JPS61151528A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To remarkably accelerate a developing rate, without affecting a photographic performance such as a sensitivity, a gradation, and a fog by incorporating a polymer contg. at least one of repeating units shown by formula I to at least one of photographic constituting layers provided on a substrate. CONSTITUTION:At least one of the photographic constituting layers comprises the polymer having the repeating unit shown by formula I in at least one of the photographic constituting layer provided on the substrate. Concretely, said polymer is incorporated to a silver halide emulsion layer such as a blue sensitive layer, a green sensitive layer and a red sensitive layer, and a nonsensitive layer such as an under-coating layer, an intermediate layer and a protective layer, preferably silver halide emulsion layer. The compounding amount of the polymer depends upon a halogen composition, an amount of silver and a constituting ratio of the silver halide emulsion, and is about 0.01-100g, preferably 0.5-50g per one mol of the silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material containing a black and white developing agent.

[Prior art]

Silver halide photographic materials (hereinafter simply referred to as "photosensitive materials") are generally exposed to light and then subjected to a development process to form a dye image instead of a silver image. At that time, l-aryl-
It is well known that 3-pyrazolidones or 1-aryl-2-pyrazolines (hereinafter abbreviated as 3-pyrazolidones) function as development accelerators in either black-and-white development or color development.

It is also known to incorporate 3-pyrazolidones into a color photosensitive material in advance, and to perform color development after exposure.

For example, U.S. Pat. No. 3.902.905, U.S. Pat.
No. 209.580, JP-A-56-64339, JP-A No. 57
-144547, 58-50532, 58-5
No. 0533, No. 58-50534, No. 58-5053
No. 5, No. 58-50536, No. 59-104641, No. 59-116649, No. 59-121328, etc. Regarding the mechanism of color development promotion by 3-pyrazolidones, for example, as superadditivity 1 in color development, G. F. van Veele
J, Phot, Set,, 20, 94 by n.
(1972).

However, conventionally, when 3-pyrazolidones are incorporated into color light-sensitive materials, there are several problems.

That is, (1) when an amount sufficient to impart a sufficient development accelerating effect is incorporated, color turbidity occurs. For example, when color development occurs in a silver halide emulsion layer containing a yellow coupler,
The presence of 3-pyrazolidones partially induces color development in layers containing other couplers (for example, magenta couplers) that are unrelated to the yellow coupler-containing layer, thereby reducing the color purity of the image.

(2) A decrease in @ tone (γ) occurs. This is a particularly significant problem when the couplers used have relatively slow color development rates.

(3) Desensitization during storage of photosensitive materials results in the generation of capri. This depends on the built-in amount of 3-pyrazolidones, so it can be alleviated by reducing the amount, but the effect of promoting development cannot be exerted.

(4) When a photosensitive material is immersed in a color developer, a considerable portion of the incorporated 3-pyrazolidones dissolves into the developer before contributing to color development.

This not only means that more than the required amount must be incorporated, but also means that 3-pyrazolidones accumulate in the developer when color photosensitive materials are continuously processed. In general, 3-pyrazolidones in color developing solutions have a large effect on photographic performance (especially sensitivity and gradation), so 3-pyrazolidones are used during processing.
Fluctuations in the concentration of pyrazolidones are extremely disadvantageous.

In order to solve these problems, various improved techniques have been proposed. For example, JP-A-57-21114
No. 7, No. 58-50532, No. 58-50533,
Although 3-pyrazolidones having a phenyl group at the 5-position are described in No. 58-50534, the development accelerating effect of these compounds is extremely insufficient.

Also, JP-A-59-104641, JP-A No. 59-1213
No. 28 describes 3-pyrazolidones blocked at the 2- or 3-position, but although these compounds can alleviate the disadvantages during storage, they do not meet the requirements of the above (IL (2)
Problems (4) and (4) are not resolved at all.

JP-A-59-116649 discloses a method for adding 3-pyrazolidones;
), (3) and (4) remain unresolved.

Furthermore, JP-A-56-fi4339 and JP-A-56-86
No. 165 discloses a 3-pyrazolidone compound in which the hydroxymethyl group at the 4-position is acylated. Although the Kono compound provides relatively good photographic performance (development progress, gradation), it has not completely solved the problem (4) above.

[Purpose of the invention]

The present invention has been made to solve the problems of the prior art described above, and its first purpose is to provide a photosensitive material that has a significantly increased development speed without adversely affecting photographic performance such as sensitivity, gradation, fog, etc. Our goal is to provide the following. The second purpose is 3
- It is an object of the present invention to provide a color photosensitive material that does not cause a decrease in color purity (color turbidity) even when it incorporates pyrazolidones. A third object of the present invention is to provide a photosensitive material that can be stably and continuously processed without substantially eluting 3-pyrazolidones into a developing solution even when 3-pyrazolidones are incorporated therein.

[Structure of the invention]

The above object of the present invention can be achieved by incorporating a polymer having at least a repeating unit represented by the following general formula [1] into at least one of the photographic constituent layers on the support.

[I) +CHt-C→- AP In the formula, R represents an alkyl group (methyl group, ethyl group, butyl group, etc.) before the hydrogen atom, and X represents a divalent organic group.

Preferred examples of X include an alkylene group (methylene group, ethylene group, etc.), an arylene group (substituted or unsubstituted 22dine group, naphthylene group, etc.), -CONH- group, -
C0NH-R7- group, -R-r -C0NH- group, -C
OO- group or -coo-i (R, is a substituted or unsubstituted alkylene group or arylene group.

) A plurality of these divalent groups may be combined. AP is 1-tri-3-pyrazolidone compound residue or 1
-Aryl-2-pyrazoline compound residues are all represented, preferably represented by the following general formula [IID or [Seki].

In the formula, V, , V, and V each represent a hydrogen atom, a halogen atom, a carboxy group, a substituted or unsubstituted alkyl group (methyl group, ethyl group, butyl group, etc.) or an alkoxy group (methoxy group, ethoxy group, etc.). etc.), R1 and - each represent a hydrogen atom or an aryl group optionally substituted with an alkyl group (phenyl group, naphthyl group, etc.), and R1 and RIFi each represent a hydrogen atom or a substituted or unsubstituted alkyl group. Groups (methyl group, ethyl group, butyl group, etc.)' (i-represented. Horse is a hydrogen atom, acetyl group, or , ethyl group, etc.), alkenyl group (
vinyl group, allyl group, etc.), alkoxy group (methoxy group,
ethoxy group, etc.), alkylthio group (methylthio group, ethylthio group, etc.), or aryl group (phenyl group, naphthyl group, etc.). )
t or represents an aryl group (phenyl group, naphthyl group, etc.).

(9) R11 and R1 may be ring-closed to form a benzene nucleus. n is an integer of 2 or 3. R1 represents t- (hydroxy group, 2.2.2-trichloroethoxy group, phenoxy group, 2.4-dinitrophenoxy group, etc.). It
tt represents a hydrogen atom, an alkyl group (methyl group, ethyl group, butyl group, etc.) or an aryl group (phenyl group, naphthyl group, etc.), and RIM represents a hydrogen atom or an acyl group (acetyl group, benzoyl group, etc.). ) Ro is a substituted or unsubstituted alkyl group (methyl group, ethyl group, butyl group, etc.), alkoxy group (methoxy group, ethoxy group, etc.), aryl group (phenyl group, naphthyl group, etc.) or aryloxy group ( phenoxy group, etc.).

Substituents that the alkyl groups of V, V, and V above may have include a halogen atom, a hydroxy group,
Preferred are a carboxyl group, a cyano group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an aryl group, and an aryloxy group. Vl, V, and V
Examples of substituents that the alkoxy group of
Preferred are an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an aryl group, and an aryloxy group.

Substituents that the alkyl groups of R1 and R4 can have include a halogen atom, an alkoxy group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an arylcarbonyloxy group, an aryloxycarbonyloxy group, an alkylsulfonyloxy group, and an arylsulfonyl group. An oxy group is preferred.

Substituents that the bird alkyl group can have include:
Preferred are halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. As the substituent that the bird aryl group can have, an alkyl group is preferable.

In addition, since AP is bonded to the polymer backbone via the divalent linking group X, ■2, V2, Vs% R+% &,
At least one of R8, 也 and 也 is a divalent group or a single bond.

In the present invention, by constructing the general formula CI'l, AM
-I AM-4 (H.

AM-7 AM-10 AM-8 Silent 9 AM-12, m
-17 AM-19Ha←22 AM-21AM-24 AM-25AM-28 AM-26AM-29 AM-27AM-30 CH1l The polymer of the present invention is a water-soluble polymer represented by the following general formula [II]. It is preferable that there be.

III P In the formula, RX and AP are as described above.

B is a repeating unit formed from an unsaturated monomer having no hydrophilic group in its constituent units, and D is a repeating unit formed from an unsaturated monomer having a hydrophilic group in its constituent units. More specifically, it is represented by the following general formula [IIa].

[II&) BoP In the formula, H/ is a hydrogen atom, an alkyl group or an alkoxycarbonyl group, R'' and nnl are a hydrogen atom or an alkyl group, respectively, and R'''' represents a hydrogen atom, a carboxy group, or a salt thereof. Ro is Represents a non-hydrophilic group, such as an alkyl group, alkoxy group, alkenyloxy group, acyl group, alkylcarbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, aryl group, heterocyclic residue (non-hydrophilic imidazolyl group, triazolyl group) Rw represents a hydrophilic group, such as a carboxy group or a salt thereof, a sulfo group or a salt thereof,
Examples include carboxyalkyl groups, carboxyaryl groups, carbamoyl groups, sulfoalkylcarbamoyl groups, and heterocyclic residues (hydrophilic 2-oxopyrrolidin-1-yl groups, pyridinyl groups, etc.). ! , 7 and 2 are indexes representing the copolymerization ratio, and X is 5 to mol%, preferably 1
It is 0 to 70 mol%. y is θ to 50 mol%, preferably 0 to 30 mol%.

2 is 10 to 90 mol%, preferably 30 to 70 mol%.

Specific examples of the unsaturated monomer forming the repeating unit Bt constituting the polymer of the present invention include all of the following compounds, but are not limited thereto.

B −I CH,=CHC0NHC, HaB −2
CH,=cucoNI(c,H,(t)B-3CH,
=CHC0NHC,Hl, (t)B -4CI(, =C
HC0NECH, C0CI(, C0CHjB -6CH
,=CC0■C4H9(t)CH.

B-7CH,=CC0NHC,Hl.

Hs B-8C chicken=CHC00CH.

B −9CH,=CHC00C,I(, (t)B −1
0CH1=CHCOOC,H,.

B-11C horse=CHC00CttHzsB -12CH
,=CHOCOCH.

B −17CH,=CH0CsHs* B-18CH,=CH0C,sH,.

B -19CH, =CHC chicken C ■, CM wealth B -20C
M,=CH0CH=CH.

B-2I C,H1lOCOCH=CHCO
OC4H.

B-22Ca H1? OCOCH=CHC00Ca
HItB -23C=CHCH(OCtlm)tB
−25CH,=CHC0CH.

Next, specific examples of unsaturated monomers forming the repeating unit that constitutes the entire polymer of the present invention will be given, but the invention is not limited thereto.

D -I CJ(,=CHC00HD -2C
H,=CCOOH CH.

D −3HOOCCH=CHCOOH D −4HOOCCH=,=CHOCOCOOH D-5? H1 CH,=CHC0NHCCHtSO,Na■ CH.

D-6CH! =CHC0NHCH,CH,So,HD
-9CHt =CH8=CH3 O-10CH, =CHCH,CH,C00HD-11C
−=CIC0NHt D −12CHt=CCONHt CH.

D-140)It,,CHC)I,('IcI(2C
) (tSo, H As is clear from the above description, the water-soluble polymer of the present invention does not need to have one type of repeating unit B and one type of Dt-, but two or more types may be combined as long as the effects of the present invention are not impaired. They may also be configured together.

To produce the polymer of the present invention, polymerization methods known in the art, such as emulsion polymerization and solution polymerization, are used. Generally, water, alcohol (methanol, ethanol,
In the presence of a polymerization initiator, a monomer mixture dissolved in a single or mixed solvent such as a water-fluoricol mixed solvent, N,N-dimethylformamide, acetone, dimethyl sulfoxide, etc. is reacted by heating in the presence of a polymerization initiator. As the polymerization initiator, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used. Examples of water-soluble polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, sodium 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis(2-amidinopropane). ) Water-soluble azo compounds such as hydrochloride and hydrogen peroxide can be used. Examples of lipophilic polymerization initiators used in the solution polymerization method include azobisisobutyronitrile, 2.
2'-azobis(2,4-dimethylvaleronitrile),
Lipophilic azo compounds such as 2.2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2.2'-dimethyl azobisisobutyrate, 1°1'-azobis(cyclohexanone-1-carbonitrile), Lipophilic peroxides such as benzoyl peroxide, lacryl peroxide, diisopropyl peroxydicarbonate, and di-ttrt-butyl peroxide can be mentioned.

The polymer of the present invention has a molecular weight of 2.000 to 2.00, although the degree of polymerization varies depending on the type of constituent monomers and reaction conditions.
200.000 is preferable, more preferably s,
ooo~100.000.

Examples of producing the polymer of the present invention are shown below.

Production Example 1 (Synthesis of monomer pigeon 2) 26.2.9 (0.15 mol) of 1-p-aminophenyl-3-pyrazolidone and pyridine 13.4 Ji”t
Dissolve in 250-N acetonitrile and heat at 15.5 N (0
, 17 mol) of acrylic acid chloride was added dropwise over a period of about 10 minutes. After removing the external temperature, the mixture was further stirred at room temperature for 4 hours, and then left for 1 day.

The reaction solution was concentrated to dryness under reduced pressure and then dissolved in ethyl acetate. The mixture was washed with a 3% bicarbonate solution and then with water, and the ethyl acetate layer was dried over sodium sulfate and concentrated to dryness.

Recrystallization was performed using a mixed solvent of methanol/water, and further recrystallization was performed using n-hexane/ethyl acetate. Yield 21.1N
(Yield 60%). Elemental analysis, NMR and IR measurements supported that the obtained compound was 1-(4-acryloylamino)phenyl-3-pyrazolidone.

Elemental analysis value CHN as Cttutal'Jsot Theoretical value 62.33% 5.66% 18.17% Actual value 62.24% 5.61% 18.29% Production example 2
(Synthesis of monomer AM-8) 1-p-)dyl-4-methyl-4-hydroxymethyl-3-pyrazolidone t-2 of 22, OF (0.1 mol)
12.5.9 (0.0
, 12 mol) of methacrylic acid chloride was added dropwise over a period of approximately 1 minute. After removing the ascending column and stirring at room temperature for an additional 4 hours, the outside i'
The temperature was increased to 50'c and the mixture was stirred for several minutes. The reaction solution was treated in exactly the same manner as in Production Example 1 to obtain 22.6.9 (yield 78%) of the desired product. Elemental analysis, spectral and IR measurements supported the identity of this compound as 1-p-) true 4-methyl-4-methacryloyloxymethyl-3-pyrazolidone.

Elemental analysis value CHN as C15HtON103 Theoretical value 66.65% 6.99% 9.71% Actual value 66.74% 6.91% 9.53% Production example 3 (synthesis of monomer AM-24) 23. 1 # (0.1 mol) of 1-(4-acryloylaminophenyl-3-pyrazolidone (AM-2) t2
Dissolve 00d in chloroform and add 23M1 triethylamine. To this solution, 12.5 # (0.1 mol) of ethyl chlorocarbonate was gradually added dropwise under nitrogen atmosphere and stirring at room temperature. After further stirring at room temperature for 2 hours, the reaction solution was transferred to a separating funnel and washed with water. After drying the oil layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of ethyl acetate/methanol. Yield: 21.51 (yield: 74%). Elemental analysis, IR measurement and IR measurement, the obtained compound was 1
-(4-acryloylamino)phenyl-3-ethoxycarbonyloxy-2-pyrazoline≠9.

C11HI? Elemental analysis value CHN as NmO< Theoretical value 59.40% 5.65% 13.85% Actual value 59.28% 5.52% 14.00% Production example 4
(Synthesis of polymer rP-1) Exemplary monomer AM-2 of 9.2 f (0.04 mol)
, 13,7PC0.06 mol) of 2-acrylamide-
Sodium 2-methylpropanesulfonate CD-5) and 0.12 t of 2,2'-azobis(2,4-dimethylvaleronitrile) were dissolved in 100 d of N,N-dimethylformamide ( The mixture was stirred for 4 hours at a bath temperature of 4°C. This solution was slowly added to 14,800 d of ether with stirring to precipitate the polymer particles. Solid particles were collected, washed with ether, and dried at room temperature to obtain 1-1 pale yellowish brown powder. This powder dissolves easily in water to give a clear light tan aqueous solution.

Production Example 5 (Synthesis of Polymer P-2) 11.5? (0.04 mol) of exemplary monomer AM-8
,0,64P (0,005 mol) of Nt-butylacrylamide (B-2), 12.2 f (0,055
mol) of potassium styrene-4-sulfonate (D-7)
Th and 0.74 f of 2.2'-dimethyl azobisisobutyrate '1i-120d was dissolved in N,N-dimethylformamide and stirred for 4 hours at a bath temperature of 0.degree. C. under a nitrogen atmosphere. This solution was slowly added to 1.000% ether with stirring to precipitate polymer particles. Production example 4
The mixture was treated in the same manner as above to obtain a pale yellowish brown powder. This polymer also dissolves easily in water, giving a clear light brown aqueous solution.

Production Example 6 (Synthesis of Polymer P-3) 17.49 (0.06 mol) of exemplified monomer AM-24
, 9.2 F (0.04 mol) of D-5 and 0.1)
2.2'-Azobis(2,4-dimethylvaleronitrile) t was dissolved in 150 d of N,N-dimethylformamide and stirred at a bath temperature of 0.degree. C. for 4 hours under a nitrogen atmosphere. Thereafter, it was treated in the same manner as in Production Example 4 to obtain a pale yellowish brown powder. This powder also dissolves easily in water to give a clear aqueous solution.

When the polymer of the present invention is applied to a color photosensitive material, it can be added to any constituent layer of the photosensitive material. Specifically, they include a blue-sensitive layer and a green-sensitive layer, preferably a silver halide emulsion layer and a layer adjacent thereto, and particularly preferably a silver halide emulsion layer. Further, the polymer of the present invention is added to at least one of the photographic constituent layers, and two
It can also be added to more than one layer.

The amount of the polymer of the present invention added varies widely depending on the halogen composition of the silver halide emulsion, the amount of silver, the composition ratio of the polymer, etc., but is approximately 0.01 to 1 per mole of silver halide.
00f, preferably 0.05 to 5o2.

The polymers of the present invention are preferably water-soluble and are added directly to the hydrophilic colloid solution forming the photographic constituent layers.

In this case, a small amount of a water-miscible organic solvent such as methanol, ethanol, or acetone may be used if necessary.

Furthermore, the timing of adding the polymer of the present invention to the coating solution is as follows:
This compound may be added to the photosensitive silver halide emulsion layer at any time after the preparation of the photosensitive silver halide emulsion. When the photosensitive silver halide emulsion is a surface latent image type emulsion in which latent gRt-formation is mainly formed on the grain surface, it may be prepared at any time after chemical ripening and optical sensitization. When the photosensitive silver halide emulsion is an internal latent scratch type emulsion in which latent cracks are mainly formed inside the grains, it may be prepared at any time after the silver halide emulsion is prepared and subjected to optical sensitization treatment. Further, when adding to the non-photosensitive emulsion layer, it may be added at any time before coating this emulsion layer, but it is preferable to add it immediately before coating.

Any silver halide composition can be used in the silver halide emulsion used in the present invention. Specifically, they are silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodide, and silver chloroiodobromide.

The grain size of these silver halide emulsions may be any size, but preferably the average grain size is about 0.1 to 3.
．． It is 0 μm.

The crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure in which the inside and outside are different. Further, the silver halide may be a surface latent image type that forms a latent image mainly on the surface, or an internal latent image type that forms a latent image mainly inside the grain.

The crystal habit of the silver halide grains may be either the (100) plane or the (111) plane, or it may be a mixture of these planes. Also, JP-A-58-95337, JP-A No. 58-95337;
No. 8-111935. The tabular grains described in et al.

These silver halide grains may be monodisperse grains having relatively uniform grain sizes or polydisperse grains.

In addition, these silver halide emulsions contain salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum, and gold (for example, ammonium chloronosiladate, potassium chlorovaladite, potassium chlorovaladite, and potassium quartz). etc.), activated gelatin, sulfur sensitization with unstable sulfur (e.g. sodium diosulfate, etc.), selenium sensitization with seleno compounds, stannous salts, polyamines, thiourea dioxide, etc., and low p
Reduction sensitization under Ag can be performed.

These silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes include, for example, U.S. Pat.
゜908, 2.739.149, 2,213,
No. 995, No. 2,493,748, No. 2,519,0
No. 01, West German Patent No. 929.080, British Patent No. 505.
The cyanine dyes, merocyanine dyes, or composite cyanine dyes described in No. 979 can be used alone or in combination of two or more. These various optical sensitizing dyes are used for purposes other than their original purpose, such as preventing fog, preventing deterioration of photographic performance during storage of silver halide color photographic materials, and controlling development (for example, gradation control, etc.). ) and other purposes.

In addition, these silver halide emulsions may contain, if necessary,
Chemical sensitizers such as thioether compounds, quaternary ammonium salt compounds, or polyalkylene oxide compounds; stabilizers such as triazoles, imidazoles, azaindenes, benzothiazolium compounds, zinc compounds, cadmium compounds, and mercaptans; can be used within a range that does not impair the effects of the present invention.

The dye image-forming coupler used in the present invention is not particularly limited, and various couplers can be used, but the compounds described in the following patents are representative examples.

Preferred yellow dye image-forming couplers are 4-equivalent or 2-equivalent couplers of the azila heptamide type and benzoylmethane type, which are described, for example, in U.S. Pat.
No. 8.658, No. 2.875.057, No. 2.908
No. 573, No. 2,908.513, No. 3,227.
No. 155, No. 3,227゜550, No. 3,253.9
No. 24, No. 3,265.506, No. 3,277゜15
No. 5, No. 3,341.331, No. 3,369.895
No. 3,384゜657, No. 3,408.194, No. 3,415.652, No. 3,447゜928,
No. 3,551.155, No. 3,582.322, No. 3,725゜072, 4th Loquat - Patent No. 1,547.86
No. 8, No. 2.057,941, No. 2,162.899
No. 2,163,812, No. 2,213,461, No. 2.219,917, No. 2.261.361,
No. 2,263,875, Special Publication No. 49-13576,
JP 48-29432, JP 48-66834, JP 49-10736, JP 49-122335, JP 50
-28834, 50-132926, 55-1
No. 44240 and No. 56-87041.

The magenta dye image-forming coupler is preferably a 4-equivalent or 2-equivalent magenta dye image-forming coupler of the 5-virazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indashilon type, or cyanoacetyl type. Patent No. 2,600.788, Patent No. 3,061.432, Patent No. 3,062゜653,
No. 3,127,269, No. 3,311.476, No. 3,152゜896, No. 3,419,391, No. 3
, 519.429, 3,558゜318, 3,
684,514. No. 3,705,896, No. 3,
888°680, 3,907,571, 3,9
No. 28,044, No. 3,930゜861, No. 3,93
No. 0,816, No. 3,933.500, Japanese Unexamined Patent Publication No. 1973-
No. 29639, No. 49-111631, No. 49-12
No. 9538, No. 51-112341, No. 52-589
No. 22, No. 55-62454, No. 55-118034
No. 56-38843, No. 56-135841,
Patent Publication No. 46-60479, No. 52-34937, No. 55-29421, No. 55-35696, British Patent No. 1.247.493, Belgian Patent No. 792.525, West German Patent No. 2.156,111 Are listed.

As the cyan dye image-forming coupler, phenol-based or naphthol-based 4-equivalent or 2-equivalent cyan dye image-forming couplers are preferred, and these are disclosed, for example, in U.S. Pat. , No. 2.434,272, No. 2,474.293, No. 2
．． No. 698.794, No. 2,706,684, No. 2.
No. 772.162, No. 2.801.171, No. 2.8
No. 95.826, No. 2.908,573, No. 3,03
No. 4,892, No. 3.046,129, No. 3,227
．． No. 550, No. 3,253,294, No. 3.311.
No. 476, No. 3,386,301, No. 3,419.3
No. 90, No. 3,458,315, No. 3,476.56
No. 3, No. 3,516.831, No. 3.560.212
No. 3,582.322, No. 3,583,971, No. 3.591.383, No. 3,619,196,
3,632.347, 3.652.286, 3,737,326, 3,758.308, 3
．． 779,768, West German Patent No. 3,839.044, West German Patent No. 2.163.811, West German Patent No. 2,207.468, Japanese Patent Publication No. 39-27563, Japanese Patent Publication No. 45-28836, Japanese Patent Publication No. 47-37425 , No. 50-10135, No. 25228, No. 50-112038, No. 50-
No. 117422, No. 50-130441, No. 53-1
No. 09630, No. 55-32071, No. 55-163
No. 537, No. 56-1938, No. 56-13643, No. 56-29235, No. 56-65134, No. 5
No. 6-104333, and Research Disclosure (R@5earch, + Disclosure)
14853 (1976) etc.

The light-sensitive material of the present invention may also contain a so-called DIR coupler, which releases a development inhibitor by coupling with an oxidized form of a color developing agent. Examples of such IR couplers include U.S. Pat.
, No. 227,554, No. 3,617,291, No. 3,
632゜345, 3,701.783, 3,7
33.201, 3,790゜384, 3,86
No. 9,291, British Patent No. 953,454, 1.20
No. 1.110, No. 1,236,767, Japanese Unexamined Patent Publication No. 1973-
No. 122335, No. 51-16141, No. 52-69
Those described in No. 624 and the like can be used.

In the light-sensitive material of the present invention, a colored coupler having a color correction effect can be used as a dye-forming coupler. Such colored couplers include U.S. Pat.
No. 1.908, No. 3,034,892, No. 3,476
No. 560, Special Publication No. 38-22335, No. 42-11
304, 44-2016, 44-32461, JP-A-51-26034, JP-A-52-42121, etc. can be used.

In the present invention, it is advantageous to use gelatin as the hydrophilic colloid for dispersing silver halide, but other hydrophilic colloids can also be used.

Examples of preferable hydrophilic colloids include alkali-treated gelatin, acid-treated gelatin, and other gelatin, which are most commonly used.
derivative gelatin, such as phenylcarbamoyl gelatin;
Albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinyl.The photosensitive material of the present invention can contain various photographic additives. Such examples include, for example, UV absorbers (e.g. benzophenone conduit compounds and benzo)
IJ azole thread compounds, etc.), dye image stabilizers (e.g. thunol compounds, bisphenol J compounds, hydroxychroman compounds, bisspirochroman compounds, alkoxybisspiroindan compounds, hydantoin compounds, dialkoxybenzene compounds, etc.) , stain inhibitors (e.g. hydroquinone derivatives, etc.), surfactants (e.g. sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkyl succinate ester sulfonate, polyalkylene glycol, etc.), water-soluble anti-irradiation dyes (e.g. azo compounds, f'JN compounds, triphenylmethane, 1% compounds, oxonol compounds, anthraquinone compounds, etc.), hardeners (e.g. halogeno-5
-) Riazine compounds, vinyl sulfone compounds, acryloyl compounds 1. (ethyleneimino compounds, N-methylol compounds, epoxy compounds, water-soluble aluminum salts, etc.), film property improvers (e.g. and colloidal silica, etc.), fluorescent brighteners (e.g. diaminostilbene compounds), and various oils. Examples include soluble paints.

Furthermore, in the photosensitive material of the present invention, non-polymeric 3-pyrazolidones can be used in combination with the polymer of the present invention. Such 3-pyrazolidones include 1-phenyl-3-hyrazolitone, 1-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1
-Phenyl-4゜4-dimethyl-3-pyrazolidone, 1
-phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 1-phenyl-4-methyl-4-acetyloxymethyl-3-pyrazolidone, l-tolyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone, 1
- p-aminophenyl-3-amino-2-pyrazoline, 1-phenyl-3-phenoxycarbonyloxy-2
-pyrazoline, 1,5-diphenyl-3-ethoxycarbonyloxy-2-pyrazoline, and the like.

Examples of the support used in the light-sensitive material of the present invention include transparent supports such as EVA, nitrocellulose film, acetylcellulose film, polyvinyl acetal film, polycarbonate film, polystyrene film, and polyethylene terephthalate film; Synthetic reflective supports filled with white pigments such as titanium dioxide, papers and polymer-coated papers such as polyethylene, polypropylene, etc. are used.

The photosensitive material of the present invention can be used for various purposes. Examples include black and white photosensitive materials, internal color photosensitive materials, photosensitive materials for silver salt diffusion transfer, photosensitive materials for dye diffusion transfer, photosensitive materials for silver dye bleaching, black and white photosensitive materials for heat development, and color photosensitive materials for heat development. .

Further, these various photosensitive materials are subjected to various development steps depending on the system used. For example, in the case of black-and-white light-sensitive materials, there are a method of developing with a black-and-white developer containing a developing agent such as hydroquinone or ascorbic acid, and a method of developing with an alkaline activation bath containing no developing agent at all.

In the color light-sensitive material particularly preferably used in the present invention, in addition to the usual color development process, direct reversal color development using a direct positive emulsion, black and white development followed by color development process, and a color developing agent may be used. There is a method in which the photosensitive material is incorporated in advance into a photosensitive material and subjected to color development processing in an alkaline activation bath.

When processing the photosensitive material of the present invention using a black and white developer,
Examples of black and white developing agents include hydroquinone, methylhydroquinone, chlorohydroquinone, carboxyhydroquinone, sulfonohydroquinone, and N-methylhydroquinone.
p-Aminephenol, ascorbic acid, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-
Examples include hydroxy'methyl-3-pyrazolidone, glycine, catechol, resorcinol, and the like.

(9) When processing the photosensitive material of the present invention using a color developer, the color developing agent is preferably an aromatic primary amine compound, %Kp-phenyl diamine type, and N,N -diethyl-p-phenylenediamine hydrochloride,
N-techf/L'-p-7 enylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)
-) toluene, N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-N-( 2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N-(β-hydroxyethyl)-3- Examples include methyl-4-aminoaniline. These color developing agents may be used alone or in combination of two or more.

Various developing solutions or alkaline activation baths used in the present invention include, in addition to the above-mentioned developing crude drugs, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Alkali agents such as potassium hydrogen carbonate and tribasic sodium phosphate, development inhibitors such as sodium bromide and potassium bromide, methanol, ethanol, acetone, phthanol, benzyl alcohol, phenoxybutanol, diethylene glycol, ethylene glycol, N, N- Various organic solvents such as dimethylformamide, preservatives such as hydroxylamine and sodium sulfite, development regulators such as citradinic acid, polyethylene glycol, and polyvinylpyrrolidone, water-soluble fluorescent brighteners such as diaminostilbene compounds, and ethylene diamine tetrachloride. Various known additives such as a heavy metal ion masking agent such as acetic acid and alkyliminodiacetic acid, and a development accelerator may be included as necessary.

Furthermore, these developers or alkaline activation baths (1-aryl-3-bilacy) are added in advance.

A lydone compound can be included. Specifically, for example, 1-phenyl-3-pyrazolidone, 1-)dyl-
Examples include 3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-bilacy-3-pyrazolidone, and the like.

After the photosensitive material of the present invention is developed in black and white, it is generally fixed,
A silver painting is obtained by performing treatments such as stabilization and washing with water as necessary. First, when the light-sensitive material of the present invention is an internal color light-sensitive material, various steps such as bleaching, fixing (or bleach-fixing), washing, stabilization, etc. are performed as necessary following color development.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 A photosensitive material was prepared by sequentially coating the following two layers on a polyethylene laminate M support (Sample 1).

In the following examples, unless otherwise specified, the amount added is 1
The value per d is shown, and the silver halide emulsion is shown in terms of silver.

Layer 1: 1.4F gelatin and 1.0T blue-sensitive silver chloroiodobromide monodispersed emulsion (AgBr 65 mol%, A
gI 0.5 moA/%, AgCJ 34.5 mole%, average A, 3 spm.

After sulfur sensitization, the following blue sensitizing dye was added to silver halide 1
Contains 7.0XIO moles per mole and 4-hydroyac-6-methyl-1,3,3m as a stabilizer.

7-thitrazaindene at 5X1 per mole of silver halide
0 mol) t-containing blue-sensitive emulsion layer.

Layer 2: 1. Of gelatin and 0.0 as hardener.
Gelatin protective layer containing 05 F bis(vinylsulfonylmethyl)ether.

In addition, as shown in Table 1, non-polymeric 1-phenyl-
Samples in which 3-pyrazolidone (A-1) or the polymer of the present invention was added immediately before coating were also prepared (Samples 2 to 6).
).

The six samples obtained from the blue sensitizing dye were stored at 40° C. and 80% relative humidity for 2 days. Next, optical wedge exposure was performed and the following steps were performed.

Treatment process Temperature Time: 15 seconds, stop for 30 seconds, fix at room temperature, 5 seconds, wash with water, 45℃, 15 seconds
30P-A"C 30 seconds drying 70~80
C. I second stop solution formulation 1.5% acetic acid aqueous solution fixer formulation Each developed sample was subjected to reflection density measurement under zero light, and the results shown in Table 1 were obtained. In the table, relative sensitivity is development time I
The sensitivity of sample (1) in seconds is shown as 100.

Table 1 P-5 From the results shown in Table 1, sample (2) to which non-polymeric 1-phenyl-3-pyrazolidone was added had a higher Ic than sample (1) to which no development accelerator was added. Although the initial developability has been slightly promoted, the effect is still not sufficient and the sensitivity is rather low when the development time is in seconds.

On the other hand, it can be seen that samples (3) to (6) of the present invention not only exhibit extremely high development progress but also have good photographic properties.

Example 2 Seven types of multilayer color light-sensitive materials were prepared by sequentially coating the following layers from the support side onto a paper support whose both sides were coated with polyethylene subjected to corona discharge (Samples 7 to 13).

Layer (1) Blue-sensitive silver halide emulsion layer 1.5F gelatin, 0.32F blue-sensitive silver chlorobromide emulsion (90% silver bromide, average grain size 0.68 μm), 1.
2 X 10-” moles of the following yellow coupler (Y-1
), 0. O15#) 2.5-di-t-octylhydroquinone (HQ-1) and 0.13 f of the following image stabilizer (S-1)'i dissolved in 0.6 f of dioctyl phthalate (DOP). Contains a blue-sensitive emulsion layer.

Layer (2) Intermediate layer Intermediate layer containing 0.9 f of gelatin and 0.06 f of DOP dissolved in 0.09 r of HQ-1.

Layer (3) a photosensitive silver halide emulsion layer 1.32 gelatin, 0.19F edge-sensitive silver chlorobromide emulsion (silver bromide 65 mol%, average grain size 0.45μ7N, 0
．． 59 x 10 moles of the following magenta coupler (M-1)
, 0.015 f OHQ −1 and 0.24 f O
0.2 f DO in which the following image stabilizer (S-2) was dissolved
P and 0.01 f of the following water-soluble dye (AID-1)
A green light-sensitive emulsion layer containing.

Layer (4) Intermediate layer 1.5f of gelatin, 0.8t of the following ultraviolet absorber (0
, 42 UV -1 and 0.4f (D U'v-2) and 0
．． 05 f (2) HQ -1t-dissolved 0,6
Interlayer containing f DOP and 0.2 f polyvinylpyrrolidone.

Layer (5) Red-sensitive silver halide emulsion layer 1.61 gelatin, 0.3 f red-sensitive silver chlorobromide emulsion (silver bromide 70 mol%, average grain size 0.40 μm), 0.
35, 0-1 mol of the following cyan coupler (C-1) and 0
．． 35 o 1 mole of the following cyan coupler (C-2) and 0.01 f of I (0,25 f of D in which Q-1 was dissolved)
OP and 0.029 of the following water-soluble dye (AID-2
) containing a red-sensitive emulsion layer.

Layer (6) Intermediate layer 1.2f gelatin, 0.2f OUV-1 and 0.2f
of UV-2 and 0.02 P of HQ-1 dissolved in 0
, 31 DOP t-containing interlayer.

Layer (7) Protective layer Protective layer containing 1.01 gelatin.

As shown in Table 2, various non-polymeric 3-pyrazolidone compounds and the polymer of the present invention are added to layer (1), and the coating liquid constituting layers (2), (4) and (7) is prepared. Inside, 0.015r of 2,4-dichloro-6-hydroxy-5-)riazine-sodium salt per 11 gelatin was added as a hardening agent just before coating. I V -2 A I AID -2 The obtained samples (7 to 13) were cut at ℃ and 60% relative humidity for 2 hours.
After storing it for a day, it was exposed to white light through an optical wedge and processed according to the following steps.

Processing process Temperature Time color development Seki°C 2 minutes, 3 minutes I seconds bleach fixing
Wash with water for 1 minute and 1 second at 33℃~A℃
3 revolution drying ω~Seki°C 2 minutes The compositions of the color developing solution and bleach-fixing solution used are as follows.

For each sample treated with a color developing solution, a bleach-fixing solution, and a reflection density t-meter measurement using each monochromatic light of blue, green, and red, sensitivity, gradation, and maximum density were determined. The results are shown in Table @2. In the table, I did. Moreover, the gradation indicates the reflection density [0.5 to 1.5].

From the results shown in Table 2, the developability of the blue-sensitive layer of samples (8) and (9) containing a non-polymeric 3-pyrazolidone compound was lower than that of the sample containing no development accelerator.
7) Although it has been improved, the effect is not sufficient, and the gradation of each photosensitive layer is lowered and desensitization occurs. On the other hand, samples (10) to (13) in which the polymer of the present invention was added to layer (1) provided extremely high development progress of the blue-sensitive layer, and did not have any adverse effect on the photographic properties of each photosensitive layer. It is clear that there is no.

Example 3 The 7 m long sample used in Example 2 was subjected to light wedge exposure with blue light, and then processed in the same manner as in Example 2 (development time: 3 minutes force seconds) to obtain a yellow dye surface gI. The obtained yellow image scratches are shown as blue, a
The reflection density was measured using each monochromatic light of red and green, and the green and red reflection densities at a point giving a yellow reflection density of 1.0 were determined. The results are shown in Table 3.

Table 3 From the results shown in Table 3, in contrast to sample (7) K to which no development accelerator was added, samples (8) and (9) to which a non-polymeric 3-pyrazolidone compound was added were green and green. Although the red reflection density is high and the color is obviously cloudy, in samples (1o) to (13) according to the present invention,
It can be seen that such color turbidity hardly occurs.

Example 4 Comparative sample (9) used in Example 2 and sample of the present invention (
After imagewise exposure of No. 1, continuous processing was performed according to the processing steps shown in Example 2 (color development for 2 minutes). For continuous processing,
Add color developer replenisher at 150X per color photosensitive material,
The bleach-fixing replenisher was added to 1 ml of the color light-sensitive material while replenishing it in 200-minute increments.

The composition of the color developer replenisher used is as follows.

Pure water
800MLl ethylene glycol
151Ll benzyl alcohol
20tJ hydroxylamine sulfate
3.02 Potassium carbonate 3
4? Potassium sulfite 3.02
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 7.5tWh
tax 8B (50% aqueous solution)
2.5dl-hydroxyethylidene-1,1
-Diphosphonic acid (60% aqueous solution)
Add 2.5 d of pure water to make the solution 11, and adjust the pH to 10.3 with 10% potassium hydroxide or dilute sulfuric acid.

The bleach-fix replenisher had the same composition as the bleach-fix solution shown in Example 2 except that the color developing solution was removed.

Sensitometry was carried out each time 100 parts of the replenisher solution was added per 11 parts of the color developing solution to examine variations in photographic performance during continuous processing. For sensitometry, relative sensitivity, gradation, and maximum density t-measurement were performed on samples (9) and (10) exposed to K light.

The results are shown in Table 4. In the table, the sensitivity is expressed as a relative sensitivity when the sensitivity of sample (9) treated with a new developer is set as 100.

〔Effect of the invention〕

By implementing the present invention, the following effects can be obtained.

(1) Addition of a small amount of the polymer of the present invention provides a remarkable effect of accelerating color development.

(2) A color image with high color purity and favorable gradation can be obtained.

(3) No desensitization or caprisis occurs during storage of the photosensitive material.

(4) Since there is no leakage into the liquid, continuous processing is possible that provides stable photographic performance.

Claims (3)

[Claims] (1) A silver halide photographic material characterized in that at least one of the photographic constituent layers on a support contains a polymer having a repeating unit represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R represents a hydrogen atom or an alkyl group, and X represents a divalent organic group. Further, AP represents a 1-aryl-3-pyrazolidone compound residue or a 1-aryl-2-pyrazoline compound residue. ] (2) Claim (1) characterized in that the polymer is a polymer represented by the following general formula [II].
The silver halide photographic material described in . General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a repeating unit formed from an unsaturated monomer having a hydrophilic group. x, y, and z are indexes representing the copolymerization ratio, where x is 5 to 90 mol%, y is 0 to 50 mol%, and z is 10
~90 mol%. R, X and AP are as described in the previous section. ] (3) AP contained in the repeating unit of the polymer represented by the above general formulas [I] and [II] is represented by the following general formula [III]
] or [IV] is a 1-aryl-3-pyrazolidone compound residue or a 1-aryl-2-pyrazoline compound residue represented by claim (1) or (IV). The silver halide photographic material described in item 2). General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, V_1, V_2, and V_3 are hydrogen atoms, halogen atoms, and carboxy groups, respectively. , represents a substituted or unsubstituted alkyl group or alkoxy group, R_1 and R_2 each represent a hydrogen atom or an aryl group optionally substituted with an alkyl group, R_2 and R
_4 each represents a hydrogen atom or a substituted or unsubstituted alkyl group. R_5 represents a hydrogen atom, acetyl group, or -COR_8COR_9 group (R_8 has a ▲ mathematical formula, chemical formula, table, etc. ▼ group or ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ Represents a group. R_1_0 is a hydrogen atom,
Represents a halogen atom, alkyl group, alkenyl group, alkoxy group, alkylthio group or aryl group, R_1
_1 and R_1_2 each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. Also R_
1_1 and R_1_2 may be ring-closed to form a benzene nucleus. n is an integer of 2 or 3. R_9 represents a hydroxy group, a ▼ group that has a numerical formula, a chemical formula, a table, etc., or a hydrolyzable group. R_1_2 represents a hydrogen atom, an alkyl group or an aryl group, and R_1_3 represents a hydrogen atom or an acyl group. ) R_5 represents a substituted or unsubstituted alkyl group, alkoxy group, aryl group or aryloxy group. However, V_1, V_2, V_3, R_1, R_2, R
At least one of _3, R_4 and R_5 is a divalent group or a single bond. ]