JP2001051377A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material adapted to a display film for direct appreciation enhanced in physical handling characteristics including antistatic property, and further, to provide a silver halide photographic sensitive material for direct appreciation enhanced in imaging characteristics including resistance to blotting of an image. SOLUTION: The silver halide photographic sensitive material is provided by coating a support with at least one photosensitive silver halide emulsion layer and the other side of the support reverse to the above emulsion layer with at least one photographic constituent layer, and this constituent layer contains an ultraviolet ray absorber in a liquid state at 25 deg.C and when contacting and peeling between the surface of the above emulsion layer and an urethane rubber are repeated ten times for 20 secs, electric displacement caused on the coated side of the emulsion layer <=700 pcoul/cm2.

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 more particularly to a direct-view silver halide photographic light-sensitive material for a photo display film which is excellent in sharpness, image bleeding resistance and physical properties in handling. About.

[0002]

2. Description of the Related Art In recent years, display advertisements using color photographs have been increasing in department stores, subway and railway station platforms, restaurants, hotel lobbies, and other downtown areas. As a display method of these photo displays,
For example, there is a method of appreciating an image formed on the support by reflected light of light radiated from the image surface, and a method of appreciating the transmitted light of light radiated from the back surface of the image, and is not limited to viewing in a bright place. It is known that a clear image can be provided even under specific conditions such as a dark room or outdoors at night.

However, this type of photosensitive material requires a higher image density than general color photography due to the nature of images used for advertisement. Inevitably, the amounts of silver and coupler used in the light-sensitive material are also increased as compared with ordinary color paper. In addition, usually, photographs for display are often displayed in large format, and therefore, higher sharpness is required. However, as described above, increasing the amounts of silver and coupler to obtain a high image density may cause problems such as deterioration of sharpness and image bleeding.

On the other hand, in the case of a photo display, similar to electrophotography, which has been remarkably developed in image elements such as mlD and magnetic recording media in the field of electronics, the original drawing is read by the scanner due to the advancement of the scanner and then edited while looking at the color display. , Corrections, changes in contrast, scaling, etc.
There has been a change in the usage of photosensitive materials. As a method of performing image exposure by scanning exposure, a so-called scanner method is used. A method of winding a photosensitive material around a cylindrical drum and exposing it while rotating it, or a method of scanning a traveling photosensitive material using a polygonal mirror at an angle close to 90 ° with respect to the transport direction, etc. Used. The light sources of these scanner type recording devices include glow lamps, xenon lamps, oscillating high pressure discharge tubes, tungsten halogen lamps, light emitting diodes, (LED), cathode ray tubes (CRT), gas lasers such as helium neon, argon, helium cadmium, etc. Gallium aluminum arsenide,
There are also semiconductor lasers such as gallium arsenide and indium gallium arsenide, and those using a secondary high frequency by combining these semiconductor lasers with a nonlinear optical element. However, the gas laser described above as a light source for scanning exposure, a semiconductor laser and a nonlinear optical element combined with these semiconductor lasers, and a silver halide photographic material is scanned and exposed using a laser using a secondary high-frequency wave, followed by development processing. When a color image is obtained by performing the above, the image becomes blurred, and the image quality is not satisfactory.

[0005] Generally, as means for improving sharpness,
It is known to use an anti-irradiation dye or to provide an antihalation layer on the silver halide emulsion layer side or on the back side thereof. However, in the case of ultra-high illuminance short-time exposure such as scanning exposure, the sharpness of an image formed after the development processing is deteriorated compared to exposure under normal conditions, and a sufficiently satisfactory image is obtained. Not in.

On the other hand, a plastic support such as polyethylene terephthalate is generally used as a support for a photo display from the viewpoint of physical strength. When handling a photosensitive material using the support, static electricity is generated particularly under low humidity. Rarely causes inconvenience in handling. In order to prevent this, it is necessary to take secondary measures such as focusing on humidity control at the time of handling, which leads to a decrease in workability and productivity. Of course, it is needless to say that a photosensitive material that can be handled with ease without taking such secondary measures is preferable.

Conventionally, studies have been made to prevent the generation of static electricity. That is, Japanese Patent Publication No. 2-28132,
-260437 and 8-101480, the technique relating to the method of using a fluorine-containing surfactant,
27409, JP-A-5-40328 and 3-179
No. 439, JP-A-2-28641, Japanese Patent Publication No. 1-45.
No. 616, a technique relating to a betaine surfactant, JP-A-1-260436 and JP-A-4-124647, a technique relating to a phosphoric acid surfactant, and 1-2.
The use of surfactants, such as the techniques relating to nonionic surfactants found in JP-A-676442 and JP-A-5-88298, has been studied diligently to improve the electrostatic properties and the antistatic effect by using techniques for using surfactants.

However, all of them are mainly used for negative films and X-ray films, and their application to direct viewing photo displays is not considered. As described above, in the case of a photo display, as described above, it is often used in a large format, and a higher antistatic effect is required depending on the frequency of occurrence of such a problem and the size of the problem. In this case, even if a conventionally known technique is directly applied to a photo display for viewing, the improvement effect is not sufficient.

[0009]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a direct-viewing silver halide photographic light-sensitive material suitable for a direct-viewing display film. Another object of the present invention is to provide a silver halide photographic light-sensitive material for direct viewing which has improved physical properties in handling, including silver halide. Another object of the present invention is to provide a silver halide photographic material for direct viewing which has improved image quality characteristics including image blur resistance and the like.

[0010]

The above-mentioned object of the present invention has been attained by the following constitution.

1. A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer; Wherein the photographic constituent layer on the side opposite to the side on which the emulsion layer is coated contains a UV absorber which is liquid at 25 ° C., and the distance between the surface on the side where the emulsion layer is coated and the urethane rubber is 20. When contact and peeling were repeated 10 times per second, the electric displacement generated on the emulsion layer coating side was 700 pco.
ul / cm ² or less.

2. A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer; Wherein the photographic layer opposite to the side on which the emulsion layer is coated contains an ultraviolet absorber liquid at 25 ° C., and the photographic layer has the following general formula (FA) or (FK) 2. The silver halide photographic light-sensitive material according to the above item 1, which contains at least one selected from fluorine-containing surfactants represented by formulas (FB) and (FB).

Formula (FA) (Cf)-(Y) _{n wherein} Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is —COO
_{M, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ . M is a hydrogen atom or an alkali metal or quaternary
Represents a cation such as a quaternary ammonium salt, wherein n is 1 or 2
It is.

[0014] Formula (FK) Rf'-L-X + Z - wherein, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen atom is substituted with a fluorine atom. L represents a chemical bond or a divalent group. X ⁺ is a cation, Z ^- represents a counter anion.

Formula (FB) R- (A) _m -X In the formula, R represents a fluorine atom-containing alkyl group, an alkoxy group, an alkenyl group, an aryl group, or an aryloxy group; A may have a substituent, and A is 2
X represents a valent linking group, X represents a betaine group, and m represents 0 or 1.

In the general formula (FN) R- (G) _m -X, R represents an alkyl group containing the fluorine atom, an alkoxy group, an alkenyl group, an aryl group, or an aryloxy group, G may have 2 or more substituents.
X represents a valent linking group, X represents a hydrophilic group of a nonionic group, and m represents 0 or 1.

3. A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer; Wherein the photographic constituent layer on the side opposite to the side on which the emulsion layer is coated contains a liquid ultraviolet absorber at 25 ° C., and fluorine atoms existing on the extreme surface on the image forming surface side before development processing Characterized in that at least 50% of the silver halide remains on the surface after the development processing.

4. A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer; Wherein the photographic constituent layer on the side opposite to the side on which the emulsion layer is provided contains an ultraviolet absorber liquid at 25 ° C. and satisfies the following formula: .

(A / B) <0.03 In the formula, A represents the fluorescence intensity at the maximum fluorescence wavelength at an excitation wavelength of 360 nm of the silver halide photographic light-sensitive material before development processing, and B is the silver halide photographic light-sensitive material. It shows the fluorescence intensity at the maximum fluorescence wavelength at an excitation wavelength of 400 nm of an unexposed part after a development step containing no fluorescent whitening agent is performed on the material.

[5] Capturing at least one silver halide emulsion layer, at least one ultraviolet absorber-containing layer, at least one optical brightener-containing layer, and at least two optical brighteners on a support; In a silver halide photographic material having a layer containing a compound and at least one photographic component layer on the support opposite to the layer, the opposite side to the side on which the emulsion layer is provided The photographic constituent layer on the side contains an ultraviolet absorber liquid at 25 ° C., and the ultraviolet absorber-containing layer and the ultraviolet absorber-containing layer provided at the farthest position from the support in the ultraviolet absorber-containing layer At least one layer selected from layers provided farther from the support than contains a compound capable of capturing a fluorescent brightener, and more than the ultraviolet absorber-containing layer provided farthest from the support Also close to the support The silver halide photographic light-sensitive material, characterized in that the fluorescent whitening agent and a fluorescent brightening agent containing a compound capable of capturing the.

6. Having a layer containing both a fluorescent whitening agent and a compound capable of capturing the fluorescent whitening agent at a position closer to the support than the ultraviolet absorber-containing layer provided at a position farthest from the support, 6. The silver halide photographic light-sensitive material according to the above item 5, wherein

7. A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer; Wherein the photographic constituent layer on the side opposite to the side on which the emulsion layer is coated contains an ultraviolet absorber liquid at 25 ° C., and at least one of the photographic constituent layers on both sides of the support has a high molecular weight component. Silver halide photography characterized by containing gelatin having a content of 8% or less and a compound capable of capturing a fluorescent brightener in a photographic component layer on the side on which the emulsion layer is provided. Photosensitive material.

8. A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer; Wherein the photographic constituent layer on the side opposite to the side on which the emulsion layer is provided contains a UV absorber in liquid at 25 ° C., and the photographic constituent layer provided on the support is water-insoluble and organic. It has a dispersion obtained by emulsifying and dispersing a mixed solvent containing at least one solvent-soluble polymer compound, and the layer adjacent to the yellow color coupler-containing layer can capture the fluorescent whitening agent and the fluorescent whitening agent A silver halide photographic material characterized by containing a compound.

9. The photographic constituent layer has the following general formula (Y):
9. The silver halide photographic light-sensitive material as described in 8 above, comprising a yellow color coupler represented by the following formula:

[0025]

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In the formula, R _A represents an alkyl group, R _B represents a halogen atom or an alkoxyl group, and R _C represents —COO
R _D1 , -COOR _D2 COOR _D1 , -NHCOR _D2 SO ₂
R _D1 , -N (R _D3 ) SO ₂ R _D1 or -SO ₂ N (R _D3 ) R
Represents _D1 . R _D1 represents a monovalent organic group, R _D2 represents an alkylene group, and R _D3 represents an alkyl group, an aralkyl group, or a hydrogen atom. Y _A represents a monovalent organic group, and n is 0 or 1
And R _E and R _F each represent a hydrogen atom or an alkyl group.

10. 10. The silver halide photographic light-sensitive material according to any one of the above items 1 to 9, wherein the support is a plastic support.

11. The oxygen transmission rate of the support is 2.0 m
11. The silver halide photographic light-sensitive material as described in any one of the above items 1 to 10, which is 1 / m ² · hr · atm or less.

12. The original drawing is scanned, exposure is performed for a time of 10 ^-4 seconds or less based on the image signal, and an image corresponding to the image of the original drawing is formed on the silver halide photographic material according to any one of the above items 1 to 9. An image forming method.

Hereinafter, the present invention will be described in detail.

The direct appreciation of the silver halide photographic light-sensitive material for direct viewing as referred to in the present invention means that a positive image is obtained and is directly viewed as an image without being inverted as in a negative image.

The silver halide photographic light-sensitive material for direct viewing according to the present invention (hereinafter, also simply referred to as a light-sensitive material) has at least one light-sensitive silver halide emulsion layer provided on a support. Is at least one on the opposite support
In the silver halide photographic light-sensitive material on which the photographic constituent layers are coated, the photographic constituent layer on the side opposite to the side on which the emulsion layer is provided contains an ultraviolet absorber liquid at 25 ° C.

The liquid ultraviolet absorber is a liquid ultraviolet absorber at room temperature, and “liquid at room temperature” is defined at 25 ° C. as defined in “Chemical Encyclopedia (1963) Kyoritsu Shuppan” or the like.
It has no constant shape, is fluid, and has a substantially constant volume. Accordingly, the melting point is not limited as long as it has the above properties, but a compound having a melting point of 30 ° C. or lower, particularly preferably 15 ° C. or lower, is preferable.

The liquid ultraviolet absorber may be a single compound or a mixture. As the mixture, those composed of structural isomers can be preferably used.

The liquid ultraviolet absorber may have any structure as long as the above conditions are satisfied. However, from the viewpoint of the light fastness of the ultraviolet absorber itself, the liquid represented by the following general formula (a):
-(2'-Hydroxyphenyl) benzotriazole compounds are preferred.

[0036]

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In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like, and a chlorine atom is particularly preferable.

The alkyl group and the alkoxy group preferably have 1 to 30 carbon atoms, and the alkenyl group preferably has 2 to 30 carbon atoms. These groups may be linear or branched. These alkyl group, alkoxy group and alkenyl group may further have a substituent. Specific examples of an alkyl group, an alkoxy group, and an alkenyl group include
For example, methyl group, ethyl group, isopropyl group, t-butyl group, sec-butyl group, n-butyl group, n-amyl group, sec-amyl group, t-amyl group, octyl group, nonyl group, dodecyl group, eicosyl Groups, α, α-dimethylbenzyl group, octyloxycarbonylethyl group, methoxy group, ethoxy group, octyloxy group, allyl group and the like. As the aryloxy group and the aryl group,
For example, a phenyl group and a phenyloxy group are particularly preferred,
It may have a substituent. Specific examples include a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, and the like.

Among the groups represented by R ₁ and R ₂ , a hydrogen atom, an alkyl group, an alkoxy group and an aryl group are preferred, and a hydrogen atom, an alkyl group and an alkoxy group are particularly preferred.

Among the groups represented by R ₃ , in particular, a hydrogen atom,
A halogen atom, an alkyl group, and an alkoxy group are preferable, and a hydrogen atom, an alkyl group, and an alkoxy group are more preferable in terms of light fading.

Of the groups represented by R ₁ , R ₂ and R ₃ , at least one is preferably an alkyl group, more preferably at least two are alkyl groups in order to be liquid at room temperature. is there.

The alkyl group can be any, but at least one is a tertiary alkyl group or a secondary alkyl group.
It is preferably a lower alkyl group. In particular, at least one of the alkyl groups represented by R ₁ and R ₂ is preferably a tertiary alkyl group or a secondary alkyl group.

The following are typical specific examples of the liquid ultraviolet absorber according to the present invention.

[0045]

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[0046]

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The liquid UV absorber may be added in any amount, but may be in the range of 0.1 to 3 based on the weight of the binder in the photographic constituent layer containing the UV absorber.
00%, preferably 1 to 20%.
It can be used in the range of 0%, more preferably in the range of 5 to 100%. In addition, the coating amount is 0.01 to 100 mg / 1.
00 cm ² can be preferably used.
50 mg / 100 cm ² , especially 0.5 to 30 mg / 10
It can be used at 0 cm ² .

According to the first aspect of the present invention, a photographic constituent layer provided on the side opposite to the side on which the emulsion layer is coated of a light-sensitive material has a temperature of 25 ° C.
, A liquid ultraviolet absorber is contained, and the electric displacement generated on the emulsion layer-coated side when the contact and peeling between the surface on the emulsion layer-coated side and the urethane rubber is repeated 10 times in 20 seconds is repeated. Is 700 pcoul / cm ² or less.

The electric displacement in the present invention will be described.

When two objects A and B come into contact with each other, a positive charge layer on one side and a negative charge layer on the other side with a surface density of + σ and −σ and a distance of d from the contact surface. And the contact potential difference is ΔV = (σ / ε0) d. Here, d is extremely small, while σ / ε0 is quite large, and it can be seen that a product of the contact potential difference is usually large (about 1 V). Such positive and negative charge layers are called electric double layers. Carriers of charge through the contact surface include electrons, ions, and holes, which are determined by the properties of the objects in contact. Due to this movement of the carrier, the side losing the carrier is charged with the opposite sign of the carrier, and the side having obtained the carrier is charged with the same sign, thereby generating a Coulomb electric field which prevents further movement of the carrier. The electric double layer grows until the non-coulomb-like factor for moving the carrier and the Coulomb force that hinders the movement of the carrier are balanced. In this way, a Coulomb electric field is generated in a conductor in a place where a non-Coulomb force acts on the carrier, even if there is no current. The intensity of the electric field here is represented by E.

In general, when an insulator is present in an electric field, positive and negative charges appear, and this phenomenon is called dielectric polarization, and charges generated by dielectric polarization are called polarization charges. 1) Direction: direction in which positive charge moves, 2) magnitude: charge moving through a unit area perpendicular to that direction (negative charge moves positive charge in the opposite direction) ), Define the above vector quantities and call them electric polarization,
Expressed by P.

When the intensity of the electric field at each point of the dielectric is E and the electric polarization is P, the vector amount D defined by D = ε0E + P is the electric displacement (electric flux density) and is generated in the dielectric. Represents the charge amount (Asakura Shoten; see Electromagnetism).

The electric displacement mentioned here is based on a contact potential difference caused by contact (peeling) between two objects, and can be shown by obtaining a contact potential difference between objects.

In the present invention, the electric displacement can be obtained as follows.

The support is placed on a stainless steel stage facing the front side having at least one photosensitive layer on the support. On the other hand, urethane rubber is installed on a stainless steel support plate. The stainless steel stage and the stainless steel support plate are connected by a circuit, and the photosensitive layer surface of the photosensitive material installed on each and the urethane rubber come into contact with and separate from each other, and a contact potential difference is generated, and this is repeated. An expansion of the contact potential difference occurs. Install a voltmeter in this circuit,
Measurement of the generated potential difference can be performed. This device can be manufactured in a simple form.

Assuming that the generated potential difference is V and the capacitance between the contacting objects is C, the generated charge Q is expressed by Q = CV, and when the contact area is S, the electric displacement D is expressed by D = CV / S. . Here, the capacitance between the contacting objects is a constant caused by the material, size, and shape of the two objects, and the contact area S is also a constant. Therefore, the electric displacement can be obtained by obtaining the generated potential difference V. it can.

In the present invention, when contact and peeling between the surface having at least one photosensitive layer with respect to the support and the urethane rubber is repeated 10 times in 20 seconds, The electric displacement generated on the surface of the silver halide photographic material on the side having the photosensitive layer is 700 pcoul / cm ^2.
If it exceeds this value, the frequency of occurrence of static marks in the photosensitive material increases, which is not practical. That is, the present invention has the knowledge that the frequency of occurrence of a static mark can be extremely effectively suppressed by controlling the electrical displacement generated by a photosensitive material and the frequency of occurrence of a static mark to a specific electrical displacement or less. And what was done. When the electric displacement is 400 pcoul / cm ² , the effect of the present invention is further expanded, so that the preferable range of the electric displacement is set.

According to a second aspect of the present invention, at least one of the photographic constituent layers on the side opposite to the side on which the emulsion layer of the light-sensitive material is coated contains an ultraviolet absorber liquid at 25 ° C. At least one of the layers has the following general formula (FA) or (F)
K), characterized by containing at least one selected from fluorine-containing surfactants represented by (FB) and (FN).

First, the fluorine-containing anionic surfactant will be described. Specifically, the fluorine-containing anionic surfactant is preferably a compound represented by the following formula (FA).

Formula (FA) (Cf)-(Y) _{n In the} formula (FA), Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is- _{COOM, -SO 3 M, -OSO 3} M or -P
(= O) (OM) ₂ . M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2.

More preferred fluorine-containing anionic surfactants are those represented by the following formula (FA ').

General formula (FA ') Rf- (D) _t -Y In general formula (FA'), Rf has 3 to 30 carbon atoms.
It represents a fluorine-substituted alkyl group or a fluorine-substituted aryl group, D is -O -, - COO -, - CON (R 3) - or -SO ₂ N (R ₃₎ - number of carbon atoms comprising including at least one bond Represents a divalent group of 1 to 12. R ₃ has 1 carbon atom
Represents an alkyl group of 5 to 5, t is 1 or 2, and Y is-
_{COOM -, - SO 3 M,} -OSO 3 M or -P (= O)
(OM) ₂ , wherein M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt.

Specific examples of the compound represented by formula (FA) are shown below, but the present invention is not limited thereto.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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It is particularly preferable to use a fluorine-containing anionic surfactant containing at least one bond of —SO ₂ N (R ₃ ) —.

The amount of the fluorinated anionic surfactant used is about 0.05 to 1000 mg, preferably 0.1 to 500 mg, more preferably 0.5 to 200 mg per m ² of the light-sensitive material.

Next, the fluorine-containing cationic surfactant will be described. Specifically, the fluorine-containing cationic surfactant is preferably a compound represented by the following general formula (FK).

[0072] Formula (FK) Rf'-L-X + Z - in formula (FK), Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen atom is substituted with fluorine atoms ing. L represents a chemical bond or a divalent group.
X ⁺ is a cation, Z ^- represents a counter anion.

As an example of Rf ′, −C _k F _{k + 1} (k = 1
20, particularly 3 to 12 is _{preferred), - C m F 2m,} -C m
F _2m-1 (m = 2 to 20, particularly preferably 3 to 12) and the like.

The following are specific examples of the fluorine-containing cationic surfactant preferably used in the present invention, but the present invention is not limited to these.

[0075]

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[0076]

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[0077]

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In the present invention, particularly the hardly soluble —SO ₂ N (R ₁ )
It is more preferable to use a fluorine-containing cationic surfactant containing at least one bond of Here, the term "poorly soluble" means that when 2.0 g of the activator is added to 100 ml of pure water at 23 ° C., the mixture is stirred for 1 hour, and left at 23 ° C. for 24 hours to form a precipitate or to observe suspended matter. Insoluble in water. For example, FK-1, FK-8, FK-15, FK-1
6 and the like, but are not limited to these, and can be classified by the above test.

The amount of the cationic surfactant used is about 0.01 to 500 mg, preferably 0.05 to 200 mg, and more preferably 0.1 to 100 mg per 1 m ² of the light-sensitive material.

The above-mentioned fluorinated anionic surfactant or fluorinated cationic surfactant is described, for example, in US Pat. Nos. 2,559,751, 2,567,011, 2,732,398, Nos. 2,764,602, 2,806,866, 2,809,998, 2,915,376, 2,915,528, 2,918,501, 2, No. 934,450, No. 2,937,098, No. 2,957,031, No. 3,472,894, No. 3,555,089, British Patent Nos. 1,143,927, 1, 130,822
No., JP-B-45-37304, JP-A-47-9613.
Nos. 49-134614 and 50-117705
No. 50-117727, No. 50-112243
No. 52-41182 and No. 51-12392,
Journal of the British Chemical Society (J. Chem. Soc.) 1950 2
789, 1957, pages 2574 and 2640, American Chemical Society (J. Amer. Chem. Soc.) 79
2549 (1957), Oil Chemistry (J. Japan)
Oil Chemist Soc. ) Volume 12 653
Page, Journal of the Society of Organic Chemistry (J. Org. Chem.), Vol. 30, No. 3
It can be synthesized by the method described on page 524 (1965) and the like.

Certain of these fluorine-containing surfactants are trade names Megafac F from Dainippon Ink and Chemicals, Inc., and Fluorad (Minnesota Mining and Manufacturing Company). Fluorad) under the trade name of FC, Imperial Chemical Industry under the trade name of Monflor, E.I.Dupont Nemelas and Company under the trade name of Zonyls, and Farbeberke. Licovet V from Hoechst
Each is marketed under the trade name PF.

It is preferable to use these fluorine-containing cationic surfactants and fluorine-containing anionic surfactants in combination. The total amount of the fluorinated cationic surfactant and the fluorinated anionic surfactant used is about 0.1 to 1000 mg, preferably 0.5 to 3 mg / m ² of the photosensitive material.
00 mg, and more preferably 0.1 to 150 mg. The ratio of the two is preferably 1: 9 to 9: 1 in terms of molar ratio, and more preferably 3: 7 to 7: 3.

The layer to be used is preferably a surface protective layer, a back surface protective layer, a surface layer of an intermediate product, or the like, and may be used by being coated on the surface protective layer or the back surface protective layer.

The fluorine-containing betaine surfactant will be described. Specifically, the fluorine-containing betaine surfactant is preferably a compound represented by the following formula (FB).

Formula (FB) R- (A) _m -X In Formula (FB), R represents an alkyl group containing the fluorine atom, an alkoxy group, an alkenyl group, an aryl group, or an aryloxy group. And these may have a substituent, A represents a divalent linking group, X represents a betaine group, and m represents 0 or 1.

A is preferably an alkylene group (such as an ethylene group or trimethylene group), an arylene group (such as a phenylene group) or an arylalkylene group (such as a phenylethylene group), which may have a substituent. Also included are divalent linking groups interrupted by heterogeneous atoms or groups such as atoms, ester groups, amide groups, sulfonyl groups, sulfur atoms, sulfonamide groups.

Examples of the betaine group represented by X include the following.

[0088]

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In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent or an aryl group which may have a substituent (a methyl group) , An ethyl group, a benzyl group, etc.) and R ₃ represent an alkylene group having 1 to 5 carbon atoms (methylene group, ethylene group, propylene group, butylene group, etc.).

The following are specific examples of typical fluorine-containing betaine surfactants, but the present invention is not limited to these.

[0091]

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[0092]

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The amount of the fluorine-containing betaine-containing surfactant used is about 0.1 to 1000 mg, preferably 0.5 to 300 mg, and more preferably 1.0 to 150 mg per m ² of the light-sensitive material.
It is.

The layer to which the fluorine-containing betaine surfactant is added is preferably the uppermost layer or the back layer. or,
It may be applied on the surface protective layer of the photosensitive material.

The fluorinated nonionic surfactant will be described. Specifically, the fluorine-containing nonionic surfactant is preferably a compound represented by the following formula (FN).

Formula (FN) R- (G) _m -X In the formula (FN), R represents an alkyl group containing the fluorine atom, an alkoxy group, an alkenyl group, an aryl group, or an aryloxy group. And these may have a substituent, G represents a divalent linking group, X represents a hydrophilic group of a nonionic group, and m represents 0 or 1.

G is preferably an alkylene group (including those having a substituent, for example, an ethylene group, a trimethylene group, etc.) and an arylene group (including those having a substituent, for example, a propyl group, a phenylene group, etc.) ) Or an arylalkylene group (including those having a substituent, for example, a phenylethylene group).
It also includes a divalent linking group interrupted by a different atom or a different group such as an oxygen atom, an ester group, an amide group, a sulfonyl group, a sulfur atom.

The nonionic group represented by X is, for example,-(BO) _n -Rs. Where B, -CH ₂ CH
_{2 -, - CH 2 CH 2} CH 2 -, - CH 2 CH (OH) -C
Represents H ₂ — or —CH (CH ₃ ) —CH ₂ —, and n represents an average degree of polymerization of the polyoxyalkylene group, and is an integer of 1 to 50. Rs represents a hydrogen atom, an alkyl group including a substituent, or an aryl group including a substituent.

Specific examples of typical fluorine-containing nonionic surfactants of the present invention are shown below, but the present invention is not limited to these.

[0100]

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[0101]

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[0102]

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The amount of the fluorinated nonionic surfactant to be used is preferably 0.1 to 1000 mg, more preferably 0.5 to 300 mg, and more preferably 1.0 to 1000 mg per m ^{2 of} the light-sensitive material.
150 mg is particularly preferred. As the fluorinated nonionic surfactant, the fluorinated nonionic surfactant may be used alone or in combination of two or more.

The layer to which the fluorine-containing betaine surfactant or the nonionic surfactant is added is not particularly limited, but is preferably a surface protective layer, a back surface layer, or a layer closest to the support. Alternatively, it may be coated on the surface protective layer of the light-sensitive material. That is, in the multilayer structure,
It is particularly preferred to use the layer closest to the support and the layer farthest from the support.

The third aspect of the present invention relates to a method for forming an image before development while the photographic constituent layer of the photosensitive material opposite to the side on which the emulsion layer is coated contains a liquid ultraviolet absorber at 25 ° C. It is characterized in that 50% or more of the fluorine atoms present on the surface-side extremely surface remain on the surface after the development processing.

In general, a surfactant is used in a photosensitive material. However, the surfactant present in the photosensitive material has a surface orientation property as a characteristic, and therefore, the surfactant is used during coating and drying. Attempts to orient on the surface. Therefore, a surfactant is selectively present on the surface of the photosensitive material. Among them, a fluorine-based surfactant has remarkable properties due to its large surface orientation.

Further, the direct-viewing photographic material becomes a viewing photograph through a developing process. Generally, in a development processing step, when a photographic material passes through each processing solution of development, bleach-fix, and stabilization (or washing), photographic materials, binders, etc. contained in the photographic material are contained in each processing solution. Elute.

Surfactants are also eluted without leakage and are more easily eluted, but the residual fluorine is still oriented on the photosensitive material surface after development processing. Generally, the amount of the surfactant present on the photographic surface after the development processing is smaller than the amount of the surfactant existing on the photosensitive material surface before the development processing.

According to the present invention, it is required that 50% or more of fluorine atoms remain on the surface of the silver halide photographic light-sensitive material after the development processing with respect to the fluorine atoms existing on the image forming side of the photosensitive material before the development processing. Features. 60% of the remaining fluorine atoms
It is preferably at least 70%, more preferably at least 70%, even more preferably at least 80%.

Here, the term “extreme surface” refers to the thickness of the chemical substance on the image forming surface at the molecular level or the thickness thereof when a chemical substance having a surface orientation such as a surfactant is oriented on the surface on the image forming surface side. Refers to a part that is comparable.

In the present invention, the ratio of fluorine atoms present on the surface of the image forming surface before and after the development processing can be quantified by the ratio of the fluorine atom abundance to all the atoms present on the surface. The presence of atoms on the surface is recognized as the presence of atoms forming the extreme surface portion of the outermost layer, and the average abundance ratio of the atoms can be measured using an XPS surface analyzer.

Next, the measuring method will be described.

The XPS surface analyzer is set under the following conditions.

X-ray anode; Mg resolution: 1.5 to 1.7 eV (resolution is clean A
g3d5 / 2 peak width) The XPS surface analyzer is not particularly limited, and any model can be used.
ESCALAB-200R manufactured by VG was used.

A narrow scan is performed in the following measurement range.
The spectrum of each element was measured. At this time, the data capturing interval is set to 0.2 eV, and it is necessary to integrate the target peaks until a count equal to or more than the minimum count shown below is obtained.

Peak Measurement range Minimum detection intensity (Binding energy eV) (Count) C1s 305-280 Arbitrary Fe2p3 / 2 730-700 600,000 Na (KL ₂₃ L ₂₃ ) 280-250 600,000 Auger peak The peak position of C1s is 2
The energy position is corrected so as to be 84.6 eV.

Next, COMMON DATA PROCESSING S manufactured by VAMAS-SCA-JAPAN
YSTEM Ver. 2.3 (hereinafter referred to as “VAMAS software”), the above spectra were converted to VAMAS software using software provided by each device manufacturer.
Transfer to a computer where you can use the software. Then, using the VAMAS software, the transferred spectrum is converted into the VAMAS format, and then data processing is performed.

Before starting the quantitative processing, Co for each element
Unscale is calibrated, and a 5-point smoothing process is performed. With the peak position of each element as the center, the peak area intensity (cps × eV) is determined in the quantitative range shown in the following table.

Using the sensitivity coefficients shown below, the atomic% of each element is determined. The number of atoms is converted into the number of atoms with respect to 100 Fe atoms, and is used as a quantitative value.

Element Peak position (BE: eV) Quantitative range (BE: eV) Sensitivity coefficient F High B. E. FIG. Side 6 eV, low B. E. FIG. 6eV 4.26 Fe 719.8 near side, high B.V. E. FIG. Side 5eV, low B. E. FIG. Side 7e near 10.54 Na 264.0, high B.I. E. FIG. Local minimum value near 2 eV 7.99 Low B. E. FIG. Side 6 eV Elements other than the above can be measured under the following conditions as needed.

[0121]

[Table 1]

By adding a fluorine-based surfactant to at least one of the constituent layers on the image forming surface side of the light-sensitive material by the surface orientation described above, fluorine atoms can be present on the surface on the image forming surface side. Can be.

The invention according to claim 4 is a photosensitive composition wherein at least one emulsion layer is coated on a support, and at least one photographic component layer is coated on the support opposite to the emulsion layer. The material is characterized in that the photographic component layer on the side opposite to the side on which the emulsion layer is provided contains an ultraviolet absorber liquid at 25 ° C. and satisfies the following formula.

(A / B) <0.03 In the formula, A represents the fluorescence intensity at the maximum fluorescence wavelength at an excitation wavelength of 360 nm of the silver halide photographic light-sensitive material before development processing, and B represents the silver halide photographic light-sensitive material. It shows the fluorescence intensity at the maximum fluorescence wavelength at an excitation wavelength of 400 nm of an unexposed part after a development step containing no fluorescent whitening agent is performed on the material.

In the formula, A and B can be easily measured by a commercially available spectrofluorometer which can scan the excitation wavelength and the fluorescence wavelength, respectively. The procedure of the measurement is as follows. First, an undeveloped photosensitive material sample is placed in a reflection sample measurement holder of a spectrofluorometer,
Excitation light is irradiated at an incident angle of 45 °, the fluorescence is fixed at an angle of 45 ° from the sample surface, and the excitation wavelength and the fluorescence wavelength are respectively scanned to determine the maximum excitation wavelength and the maximum fluorescence wavelength. Match the fluorescence detection wavelength to the maximum fluorescence wavelength,
The excitation spectrum is measured by scanning the excitation wavelength under the following measurement conditions. Let A be the intensity of the excitation spectrum at 360 nm. Subsequently, the excitation spectrum of a white background sample obtained by processing the same photosensitive material sample in a development processing step not containing a fluorescent whitening agent as shown below without exposure was measured in the same procedure, and the obtained excitation spectrum was measured. B is the intensity at 400 nm.

Measurement conditions Light source 150 W xenon lamp Excitation side band pass 1.5 nm Fluorescence side band pass 1.5 nm Wavelength scanning speed 60 nm / min Response speed 2 seconds Measurement wavelength range 300 nm to 500 nm The rhodamine B reagent for fluorescence analysis is used as a reference. Then, the spectral correction is performed to correct the influence of the wavelength characteristic of the measuring device (spectrometer, photomultiplier, etc.).

・ Development process Step Processing temperature Time Color development 38.0 ± 0.3 ° C. 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds Washing 30-34 ° C. 90 seconds Drying 60-80 ° C. 30 seconds -Composition of development processing solution Pure water 800 ml Triethylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline sulfate 6.0 g N, N-diethylhydroxylamine 6.8 g Triethanolamine 10.0 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g Potassium carbonate 30 g Water is added to make the whole volume 1 liter, and the pH is adjusted to 10.10. adjust.

Composition of Bleach-Fix Solution Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

In the present invention, A / B needs to be less than 0.03. Preferably, 0 <A / B <0.
03, more preferably 0.010 <A / B <0.
025.

[0130] The invention of claim 5 provides a support, wherein at least one silver halide emulsion layer, at least one ultraviolet absorber-containing layer, at least one layer containing a fluorescent whitening agent, and A silver halide photographic light-sensitive material comprising at least two layers containing a compound capable of capturing a fluorescent whitening agent, and at least one photographic component layer provided on a support opposite to the layer; The photographic constituent layer on the side opposite to the side on which the layer is provided contains a UV absorber in a liquid state at 25 ° C., and the UV absorber provided at the farthest position from the support in the UV absorber-containing layer At least one layer selected from the agent-containing layer and the layer provided at a position farther from the support than the ultraviolet absorber-containing layer contains a compound capable of capturing a fluorescent whitening agent, and at a position furthest from the support. UV absorption provided in Characterized in that than agent-containing layer containing a compound capable of capturing the fluorescent whitening agent and a fluorescent whitening agent at a position closer to the support.

[0131] The invention of claim 6 relates to both the fluorescent whitening agent and the compound capable of capturing the fluorescent whitening agent at a position closer to the support than the ultraviolet absorber-containing layer provided farthest from the support. Characterized by having a layer containing

Examples of the fluorescent whitening agent include diaminostilbene, benzidine, imidazole, triazole, and the like.
Examples include imidazolone-based, bis (benzoxazolyl) thiophene-based, and bis (benzoxazolyl) stilbene-based fluorescent whitening agents. Preferred optical brighteners are
A water-soluble fluorescent whitening agent having at least one organic acid group having a pKa of 6.0 or less or an organic base having a pKb of 7.5 or less in a molecule. More preferably, 5.0.
An organic acid group having the following pKa, or 4.0 to 7.5:
Is a water-soluble fluorescent whitening agent having at least one organic base having a pKb in the molecule, more preferably at least one organic acid group having a pKa of 5.0 or less, and 4.0 or more.
It is a water-soluble optical brightener having at least one organic base having a pKb of ７7.5 in the same molecule. Most preferably, the pKb of the organic base is 4.0 to 7.0.

In the present invention, pKa is a so-called acid dissociation constant, for example, Chemical Handbook (Basic Edition II) (edited by The Chemical Society of Japan).
It is defined on page 1053. Similarly, pKb is a base dissociation constant, and pKa and pKb are described in JP-A-59-71050.
The definition is also described in lines 2 to 10 in the upper left column on page 3 of the issue.

The fluorescent whitening agent used in the present invention is preferably represented by the following general formula.

[Diaminostilbene-based fluorescent whitening agent]

[0136]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, a halogen atom, a sulfo group or a salt thereof, a carboxyl group or a salt thereof, an alkylamino group, an arylamino group, a hydroxyl group, Group, an alkoxyl group, an aryloxy group, or a morpholino group. X
₁ represents a sulfo group or a carboxyl group, or a salt thereof.

[Benzidine-based fluorescent whitening agent]

[0139]

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In the formula, R ₅ , R ₆ and R ₇ each represent a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxyl group. X ₂ represents a sulfo group or a carboxyl group, or a salt thereof. Particularly preferred R ₇ is a hydroxyl group.

[Imidazole-based fluorescent whitening agent]

[0142]

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In the formula, R ₈ and R ₁₁ each represent a hydrogen atom, an alkyl group, an alkoxyl group, a sulfo group or a salt thereof. R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group or a hydroxyalkyl group. X ₃ represents a sulfo group or a carboxyl group, or a salt thereof.

[Triazole fluorescent brightener]

[0145]

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In the formula, X ₄ and X ₅ are each a hydrogen atom,
Represents a sulfo group or a carboxyl group, or a salt thereof. X ₆ represents a sulfo group or a carboxyl group, or a salt thereof.

Hereinafter, specific examples of the fluorescent whitening agent used in the present invention will be shown, but the present invention is not limited to these.

[0148]

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[0149]

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[0150]

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The effect of the present invention is that the fluorescent whitening agent is contained in a layer closer to the support than the ultraviolet absorber-containing layer provided farthest from the support in the ultraviolet absorber-containing layer. Is more preferable in that the above is more effectively exhibited. Any layer may be used as long as it is closer to the support than the ultraviolet absorber-containing layer provided farthest from the support, and may be the same layer as the silver halide emulsion layer. The whitening agent may adversely affect the emulsion performance such as sensitivity, gradation and fog, and the non-emulsion layer is more preferable. For example, from the support side, a blue-sensitive silver halide emulsion layer, an intermediate layer, a green-sensitive silver halide emulsion layer, an intermediate layer or a layer containing an ultraviolet absorber, a red-sensitive silver halide emulsion layer, a layer containing an ultraviolet absorber, When coated in the order of the protective layer, the fluorescent whitening agent may be a layer between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer, and / or a layer between the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. It is preferable that the compound is contained in a layer between the light-sensitive silver halide emulsion layers. The layer containing the fluorescent whitening agent may be the same layer as the layer containing the compound capable of capturing the fluorescent whitening agent, and the same layer is more preferable in terms of the effects of the present invention. Further, as long as the effect of the present invention is not impaired, at least one layer selected from the ultraviolet absorber-containing layer provided farthest from the support and the layer farther from the support than the layer contains a fluorescent whitening agent. May be.

In the present invention, the coating amount of the fluorescent whitening agent is preferably 0.01 to 0.5 g / m ² , more preferably 0.02 to 0.2 g / m ² .

As the compound capable of capturing the fluorescent whitening agent, that is, the compound that enhances the whitening effect (hereinafter, referred to as a capturing agent), many conventionally known compounds can be used. Particularly useful are hydrophilic polymers, for example, polyvinylpyrrolidone, polymers containing vinylpyrrolidone as a repeating unit (monomer forming a repeating unit together with vinylpyrrolidone include acrylic acid, methacrylic acid, acrylic acid and Amides of methacrylic acid (for example, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N
-Methylol acrylamide, N-hydroxyethyl acrylamide, N-tert-butyl acrylamide,
N-cyclohexylacrylamide, diacetone acrylamide, N- (1,1-dimethyl-3-hydroxybutyl) acrylamide, N- (β-morpholino) ethylacrylamide, N-benzylacrylamide, N-acryloylmorpholine, N-methacryloylmorpholine ,
N-methyl-N'-acryloylpiperazine, N-acryloylpiperidine, N-acryloylpyrrolidine, N
-Acryloyl hexamethylene imine), alkyl ester acids of acrylic acid and methacrylic acid (e.g. methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate,
Decyl acrylate, β-cyanoethyl acrylate,
β-chloroethyl acrylate, 2-ethoxyethyl acrylate, sulfopropyl methacrylate, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl lactate), vinyl ethers (eg, methyl vinyl ether, butyl vinyl ether, oleyl vinyl ether) ), Vinyl ketones (eg, methyl vinyl ketone, ethyl vinyl ketone, etc.), styrenes (eg, styrene, methyl styrene,
Dimethylstyrene, 2,4,6-trimethylstyrene,
Ethyl styrene, lauryl styrene, chlorostyrene,
Dichlorostyrene, methoxystyrene, cyanostyrene, dimethylaminostyrene, chloromethylstyrene,
Vinylbenzoic acid, styrenesulfonic acid, α-methylstyrene, etc., vinyl heterocyclic compounds (eg, vinylpyridine, vinylpyrrolidone, vinylisoxazoline, vinylimidazole, etc.), acrylonitrile, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, isoprene Chloroprene, maleic anhydride, itaconic anhydride, citraconic anhydride, vinyl sulfonic acid and the like. ) And others
No. 842, poly-N-vinyl-5-methyl-2-oxazolidinone, a hydrophilic polymer containing a cationic nitrogen-containing active group described in JP-A-48-42723, and JP-B-44-2522. N described in the number
A morpholinoalkylalkenoylamide polymer, a copolymer of vinyl alcohol and vinylpyrrolidone described in JP-B-47-20738, JP-B-47-49
General formula described in No. 028

[0154]

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A polymer represented by the formula: JP-B-48-3841
General formula described in No. 7

[0156]

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The polymer represented by the following formula: Among them, particularly preferred scavengers are polyvinylpyrrolidone and its copolymer.

The weight average molecular weight of the hydrophilic polymer is preferably 1,000 or more, more preferably 10,000 or more. Even more preferably from 50,000
1,000,000.

In an embodiment of the present invention, the capturing agent is contained in at least two layers. In this case, the scavenger is contained in the ultraviolet absorber-containing layer provided farthest from the support and / or in a layer provided farther from the support than the ultraviolet absorber-containing layer, and It is also contained in a layer closer to the support than the ultraviolet absorber-containing layer provided farthest from the body.

As the ultraviolet absorbent-containing layer provided farthest from the support and / or the layer provided farther from the support than the ultraviolet absorbent-containing layer, layers other than the surface protective layer are preferable. . Further, it is preferable that the above-mentioned fluorescent whitening agent is simultaneously contained in the scavenger-containing layer closer to the support than the ultraviolet absorber-containing layer provided farthest from the support.

The amount of the scavenger contained in the ultraviolet absorber-containing layer provided farthest from the support and / or the layer provided farther from the support than the ultraviolet absorber-containing layer is preferably Is 0.005 to 0.1 g / m ² , and the amount of the scavenger contained in the layer closer to the support than the ultraviolet absorber-containing layer provided farthest from the support is preferably 0. 01 to 0.2 g / m ² .

The ultraviolet absorbent-containing layer used in the present invention may be a single layer or a plurality of layers. In the case of a plurality of layers, the layer is provided at a position farthest from the support. It is preferable that the obtained ultraviolet absorber-containing layer is disposed in the above-described layer order with the fluorescent brightener-containing layer and the scavenger-containing layer.

As the ultraviolet absorber, the following general formula [UV]
A benzotriazole-based ultraviolet absorber represented by the formula:

[0164]

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In the formula, Ra, Rb and Rc represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Represents an aryloxy group, an alkenyl group, or a hydroxyl group. Rx is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group,
Represents a ureido group, urethane group and amino group.

Specific compounds represented by the general formula [UV] are shown below, but are not limited thereto.

[0167]

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[0168]

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Other examples of the ultraviolet absorber preferably used in the light-sensitive material of the present invention include JP-A-1-250944.
Compound represented by general formula III-3 described in
Compounds represented by the general formula III described in -66646, UV-1L to UV-27 described in 63-187240.
L, compounds represented by formula I described in JP-A-4-1633, and compounds represented by formulas (I) and (I) described in JP-A-5-165144.
Compounds represented by I) and 2-hydroxyphenyltriazine compounds described in JP-A-8-234364 can be mentioned.

In the light-sensitive material of the present invention, the coating amount of the ultraviolet absorber is preferably 0.1 to 5 g / m ² , more preferably 0.4 to ² g / m ² .

The invention according to claim 7 is characterized in that the photographic constituent layer on the side opposite to the side on which the emulsion layer of the light-sensitive material is coated contains an ultraviolet absorber liquid at 25 ° C. At least one of the constituent layers contains gelatin having a high molecular weight component content of 8% or less, and contains a compound capable of capturing a fluorescent whitening agent in the photographic constituent layer on the side on which the emulsion layer is provided. It is characterized by doing. This will be described.

Regarding the molecular weight of gelatin, see D.E. Lor
ry and M.R. Vedlines, Proceed
ings of the 4th IAG Confe
rence, Friborg, Sept. , 198
3, p. 35. As described in Takashi Ohno, Hiroyuki Kobayashi, Shinya Mizusawa, Journal of the Photographic Society of Japan, 47, 237 (1984), etc., an alpha component (molecular weight of about 100,000), which is a structural unit of collagen, and its two quantities Β component, γ
In general, these components are composed of high molecular weight components which are multimers, and low molecular weight components in which these components are irregularly cleaved. The measurement of the gelatin molecular weight distribution is based on the above literature,
JP-A Nos. 60-80838, 62-87952, 62-265645, 62-279329, and 6
As described in JP-A-4-46742 and the like, the reaction is carried out by gel permeation chromatography (hereinafter referred to as "GPC method").

The proportion of the high molecular weight component of the gelatin of the present invention can be determined by the GPC method under the following conditions.

(GPC method) a) Column: Asahipak, GS-620 (manufactured by Asahi Kasei Kogyo) Two columns connected in series Column temperature 50 ° C. b) Eluent: 0.1 M KH ₂ PO ₄ and 0.1 M Na ₂ HPO ₄ C) Sample: 0.2% eluent solution of gelatin Injection volume 100 μl d) Detection: UV absorption spectrophotometer (UV wavelength 230 nm) Retention time ( Retention Time)
In the chart showing the change in absorption at 230 nm, peaks at the exclusion limit appear first, then peaks due to the γ component, β component, and α component of gelatin appear in sequence, and further, gradually attenuate as the retention time becomes longer. It takes shape.

The content of the high molecular weight component in the present invention is as follows:
It can be obtained by calculating the ratio of the area of the exclusion limit peak to the entire area. Specifically, a vertical line is drawn on the horizontal axis from the minimum point on the right side (the side where the retention time increases) of the peak appearing at about 15 minutes of the retention time, and the vertical line and the measurement curve on the left side (the side where the retention time is small). And the ratio of the area of the portion surrounded by the baseline to the total area is calculated.

The present invention is characterized in that it has a layer containing gelatin having a high molecular weight component content of 8% or less, but preferably has a low molecular weight component content of 4% or less. Is preferably 0.5% to 3% from the viewpoint of further increasing the effect of the present invention. In order to enhance the effect, the content of the α component of gelatin is preferably 40% or more, more preferably 45% or more.

The content rate of the α component is determined by the retention time 2
A line b perpendicular to the horizontal axis is drawn from the minimum point on the left (in the direction in which the retention time is smaller) of the peak a of the α component appearing in the third tertile, and the horizontal axis is located at +1.5 minutes of the retention time from the peak a. Draw a vertical line c. It is determined by calculating the ratio of the area surrounded by the measurement curves, b, c and the baseline to the total area.

The content of the high molecular weight component and the α component of the gelatin are those of the gelatin before the hardening treatment, that is, the gelatin added to the coating solution for forming the photographic component layer. When a plurality of different gelatins are used, the average of the respective contents of the used gelatins is used.

The gelatin may be gelatin made from any of bovine bone, cow skin, pig skin and the like, and is preferably a lime-processed gelatin produced from bovine bone.

The gelatin used in the present invention preferably has a jelly strength (based on the Paggy method) of 250 g or more.

The calcium content (according to the Paggy method) of gelatin is preferably at most 1,000 ppm, particularly preferably at most 500 ppm. In order to reduce the calcium content in gelatin, generally, treatment with an ion exchange resin column is preferably used.

Gelatin may be subjected to an oxidation treatment with hydrogen peroxide or the like for the purpose of reducing photographic activity.
For details of the method for producing gelatin, see, for example, Arthur
Veis, The Macromolecular
Chemistry of Gelatin ", Aca
Demic Press, pp. 187-217 (1964)
Year), T. H. James: The Theory o
f the Photographic Processes
s4th. ed. 1977, (Macmillan) 5
5 pages, Handbook of Scientific Photography (above), 72-75 (Maruzen), Basics of Photographic Engineering-Silver halide photography, pages 119-124 (Corona)
And so on.

For example, lime-processed gelatin is prepared as follows. First, ossein consisting only of collagen from which calcium phosphate has been removed is immersed (lime immersed) in saturated lime water for 2 to 3 months, washed with water, neutralized, and extracted with warm water of about 60 ° C (first extraction). Do. Next, the second extraction is performed at about 65 ° C., the third extraction is performed at about 75 ° C., and the fourth extraction is performed at 80 ° C. or more. Each extract is filtered, concentrated under reduced pressure, cooled at about 10 ° C., coagulated, and dried to obtain.

In the above production method, the content of the high molecular weight component increases as the extraction number advances from No. 1 to No. 4, and α
The components decrease. As the photographic gelatin, those extracted first and second at a low temperature are generally used, and the high molecular weight component of these gelatins is 3 to 10% by weight.

Means for reducing the high molecular weight component of gelatin include, for example, adjusting the conditions such as the period of lime treatment of the raw material and the temperature, and the temperature and the temperature at which gelatin is extracted from the pretreated raw material into the aqueous phase. Adjust the time and extract at relatively low temperature of 50-60 ° C. In general, extraction is performed in the order of the first extraction, the second extraction, and the third extraction.
The extraction is performed, but the first extract is preferable, and it is preferable that the extraction is performed in a short extraction time. Ultrasonic irradiation is performed on the gelatin solution, an aqueous hydrogen peroxide solution is added to the gelatin solution, an ultrafiltration membrane Using a molecular weight fractionation method using a coacervation method using an organic solvent such as alcohols.The gelatin of the present invention can be obtained by employing alone or in combination. .

As the binder (or protective colloid) used in the light-sensitive material of the present invention, in addition to the above-mentioned gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein, a sugar derivative, a cellulose derivative, a single or copolyester A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a coalescence can also be used.

Further, the invention of claim 7 is characterized in that the photographic constituent layer on the side on which the emulsion layer is provided contains a compound capable of trapping a fluorescent whitening agent. As the scavenger, those described in claim 5 can be similarly used.

According to the invention of claim 8, the photographic constituent layer on the side opposite to the side on which the emulsion layer of the light-sensitive material is coated contains a liquid ultraviolet absorber at 25 ° C., and is coated on the support. The photographic constituent layer has a dispersion obtained by emulsifying and dispersing a mixed solvent containing at least one water-insoluble and organic solvent-soluble polymer compound, and increases the fluorescence in the layer adjacent to the layer containing the yellow color coupler. It is characterized by containing a compound capable of capturing a whitening agent and a fluorescent whitening agent.

The reason why the fluorescent whitening agent and the scavenger are contained in the layer adjacent to the layer containing the yellow color coupler is that static fog generated when static electricity is generated in the photosensitive material (yellow color development in the unexposed area) This is because fog is effectively suppressed.

A ninth aspect of the present invention is characterized in that the photographic constituent layer having the emulsified dispersion contains a yellow color coupler represented by the following formula (Y).

[0191]

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In the formula, R _A represents an alkyl group, R _B represents a halogen atom or an alkoxyl group, and R _C represents —COO
R _D1 , -COOR _D2 COOR _D1 , -NHCOR _D2 SO ₂
R _D1 , -N (R _D3 ) SO ₂ R _D1 or -SO ₂ N (R _D3 ) R
Represents _D1 . R _D1 represents a monovalent organic group, R _D2 represents an alkylene group, and R _D3 represents an alkyl group, an aralkyl group, or a hydrogen atom. Y _A represents a monovalent organic group, and n is 0 or 1
And R _E and R _F each represent a hydrogen atom or an alkyl group.

First, the yellow color coupler represented by formula (Y) will be described.

In the formula (Y), examples of the alkyl group represented by R _A include a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, an i-propyl group, and a t-group.
-Butyl, dodecyl, 1-hexylnonyl, cyclopropyl, cyclohexyl, adamantyl and the like.

These alkyl groups may be further substituted. Examples of the substituent include a halogen atom (a chlorine atom, a bromine atom, etc.), an aryl group (for example, a phenyl group,
pt-octylphenyl group, etc.), alkoxyl group (eg, methoxy group, etc.), aryloxy group (eg, 2,
4-di-t-pentylphenoxy group, etc.), sulfonyl group (eg, methanesulfonyl group, etc.), acyl group (eg,
Acetyl group, benzoyl group, etc.), sulfonylamino group (eg, dodecanesulfonylamino group, etc.), hydroxyl group and the like.

As _RA , a branched alkyl group is preferable, and a t-butyl group is particularly preferable.

As the alkoxyl group represented by R _B ,
A straight-chain or branched alkoxyl group, for example, methoxy group, ethoxy group, 1-methylethyloxy group, t-butyloxy group, dodecyloxy group, 1-hexylnonyloxy group and the like can be mentioned. Among them, a methoxy group is preferable.

Examples of the halogen atom represented by R _B include a chlorine atom, a bromine atom and a fluorine atom, and a chlorine atom is preferred.

-COOR _D1 and -COOR represented by R _{C
D2 COOR D1, -NHCOR D2 SO 2} R D1, -N
In (R _D3) SO ₂ R _D1 or _{-SO 2 N (R D3) R} D1, as the monovalent organic group represented by R _D1, is preferably a group having a function as a diffusion-resistant group, for example, the number of carbon atoms 10 or more linear or branched alkyl groups (for example, dodecyl group,
An octadecyl group or the like) or an aryl group (a 2,4-dipentylphenyl group or the like) is preferable, and a linear or branched alkyl group having 14 or more carbon atoms is more preferable. R _D2
As the alkylene group represented by, for example, a propylene group, a trimethylene group and the like are preferable. The alkyl group represented by R _D3 is preferably a linear or branched alkyl group such as a methyl group, an ethyl group, an i-propyl group, and the like, and the aralkyl group is, for example, a benzyl group.

R _C is preferably a —COOR _D1 group.

The alkyl group represented by R _E and R _F is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, i-propyl, butyl, hexyl. And a methyl group is particularly preferred.

Examples of the monovalent organic group represented by Y _A include an alkyl group (for example, an ethyl group, an i-propyl group,
t-butyl group, etc.), alkoxyl group (eg, methoxy group, etc.), aryloxy group (eg, phenyloxy group, etc.), acyloxy group (eg, methylcarbonyloxy group, benzoyloxy group, etc.), acylamino group (eg, acetamido group, phenyl group) A carbamoyl group (eg, N-methylcarbamoyl group, N-
Phenylcarbamoyl group, etc.), alkylsulfonylamino group (eg, ethylsulfonylamino group), arylsulfonylamino group (eg, phenylsulfonylamino group), sulfamoyl group (eg, N-propylsulfamoyl group, N-phenylsulfamoyl) Group) and an imide group (for example, a succinimide group and a glutarimide group).

The yellow coloring coupler represented by formula (Y) can be synthesized by a conventionally known method.
Further, the compounds represented by the general formula (Y) may be used in combination,
The coupler of the general formula (Y) may be used in combination with another coupler as long as the effects of the present invention are not impaired.

In the present invention, the coating amount of the yellow color coupler in the silver halide photographic light-sensitive material is 0.50 × 10 ^−3.
~ 1.60 × 10 ⁻³ mol / m ² ,
More preferably 0.60 × 10 ^{−3 to} 1.40 × 10 ⁻³ mol / m ² , particularly preferably 0.70 × 10 ^{−3 to} 1.20.
× 10 ^-3 mol / m ² . The coating amount of the coupler referred to herein means the total amount of the yellow color coupler, not the amount of only the compound represented by the general formula (I).

Next, specific examples of the yellow color coupler represented by formula (Y) will be shown, but the invention is not limited thereto.

[0206]

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[0207]

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The yellow coloring coupler of the present invention represented by the general formula (Y) is used as a dispersion obtained by emulsifying and dispersing a mixed solvent in which at least one water-insoluble and organic solvent-soluble polymer compound is present.

The polymer compound insoluble in water and soluble in an organic solvent will be described below.

The water-insoluble and organic solvent-soluble polymers usable for the above purpose include (1) vinyl polymers and copolymers (2) polycondensates of polyhydric alcohols and polybasic acids (3) ring opening Polyester obtained by the polymerization method (4) Other polymers and the like. Hereinafter, (1) to (4) will be described.

(1) Vinyl Polymer and Copolymer The monomers forming the vinyl polymer and copolymer include methyl acrylate, butyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, t-octyl acrylate, 2-chloroethyl acrylate, cyanoethyl acrylate, 2-
Acrylates such as acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, and phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isopropyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, sulfo Methacrylic esters such as propyl methacrylate, phenyl methacrylate, cresyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate , Vinyl benzoate Vinyl esters such as vinyl salicylate, acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, t- butyl acrylamide, cyclohexyl acrylamide,
Acrylamides such as benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, N- (2-hydroxy-5-ethylsulfonylphenyl) acrylamide, methacrylamide, methylmethacrylamide,
Ethyl methacrylamide, propyl methacrylamide,
Butyl methacrylamide, t-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethyl methacrylamide, dimethylaminoethyl, phenyl methacrylamide, N- (3-hydroxyphenyl) methacrylamide Methacrylamides, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, butadiene, isoprene, olefins such as chloroprene, vinyl chloride, vinylidene chloride, styrene, methyl styrene, trimethyl styrene, ethyl styrene, chloro Styrenes such as methylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, and vinylbenzoic acid are exemplified. In addition, crotonic esters such as butyl crotonate, itaconic diesters such as diethyl itaconate, maleic diesters such as dimethyl maleate, fumaric diesters such as dimethyl fumarate, and allyl such as allyl acetate. Compounds, methyl vinyl ether, vinyl ethers such as methoxyethyl vinyl ether, vinyl ketones such as methyl vinyl ketone, vinyl pyridine,
Examples thereof include vinyl heterocyclic compounds such as N-vinyloxazolidone, glycidyl esters such as glycidyl acrylate, and unsaturated nitriles such as acrylonitrile.

[0212] The polymer compound used in the present invention may be a homopolymer of the above-mentioned monomers or, if necessary, a copolymer of two or more monomers. Further, the polymer used in the present invention may contain a monomer having an acid group shown below to such an extent that the polymer does not become water-soluble, but is preferably 20% or less, and more preferably contains no monomer at all. .

Examples of the monomer having an acid group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, monoalkyl maleate, citraconic acid, styrenesulfonic acid, vinylbenzylsulfonic acid,
Examples include acryloyloxyalkylsulfonic acid, methacryloyloxyalkylsulfonic acid, acrylamidoalkylsulfonic acid, methacrylamidoalkylsulfonic acid, acryloyloxyalkylphosphate, and methacryloyloxyalkylphosphate. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions.

As the monomers forming the polymer used in the present invention, acrylates, methacrylates, acrylamides and methacrylates are preferred.

The polymer formed from the above monomers can be obtained by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a latex polymerization method. As the initiator used for these polymerizations, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, sodium 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis (2-amidino Water-soluble azo compounds such as propane) hydrochloride and hydrogen peroxide can be used. Examples of the lipophilic polymerization initiator include azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexanone-1-carbonitrile), Lipophilic azo compounds such as dimethyl 2'-azobisisobutyrate, diethyl 2,2'-azobisisobutyrate, benzoyl peroxide,
Lauryl peroxide, diisopropyl peroxydicarbonate and di-t-butyl peroxide can be mentioned.

(2) Polyester Resin Obtained by Condensing Polyhydric Alcohol and Polybasic Acid As the polyhydric alcohol, HO—R ₁ —OH (R ₁ is a hydrocarbon chain having 2 to about 12 carbon atoms, especially Glycols having a structure of (aliphatic hydrocarbon chain) or polyalkylene glycol are effective,
Examples of the polybasic acids, HOOC-R ₂ -COOH (or R ₂ represents a mere bond or a hydrocarbon chain having 1 to 12 carbon atoms)
Are effective.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylene diol, 1,5-pentane Diol, neopentyl glycol, 1,6-hexanediol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Decanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythrit, mannitol, sorbit and the like.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cornic acid, azelaic acid, sebacic acid, decanedicarboxylic acid,
Dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohimeric acid, cyclopentadiene-maleic anhydride adduct,
Rosin-maleic anhydride adduct;

(3) Polyester Obtained by Ring-Opening Polymerization These polyesters include β-propiolactone, ε-
It can be obtained from caprolactone, dimethylpropiolactone and the like.

(4) Other Polymers Novolak resin, polycarbonate resin obtained by polycondensation of glycol or dihydric phenol with carbonate or phosgene, polyurethane resin obtained by polyaddition of polyhydric alcohol and polyisocyanate Or a polyamide resin obtained from a polyvalent amine and a polybasic acid.

The number average molecular weight of the polymer used in the present invention is not particularly limited, but is preferably 200,000 or less, more preferably 5,000 to 100,000.

The ratio (weight ratio) of the polymer of the present invention to the coupler is preferably from 1:20 to 20: 1, and more preferably from 1:10 to 10: 1.

Specific examples of the polymer used in the present invention are shown below, but it should not be construed that the invention is limited thereto. (The composition of the copolymer is shown by weight ratio.) P-1 poly (N-sec-butylacrylamide) P-2 poly (Nt-butylacrylamide) P-3 diacetoneacrylamide-methyl methacrylate copolymer (25:75) P-4 polycyclohexyl methacrylate P-5 Nt-butylacrylamide-methyl methacrylate copolymer (60:40) P-6 poly (N, N-dimethylacrylamide) P-7 poly (t- (Butyl methacrylate) P-8 polyvinyl acetate P-9 polyvinyl propionate P-10 polymethyl methacrylate P-11 polyethyl methacrylate P-12 polyethyl acrylate P-13 vinyl acetate-vinyl alcohol copolymer (9
0:10) P-14 polybutyl acrylate P-15 polybutyl methacrylate P-16 polyisobutyl methacrylate P-17 polyisopropyl methacrylate P-18 polyoctyl acrylate P-19 butyl acrylate-acrylamide copolymer (95: 5) P -20 Stearyl methacrylate-acrylic acid copolymer (90:10) P-21 Methyl methacrylate-vinyl chloride copolymer (70:30) P-22 Methyl methacrylate-styrene copolymer (90:10) P-23 methyl Methacrylate-ethyl acrylate copolymer (50:50) P-24 butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:30) P-25 vinyl acetate-acrylamide copolymer (8
5:15) P-26 vinyl chloride-vinyl acetate copolymer (65: 3)
5) P-27 methyl methacrylate-acrylonitrile copolymer (65:35) P-28 butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38: 3)
8:24) P-29 methyl methacrylate-butyl methacrylate-isobutyl methacrylate-acrylic acid copolymer (37: 29: 25: 9) P-30 butyl methacrylate-acrylic acid copolymer (95: 5) P-31 methyl Methacrylate-acrylic acid copolymer (95: 5) P-32 benzyl methacrylate-acrylic acid copolymer (93: 7) P-33 Butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (3
5: 35: 25: 5) P-34 butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (40: 30: 3)
0) P-35 diacetone acrylamide-methyl methacrylate copolymer (50:50) P-36 methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) P-37 ethyl methacrylate-butyl acrylate copolymer (70: 30) P-38 diacetone acrylamide-butyl acrylate copolymer (60:40) P-39 methyl methacrylate-styrene methacrylate-diacetone acrylamide copolymer (40: 4)
0:20) P-40 butyl acrylate-styrene methacrylate-diacetone acrylamide copolymer (70:20:
10) P-41 Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) P-42 Methyl methacrylate-styrene-vinylsulfonamide copolymer (70:20:10) P-43 Methyl methacrylate- Phenyl vinyl ketone copolymer (70:30) P-44 butyl acrylate-methyl methacrylate-butyl methacrylate copolymer (35:35:30) P-45 butyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90 : 10) P-46 polypentyl acrylate P-47 cyclohexyl methacrylate-methyl methacrylate-propyl methacrylate copolymer (37:
29:34) P-48 Polypentyl methacrylate P-49 Methyl methacrylate-butyl methacrylate copolymer (65:35) P-50 Vinyl acetate vinyl propionate copolymer (75:25) P-51 Butyl methacrylate-
3-acryloxybutane-1-sulfonic acid sodium copolymer (97: 3) P-52 butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) P-53 butyl methacrylate-methyl methacrylate-vinyl chloride Copolymer (37:36:27) P-54 butyl methacrylate-styrene copolymer (82:12) P-55 t-butyl methacrylate-methyl methacrylate copolymer (70:30) P-56 poly (N- t-butyl methacrylamide) P-57 N-t-butylacrylamide-methylphenyl methacrylate copolymer (60:40) P-58 methyl methacrylate-acrylonitrile copolymer (70:30) P-59 methyl methacrylate-methyl Vinyl ketone copolymer (38: 72) P-60 methyl methacrylate-styrene copolymer (75:25) P-61 methyl methacrylate-hexyl methacrylate copolymer (70:30) P-62 butyl methacrylate-acrylic acid copolymer (85:15) P -63 Methyl methacrylate-acrylic acid copolymer (80:20) P-64 Methyl methacrylate-acrylic acid copolymer (90:10) P-65 Methyl methacrylate-acrylic acid copolymer (98: 2) P-66 Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) P-67 Butyl methacrylate-vinyl chloride copolymer (90:10) P-68 Butyl methacrylate-styrene copolymer (70:30) P -69 1,4-butanediol-adipate polyester P-70 Lenglycol-sebacic acid polyester P-71 polycaprolactam P-72 polypropiolactam P-73 polydimethylpropiolactone P-74 Nt-butylacrylamide-dimethylaminoethylacrylamide copolymer (85:15) P-75 Nt-butyl methacrylamide-vinylpyridine copolymer (95: 5) P-76 diethyl maleate-butyl acrylate copolymer (65:35) P-77 Nt-butyl acrylamide-2-methoxyethyl acrylate Copolymer (55:45) P-78 ω-methoxy polyethylene glycol methacrylate (additional mole number n = 6) -methyl methacrylate (40:60) P-79 ω-methoxy polyethylene glycol acrylate (additional mole number n = 9) -Nt-butyl Acrylamide (25:75) P-80 poly (2-methoxyethyl acrylate) P-81 poly (2-methoxyethyl methacrylate) P-82 poly [2- (2-methoxyethoxy) ethyl acrylate] P-83 2- ( 2-butoxyethoxy) ethyl acrylate-methyl methacrylate (58:42) P-84 poly (oxycarbonyloxy-1,4-phenyleneisobutylidene-1,4-phenylene) P-85 poly (oxyethyleneoxycarbonyliminohexa) Methyleneiminocarbonyl) P-86 N- [4- (4'-hydroxyphenylsulfonyl) phenyl] acrylamide-butyl acrylate copolymer (65:35) P-87 N- (4-hydroxyphenyl) methacrylamide-N- t-butylacrylamide Polymer (5
0:50) P-88 [4- (4'-hydroxylphenylsulfonyl) phenoxymethyl] styrene (m, p mixture)-
Nt-butylacrylamide copolymer (15:85) In a preferred embodiment of the present invention, the layer containing a yellow color coupler contains a stain inhibitor in an amount of 1 to 5 mol% based on the yellow color coupler. Further, it is preferable that the compound represented by the following general formula (B) is contained in the layer containing a yellow color coupler.

[0224]

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[0225] In the formula, R _11, R ₁₂ and R ₁₃ are a hydrogen atom or represents an unsubstituted linear or branched alkyl group, R ₁₄
Represents an alkyl group or a halogen atom. Where R ₁₁ and R
₁₂ and R ₁₃ are not hydrogen atoms at the same time. n is 0,
Represents 1 or 2, and when n is 2, two R ₁₄ may be the same or different.

In the general formula (B), R ₁₁ , R ₁₂ and R ₁₃
Examples of the linear or branched alkyl group represented by are methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, pentyl, t
tert-pentyl, hexyl, octyl, tert-octyl, nonyl, decyl, dodecyl, tert-dodecyl, sec-tetradecyl, iso-palmityl, stearyl, iso-stearyl and the like.

The alkyl group represented by R ₁₄ includes R ₁₁ and R ₁₂
And R ₁₃ represent the same groups as above, but may have a substituent. Examples of the halogen atom represented by R ₁₄ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Preferably, n is 0, and one of R ₁₁ and R ₁₂ is a hydrogen atom. Particularly preferably, n is 0
R ₁₁ and R ₁₂ are hydrogen atoms, and R ₁₃ is a branched alkyl group (that is, a phenol compound having a branched alkyl group only at the para position). More preferably, n is 0
R ₁₁ and R ₁₂ are hydrogen atoms, and R ₁₃ is a branched alkyl group having 8 to 12 carbon atoms. Most preferably,
n is 0, R ₁₁ and R ₁₂ are hydrogen atoms, and R ₁₃ is a branched alkyl group having 9 to 12 carbon atoms.

Hereinafter, typical specific examples of the compound represented by formula (B) will be shown, but the present invention is not limited thereto.

[0230]

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[0231]

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The compound of the general formula (B) is used in an amount of 1 × 10 ^{-2 to} 5 mol, preferably 5 × 10 ^-2 to 2 mol, per 1 mol of the yellow color coupler represented by the general formula (Y) of the present invention. It can be used in the molar range.

These compounds may be dissolved and emulsified and dispersed in a high boiling point solvent together with a yellow coloring coupler.
It may be independently dissolved in a high boiling point solvent, emulsified and dispersed, and then added.

The yellow color coupler of the present invention preferably has a dielectric constant of 3.0 to 6.0 other than the polymer of the present invention.
The mixture is emulsified and dispersed as a mixed solution in which at least one of the solvents having a high boiling point is present. The high-boiling organic solvent as used herein means a solvent having a boiling point of 100 ° C. or higher,
A water-insoluble high-boiling organic solvent having a temperature of not lower than 0 ° C is preferred. The dielectric constant indicates a dielectric constant at 30 ° C. Examples of preferably used high-boiling organic solvents include phthalates,
Phosphoric acid esters, phosphonic acid esters, benzoic acid esters, fatty acid esters, organic acid amides, ethers, phenols, ethers, ketones and the like.

Specific examples of the high boiling point organic solvent are shown below, but the present invention is not limited to these.

[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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In the high-boiling solvent dispersion in which the yellow coloring coupler is dissolved, the ratio of the amount of high-boiling organic solvent / the amount of coupler (weight ratio) is preferably from 0.05 to 0.8, particularly preferably from 0.1 to 0.4. Is more preferable.

In the emulsification and dispersion, if necessary, the coupler is dissolved using a low boiling point and / or a water-soluble organic solvent in combination, and the emulsion is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added.

Examples of the low boiling organic solvent include ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β
-Ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone and the like. Examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, acetone, and tetrahydrofuran.
These organic solvents can be used in combination of two or more as necessary.

The coating amount of gelatin in the layer containing a yellow color coupler of the present invention is preferably optimized, and the coating amount is preferably 0.80 to 1.50 g / m ² , and more preferably 1.00 to 1.50 g / m ² . More preferably, it is 30 g / m ² .

In the present invention, the layer adjacent to the layer containing the yellow color coupler contains a fluorescent whitening agent and a compound capable of capturing the fluorescent whitening agent. As the fluorescent whitening agent and the scavenger, those described in the fifth aspect can be used in the same manner.

A tenth aspect of the present invention is characterized in that the support of the light-sensitive material of the first to ninth aspects is a plastic support, and the eleventh aspect has an oxygen transmission rate of the support of 2.0 ml.
/ M ² · hr · atm or less.

Examples of the polymer forming the plastic film constituting the support include homopolymers and copolymers such as polyester (eg, polyethylene terephthalate), vinyl alcohol, vinyl chloride, vinyl fluoride, vinyl acetate, cellulose acetate, acrylonitrile, and acrylic acid. Examples thereof include homopolymers and copolymers of alkyl esters, alkyl methacrylates, methacrylonitriles, alkyl vinyl esters, alkyl vinyl ethers, polyamides and the like.

Particularly preferred among these polymers are polyesters. The polyester mentioned here is
Not to mention thermoplastic resin consisting of polyester only,
As long as the resin properties of the polyester as the main component do not fluctuate practically, those containing other polymers, additives and the like are also included.

Examples of the polyester include a condensate of an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid with a glycol such as ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Such as polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and copolymers thereof.

As the polyester, polyethylene terephthalate (hereinafter abbreviated as PET) is preferable. P
The ET film does not penetrate water, has excellent smoothness, has excellent mechanical properties such as tensile strength and tear strength, has excellent dimensional stability such as heat shrinkage, and has excellent chemical resistance during development processing. .

The support may be a reflective support or a transmissive support. In the case of a reflective support, a white pigment may be contained in order to impart reflectivity, or a hydrophilic colloid layer containing a white pigment may be provided on a transparent support.

As the white pigment, an inorganic and / or organic white pigment can be used, and preferably an inorganic white pigment, specifically, a sulfate of an alkaline earth metal such as barium sulfate, calcium carbonate, etc. And alkaline earth metal carbonates, finely divided silica, synthetic silicate silica, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate, calcium carbonate, titanium oxide.

When the white pigment is contained in the plastic film support, the white pigment is preferably present in an amount ranging from 5 to 50% by weight based on the weight of the polymer forming the plastic film.

The light-sensitive material of the present invention is for direct viewing, and in this case, the reflective support or the transmissive support used is preferably visually white. A characteristic representing whiteness is whiteness.

As the whiteness, for example, JIS Z-872
2. There is a value (L ^* a ^* b ^* ) measured according to the method specified in Z-8730, and according to this, L ^* is 80%
Or more, more preferably L ^* is 90% or more, a ^* is -1.0 to +1.0, and b ^* is -2.0 to -5.
Those in the range of 0 are preferred.

The reflective support or the transmissive support is preferably glossy. Gloss is one of the characteristics representing gloss. As the glossiness, for example, there is a value measured according to the method specified in JIS Z-8741. According to this, the glossiness is preferably 90% or more, more preferably 95% or more.

The reflective support or the transmissive support only needs to have appropriate rigidity in handling. A characteristic representing rigidity is rigidity. As the stiffness, for example, TAPPI T-
There is a value measured according to the method defined in H.489, and according to this, the stiffness is preferably 8 g or more in LD (vertical stiffness) and 8 g or more in TD (lateral stiffness).

In the present invention, the oxygen permeability of the support is preferably 2.0 ml / m ² · hr · atm or less. The oxygen permeability of the support can be measured by a known method, and is determined, for example, by the ASTM D-1434 method.

The support is preferably 1.0 ml / m ² · h
As a support that satisfies the requirement and is not more than r · atm, a plastic film and the like can be mentioned.

In the present invention, the silver halide used in the silver halide emulsion layer may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and the like. And silver halide. In the present invention, the silver halide emulsion preferably has a silver chloride content of 95 mol% or more, and more preferably silver chlorobromide containing substantially no silver iodide.
From the viewpoint of rapid processing property and processing stability, preferably 97 mol%
As described above, a silver halide emulsion containing 98 to 99.9 mol% of silver chloride is more preferable.

As a preferred embodiment of the silver halide emulsion, a metal compound of Groups 5 to 14 of the periodic table can be contained. The application of such a metal compound is particularly useful for improving reciprocity failure characteristics required for a silver halide photographic material and adjusting sensitometric characteristics. Further, it is effective for improving the change in gradation due to the stagnation of the coating liquid.

The metal compounds that can be used for such purposes include manganese, iron, cobalt, nickel,
Molybdenum, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, zinc,
Mercury, cadmium, gallium, indium, lead and the like can be mentioned. Among the preferred metal elements, iron,
Osmium and ruthenium can be mentioned.

These metal compounds can be added to a silver halide emulsion in the form of a salt or a complex salt.

When the metal compound is used as a complex, its ligand may be cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, or the like.
Examples include chloride ion, bromide ion, iodide ion, nitrate ion, nitrosyl, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion, nitrosyl and the like are preferable.

In order to make the silver halide emulsion contain a metal compound in the present invention, the metal compound is physically ripened before silver halide grains are formed, during silver halide grains, and after silver halide grains are formed. What is necessary is just to add in the arbitrary places of each process inside. In order to obtain a silver halide emulsion satisfying the above conditions, the metal compound can be dissolved together with the halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the metal compound to be added to the silver halide emulsion is preferably from 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol, more preferably from 1 × 10 ⁻⁸ mol to 1 × 10 ⁻² mol, per mol of silver halide. 5 × 10 ^-5 mol is preferred.

Specific examples of metal compounds that can be preferably used are shown below.

[0268]

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The shape of the silver halide grains used in the present invention may be any. One preferable example is a cube having a {100} plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,22;
5,666, JP-A-55-26589, and JP-B-55-55.
No. 42737 and the Journal of Photographic Science (J. Photogr. Sc.
i. ) Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). Furthermore,
Particles having twin planes may be used. As the silver halide grains, grains having a single shape are preferably used,
It is particularly preferred to add two or more monodispersed silver halide emulsions to the same layer.

In the present invention, the particle size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing property and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

The particle size can be measured by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

In the present invention, the grain size distribution of the silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of preferably 0.22 or less, more preferably 0.15 or less.
Particularly preferably, a monodisperse emulsion having a variation coefficient of 0.15 or less is used.
More than one kind is added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S represents the standard deviation of the particle size distribution, and R represents the average particle size.) Various apparatuses and methods known in the art can be used for preparing silver halide emulsions. A method can be used.

In the present invention, the silver halide emulsion may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No. 92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt described in, for example, German Offenlegungsschrift 2,921,164. And a device for continuously adding an aqueous solution of a water-soluble halide salt while changing its concentration, Japanese Patent Publication No. 56-5
No. 01776 or the like, a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form a grain while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

In the present invention, the silver halide emulsion can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. In particular, by using gold sensitization, it is possible to reduce the change in gradation when the coating solution is stagnated, which is a preferred embodiment of the present invention.

As the gold sensitizer used in the present invention, various gold complexes such as chloroauric acid and gold sulfide can be used. When a gold complex is used, examples of the ligand compound include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole.
The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually from 1 × 10 ⁻⁴ mol per mol of silver halide.
It is preferably 1 × 10 ⁻⁸ mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

As the chalcogen sensitizer applied to the silver halide emulsion in the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but a sulfur sensitizer is preferable. As a sulfur sensitizer, thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate,
Rhodanin, inorganic sulfur and the like.

In the present invention, the amount of the sulfur sensitizer to be added is preferably changed depending on the kind of the silver halide emulsion to be applied, the size of the expected effect, and the like, but 5 × 10 ⁻ per mol of silver halide. The range is preferably from ^{10 to} 5 × 10 ⁻⁵ mol, more preferably from 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

In the present invention, a reduction sensitization method may be used as a chemical sensitization method for a silver halide emulsion.

The silver halide emulsion used in the present invention can prevent fogging that occurs during the preparation process of a silver halide photographic light-sensitive material, reduce performance fluctuations during storage,
Known antifoggants and stabilizers can be used for the purpose of preventing fogging during development. Examples of preferred compounds that can be used for such purposes are described in
Compounds represented by the general formula (II) described in the lower column of page 1 of JP-A-146036 can be mentioned. More preferred specific compounds are (IIa-) described on page 8 of the same publication.
1) to (IIa-8), (IIb-1) to (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5
Compounds such as mercaptotetrazole can be mentioned.

These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, a step of finishing a chemical sensitization step, a step of preparing a coating solution and the like according to the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol per mol of silver halide is used.
It is preferably used in an amount of about ^-4 mol.

When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide, and is preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻ mol. ³ moles are more preferred. In the step of preparing a coating solution, when adding to the silver halide emulsion layer, 1 mol per mol of silver halide is used.
Preferably the amount of about × 10 ^-6 mol to 1 × 10 ^-1 mol, 1
More preferably, it is from × 10 ⁻⁵ mol to 1 × 10 ⁻² mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

When the light-sensitive material of the present invention is used as a color photographic light-sensitive material, the light-sensitive material may be used in combination with a yellow coupler, a magenta coupler, and a cyan coupler in an amount of 400 to 900 nm.
It has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the m wavelength range. The silver halide emulsion is one kind or
It contains two or more sensitizing dyes in combination.

As the spectral sensitizing dye for use in the silver halide emulsion of the present invention, any of the known compounds can be used.
BS-1 to 8 described on page 28 of No. 251840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-1 described on page 28 of the same publication
5 is preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye.
The dyes of IRS-1 to 11 described in JP-A-285950, pages 6 to 8 are preferably used.

Further, these infrared, red, green, and blue photosensitive sensitizing dyes include supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-285. -66515 1
It is preferable to use compounds S-1 to S-17 described on pages 5 to 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A-1 to A-11 described in JP-A-64-26854
Is mentioned. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution after the addition are preferably 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

As the hardener of the binder, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24905
It is preferable to use the compounds described in JP-A Nos. 4 and 61-245153. Further, in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image preservability, Japanese Patent Application Laid-Open No.
It is preferable to add a preservative and an antifungal agent as described in JP-A-157646. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, a protective layer is disclosed in JP-A-6-11854.
No. 3 or JP-A-2-73250 is preferably added.

The light-sensitive material of the present invention may further include a color fogging inhibitor, a plasticizer, an anti-irradiation dye, a polymer latex, a formalin scavenger, a development accelerator,
A development retardant, a matting agent, a lubricant, an antistatic agent and the like can be optionally used. These compounds are described in, for example, JP-A Nos. 62-215272 and 63-46436.

At the time of coating a photographic material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

According to a twelfth aspect of the present invention, the original material is scanned with respect to the photosensitive material according to any of the first to eleventh aspects, and the photosensitive material is exposed for a time of 10 ^-4 seconds or less based on the image signal. This is a method for forming an image or a positive image.

The principle of obtaining a color image by a so-called scanning type exposure device that scans a light-sensitive material surface with a light beam will be described.

The color image data separated into the three colors B, G, and R are converted into light intensities in different wavelength bands, and the light is scanned on the photosensitive material using the light. The term “scanning” used herein refers to the movement of light or the movement of a photosensitive material, and refers to the movement of light relative to the photosensitive material. As the photosensitive material, a material having a spectral sensitivity distribution corresponding to the intensity distribution of the three types of light used is used. The photosensitive material receives a light signal that is intensity-modulated based on color image data of B, G, and R corresponding to each of the three types of spectral sensitivities, and forms an appropriate color according to the light signal, thereby forming a color image. Obtainable.

As three types of light sources, those using three colors of B, G, and R are known. Known light sources include a combination of a white light source such as a glow lamp, a xenon lamp, a mercury lamp, and a tungsten lamp and a filter, a light emitting diode, a gas laser, a solid-state laser, and a semiconductor laser. Generally, a coherent laser is often used as a light source in terms of high brightness, focusing, and monochromaticity.

The light source used in the present invention is preferably a combination of a white light source such as a glow lamp, a xenon lamp, a mercury lamp, and a tungsten lamp and a filter, a light emitting diode, a gas laser, a solid laser, and a semiconductor laser. Laser light having a narrow intensity distribution is preferred.

Also, a combination of various lasers and a wavelength conversion element may be used, and a combination of an infrared semiconductor laser and an SHG element is preferable in terms of compactness.

[0301] As a specific example, He-C
d gas laser (441.6 nm), Ar ⁺ gas laser (488.0 nm), He-Ne gas laser (44
He-Ne gas laser (543.5 nm), Ar ⁺ gas laser (514.5 nm)
nm), Kr ⁺ gas laser (520.8 nm), YA
As a yellow light such as a G laser or a combination of an infrared semiconductor laser and an SHG element, a He-Ne gas laser (59
He-Ne gas laser (632.8 nm), Kr ⁺ gas laser (647.7 nm), red light such as a combination with a light emitting diode (peak wavelength 570 nm), an infrared semiconductor laser SHG element, etc.
1 nm), semiconductor laser (678 nm, 750 nm,
780 nm).

If a He-Ne gas laser is used as a light source, a stable, inexpensive and compact device can be obtained.

[0303] A plurality of oscillations may be obtained from one He-Ne gas laser, and the oscillations may be separated by a dichroic mirror or the like. For example, from one He-Ne gas laser to 4
Oscillation lines (442 nm, 543.5 nm, 59
4.1 nm, 632.8 nm).

In the case of flash exposure, the exposure time in the present invention refers to the time variation of the light intensity that starts from when it reaches half of its maximum value and attenuates to its maximum value. In the case of scanning exposure with a laser beam, in a spatial change in the intensity of the light beam, the time when the light intensity becomes 1/2 of the maximum value 2 where the outer edge of the light beam intersects with a line passing through a point parallel to the scanning line and having the maximum light intensity as the outer edge
When the distance between the points is the diameter of the light beam, (light beam diameter) / (scanning speed) = exposure time.

In scanning exposure using a linear light source,
It may be considered the same as the case of the laser light described above.

As a laser printer device which is considered to be applicable to such a system, for example, Japanese Patent Application Laid-Open
No. 4071, No. 59-11062, JP-B-56-14
No. 963, No. 56-40822, European Patent 77,41
No. 0, IEICE Technical Report Vol 80, No. 2
44 and Movie Television Technology 1984/6 (382), 34
On page 36 and the like.

(Development treatment) As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD -4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-(Β- (methanesulfonamido) ethyl) aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-
N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in any pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature for color development used in the present invention is preferably 35 to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high, and the processing is preferably performed at 37 to 60 ° C.

[0310] Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 45 seconds, more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

The developing apparatus used for developing the photosensitive material of the present invention may be a roller transport type in which the photosensitive material is conveyed between rollers arranged in a processing tank, and the photosensitive material may be fixed to a belt. An endless belt system may be used, in which the processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and the photosensitive material is transported, or a spray method in which the processing liquid is sprayed Alternatively, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

[0314]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Relating to Claims 1 and 2) A transparent polyester film support made of polyester (polyethylene terephthalate) having a thickness of 180 μm was used as a support, and gelatin undercoat layers were provided on both sides of the support. Each layer having the composition shown in Tables 2 and 3 was applied to prepare a silver halide photographic material for direct viewing. The coating solution was prepared as follows.

The support used here had an oxygen permeability of 1.6 ml / m ² · hr · atm.

First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 1.67
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
4) 0.34 g, 4.98 g of high boiling point organic solvent (DNP)
60 ml of ethyl acetate was added to the solution to dissolve the solution.
Using an ultrasonic homogenizer, the mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of a surfactant (SU-1) to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts shown in Tables 2 and 3 were obtained.

Further, (H-1), (H-2)
Was added. Surfactants (SU-
2) A fluorinated surfactant (SU-3) was added to adjust the surface tension. The total amount of F-1 was 0.04 g /
m ² .

[0320]

[Table 2]

[0321]

[Table 3]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-4: 2,5-di-t-octylhydroquinone HQ-7: 2,5-di-sec-dodecylhydroquinone HQ-8: 2 5-di-sec-tetradecylhydroquinone HQ-9: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-19: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A: pt-octylph Enol compounds B, C, D, E: HQ-7, 8, 9, 19, respectively
Quinone body

[0323]

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[0324]

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[0325]

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[0326]

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[0327]

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

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the addition time of (Solution A) and (Solution B) and (Solution C) and (Solution D)
Monodisperse cubic emulsion EMP- having an average particle size of 0.64 μm, a variation coefficient of particle size distribution of 0.07, and a silver chloride content of 99.5 mol% in the same manner as in EMP-1 except that the addition time was changed.
1B was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Similarly, EMP-1B was optimally chemically sensitized and then sensitized to EM.
P-1 and EMP-1B were mixed at a silver ratio of 1: 1;
A blue-sensitive silver halide emulsion (Em-B) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, an average particle size of 0.50
A monodisperse cubic emulsion EMP-2B having a thickness of 0.08 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Similarly, EMP-2B was optimally chemically sensitized and then sensitized to EM.
P-2 and EMP-2B were mixed at a silver ratio of 1: 1;
A green-sensitive silver halide emulsion (Em-G) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. Average particle size 0.38μ
m, a coefficient of variation of 0.08, and a monodispersed cubic emulsion EMP-3B having a silver chloride content of 99.5% were obtained.

The above EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Similarly, EMP-3B was optimally chemically sensitized and then sensitized to EM.
P-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole SS-1 was added in an amount of 2.0 × 10 ⁻³ per mol of silver halide.

[0336]

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[0337]

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The sample thus prepared was designated as 101, and the yellow coupler of the first layer and its coating amount (mol / m
² ) and the amount of gelatin applied were changed as shown in Table 4, and 4.68 g of each of the polymer compounds (Exemplary P-2) shown in Table 4 was added to the yellow coupler dispersion. Samples 102 to 120 were produced in the same manner as in Sample 101 except that the fluorine-containing surfactant described in (1) was added. However, in Sample 115 (HQ-4 = 0.34 g (that is, HQ-4 was 2.5 mol% with respect to the yellow coupler)), the addition amount of HQ-4 was 0.0
8, 0.15, 0.58, 0.76 (i.e., HQ-4 is 0.6, 1.1,
4.3 to 5.6 mol%), and samples prepared in the same manner as in 115 except for changing to 117 to 120.

The thus prepared sample was exposed to light wedge by a conventional method, and then subjected to a developing process in the following developing process.

An image reading apparatus using a scanner system was used, and the input signal obtained by this was subjected to scanning exposure on a photosensitive material by a commercially available laser printer using a connected signal output apparatus. . The following light sources and wavelengths were used for scanning exposure.

Blue light He-Cd gas laser (441.6 nm) Green light He-Ne gas laser (543.5 nm) Red light He-Ne gas laser (632.8 nm) The original image is a very ordinary scene. Color prints and slides, and wedges as needed for evaluation were used.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 18 seconds 60 ml Bleaching and fixing 35.0 ± 0.5 ° C. 22 seconds 80 ml Stabilization 30-34 ° C. 40 seconds 120 ml Drying 60-80 30 ° C. The composition of the developing solution is shown below.

Color developer tank liquid and replenisher tank liquid Replenisher pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 4.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 8.0 g N, N-diethylhydroxylamine 5.5 g 7.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriamine Pentaacetic acid pentasodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. pH = 1
At 0.60, the replenisher is adjusted to pH = 11.00.

Bleach-fix solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 75 g 3.5 g diethylenetriaminepentaacetic acid 3.5 g Ammonium thiosulfate (70% aqueous solution) 150 ml 2-amino-5-mercapto-1,3,4- Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 33.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water.

The residual fluorine ratio of the sample after the development was measured by the method described in the above detailed description. On the other hand, the electric displacement of the photosensitive material surface was measured by the following method.

Electric Displacement of Photosensitive Material Surface The electric displacement of the sample surface of the raw sample on the photosensitive layer side of the raw sample was determined under the following conditions by using a “peeling charge amount measuring device” manufactured by Konica Corporation.

Photosensitive material installation stage material Stainless steel Contact member Polyurethane rubber Contact member installation support plate Stainless Contact-separation frequency when contact potential is generated 10 times / 20 seconds As contact potential difference V, electric displacement D is D = V × 1000
Calculated for convenience as / 3 × 10. The unit of the calculated numerical value is pcoul / cm ² .

Table 4 also shows the results. The obtained sample was evaluated as follows. Table 5 shows the results.

[Evaluation] Static mark generation degree A sample was mounted in a loop on a transfer device in which the rotation axes of the three transfer rollers were mounted at the positions of the vertices of a triangle under light-shielding conditions, and the rotation speed of 265 rpm was 3 minutes. After continuous rotation, the taken-out sample was subjected to development processing according to a conventional method, and a static mark generated was evaluated. The evaluation was performed five times, and the average of the grades is shown.

Grade 1 No static mark generation Grade 2 Slight static mark generation Grade 3 Medium static mark generation Grade 4 Large static mark generation Grade 5 Extremely large static mark There is a tick mark.

The sticking resistance of the sample surface An undeveloped raw sample and a sample which has been subjected to development processing according to a conventional method are used. Make it bundled. After fixing, it was allowed to stand at 40 ° C. and 80% RH for 7 to 15 hours. Thereafter, the sample in a state where the sample surfaces were stuck together was peeled off, and the following five-level evaluation was performed with the sense of resistance at that time being sensed. The closer to 1, the better, and the closer to 5, the worse.

Grade 1 Sample surface is not adhered. Grade 2 Intermediate between 1 and 3 Grade 3 Resistance enough to make sound when peeled off Grade 4 Intermediate between 3 and 5 Grade 5 Sample surface adhered In a state where it cannot be peeled off.

Image Bleeding and Changes Over Time The original image of the color print was subjected to scanning exposure, and then developed, and the image bleeding of the color print obtained was visually evaluated for grade. The same evaluation was performed after storing this sample for one month under the conditions of 75 ° C. and 80%.

Grade 1 No image bleeding at all. Grade 2 Slight image bleeding. Grade 3 Medium-level image not yet graded. Grade 4 Image bleeding is large. There is.

[0356]

[Table 4]

* 1: The ratio, expressed as a percentage, of the amount of fluorine atoms present on the surface after development to the fluorine atoms existing on the surface before development.

[0358]

[Table 5]

As is clear from Tables 4 and 5, the samples of the present invention not only have improved surface properties such as static resistance and sticking resistance, but also have improved image blur resistance. However, the comparative examples show that all of these properties are inferior. This effect cannot be achieved by itself, and is, of course, not a mere sum of the effects of the respective technologies, but a remarkably improved effect which cannot be expected from the conventional technology.

In the samples of the present invention, no abnormalities in basic photographic performance (sensitivity, tone, fog) were observed.

Example 2 As a support, a 180 μm-thick translucent polyester (polyethylene terephthalate) containing ² g / m ² of barium sulfate was used as a translucent polyester film support, and both sides of this were subbed with gelatin. The layers were provided, and a silver halide photographic light-sensitive material for direct viewing was produced in the same manner as in Sample 101 of Example 1. This is designated as Sample 201. The oxygen permeability of the support used here was 1.8 ml / m ² · h
r · atm.

Sample 201 was prepared in the same manner as in Sample 201 except that the fluorine-containing surfactant, electric displacement (Pcoul / cm ² ), and the ratio (%) of residual fluorine atoms were changed as shown in Table 6 below.
In the same manner as in the above, samples 202 to 214 were produced. At this time, the ratio of the residual fluorine atoms after the development processing of the sample was measured by the method described in the detailed description.

[0363]

[Table 6]

* 2: The ratio of the amount of fluorine atoms present on the surface after the development processing to the number of fluorine atoms existing on the surface before the development processing expressed as a percentage.

Samples 222 to 234 were prepared in the same manner as in Sample 201 except that the amounts of the fluorescent whitening agent and the scavenger in the second layer and the A / B were changed as shown in Table 7 below. .

A / B was determined as follows.

The above undeveloped sample was fixed to a reflection sample measuring holder of the spectrofluorometer so that excitation light was irradiated at an incident angle of 45 ° and fluorescence was detected at an angle of 45 ° from the sample surface. The excitation wavelength and the fluorescence wavelength are respectively scanned, and the maximum excitation wavelength and the maximum fluorescence wavelength are obtained. The fluorescence detection wavelength is set to the maximum fluorescence wavelength, and the excitation wavelength is scanned under the following measurement conditions to measure the excitation spectrum. Let A be the intensity of the excitation spectrum at 360 nm. Subsequently, the excitation spectrum of the white background of the sample obtained by processing the same photosensitive material sample in the development processing step not containing the fluorescent whitening agent as shown below without exposure was measured by the same procedure, and the obtained excitation spectrum was obtained. Is B at 400 nm. A / B was determined from the measured values of A and B obtained.

Measurement Conditions Spectrofluorometer Hitachi F-3010 Model Spectrofluorometer Light Source 150W Xenon Lamp (USHIO UXL-157) Excitation-side bandpass 1.5 nm Fluorescence-side bandpass 1.5 nm Wavelength scanning speed 60 nm / min Response speed 2 seconds Measurement wavelength range 300 nm to 500 nm The spectrum was corrected using Rhodamine B reagent for fluorescence analysis as a reference to correct the influence of the wavelength characteristics of the measurement device (spectrometer, photomultiplier, etc.).

Development process Step Processing temperature Time Color development 38.0 ± 0.3 ° C. 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds Washing 30-34 ° C. 90 seconds Drying 60-80 ° C. 30 seconds Development Composition of treatment liquid Pure water 800 ml Triethylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline Sulfate 6.0 g N, N-diethylhydroxylamine 6.8 g Triethanolamine 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g Potassium carbonate 30 g Add water to make the total volume 1 liter, and adjust the pH to 10.10 I do.

Composition of Bleaching-Fixing Solution Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfate (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

[0371]

[Table 7]

* 3: Fluorescence intensity ratio Undeveloped sample (360
nm) / white background sample (400 nm) Further, the amount of the fluorescent whitening agent and the scavenger in the second layer, the amount of gelatin applied in the first layer, and the amount of the yellow coupler added were changed from Sample 201 as shown in Table 8 below. Others are the same as the sample 201 and the sample 242
To 254.

[0373]

[Table 8]

The obtained sample was exposed and developed in the same manner as in Example 1 and evaluated as follows. The results are shown in Tables 9, 10 and 11.

[Evaluation] Whiteness The sample was processed in the development processing step described in the section on fluorescence measurement while the sample was left unexposed, and the blue reflection density (D ₄₄₀ ) at ₄₄₀ nm of the obtained print was measured using a model 607 manufactured by Hitachi, Ltd. It was measured with a color analyzer. The difference was shown based on _D440 of Sample 201 as a reference.

Image bleeding was performed in the same manner as in the evaluation method described in Example 1 above.

Image aging change over time The sample used for the above-described image bleeding evaluation was stored for one month under the conditions of 75 ° C. and 80% temperature and humidity, and then the grade of dye image generation was evaluated by feeling. .

Grade 1 No image bleeding occurred. Grade 2 Slight image bleeding occurred. Grade 3 Medium image had no bleeding. Grade 4 Large image bleeding occurred. There is.

-Film peeling After the sample after the development treatment was immersed in water, the image forming surface side was scratched with a nail to add physical strength. At that time, the grade of the surface peeling state was evaluated by feeling.

Grade 1 No film peeling occurred. Grade 2 Slight film peeling occurred. Grade 3 Medium film peeling occurred. Grade 4 Large film peeling occurred. Grade 5 Extremely large film peeling occurred. is there.

The degree of occurrence of static marks The evaluation was performed in the same manner as in the evaluation method described in Example 1 above.

[0382]

[Table 9]

As can be seen from Table 9, the sample of the present invention showed only a slight occurrence of static marks.
It can be seen that physical properties such as image bleeding and image bleeding over time have been improved. However, the comparative examples show that all of these properties are inferior.

[0384]

[Table 10]

As is clear from Table 10, the samples of the present invention show only a slight occurrence of static marks, and have not only improved physical properties such as white background, but also improved the image forming layer support. It can be seen that the resistance to film peeling was also improved. However, the comparative examples show that all of these properties are inferior.

[0386]

[Table 11]

As is clear from Table 11, the samples of the present invention show only a slight occurrence of static marks, and have only improved physical properties such as image bleeding, image bleeding over time, and white background. It can be seen that the resistance of the image forming layer to film peeling from the support was also improved. However, the comparative examples show that all of these properties are inferior.

As is apparent from the second embodiment, these effects cannot be achieved by themselves, and are not merely sums of the effects of the respective technologies, but are significantly improved which cannot be expected from the conventional technology. The effect is. In addition, about the sample in this invention, basic photographic performance (sensitivity, tone, fog)
No abnormal performance was observed.

Example 3 As a support, a 180 μm thick polyester (polyethylene terephthalate) containing 60 g / m ² of barium sulfate was used as a white polyester film support, and gelatin undercoat layers were provided on both sides of the support. Sample 1 of 1
Sample 301 was prepared in the same manner as in Sample No. 01 to obtain a silver halide photographic light-sensitive material for direct viewing.

The support used here had an oxygen permeability of 1.9.
It was 5 ml / m ² · hr · atm.

First layer coating solution 0.98 g of yellow coupler (Y-1), 0.14 g of dye image stabilizer (ST-1), 0.14 g of (ST-2)
g, (ST-5) 0.14 g, a stain inhibitor (HQ-
4) 0.014 g, high boiling point organic solvent (DNP) 0.21
g of ethyl acetate and dissolve it.
A 10% aqueous gelatin solution containing 7 ml of a 10% surfactant (SU-1) was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 12 and 13.

(H-1), (H-2)
Was added. Surfactants (SU-
2) A fluorinated surfactant (SU-3) was added to adjust the surface tension. The total amount of F-1 was 0.04 g /
m ² .

[0394]

[Table 12]

[0395]

[Table 13]

The gelatin a used for each layer of the sample 301 was changed to gelatins be as shown in Table 14, respectively.
Sample 30 was used except that the total amount of gelatin applied was changed.
Samples 302 to 317 were prepared in the same manner as in Example 1, and exposed and developed in the same manner as in Example 1.

[0397] The results are shown in Table 14. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 15.

[0398]

[Table 14]

Gelatin a Lime-processed gelatin from beef bone as a raw material High molecular weight component 8.5% α component 35% Gelatin b Lime-processed gelatin from beef bone as a raw material High molecular weight component 6.0% α component 35% Gelatin c Beef Lime-processed gelatin using bone as a raw material High molecular weight component 3.5% α component 35% Gelatin d Lime-processed gelatin using pig skin as a raw material High molecular weight component 3.5% α component 44% Gelatin e Lime made from pig skin Treated gelatin High molecular weight component 2.5% α component 48%. Here, the high molecular weight components were reduced as described above and by.

[0400]

[Table 15]

As is clear from Table 15, the sample of the present invention has not only improved surface properties such as sticking resistance but also improved image bleeding resistance. However, the comparative examples show that all of these properties are inferior. This effect cannot be achieved by itself, and is, of course, not a mere sum of the effects of the respective technologies, but a remarkably improved effect which cannot be expected from the conventional technology.

In the sample of the present invention, no abnormality in basic photographic performance (sensitivity, tone, fog) was observed.

[0403]

According to the present invention, in a direct-viewing silver halide photographic light-sensitive material suitable for a direct-viewing printing material, an increase in the fluorescent whitening effect in an unexposed portion of the obtained display film and an improvement in whiteness can be achieved. Achieved, the static resistance is more effectively suppressed, the sticking resistance of the film surface and the peeling resistance of the image forming layer from the support are improved, and it is possible to exert an effect excellent in physical properties in handling. It has excellent effects.

Further, in a silver halide photographic light-sensitive material for direct viewing, the occurrence of bleeding of an image obtained after the development processing during scanning exposure is suppressed, and the bleeding of the image is not deteriorated even after long-term storage at high temperature and high humidity. It also has an effect.

Claims (12)

[Claims] 1. A halogen comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer. In the silver halide photographic light-sensitive material, the photographic constituent layer on the side opposite to the side on which the emulsion layer is provided contains an ultraviolet absorber liquid at 25 ° C., and the surface on the side on which the emulsion layer is provided is coated with urethane rubber. When contact and peeling were repeated 10 times for 20 seconds between the above and the above, the electric displacement generated on the emulsion layer coating side was 700 pcu.
1 / cm ² or less. 2. A halogen comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer. In the silver halide photographic light-sensitive material, the photographic constituent layer on the side opposite to the side on which the emulsion layer is coated contains an ultraviolet absorber liquid at 25 ° C., and the photographic constituent layer has the following general formula (F)
2. The silver halide photographic material according to claim 1, comprising at least one selected from the group consisting of fluorine-containing surfactants represented by A), (FK), (FB) and (FN). Formula (FA) (Cf)-(Y) _n [wherein, Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is —COO
_{M, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ . M is a hydrogen atom or an alkali metal or quaternary
Represents a cation such as a quaternary ammonium salt, wherein n is 1 or 2
It is. ] Formula (FK) Rf'-L-X + Z - wherein, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms,
At least one hydrogen atom has been replaced by a fluorine atom. L represents a chemical bond or a divalent group. X ⁺ is a cation, Z ^- represents a counter anion. General Formula (FB) R- (A) _m -X wherein R represents an alkyl group, an alkoxy group, an alkenyl group, an aryl group, or an aryloxy group containing a fluorine atom, and these are substituted. A may represent a divalent linking group, X represents a betaine group, and m represents 0
Or represents 1. Formula (FN) R- (G) _m -X wherein R represents an alkyl group, an alkoxy group, an alkenyl group, an aryl group, or an aryloxy group containing a fluorine atom, and these are substituted. G may represent a divalent linking group, X represents a hydrophilic group of a nonionic group, and m represents 0 or 1. ] 3. A halogen comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer. In the silver halide photographic light-sensitive material, the photographic component layer on the side opposite to the side on which the emulsion layer is coated contains a liquid ultraviolet absorber at 25 ° C., and the extreme surface on the image forming surface side before development processing Silver halide photographic material, wherein 50% or more of the fluorine atoms existing in the surface remain after development processing. 4. A halogen comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer. A silver halide photographic light-sensitive material, wherein the photographic constituent layer on the side opposite to the side on which the emulsion layer is provided contains an ultraviolet absorber liquid at 25 ° C. and satisfies the following formula: Silver halide photographic material. (A / B) <0.03 wherein A represents the fluorescence intensity of the silver halide photographic material before development at the maximum fluorescence wavelength at an excitation wavelength of 360 nm, and B represents the fluorescence intensity of the silver halide photographic material. It shows the fluorescence intensity at the maximum fluorescence wavelength at an excitation wavelength of 400 nm of an unexposed portion after a development step containing no fluorescent brightener. ] 5. A support comprising at least one silver halide emulsion layer, at least one ultraviolet absorber-containing layer, at least one fluorescent whitening agent-containing layer, and at least two fluorescent light-enhancing layers. A silver halide photographic light-sensitive material comprising a layer containing a compound capable of capturing a whitening agent and at least one photographic component layer provided on a support opposite to the emulsion layer, wherein the emulsion layer is provided; The photographic constituent layer on the opposite side contains a UV absorber in a liquid state at 25 ° C., and the UV absorber-containing layer provided at a position farthest from the support in the UV absorber-containing layer, and At least one layer selected from layers provided farther from the support than the ultraviolet absorber-containing layer contains a compound capable of capturing a fluorescent whitening agent, and ultraviolet light provided farthest from the support More support than absorbent-containing layer A silver halide photographic material comprising a fluorescent whitening agent and a compound capable of capturing the fluorescent whitening agent at a position close to the carrier. 6. A layer containing both a fluorescent whitening agent and a compound capable of capturing the fluorescent whitening agent at a position closer to the support than the ultraviolet absorber-containing layer provided farthest from the support. 6. The silver halide photographic light-sensitive material according to claim 5, wherein 7. A halogen comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer. In the silver halide photographic light-sensitive material, the photographic constituent layer on the side opposite to the side on which the emulsion layer is coated contains an ultraviolet absorber liquid at 25 ° C., and at least one of the photographic constituent layers on both sides of the support is provided. A layer containing gelatin having a high molecular weight component content of 8% or less, and a compound capable of capturing an optical brightener in a photographic component layer on the side on which the emulsion layer is provided. Silver halide photographic light-sensitive material. 8. A halogen comprising at least one photosensitive silver halide emulsion layer provided on a support, and at least one photographic component layer provided on the support opposite to the emulsion layer. In the silver halide photographic light-sensitive material, the photographic constituent layer opposite to the side on which the emulsion layer is provided contains a liquid ultraviolet absorber at 25 ° C. and is coated on a support. Has a dispersion obtained by emulsifying and dispersing a mixed solvent containing at least one water-insoluble and organic solvent-soluble polymer compound, and the layer adjacent to the yellow color coupler-containing layer has a fluorescent whitening agent and a fluorescent brightening agent. A silver halide photographic material containing a compound capable of capturing a whitening agent. 9. The silver halide photographic material according to claim 8, wherein the photographic constituent layer has a yellow color coupler represented by the following general formula (Y). Embedded image [Wherein, R _A represents an alkyl group, R _B represents a halogen atom or an alkoxyl group, and R _C represents —COOR _D1 , —C
_{OOR D2 COOR D1, -NHCOR D2 SO} 2 R D1, -N
(R _D3 ) SO ₂ R _D1 or —SO ₂ N (R _D3 ) R _D1 .
R _D1 represents a monovalent organic group, R _D2 represents an alkylene group, and R _D3 represents an alkyl group, an aralkyl group, or a hydrogen atom. Y _A represents a monovalent organic group, n represents 0 or 1,
R _E and R _F each represent a hydrogen atom or an alkyl group. ] 10. The silver halide photographic light-sensitive material according to claim 1, wherein the support is a plastic support. 11. The oxygen permeability of the support is 2.0 ml.
/ M ² · hr · atm or less, wherein the silver halide photographic light-sensitive material according to any one of claims 1 to 10, wherein 12. The halogenation method according to claim 1, wherein the original figure is scanned, exposure is performed for a time of 10 ^-4 seconds or less based on the image signal, and an image corresponding to the original figure image is formed. An image forming method comprising forming a silver photographic material.