the like. Preferably, the surface of the water-resistant resin is subjected to an activation treatment such as a corona discharge treatment, a flame treatment, or a plasma treatment. After the activation treatment, a subbing treatment as described in JP-A-61-84643 is performed. Is preferred. It is also preferable to coat an undercoat liquid containing the compound represented by the general formula [U] on the surface of the water-resistant resin.

[0048]

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The coating amount of the compound represented by the general formula [U] is preferably 0.1 mg / m ² or more, more preferably 1 mg / m ^2.
As described above, the content is most preferably 3 mg / m ² or more. The more the content is, the more the adhesion can be strengthened. Further, it is preferable to add alcohols such as methanol in order to improve the suitability of applying the undercoat liquid to the resin surface. In this case, the proportion of alcohols is preferably 20% by weight or more, more preferably 40% by weight or more, and most preferably 60% by weight or more. Further, in order to further improve the coating suitability, anionic, cationic, amphoteric, nonionic, fluorocarbon,
It is preferable to use various surfactants such as an organic silicon-based surfactant.

It is preferable to add a water-soluble polymer such as gelatin in order to obtain a good undercoating surface. Considering the stability of the compound of the general formula [U], the pH of the solution is
4 to pH 11 are preferable, and pH 5 to p are more preferable.
H10. It is more preferable that the surface of the water-resistant resin is subjected to the above-mentioned surface activation treatment before the undercoat liquid is applied. In applying the undercoating liquid, a gravure coater, a bar coater, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a doctor coating method, an extrusion coating method, and the like, by a generally well-known coating method. Can be applied. The drying speed of the coating is preferably 30C to 100C, more preferably 50C to 100C, and most preferably 70C to 100C. The upper limit is determined by the heat resistance of the resin, and the lower limit is determined by the productivity efficiency.

The substrate used for the reflective support of the present invention comprises:
Natural pulp paper made from natural pulp as a main raw material, mixed paper made from natural pulp and synthetic fiber, synthetic fiber paper containing synthetic fiber as a main component, so-called synthetic paper made from synthetic resin films such as polystyrene and polypropylene And plastic films such as polyester films such as polyethylene terephthalate and polybutylene terephthalate, and polyolefin films such as cellulose triacetate film, polystyrene film, and polypropylene film. (Hereinafter simply referred to as base paper) is particularly preferably and advantageously used. Additives to base paper include fillers such as clay, talc, calcium carbonate, urea resin fine particles, rosin, alkyl ketene dimer, sizing agents such as higher fatty acids, epoxidized fatty acid amides, paraffin wax, alkenyl succinic acid, starch, polyamide What added paper strength enhancers, such as polyamine epichlorohydrin and polyacrylamide, and fixing agents, such as a sulfate band and a cationic polymer, are used. In addition, if necessary, a dye, a fluorescent dye, a slime control agent, an antifoaming agent, and the like are added.
Further, the following softeners can be added as required.

Regarding the softening agent, for example, New Paper Processing Handbook (edited by Paper Pharmaceutical Times Co .; published in 1980), pages 554-5.
It is described on page 55. Particularly, those having a molecular weight of 200 or more are preferable. That is, having a hydrophobic group having 10 or more carbon atoms,
Further, it has an amine salt or a quaternary ammonium salt which self-fixes to cellulose. Specifically, a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine, a reaction product of a higher fatty acid and a polyalkylene polyamine, a reaction product of a urethane alcohol and an alkylating agent, a quaternary ammonium salt of a higher fatty acid, and the like Among them, a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine, and a reaction product of a urethane alcohol and an alkylating agent are particularly preferable.

The surface of the pulp can be treated with a film-forming polymer such as gelatin, starch, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, or a modified product of polyvinyl alcohol. In this case, examples of the modified polyvinyl alcohol include carboxyl group-modified products, silanol-modified products, and copolymers with acrylamide. The coating amount of the film-forming polymer in the case of surface sizing treatment with a film-forming ^{polymer, 0.1g / m 2 ~5.0g / m} 2, is preferably 0.5g / m ² ~2.0g / m ² . Further, an antistatic agent, a fluorescent whitening agent, a pigment, an antifoaming agent and the like can be added to the film-forming polymer at this time, if necessary.

The base paper is prepared by making a pulp slurry containing the above-described pulp and, if necessary, a filler, a sizing agent, a paper reinforcing agent, a fixing agent, and the like, using a paper machine such as a fourdrinier paper machine. It is manufactured by winding. The surface sizing is performed before or after the drying,
Further, it is preferable that a calendering process is performed after the drying and winding. This calendering treatment can be performed before or after the surface sizing treatment when the surface sizing treatment is performed after drying. However, it is preferable to perform the calendering treatment in the final finishing step in which various treatments have been performed. . In the calendering process, known metal rolls and elastic rolls used for ordinary paper production are used.

The thickness of the base paper of the support used in the present invention is not particularly limited, but the basis weight is 50 g.
/ M ^{2 to} 250 g / m ² , and the thickness is 50 μm to 25
0 μm is desirable.

The support used in the present invention has antistatic,
Various back coat layers can be applied to prevent curl and the like. For the back coat layer, use JP-B No. 52-180.
No. 20, JP-B-57-9059, JP-B-57-539
No. 40, JP-B-58-56859, JP-A-59-21
No. 4849, inorganic antistatic agents or organic antistatic agents described or exemplified in JP-A-58-184144 and the like.
A hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like can be appropriately combined and contained.

As the photographic support, those having excellent smoothness on the surface on which the photosensitive layer is coated are preferred. This "smoothness"
Expressed as a measure of the surface roughness of the support. The surface roughness of the support of the present invention will be described. As the surface roughness, the center line average surface roughness is used as this scale. The center line average surface roughness is defined as follows. From the roughness surface, a portion of the area SM is extracted on the center plane, the orthogonal coordinate axes, the X axis, and the Y axis are set on the center line of the extracted portion, and the axis orthogonal to the center line is set as the Z axis. Is defined as the center line average surface roughness (SRa),
Expressed in μm.

[0058]

(Equation 1)

The values of the center line average surface roughness and the height of the protrusion from the center line can be determined, for example, by using a three-dimensional surface roughness measuring instrument (SE-30H) manufactured by Kosaka Laboratory Co., Ltd. It can be obtained by measuring an area of 5 mm ^{2 with} a needle at a cutoff value of 0.8 mm, a magnification of 20 times in the horizontal direction, and a magnification of 2000 times in the height direction. Further, the feeding speed of the measuring needle at this time is preferably about 0.5 mm / sec. The support obtained by this measurement preferably has a value of 0.15 μm or less, more preferably 0.10 μm or less. By using a support having such surface roughness (smoothness),
A color print having a surface with excellent smoothness can be obtained.

The constitution of the photographic material of the present invention can be applied to various silver halide photographic materials using a reflective support. For example, a color light-sensitive material using the present invention
It can be constituted by coating at least one layer of a yellow-forming silver halide emulsion layer, a magenta-forming silver halide emulsion layer, and a cyan-forming silver halide emulsion layer on a reflective support. In a general color photographic paper, the color reproduction by the subtractive color method can be performed by including a color coupler that forms a dye having a complementary color with the light to which the silver halide emulsion is exposed. In general color photographic paper, silver halide emulsion grains are spectrally sensitized by blue-sensitive, green-sensitive, and red-sensitive spectral sensitizing dyes in the order of the above-described color-forming layers, respectively. And can be constituted by coating. In a reversal color paper, silver halide emulsion grains are spectrally sensitized by a blue-sensitive, green-sensitive, and red-sensitive spectral sensitizing dye in the order of the above-described color forming layer, and a red-sensitive layer and a green-sensitive layer are formed on a support. And a blue-sensitive layer in this order. However, the order may be different.
In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the silver halide grains having the largest average grain size be the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer should be the magenta coloring photosensitive layer. It may be preferable to do so. The photosensitive layer and the color hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer may be used. Further, each of these photosensitive layers may be provided in a plural number. Further, between the photosensitive layer and the support of these photosensitive materials, between the photosensitive layer and the photosensitive layer, and on the upper layer of the photosensitive layer (the layer farthest from the support), color mixing prevention, irradiation / halation prevention, an optical filter, A non-photosensitive layer is provided for various purposes such as protection of the photosensitive layer. In the case of black-and-white printing paper, the support is provided with at least one silver halide emulsion layer spectrally sensitized or not spectrally sensitized in the panchromatic or ortho region.

In the silver halide photographic light-sensitive material of the present invention, the silver halide grains include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and the like. Any of these can be used, but a silver chlorobromide emulsion is preferred for the purpose of speeding up and simplifying the processing. As these silver chlorobromide emulsions, silver chloride, silver chlorobromide or silver chloroiodobromide grains having 95 mol% or more of silver chloride can be preferably used. In particular, in order to speed up the development processing time, those made of silver chlorobromide or silver chloride substantially free of silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of increasing the high illuminance sensitivity, increasing the spectral sensitization sensitivity, or increasing the aging stability of the light-sensitive material, the emulsion surface described in JP-A-3-84545 is coated with 0.01-3. Mol%
In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

The high silver chloride emulsion used in the present invention preferably has a structure in which the silver bromide localized phase is in the form of a layer or a non-layer as described above inside and / or on the surface of silver halide grains. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. The silver bromide content of the silver bromide localized phase is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis”, Maruzen) and the like. can do. And these localized phases are inside the particle, at the edge of the particle surface,
Although it can be on a corner or on a plane, one preferred example is one that is epitaxially grown at the corner of a grain. It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, a substantially pure silver chloride emulsion having a silver chloride content of 98 to 100 mol% is also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is calculated) is 0.1. 1μ to 2μ is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion has a regular (regular) shape such as cubic, tetrahedral or octahedral.
One having an lar) crystal form, one having an irregular (for example, spherical or plate-like) crystal form, or one having a complex 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 above-mentioned regular crystal form are contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more. In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected areas exceed 50% of all grains can be preferably used.

The silver chloro (bromo) chloride emulsion used in the present invention is P.Gl
afkides, Chimie et Phisique Photographique (Paul
Montel, 1967), Photographi by GFDuffin
c Emulsion Chemistry (Focal Press, 1966
Year), Making and Coating Phot by VLZelikman et al
It can be prepared using a method described in, for example, ographic 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. A 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 in which pAg in a liquid phase in which silver halide is formed is kept constant, 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 localized phase of silver halide grains of the present invention or the substrate thereof preferably contains a foreign metal ion or a complex ion thereof. Preferred metals are selected from metal ions or metal complexes belonging to Groups VIII and IIb of the periodic table, lead ions and thallium ions. Ion selected from iridium, rhodium, iron, etc. or its complex ion for the localized phase, and metal ion selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, etc. for the substrate Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. A plurality of these metals may be used. In particular, the iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are added to a gelatin aqueous solution serving as a dispersion medium when silver halide grains are formed.
The silver halide grains of the present invention may be dissolved in an aqueous halide solution, an aqueous silver salt solution or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. Include in the localized phase and / or other particle parts (substrates). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on where the metal ions are contained in the particles.

The silver halide emulsion used in the present invention is:
Usually, chemical sensitization and spectral sensitization are applied. Chemical sensitization includes chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization typified by addition of an unstable sulfur compound, selenium sensitization by a selenide compound, tellurium sensitization by a tellurium compound). Sensitization), noble metal sensitization represented by gold sensitization, reduction sensitization or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The effect of the constitution of the light-sensitive material of the present invention is more remarkable than when a gold-sensitized high silver chloride emulsion is used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide emulsion used in the present invention may contain various compounds or their precursors for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are disclosed in the above-mentioned JP-A-62-2.
Those described on page 39 to page 72 of JP-A-15272 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

The spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, FM Harmer's Heterocyclic compounds-Cyanine
dyes and related compounds (John Wiley & Sons New
York, London, 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used. Particularly, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a high silver chloride content, JP-A No. 3-12 / 1991
The spectral sensitizing dye described in No. 3340 is very preferable from the viewpoints of stability, strength of adsorption, temperature dependency of exposure and the like.

For efficient spectral sensitization in the infrared region of the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15 Lower left column, EP-0,420,011
No. 4, page 21 line to page 6, line 54, EP-0,420,012
No. 4, page 12, line 10 to page 33, EP-0,443,46
No. 6, US Pat. No. 4,975,362 are preferably used.

In order to incorporate these spectral sensitizing dyes into a silver halide emulsion, they may be directly dispersed in the emulsion, or may be dispersed in water, methanol, ethanol, propanol, methylcellosolve, 2,2, It may be dissolved in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent and added to the emulsion. In addition, Tokiko Sho 44-2
No. 3389, JP-B-44-27555, JP-B-57-
An aqueous solution or a colloidal dispersion obtained by coexisting an acid or a base as described in 22089 or the like or an aqueous solution or a colloidal dispersion obtained by coexisting a surfactant as described in US Pat. No. 3,822,135 or US Pat. It may be added to the emulsion. After dissolving in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion. JP-A-53-102733, JP-A-58-105141
The dispersion may be directly dispersed in a hydrophilic colloid as described in the above item, and the dispersion may be added to the emulsion. The timing of addition to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful. In other words, before the silver halide emulsion is formed, during the grain formation, immediately after the grain formation, before entering the washing step, before the chemical sensitization, during the chemical sensitization, and immediately after the chemical sensitization until the emulsion is cooled and solidified, during the preparation of the coating solution. , You can choose from. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-628969 and JP-A-4222566, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before completion of precipitation of silver halide grains to start spectral sensitization. It is also possible to add the spectral sensitizing dye separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add part prior to chemical sensitization and to add the remainder after chemical sensitization. It is possible at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Among them, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 to 0.5 mol per mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ^−3.
Range of moles. In the present invention, particularly when a sensitizing dye having spectral sensitization sensitivity from the red region to the infrared region is used, the compounds described in JP-A-2-157747, page 13, lower right column to page 22, lower right column may be used in combination. preferable. By using these compounds, the preservability of the photographic material, the stability of the processing, and the supersensitizing effect can be specifically enhanced. Among them, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of from 0.5 × 10 ^-5 mol to 5.0 per mol of silver halide.
× 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol to 5.0.
× 10 ^-3 mol is used, and 0.1 to 10,000 times, preferably 0.5 to 500 times per mol of the sensitizing dye.
There is an advantageous usage in the 0-fold range.

The light-sensitive material of the present invention can be used not only in a printing system using a normal negative printer but also in a nonlinear manner with a gas laser, a light-emitting diode, a semiconductor laser, a solid-state laser using a semiconductor laser as an excitation light source. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) combined with an optical crystal. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) combining a solid-state laser and a nonlinear optical crystal. Particularly, in order to design a device which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The maximum spectral sensitivity of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a non-linear 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 can be provided in the usual three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable, and compact, at least two layers preferably have a spectral sensitivity maximum at 670 nm or more. This is because the currently available, inexpensive and stable III-V semiconductor laser has an emission wavelength range only from the red to the infrared region. However, at the laboratory level, oscillations of II-VI group semiconductor lasers in the green and blue regions have been confirmed, and if semiconductor laser manufacturing technology develops, these semiconductor lasers can be used stably at low cost. It is fully anticipated. In such a case, it is less necessary that at least two layers have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time during which the silver halide in the photosensitive material is exposed is the time required to expose a small area. As the minute area, a minimum unit for controlling the amount of light from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of the pixel. The size of this pixel depends on the pixel density, and is a practical range of 50 to 2000 dpi. The exposure time is preferably defined as ^10-4 seconds or less, and more preferably ^10-6 seconds or less, when the pixel density is defined as 400 dpi and the pixel size is defined as the exposure time.

In the photographic material according to the present invention, it is preferable to color the hydrophilic colloid layer for the purpose of preventing irradiation and halation and improving safelight safety and the like. The compound of the present invention can be used as the coloring substance, and is preferably used in combination with the object of improving pressure resistance. As water-soluble dyes that can be used in combination with the compounds of the present invention, there are dyes (in particular oxonol dyes and cyanine dyes) which can be decolorized by treatment, described on pages 27 to 76 of EP 0 337 490 A2. Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. Dyes which can be used without deteriorating color separation are disclosed in European Patent EP05.
There are water-soluble dyes described in Japanese Patent Application No. 39978A1, Japanese Patent Application No. 3-310189, and Japanese Patent Application No. 3-310139, and it may be preferable to use these in combination. In such coloring, the coloring material diffuses regardless of the position of the coloring material addition layer and extends over the entire photosensitive material constituting layer. This coloring density is 0.2 or more, preferably 0.3 or more, more preferably 0.5 or more at the maximum wavelength of the light amount of the light source to be exposed. In particular, the concentration of the absorption maximum in the colored region colored using the compound of the present invention is preferably 0.3 or more.

In the present invention, a colored layer that can be decolorized by treatment in place of the above water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing 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. It is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. The optical reflection density of these colored layers is within the wavelength range used for exposure (4 in normal printer exposure).
It is preferable that the optical density value at the wavelength having the highest optical density in the visible light region from 00 nm to 700 nm, or the wavelength of the scanning exposure light source used in the case of scanning exposure) is 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, particularly preferably 0.8 or more and 2.0 or less.

For forming a colored layer, a conventionally known method can be applied. For example, Japanese Patent Application Laid-Open No. 2-282244-3
Dyes described from the upper right column of the page to page 8 and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method in which solid fine particle dispersion is contained in a hydrophilic colloid layer, a method in which an anionic dye is mordanted to a cationic polymer, and a dye is halogenated. Examples thereof include a method of adsorbing on fine particles such as silver and fixing in a layer, and a method of using colloidal silver as described in JP-A-1-239544. As a method of dispersing a fine powder of a dye in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in 2-30824
No. 4, pp. 4-13. Also, for example,
A method of mordanting an anionic dye into a cationic polymer is described in JP-A-2-84637, pp. 18-26. The preparation method of colloidal silver as a light absorber is described in U.S. Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Also, Japanese Patent Application Laid-Open No. 5-134
It is also preferable to use thin tabular colloidal silver particles having a thickness of up to 20 nm described in JP-A-358. Among these methods, a method of incorporating a fine powder dye, a method of using colloidal silver, and the like are preferable.

As a binder or protective colloid that can be used in the light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. Preferred gelatin has a calcium content of 800 ppm
It is preferable to use a low calcium gelatin of 200 ppm or less, more preferably 200 ppm or less. In order to prevent various fungi and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a fungicide as described in JP-A-63-271247.

When exposing the light-sensitive material of the present invention to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to conventional color development processing. In the case of the color light-sensitive material of the present invention, it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is adjusted to about 6.
It is preferably 5 or less, more preferably about 6 or less.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods applied for processing this light-sensitive material As the additives for the treatment, those described in the following patent publications, in particular, those described in European Patent EP 0,355,660 A2 (JP-A-2-139544) are preferably used.

[0083]

[Table 15]

[0084]

[Table 16]

[0085]

[Table 17]

[0086]

[Table 18]

[0087]

[Table 19]

Cyan, magenta, or yellow couplers impregnate a rollable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents listed in the preceding table. It is preferable to emulsify or disperse the polymer in a water-insoluble and organic solvent-soluble manner in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and International Publication WO88 / 007.
Homopolymers or copolymers described on pages 12 to 30 of the specification of JP-A No. 23 are mentioned. More preferably, methacrylate-based or acrylamide-based polymers, particularly acrylamide-based polymers, are used in view of color image stability and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0277589 A2 together with a coupler. In particular, a combination with a pyrazoloazole coupler or a pyrrolotriazole coupler is preferable. That is, it is chemically bonded to the aromatic amine-based developing agent remaining after the color development processing,
Chemically bonding to an oxidized compound of an aromatic amine-based color developing agent remaining after the color developing process and / or a compound described in the above-mentioned patent specification which produces a chemically inert and substantially colorless compound; It is possible to simultaneously or solely use the compounds described in the above-mentioned patent specifications which produce an inert and substantially colorless compound, for example, the reaction of a coupler with a color developing agent remaining in a film or an oxidized form thereof upon storage after processing and a coupler. From the viewpoint of preventing the occurrence of stains and other side effects due to the formation of color-forming dyes.

Further, as the cyan coupler, JP-A-2-
In addition to the diphenylimidazole cyan coupler described in JP-A-33144, European Patent EP 0 333 185 A2
3-hydroxypyridine-based cyan couplers (in particular, couplers (4)
(2) 4-equivalent coupler having a chlorine leaving group to give a 2-equivalent coupler, and couplers (6) and (9) are particularly preferred)
And cyclic active methylene cyan couplers described in JP-A-64-32260 (particularly preferred are coupler examples 3, 8, and 34 listed as specific examples), and pyrrolo described in European Patent EP 0 456 226 A1. Pyrazole type cyan couplers, European Patent EP 048490
No. 9, pyrroleimidazole type cyan couplers described in EP 0 488 248 and EP 04911.
Use of a pyrrolotriazole type cyan coupler described in JP-A-97A1 is preferred. Among them, use of a pyrrolotriazole type cyan coupler is particularly preferred.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969
No. A1, an acylacetamide-type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group, a malondianilide-type yellow coupler having a cyclic structure described in EP 0 482 552 A1, described in US Pat. An acylacetamide type yellow coupler having a dioxane structure described in JP-A-118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides forms an indoline ring. These couplers can be used alone or in combination.

As the magenta coupler used in the present invention, 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known documents in the above table are used.
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245 in terms of color development and the like. Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-65246, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254, and Europe Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position described in A or 294,785A.

The processing method of the color light-sensitive material of the present invention includes:
Other than the methods described in the above table, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, lines 17 to 18 The processing material and processing method described in the lower right column, line 20 are preferred.

Example 1 (Preparation of Support) A low-density polyethylene having an MRF of 3
Titanium dioxide was added at the ratios shown in Table 20.
Zinc phosphate is added at a ratio of 3.0% by weight to the amount of titanium dioxide.
Together with ultramarine (DV-1 manufactured by Daiichi Kasei Kogyo Co., Ltd.)
Into a pellet after kneading in a Banbury mixer.
To form a master batch. Titanium dioxide is electron microscopic
Aluminum oxide hydrated with a mirror at 0.15 μm-0.35 μm
Al coating amount_TwoO _ThreeConversion to titanium dioxide
0.75% by weight. 170 g / m basis weight^Twoof
After a corona discharge treatment of 10 kVA on the paper substrate,
Melting extrusion at 320 ° C using a printing die
And a polyethylene laminate layer with the thickness shown in Table 20
I did. The surface of this polyethylene layer is subjected to glow discharge treatment.
Was.

[0095]

[Table 20]

(Preparation of Photosensitive Material 100) Various photographic constituent layers were applied on the reflective support (A) to prepare a multilayer color printing paper (100) having the following layer constitution. The coating solution was prepared as follows.

Preparation of coating solution for first layer 153.0 g of yellow coupler (ExY), 15.0 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-2)
7.5 g, 16.0 g of color image stabilizer (Cpd-3), 25 g of solvent (Solv-1), 25 g of solvent (Solv-2)
g and ethyl acetate (180 cc).
Emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% aqueous gelatin solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid. On the other hand, silver chlorobromide emulsion A-1 (cubic, 3: 7 mixture of large size emulsion having an average grain size of 0.88 μm and small size emulsion having an average grain size of 0.70 μm (silver molar ratio). 0.08 and 0.10, respectively, 0.3 mm of silver bromide for each size emulsion
Molar% was locally contained on a part of the surface of the silver chloride base particles.
The inside of the grains and the localized phase of silver bromide contained 0.1 mg of potassium hexachloroiridate (IV) in total and 1.0 mg of potassium ferrocyanide in total. ) Was prepared. This emulsion contains the following blue-sensitive sensitizing dyes A and
B was added to the large-size emulsion and the small-size emulsion, respectively, at 2.0 × 10 ^-4 mol and 2.5 × 10 ^-4 mol per mol of silver, and then a sulfur sensitizer and a gold sensitizer were decomposed into nucleic acids. Was added in the presence of a substance to perform optimal chemical sensitization. The above emulsified dispersion A and this silver chlorobromide emulsion A-1 were mixed and dissolved to prepare a coating solution for the first layer so as to have 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. Also, Cpd-14 and C
The total amount of pd-15 was 25.0 mg / m ² and 50.0 mg, respectively.
mg / m ² . The silver chlorobromide emulsion of each photosensitive emulsion layer was adjusted in size by the same preparation method as the silver chlorobromide emulsion A-1, and the following spectral sensitizing dyes were used. Blue-sensitive emulsion layer

[0099]

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(Per mol of silver halide: 2.0 × 10 ⁻⁴ mol for large-size emulsions and 2.5 × 10 ⁻⁴ mol for small-size emulsions, respectively) Emulsion layer

[0101]

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(Per mol of silver halide, 4.0 × 10 ⁻⁴ mol for large-size emulsion, and 5.6 × 10 ⁻⁴ mol for small-size emulsion) and

[0103]

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(Per mol of silver halide: 7.0 × 10 ⁻⁵ mol for large-size emulsion, 1.0 × 10 ⁻⁴ mol for small-size emulsion) Red-sensitive emulsion layer

[0105]

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(Large size emulsion per mole of silver halide
0.9 × 10^-FourFor moles and small size emulsions
Then, each 1.1 × 10^-FourMol) In the red-sensitive emulsion layer, the following compound was further added to silver halide 1
2.6 × 10 per mole ^-3Mole was added.

[0107]

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A blue-sensitive emulsion layer, a green-sensitive emulsion, a red-sensitive emulsion
1- (5-methylureidophenyl)
) -5-mercaptotetrazole with halogen
8.5 × 10 per mol of silver halide^-FourMol, 3.0 × 10^-3
Mol, 2.5 × 10^-FourMole was added. Blue-sensitive emulsion layer
And green sensitive emulsion layer, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene is halogenated
1 × 10 per mole of silver halide ^-FourMole, 2 × 10^-FourMoles
Added. (Layer Structure) The composition of each layer is shown below. The number is the coating amount (g
/ M^Two). For silver halide emulsions, the coating amount is expressed in terms of silver.
You. Support (A) The resin layer on the first layer side contains a bluish dye (ultramarine).

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A-1 0.27 Gelatin 1.22 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image Stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13 Second layer (color mixture prevention layer) Gelatin 0 .90 Color mixture inhibitor (Cpd-4) 0.06 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Solvent (Solv-7) 0.03

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B-1 (cubic, 1: 3 mixture of large-sized emulsion having an average grain size of 0.55 μm and small-sized emulsion having a size of 0.39 μm (silver) The variation coefficients of the grain size distribution are 0.08 and 0.06, respectively, and 0.8 mol% of silver bromide is locally contained in a part of the grain surface based on silver chloride in each size emulsion. Further, 0.1 mg of potassium hexachloroiridate (IV) and 1 mg of potassium ferrocyanide were contained per mole of silver in the inside of the grains and in the above-mentioned localized phase of silver bromide.) 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.15 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer Agent (Cpd-7) 0.01 Agent (Cpd-8) 0.08 solvent (Solv-3) 0.50 solvent (Solv-4) 0.15 solvent (Solv-5) 0.15

Fourth layer (color mixture prevention layer) Gelatin 0.70 Color mixture prevention agent (Cpd-4) 0.04 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C-1 (cubic, 1: 4 mixture of a large-size emulsion having an average grain size of 0.50 μm and a small-size emulsion of 0.41 μm (silver) The variation coefficients of the grain size distributions are 0.09 and 0.11, respectively. Each size emulsion contains 0.8 mol% of silver bromide localized on a part of the surface of the grains based on silver chloride. Further, 0.3 mg of potassium hexachloroiridate (IV) and 1.5 mg of potassium ferrocyanide were contained per mole of silver in the inside of the grains and the localized phase of silver bromide.) 18 gelatin 0.80 cyan coupler -(ExC) 0.33 UV absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) ) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0 0.01 solvent (Solv-1) 0.01 solvent (Solv-6) 0.22

Sixth layer (UV absorbing layer) Gelatin 0.48 UV absorbing agent (UV-1) 0.38 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-12) 0.15 Seventh layer (protective layer) Gelatin 1.10 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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As shown in Table 21, samples 101 to 1 similar to sample 100 except that the type of the support was changed and the additive compound was added to the sample 100 prepared as described above.
69 were produced. The added compound was added to the second layer and the fourth layer (color mixture prevention layer) so that the total coating amount was 4 × 10 ⁻⁵ mol / m ² . In addition, it was confirmed from the cross-sectional photograph that these additive compounds were diffused during the application and remained almost uniformly in all the layers, not limited to the additive layer.

[0120]

[Table 21]

[0121]

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The prepared photosensitive material was evaluated by the following scratch test in order to examine the degree of pressure fogging using a sample after the hardening reaction was completed. (Scratch test method) A 200 g load is applied to an acrylic plate on which a nylon scourer piece (1 cm x 3 cm) is stretched to be fixed. A photosensitive material cut into 3 cm x 15 cm is sandwiched between the acrylic plates (so that the surface coated with the photosensitive layer is in contact with a nylon scourer), and is pulled in a dark room at a constant speed in a direction perpendicular to the load to apply a nylon scrubber to the photosensitive material surface. Give a scratch. This scratching experiment was performed in a room at a constant condition of 25 ° C. and 55% RH.

The scratched sample was developed using the following processing steps. The obtained sample was visually evaluated for the degree of yellow fogging caused by this scratching. [Evaluation criteria: ○; almost no scratching is observed. Δ: Scratching is slightly observed. ×: scratching is observed.
XX: Scratching was observed on the entire surface, not practical. ]
Table 22 shows the obtained results.

[0124]

[Table 22]

For the purpose of evaluating the effect of the support on the sharpness of the light-sensitive material,
Using a light source of a sensitometer (manufactured by Fuji Photo Film Co., Ltd.) and light passing through a vapor-deposition interference filter of 470 nm, an optical wedge having a rectangular pattern of various frequencies is contact-exposed to the photosensitive material to obtain a yellow color resolution. Was. As an index of the resolution, the CTF value (frequency 0, that is, the density difference between the high-density portion and the low-density portion when the high-light portion and the low-light portion are continuously exposed over a very large area without repeating the rectangular pattern) ΔD _O and frequency C of rectangular pattern
(Density / mm) Ratio of similar density difference ΔD _C : ΔD _C /
The frequency C (lines / mm) at which ΔD _O ) was 0.5 was determined.
The results obtained are shown in Table 22 at the same time. (The larger the value of C, the higher the resolution.) If the value of C is about 10 or more, a photosensitive material with high sharpness can be provided.

Processing Step Temperature Time Replenisher * Tank capacity Color development 35 ° C 45 seconds 161 ml 10 liter Bleaching and fixing 30-35 ° C 45 seconds 215 10 liter Rinse 30-35 ° C 20 seconds-5 liter Rinse 30-35 ° C 20 seconds - 5 liters rinse 30 to 35 ° C. 20 seconds 350 5 liters drying 70 to 80 ° C. 60 seconds * replenishment rate is per photosensitive material 1 m ² (rinse was 3 tank countercurrent system to →)

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 800ml 800ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5g 2.0g Potassium bromide 0.015g-Triethanolamine 8.0g 12.0g Sodium chloride 1.4g-Potassium carbonate 25 g 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N -Di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Fluorescent brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g Add water 1000 ml 1000 ml pH (25 ° C.) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water is added. PH 1000 (25 ° C) 6.0

Rinse solution (tank solution and replenisher are the same) Deionized water (Calcium and magnesium are each 3 pp
m or less)

The following can be understood from the obtained results. Samples 100, 110, 1 having supports A and E having a water-resistant resin coating layer in which the amount of titanium oxide used is less than 2.0 g / m ²
In No. 20 and Samples 104, 114 and 124, the problem of scratching does not occur even if the compound of the present invention is not used, but the problem is that the sharpness is low. By using a support having a water-resistant resin coating layer containing at least 2.0 g / m ^{2 of} titanium oxide, a photosensitive material having excellent sharpness can be provided, but at the same time, fogging due to scratching increases. (Samples 102, 112, 122, etc.). It can also be seen that the extent of this fogging worsens as the amount of titanium oxide used increases (samples 103, 113, 123, etc.). On the other hand, it can be seen that the use of the compound of the present invention can suppress this scratching, provide a photosensitive material having excellent sharpness and improved scratching (samples 131 , 141 , and 1).
61 etc.). Example 2 (Production of Support) Polyester (intrinsic viscosity = 6.5) synthesized by condensation polymerization from dicarboxylic acid composition and ethylene glycol and titanium oxide (titanium industry) shown in Table 23 on the surface of a base paper having a thickness of 180 μm. KA-10) was melt-mixed at 300 ° C. with a twin screw extruder, and extruded from a T-die to form a laminate layer having a thickness of 30 μm. On the other side, melt-extrude the calcium carbonate-containing resin composition at 300 ° C.
A laminate layer having a thickness of 0 μm was formed. After applying a corona discharge treatment to the resin surface on the side on which the emulsion of the reflective support on which the laminate is formed is applied, a coating solution having the following composition is applied at 5 cc / m ^2.
And dried at 80 ° C. for 2 minutes to obtain a photographic support and K to R. [Undercoat Formulation] Compound EXU1 0.2 g compound ExU2 0.001g H ₂ O 35cc methanol 65cc gelatin 2 g pH 9.5

[0131]

[Table 23]

[0132]

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[0133]

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(Preparation and Evaluation of Photosensitive Material) A photosensitive material 200 in which a photosensitive layer similar to that of the photosensitive material 100 of Example 1 was provided on the reflective support K was prepared. To this photosensitive material 200, as shown in Table 24, except that the type of the support was changed and an additive compound was added,
63 were produced. The added compound was added to the second layer and the fourth layer (color mixture prevention layer) so that the total coating amount was 4 × 10 ⁻⁵ mol / m ² . In addition, it was confirmed from the cross-sectional photograph that these additive compounds diffused during coating and remained almost uniformly in all the layers, not limited to the additive layer.

[0135]

[Table 24]

The same evaluation as in Example 1 was performed on the obtained sample. For the purpose of evaluating the effect of the support on the sharpness of the light-sensitive material, the same CTF evaluation as in Example 1 was performed on the light-sensitive materials 201 to 207. Table 2 shows the obtained results.
It is shown in FIG.

[0137]

[Table 25]

From the results obtained, it is possible to provide a photosensitive material having excellent sharpness by using a support having a water-resistant resin coating layer containing titanium oxide in an amount of 2.0 g / m ² or more. However, at the same time, the cover due to scratching increases. It can also be seen that the extent of this fogging worsens as the amount of titanium oxide used increases. On the other hand, it can be seen that the use of the compound of the present invention can provide a photosensitive material which suppresses the scratching, has excellent sharpness, and has improved scratching.

Example 3 Photosensitive materials 100 to 169, 2 prepared in Examples 1 and 2
The second, third and fourth layers of Nos. 00 to 263 were changed to the compositions shown below, and the following dyes were used as irradiation prevention dyes. And the actual anti-irradiation effect of the light-sensitive material is the sum of the anti-irradiation dye and the compound of the present invention.) The same light-sensitive material 100 as each light-sensitive material '~ 169', 200 '~ 26
3 ′ was prepared. Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-A) 0.04 Color mixture prevention agent (Cpd-B) 0.04 Solvent (Solv-2) 0.16 Solvent (Solv-3) 0 .08

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B-1 0.13 Gelatin 1.24 Magenta coupler (MA) 0.26 Color image stabilizer (Cpd-8) 0.03 colors Image stabilizer (Cpd-5) 0.04 Color image stabilizer (Cpd-6) 0.02 Color image stabilizer (Cpd-2) 0.02 Solvent (Solv-8) 0.30 Solvent (Solv-9) 0.15

Fourth layer (color mixture prevention layer) Gelatin 0.70 Color mixture inhibitor (Cpd-A) 0.03 Color mixture inhibitor (Cpd-B) 0.03 Solvent (Solv-2) 0.11 Solvent (Solv-A) 3) 0.06 Solvent (Solv-10) 0.02

[0142]

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[0143]

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The obtained photosensitive material was evaluated in the same manner as in Example 1. The results obtained are shown in Example 1.
The effect was remarkable in the configuration of the present invention.

Example 4 Using a color negative film (a) in which the support is triacetyl cellulose and a color negative film (b) in which the support is made of polyethylene terephthalate and polyethylene naphthalate, frames of the same scene were taken. The photosensitive materials prepared in Examples 1 and 2 were printed using an automatic printer to evaluate the sharpness of the present invention. The obtained results were such that the larger the value of the sharpness evaluation scale C (book / mm) obtained in Examples 1 and 2, the better the sharpness in practical printing. Furthermore, when the color negative film (b) composed of polyethylene terephthalate and polyethylene naphthalate was used as the support, it was found that the light-sensitive material of the present invention had better sharpness.

Example 5 The photosensitive materials prepared in Examples 1 and 2 were evaluated in the same manner as in Example 1 except that the following exposure was performed. The obtained results were the same as in Examples 1 and 2. (Exposure) A YAG solid laser (oscillation wavelength, 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as an excitation light source as a light source is SHG of KNbO ₃ .
A 473 nm semiconductor laser GaAlAs (oscillation wavelength: 808.7 nm) extracted by wavelength conversion by a crystal and a YVO ₄ solid-state laser (oscillation wavelength: 106
532 nm, AlGaInP (oscillation wavelength, about 6 nm)
70 nm: Type No. TOLD9211 manufactured by Toshiba) was used. Each of the laser beams is a device capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to a scanning direction by a rotating polyhedron. Using this apparatus, the relationship between the density (D) of the photosensitive material and the light amount (E) is obtained by changing the light amount.
-LogE was determined. At this time, the amount of the laser light of three wavelengths was modulated using an external modulator to control the exposure amount. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress fluctuations in light quantity due to temperature.

[0147]

By incorporating the compound of the present invention into a photographic component layer, pressure fogging can be effectively suppressed even when a reflective support providing high sharpness is used.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-185755 (JP, A) JP-A-2-234156 (JP, A) JP-A-4-256948 (JP, A) JP-A 5- 204091 (JP, A) JP-A-4-335337 (JP, A) JP-A-64-542 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/83

Claims (15)

(57) [Claims] 1. A silver halide photographic material having at least one layer containing a photosensitive silver halide emulsion grain on a reflective support, wherein a water-resistant resin coating layer on the side of the reflective support on which the photosensitive layer is provided. Means that at least ² g / m ² of a white pigment is contained and at least one compound represented by the following general formula (I) is contained in a monolayer or dimer molecular dispersion state in at least the photosensitive layer. Characteristic silver halide photographic material. Embedded image (In the general formula (I), R _{1 to} R ₄ represent a hydrogen atom or a substituent (provided that
And both R ₃ and R ₄ are alkoxycarbonyl groups.
And not. ) . However, (R ₁ + R ₃ ) and (R ₂
+ R ₄ ) has a total atomic weight of 160 or less. n represents 0, 1, and 2. M represents a hydrogen atom or an alkali metal. ) 2. The silver halide photographic light-sensitive material according to claim ₁ , wherein the substituents R ₁ , R ₂ , R ₃ and R ₄ in the formula (I) have no dissociable group. 3. The substituents R ₁ , R ₂ , R ₃ and R ₄ in the general formula (I) are a hydrogen atom, an alkyl group, —COOR ₅ , —CONR ₆ R ₇ , —CO
NHR ₈ , -NR ₉ COR ₁₀ , -NR ₁₁ R ₁₂ , -CN, OR ₁₃ , -NR ₁₄ CONR ₁₅ R
₁₆ (R _{5 to} R ₁₆ represent a hydrogen atom or an alkyl group which may be substituted by a substituent having no dissociable group, and R ₆ , R ₇ or R ₁₁ , R ₁₂ or R ₁₅ , R ₁₆ represent a ring May be formed) (provided that R ₃ and R ₄ are
Neither is an alkoxycarbonyl group. ) The silver halide photographic material according to claim 2, characterized in that the. 4. The compound of the general formula (I) is a compound of the general formula (II)
2. The silver halide photographic material according to claim 1 , which is a compound represented by the formula: Embedded image (In the general formula (II), R ₁ , R ₆ and R ₇ represent a hydrogen atom or an alkyl group which may be substituted. R ₆ and R _{7 each} represent a ring
May be implemented. However, the sum of the atomic weights of (R ₁ + R ₆ + R ₇ ) is 120 or less, and n represents 0, 1, or 2. M represents a hydrogen atom or an alkali metal. ) 5. The silver halide photographic light-sensitive material according to claim 4, wherein the substituents R ₁ , R ₆ and R ₇ in the formula (II) have no dissociable group. 6. A reflective support wherein the water-resistant resin coating layer on the photosensitive layer coating side comprises two or more water-resistant resin coating layers having different white pigment contents (% by weight) and a substrate. The silver halide photographic material according to claim 1, 2, 3, 4, or 5. 7. At least one layer of photosensitive material on a reflective support
Silver halide photography with silver halide emulsion grain containing layer
In a photosensitive material, water resistance on the photosensitive layer coating side of the reflective support
White pigment is contained in the conductive resin coating layer at 2 g / m ² or more.
The reflective support is provided with a water-resistant resin coating on the photosensitive layer coating side.
Two or more layers having different white pigment contents (% by weight)
A reflective support comprising an aqueous resin coating layer and a substrate, and among two or more water resistant resin coating layers having different white pigment contents , the white pigment content of the water resistant resin coating layer closest to the substrate ( weight percent), at least one waterproof resin coated layer white pigment content of in the substrate opposite to the layer (wt%) rather lower than, the lower and more at least a photosensitive layer
At least one compound represented by the general formula (XI)
Ruha androgenic halide photographic light-sensitive material to <br/> comprising a molecular dispersion state of a single molecule or dimer. Embedded image (In the general formula (XI), R _{1 to} R ₄ represent a hydrogen atom or a substituent.
Represent. However, (R ₁ + R ₃ ) and (R ₂ + R ₄ )
At least one of the atomic weights is 160 or less. n is
Represents 0, 1, and 2. M is a hydrogen atom or an alkali metal
Represents ) 8. The water-resistant resin coating layer closest to the photosensitive layer has the highest white pigment content (% by weight) among two or more water-resistant resin coating layers having different white pigment contents. The silver halide photographic light-sensitive material according to claim 6, wherein 9. The water-resistant resin coating layer of the reflective support having different white pigment contents from at least three layers, and the water-resistant resin coating layer closest to the photosensitive layer of the multilayer water-resistant resin layer and the substrate most 7. The silver halide photographic light-sensitive material according to claim 6, wherein the content (% by weight) of the white pigment in the intermediate layer between the near water-resistant resin coating layer and the water-resistant resin coating layer is the highest. 10. The weight ratio of the resin of the water-resistant resin coating layer having the highest content (wt%) of the white pigment to the white pigment in the water-resistant resin coating layer of the reflective support is titanium oxide. Is 10/90 (titanium oxide / resin) or more white pigment
The content of any one of claims 6 to 9 ,
4. The silver halide photographic light-sensitive material according to item 1 . 11. A water-resistant resin coating layer on the side of the reflective support on which a photosensitive layer is provided is a composition layer obtained by mixing and dispersing a resin mainly composed of polyester synthesized from dicarboxylic acid and diol by condensation polymerization and titanium oxide. Wherein the weight ratio of the resin to titanium oxide is 10/90 (titanium oxide / resin) or more .
The content of titanium oxide , characterized in that,
2. The silver halide photographic light-sensitive material according to 2, 3, 4 or 5. 12. The silver halide photographic light-sensitive material according to claim 11, wherein the polyester of the reflection support is a polyester containing polyethylene terephthalate as a main component. 13. A light-sensitive silver halide emulsion layer on the reflection support, comprising at least three types of silver halide emulsion grains each of which has a color sensitivity different from that of a coupler which develops yellow, magenta or cyan. 13. The photosensitive hydrophilic colloid layer of claim 1, wherein each of said photosensitive hydrophilic colloid layers contains silver halide emulsion grains having a silver chloride content of 95 mol% or more. The silver halide color photographic light-sensitive material according to any one of the above items . 14. A color image forming method, wherein the silver halide photographic light-sensitive material according to claim 13 is printed through a color negative film made of polyethylene terephthalate or polyethylene naphthalate. 15. A color method comprising exposing the silver halide color photographic material according to claim 13 to a scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds, and thereafter subjecting the material to color development. Image forming method.