JPH0915803A - Sliver halide color photosensitive material and image forming device - Google Patents

Abstract

PURPOSE: To provide the same gradation and sensitivity when either of general processing and superquick processing is performed by containing a specified anionic water-soluble polymer and a specified alkali-soluble polymer dispersion having an average particle size within a specified range. CONSTITUTION: An anionic water-soluble polymer represented by the formula I and an alkail-soluble polymer dispersion with an average particle size of 0.01-0.5μm represented by the formula II are contained in a hydrophilic colloid layer constituting a photosensitive material, and the gradations obtained when processings differed in color developing time are performed are substantially the same. In the formulae, R<1> represents hydrogen atom or the like, L represents a divalent quandrivalent connecting group, M represents hydrogen atom or a cation, (m) represents 0 or 1, (n) represents an integer of 1-3, D and D2 each represent the repeat unit of an ethylenic unsaturated monomer. (y) and (z) each represent the weight percent ratio of each monomer component, wherein (y) is 0-05, (z) is 5-100, and y+z=100. (p) and (q) each represent weight percent ratio of each monomer, wherein (p) is 0-85, (q) is 15-100, and p+q=100.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material suitable for rapid processing and a color image forming method. More specifically, the invention relates to gradation balance and sensitivity balance associated with shortening of color development processing time. The collapse is improved,
A silver halide that makes it possible to obtain an image with the same gradation and sensitivity in both the development processing and the rapid development processing that are currently widespread, and in which the time dependence of the development progress during the rapid development processing is improved. The present invention relates to a color photographic light-sensitive material and a color image forming method.

[0002]

2. Description of the Related Art The processing time for developing a color negative film is
The C-41 treatment introduced by Kodak Company in 1972 significantly accelerated the wet treatment time to 17 minutes and 20 seconds without the drying step time. In addition, CN-of Fuji Photo Film Co., Ltd., which was recently introduced into the minilab market
Wet processing time of 16FA processing is further shortened to 8
It's 15 minutes.

Even when the development process is being accelerated, if a user requests simultaneous printing of color negative film taken, it takes about 30 minutes to complete even the fastest in-store processing (so-called minilab). The current situation is to force the majority of users to visit the photo shop twice. In the current system based on the combination of color negative film and color paper, further shortening of development processing time is desired in order to meet the user's desire to visit a photo shop at once.

The speeding up of conventional development processing is mainly done in the desilvering step after the color development processing step. Taking the above-mentioned C-41 processing and CN-16FA processing as an example, the former color development processing is carried out. The processing time is 3 minutes and 15 seconds and that of the latter is 3 minutes and 5 seconds.
Seconds, there is almost no change in the color development processing time. In the CN-16FA process, the color development processing time accounts for about 40% of the total development processing time. To further shorten the development processing time, the color development processing time must be shortened. Is inevitable.

On the other hand, the C-41 process and the developing process compatible with it (for example, the CN-16FA process) are now widely used all over the world. In such a situation, in order to promptly introduce the rapid development processing in which the color development processing time is shortened and the photosensitive material for rapid development processing into the market, the photosensitive material for rapid development processing and C-41 It is desirable to be compatible with the processing.

Usually, a color negative film is composed of a plurality of color-sensitive silver halide emulsion layers, and when developed,
It is designed so that the gradation and sensitivity of each color-sensitive layer have a certain balance. However, when the rapid development processing in which the color development processing time is shortened is performed, the gradation and sensitivity balance are lost, and the color reproducibility and tone reproduction are deteriorated. Such an imbalance was remarkable in the lower layer than the upper layer of the light-sensitive material having a plurality of color-sensitive layers, in other words, in the color-sensitive layer close to the support (usually a red-sensitive silver halide emulsion layer in a photographic material). .

On the other hand, photographic performance such as gradation and sensitivity is influenced by fluctuations in processing conditions such as processing time of color development processing, processing temperature, processing solution pH, concentration of developing agent, etc. for stable finish of development processing. It is necessary to develop a photosensitive material that is difficult to receive, in other words, has little processing condition dependency. But,
When the color development processing time is shortened, it is extremely difficult to reduce the processing time dependency. Because, for example, 3 minutes 15 seconds processing and 1 in color development processing
When it is desired to obtain the same gradation and sensitivity in the minute processing, the developing speeds in these two processings are of course very different, and even if the processing time error is the same 10 seconds,
This is because the change in sensitivity varies greatly.

A processing method for obtaining the same gradation even if development processing is performed at different color development processing times is disclosed in, for example, Japanese Patent Application Laid-Open No. 2553/1990. According to the processing method, the same gradation can be obtained by the two processes by changing the processing temperature, the concentration of the color developing agent in the color developing solution and the color development processing time. Specifically, in Example 1 of the publication, the gradation is equivalent to that obtained at a processing temperature of 38 ° C., a color developing agent concentration of 15 mmol / liter, and a color developing processing time of 3 minutes 15 seconds (corresponding to C-41 processing). Gradation: processing temperature 38 ° C, color developing agent concentration 150
It is shown that it can be obtained in millimoles / liter and a color development processing time of 1 minute and 30 seconds.

However, shortening the color development processing time by the processing method causes various problems because the concentration of the color developing agent exceeds 100 mmol / liter. That is, as a result of the self-coupling reaction of the color developing agent being significantly promoted in the processing solution, the deterioration of the color developing processing solution is promoted, the fluctuation of photographic performance is increased, and at the same time, the photosensitivity by the self-coupling reaction product is increased. The coloring of the material is increased. Further, as a result of an increase in the residual amount of the color developing agent in the light-sensitive material after the development processing, a minimum density increase (stain) occurs during storage of the light-sensitive material.

In order to avoid the above problems, if the concentration of the color developing agent is set to 80 mmol / l or less and the processing temperature is set to 40 ° C. or higher, the color development processing time is shortened to 1 minute 30 seconds or less. The rate of diffusion of the color developing agent is rate-determining, and the lower layer (color-sensitive layer on the side closer to the support) with respect to development of the upper layer of the light-sensitive material (color-sensitive layer on the side farther from the support)
Development was delayed, the gradation and sensitivity balance between the upper layer and the lower layer were lost, and color reproducibility and tone reproducibility were significantly deteriorated.

[0011]

SUMMARY OF THE INVENTION Therefore, firstly, the object of the present invention is to improve the imbalance of gradation and sensitivity due to the shortening of the color development processing time, and the development processing and color development currently widely used. It is to provide a silver halide color photographic light-sensitive material and a color image forming method capable of obtaining an image having the same gradation and sensitivity in any of the ultra-rapid processing in which the development processing time is greatly shortened including the processing. . Secondly, an object of the present invention is to provide a silver halide color photographic light-sensitive material and a color image forming method in which the deterioration of photographic performance in color development processing time dependency is suppressed even when subjected to ultra-rapid processing.

[0012]

The above objects of the present invention have been achieved by the following silver halide color photographic light-sensitive materials or color image forming methods. A silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, each of which is provided on a support. At least one kind of anionic water-soluble polymer represented by the following general formula (1) in at least one of the hydrophilic colloid layers, and an average particle diameter of 0.01 to 0. The following two kinds of development processing I and development processing II containing 5 μm of an alkali-soluble polymer dispersion or at least one polymer dispersion represented by the following general formula (3) and having different color development times Characteristic curve obtained when applied (D-Log
In E), the gradation of blue density, the gradation of green density, and the gradation of red density satisfy the following conditional expression, a silver halide color photographic light-sensitive material.

[0013]

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[In the general formula (1), R ¹ is a hydrogen atom, a substituted or unsubstituted lower alkyl group, a halogen atom, L is a divalent to tetravalent linking group, M is a hydrogen atom or a cation, m is an integer of 0 or 1, n is an integer of 1 to 3, D is a repeating unit of an ethylenically unsaturated monomer,
Respectively. y and z represent the weight percentage ratio of each monomer component, y represents 0 to 95, and z represents 5 to 100. However, y + z = 100. ]

[0015]

[Chemical 6]

[In the general formula (2), D ² represents a repeating unit of at least one or more ethylenically unsaturated monomers, and R ¹ , L, M, m, and n are R ¹ in the general formula (1), It has the same meaning as L, M, m, and n. p and q represent the weight percentage ratio of each monomer component, p is 0 to 85,
q represents 15 to 100. However, p + q = 100. ]

[0017]

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[In the general formula (3), A represents a repeating unit obtained by copolymerizing a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups. B is the following general formula (4) in which the homocopolymer has a cloud point in an aqueous solution.
Represents a repeating unit obtained by copolymerizing the monomer represented by
D ³ represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer other than the above. p ', q',
r ′ and s ′ represent the weight percentage ratio of each monomer component,
p'is 0.1 to 60, q'is 10 to 70, r '
Has a value of 0 to 30, and s'has a value of 25 to 85. However, p '+ q' + r '= 100. m and n have the same meaning as in general formula (1). ]

[0019]

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[In the general formula (4), R ² represents a hydrogen atom or a lower alkyl group. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents a substituted alkyl group. R ² and R ³ do not become hydrogen atoms at the same time, and R ³ and R ⁴ may combine to form a nitrogen-containing heterocycle. Conditional Expression 0.8 ≦ γ _II (B) / γ _I (B) ≦ 1.2 0.8 ≦ γ _II (G) / γ _I (G) ≦ 1.2 0.8 ≦ γ _II (R) / Γ _I (R) ≦ 1.2 [γ _I (B), γ _I (G), and γ _I (R) are the gradations of blue density, green density, and red density when development processing I is applied, respectively. Γ _II (B), γ _II (G), and γ _II (R) represent gradations of blue density, green density, and red density when development processing II is applied, respectively. [Development Processing I] Color development processing time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N is used as a color developing agent. -(Β
-Hydroxyethyl) amino] aniline: a color developing treatment using a color developing solution containing 15 to 20 mmol / l. [Development processing II] Color development processing time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N- (β-
Development processing in which a color developing solution containing 35 to 40 mmol / liter of hydroxyethyl) amino] aniline is used for color development processing.

An image forming method characterized in that a color image is formed by performing the following development processing A using the silver halide color photographic light-sensitive material described above. [Development Processing A] Color developing processing time is 150 to 200 seconds, temperature of the color developing solution is 37 to 40 ° C., and a color developing solution containing 15 to 20 mmol / liter of a color developing agent is used. And development processing. An image forming method characterized in that a color image is formed by performing the following development processing B using the silver halide color photographic light-sensitive material described above. [Development treatment B] Color developing treatment time is 25 to 90 seconds, color developing solution temperature is 40 to 60 ° C., and a color developing solution containing a color developing agent in an amount of 25 to 80 mmol / liter is used. And development processing.

The present invention will be described in detail below. The compounds represented by the general formula (1), the general formula (2) and the general formula (3) (hereinafter referred to as the polymer of the present invention) will be described in detail below. One of the preferable embodiments of the polymer of the present invention is an anionic water-soluble polymer represented by the general formula (1).

[0023]

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In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, or a halogen atom. L is 2
~ Represents a tetravalent linking group, and M represents a hydrogen atom or a cation. m represents 0 or 1, and n represents 1, 2 or 3. D represents a repeating unit of an ethylenically unsaturated monomer. y and z represent the weight percentage of each monomer component, y represents 0 to 95, z represents 5 to 100, and y + z = 1.
00.

More specifically, the ethylenic monomer represented by D is preferably a water-insoluble hydrophilic monomer such as acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide. , N-ethylacrylamide, N
-Methyl-N-ethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide,
N-isopropylacrylamide, N-cyclopropylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylmorpholine, N-acryloylpyrrolidine, N-methacryloyl N-vinyl cyclic compounds such as acrylamide, methacrylamides, N-vinylpyrrolidone, N-vinylcaprolactam, and the like, such as piperidine, N-n-propylmethacrylamide, N-isopropylmethacrylamide, and N-cyclopropylmethacrylamide.

2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-methoxyethyl acrylate,

[0027]

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Esters of acrylic acid or methacrylic acid such as 2-methanesulfonamide ethyl acrylate,
Examples thereof include 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, styrene sulfonate, styrene sulfinate, and other monomers having an anionic functional group other than the -COOH group. Further, D may be a repeating unit of vinyl alcohol obtained by hydrolysis of vinyl esters (for example, vinyl acetate).

The ethylenically unsaturated monomer represented by D may be a water-insoluble monomer as long as it does not impair the solubility of the polymer of the general formula (1) in an aqueous medium.
Such monomers include ethylene, propylene, 1
Butene, isobutene, styrene, α-methylstyrene, vinyl ketone, monoethylenically unsaturated esters of aliphatic acids (eg vinyl acetate, allyl acetate), ethylenically unsaturated esters of molar carboxylic or dicarboxylic acids

(For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-
Hexyl acrylate, 2-ethylhexyl acrylate) monoethylenically unsaturated compounds (e.g., acrylonitrile) or dienes (e.g., butadiene, isoprene), but are not limited thereto.

Examples of R ¹ include a hydrogen atom, an unsubstituted alkyl group such as a methyl group, an ethyl group and an n-propyl group, and a substituted alkyl group such as a carboxymethyl group. Of these, a hydrogen atom, a methyl group or a carboxymethyl group is preferred.

L is a divalent, trivalent or tetravalent linking group,
In the case of a divalent linking group, -Q-

[0033]

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Is preferred. Here, Q is a divalent linking group, examples of which are an alkylene group (for example, methylene group, ethylene group, trimethylene group), an arylene group (for example, phenylene group), -COO-X- (where X is the number of carbon atoms). 1 to
Represents about 6 alkylene or arylene groups. The same applies hereinafter) (for example, -COOCH ₂ CH _2- ),

--COO--X--OCO-- (for example, --CO
_{OCH 2 CH 2 OCO -),} - OCO-X- ( e.g. -
OCOCH ₂ CH ₂ —), —OCO—X—COO— (eg, —OCOCH ₂ CH ₂ CH ₂ CH ₂ COO—), —
CONH-X- (e.g. _{-CONH-C 6 H 4 (p} )
-), -CONH-X-NHCO- (for example, -CONH
_{CH 2 CH 2 NHCO -),} - CONH-X-OCO-
(E.g. -CONHCH ₂ CH ₂ OCO-), and the like.

M is 0 or 1. n is 1, 2 or 3. M represents a hydrogen atom or a cation. Examples of the cation include an alkali metal ion (sodium ion, potassium ion), ammonium ion (for example, trimethylammonium ion, triethylammonium ion, tributylammonium ion), and the like, but an alkali metal ion is particularly preferable.

As described above, --COOM in the general formula (1) is used.
Specific examples of the ethylenically unsaturated monomer containing a group include:
Acrylic acid, methacrylic acid, itaconic acid, p-vinylbenzoic acid, maleic anhydride,

[0038]

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[0039]

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The following can be mentioned. Among them, those soluble in distilled water at normal temperature are particularly preferable. Such anionic monomers include acrylic acid, methacrylic acid, itaconic acid,

[0041]

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The following can be cited.

Monomers having these anionic groups are salts thereof, for example, alkali metal salts (for example, Na and K).
Salt) and an ammonium salt (for example, a salt with ammonia, methylamine, dimethylamine, etc.).
Two or more kinds of each of the monomer represented by D and the monomer containing -COOM may be used.

Y and z represent the weight percentage of each monomer component, y is 0 to 95, preferably 0 to 80, and z is 5 to 100, preferably 20 to 100.
It is. Here, y + z = 100 is represented.

Among the aqueous medium-soluble polymers of the present invention, the polymer represented by the following general formula (1-a) is particularly preferable. General formula (1-a)

[0046]

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E is N, N-dimethylacrylamide,
It represents a monomer unit obtained by copolymerizing at least one selected from N-acryloylmorpholine and N-acryloylpiperidine. D ¹ represents a repeating unit obtained by copolymerizing an ethylenically unsaturated monomer except D, N, N-dimethylacrylamide, N-acryloylmorpholine and N-acryloylpiperidine. R ¹ , L, M, m and n are the same as above. x ', y', z'represent the weight percentage of each monomer component, x'has a value of 1 to 99, y'has a value of 0 to 50, and z'has a value of 1 to 99. Where x '+
y '+ z' = 100.

More specifically, D ¹ is the above D except N, N-dimethylacrylamide, N-acryloylmorpholine and N-acryloylpiperidine, and specific examples and preferred compounds thereof are listed in D above. It is the same as the one. The same applies to specific examples and preferred examples of R ¹ , L, M, m and n. x ',
y'and z'represent the weight percentage of each monomer component. x '
Is 1 to 99, preferably 5 to 95, y'is 0 to 50, preferably 0 to 30, and z'is 1 to 9.
It takes a value of 9, preferably 5 to 95. Where x '+
y '+ z' = 100.

The polymer represented by the general formula (1) of the present invention can be prepared by a well-known radical polymerization method (for example,
For details, please refer to Takayuki Otsu and Masayoshi Kinoshita, "Experimental Method of Polymer Synthesis", Kagaku Dojin, 1972, pp. 124-154. )
However, it is particularly preferable to use a solution polymerization method.

When the solution polymerization method is used, each monomer is used in an appropriate solvent (for example, water or an organic solvent miscible with water (for example, methanol, ethanol, acetone,
After dissolving in a mixed solvent (N, N-dimethylformamide etc.)), the polymerization reaction may be carried out, or the polymerization reaction may be carried out while dropping each monomer into the solution.
At that time, an appropriate auxiliary solvent (the same as above) may be used in the dropping solution.

The above solution polymerization is carried out by using a conventional radical initiator (for example, an azo initiator such as 2,2'-azobis (2-amidinopropane) dihydrochloride) and a peroxide initiator such as potassium persulfate. The agent) is generally used at a temperature of 30 ° C to about 100 ° C, preferably 60 ° C to about 95 ° C.

The polymers represented by the general formula (1) of the present invention and their synthesis examples are shown below, but the present invention is not limited thereto. The copolymerization ratios given in the polymer examples represent the polymerization percentage ratios and the M ratios represent the molar ratios.

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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Another preferred embodiment of the polymer of the present invention is an alkali-soluble polymer dispersion represented by the following general formula (2) or a polymer dispersion represented by the following general formula (3).

[0059]

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[0060]

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In the general formula (2), D ² represents a repeating unit of at least one kind of ethylenically unsaturated monomer,
R ¹ , L, M, m and n have the same meanings as described above. p, q
Represents the weight percentage ratio of each component, p is 0 to 85, q
Represents 15 to 100. Here, p + q = 100 is represented.

In the general formula (3), A is at least 2
Represents a repeating unit obtained by copolymerizing a copolymerizable crosslinkable monomer having ethylenic unsaturation. B represents a repeating unit obtained by copolymerizing a monomer represented by the following general formula (4) whose homopolymer has a cloud point in an aqueous solution. D ³ represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer other than the above. General formula (4)

[0063]

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In the formula, R ² represents a hydrogen atom or a lower alkyl group. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted alkyl group. R ² and R ³ do not become hydrogen atoms at the same time, and R ³ and R ⁴ may combine with each other to form a nitrogen-containing heterocycle with the nitrogen atom. p ', q', r ', and s' represent the weight percentage ratio of each monomer component, and p'is 0.1 to 6
0, q'is 10 to 70, r'is 0 to 30, s'
Has a value of 25 to 85. Where p '+ q' + r '
+ S '= 100. m and n have the same meanings as m and n in the general formula (1).

Explaining in more detail, D in the general formula (2)
^{In 2} , a water-insoluble ethylenically unsaturated monomer is preferably used, for example ethylene, propylene, 1-
Butene, isobutene, styrene, α-methylstyrene,
Vinyl ketone, monoethylenically unsaturated ester of aliphatic acid (eg vinyl acetate, allyl acetate), ester of ethylenically unsaturated molcarboxylic acid or dicarboxylic acid

(For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-
Hexyl acrylate, 2-ethylhexyl acrylate) monoethylenically unsaturated compounds (e.g., acrylonitrile) or dienes (e.g., butadiene, isoprene), but are not limited thereto.

As D ² , a water-soluble ethylenically unsaturated monomer may be copolymerized, and examples of such a monomer include acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide. , N-ethylacrylamide, N-methyl-
N-ethyl acrylamide, N, N-diethyl acrylamide, Nn-propyl acrylamide, N-isopropyl acrylamide, N-cyclopropyl acrylamide, N-methyl-Nn-propyl acrylamide,
N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylmorpholine,
Acrylamide such as N-acryloylpyrrolidine, N-methacryloylpiperidine, Nn-propylmethacrylamide, N-isopropylmethacrylamide, N-cyclopropylmethacrylamide, methacrylamides, N-vinylpyrrolidone, N-vinylcaprolactam and the like N-vinyl cyclic compound,

2-hydroxyethyl acrylate, 2-
Esters of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-methoxyethyl acrylate, 2-methanesulfonamide ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid and its salts, styrenesulfonic acid Salt, styrene sulfinate,
Examples thereof include monomers having an anionic functional group other than the -COOH group. As the ethylenically unsaturated monomer in D, various monomers can be used in any proportion as long as the polymer of the general formula (2) can exist as a water-insoluble dispersion, and the polarities of the -COOM monomer can be changed. It can change depending on the size.

Therefore, in the weight percentages p and q of each component, p represents 0 to 85 and q represents 15 to 100. More specifically, the -COOM-containing monomer is a non-neutralized water-soluble monomer. In this case, p is 30 to 85, q
Is 15 to 70, and when the —COOM-containing monomer is a non-neutralized water-insoluble monomer, p is 0 to 70 and q is 30.
Represents ~ 100. Here, p + q = 100.

Next, the polymer represented by the general formula (3) will be described in detail. Examples of the copolymerizable ethylenically unsaturated monomer which gives the repeating unit represented by A include methylene bisacrylamide, ethylene bisacrylamide, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and ethylene. Glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, tetramethylene dimethacrylate and the like, among which methylenebisacrylamide, divinylbenzene and ethylene glycol dimethacrylate are particularly preferable.

B represents a repeating unit derived from a monomer represented by the general formula (4) whose homopolymer has a cloud point in water. Here, the cloud point means that the homopolymer is 1 in distilled water.
It is a phenomenon that when water-soluble formed by being dissolved in wt% is heated, it precipitates from a transparent state at a certain temperature or higher (0 ° C to 100 ° C) and becomes cloudy.

The monomer represented by the general formula (4) will be described in more detail. R ² is a hydrogen atom or has 1 to 4 carbon atoms.
Represents a lower alkyl group (preferably a methyl group).
R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4), a cycloalkyl group or a substituted alkyl group. Of these alkyl groups, a methyl group, an ethyl group, an n-propyl group, a cyclopropyl group, an isopropyl group, an n-butyl group, and a sec-butyl group are preferable.

R ³ and R ⁴ may be bonded to each other to form a nitrogen-containing heterocycle together with a nitrogen atom, and preferable heterocycles include a pyrrolidine ring and a piperidine ring. R ³ and R ⁴ do not become hydrogen atoms at the same time.

Preferred examples of the monomer represented by the general formula (4) include N-ethylacrylamide, N-methyl-N-ethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide and N-isopropyl. Acrylamide, N-cyclopropylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N
-Acryloyl pyrrolidine, N-acryloyl piperidine, Nn-propyl methacrylamide, N-isopropyl methacrylamide, N-cyclopropyl methacrylamide, etc. can be mentioned. For the cloud point of homopolymers of these monomers, see JSME Proc.
Vol. 104, p.

As the ethylenically unsaturated monomer represented by D ³ , a monomer soluble in distilled water at room temperature is preferable. Such monomers include acrylamide, methacrylamide, N-methylacrylamide, N
-Acryloylmorpholine, N-methacryloylmorpholine, acrylamides such as N, N-dimethylacrylamide, N-vinyl cyclic compounds such as N-vinylpyrrolidone and N-vinylcaprolactam,

2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-methoxyethyl acrylate,

Esters of acrylic acid or methacrylic acid such as 2-methanesulfonamide ethyl acrylate,
Examples thereof include 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, styrene sulfonate, styrene sulfinate, and other monomers having an anionic functional group other than the -COOH group. Of these, -COO
It is particularly preferable to use one or more monomers having an anionic group other than the H group.

As the ethylenically unsaturated monomer represented by D ³ , a monomer other than the above may be used,
Such monomers include ethylene, propylene,
1-butene, isobutene, styrene, α-methylstyrene, vinyl ketone, monoethylenically unsaturated ester of aliphatic acid (eg vinyl acetate, allyl acetate), ester of ethylenically unsaturated monocarboxylic acid or dicarboxylic acid

(For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-
Examples include hexyl acrylate, 2-ethylhexyl acrylate) monoethylenically unsaturated compounds (eg acrylonitrile), dienes (eg butadiene, isoprene) and the like.

R ¹ , L, M, m and n are the same as above. p ', q', r ', and s' represent the weight percentage ratio of each monomer, and p'is 0.1 to 60, preferably 0.5.
To 40, particularly preferably 1 to 20, q '
Is 10 to 70, preferably 20 to 60, particularly preferably 25 to 55, and r ′ is 0 to 30,
It is preferably 0.5 to 25, particularly preferably 1 to 20, and s'is 25 to 85, preferably 30 to 75, particularly preferably 35 to 70.

In the polymer represented by the general formula (3) of the present invention, it is preferable that 80% by weight or more of all the constituent components are repeating units derived from a water-soluble monomer.

Particularly preferred among the polymer dispersions of the present invention are the polymer dispersions of the general formula (3), and as D ³ or B, N, N-dimethylacrylamide, N
-Acryloyl piperidine and N-acryloyl morpholine are more preferably copolymerized.

The method for preparing the polymer of the present invention will be described below. The preparation method of the polymer of the general formula (2) of the present invention is a well-known radical polymerization method (for example, Takayuki Otsu and Masaetsu Ohshita, “Experimental Method of Polymer Synthesis”, Kagaku Dojin, 1972, For details, see pages 124 to 154, etc.), and especially according to the emulsion polymerization method.

In emulsion polymerization, an emulsifier is used if necessary,
Generally, the monomer is emulsified in water or a mixed solvent of water and an organic solvent miscible with water (eg, methanol, ethanol, acetone, etc.) and a radical polymerization initiator is used at 30 ° C.
It is carried out at a temperature of from about 100 ° C to about 100 ° C, preferably from 40 ° C to about 90 ° C. The amount of the organic solvent miscible with water is 0 to 300% by volume, preferably 0 to 15% with respect to water.

The polymerization reaction is usually carried out using 0.05 to 5% by weight of a radical polymerization initiator and, if necessary, 0.1 to 10% by weight of an emulsifier based on the monomers to be polymerized. As the polymerization initiator, azobis compounds, peroxides,
Hydroperoxide, redox catalyst, etc., such as potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, diquat Examples include mill peroxide, azobisisobutyronitrile, and 2,2'-azobis (2-amidinopropane) hydrochloride.

Examples of the emulsifier include anionic, amphoteric and nonionic surfactants as well as water-soluble polymers. For example, sodium laurate, sodium dodecyl sulfate, 1-
Sodium octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium lauryl phosphate, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, special Examples include emulsifiers and water-soluble polymers described in JP-B No. 53-6190.

In emulsion polymerization, depending on the purpose,
Wide range of polymerization initiator, concentration, polymerization temperature, reaction time, etc.
Needless to say, it can be easily changed.

The compound represented by the general formula (3) of the present invention is generally a copolymerizable monomer containing at least two ethylenically unsaturated groups represented by A, and a monomer represented by the general formula (4). , D ³ and the ethylenically unsaturated monomer having at least one anionic functional group can be synthesized by using a well-known emulsion polymerization method.

When the anionic functional group in the polymer is used in the form of a salt, the monomer may be polymerized in the form of a salt or a basic compound may be added after the polymerization. It is particularly preferred to add the compound. In the finally obtained polymer dispersion represented by the general formula (3), the proportion of M having a salt structure such as an alkali metal or ammonium ion is preferably 70 to 100 mols based on all -COOM. %.

Since the anionic crosslinked polymer produced has a charge and is present in a relatively stable dispersed state in water, it is often unnecessary to add a surfactant in water, but an auxiliary An activator may be added to stabilize the dispersion state of the anionic crosslinked polymer in water.

Examples of the surfactant to be used include anionic surfactants (for example, sodium dodecyl sulfate, Triton 770 (commercially available from Rohm & House)), nonionic surfactants (for example, Emarex NP-20).
(Commercially available from Nippon Emulsion)). Also,
Water-soluble polymers such as polyvinyl alcohol and gelatin may be used.

The polymerization reaction is generally a radical polymerization initiator (for example, a combination of potassium persulfate and sodium hydrogen sulfite, commercially available from Wako Pure Chemical Industries under the name V-50).
In the presence of, generally at temperatures of from 30 ° C to about 100 ° C.

The polymerization may be carried out by adding all of the monomers to be used to a medium (water or an organic solvent miscible with water—for example, a mixed solvent of methanol and acetone), or the monomer mixture may be added dropwise. It may be carried out, but it is particularly preferred to carry out by dropping.

Regarding the surfactant, the polymerization initiator and the polymerization method explained above, the description can be made by referring to the description of "Experimental Method of Polymer Synthesis" by Takayuki Otsu and Masayoshi Kinoshita (Kodojin). .

Preferred examples of the polymer dispersion according to the present invention are shown below, but the present invention is not limited thereto. The proportion of each monomer component in the polymer dispersion represents weight percent and M represents mole percent.

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The polymer of the present invention has a high water absorbency, and when added to a light-sensitive material, it has the effects of increasing the swelling thickness of the film (increasing the swelling ratio of the film) and increasing the swelling rate.
Japanese Unexamined Patent Publication (Kokai) No. 61-156252 contains a highly water-absorbing polymer compound having a degree of swelling in water of 5 or more (for example, a hydrolyzate of an acrylonitrile copolymer, a saponification product of an acrylic ester copolymer). A light-sensitive material is disclosed, which is said to promote the development and desilvering. But,
This publication does not give any suggestion about the effect of aligning the sensitivity and gradation between the ordinary processing and the ultra-rapid processing, which is the object of the present invention, and the effect of improving the time dependency of color development processing in the ultra-rapid processing. Further, the effect of promoting development by the described superabsorbent polymer was not sufficient.

The polymer of the present invention can be added to any hydrophilic colloid layer constituting the light-sensitive material. For example, light-sensitive silver halide emulsion layers (blue-sensitive silver halide emulsion layers, green-sensitive silver halide emulsion layers, red-sensitive silver halide emulsion layers, etc.) and non-light-sensitive layers (eg protective layers, yellow filter layers, intermediate layers). Layer, antihalation layer). Although it may be added only to a specific layer, it is preferably added uniformly to each layer in order to balance the swelling property of each layer. The amount of the polymer of the present invention added to the light-sensitive material is 0.1% by weight with respect to the hydrophilic colloid such as gelatin.
It is 01 to 30%, preferably 0.1 to 20%, more preferably 0.5 to 10%. If the added amount is too small, the effect cannot be expected, and conversely, if the added amount is too large, gelatin hardening inhibition occurs, the film is soft and easily scratched, reticulation occurs, the film thickness increases and the image This is because problems such as a decrease in sharpness will occur. The addition of the polymer of the present invention to the light-sensitive material is
Usually, it is carried out by directly adding an aqueous solution of a polymer or a dispersion of the polymer to an emulsion, an emulsion or a coating solution in which these are mixed.

The gradation degree in the present invention is obtained as follows. The test was conducted at a temperature of 20 ± 5 ° C and a relative humidity of 60 ±.
The test is carried out in a room of 10%, and the light-sensitive material is stored in the room for 10 hours or more and then tested. (1) The photosensitive material is exposed through an optical wedge with a light source having an energy distribution of 4800K. Exposure time is 1 /
100 seconds. (2) Perform the designated development processing I or development processing II.
The development process is completed within 30 minutes to 6 hours after exposure. (3) Density measurement is blue, green, red status M density,
The blue density D _B , the green density D _G , and the red density D _R are measured. (4) Plot the blue density D _B , the green density D _G , and the red density D _R against the common logarithmic value (LogE) of the exposure amount,
Get the characteristic curve. (5) In the obtained characteristic curve, fog +0.2, for each density of blue density D _B , green density D _G , and red density D _R
Each point of density of fog +0.5, fog +1.0, fog +1.5, fog +2.0 is obtained, and after linearly approximating from these 5 points by the least square method, the straight line and the horizontal axis (the axis of LogE) ) With the angle θ. Let tan θ be a gradation degree γ, γ for blue density D _{B be} γ (B), γ for green density D _{G be} γ (G), and γ for red density be γ (R).

The light-sensitive material of the present invention has gradations γ _I (B), γ of blue density, green density, and red density after development processing I is performed.
_I (G), γ _I (R) and gradation of blue density, green density, and red density when development processing II is applied γ _II (B), γ _II (G),
γ _II (R) satisfies the following conditional expression. Conditional expression 0.8 ≦ γ _II (B) / γ _I (B) ≦ 1.2 0.8 ≦ γ _II (G) / γ _I (G) ≦ 1.2 0.8 ≦ γ _II (R) / γ _I (R) ≦ 1.2 The light-sensitive material of the present invention preferably satisfies the following conditional expression. Conditional Expression 0.9 ≦ γ _II (B) / γ _I (B) ≦ 1.1 0.9 ≦ γ _II (G) / γ _I (G) ≦ 1.1 0.9 ≦ γ _II (R) / γ _I (R) ≦ 1.1 The light-sensitive material of the present invention more preferably satisfies the following conditional expression. Conditional expression 0.95 ≦ γ _II (B) / γ _I (B) ≦ 1.05 0.95 ≦ γ _II (G) / γ _I (G) ≦ 1.05 0.95 ≦ γ _II (R) / γ _I (R) ≦ 1.05

If the above conditions are not satisfied, the gradation balance of the print obtained from the color negative developed in at least one of the development processing I and the development processing II will be lost, and it will not be possible to obtain color reproduction that is endurable for viewing. .

In the present invention, γ _I (B), γ
_I (G), γ _I (R), γ _II (B), γ _II (G), γ _II
(R) is preferably in the range of 0.50 to 0.90, more preferably in the range of 0.60 to 0.85, and particularly preferably in the range of 0.65 to 0.80. preferable.

In the present invention, any commercially available color paper may be used for printing. The preferred gradation of color paper is about 2.7 ± 0.1 in colorimetric density. (For the colorimetric density, see page 387, "Basics of Photographic Engineering," edited by the Photographic Society of Japan, "Silver Salt Photography")

The light-sensitive material of the present invention is subjected to development processing I, development processing.
It is desirable that the characteristic curves of the blue density, the green density, and the red density have good linearity regardless of the development processing of II. Wherein in JP-A-3-215853 specifically (3), i.e. j = g _i / h is 1.00 ± 0.
2, preferably a photographic material having a range of 1.00 ± 0.1. Such a light-sensitive material has a good gray balance when printed on a print from low density to high density, and a latitude of exposure amount is widely desired.

The light-sensitive material of the present invention preferably has a specific photographic sensitivity of 160 or more. The photographic specific sensitivity in the present invention is determined by the method described in JP-A-63-236035. This measuring method is based on JIS K 7
It is based on 614-1981. However, the difference lies in that the development processing is completed within 30 minutes to 6 hours after exposure for sensitometry, and the development processing is carried out according to Fuji Color Standard Development Prescription CN-16. The specific photographic sensitivity is more preferably 200 or more. The upper limit is 3,200.

The color developing solutions of the developing treatments I and II of the present invention will be described below. The development processing I of the present invention is a processing based on Kodak C-41 which is a processing for color negative which is widely used in the world at present.
It is designed so that a preferable gradation can be obtained in seconds. Further, the development processing II is a processing in which the development processing I is speeded up, and the development activity is increased by increasing the concentration of the main agent and the processing temperature.
It is designed so that a gradation close to that of the development processing I can be obtained in a color development processing time of a minute. However, when a light-sensitive material which is not included in the present invention is processed, development delay occurs in the red-sensitive layer, which is the lowermost layer, so that the gradation cannot be perfectly adjusted.

In the development processing I, the color development time is 3 minutes to 3 minutes 1
5 seconds, the temperature of the color developing solution is 37 to 39 ° C.,
2-Methyl-4- [N-ethyl-N as color developing agent
15- (β-hydroxyethyl) amino] aniline
This is a developing process characterized by carrying out a color developing process using a color developing solution containing 20 mmol / liter. In the development processing II, the color developing time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and the color developing agent is 2
The development processing is characterized in that the color development processing is performed using a color development solution containing 35-40 mmol / liter of -methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline.

The pH of the color developing solutions used in development processes I and II is 1
It is 0.05. It is preferable to use a carbonate in order to keep the pH of the treatment liquid at 10.05. The addition amount is preferably 0.1 mol / liter or more, and particularly preferably in the range of 0.2 mol / liter to 0.3 mol / liter.
Further, as a preservative for the color developing agent, it is preferable to use hydroxylamine and sulfite. The addition amount of hydroxylamine is preferably in the range of 0.05 mol / liter to 0.2 mol / liter. The amount of sulfite added is 0.
The range of 02 mol / liter to 0.04 mol / liter is preferable. Bromide ions can be added to the color developing solution in order to control the developing rate. Further, various chelating agents can be added to the color developing solution.

The steps (desilvering step, washing step, stabilizing step) subsequent to the color development of development processing I and II are carried out by the methods described in development processing A and B described later.

Specific examples of the development processing I and the development processing II are shown below. In the present invention, it is preferable to use the following specific examples. Development Processing I Development processing in which color development is the following liquid composition, temperature, and processing time. (Color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1 0.5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (with potassium hydroxide Adjusted with sulfuric acid) 10.05 Temperature 38 ° C Treatment time 3 minutes 15 seconds

Development Processing II Development processing in which the color development is the following liquid composition, temperature and processing time. (Color developer) Tank (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 2.0 Potassium iodide 1. 3 mg Hydroxylamine sulfate 4.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 Water was added to 1.0 liter pH (potassium hydroxide and sulfuric acid 10.05 temperature 45 ° C processing time 60 seconds

Next, the development processing A and the development processing B of the present invention.
Will be described in detail.

The development processing A and the development processing B of the present invention each include a color development step, a desilvering step and a drying step. Specific preferred examples are shown below, but the invention is not limited thereto. Color development-bleach-fix-wash-stable-dry Color development-bleach-bleach-fix-fix-wash-stable-dry Color development-bleach-fix-wash-stable-dry Color-bleach-bleach-fix-wash-stable- Drying Color development-bleach-fixing-fixing-washing-stabilization-drying Color development-bleaching-washing-fixing-washing-stability-drying In the above processing step, washing in the step before stabilization can be omitted. The final stability can also be omitted. In the development processing A and the development processing B of the present invention, the desilvering step after color development may be the same or different.

Color development processing A in development processing A of the present invention will be described below. The color development time of the color development processing A of the present invention is 150 seconds or more and 200 seconds or less, preferably 165 seconds or more and 195 seconds or less. The color development time can be changed depending on the type and concentration of the developing agent in the processing liquid, the halogen ion (particularly Br ⁻ ) concentration, the temperature of the processing liquid, the pH and the like.

The developing agent in color development processing A of the present invention is 2
-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino)] aniline, 2-methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl- 4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline is preferred, and 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline is particularly preferred. The concentration of the developing agent is 10 mmol or more and 20 mmol or less, and preferably 14 mmol or more and 18 mmol or less, per liter of the processing liquid. These developing agents are preferably hydrochloride, p-toluenesulfonate or sulfate.

[0121] Bromide ion concentration, Br from a silver halide color photographic material ^- and elution, Br is replenished in the color developing solution ^- is determined by the amount, to keep the photographic properties during continuous processing stably The amount is 6 millimoles or less and 14 millimoles or less, preferably 9 millimoles or more and 13 remoles or less, per liter of the treatment liquid.

The temperature of the treatment liquid is 35 ° C. or higher and 40 ° C. or lower, preferably 36 ° C. or higher and 39 ° C. or lower.

The pH of the treatment liquid is 9.9 or more and 10.3 or less, preferably 10.0 or more and 10.2 or less.

Specifically, a color negative film processing agent, CN-16 or CN-1 manufactured by Fuji Photo Film Co., Ltd.
6X, CN-16Q, CN-16FA color developing solution and color developing replenishing solution, or color negative film processing agent C-41, C-41B manufactured by Eastman Kodak Company,
A color developing solution of C-41RA can be preferably used.

Color development processing B in development processing B of the present invention will be described below. The color development time of the color development processing B of the present invention is 25 seconds or more and 90 seconds or less, preferably 35 seconds or more and 75 seconds or less, and most preferably 45 seconds or more and 65 seconds or less.

The color development time of the present invention is a time including the crossover time (the time from the exit of the color development solution to the processing solution of the next step). The shorter the crossover time is, the more preferable the processing is. 2 seconds or more and 10 seconds or less are preferable, and 3 seconds or more and 7 seconds or less are more preferable in terms of device performance.

The color developing time can be changed in the same manner as in the color developing treatment A depending on the kind and concentration of the developing agent in the processing liquid, the halogen ion (particularly Br ⁻ ) concentration, the temperature of the processing liquid, the pH and the like.

The developing agent in color development processing B of the present invention is p
-Phenylenediamine derivatives, preferable representative examples of which are shown below. (D-1) 2-methyl-4- [N-ethyl-N- (β
-Hydroxyethyl) amino] aniline (D-2) 2-methyl-4- [N-ethyl-N- (3
-Hydroxypropyl) amino] aniline (D-3) 2-methyl-4- [N-ethyl-N- (4
-Hydroxybutyl) amino] aniline (D-4) 2-methyl-N, N-diethyl-p-phenylenediamine (D-5) 2-methyl-4- [N-ethyl-N- (β
-Methanesulfonamidoethyl) amino] aniline (D-6) 2-methoxy-4- [N-ethyl-N-
(Β-Hydroxyethyl) amino] aniline (D-7) 4-amino-3-methoxy-N, N-bis (3-hydroxypropyl) aniline (D-8) 4-amino-3-isopropoxy-N,
N-bis (β-hydroxyethyl) aniline (D-9) 1- (β-hydroxyethyl) -5-amino-6-methyl-indoline (D-10) 1,2,3,4-tetrahydro-1-
(3,4-dihydroxybutyl) -2,2,4,7-tetramethyl-6-amino-quinoline (D-11) 1,2,3,4-tetrahydro-1- (β
-Hydroxyethyl) -4-hydroxymethyl-6-amino-7-methyl-quinoline

In the color developing treatment B of the present invention, D-
1, D-2, D-3, D-6, D-7, D-8, D-1
0, D-11 are particularly preferable, and D-1, D-2, D-3
Is more preferable, and D-1 is the most preferable.

The concentration of the developing agent is 25 mmol or more and 80 mmol or less, preferably 25 mmol or more and 60 mmol or less, more preferably 27 mmol or more and 50 mmol or less, and particularly preferably 30 mmol or more and 45 mmol per liter of the processing liquid. It is below millimolar.

Within the developing agent concentration range, two or more developing agents may be used in combination.

In the color developing treatment B of the present invention, bromide ion is particularly important as an antifoggant, and the Br ^- concentration is not less than 15 mmol and not more than 60 mmol, preferably not less than 16 mmol and not more than 42 mmol per liter of the processing solution. Yes, and particularly preferably 16 mmol or more and 35 mmol or less.

The temperature of the treatment liquid is 40 ° C. or higher and 60 ° C. or lower, preferably 42 ° C. or higher and 55 ° C. or lower, and particularly preferably 43 ° C. or higher and 50 ° C. or lower.

The pH of the treatment liquid is 9.9 or more and 11.0 or less, preferably 10.0 or more and 10.5 or less.

Further, a silver halide solvent may be contained as a development accelerator, and thiosulfates, methanethiosulfonates, imidazoles described in JP-A-3-203735, and JP-A-4-130431. And the thioethers described in JP-A-4-317055 are preferred. Color development processing A and / or B of the present invention
Can contain the following compounds. For example, hydroxylamine, diethylhydroxylamine, hydroxylamines represented by the general formula (I) of JP-A-3-144446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, Various preservatives such as triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye forming couplers and competitive couplers. , Chelating agents such as auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenedia. Down tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

Among the above, substituted hydroxylamine is most preferable as the preservative, and among them, diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is used as a substituent. Those having are preferred. The most preferable example is N, N-bis (2-sulfoethyl).
Hydroxylamine, monomethylhydroxylamine,
And diethylhydroxylamine.

Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers and 1-phenyl-3-pyrazolidone. Auxiliary developing agents, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid , D Diamine - di (o-hydroxyphenylacetic acid) and may contain a salt thereof.

Further, any antifoggant can be added.
As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
Representative examples thereof include nitrogen-containing heterocyclic compounds such as 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

In order to maintain the pH of the color developing solution, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyric acid salt, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, use of a carbonate is preferred.

The amount of the buffer agent added to the developing solution is preferably 0.1 mol / liter or more, and particularly preferably 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. An example of this is Japanese Patent Laid-Open No. 63-14.
6998, JP-A-63-199295, JP-A-63
Examples include chelating agents described in JP-A-267750, JP-A-63-267751, JP-A-2-229146, JP-A-3-186841, German Patent 3739610, and European Patent 468325. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferred as the liquid shielding agent. It is particularly preferable to use it as a replenisher.

The replenishing amount is 30 to 800 ml, preferably 50 to 500 ml per square meter of the light-sensitive material.

Any development accelerator can be added to the color developer of the present invention, if necessary. Examples of the development accelerator include JP-B-37-16088, 37-5987, and 38-
Nos. 7826, 44-12380 and 45-9919
And thioether compounds represented by U.S. Pat. No. 3,813,247, p-phenylenediamine compounds represented by JP-A-52-49829 and 50-15554, JP-A-50-137726, Japanese Patent Publication 4
4-30074, Japanese Patent Publications Nos. 56-156826 and 52-43429, and the like, quaternary ammonium salts, U.S. Pat. Nos. 2,494,903 and 3,128,
182, 4,230,796, 3,253,9
No. 19, Japanese Patent Publication No. 41-11431, U.S. Pat.
82,546, 2,596,926 and 3,5
No. 82,346 and the like.
-16088, 42-25201, U.S. Pat. No. 3,128,183, Japanese Patent Publications 41-11431, 42-238883 and U.S. Pat. No. 3,532,50.
Polyalkylene oxide represented by No. 1, etc., other 1-phenyl-3-pyrazolidones, imidazoles,
Etc. can be added as needed.

Next, the desilvering process of the present invention will be described in detail. As the bleaching agent used in the processing solution having a bleaching ability, aminopolycarboxylic acid iron (III) complex, persulfate,
Bromate, hydrogen peroxide, and red blood salt are used,
The aminopolycarboxylic acid (III) complex can be most preferably used. The ferric iron complex salt used in the present invention may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and the ferric iron salt (for example, ferric sulfate, ferric chloride) may be added. Iron, ferric bromide, iron (III) nitrate, iron (III) sulfate ammonium, etc.) may coexist to form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in excess, it is usually preferably in the range of 0.01 to 10%.

In the present invention, as the compound forming the ferric complex salt in the liquid having a bleaching ability, ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-Carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, 1,
4-diaminobutane tetraacetic acid, glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-
N, N'-disuccinic acid, 1,3-diaminopropane-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Examples thereof include dimaleonic acid and 1,3-diaminopropane-N, N′-dimalonic acid, but are not particularly limited thereto.

The concentration of the ferric complex salt in the processing solution having bleaching ability of the present invention is appropriately in the range of 0.005 to 1.0 mol / liter, and 0.01 to 0.50 mol / liter.
It is preferably in the range of liter, more preferably 0.02.
０．３0.30 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is
The amount is preferably 0.005 to 2 mol / liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in a bath having a bleaching ability or a prebath thereof. For example, US Pat. No. 3,893,858,
German Patent No. 1,290,812, JP-A-53
-95630, Research Disclosure No. 1
No. 7129 (July 1978), compounds having a mercapto group or a disulfide bond, and JP-B-45.
-8506, JP-A-52-20832, 53-3
The thiourea compounds described in U.S. Pat. No. 2,735, U.S. Pat. No. 3,706,561 and the like or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

Other bleaching baths applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Alternatively, a rehalogenating agent such as iodide (eg, ammonium iodide) can be included. PH buffering capacity of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid as required And at least one of inorganic acids, organic acids and alkali metal or ammonium salts thereof, or a corrosion inhibitor such as ammonium nitrate and guanidine. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution and the fixing agent component in the fixing solution are
Known fixing agents, ie, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-
It is a water-soluble silver halide solubilizer such as thioether compounds such as octanediol, mesoionic compounds and thioureas, and these can be used alone or in admixture of two or more. Also, Japanese Patent Application Laid-Open No. 55-15535
A special bleach-fixing solution comprising a combination of the fixing agent described in No. 4 with a large amount of a halide such as potassium iodide or the like can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate, is preferred. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5 to 2 mol.
１．０1.0 mol. The bleach-fixing solution and the fixing solution of the present invention preferably contain sulfite (or bisulfite or metabisulfite) as a preservative, but especially 0.08 to 0.4 mol / liter, Preferably 0.
It is preferable to contain 1 to 0.3 mol / liter. By using this concentration range and further using the final bath of the present invention,
Not only the magnetic recording performance was remarkably improved, but also desirable results were obtained in terms of image storability. The bleach-fixing solution and the fixing solution of the present invention include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite) described above as preservatives. , Metabisulfite (eg, potassium metabisulfite, sodium metabisulfite,
In addition to containing sulfite ion-releasing compounds such as ammonium metabisulfite), aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.),
Ascorbic acids, hydroxylamines and the like can be added as necessary.

Further, a bleaching solution, a bleach-fixing solution, and a fixing solution may be added with a buffering agent, a fluorescent brightening agent, a chelating agent, a defoaming agent, an antifungal agent and the like, if necessary. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferred pH range is 4.5.
It is -6.2 and more preferably 5-6. Even if the pH is higher or lower than the present pH, the magnetic recording performance may not be sufficiently exhibited. In the case of a fixer, pH 5
About 8 is desirable.

Bleaching solution, bleach-fixing solution used in the present invention,
The replenishing amount of the fixing solution is 50 to 200 per 1 m ² of the light-sensitive material.
0 ml. Particularly preferably 100 to 100
0 ml. Further, washing water as a post-bath or overflow solution of a stabilizing bath may be replenished as necessary. The processing temperature of the bleaching solution, the bleach-fixing solution, and the fixing solution is 20 to 5
The temperature is 0 ° C, preferably 30 to 45 ° C. The processing time is 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak's Z-121, Using Process C-41 No. 3
Edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened.
Page, upper right column, line 6-lower left column, line 2
Can be used as is.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method of increasing the effect, a method of moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and increasing the stirring effect by turbulently flowing the emulsion surface, and circulating the entire processing solution. There is a method of increasing the flow rate. Such stirring improving means include a bleaching solution, a bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
No. 8, No. 60-191259. JP-A-60-1
As described in JP-A-91257, such a transporting means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various other factors. It can be set in a wide range depending on the condition.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picturean.
d Television Engineers Volume 64, P. 248-25
3 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-28838 can be used very effectively. Also, Japanese Patent Application Laid-Open No.
No. 8,542, isothiazolone compounds, thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986) Sankyo Published by Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982
It is also possible to use the bactericides described in "Bacterial and Antifungal Dictionary" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 3 to 9, preferably 4 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but are generally at 15 to 45 ° C. for 20 seconds to 10 minutes,
Preferably, a range of 30 seconds to 5 minutes at 25 to 40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilizing process, JP-A-57-8543 and JP-A-58-8543 are used.
All known methods described in JP-A-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. However, the lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4) described in JP-A-4-359249 (corresponding to EP-A-519190A2).
A combination of azolylmethylamine and its derivative such as (-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 86,583, and a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231105 is also preferable. .

The washing water and / or the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. It is also preferable to use a silicon surfactant having a high defoaming effect.

It is preferable to add various chelating agents to the washing water and / or the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N '.
-Trimethylene phosphonic acid, diethylene triamine-
Organic phosphonic acids such as N, N, N ′, N′-tetramethylenephosphonic acid, or European Patent 345,172A
Examples thereof include the hydrolyzate of the maleic anhydride polymer described in No. 1 and the like.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher. There is no particular limitation on a specific method for performing water replenishment. Among them, a monitor water tank separate from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed, and water in the monitor water tank is provided. The amount of evaporation of water is calculated, the amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and water is supplied to the bleaching tank in proportion to the amount of evaporation.
Nos. 3,249,644, 3,249,645, and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
Tap water may be used as water for correcting the evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

The light-sensitive material of the present invention is provided in order of the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is DE 1,121,470 or GB 923,0
As described in 45, it is preferable to arrange two layers, a high-speed emulsion layer and a low-speed emulsion layer, so that the photosensitivity becomes lower toward the support. Also, JP-A-57-112751, 62
As described in 200350, 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side remote from the support and a high-speed emulsion layer may be provided on the side near the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) or BH / BL / GL / GH / RH / RL
Or BH / BL / GH / GL / RL / RH. Also, as described in JP-B-55-34932, the blue-sensitive layer / GH from the side farthest from the support.
It can also be arranged in the order of / RH / GL / RL. Also JP
As described in 56-25738 and 62-63936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. US 4,663,271, 4,705,744, 4,707,4 to improve color reproducibility
36, a donor layer (CL) having a multilayer effect different in spectral sensitivity distribution from the main photosensitive layer such as BL, GL, RL described in the specification of JP-A-62-160448 and JP-A-63-89850 is adjacent to the main photosensitive layer. Alternatively, it is preferable to arrange them close to each other.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-.
Page 23, "I. Emulsion preparation and typ
es) ”, and No. 18716 (November 1979), p.648,
Id. No. 307105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie et PhisiquePhotographique, P.
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emul
sion Chemistry, Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (V.
L. Zelikman, et al., Making and Coating Photograph
ic Emulsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are RD No. 17643 and No. 17643.
18716 and No. 307105, and the relevant locations are summarized in the table below. The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, a grain size distribution,
Two or more kinds of emulsions having different characteristics of at least one of halogen composition, grain shape, and sensitivity can be mixed and used in the same layer. U.S. Pat.No.4,082,553.
It is preferable to apply the silver halide grains and the colloidal silver covered with the inside of the grains described in 9-214852 to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm
, Particularly preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least the weight or the number of silver halide grains).
95% have a particle size within ± 40% of the average particle size)
It is preferred that

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); A-4 -6 of EP 456,257
3 (p. 134), A-4 -73, -75 (p. 139); M-4, -6 in EP 486,965
(Page 26), M-7 (page 27); EP-571,959A M-45 (page 19);
5-204106 (M-1) (page 6); JP-A-4-362631, paragraph 0237 M-
twenty two. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

As couplers in which the color forming dye has an appropriate diffusibility, US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), the compound of formula (1) of EP 568,037A (especially (23) (page 11)), and the compounds of formulas (I), (II), Compounds represented by (III) (especially I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69-118
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29 SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII),
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention are
For example, the RD. Page 28 of No.17643, 6 of No.18716
From page 47, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. It is defined as The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and T _1/2 is A Green (A.Gr
een) et al., Photographic Science and Engineering (Photogr.Sci.Eng.), 19 volumes, 2,124 ~
It can be measured by using a swellometer (swelling meter) of the type described on page 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite ,, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic Alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co deposited γFe ₂ O
Co-coated ferromagnetic iron oxides such as ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably 20 m ² / g or more S _BET is the specific surface area, 30 m ²
/ g or more is particularly preferred. The saturation magnetization (σs) of a ferromagnet is
It is preferably from 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, and particularly preferably from 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 161032. Further, magnetic particles having a surface coated with an inorganic or organic material described in JP-A-4-259911 and 5-81652 can also be used.

The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer described in JP-A-4-219569, a natural product Coalescence (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3mol of isocyanate and 1m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is described in JP-A-6-59357.

As a method of dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably from 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.
The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll,
Transfer rolls, gravure, kisses, casts, sprays, dips, bars, extrusions and the like can be used, and the coating solutions described in JP-A-5-341436 are preferred.

The lubricating property is improved, the curl is adjusted,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support used in the present invention will be described. For details including the light-sensitive material, processing, cartridges and examples described later, open technical report, Japanese Patent No. 94-6023 (Invention Society; 1994.3). .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to
It is 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web.
Surface irregularities may be imparted (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments are performed after forming the support, after surface treatment,
It may be carried out at any stage after application of the back layer (antistatic agent, slip agent, etc.) and after application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Examples include a copolymer using a monomer selected from acrylic acid, itaconic acid, maleic anhydride and the like as a starting material, polyethylene imine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
_{nO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
MoO ₃ , at least one selected from V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Fine particles of oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), and sol-like metal oxides or fine particles of these composite oxides. The content in the photosensitive material should be between 5 and
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to simultaneously add fine particles of 0.8 μm or less in order to enhance the matting property. Particles (0.25μm), colloidal silica (0.03μm)
Is mentioned.

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and JP-A 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be 135 size at present, and for miniaturization of the camera,
It is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, a patrone used in the present invention may be used in which the spool is rotated to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
Different patrones may be used.

[0182]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the present invention. (Example 1) 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co.) as an ultraviolet absorber, 300 ° C.
After being melted at, it was extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to form a 90 μm thick PEN.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione on each side. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005 g / m ²
And resorcinol. 3-2) Coating of magnetic recording layer 3-Poly (degree of polymerization 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, Long axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² was diacetyl cellulose 1.1 g / m ² (iron oxide was dispersed in an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 7 as a curing agent
5 mg / m ² as a solvent, acetone, methyl ethyl ketone,
Cyclohexanone and dibutyl phthalate were applied by a bar coater to obtain a magnetic recording layer having a thickness of 1.2 μm. 15 mg / m ² of C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ as a slip agent, silica particles (1.0 μm) as a matting agent and 3-poly (degree of polymerization 1
5) Abrasive aluminum oxide (0.20 μm and 1.0 μm) coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) was treated with 50 mg / m ² and 10%, respectively.
mg / m ² . Drying was carried out at 115 ° C for 6 minutes.
° C). X- write saturation magnetization moment of the magnetic recording layer of the D color density increment of about 0.1 of ^B, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m, the squareness ratio in (blue filter) Was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (6mg / m ² ), polydimethylsiloxane (molecular weight
3,000) (1.5 mg / m ² ) of the mixture was applied. This mixture was prepared by melting it in xylene / propylene glycol monomethyl ether (1/1) at 105 ° C, pouring it into propylene glycol monomethyl ether (10 times the volume) at room temperature, and then dispersing it in acetone. (A mean particle size of 0.01 μm) and then added. Drying was carried out at 115 ° C. for 6 minutes (all the rollers in the drying zone and the conveying device were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (stainless steel balls of 5 mmφ, load 100
g, speed 6 cm / min), static friction coefficient 0.08 (clip method), and the dynamic friction coefficient between the emulsion surface and the sliding layer, which will be described later, is also 0.20.
And excellent characteristics.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multilayer coated to form a color negative film.
This is designated as Sample 101.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: Ultraviolet absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.25 Silver iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.005 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0020 ExC-8 0.015 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.005 ExC-7 0.010 ExC-8 0.030 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0203]

[Table 1]

In Table 1, (1) Emulsions J to L were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high voltage electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 below was dispersed by the following method. That is, 1430 g of a wet cake of dye containing 30% of methanol was added to water and BA.
200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by SF Co. was added and stirred to obtain a slurry having a dye concentration of 6%. Next, Imex Corporation
1700 ml of zirconia beads with an average particle size of 0.5 mm was filled in Ultra Viscomill (UVM-2) manufactured by Kuraray Co., Ltd.
It was pulverized at a rate of 10 m / sec and a discharge rate of 0.5 liter / min for 8 hours. The beads were filtered off, diluted with water to a dye concentration of 3% and then heated at 90 ° C. for 10 hours for stabilization. The obtained dye fine particles had an average particle size of 0.60 μm, and the breadth of the particle size distribution (particle size standard deviation × 100 / average particle size) was 18%.

Similarly, ExF-4, ExF-5, E
A solid dispersion of xF-6 was obtained. The average particle diameter of the dye fine particles was 0.45 μm, 0.54 μm, and 0.52 μm, respectively. Ex
F-2 was dispersed by the fine precipitation dispersion method by pH shift described in the example of JP-A-3-182734. The average particle size of the fine dye particles was 0.05 μm.

[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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[0222]

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The light-sensitive material prepared as described above has a width of 24 mm,
Cut to 160 cm, and then apply a 2 mm square perforation 0.7 mm from the width of one side of the length of the photosensitive material
Two are provided at 5.8 mm intervals. These two sets were prepared at intervals of 32 mm, and were described in FIGS. 1 to 7 of US Pat. No. 5,296,887.
In a plastic film cartridge described in (1). FM signals were recorded on the sample at a feed rate of 1,000 mm / s during the perforation of the photosensitive material using a head capable of inputting and outputting data from the coated surface side of the magnetic recording layer with a head gap of 5 μm and 2,000 turns. After recording the FM signal, the emulsion surface was uniformly exposed for 1,000 cms, and each processing was performed by the methods described below, and then the emulsion was stored again in the original plastic film cartridge.

Samples 102 to 130 shown in Table 2 were prepared in the same manner as Sample 101, except that an aqueous solution or dispersion of the polymer of the present invention or the comparative polymer was added to the coating solution of Sample 101 as shown in Table 2. Was produced.

[0225]

[Table 2]

[0226]

[Table 3]

[0227]

[Table 4]

The chemical structure of comparative polymer CP-1 is shown below. CP-1 is the polymer P-20 to P-2 of the present invention.
Although it has the same chemical composition as No. 2, it is a polymer outside the scope of the present invention because the average particle size exceeds 0.5 μm.

[0229]

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Two film pieces of Samples 101 to 130 were prepared, exposed using a light source having an energy distribution of 4800K through an optical wedge for sensitometry, and developed in a development step I or a development step II shown below. Processed.

[Development Treatment I] Step and Processing Solution Composition Step Processing Time Processing Temperature Color Development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching Fixing 3 minutes 15 seconds 38 ° C Washing with water (1) 1 minute 00 Second 38 ℃ Washing with water (2) 1 minute 00 seconds 38 ℃ Dry 2 minutes 00 seconds 60 ℃

Next, the composition of the processing liquid will be described. (Color developer) Tank solution (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N -Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching solution) Common to tank solution and replenisher (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) was added to 15.0 ml water 1.0 l pH (adjusted with aqueous ammonia and nitric acid) 6.3

(Bleach-fixing solution) Tank solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / liter) 240.0 ml Ammonia water (27%) Add 6.0 ml water to 1.0 liter pH (adjust with ammonia water and acetic acid) 7.2

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR manufactured by Rohm and Haas Company).
-120B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust calcium and magnesium ion concentrations to 3
mg / L or less, followed by 20 mg / L of sodium diisocyanurate and 15 mg of sodium sulfate.
0 mg / liter was added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 1,2-Benzisothiazolin-3-one Sodium 0.10 Ethylenediaminetetraacetic acid Disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

(Development processing II) step and processing solution composition Processing step Temperature time Color development 45 ° C. 60 seconds Bleach fixing 40 ° C. 60 seconds Water washing (1) 40 ° C. 15 seconds Water washing (2) 40 ° C. 15 seconds Water washing (3) 40 ℃ for 15 seconds Stability 40 ℃ for 15 seconds Drying 80 ℃ for 60 seconds (Washing was done with 3 tanks countercurrent from (3) to (1).)

Composition of processing solution (color developing solution) Tank solution (g) Diethylene trimian pentaacetic acid 2.0 1-Hydroxyethylidene-1,1 diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 2.0 Potassium iodide 1.3 mg Hydroxylamine Sulfate 4.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleach-fixing solution) (Unit mol) Ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.17 Ferric nitrate nonahydrate 0.15 Ammonium thiosulfate 1.25 Ammonium sulfite 0.10 Metacarboxybenzene Sulfinic acid 0.05 Water added 1.0 liter pH (prepared with acetic acid and ammonia) 5.8 (wash water) Same composition as described in Treatment I (Stabilizer) Same composition as described in Treatment I

Next, regarding the processed light-sensitive material, blue,
The density was measured with the status M densities of green and red to obtain a characteristic curve. Table 2 shows the results of obtaining the gradation ratio and the sensitivity difference between the treatments from this characteristic curve. Sample 12
In No. 2, reticulation occurred on the film surface after treatment, and in Sample 123, reticulation occurred on the film surface after treatment and film peeling occurred partially.

In Table 2, the number of the layer to which the polymer of the present invention is added represents the number of the layer counted from the side of the support, and the amount of the polymer of the present invention to be added is% by weight based on the weight of the hydrophilic colloid in the layer to be added. Represent In Table 2, the film swelling speed is the maximum swelling thickness obtained by subtracting the film thickness from the swelling film thickness when immersed in the color developing solution of the developing treatment step I (of this example) at 25 ° C. for 3 minutes and 15 seconds. , Expressed in time (seconds) required to reach 1/2 of this. The smaller the film swelling rate, the higher the swelling rate. The film swelling rate experiment is carried out using a film sample stored for 2 days under the conditions of 25 ° C. and 55% relative humidity. In Table 2, the gradation speed ratio between the processes is defined as γ _II (B) / γ
_I (B), γ _II (G) / γ _I (G), γ _II (R) / γ _I
Represents (R). In Table 2, the sensitivity difference ΔS = S _I −S _II
Is the logarithmic value of the exposure amount that gives a density of fog + 0.2 in the characteristic curve of red density D _R , and is represented by a value obtained by subtracting that of processing step I from that of processing step II. The smaller the number is, the lower the sensitivity in processing step II is.

From Table 2, it is found that the photographic material containing the polymer of the present invention promotes the swelling of the film during color development processing and, at the same time, the gradation ratio γ _II (R) / γ _I (R) is 1 at the same time. It can be seen that even when the development processing is performed in the development processing step II which is an ultra-rapid development processing, a good gradation balance is maintained.
Further, it can be seen that the photosensitive material containing the polymer of the present invention has a surprisingly improved decrease in sensitivity in the characteristic curve of red density when developed in the development processing step I. In the case of the sample 130 containing the dispersion of the comparative polymer CP-1, the effect on the gradation ratio and the sensitivity is very small. This suggests that the average particle size of the dispersion is an important factor.

(Example 2) Samples 101 to 13 of Example 1
After the same exposure as in Example 1 was applied to No. 0, the following standard development processing was performed. (Processing step) Processing time Processing temperature Replenishment rate * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 20 ml 17 liters Bleach 50 seconds 38.0 ° C 5 ml 5 liters Settling (1) 50 seconds 38.0 ° C-5 liters settling (2) 50 seconds 38.0 ° C 8 ml 5 liters Washing with water 30 seconds 38.0 ° C 17 ml 3.5 liters Stability (1) 20 seconds 38.0 ° C-3 liters Stability (2) 20 seconds 38.0 ° C 15 mls 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 35m width of photosensitive material 1.1m (equivalent to 24Ex. 1) Stabilizer is countercurrent from (2) to (1), and overflow liquid of washing water is fixed (2) ) Was introduced. The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of developer brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 2.5 ml, 2.0 ml and 2.0 ml, respectively, per 35 mm width of photosensitive material of 1.1 m. Was. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the treatment liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.3 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 2.0 2.0 Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.4 Add water 1.0 liter 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ammonium Ferric Acid Monohydrate 118 180 Ammonium Bromide 80 115 Ammonium Nitrate 14 21 Succinic Acid 40 60 Maleic Acid 33 50 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.4 4.0

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium methanesulfinate 10 30 Ammonium methanethiosulfonate 4 12 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 7 20 Ethylenediaminetetraacetic acid 15 45 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4 7.45

(Wash water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120 manufactured by Rohm and Haas).
Water is passed through a mixed-bed column packed with B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3 mg / L or less. Sodium isocyanurate 20mg
/ L and 150 mg / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Common to tank and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 Water added 1.0 liter pH 8.5

A characteristic curve was obtained for each of the treated samples in the same manner as in Example 1. The sample of the present invention had good gradation balance, sensitivity balance, and gradation linearity.

(Example 3) Samples 101 to 13 of Example 1
After preparing two 0s each and applying the same exposure as in Example 1,
The following ultra-rapid development processing was performed. In this experiment, in order to examine the progress of development (dependence on color development processing time), two development processings of 60 seconds and 70 seconds were performed. If the standard processing time for color development is 60 seconds, 60
The smaller the change in the characteristic curve before and after the second is, the smaller the change in the sensitivity and the gradation due to the variation in the processing time is. Therefore, the variation in the finish is small, which is preferable.

(Treatment process) Process Treatment time Treatment temperature Replenishment amount ^* Tank capacity Color development 60 seconds or 70 seconds 45.0 ° C 260 ml 1 liter Bleach 20 seconds 45.0 ° C 130 ml 1 liter Fixed 40 seconds 45.0 ° C 100 ml 1 liter Washing with water (1) 15 seconds 45.0 ° C-1 liter Washing with water (2) 15 seconds 45.0 ° C-1 liter Washing with water (3) 15 seconds 45.0 ° C 400 ml 1 liter Drying 45 seconds 80 ° C * Replenishment amount per 1 m ² of photosensitive material ( Washing with water (4) counter-current multi-stage cascade from (3) to fixing)

The composition of the treatment liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 2.0-Potassium iodide 1.3 mg-Disodium N, N-bis (sulfonate ethyl) hydroxylamine 12.0 17.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.5 15.0 Water was added to 1.0 liter 1.0 Liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (mol) Replenishing solution (mol) 1,3-Diaminopropanetetraacetic acid Ferric acid ammonium monohydrate 0.33 0.50 Ferric nitrate nonahydrate 0.30 4.5 Ammonium bromide 0.80 1.20 Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water] 4.5 4.0

(Fixer) Common to tank and replenisher (g) Ammonium sulfite 28 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml Imidazole 15 Ethylenediaminetetraacetic acid 15 Water-added 1.0 liter pH [Prepared with ammonia water and acetic acid] 5.8

(Washing Water) The same composition as the washing water of the developing treatment A-1 was used.

(Stabilizer) A stabilizer having the same composition as that of the stabilizer in the developing treatment step I was used.

A characteristic curve was obtained for each of the treated samples in the same manner as in Example 1, and the characteristic curve for red density D _R was compared between treatments. Here, the range of change in red density at a constant exposure amount was used as a measure of development progress (dependence on color development processing time). That is, color development 6 of sample 101
Based on the exposure amount giving a red density of 1.5 in the processing step of 0 seconds, the red density D ₇₀ in the processing step of color development 70 seconds and the red density D in the processing step of color development 60 seconds at the same exposure amount.
The difference from ₆₀ was obtained and the results are shown in Table 3.

[0258]

[Table 5]

[0259]

[Table 6]

From Table 3, surprisingly, the samples of the present invention had a small difference in color density D ₇₀ -D ₆₀ and had good development progress characteristics. The mechanism of the effect of the addition of the polymer of the present invention is largely unknown, but the hypothesis is as follows. That is, by containing the polymer of the present invention in the hydrophilic colloid, the swelling speed of the film in the early stage of the color developing process is increased, and the diffusion to the lower layer of the developing agent or alkali is promoted, resulting in the red-sensitive silver halide emulsion. Development of lower layers such as layers is accelerated. On the other hand, in the latter stage of the color development process, the swollen film thickness of the film increases and the coupler concentration decreases. As a result, the color development speed decreases and the development progress becomes slow. It is presumed that the above effect is produced by the balance of these two actions.

[0261]

According to the present invention, the same gradation and sensitivity can be obtained regardless of whether the ordinary development processing or the ultra-rapid development processing is performed.
Further, it becomes possible to provide a silver halide color photographic light-sensitive material and a color image forming method in which development progress in ultra-rapid development processing is improved.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 22, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image [In the general formula (1), R ¹ represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, a halogen atom, and L represents 2 to 4
A valent linking group, M is a hydrogen atom or a cation, and m is 0
Or an integer of 1, n is an integer of 1 to 3, and D is a repeating unit of an ethylenically unsaturated monomer.
y and z represent the weight percentage ratio of each monomer component, and y is 0
To 95 and z represent 5 to 100. However, y + z
= 100. ]

Embedded image [In the general formula (2), D ² represents a repeating unit of at least one ethylenically unsaturated monomer,
R ¹ , L, M, m and n are R ¹ in the general formula (1),
It has the same meaning as L, M, m, and n. p and q represent the weight percentage ratio of each monomer component, p is 0 to 85, and q is 1
Represents 5 to 100. However, p + q = 100. ]

Embedded image [In the general formula (3), A represents a repeating unit obtained by copolymerizing at least two copolymerizable crosslinkable monomers having an ethylenically unsaturated group. B represents a repeating unit obtained by copolymerizing a monomer represented by the following general formula (4), which homopolymer has a cloud point in an aqueous solution. D ³ represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer other than the above. p ', q', r ', s' represent the weight percentage ratio of each monomer component, p'is 0.1 to 60, q'is 10 to 70, r'is 0 to 30,
s'has a value of 25 to 85. However, p '+ q' +
r ′ + s ′ = 100. m and n have the same meaning as in general formula (1). ]

Embedded image [In the general formula (4), R ² represents a hydrogen atom or a lower alkyl group. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted alkyl group. R ² and R ³ do not become hydrogen atoms at the same time, and R ³ and R ⁴ may combine to form a nitrogen-containing heterocycle. Conditional Expression 0.8 ≦ γ _II (B) / γ _I (B) ≦ 1.2 0.8 ≦ γ _II (G) / γ _I (G) ≦ 1.2 0.8 ≦ γ _II (R) / Γ _I (R) ≦ 1.2 [γ _I (B), γ _I (G), and γ _I (R) are the gradations of blue density, green density, and red density when development processing I is applied, respectively. Γ _II (B), γ _II (G), and γ _II (R) represent gradations of blue density, green density, and red density when development processing II is applied, respectively. [Development Processing I] Color development processing time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N is used as a color developing agent. -(Β
-Hydroxyethyl) amino] aniline: a color developing treatment using a color developing solution containing 15 to 20 mmol / l. [Development processing II] Color development processing time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N- (β-
Development processing in which a color developing solution containing 35 to 40 mmol / liter of hydroxyethyl) amino] aniline is used for color development processing.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0205

[Correction method] Change

[Correction contents]

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 below was dispersed by the following method. That is, 1430 g of a wet cake of dye containing 30% of methanol was added to water and BA.
200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by SF Co. was added and stirred to obtain a slurry having a dye concentration of 6%. Next, Imex Corporation
1700 ml of zirconia beads with an average particle size of 0.5 mm was filled in Ultra Visco Mill (UVM-2) manufactured by Kuraray Co., Ltd.
It was pulverized at a rate of 10 m / sec and a discharge rate of 0.5 liter / min for 8 hours. The beads were filtered off, diluted with water to a dye concentration of 3% and then heated at 90 ° C. for 10 hours for stabilization. The obtained dye fine particles had an average particle size of 0.60 μm, and the breadth of the particle size distribution (particle size standard deviation × 100 / average particle size) was 18%.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 7/407 G03C 7/407

Claims (3)

[Claims] 1. At least one layer each on a support,
In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, the hydrophilic colloid layer constituting the light-sensitive material has the following general formula (1 ) At least one of the anionic water-soluble polymers represented by the formula (1), an alkali-soluble polymer dispersion having an average particle size of 0.01 to 0.5 μm represented by the following general formula (2) or the following general formula ( 3) containing a polymer dispersion represented by 3) and having different color development times.
In the characteristic curve (D-LogE) obtained when the development processing I and the development processing II of various types are performed, the gradation degree of the blue density,
A silver halide color photographic light-sensitive material, characterized in that the gradation of green density and the gradation of red density satisfy the following conditional expressions. Embedded image [In the general formula (1), R ¹ represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, a halogen atom, and L represents 2 to 4
A valent linking group, M is a hydrogen atom or a cation, and m is 0
Or an integer of 1, n is an integer of 1 to 3, and D is a repeating unit of an ethylenically unsaturated monomer.
y and z represent the weight percentage ratio of each monomer component, and y is 0
To 95 and z represent 5 to 100. However, y + z
= 100. [Chemical formula 2] [In the general formula (2), D ² represents a repeating unit of at least one ethylenically unsaturated monomer,
R ¹ , L, M, m and n are R ¹ in the general formula (1),
It has the same meaning as L, M, m, and n. p and q represent the weight percentage ratio of each monomer component, p is 0 to 85, and q is 1
Represents 5 to 100. However, p + q = 100. ] [Chemical 3] [In the general formula (3), A represents a repeating unit obtained by copolymerizing at least two copolymerizable crosslinkable monomers having an ethylenically unsaturated group. B represents a repeating unit obtained by copolymerizing a monomer represented by the following general formula (4), which homopolymer has a cloud point in an aqueous solution. D ³ represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer other than the above. p ', q', r ', s' represent the weight percentage ratio of each monomer component, p'is 0.1 to 60, q'is 10 to 70, r'is 0 to 30,
s'has a value of 25 to 85. However, p '+ q' +
r ′ = 100. m and n have the same meaning as in general formula (1). [Formula 4] [In the general formula (4), R ² represents a hydrogen atom or a lower alkyl group. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted alkyl group. R ² and R ³ do not become hydrogen atoms at the same time, and R ³ and R ⁴ may combine to form a nitrogen-containing heterocycle. Conditional Expression 0.8 ≦ γ _II (B) / γ _I (B) ≦ 1.2 0.8 ≦ γ _II (G) / γ _I (G) ≦ 1.2 0.8 ≦ γ _II (R) / Γ _I (R) ≦ 1.2 [γ _I (B), γ _I (G), and γ _I (R) are the gradations of blue density, green density, and red density when development processing I is applied, respectively. Γ _II (B), γ _II (G), and γ _II (R) represent gradations of blue density, green density, and red density when development processing II is applied, respectively. [Development Processing I] Color development processing time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N is used as a color developing agent. -(Β
-Hydroxyethyl) amino] aniline: a color developing treatment using a color developing solution containing 15 to 20 mmol / l. [Development processing II] Color development processing time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N- (β-
Development processing in which a color developing solution containing 35 to 40 mmol / liter of hydroxyethyl) amino] aniline is used for color development processing. 2. An image forming method, wherein a color image is formed by performing the following development processing A using the silver halide color photographic light-sensitive material of claim 1. [Development Processing A] Color developing processing time is 150 to 200 seconds, temperature of the color developing solution is 37 to 40 ° C., and a color developing solution containing 15 to 20 mmol / liter of a color developing agent is used. And development processing. 3. An image forming method, wherein a color image is formed by performing the following development processing B using the silver halide color photographic light-sensitive material according to claim 1. [Development treatment B] Color developing treatment time is 25 to 90 seconds, color developing solution temperature is 40 to 60 ° C., and a color developing solution containing a color developing agent in an amount of 25 to 80 mmol / liter is used. And development processing.