JPS63311251A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material permitting quick processing and having superior stability for processing by incorporating a monodisperse silver halide emulsion and a specified Yellow coupler into a blue sensitive silver halide emulsion layer. CONSTITUTION:A monodisperse silver halide emulsion and a Yellow coupler expressed by formula I are incorporated into a blue sensitive silver halide emulsion layer, and at least one nonsensitive layer located at further position from a reflecting base body than the blue sensitive silver halide emulsion layer is transformed to a hydrophilic colloid layer contg. at least one hydrophobic compd. expressed by formula II, and the relative refractive index of the hydrophilic colloid layer is adjusted to 0.9875-1.0125 basing on the refractive index of a hydrophilic high molecular thin film which forms the nonsensitive phase by removing volatile org. solvent and amphipathic solute from an org. layer contg. the hydrophobic compd. In formulas I and II, R1 is a halogen atom, alkoxy group; R2 is an H atom, halogen atom, etc.; A is -NHCOR3, -NHSO2-R3, etc.; R3 is an alkyl group; Y is a group eliminable by a coupling reaction with an oxidized body of a developing agent bonded with an interposed O atom or N atom; each R5-R9 is an H atom, or a nitro group, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has a blue-sensitive emulsion layer that has sufficient color development and has a reduced amount of coated silver. The present invention relates to a silver halide color photographic light-sensitive material, and a further object is to provide a silver halide color photographic light-sensitive material that can be rapidly processed and has excellent processing stability.

(Conventional technology) Silver halide color photographic light-sensitive materials emit blue light.

A photosensitive layer consisting of a J'IN silver halide emulsion layer selectively sensitized to be sensitive to green and red light is coated on the support in a multilayer configuration.

For example, in so-called color photographic paper C (colors below C are referred to as 1-no), the red-sensitive emulsion layer,
A green-sensitive emulsion layer and a blue-sensitive emulsion layer are coated, and furthermore, between each photosensitive layer, an intermediate layer for preventing color mixture, a UV-absorbing intermediate layer, a protective layer, etc. are provided.

In order to form a color photographic image, three color photographic couplers of yellow, magenta and cyan are contained in the photosensitive layer, and the exposed photosensitive material is subjected to color development processing using a so-called color developing agent. The oxidized product of the aromatic primary amine undergoes a coupling reaction with the coupler to give a coloring dye, but in this case it is necessary to give as high a coloring density as possible within a limited development time.

In recent years, in this industry, there has been a demand for products that can be returned to users as soon as possible after being processed and developed, and for this reason, silver halide color photographic sensitizers that can be processed quickly and have excellent processing stability are required. materials are desired. Moreover, there is an overwhelming need for it to be provided economically at low cost.

By the way, as mentioned above, in color paper, the blue-sensitive silver halide emulsion layer is coated at the position closest to the support, so the development speed is the slowest, and in order to enable rapid processing, In this case, it is most necessary to improve the developability of the blue-sensitive silver halide emulsion layer.

In order to obtain high color density, one should use couplers with as high a coupling rate as possible, or couplers that are easily developed and
It is thought that this can usually be achieved by using a silver halide emulsion with a high development rate such as a unit coating sketch, or by using a color developing solution with a high development speed.

Therefore, when looking at the conventional techniques for silver halide color photographic materials that can be processed quickly, for example, fP Kaisho! /-77223, technology for making silver halides into fine grains, ■JP-A-5R-ITμ/4A, JP-A-Shoj
Low silver bromide technology for silver halide as described in No. 6-/lr-3, ■JP-A-Sho! The technique of adding l-aryl-3-pyrazolidone having a specific structure as described in No. 6-4f-JJ No.
7-/1114-117-7, 61-406317
No. tr-J-OrJJ- No. jlr-40136
A technique is known in which l-arylpyrazolidones such as those described in the above are added to a silver halide color photographic light-sensitive material, and a technique in which a color development accelerator is used is also known. For example, there is a US patent on this kind of color current accelerator, ? go, tt.

No., same co,, jt/! , Lda No. 7, λ, March 6.20
No. 3, same article, 0311.07! No., sameμ, itri.

No. 6, British Patent/, 4AJO, No. tr, Ibid.

4Lss, 4ciJ, JP-A-1989-/jIl1.

Same! -6 Koda j0, same j! −≦24cj No.1.

Same, tj-42 No., same tj-624A! No. 3.

Special public Akira! l-12u22, same j! There are compounds described in -u972r and the like. .

(Problems to be solved by the invention) However, when using ■ or ■ of these conventional techniques,
Although the processing time was shortened, the processing stability in the rapid processing was poor, and Capri also had problems. Also when the low silver bromide emulsion of (2) above is used.

Although rapid processing can be achieved, it has the disadvantage of poor processing stability.

Furthermore, when using the fine-grain silver halide described in (1) above, there is a drawback that processing stability is poor.

Above all, it has the serious drawback that sensitivity is compromised.

Recently, Japanese Patent Application Publication No. 6/-4Jr911μ.

Same 6/-t264A'1, same j/-10λj3.

Same t/-1102! IA4j, same t/-'? 7A! j
No. 4/-1007! I and the same j/-/, 36
The average grain size of the silver halide in the blue-sensitive emulsion layer is O, 0 to 0. J-! A technique using emulsion grains of r .mu.m has been disclosed, but although it has been shown to improve rapid processing properties and processing stability, it still has the drawback of a large decrease in sensitivity.

Further, it is preferable to use a coupler having a high color pre-lag activity in order to provide rapid processability, but it has the serious drawback that as the activity increases, fog increases significantly.

The present invention has been made in view of the above, and relates to a blue-sensitive emulsion layer that has conventionally been problematic in terms of suitability for rapid processing.

By providing a low-cost silver halide color photographic material that has sufficient color development, can be processed rapidly by reducing the amount of coated silver, and has excellent processing stability. be.

(Means for Solving the Problems) The present inventors have investigated techniques for improving the coloring properties of blue-sensitive emulsion layers from a different perspective from conventional techniques, and have found that silver halide color photographic light-sensitive materials with multilayer It was discovered that the color density of the blue-sensitive emulsion layer was optically reduced due to the structure of the blue-sensitive emulsion layer. Therefore, as a result of intensive investigation into techniques for preventing the decrease in optical density, the inventors discovered that a combination with a monodispersed emulsion had an extremely significant improvement effect, which led to the present invention.

That is, the above purpose.

1) A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a plurality of non-light-sensitive layers on a reflective support. , the blue-sensitive silver halide emulsion layer contains a monodisperse silver halide emulsion and a yellow coupler represented by the following general formula (I), and the blue-sensitive silver halide emulsion layer contains a monodisperse silver halide emulsion and a yellow coupler represented by the following general formula (I), and At least one of the non-photosensitive layers located far away is a hydrophilic colloid layer containing at least one hydrophobic compound represented by the general formula (If), and the hydrophobic compound is volatilized from the organic phase containing the hydrophobic compound. The relative refractive index of the material excluding the polar organic solvent and the amphiphilic solute is 0.0% relative to the hydrophilic polymer thin film forming the non-photosensitive layer. Ri17! , /, 012j.

General formula (I) (in the formula, R represents a halogen atom or an alkoxy group,
R2 is a hydrogen atom, a halogen atom, or.

Represents an alkoxy group. People are -NHCORa, -NH8O
2-13,-802-NHR3,-COOR3゜-80
2-NRa.

■ However, R3 and R4 represent an alkyl group.

Y was bonded via an oxygen atom or a nitrogen atom.

Represents a group that can be separated by a coupling reaction with an oxidized form of a developing agent. ) General formula (■) (In the formula, R5, R6, R7, R8 and R9 may be the same or different, hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group,
Contains an alkoxy group, an acyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a mono- or dialkylamino group, an acylamino group, an oxygen atom or a nitrogen atom! It represents a 6-membered or 6-membered heterocycle, and R8 and R9 are ring-closed and consist of carbon atoms! or 6-membered aromatic ring. ) The present invention will be explained in more detail below.

The monodispersed silver halide emulsion used in the blue-sensitive silver halide emulsion layer in the present invention has an average grain size of 0.2 μm to 0.2 μm as expressed by the diameter of an equivalent circle in projection.
is preferable, more preferably from o, zzBm/, 3μ
It is m. In addition, the particle size distribution representing the degree of monodispersity is preferably a ratio (S/τ) of the statistical standard side difference (S) to the average particle size (di), that is, a coefficient of variation of O1λ or less, and more preferably #' io, is or less.

The monodispersed silver halide emulsion used in the present invention is composed of silver bromide and/or silver chlorobromide that substantially does not contain silver iodide, and preferably contains silver chloride in a molar proportion of λ or more and 10 or less,
More preferred is silver chlorobromide having a molar coefficient of λ or more and less than 10 molar coefficients.

The silver halide grains used in the present invention have regular shapes such as cubes, octahedrons, dodecahedrons, and dodecahedrons.
r), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Tabular grains may also be used, especially the value of the length/thickness ratio! In particular, tabular grains with a size of r or more account for the total projected area of one grain! An emulsion having a density of 0 or more may be used. Although the emulsion may consist of a mixture of these various crystal forms and is not limited to 1%, cubic or tetradecahedral grains are preferred. Further, these various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside one grain.

The photographic emulsion used in the present invention is manufactured by Glafkides [Chemistry and Physics of Photography J (P., Glafkides).

Chimie et Physique Photo
ographique (published by Paul Monte 1, 1267)], Photographic Emulsion Chemistry J (G
, F. Duffin, Photographic
Emulsion Chemistry (Focal
Press, / 1966)], written by Zelikman et al.
Production and coating of photographic emulsions J [V, L.

Making a by Zelickman et al.
ndCoating Photographic E
mulsion (published by Focal Press, li 6
≠ year)], etc., and can be prepared using a friendly method. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, it is preferable to use a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, a so-called Chondrald double jet method. According to this method.

A silver halide emulsion with a regular crystal shape and nearly uniform grain size can be obtained.

Furthermore, the halogen [arsenic? Emulsions prepared by the so-called conversion method, which includes a process of converting silver halide to a silver halide having a smaller solubility product, and emulsions prepared by similar halogen conversion after the completion of the silver halide grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Silver halide emulsions are usually physically ripened after the formation of one grain.

It is desalted and chemically aged before being used for coating.

Known silver halide solvents (e.g. ammonia).

Rodan Kali or U.S. Pat. J-12 or No. 1
3-/$443/f, same za-t.

No. 0717 or Tokukai Sho! Hiro-/! Although thioethers and thione compounds described in No. IIJr etc. can be used in precipitation, physical ripening, and chemical ripening, it is preferable to use them in the presence of one particle during formation. In order to remove water-soluble salts from the emulsion after physical ripening, the emulsion is subjected to a Nudel water washing, a 70-curation sedimentation method, an ultrafiltration method, or the like.

The silver halide emulsion used in the present invention can be produced by sulfur sensitization using active gelatin and compounds containing sulfur that can react with silver (for example, thiosulfates, thioureas, mercapto compounds, rhodanines, etc.). ; Reduction sensitization method using reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc.); Metal compounds (e.g., total complex salts, Pt, It , P
d.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as Rh and Fe can be used alone or in combination. Among the above chemical sensitization methods, sulfur sensitization alone is preferred.

In order for the color photographic light-sensitive material of the present invention to satisfy the target gradation, two or more types of monodisperse silver halide emulsions (monodisperse (Preferably, those having the above-mentioned fluctuation rate) can be mixed in the same layer or coated in different layers.

In the yellow coupler represented by the general formula (I) used in the present invention, R1 represents a halogen atom or an alkoxy group, R2 represents a hydrogen atom, a halogen atom, or an alkoxy group, and R3 and R4 represent the number of carbon atoms ~32 linear or branched alkyl groups. Here, the alkoxy group of R2 and the alkyl group of R3 and R4 further include an alkyl group,
Aryl group, heterocyclic group, alkoxy group (for example, methoxy group, ethoxy group, comethoxyethoxy group, etc.).

Aryloxy groups (e.g., co-, di-tert-amylphenoxy, cochlorophenoxy, etc.), alkenyloxy groups (e.g., nyloxy, etc.), acyl groups (e.g., acetyl, benzoyl, etc.) ), ester groups (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyl group), amide groups (e.g., acetylamino group, methanesulfonamide group, dipropylsulfonyl group) moylamino group), carbamoyl group (e.g. dimethylcarbamoyl group, ethylcarbamoyl group).

Sulfamoyl groups (e.g., butylsulfamoyl groups, etc.), imide groups (e.g., succinimide groups, hydantoinyl groups, etc.), ureido groups (e.g., phenylureido groups, dimethylureido groups, etc.), aliphatic or aromatic sulfonyl groups (e.g. c, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (
For example, ethylthio group, phenylthio group, etc.), hydroxyl group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. may be substituted.

Y was bonded via an oxygen atom or a nitrogen atom.

It represents a group that can be separated by a coupling reaction with an oxidized product of a developing agent, and preferably includes a group represented by the following general formulas (III) to 1).

(III) ORt.

R1oFi represents an optionally substituted aryl group or heterocyclic group.

R11 and R12 are each hydrogen atom, halogen atom, carboxylic acid ester, amine group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted phenyl group or represents a heterocyclic group, and these groups may be the same or different.

(■) Or represents a nonmetallic atom required to form a Via-membered ring.

Among general formula (M), preferably (■), (■)NX)
can be mentioned.

(■)1 In the formula, R13 and R14 are each a hydrogen atom, an alkyl group,
It represents an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, and R15, R16 and R17 are each a hydrogen atom, an alkyl group or an aryl group.

It represents an aralkyl group or an acyl group, and W2 represents an oxygen or sulfur atom.

Specific examples of these couplers are shown below, but the invention is not limited thereto.

(I-/’) (Knee λ) (I-'I) (I-j) H3 (I-4) (I-7) H (I-r') (I-9) 5 (hCHs (I-/1 (I-/　/　) (I-/ko) (l　　/J) U (1-/j) (I-/6) (CH2)sOH (I-/r) (■-7ri) (I-CoO) (Ace 1) (I-Here) (I-23) H (I-co 4c) (Ecori H3 CI-26) (I-J7) COOCH.

(!--1) (I-29>(I-30') (I-J/) H3 (knee 32) H3 (1-JJ) (I-34') (I-37) (knee 31) ( I-37) H (I-3t') CI-39) In the hydrophobic compound represented by general formula (II) used in the present invention, R5, R6, R7, R, and R9 are the same or different. Well, a hydrogen atom.

Halogen atoms (chlorine, bromine, iodine, fluorine), nitro groups, hydroxyl groups, alkyl groups (eg.

Methyl group, ethyl group, n-propyl group, 1so-propyl group, aminopropyl group, n-butyl group.

5ec-butyl group, tert-dutyl group, chlorobutyl group, n-amyl group, 1so-amyl group, hexyl group, octyl group, nonyl group, methoxycarbonylethyl group, dodecyl group, pentadecyl group, cyclohexyl group, indyl group, phenyl group ethyl group, phenylpropyl group, etc.), alkenyl group (e.g.

vinyl group, allyl group, meta-allyl group, dodecenyl group, octadecenyl group, etc.), aryl group (e.g., phenyl group, μm methylphenyl group, ethoxyphenyl group,
3-hexoxyphenyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, propoxy group, butoxy group, chlorobutoxy group, methoxyethoxy group, pendecoxy group, etc.), aryloxy group (e.g., phenoxy group, comethylphenoxy group, 4cm chlorophenoxy group, etc.), acyloxy group (e.g., carbomethoxy group, carbobutoxy group, carbobentadecoxy group, etc.)
, alkylthio groups (e.g. methylthio group, ethylthio group, tert-butylthio group).

octylthio group, benzylthio group), arylthio group (e.g. phenylthio group, methylphenylthio group,
Ethylphenylthio group, methoxyphenylthio group, 7
methylthio group, etc.), mono- or dialkylamino group (e.g., N-ethylamino group, N-1ert-octylamino group, etc.), acylamino group (e.g., N,N-diethylamino group, etc.).

acetylamino group, benzoylamino group, methanesulfonylamino group, etc.), a j-membered ring containing oxygen or nitrogen, or a 6-membered ring
It represents a membered heterocyclic group (for example, a pyridino group, a 1-morphorno group, a pyrrolidino group, a piperazino group, etc.), and R8 and R9 may be closed to form a j-membered or t-membered ring consisting of carbon atoms. In general formula (II), the substituents represented by R5 to R9 preferably have a total number of carbon atoms of j to 36.

Further, it is preferable that the alkyl group has carbon atoms of i and it.

Among the compounds represented by the general formula (I[), especially the general formula (X
) are more preferred.

Here, R5 and R6 have the same meanings as in general formula (II), and R8 is a hydrogen atom or a halogen atom.

An alkyl group having the same meaning as in general formula (I[).

Particularly preferred are compounds which represent an alkoxy group, an aryl group or an aryloxy group, and R8 represents a halogen atom.

Specific examples of the compound represented by the above general formula are shown below.
The present invention is not limited to these examples.

(II-ノ) C4H9(t) (π-2) (IF-3) CsHn(t) (■-da) (It--t) (π-6) (4H17(iso) (It-7) ( II-4') (■-ta) CR3 (π-IO) (π-ii') (■-/2) (2H5 (II-/J) (It-/4') (If-/j) C4H *(t) ([-#) CI[-17) (M-/I) (■-/ri) (I[-20) (II-,2/) (■-22) (If-23) ( If-24') C4H9(t) (■-2ri(■-27) (■-koj) (TI-,2Ir) (II-22) C8H17(1so) (II-30) In the present invention, general The nonvolatile organic solvent used for dispersing the hydrophobic compound represented by formula (If) has a relative refractive index of the organic phase containing the hydrophobic compound minus the volatile organic solvent and the amphipathic solute.

Oo to the hydrophilic polymer thin film forming the non-photosensitive layer.
ri173~/, 0/2! was selected to be within the range of

The boiling point is / 7! Any organic solvent with a high boiling point of C or higher may be used, but preferably has a refractive index of 1. ≠6
Non-volatile organic solvents of less than 10% are preferred, and preferred are alkyl phosphate esters, citric acid esters, fatty acid esters, carbonic acid esters, amides, and esters and ethers of 7-alcohols.

Specific examples of these nonvolatile organic solvents are shown below, but the invention is not limited thereto.

Refractive index (0-/) O-P+OC4Hg)3
/, daytime λ≠(0-2)0:P+OCH2CHC4Hg)
3 t, a<su2H5 (0-4L) O=P÷0C9H19)3
/,! ! 7(0-j) O=P÷0C10H21)3
/, arl(0-A) 0=P(-OCt
oHzl-iso) i, as3(0-7)O-
P+0C10H21-iso) Ha≠j30C12H
25 (0-4') 0=P÷0C14H29)3
/,≠31(0-?) O=P+OCH2CH2
0C4)(g)3/, 4L3≠(0-10”)
CH2COOC2H5/, 4L3r CH3COOCCOOC2H5 CH2C00C2H5 (0//) CH2COOC4Hg
i, ap/CH3CO0CCOOC4H9 CH2COOC4H9 (0-/2) C2H5/, 4ca
tl CH2C00CH2CHC4H9 CH2C00CH2CHC4H11 薯2H5 (0-/J) CH2C00C1jtH2s
1. jAJJCH3CO0CCOOC12H25 CH2C00C12H25 (0-/4') CH2COOC6H13t, uz.

■ HOCCOOC6H13 CH2C00C6H13 (0-/j) CH2C00C7H15t, ar4A
HOCCOOC7H15 Doro CH2C00C7HB.

(0-74) C2H8/, 4416CH2
C00CH2CHC4H.

HOCCOOCH2CH(C2H5)C4HgCH2C
00CH2CHC4H.

Iris C1mu (Q-/7) CH2C00C10H21'
, Hiroj de HOCCOOC10H21 CH2C00C10H21 (0-/I') CH2C00C9H19
-iso / , 3HOCCOOCgHlg-i
s.

CH2C00C9H19-is.

HOCHC00C16H37 (iso) (0-20)
C1? H33COOCH3t, da 11 (O-2/)
CH2COOC4Hg '-μco1CH2
C00CaHe C00CH2CHCaH9 2H5 ■ (CH2)? C00CHz (CzHs) C4H9 (0-λ)
COOC4H9/, 41J? (CH2')s C00C4H11 CC00CH2CHC4H 2H5 (0-xa) OCOCH3・t0ga3(CH2
)10 C0CH5 (0-J7) CH20COC17H35/, 4'
Da! CH20COCH3 (O-2r) CH2C00C4H@
/, 33CHCQOC4H11 CH2COOC4H9 Station C00C4H9 (0-JO) CtsH2yCOOCxsHsy-iso i,
era(0-J/) C13H27COOCH2CHC8H17t, assI
IH13 (0-72) CIIH170COOC8H17/ -
” '(Q-JJ) Cl2H2BOCOC12H
25'-”'(0-74') CyHtsCON(C
Hs) 2t, Hiromu! 3 (0-71) C7H1
5CON(C2Hs)2/, +l0(Q-J4'
) C11H23CON(CH3)2 /-4
'j' (0-37) C7H15CON ((4H5)
z i, assCo-41') (0-μ0) (O-ri/) (0-μ, 2) (0-μ3) The usage amount of the yellow coupler represented by the general formula (I) of the present invention is: There is no particular limit, but usually (7, J~/, 1ri7
m2. o per mole of blue-sensitive silver halide, oi~0
, 1 mol, preferably 0. mol each. j 〜／、／
77m2.0,0ko! ~0, ≠3 moles. The amount of the hydrophobic compound represented by general formula (II) to be used is usually 0, J ~ /, 2 y 7 m2, since using a large amount may cause yellowing in the unexposed area (white background area). , preferably 0°≠! ~/, 07m2. Further, there is no particular restriction on the amount of the nonvolatile organic solvent used for dispersing the hydrophobic compound represented by the general formula ('II) of the present invention and whose refractive index is less than 414, but it is usually 0.7.
~0. rcc/m2, preferably 0.2 to o, r
a, 'mz. 'The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and others so that they have color sensitivity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus.

A tetrazole nucleus, a pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is.

Applicable examples include indolenine nucleus, pendi/drenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, and quinoline nucleus. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -one nucleus, thiohydantoin nucleus, corchioxazolidine nucleus, Hiro-dione nucleus, thiazolidine nucleus, 1 μm dione nucleus, rhodanine nucleus, thiobarbyl acid nucleus, etc.! ~6-membered heteroartic ring nuclei can be applied.

These sensitizing dyes may be used individually or in combination. Combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are U.S. patents Ko, i, rr, s≠j, and λ.

77.2 Kota No. J, J5'7,040, No. 3,
jkoλ, O! - No., same J,! 27. A Hiro 1, same J, l
, /7. Kota No. 3, Kota J, 1. All, 7
6μ, Plj, gta, gta, same?
, j7,1. t number - same j, j75', u2
No. r, J, 703゜377, J, 76? ,3
0/No. 3. r/4A, tori issue, same 3. ♂37.1
No. 6-1 turn.

Oλl, No. 707, British Patent 1. JIA≠, 2g1 issue, (ifJ/, 107,103, special public show≠3-geta3
No. 6, J3-/2371, Unexamined Japanese Patent Publication No. 1973-//θ41
No. 1, r? It is described in fJ, tco lO tatako j issue.

Along with the sensitizing dye, it is a dye that itself has no spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting strong color enhancement may also be included in the emulsion.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group is better than a four-equivalent color coupler whose coupling active position is a hydrogen atom.

The amount of coated silver can be reduced. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a reaction inhibitor or release a reaction promoter upon coupling reaction can also be used.

Magenta couplers that can be used in the present invention include:

Examples include indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as j-pyrazolone and pyrazolotriazoles, manufactured by Oil Protect. ! - Pyrazolone couplers are preferably substituted at the 3-position with a lylamino group or an acylamino group from the viewpoint of the hue and coloring density of the coloring dye,
Typical examples are U.S. Pat.

Same No. 2.2 Dr, No. 173, No. 3.0t1.6jJ, No. 3. /jλ, jri No. 6 and same No. 3゜934.0
1! It is written in the number etc. As a leaving group for a two-equivalent pyrazolone coupler, U.S. Pat. t
The nitrogen atom leaving group described in No. /R or U.S. Patent No. a
, szi, rri No. 7 is preferred. It also has a pallast group as described in European Patent No. 7J, 434! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
Pyrazolobenzimidazoles as described in US Pat.
0 (June 1991) and Research Disclosure 2≠230 (
Examples include pyrazolopyrazoles described in /rir4A year to month). Imidazo[t,, z-b:l pyrazoles described in European Patent No. 1/'/, 71A1 are preferred from the viewpoint of low yellow side absorption of coloring dyes and light fastness;
Pyrazolo [/.

t-1)][/, ko, lA]) Riazole is particularly preferred.

Cyan couplers that can be used in the present invention include:

Oil Protect M naphthol-based and phenolic couplers are available, and are covered by U.S. Patent Nos. 7 and 7.

Naphthol couplers as described in US Pat. No. 223, preferably US Pat.

/dat, 391. Typical examples include two-equivalent naphthol couplers of the oxygen atom separation type described in Coco R, No. 233 and Coco R, No. 6,200. Further, specific examples of phenolic couplers are given in US Patent No. 2. J6? , Octopus No. 2, No. 2, 101. /7/ No. J, 772. /No. 62, No. 2. ttr, r
It is written in the AT issue, etc. A cyan coupler that is stable against humidity and temperature is preferably used in the present invention, and a typical example thereof is the one described in U.S. Pat. Phenolic cyan coupler having U.S. Pat. Nos. 2,77, 142 and 3,711,301
No. 6.394, No. 4c, JJ4
A, No. 0//, No. 3, 3 cores.

173, West German Patent Publication No. J, J Kota, No. 722, and Patent Application No. 11-4CJ47/2,
J-Diacylamino Substituted Phenolic Couplers and U.S. Patent No. 3. Dada 4, 1h22, same No. 3, JJJ, Tade No. 2, same No. 4A, l-! /l! It has a phenylureido group at the co-position described in No. tj and No. 27,747, etc., and! These include phenolic couplers having an acylamino group at the - position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Dye-diffusing couplers such as those described in U.S. Pat. No. 44,366, . No. 237 and British Patent No. 2. Specific examples of magenta couplers are given in European Patent No. 170 and German Published Application No. 3.23μ.

No. 133 describes specific examples of yellow, magenta or cyan couplers.

Dye-forming couplers and special couplers listed above.

A dimer or higher polymer may also be formed. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. ≠j1
．． rJQ issue and the same number, oro.

It is described in issue 2//. Specific examples of polymerized magenta couplers are described in British Patent No. 2,10,173 and US Patent No. $, JA 7,212.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for 1 g optical material, or the same compound can be used in two or more different layers. It can also be introduced into

The coupler used in the present invention can be introduced into the cine optical material by the oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is /
After dissolving in either a high boiling point organic solvent of 7!0C or higher and a low boiling point so-called auxiliary solvent, or a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. do. Examples of high boiling organic solvents are described in U.S. Patent No. 322,027 and others. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
esters of phosphoric or phosphonic acids M() liphenyl phosphate, tricresyl phosphate, co-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-coethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, dicoethylhexyl phenylphosphonate, etc.), benzoic acid esters (coethylhexylbenzoate,
Dodecyl benzoate.

coethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecaneamide, etc.).

N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol,
Tert-amylphenol).

Aliphatic carboxylic acid esters (dioctyl azelate,
glycerol trizotyrate, instearyl lactate, trioctyl citrate, etc.).

Aniline derivative (N,N-dibutyl phthaltoxy)
tert-octylaniline, etc.), hydrocarbons (norahuin, dodecylbenzene, diimpropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about JO0 (knee or higher, preferably jO°C or higher or about /1
, 0°C or less, typical examples include ethyl acetate 1, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.

No. 363, West German Patent IIN (OLS) No. 2. ! Dal.

Core No. 1 and Core No. 1, ! 4t/, No. 230, etc.

The standard usage of color couplers is in the range of o, oi to 1 mole per 7 moles of photosensitive silver halide, preferably o, oi to 0 for yellow couplers.
0.03 moles, and 0.003 to 0.03 moles for magenta couplers.
3 mol, and for cyan couplers 0.002 to 0,
It is 7 moles.

The photosensitive materials produced using the present invention contain hydroquinone rust conductors, aminophenol derivatives, and amines as color fogging inhibitors or color mixing inhibitors.

It may contain gallic acid derivatives, catechol derivatives, ascorbidic acid derivatives, colorless couplers, sulfonamidophenol derivatives, and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-Hydroxychromans! - Hydroxycoumarans, spirochromans, p-alkoxyphenols, bisphenols - Mainly hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and the phenolic properties of these compounds Typical examples include ether or ester derivatives in which the hydroxyl group is silylated or alkylated. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
Compounds having a fractional structure of a hindered amine and a hindered phenol in the same molecule, as described in US Pat. No. 21,1.193, give good results. In addition, in order to prevent deterioration of agenta pigment compensation, especially deterioration due to light, spiroindanes described in JP-A No. 12-12 RJJ and spiroindanes described in JP-A No. 7-12RJJ are recommended. Diether or monoether substituted chromans give preferred results.

In order to improve the storage stability of cyan images, especially the light resistance, it is preferable to use a benzotriazole ultraviolet absorber. This UV absorber may be co-emulsified with the cyan coupler.

The coating amount of the ultraviolet absorber containing the compound of general formula (If) may be sufficient to impart photostability to the cyan dye image, but if it is used in too large a quantity, the unexposed areas (white background areas) of the color photographic light-sensitive material may be damaged. ) Since it may cause yellowing, it is usually preferable to use 7 m2 to J'
X/0-3 Jl;:ni/ln2. %l1ct
/ 0""' 7 m2 ~ J, j X / 0-
”% is set within a range of 7m2.

In the normal colorpeno N- sensitive material layer structure, either one of the layers on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer,
Preferably, both layers contain an ultraviolet absorber.

When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The photosensitive material of the present invention can be used as a filter dye.

Alternatively, a water-soluble dye may be contained in the hydrophilic colloid layer for various purposes such as preventing irradiation or irradiation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually consist of a red-sensitive emulsion layer on a support;
It has at least one green-sensitive emulsion layer and at least one back-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Furthermore, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities! A non-light sensitive layer may also be present between two or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate M, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a pack layer.

The binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention includes:

Although gelatin is advantageously used, other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein:
Cellulose derivatives such as hydroxyethyl cellulose, carmeximethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial acetal.

Poly-N-vinylpyrrolidone, polyacrylic acid.

A wide variety of synthetic hydrophilic, highly dryable materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, and Phot.

Japan, A/t, p. 317 (l. 66) [Enzyme-treated gelatin as described may also be used;
Hydrolyzed gelatin and enzymatically decomposed products can also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention contains additives.

Furthermore, various stabilizers, antifouling agents, developing agents or their precursors, development accelerators or their precursors.

Lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are listed in Research Disclosure/71. It is described in ≠3 (1-month, 1971) and tr7it (1-month, 1971).

The "reflective support" used in the present invention refers to one that enhances the 5-reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, one radiation layer of baryta paper, polyethylene coated paper, and polypropylene synthetic paper was provided. Alternatively, a transparent support 1 that uses a reflective material in combination, such as a glass plate, a polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film,
A support such as a polystyrene film can be selected as appropriate depending on the purpose of use.

Next, the processing step (image forming step) K in the present invention will be described.

The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As the color developing agent, p-fuynylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-hiro-amino-N, N-diethylaniline, and 3-methylgu-amine-N-ethyl. −
N-β-hydroxylethylaniline, 3-methyl-≠
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-stoxy-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-toluene Sulfone I
! salt, tetraphenylborate, p-(t-octyl)
Examples include benzenesulfonate.

Examples of aminephenol derivatives include 0-aminophenol, p-aminophenol, and guamino-2-
These include methylphenol, 2-amino-3-methylphenol, -1oxy-3-amino-/, Hiro-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by A. Menn, Focus Press (1966) (L. F. A. Mason).

-Photographic ProcessingC
"hemistry", Focal Press) 1
226~Kokota page, U.S. Patent No. 1, 3. oiz issue, same 2゜! 92. JtlA No., % Kaisho μl-Otsu 4de No. 33, etc. may be used. If necessary, more than one color developing drug may be used in combination.

The processing temperature of the color developer in the present invention is 300~!
0'(: is preferable, more preferably 3!0C-daj
'C.

Further, as the development accelerator, various compounds may be used, except that they do not substantially contain benzyl alcohol. For example, US Pat. No. 6μr, to4L.

Special Publication Showμ≠-ta J03, US Patent J, /7/.

Various birimidium compounds represented by No. J4C7 and other karaonic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 4c≠-230≠, U.S. Patent Co., J- 3
3, Tata O, same λ, j-j/.

! No. 32, same λ, qzo, No. 270, same co, J
- Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. 77,727,
US Patent 3. λoi, thionyi described in issue -2ttx
Chill-based compounds and other Tokukaisho! r-/jtri31. Same 6
Examples include the compounds described in No. 0-J Co.theta.34!1.

Preferred antifoggants in the present invention include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants. Examples of organic anti-capri agents include benzotriazole and 6-nitrobenzimidazole.

j-nitroisoindazole%! -Methylbenzotriazole,! -Nitrobenzotriazole,! -Nitrogen-containing heterocyclic compounds such as chlorobenzotriazole, cochprirubenzimidazole, cochiazolylmethyl-benzimidazole, hydroxyazaindolizine, and I-phenyl-! -Mercaptotetrazole, 2-
Mercapto-substituted heterocyclic compounds such as mercaptobenzimidazole, --mer-butobenzothiazole.

Additionally, it can be used on mercapto-substituted aromatic compounds such as thiosalicylic acid. Particularly preferred are halides. These antifoggants may be eluted from the color photosensitive material during processing and accumulate in the color developer.

In addition, the color developer according to the present invention includes pH buffering agents such as carbonates, borates, or phosphates of alkali metals; hydroxylamine, triethanolamine, and OLS Patent Publication No. 26 Cocota! Preservatives such as compounds described in subparagraph O, sulfites or bisulfite e1 salts; organic solvents such as diethylene glycol; dye-forming couplers;
Competitive couplers; nucleating agents such as sodium boron hydride; co-developers such as t-phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N -Hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids, l-hydroxyethylidene-1,l', typified by compounds described in JP-A-31-1999/Rijtar No. -Diphosphonic acid, Research Disclosure
organic phosphonic acid, aminotris (methylene phosphonic acid) described in 4/I/70
.

Aminophosphonic acids such as ethylenediamine-'N, N, N/, N/-tetramethylenephosphonic acid, JP-A-72-102726, J3-127JO, JP-A-1
11--/ko//No. 27, same j! -4028, same jj
- Pi 021, same zz-txt μ! No. J! -1,
! 19! ! No. J"!T-41911゜, and Research Disclosure (Research Di
sclosure) A/t/No. 70c/972!
It may contain a chelating agent such as the phosphonocarboxylic acid described in 1).

In addition, the color existing bath can be divided into two or more parts as necessary.
Replenish color developer replenisher from the first bath or last bath,
The development time may be shortened or the amount of replenishment may be reduced.

After color development, the silver halide color photosensitive material is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching and fixing) or may be carried out separately. Examples of bleaching agents include iron (■).

Compounds of polyvalent metals such as cobalt (■), chromium (■), and copper (If), peracids, quinones, nitrone compounds, and the like are used. For example, ferricyanide, dichromate, organic complex salts of iron (III) or copal (I[), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid.

1. Complex salts of aminopolycarboxylic acids such as 3-diamino-coprobanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates.

Manganate-nitrosophenol and the like can be used. Among these, potassium ferricyanide, iron(I[) sodium ethylenediaminetetraacetate, and ammonium iron(I[) ethylenediaminetetraacetate].

Triethylenetetraminepentaacetate iron(II[) ammonium persulfate salt is particularly useful. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Further, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution, if necessary. For example, bromine ion.

In addition to iodine ions, U.S. Patent J, 704. ! 1, No. 1, Special Publication No. 4 Lt-Photo, No. 179-AtjIt.

JP-A-33-3273! Same issue! 3-El, No. 233 and the same! 3-470/l, a thiourea compound as shown in the specification, or JP-A No. 3-470/2≠μ24A, same! No. 3-95631, same j3-! 7rJ1 issue, same!
No. 3-32736, same! 3-6! No. 732, same j 44
-jλjJμ and U.S. Patent No. J, Iri J, try
Thiol-based compounds as shown in No. A, etc., or JP-A No. 4 AP-J Rit≠μ, same! 0-/μ0/λ, same! 3-2tμ26, same J'J-/≠/jλ3, same j3-10 hiro 232, same! ≠ Heterocyclic compounds described in -357co No. 7 specification etc., or JP-A-Shoj2-
201J2 issue, same! ni-4101, No. 41, and the same!
11-J, 6414, etc., or quaternary amines described in JP-A No. 4 At-r ≠≠ Q specification, or % KAI Sho 4A2JI.
Compounds such as thiocarbamoyls described in Specification No. I may also be used.

As a fixing agent, thiosulfate, thiocyanate.

Examples include thioether compounds, thioureas, and large amounts of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing process and the fixing process, a washing process is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid to prevent precipitation, fungicides and anti-spiking agents to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum salts. Typical hardeners, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or L.E. West (L,
E. West), Photographic Science and Engineering (Photo.

Sci, and Eng,), Vol. 6, No. 6, (l
4t) etc. may be added. The addition of chelating agents and anti-piping agents is particularly effective. Also.

It is also possible to save one amount of water by using a multi-stage (for example, J-3 stage) countercurrent method in the water washing process.

Also, after or during the water washing process, JP-A-77-
4 j $ Multi-stage countercurrent stabilization treatment for one culm as described in No. 3 may be performed. In the case of this step, a countercurrent column made of corylic cypress is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.

For example, buffers to adjust membrane pH (e.g.

borate, metaborate, borax, phosphate, carbonate,
Examples include potassium hydroxide, sodium hydroxide, ammonia water, monocarmenic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (floxel, isothiazolone, ≠-thiazolylbenzimidazole, halogenated phenol benzotriazoles, etc.), a surfactant, a fluorescent brightener, a hardening agent, etc. may be added.

Furthermore, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can be added as membrane pH adjusting agents after treatment.

(Example) The present invention will be described below with examples, but the present invention is not limited thereto.

(Example 1) A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating liquid preparation Yellow coupler (Nie 4j)/Li, 19 and anti-fading agent (Cpd-/) II, 4cOP diacetic acid z
Chill 27. -2CC and solvent (5olv-t)7.
7 cc was added and dissolved, and this solution was emulsified and dispersed in 1 rzcc of a lO tizelatin aqueous solution containing io4 sodium dodecylbenzenesulfonate (tcc). On the other hand, silver chlorobromide emulsion (
Silver bromide to, omoh%-Ag 70y/KIi) K
The following blue-sensitive sensitizing dyes were added to silver, 0x
A 10-' mole addition was prepared.

The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is l-oxy-3
, terdichloro-S-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (t)z, oxio-' mol per mol of silver halide) Green-sensitive emulsion layer (μ, oxio-' mol per 7 mol of silver halide) -
and (9 tons per 7 moles of silver halide) 7,0 x 10-5 moles)
(Oo x 10-' mol per mol of silver halide) To the red-sensitive emulsion layer, 2.4 x 10'''-3 mol of the following compound was added per mol of silver halide.

Also, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, /-(j-methylureidophenyl)-! Nimelkabutotetrazole in 3°0 x 10' moles per mole of silver halide, respectively;
0x10'' was added.

Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, ≠-hydroxy-6-methyAt-/, J, J 21. 7-
Citrazaindene, respectively, per mole of silver genide/, 2×10 Motb, /, /X10
Mol added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (layer structure) The composition of each layer is shown below. The number is the amount of coating (7m2)
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support Paper support laminated on both sides with polyethylene [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine blue)] First layer (actual layer) Silver halide emulsion 0.3! Gelatin /, 13 yellow coupler (I-43”) 0. l'3 color image stabilizer (Cpd-/) o, i y solvent (S
olv-/ ) o, 3r second layer (
Color mixing prevention layer) Gelatin. , Tata color mixing inhibitor (Cpd-co) o, or third layer (green sensitive layer) /TIO silver generator emulsion (Br: 18) 0.7 J
Gelatin /, 7 magenta coupler (ExM-/) a, 3x color image stabilizer (Cpd-J) o, l tastain inhibitor (Cpd-4') o, o2 stain inhibitor (
Cpd-yo) 0.02 Solvent (Solv-, 2)
o+br 4th layer (ultraviolet absorption layer) Gelatin /, jI color mixing inhibitor (Cpd-6) 0.0! Ultraviolet absorber (II-//') 0.24 (■-/j
)0. Kota (: [-/4) 0.07 Solvent (Solv
-/ ) o, 2ia 5th layer (red-sensitive layer) Silver halide emulsion (BY near 0) o, Cono gelatin '・3'' cyan coupler (ExC-/) o, 33 color image stabilizer (C
ryd-7) 0. / 7 volley v −(
cpci-♂) 0.4t.

Solvent (Solv-J) o, x3 6th layer (ultraviolet absorption layer) Gelatin o,! 3 violet ultraviolet absorbing layer M-1/) o, ori (It -
1 0.10 (π-/bu) o, o3 Solvent (Solv-/) o, DI
Seventh layer (retention layer) Gelatin 7.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17) o, /7 Liquid paraffin 0.0.3 (ExM-/)
Magenta coupler (4H1,7(t) (ExC-t) Cyan coupler α (Cpd-/) Color image stabilizer (Cpd-2) Color mixing inhibitor (Cpd-j) Color image stabilizer (Cpd-4') Stin Inhibitor (Cpd-3) Anti-stain agent (Cpd-4) Color mixture inhibitor (Cpd-7) Color image stabilizer z:r”, mixture (weight ratio) (Cpd-1) Polymer average molecular weight fO, 000 (Solv-i) Solvent (Solv-2) Solvent (Solv-J) Solvent Silver 10-genide emulsion (1) of the blue-sensitive emulsion layer of the present invention was prepared as follows.

(l liquid) (-liquid) Sulfuric acid (/N)
Solution) The following silver halide solvent CI'II) JCCH3 H3 (μ solution) (J solution) (6 solution) (7 solution) (L solution) was heated to 7!0C, and (2 solution) and (3 solution )'f
: Added. Thereafter, cμ solution) and solution (!) were added at the same time after stirring for a minute. Another 10 minutes later.

(Liquid 6) and (Liquid 7) were added simultaneously over a period of 6 et minutes. The temperature was lowered and desalted. Add water and dispersed gelatin, adjust pH to 6.2, average particle size/
, 0/μm, coefficient of variation (standard deviation divided by average particle size: s/cr) 0. .

A monodispersed cubic silver chlorobromide emulsion containing 10 mmol of silver bromide was obtained. Sodium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

Silver emulsion (2) with a ratio of 7.logen in the blue-sensitive emulsion layer of the present invention was also prepared in the same manner as above by varying the amount of chemicals, temperature, and time.

Silver halide emulsion (3) of the blue-sensitive emulsion layer for comparison was prepared as follows.

(R liquid) (R liquid) Sulfuric acid (IN) 10al: (1
0 liquid) (// liquid) (R liquid) is heated to 77'C and C liquid) is added. Thereafter, (10 liquids) was added for ≠θ minutes. Furthermore, 1 minute after the start of addition of (IO solution), (11 solutions) were added for a0 minutes. Addition! The diameter and temperature were lowered and desalted. Add water and dispersed gelatin and adjust the pH to 6.2.
A polydisperse silver chlorobromide emulsion having an average grain size of 0.12 μm, a coefficient of variation of 0.27, and a silver bromide ratio was obtained. Sodium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

Average grain size of silver halide emulsions (1) to (3),
Table 7 shows the coefficient of variation and halogen composition.

Table 1 Among the above layer structures, samples &l~// were prepared by changing the silver halide emulsion and yellow coupler in the first layer and the solvents in the fourth and sixth layers as shown in Table 1.

Table 1 Note 1) The emulsions of samples &7 to // are mixtures of milk it (/) and emulsion (-2) at a weight ratio μ:6.

Note-2) Silver amount represents coating fjk (p/m2>).

Note 3) Relative refractive index is the hydrophilicity of the organic phase containing the hydrophobic compound represented by the general formula (■) in the fourth and sixth layers, excluding volatile organic solvents and amphipathic solutes. Relative value for polymer thin film Using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the above sample plate /~//,
Sensitometric (IJ-) gradation exposure was applied through a three-color separation filter.

The exposure at this time was carried out with a cod light time of 0.7 seconds and an exposure amount of 2jOCMS. Thereafter, the following treatment step (A) was performed.

At this time, compared to the standard processing time of 3 minutes and 30 seconds.

Processing for 30 seconds was performed at the same time, and the rapid processability was evaluated based on the sensitivity and maximum color density (Dmax) of each. The sensitivity was expressed as a relative value to the sensitivity at 3 minutes and 30 seconds for the sample &/or.

Furthermore, as an evaluation of processing stability, only the amount of potassium bromide in the color developer from processing step (A') was 1.2y/arc.
Processing is carried out in the changed processing step (B), and then the processing step (A)
So the concentration is O0! Processing process (B) for points that give and concentration/, j
Find the change in concentration at 9.

Processing process 8 (A) Processing process Temperature Time Color development 33°C/min 30 seconds Bleach fixing 33°C/min 30 seconds Water washing Coμ~34c0C3 revolution Drying
70-40'C/min The composition of each treatment solution is as follows.

Color developer water 100t
ddiethylenetriaminepentaacetic acid/Ofnitrilotriacetic acid 1. ! 1 Benzyl alcohol /jmJ diethylene glycol IO-sodium sulfite
co-op potassium bromide
o, zp potassium carbonate JO
pN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl 1 μm aminoaniline sulfate j, oy hydroxylamine sulfate e, op fluorescent whitening agent (WHI
TEX4AB, add water 1000mp100
O'C) 10.20 Bleach-fix solution water da00
vU ammonium thiosulfate (704) 110w
lSodium sulfite /IrpEthylenediaminetetraacetic acid iron (I[) Ammonium j! Taethylenediaminetetraacetic acid disodiumtrirum! Add y water / 000w1pH (Jj'C
) &. 7゜As is clear from the results shown in Table 3, the sample layer μ~horn of the present invention had sufficiently good color development at 2 minutes and 30 seconds, despite the reduced amount of coated silver. It can be seen that the concentration change with respect to fluctuations in the amount of potassium bromide in the color developer is small, and that the processing stability is excellent.

(Example 2) Multilayer color printing was performed in the same manner as in Example 1 by changing the anti-irradiation dye, third layer, fourth layer, fifth layer, and sixth layer from Example 1 as shown below. Paper was made.

Anti-irradiation dye and third layer (green-sensitive layer) Silver halide emulsion (Br:to) 0. l Tagelatin 1. Coco magenta coupler (ExM-2) o, 22 color image stabilizer (Cpd
-J) o, o color image stabilizer (Cpd-ta)
o, o4 stain inhibitor (CQd-10)
0. /ni' solvent (Solv-p)
0.27 Fourth layer (ultraviolet absorption layer) Gelatin /, ,t! Ultraviolet absorber (■-/) 0.07 (ll'
-J) 0.30 (l[-/ri0.2! Solv -/ ) 0.21A Fifth layer (red-sensitive layer) Silver halide emulsion (Br 0%) o, 23 gelatin /, jlI .

Cyan coupler (ExC-2) o, ty Cyan coupler (ExC-J) 0,2/color stabilizer (Cpd-7) o,/7 solvent (So
l v-)) θ, ko3 6th layer (ultraviolet absorbing layer) Gelatin 0.13 ultraviolet absorber (■-/) o, oko (I[-j)
o, l.

(M-/j) 0.01 Solvent (5olv-/) o, o
r (ExM--2) Magenta coupler (ExC-2) Cyan coupler (ExC-J) Cyan coupler L (CQd-ta) Color stabilizer (Cpd-10) Stain inhibitor 0"1°\, C ,H.

(Solv-μ) Solvent Samples &/2 to -22 were prepared in exactly the same manner as in Example 1, changing the silver halide emulsion and yellow coupler in the first layer and the solvents in the fourth and sixth layers. When the same evaluation was carried out, similar results were obtained.

C) Effects of the Present Invention) By carrying out the present invention, a silver halide color photographic light-sensitive material that can be rapidly processed and has excellent processing stability can be provided at low cost.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Form C) Date of 1966 l≦Japan Commissioner of the Patent Office ′”−°
71, Display of the incident Showa Buko year special application No. 430
No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant contact information 10
6 Fuji Photo Film Co., Ltd. Tokyo Head Office, 2-26-30 Nishiazabu, Minato-ku, Tokyo Telephone: (406) 2 S 37
/Go:']Sa\J Series 9.1r-) l 4. Date of amendment order Showa tko year 2 month 2! Date (shipment date) 5. Subject of the amendment 6. We will submit an engraving of the amended statement of contents (no changes to the contents).

Claims (1)

[Scope of Claims] 1) A silver halide having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a plurality of non-light-sensitive layers on a reflective support. In a color photographic light-sensitive material, the blue-sensitive silver halide emulsion layer contains a monodisperse silver halide emulsion and a yellow coupler represented by the following general formula (I), and has a higher reflection than the blue-sensitive silver halide emulsion layer. At least one of the non-photosensitive layers located far away from the support is a hydrophilic colloid layer containing at least one hydrophobic compound represented by general formula (II), and contains the hydrophobic compound. The relative refractive index of the organic phase excluding the volatile organic solvent and amphiphilic solute is 0.98 with respect to the hydrophilic polymer thin film forming the non-photosensitive layer.
A silver halide color photographic material having a silver halide color in the range of 75 to 1.0125. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a halogen atom or an alkoxy group, and R_2 represents a hydrogen atom, a halogen atom, or an alkoxy group. A is -NHCOR_3, - NHSO_2-R
Represents _3, -SO_2-NHR_3, -COOR_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, R_3 and R_4 represent an alkyl group. Y represents a group bonded to the coupling position via an oxygen atom or a nitrogen atom and capable of being separated by a coupling reaction with an oxidized product of a developing agent. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_5, R_6, R_7, R_8 and R_9 may be the same or different and are hydrogen atoms, halogen atoms, nitro groups, hydroxyl groups, alkyl groups, An alkenyl group, an aryl group, an alkoxy group, an acyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a mono- or dialkylamino group, an acylamino group, a 5- or 6-membered heterocyclic group containing an oxygen atom or a nitrogen atom, R_8 and R
_9 may be ring-closed to form a 5- or 6-membered aromatic ring consisting of carbon atoms. 2) In the non-photosensitive layer, the refractive index of the nonvolatile organic solvent used for dispersing the hydrophobic compound represented by general formula (II) is less than 1.46. Silver halide color photographic material according to item 1. 3) In the non-photosensitive layer, the nonvolatile organic solvent used for dispersing the hydrophobic compound represented by general formula (II) is an alkyl phosphate ester, a citric acid ester, a fatty acid ester, a carbonic ester, an amide, a fluorine-containing ester, etc. The silver halide color photographic material according to claim 1, wherein the silver halide color photographic material is selected from alcohol esters and ethers.