JPS6330844A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material small in color mixing and superior in resolution by forming a green-sensitive emulsion layer having a spectral sensitivity peak in a 500-530nm wavelength region, and incorporating flat silver halide grains having an average aspect ratio of >=5 in at least one of red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layers. CONSTITUTION:The green-sensitive emulsion layer has the peak of spectral sensitivity in 500-530mum wavelengths, and at least one of the red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layers contains the flat silver halide grains having an average aspect ratio of >=5. The silver halide grains except said flat grains may be ones each having regular crystal forms, such as cubic, octahedral, and tetradecahedral crystal forms, i.e., so-called regu lar grains, and irregular crystal forms, such as spherical ones, or ones having crystal defects, such as twin crystals, or one of their combinations, or mixtures of any of them, thus permitting the sensitivity of the green-sensitive emulsion layer to argon laser beams to be higher enough as compared with that of the blue-sensitive emulsion layer, and consequently, a remarkable color mixing prevention effect to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a film used for converting electrical signals (such as video signals) into full film images;
In particular, the present invention relates to color photosensitive materials used in laser film recording, which is a high-performance film recording means.

(Prior art) Methods for creating movies using television systems have been considered for quite some time, but due to the insufficient amount of information in the television system and the establishment of an excellent means of converting video signals into film images. As a result, there were only limited practical examples, and it was not widely used.

Under these circumstances, high-quality turpentine stems were developed, and laser film recording, an unprecedented high-performance film recording method, was developed, and film production methods that utilized all of these became popular. became.

The laser recording device consists of a laser light source, a light modulator, a light deflector, a recording camera, and a video processing circuit. , green, and blue laser beams are combined into seven beams by a dichroic mirror, horizontally polarized by an optical deflector, and then
As if focused onto a 3mm film.

For details, see Sugiura: 3 Jmm Film Laser Recording, Television Society Technical Report, PTTG, /3~
/ page (Showa J-7). In laser film recording, a helium-neon (He-Ne) laser (wavelength: 32.0 nm) is used as a red light source.
The green light source was an argon (A r ) laser (wavelength 1/μ, !nm), and the blue light source was a helium cadmium ()ie-Cd) laser (wavelength 4 nm).
'4'/, Anm) are used, respectively. In addition, as a recording film, the above-mentioned Technical Report of the Television Society, (J
PT/,! .

As described in page 3-/J' (1981), color positive film for cinema, color negative film for cinema, and color internegative film for cinema are used.

(Problems to be Solved by the Invention) Since the sensitivity of the green-sensitive layer to the argon (Ar) laser as the green light source is not sufficiently higher than the sensitivity of the blue-sensitive layer, there is a drawback that so-called color mixing is likely to occur. In addition, the wavelength ranges of the three types of lasers mentioned above are considerably different from the peak wavelengths of the spectral sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer of the color positive film, color negative film, and color internegative film, so the limitations on sensitivity are Because the size of silver halide cannot be lowered,
The situation is such that it must be used in conditions that are disadvantageous in terms of graininess and resolution.

Furthermore, the sensitivity/granularity ratio is also unsatisfactory.

SUMMARY OF THE INVENTION An object of the present invention is to provide a halogenated color light-sensitive material for laser recording which has less color mixture and excellent resolution.

(c) Means for Solving Problems) The object of the present invention is to provide a color photosensitive material having at least a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support. In materials,
The spectral sensitivity of the above recording-sensitive emulsion is 00 nm~j J O
This was achieved by containing tabular grains having an average aspect ratio of 5 or more in at least one of the red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers.

The spectral sensitivity of the green-sensitive emulsion layer of the color light-sensitive material is r00n
m~! In order to have a peak at J Onm, the following general formula [
/] or [2] by spectrally sensitizing with at least one compound selected from [2].

General formula (1) (In the formula, ZL is a ! member or a 2-membered heterocycle? Is it completed?
Attenuates the atomic groups necessary for Q is rhodanine ring, thiohydantoin ring,! - represents the necessary Kyoko gun metal to complete the thioxazolidine ring.

R1 represents an alkyl group or a substituted alkyl group.

R2 represents all hydrogen atoms, alkyl groups, and substituted alkyl groups. ) The petero ring formed by Zl is, for example, an oxazoline ring, a U, t, t-dimethyloxazoline ring, a tetrazole ring, an oxazole ring, a ≠-methyloxazole ring,
! -Methyloxazole ring, ≠.

! -dimethyloxazole ring, benzoxazole ring,
A substituted or unsubstituted 〈zuoxazole ring or thiazoline ring such as a j-fluoro〈/zuoxazole ring, hyrolidine ring, thiazoline ring, thiazole ring, or goomethylthiazole ring is particularly preferred.

Specific examples of 几 include lower alkyl groups such as methyl groups,
Substituted alkyl groups such as ethyl group, n-propyl group, etc., such as β-carboxyethyl group, r-carboxypropyl group,
δ-carboxybutyl group, ω-carboxy is methyl group,
Examples include r-sulfopropyl group, r-sulfobutyl group, δ-sulfobutyl group, β-hydroquinethyl group, and vinylmethyl group.

Specific examples of P-2 include lower alkyl groups such as methyl and ethyl groups, benzyl groups, and phenethyl groups.

- Makio [λ] (In the formula, Z and 2 represent a tetrazole ring, a thiazoline ring, an oxazole ring, or an atomic group necessary to form the entire form of the oxazole ring.

Z3 (represents two necessary atomic groups forming an imidazole ring or penzcyanol ring).

R3 and R5ri represent an alkyl group or a substituted alkyl group.

R represents a hydrogen atom, and an alkyl group represents a substituted alkyl group.

Full representation of Xerj anions.

mVi/Matakeko is the total expression, and when the dye forms all the intramolecular salts, it is /. ) Z2 is, for example, a tetrazole ring, thiazoline ring, oxazole ring, ψ-methyloxazole ring, ≠.

j-dimethyloxazole ring, benzoxazole ring,
j-fluorobenzoxazole ring,! -Chlorobenzoxazole El, j-trifluoromethylbenzoxazole R The atomic groups necessary for the total formation are shown.

Z3HFJ e/-methyl-! -chlorobenzimidazole, l-methyl-y-fluorobenzimidazole,
/-Methyl-! , A-cyclohenzimidazole, /
-methyl-yo, ro-difluorobenzimidazole, /
-Ethyl-yo-chlorobenzimidalur, /-ethyl-! -fluorobenzimidazole, /-ethyl-ylt-dichlorobenzimidazole, l-ethyl-! ,
4-difluorobenzimidazole, l-propyl-y-chlorobenzimidazole, /-propyl-! -fluorobenzimidazole, l-propyl-2,1-dichlorobenzimidazole, /--t'ropyl-! , 6-
Cyfluoropenzimidazole, l-allyl-j-chlorobenzimidazole, /-allyl-I-fluorobenzimidazole, /-allyl-r, t-dichlorobenzimidazole, l-allyl-j16-difluorobenzimidazole, /- Ethyl-yo-methoxycarbonylbenzimidazole, /-ethyl-yo-methylsulfonylbenzimidazole, /-phenyl-! -chlorhensimitasol, /-phenyl-j-fluorobenzimidazole, l-phenyl-j.

t-cyclobenzimidazole, l-phenyl-r
, g-difluorobenzimidazole, /-ethyl-t
-) Benzimidazole ring such as IJ fluoromethylbenzimidazole, /-ethyluo, O-ditrifluoromethylbenzimidazole, benzothiazole, j-chloro and nzothiazole/U.

! - Represents the atomic group necessary to form a thiazole ring such as promoinzothiazole, j-methylbenzothiazole, j-methoxybenzothiazole, and j-anobenzothiazole.

The specific examples of 几 and R5 have the same meaning as those of 81 in the general formula [/], and the specific examples of 4 also have the same meaning as R2 in the general formula [/].

X- represents an anion commonly used in the field of dyes, such as a halogen ion, perchlorate ion, thioanate ion, benzenesulfonate ion, p-toluenesulfonate ion, methylsulfate ion, and ethylsulfate ion.

In order to provide a silver halide color light-sensitive material with less color mixture, the green-sensitive silver halide emulsion layer of the silver halide color light-sensitive material has a wavelength of argon (Ar) laser C! /μ
, rnm), and the blue-sensitive silver halide emulsion layer of the silver halide color light-sensitive material has a high spectral sensitivity near the wavelength of argon IAr) laser (wavelength!l hiro, jnm).
) should have low photosensitivity near the wavelength.

For the above purpose, the edge-sensitive silver halide emulsion layer of the silver halide color light-sensitive material and the blue-sensitive halogenation of the silver halide color light-sensitive material to light with a wavelength of σ-j/≠, J'nm. Sensitivity ratio with silver emulsion (sensitivity of blue-sensitive emulsion layer/
green-sensitive emulsion layer) is o, or less, preferably θ,
O! It is preferably 0.03 or less.

In order for the silver halide color light-sensitive material of the present invention to obtain excellent graininess, it is desirable to reduce the grain size of the silver halide emulsion in the color light-sensitive material. It is important to minimize light scattering for light with wavelengths of ! nm and ≦32. ratio 1
It is effective to use the above tabular grains. Techniques for producing photosensitive materials with excellent sharpness, high sensitivity, and good graininess using such tabular grains are described in Research Disclosure magazine A22JJllI/R3, published in July 2003) and U.S. Patent Nos. ≠, ≠ 3, and 520. However, there is no mention of the case where a coherent light such as a laser beam is used as a light source. It has been found that when a coherent light source with good straightness is used as described above, the effect of improving the degree of sharpness is significantly greater than when using light with a normal wavelength spread. This is an effect that occurs because light reflection on tabular grains becomes significantly smaller when such coherent light is irradiated at an angle close to perpendicular to the surface of the photosensitive material, and is unique to the present invention. be.

! /≠,jnm and t3ko,! Considering the light scattering of light having a wavelength of rnm, among the tabular grains having an aspect ratio of 5 or more, those having an average grain thickness of 0.2 μm or less are particularly preferable.

As a blue-sensitive silver halogen emulsion for the color light-sensitive material of the present invention, this is the best! When using the above tabular grains,
It is better to spectrally sensitize the blue-sensitive silver halide emulsion.

When spectrally sensitizing the blue-sensitive layer of the color photosensitive material, the wavelength of the argon (A r ) laser beam! /Hiroshi.

! Care must be taken that the sensitivity of the blue-sensitive layer in nm does not increase and cause color mixing.

To satisfy this purpose, the general formula [3 or [7], which will be explained in detail after the blue-sensitive layer of the color photosensitive material
] This is achieved by spectral sensitization with at least one compound selected from the following.

Any of silver monobromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as silver halide in the redundant emulsion of the present invention; In order to provide a color light-sensitive material, the composition of the silver halide in the blue-sensitive silver halide emulsion layer of the silver halide color light-sensitive material is silver chloride, silver bromide, silver chlorobromide or silver chloroiobromide. It is preferable that it be either one of them. It is important to provide a silver halide color light-sensitive material for laser recording that has less color mixture, excellent resolution, and has an excellent sensitivity/grain ratio. Take a peak! 0
0 nm to 530 nm KL-Furthermore, the halide emulsion layer contains tabular grains having an average contrast ratio of j or more-Furthermore, the red-sensitive silver halide emulsion layer of the color light-sensitive material has the following general formula [3] ~ [! ] This was achieved by containing at least one of the compounds shown below.

General formula [3] (2, Z2 is the atomic group 'tff necessary to complete the benzothiazole nucleus, benzoselenazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, and the benzene ring of the heterocyclic nucleus is a substituent may be replaced with

The benzothiazole nucleus is, for example, benzothiazole,! −
Methylbenzothiazole, yo-chlorobenzothiazole! -Methoxy and inzothiazole! -Hydroxybenzothiazole,! , B-dimethylbenzothiazole,!
-ethoxy+-methylbenzothiazole,! -Hydroquine-2-methylbenzothiazole,! -Phenylbenzothiazole,! -Carpoquimbe/Zothiazole,! −
Methoxycarbonylbenzothiazole! -Acetylaminobenzothiazole, etc., the benzoselenazole nucleus is, for example, benzoselenazole,! -Methylbenzoselenazole, yo-chlorobenzothiazole! -Methoxybenzothiazole,! -Hydroxybenzoselenazole,! ,6
-Simethylbenzoselenazole,! -Ethoxy 2-methylbenzoselenazole,! -Hydroxy-6-methylbenzoselenazole,! -phenylbenzoselenazole, etc., the naphthothiazole nucleus represents, for example, β-naphthothiazole, β.β-naphthothiazole, etc., and the naphthoselenazole nucleus represents, for example, β-naphthoselenazole.

R1 and R2 are lower alkyl groups such as methyl group, ethyl group, n-propyl group, substituted alkyl groups such as β-carboxy/ethyl group, r-carboxypropyl group, δ-carboxybutyl group, ω-carboxypentyl group , r-sulfopropyl group, γ-sulfoptyl group, δ-sulfobutyl group, vinylmethyl group, etc.

R3 represents a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, an aryl group such as a phenyl group, or a substituted aryl group such as an 0-carboxymphenyl group.

X- represents an anion commonly used in the field of cyanine dyes, such as a halogen ion, perchlorate ion, thioanate ion, benzenesulfonate ion, p-toluenesulfonate ion, methylsulfate ion, and ethylsulfate ion.

m represents O or /, and when the dye forms an inner salt, m=o. ) General formula [≠] (, <-),.

(In the formula, Zl represents an atomic group necessary to form a membered ring and/or a membered ring. Examples of the above heterocycle include a pyridine nucleus, a thiazole nucleus, a selenazole nucleus, a benzothiazole nucleus, and a benzoselenium ring. These include sol nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, quinoline nucleus, etc., and may be substituted with a substituent.

Z2 represents all the atomic groups necessary to form a thiazoline nucleus, oxazole nucleus, benzoxazole nucleus, thiazole nucleus, selenazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthothiazole nucleus or naphthoselenazole nucleus, and these are substituents. May be replaced.

R and R□ are lower alkyl groups such as methyl group, ethyl group, n-propyl group, substituted alkyl groups such as β-hydroxyethyl group, β-methoxyethyl group, β-acetoxyethyl group, β-carboxyethyl group , r-carboxypropyl group, δ-calxybutyl group, ω-carboxypentyl group, β-sulfoethyl group, r-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group , p-carboxyphenethyl group, p-sulfophenethyl group, etc.

R2 is an alkyl group, such as a methyl group, an ethyl group, a substituted alkyl group, such as a benzyl group, a vinyl methyl group, etc.
It represents an aryl group such as phenyl.

alkyl groups such as methyl groups, ethyl groups, substituted alkyl groups such as alkoxyalkyl groups, aryl groups,
For example, a phenyl group, a substituted aryl group, such as an 0-carboxyphenyl group, etc. are all represented. Furthermore, L and R, and L and R may be bonded together via a polymethylene chain.

m represents O or /.

xH anion such as chlorine ion, bromide ion, iodo ion, p-)luenesulfonate ion, etc.

p represents O or /, and in the case of an inner salt, p=O. ) General formula [! ] (In the formula, R1, R2, R3, and R4 may be the same or different, and each represents an alkyl group, a substituted aA, a kyl group f
9bj. V□, v2, V3, V4T/'i may be the same or different, and hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, acyloxy group, alkoxycarbonyl group, carbyl group , represents an alkylsulfonyl group, a cyano group or a trifluoromethyl group.

Q represents a hydrogen atom, an alkyl group, or an aralkyl group. X
e represents an anion. m is/or ko, and when the dye forms an intramolecular salt, it is l. ) The sensitizing dye used in the present invention has the general formula [! ], preferably the following substituents are used.

That is, R, R2, R3, and R4 may be the same or different, and may be an alkyl group (e.g., methine group,
Alkyl groups having the following carbon atoms are preferred, such as ethyl group, propyl group, butyl group, pentyl group, and vinylmethyl group. )
, or a substituted alkyl group [substituents include, for example, a sulfo group, a carbonyl group, a hydroxy group, a cyan group, an alkoxy group having z or less carbon atoms (for example, a methquine group, an ethquino group), an alkoxycarbonyl group having 6 or less carbon atoms groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.)
, an acyloxy group having up to 3 carbon atoms (e.g. acetoxy group, propionyloxy group, etc.), an acyl group having up to r carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, etc.), a carbamoyl group (e.g. carbamoyl group, N,
N-dimethylcarbamoyl group, morpholinocarbamoyl group, pyharidinocarbamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, +N', N-dimethylsulfamoyl group, morpholinosulfamoyl group, etc.), aryl having a carbon number of IO or less groups (e.g. phenyl group,
(p-hydroxyphenyl group, p-carboquinphenyl group, p-sulfophenyl group, etc.), an alkyl group having 2 or less carbon atoms substituted with a fluorine atom, etc.] are preferred.

■0, V2, v3, V 4H t"il'im-mol L< may be different, hydrogen atom, norogen atom, alkyl group having 2 or less carbon atoms (e.g. methyl group, ethyl group, propyl group, etc.), alkoxy groups with carbon numbers below (e.g., methquine group, ethoxy group, etc.), anlu groups with carbon numbers below (e.g., acetyl group, propionyl group, etc.)
, acyloxy group with 3 or less carbon atoms (e.g. acetoquine group, propionylokif group, etc.), carbon number? The following alkoxycarbonyl groups (eg, ethoxycarbonyl group, ethoxycarbonyl group, etc.), carboxyl group, alkylsulfonyl group, ./ano group, or trifluoromethyl group are preferred.

Q is preferably an alkyl group (for example, methyl group, ethyl group, propyl group, etc.) or an aralkyl group, especially a phenylalkyl group (for example, benzyl group, phenethyl group, phenylpropyl group, etc.) having carbon number≠ or less.

In the sensitizing dye used in the present invention, the following substituents are particularly preferably used in general formula [j]. That is, R
1, 几2, R3, and R4 may be the same or different, and the number of carbon atoms! The following alkyl groups (e.g. methyl group, ethyl group, propyl group, etc.), sulfo group, carboxy group, alkyl group with carbon number of μ or less substituted with 7 hydroxy groups, p-sulfophenyl group, p-carboquine Phenyl group, alkyl group with 3 or less carbon atoms substituted with p-hydroxyphenyl group, 6 carbon atoms substituted with fluorine atom
The following alkyl groups are particularly preferred.

V,, v2, V3, V41-1' may be the same or different, hydrogen atom, halogen atom, carbon number 3
Particularly preferred are the following acyloxy groups (eg, acetoxy group, propionyl oquine group, etc.), alkoxycarbonyl groups having carbon number≠≠ (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), cyan group, and trifluoromethyl group. Q is particularly preferably a methyl group, ethyl group, propyl group, or benzyl group.

Preferred dyes for spectral sensitization of the entire evening-sensitive silver halide emulsion layer can be selected from, for example, the following general formula [6] or [7].

General formula [B] General formula [7] (wherein Zl, Z2 and Z3 are respectively an oxazole ring, a benzoxazole ring, a naphthoxazole ring, a thiazole ring, a be/dithiazole ring, a naphthothiazole ring, an imidazole ring, and a benzoxazole ring) / Represents an atomic group necessary to complete the zimidazole ring or naphthimidazole ring, Ro represents a hydrogen atom, an alkyl group, a substituted alkyl group, approximately 1%) I, 2, R3 are each substituted or unsubstituted The alkyl group is removed. 84 represents a substituted or unsubstituted alkyl or aryl group, (X) represents an acid anion, and n represents O or l. ) above zl
, z2 and Z3 are Z□ and Z2 of the general formula [3] and Z2 of the general formula [λ], respectively.
and Z3, and specific examples of 几1 to R3 are synonymous with those of R in the general formula CI] and R and R in the general formula [≠].

Furthermore, specific examples of R4 are synonymous with those of R2 in the general formula [≠].

X- has the same meaning as in general formula (1).

Specific examples of the compounds represented by the general formulas [/] to [7] used in the present invention are shown below. However, the compounds used in the present invention are not limited thereto.

Specific examples of compounds represented by the general formula [/] C)i Ct-
t=cH2 /=(5)/-'(8)/-αO/-@Specific examples of compounds represented by the general formula [K]! -(2) C2H5(CH2)3S3 knee(3) λ-(4) C2H,.

λ-(5) (CH)SUe(CH2)3So3Naλ-(6) Co(7) (CH) Sve 2 3 3 (''2) 3S(J31NaSpecific examples of compounds represented by general formula [3] J- (1) (CM) S(J e J -(2) CH2C82C1(-CH.

3-C4) j -(5) J-(6) J-(7) J-(9) (CH)SU (CH2)3SQ3H3-αO (C2)3SO3H 3-αυ 3-+E -a3 J- 〇→ 3-@ 3-α force 3-(G) (CH2) 3S (J 3(CH2) 3S (J
3 H-al 3-(E) 3-(Wealth) 3-(A) 3-@ 3-ni) し2'5 (C日2) 3SQ3○3-(A) 3-翰CHC2H5 3-@( (:H) S(J e (C1(2)S(J3H
3-憾3-翰J -01) -q 3-靝3-(7) □ Specific examples of compounds represented by the general formula [≠] - (1) e μm(2) ■e μm(3) e ≠-(4) 工 e ≠-(5) C) 12C) i2(J[( e ≠-(7) O Hiro-(8) Hiro-(9) ■e μ-uQ ■e Hiro-αυ e e Hiro-Q4 1- (to) e Hiro-〇〇≠-α crab e Me- (to) Engineering e Hiro-01 e Hiro-(1) e ≠-〇l) e ≠-@ e ≠-(c) ■e ≠-(ha) e ≠-(to) ENGE Gu(1) e Hiro-Nue Gu 弼 goo Hiroshi-(to) CL(2CH2C?12C1-i2S(J3f(He≠
-0υ engineering e ≠-(a) re e ≠-■ μ-(7) e Specific examples of compounds represented by the general formula [j]-(1) j-(2) 01(2°'2" ( CH) SO”j-
(3) j −(4) e j −(9) j −CLQ 工et −gυ! −α→ ! -q5! −(g) j−q? ) j-(to) I C)-i2Ck゛2CF2HcH2CF2CF2HA
-(1) 1 yen 1゛nail knife β〕? ”' 1-tiz each 7
6A togo one by one U-up Y/Doo first 6-ni) A -<st -α) 6-(4') g -<g) Otsu -(q) c9 b-(to) Otsu -(//) M -(12) Ro -(/, 7) Otsu -(/4t) A -(,/6) 6-(<7) b-(lv) b-Q Wa) 6. -CIO> 6-(,2/) Ro -(,23) Otsu-(,!gu) ■ 0OH 4-9,5-) 6-(,26), 0CC)l.

Otsu - (, 27) OCI-15 碕 1, - (ag) (, - (,, xq) b - (3o) Mu (') C7) - 1゜ichidrunbe t7] 7 - Kipu Elementary School 3 no ( ΔMe+Sugi7-(<') So3H-N (C2H6).

7-(g) So3H-N(C2H5).

αX old Ku (/2) 7-<! <=) to SO2 Ku (15) 7-(lq) History S”N (02H5) 5 Ku00) OOH 2H51 CH2CO2C2H5 7-(Yu beg) So, )-1-N (C2hl, ).

The sensitizing dyes represented by the general formulas [/] to [7] used in the present invention are manufactured by F.M. Balmer (F.

"Heterocyclic Compounds - Cyanine Dye and Related Compounds" by M. Hamer
nds-Cyanine dies andrel
ated Compounds -) J (John Wiley & Sons - New York, London - 1/2009), ChiM Star? -CD, M, 8turmer) [Heterocyclic Compounds are Chassis Topics in
Heterocyclic chemistry (Heteroc)
yclic Compounds Special t
opics in heterocyclic(h
It can be synthesized based on the method described in J (John Wiley & Sons, New York, London, 1977).

The compounds represented by the general formulas [/] to [7] are used in amounts for spectral sensitization, specifically per mole of silver halide!
×10 moles to 10 moles, preferably 10 ×10 moles
mol ~/X/ 0-2 mol, particularly preferably /x1
0 mole~! It is contained in the silver halide photographic emulsion at a ratio of x10-3 moles.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. They can also be used in suitable solvents, e.g.
Methyl alcohol, ethyl alcohol, flobyl alcohol, methyl cellosolve, JP Akihiro J'-97/! , US Patent 37! It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in TR No. 30. As another addition method, Tokuko Showa 4LA-24
17♂! No. 3, U.S. Pat. ♂22. /3j issue, same 3゜1
, l, 0, 10/issue, same 2. ri/λ, 3≠3, same 1,
76, 2l7, same 3. ≠Kota,? 3! No. 3. ≠
Otori, Ri No. 27, 3,6J-♂,! r≠6, same 3.
? 22. /3! The method described in No. 1 can be used.

Also the German patent ratio,! 1j-2, / 0≠.

2J'3, U.S. Patent No. 3. Otsu≠ri, 2l6
The method described in this issue can also be used.

The sensitizing dye described above may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but it goes without saying that in any step of the preparation of the silver halide emulsion, the sensitizing dye may have a hedral or tetradecahedral shape. The particles may be so-called regular particles having a regular crystal structure such as spherical particles, particles having an irregular crystal shape such as a spherical shape, particles having crystal defects such as twin planes, or a combination thereof. Also, mixtures of particles of various crystal forms may be used.

The grain size of silver halide may generally be fine grains of about 0.1 micron or less, dog-sized grains with a projected area diameter of up to about 70 microns, monodisperse emulsion with a narrow distribution, or a monodisperse emulsion with a wide distribution. It may also be a polydisperse emulsion containing.

? '9#S1%-1ch3H"I (-u.

The average grain size of the silver halide grains of the present invention is converted into a circle having an area equal to the projected area, and is determined by the number average of the diameter. This particle size can be measured by various methods. Typical methods include Loveland's "Particle Size Analysis Method JA, S, T, ...
l, Symposium on Light Microscopy
/Riyo! Year, 2≠~/2.2 pages or T,)i, "Theory of Photographic Process" by James ≠ Edition (/777) No. 3
Chapters can be manufactured by known methods, such as Research Disclosure, Volume 77, A/7 Otsu 4L3
January), pp. 22-23, “1. Emulsion production (Emulsi
on Preparation and Type
The method described in "S)" and the same, Vol. 117, Nii l♂7/Otsu (/ri7ri years l/month), page 6≠? can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glaf'kides, Chimie et Ph
ysiquePhotographique Paul
+) fontel, /ri67), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, D
uffin, Photo-graphic Emu
lsion Chemistry (Focal P
ress, /ri 66), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Ze
Likman et al.

Making and coating photo
graphicEmulsion, Focal
It can be prepared using the method described in Press, 6≠). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may include a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. good. A method (so-called back mixing method) 2 in which particles are formed under an excess of gold and silver ions can also be used. As one type of simultaneous mixing method, a method of keeping pAg'e constant in the liquid phase in which silver halide is produced, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Also known silver halide solvents such as ammonia, rhodankali or US Pat. No. 3,27/.

No. 737, Tokukai Sho! /-/No. 2360, JP-A-Shota 3-r
21AOf issue, JP-A-33-/! Hiroj/F issue, Tokukai Akira!
≠-1007/7 issue or Tokukai Sho! ≠-1rrrxr
Physical ripening can also be carried out in the presence of thioethers and thione compounds described in No. 1, etc. This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution.

The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling I) A'g and pi during grain formation.
ic 5science andEngineeri
ng) Volume A, /jri~16! Page (/ri Otsu 2); Journal of Photographic Science (Jour
nal of Photographic Science
nce), i vol. 2, 2412-2! /page (/!P Otsu≠
), U.S. Patent No. 3.1! ! ', 3ri≠ and British Patent No. 1. 'AI3.7≠r issue.

A typical monodispersed emulsion is an emulsion in which at least the weight percent of the silver rhodanide grains is within the range of ≠θ% of the average grain diameter.

Also, at least 5% by weight or the number of particles! It is preferable to use in the present invention an emulsion having a total average grain diameter of silver halide grains within the range of ±2θ%.

A method for producing such an emulsion is described in U.S. Patent No. 3. ! 7 Hiroshi, 6
No. 2g, No. 3. Otsu! ! , 3ri μ and British Patent No. 1
, 41/3, 7≠r. Also, Tokukai Sho t
, tg-rtoo issue, 31-39027 issue, same! /-
No. 13077, same J-/37/33, same≠-≠do No. 127, same! μ-Tatahiro/ri issue, same! ? -37 Otsu 3j
Monodisperse emulsions such as those described in No. Sr-≠R No. 73R can also be preferably used in the present invention.

) 7-fr7 Otographic Signs And-x
engineering r, (Cutoff + Photogr
aphic 5ci-ence and E! 'I
gineerinH), J 1 4 @, 2 4 8
2 57 pages (1970); U.S. Patent No. 4,4
34,226, 4,414,310, 4,4
No. 33,048, No. 4,439,520, and British Patent No. 2:112.157.

The crystal structure may be -like, the inside and outside may be composed of different halogen compounds, or it may be a layered structure. These emulsion grains are described in British Patent No. i, oλ7. /
≠Otsu No. 3, U.S. Patent No. 3. ! or, otr issue, same F,
4/,! ! , No. 177 and JP-A-Sho AO-/Hiroshi 333
It is disclosed in No. 7, etc.

Furthermore, silver halides of different @ compositions may be bonded by epitaxial/diallel bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. These emulsion grains are described in U.S. Pat. J'44, same≠, /≠2. rioo issue, same≠, μ
From, 3!3, British Patent No. 2,03♂, 7 Octopus, US Patent No. ≠, 345', j, jj, 4L, JP! ,
u7J', steward.

Hiro 33. toi issue, same≠,≠43. C#7, same 3, Otsu! Otsu, Ri Otsu No. 2, Ri Otsu No. 3. It is disclosed in Japanese Patent Publication No. 2,067, Japanese Patent Application Publication No. 2003-120002, and so on.

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, a cassava complex salt, an iron salt or an iron complex salt, etc. may be coexisting.

These various emulsions may be of the surface a-image type in which latent images are mainly formed on the thorny surface, or of the internal latent image type in which latent images are formed within the grains, or may be of the type in which latent images are formed on both sides.

In order to remove soluble silver salts from the emulsion before and after physical ripening, all methods such as Nudel water washing, 70-curation sedimentation method, or ultraviolet molding method can be used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

The additives used in such processes are based on the research and research mentioned above.
Disclosure A/7JIAJ (December 1979) and the same gir'yit (January 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD/7ga3 R, Dlryibl
Chemical sensitizer page 23 J4Z♂ page right column 2 Sensitivity increasing agent Same as above 3 Spectral sensitizer,
23~Page 1, right column~Supersensitizer
6 wide page right column 4 Brightener 2 ≠ page 5 Antifoggant, 2≠~2/page O ≠ left page right column and stabilizer 6 Light absorber, F λ 1 ~ page 26 6 ≠ right page ~ Ilter Dye tro left column Ultraviolet absorber stain inhibitor 2/page right column 1. to page left to right column 8 dye image stabilizer 2/page 9 hardener 2 page 6! /page left column 10
Binder 26 pages Same as above 11
Plasticizers, lubricants Page 27 Otsu! O right column 12
Coating aids, Tables 26-27 Same as above Surface activator 13 Static prevention page 17 Same as above Stop agent All of the various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure &
776≠3, described in the patent described in ■-e-o. As dye-forming couplers, couplers that are formed by full-color development of the three primary colors (i.e., yellow, magenta, and yellow) in the subtractive color process are important. The aforementioned research disclosure/7 A4t3, ■-C
In addition to the couplers described in the patents listed in Section D and Section D, the following are preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a pallast group. A specific example is U.S. Pat.
1AO7,210, 2゜♂7, O! It is stated in No. 7, No. 3, 2 Otsu, and To Otsu No. 7 of the same. The use of two-equivalent yellow couplers is preferred for the present invention and is described in U.S. Pat.
．． No. 921, same No. 3. No. 33,107 and the same No. ≠,
0.2 pieces.

Yellow coupler of the oxygen thickness separation type described in T20 etc. or Tokko Sho! 1r-1073, US Patent No. 4tO/, 7! No. Ko, Hiromu No. 32, 02'A
No., RD/10!3 (/979 ψ month), British Patent No. i, t2r, olO, West German Application Publication Tube 2,2/ri
77, 2.2AI, 341, 2,32
the law of nature,! ? No. 7 and No. 1≠33. A typical example is the nitrogen atom separation type yellow coupler described in Ryo No. 72 and the like. The .alpha.-piparoylacetanilide coupler has excellent color fastness, particularly light fastness, while the .alpha.-benzoylacetanilide coupler provides a high color density.

The structural formula of a specific example of the yellow coupler used in the present invention is shown below. However, the yellow coupler used in the present invention is not limited to this.

Specific example of yellow coupler Y-/ Y-6cH3 α -r Y-ta Y-/　0　　.

Examples of magenta couplers that can be used in the present invention include indacylon-based or cyanoacetyl-based couplers, preferably yoichi pyrazolone-based and pyrazoloazole-based couplers, which have a ballast group and are hydrophobic. ! -Pyrazolone couplers are preferably those in which the 3-position is substituted with an arylamine group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
3//, No. 012, No. 2,! ≠3.70! No. 2. too, 'yrr No. 2,901,173, No. 3,062. ls! No. 3, same No. 3. /j Yu, ♂ri No. 6 and same No. 3. 31. ．． It is written in the 0/yo issue etc. As a leaving group for divalent pyrazolone couplers, the nitrogen atom leaving group described in US Patent No. 1I, J! Particularly preferred is the aIJ-ruthio group described in No. 1, No. 227. Furthermore, the pyranhone couplers having a pallast group described in European Patent No. 73.434 can provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 30
Otsu/Pyrazolobenzimidazoles described in No. 1A32, preferably US Pat. No. 3.72! , Ol.

Pyrazolo cr described in No. 7, /-c]cl+2,
≠] Triazoles, Research Disclosure & 21A220 (/June 914') and JP-A-1.0-3Jjj'! Pyrazolotetrazole and Research Disclosure published in No. 2 ≠ 230
(/rir≠year to month) and pyrazolopyrazoles described in JP-A No. 3-3. U.S. Pat. No. 200 in view of the low yellow side absorption of the coloring dye and the light fastness.

The imidazo(/,

The structural formula of a specific example of the magenta coupler used in the present invention is shown below. However, the magenta coupler used in the present invention is not limited to this.

n/m=/Mw=2o, oo.

M-6 i'iI j M-10 Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol and phenolic couplers such as those described in U.S. Patent No. 2. ≠7≠.

No. 273, preferably the naphthol couplers described in U.S. Patent No. ≠, O! Ko, 2/2 issue, same issue.

Typical examples include the two-equivalent naphthol couplers of the oxygen atom separation type described in /Hiro 6, 3, No. 6, No. ≠, 22♂, 233, and No. 200, No. ≠, 2, No. 200. Further, specific examples of phenolic couplers are shown in U.S. Pat.
, 3 otsuri, ri 2ri issue, same no. 2. 0/, /7/ No. 2, 772, /62, No. 2. ♂ri! ,? 26
It is written in the number etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic/Uncoupler with U.S. Pat. No. 2,772. /Nos. 1 and 2, Nos. 3 and 7! ? .

Jor No., Hiroshi No. 1, /2t, No. 3 6, No. ≠.

33I/L, oii issue, same No. 1, 3J, 7. /No.73,
2,! described in West German Patent Publication Nos. 3,32, 72 and European Patent No. 1λ/, 363, etc. -Diacylamino-substituted phenolic couplers and U.S. Patent No. 3. Hirohiro T, Otsu No. 22, Dou No. 333, Tatata No., Dou No. Hiroshi,
A phenylureido group is attached to the co-position described in ≠ti, rr and No. 27,767, etc.!
Structural formulas of specific examples of cyan couplers used in the present invention, such as phenolic couplers having an acylamino group at -position, are shown below. However, the cyan coupler used in the present invention is not limited to this.

Specific example of cyan coupler C-≠ OH -r OH -A C-♂ OOH shi8H17i) C-/ / In order to correct unnecessary absorption of chromophore, colored couplers are used in conjunction with color negative sensitive materials for photography. It is preferable to perform all masking. US Patent No.≠.

763. Otsu No. 70 and Tokko Akira! Yellow-colored magenta couplers such as those described in US Pat. No. 7-37μ/3 or US Pat.

73g, 2yo 2 and British Patent No. i, i≠B.

3rd? A typical example is the magenta-colored cyan coupler described in No. Other colored couplers can be found in the aforementioned Research Disclosure, A'71.
=≠3, described in sections ■ to G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 3, No. 237 and British Patent No. 2.
/2! ,! Specific examples of magenta couplers are given in European Patent No. P6.70 and European Patent No. P6. ! No. 70 and West German application publication tube 3, 2
No. 3≠, No. 533 describes specific examples of yellow, magenta or cyan couplers.

The dye chroma couplers and the above-mentioned special couplers may be entirely formed into dimers or higher polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. ≠! /, ♂CoO, and ≠, O♂0゜277. Specific examples of polymerized magenta couplers are described in British Patent No., 10λ, 773 and US Pat. No. 3A7. λ
It is described in the rλ issue.

Couplers that release all photographically useful residues upon coupling can also be preferably used in the present invention. As the DI coupler that releases a development inhibitor, the patented couplers described in the aforementioned Research Disclosure, &t7AIA3, Items 1 to 5 are useful.

A preferred combination with the present invention is JP-A-Sho! 7-
Developer deactivated type represented by /j/911-μ; U.S. Patent No. 1, 1? , No. 26λ and JP-A-37-/! ≠2
Timing type represented by No. 3; JP-A-1.0-/♂
The reaction type represented by Hiro J'7 is particularly preferred, as is JP-A No. 11A from JP-A-Sho J'7-/. ? -2/7
No. 32, JP-A No. 1rO-2/r44tu, No. 40-
22! /! Developer deactivated DIR, couplers, and JP-A-Sho T
This is a reactive DIR coupler described in No. o-/♂Hiroshi 2≠g.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving either a high-boiling point organic solvent with a boiling point of 77°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or water is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high-boiling organic solvents are U.S. Pat. Ju
J, No. 027, etc.

Phase inversion may be used for dispersion, and if necessary, the auxiliary solvent may be removed by distillation, noodle washing, or ultrafiltration. Ta? 'i may be reduced before use for coating.

Examples of the process, effects, and latex for impregnation of latex dispersion methods are described in U.S. Patent No. μ,/Tata.

No. 343, West German Patent Application (tJLs) No. 2. ! ≠/.

No. 27≠ and No. 2 of the same. j≠l, as described in No. 230, etc.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, amine phenol derivatives, amine pigments, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenols as color antifogging agents or color mixing inhibitors. It may also contain derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic antifading agents include hydroquinones, 6-hydroxychromans, hydroquine coumarans, spirochromans, p-alcoquinphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, and methylene. Representative examples include dioquine benzenes, aminephenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoquinato)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

The multilayer color photographic material of the present invention usually has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer, and at least one blue-sensitive emulsion layer on a support. The arrangement of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or blue sensitivity, red sensitivity, and green sensitivity from the support side. Further, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may be present between the emulsion layers having the same sensitivity. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

In addition to the silver-rodanide emulsion layer, the light-sensitive material according to the present invention is preferably provided with all auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful flexible supports include films made of cellulose derivatives (cellulose nitrate, cellulose acetate, cellulose acetate butyrate, etc.), synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.); Paper coated with or laminated with a baryta layer or an α-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene copolymer) or the like. The support may be colored with dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally
Undercoating is applied to improve adhesion to photographic emulsion layers, etc.

Before or after primer treatment, glow discharge,
Corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, dip coating, roller coating, curtain coating,
Various known coating methods such as extrusion coating method can be used. U.S. Patent No. 2, if necessary. Otsu♂/, 2ri μ
No. 2.77, /.

7ri No. 7, same No. 3. ! 2 Otsu,! 2? No. 3゜! Or
Multiple layers may be applied simultaneously by the coating method described in, eg, RI4T No. 7.

The color photographic light-sensitive material according to the present invention is described in the aforementioned Research Disclosure, page uf-29 of B/7 Otsu≠3 and the same, A/J'7/Otsu j/page left column to right column. It can be developed by a conventional method. The color photographic material of the present invention is usually subjected to water washing or stabilization treatment after development, bleaching, and fixing (or bleach-fixing).

In the washing process, it is common to use two or more tanks for countercurrent washing to save water. For stabilization treatment, use Tokukaisho instead of the water washing process! 7-g! A typical example is a multistage countercurrent stabilization treatment as described in No. 3. In the case of this step, a countercurrent column with a λ tank is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, membrane pHk
Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water,
Typical examples include monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. (used in combination) and formalin. In addition, water softeners (
Inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (indiisothiazolinones, irithiazolones, ≠−
Various additives such as thiazoline benzimidazoles, halogenated phenols, etc.), surfactants, fluorescent brighteners, and hardening agents may all be used, or two or more compounds for the same or different purposes may be used in combination. It's okay.

In addition, ammonium chloride,
Various ammoniums such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate [i-addition is preferred.

The present invention will be explained in more detail with reference to Examples below.

(Example 1) On the triacetate film base, the first
~The first layer was coated to make a color photographic material.

1st i: Antihalation layer (gelatin layer containing black colloidal silver) 2nd layer: Gelatin intermediate layer 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 3.0 molar, cubic crystal Monodisperse emulsion) contains 9 x 70 moles of sensitizing dye per 7 moles of human total silver, coupler C-/ and coupler C-,! (Molar ratio≠, /:
A cyan coupler emulsion containing /, 0) was added. However, the silver/coupler molar ratio was 3.0, and the amount of silver coated was 00117 m2.

2nd red-sensitive emulsion layer Silver iodobromide emulsion (3.0 molar silver iodide, cubic monodispersed emulsion) contains a sensitizing dye Ai at a ratio of 10 x 1 per mole of silver, and a coupler C- A cyan coupler emulsion containing 7f was added. However, the silver/coupler molar ratio was set to 0, and the amount of silver coated was 0.0717 m2.

Layer 3: Third red-sensitive emulsion layer A silver iodobromide emulsion (silver iodide 3.0 mole, cubic monodisperse emulsion) contains sensitizing dye A in an amount of 3 x 10-4 mol per mol of silver, and a coupler. A cyan coupler emulsion containing C-1f was added.

However, the amount of coated silver should be 0.3' so that the silver/coupler molar ratio is 20.0. /m2.

6th layer: Gelatin intermediate layer 7th layer: 1st green-sensitive emulsion layer A silver iodobromide emulsion (silver iodide≠,!molti, cubic monodispersed emulsion) contains 1 mol of silver sensitizing dye Bi, M, C/.

! ×10 moles, coupler C-3 and coupler C
-Pi and Coupler C-! (Molar ratio.

A magenta coupler emulsion containing j:/, 7', /, 0) was added. However, the silver/coupler molar ratio was f, 0, and the amount of silver coated was O0≠1/m2.

2nd layer: 2nd green-sensitive emulsion layer 70 mol of sensitizing dye B per mol of silver in a silver iodobromide emulsion (silver iodide emulsion, Omolti, cubic monodisperse emulsion) and coupler e-J and coupler e−≠ and coupler C−
r and coupler C-6 (molar ratio ♂, O: J, !;:
/, Rinia.

A magenta coupler emulsion containing 0) was added.

However, what is the silver/coupler molar ratio? , o, the amount of cloth silver is 0. /li/m'.

Third layer: Third green window emulsion layer Silver iodobromide emulsion (silver iodide 3.j mol, cubic monodispersed emulsion) K increased, bean paste dye B total @1 mol per 1 mol x 10 mol,
Coupler C-3 and coupler C-≠chi-yo and coupler C-r and coupler C-6 (coupler molar ratios are the same as above)? Magenta coupler emulsion containing? Added. However, the silver/coupler molar ratio is one! 0.0, and the amount of silver coated was 0,397 m2.

10th layer: Yellow filter layer (gelatin layer containing yellow colloidal silver) Coupler emulsifier = was added. However, the silver/coupler molar ratio was 2.0, and the amount of silver coated was 00117 m2.

The entire coupler emulsion was added. However, the silver/coupler molar ratio is 4. It was coated so that the amount of silver coated was 0°32/m2.

Coupler emulsion was added. However, the amount of coated silver should be 0.3 to 0.0, so that the silver/cobra molar ratio is 3.0 to 0. It was applied so that it was 2/m2.

14th L layer: 1st protective layer (gelatin protective layer containing 2 substantially non-photosensitive silver halide emulsions with an average grain size of 0.0♂μ) 1jth layer: λth protective layer (gelatin protective layer) However, Each emulsion layer further contains a stabilizer ≠-hydroxy-6-methyl-7°3.3
a, 7-chitrazaindene, hardener C-! , coating aids were sequentially added and coated, and the sample/(comparison) was exploded.

Sensitizing dye A (CH2)3SQ3Na Sensitizing dye B Field test C Coupler C-/ 1-c8i-t1□ Coupler C-2 Coupler C-j UPI 3 Coupler C-z ('1 α Coupler C-7 α Hardener c-,i' ((,:H2=Cday5U2CH2CsuNf(CH2su2
In addition, a sample was prepared in the same manner as above, except that the sensitizing dye B in the 7th layer of the first stroke and the second layer was replaced with the following compound CK.

Further, a sample λ was prepared in the same manner as above except that the sensitizing dye B in the 7th layer, the rth layer, and the 9th layer was replaced with the following compound DK.

Also, in the above, the 7th layer, bamboo? Sample 3 was prepared in the same manner as Sample/, except that the sensitizing dye B in the second layer was replaced with the compound/-fllK described in the text.

Further, in the above, Sample ≠ was prepared in the same manner as Sample 1 except that the sensitizing dye B in the seventh, second, and seventh layers was replaced with the compound λ-(1) described in the text.

Moreover, in the above, sample j was prepared in the same manner as sample / except that the seventh skin, the 12th layer, and the 73rd layer were changed as follows.

1st/Layer: First blue-sensitive emulsion layer (sample silver iodobromide emulsion (tabular grains with silver iodide/, 0 mol m-mho average grain size ≠ μ-average aspect ratio 7.!) with a sensitizing dye C with txio -5 moles per mole of silver and -coupler C
A yellow coupler emulsion containing -7 was added. However, the amount of coated silver was 0.0, so that the silver/coupler molar ratio was 0. The coating was applied so that the coating was carried out at a coating rate of 0.05 S'/m2.

72nd layer: λth blue-sensitive emulsion layer (sample) Silver iodobromide emulsion (
Sensitizing dye C was added to silver iodide (tabular grains with an average grain size of 0 mol and an average aspect ratio of 7.0) per 7 mol of silver. z x 70-5 moles and a yellow coupler emulsion containing coupler C-7 were added. One coated silver needle is 0.377 m2 so that the silver/coupler molar ratio is O.
(I applied it so that it looks like this.

73rd layer: 3'ff sensitive emulsion layer (sample) Silver iodobromide emulsion (tabular grains with i, o mole of silver iodide, average grain size o, tμ, average aspect ratio 7.0) is sensitized Dye C -j
! per mole x 10-5 mole - coupler C-7
A yellow coupler emulsion containing was added. However, silver/
Coupler molar ratio is 3. Coating silver amount is θ so that it becomes 0.
, t45' 7m2.

In addition, in the above, the silver iodobromide emulsion in the first and ninth layers is replaced with tabular grains having a semiuniform grain size O0≠jμm and an average coefficient ratio of 7°0, and sensitizing dye B is added to
'Mole to 1. Sample t was prepared in the same manner as sample yo except that the amount was changed to ≠×l0−3 mol.

Further, in the above, Sample 7 was prepared in the same manner as Sample 7 except that the sensitizing dyes in the seventh layer, the male layer, and the second layer were replaced with /-(li).

In addition, sample g was prepared in the same manner as sample t except that the sensitizing dyes in the seventh layer, r-th layer to t-th layer were replaced with /-(11).

Further, Sample 9 was prepared in the same manner as Sample j except that the sensitizing dye in the seventh, second, and ninth layers was replaced with λ-(11).

Further, in the above, Sample 10 was prepared in the same manner as Sample 2 except that the sensitizing dye in the seventh layer, second layer, and second layer was replaced with λ-(1).

In addition, in the above, the third layer - the μth layer, the ! Sample L was prepared in the same manner as Sample 7 except that the sensitizing dye in the layer was replaced with 3-.
/ was created.

In addition, in the above, the third layer - the fourth L layer, the third layer! Sample/λ was prepared in the same manner as Sample 7 except that the sensitizing dye in the layer was replaced with Hiro-06).

In addition, in the above, the third layer, the third layer - the third layer! Sample/3 was prepared in the same manner as Sample 7 except that the sensitizing dye in the layer was replaced with Tar (3).

In addition, the silver iodobromide emulsion C of the 1st tr@-1st co-layer and the 73rd layer (silver iodide/, 0 mol tsu) was replaced with a silver chloroiodobromide emulsion (silver iodide/, 0 mol tsu) of the same size. 0 moles.

Sample/Hiroshi was prepared in the same manner as Sample // except that silver chloride was replaced with j, o mole).

Further, in the above, Sample/! was prepared in the same manner as Sample L/, except that the sensitizing dye C in the 1st/layer, 12th layer, 13th layer, and 3rd layer was replaced with 4-(21).

Further, in the above, Sample/6 was prepared in the same manner as Sample 7 except that the sensitizing dyes of the 1st/IvI-7th layer and the 13th layer were not added.

Further, in the above, the silver iodobromide emulsion of the first/layer has an average grain size of 0. The silver iodobromide emulsion of the 72nd layer was applied to the tabular grains with an average diameter of 7°j and an average grain size of o, t.
The silver iodobromide emulsion of the 1st layer was applied to tabular grains with parallel grain size θ, J'θμ, average unthrow ratio of 7.0, and tabular grains with average unthrow ratio of 7.0. Sample/7 was prepared in the same manner as sample/2 except that each was replaced.

In addition, in the above, silver iodobromide emulsions (silver iodide haku moru jin) of the 11th layer, 1st co-layer, and final/3rd layer are replaced with silver chloroiodobromide emulsions of the same size (silver iodide 1.0 mol, silver chloride j, o mole 4) K
Sample/l' was tabulated in the same manner as sample/2 except for replacing it.

sample/~/! helium-cadmium (He-Cd)
Laser emission mount (manufactured by Kinmen Electric Aji Co., Ltd.), argon (kr
)l/- laser oscillation EN't (manufactured by Rex e I), helium neon (He -tNe) laser oscillation )? Using a helium cadmium (l(e-Cd) laser)
m) Light, argon (Ar) laser (wavelength / Hiro,!n
m) Light, helium neon (He -, \e) lede (
e, long 632. ♂nm) Light was exposed for lo-5 seconds through a medium-sized gray tube.

Further, the color photosensitive material was fully exposed using an equal energy spectrometer (manufactured by Fuji Photo Film Co., Ltd.).

Each sample was subjected to 19α treatment using the following method.

■ Color development tAl, /±0. / 3 minutes■
Stop 27-3♂ D in 30 seconds Bleaching acceleration λ7-! -/ 30 seconds■ Drifting
White 3♂± / 3 minutes■ Wash with water 27~3? /min ■ Fixation
3! +/ 2 minutes water wash 27~31
2 minutes ■ Stable 27-3♂ 10 seconds The formulation of the treatment liquid used in each treatment step is as follows.

2/~3?0C water r! Otd Kodak Anti Calcium Shop≠ 2.0ml Sodium Sulfite (Anhydrous) 2. Of Eastman
0, 22?
Sodium bromide (anhydrous) / , 20? Sodium carbonate (anhydrous),! j, AP Sodium bicarbonate 2.72 Color developing agent 2≠-(N・Ethyl・N-(β-methanesulfonamidoethyl)-m-toluidine ≠102 Add water /・001pH (-7°C)
io, λ021~3♂0C water
Taoogo7, ON sulphur n
add rorttl water
1. oolpH (λ7°c) o,
q water
00ml Sodium metabisulfite (%, water) 10
．． 0? Glacial acetic acid! r, 0
rnl sodium acetate 10. Of
E DTA -'I tN a
O, 77PBA-/
J', j? Add water /
049 days (u7 °C) J, r±0.
2 (1'BA-/[,!-Dimethylamine ethylinothiourea! Hydrochloride is added.) 2≠~3♂0C water ♂00 butt e gelatin O6! ? Sodium persulfate 33. Of sodium chloride /! ,Of monobasic sodium phosphate (anhydrous) 2.02 phosphoric acid (,rr%)
2. ! At the water is cut off
l・01pH (27°C) 2.3
+0.220~3♂0C water 7oo butt l Kodatsuk anti-calcium shop ≠ 2.0 goyo r%
Ammonium thiosulfate solution /r! Sodium sulfite (anhydrous) io, or bisulfite) IJum (anhydrous)? ,≠? Add water / 001pH (27°
(:) A, j2/~! 7°C water /, 001 Kodak Stabilizer Additive 0. /≠Goformin (37,! solution) /, J'0rnl Helium cadmium (He-Cd) laser (wavelength 4) of each sample
Yellow image density when exposed to Z4t'/, n m ) light and developed with the above formulation, argon (A r )
Yellow and magenta image densities when exposed to Li-zer (wavelength!/4t, j nm) light and developed with the above formulation, and helium neon (He-
Ne) The cyan image density when exposed to laser (wavelength!, 32.Inm) light and developed according to the above recipe was measured, and the relative sensitivity of each was determined.

The sensitivity was determined based on the exposure amount at which the fog density increased by 0.2.

In addition, the entire spectral sensitivity distribution of the green-sensitive layer was measured, and its peak wavelength was determined.

In addition, in order to evaluate the total color mixture, the green-sensitive emulsion layer of the color light-sensitive material was exposed to argon (Ar) laser (Y/4L, jnm) light, and the fog density was lower than O9! What is the fog density from the color density of the blue-sensitive emulsion layer of the color light-sensitive material when exposed to light sufficient to develop color? The drawn directness is 0. ! The color mixture ratio was calculated by dividing by .

The above results are shown in Table ■.

/0 Samples 7-l of the present invention! is a sample for comparison /,! ,! ,
Compared to Otsu, argon (Ar) laser (!/Hiroshi, jnm
1) The sensitivity of the green-sensitive layer to light is sufficiently higher than that of the blue-sensitive layer, and the color mixture prevention effect is remarkable.

Samples 7 to 10 of the present invention are superior in the brightness of the green-sensitive layer and the red-sensitive layer compared to the comparative sample 3゜Hiroshi.

3. The samples of the present invention are neon-helium (Ne
-He Loser 1tJ2. Inm) superior to other samples in terms of the sensitivity of the red-sensitive layer to light.

Beast Use a sensitizing dye in the blue-sensitive layer 1~ Helium-cadmium (He-Cd) laser in the blue-sensitive layer c≠≠/, A
nm) are advantageous in terms of sensitivity to light and the sharpness of the green-sensitive layer and the red-sensitive layer.

(Comparison of Samples 7, /B, and /7) (Example C) Samples / to /r prepared in Example / were exposed to light in the same manner as in Example /, and developed in the following manner.

The processing temperature is 3♂0C.

1 Color development 3 minutes/! Second 2 Drifting
Wash white for 3 minutes and 30 seconds with water.
3 minutes/4 seconds fixed
6 minutes 30 seconds 5 Wash with water
3 minutes/j seconds 6 stable
3 minutes and 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 7.02 Sodium sulfite ≠, 02 Sodium carbonate 3o, oy Potassium bromide
/・″2-hydroxylamine sulfate 2.≠?≠-(N-ethyl-N-β-hydroquinethylamino)-2-methylaniline fL salt ≠, j2
Add water /l bleaching grade ammonium bromide /1,0.09 aqueous ammonia (2,1%) 2 evenings, Occ ethyne /
Diamine-tetraacetic acid sodium iron salt /30. Of glacial acetic acid
1≠, add occ water
11th liquid sodium tetrapolyphosphate! , 07 Sodium sulfite ≠, 02 Ammonium thiosulfate (70%) /7, Occ Sodium biphosphite ≠, Otsu? add water
72 Stabilizing liquid formalin ♂ and Occ water were added and the same measurements as /e Example/ were carried out, and the same results were obtained.

(Example 3) The samples /~/l produced in Example 1 were exposed to the same light as in Example 1°-, and developed in the following manner.

Processing process Temperature Time Color development JJ-'CtO second bleach fixing 3r0C40 seconds water washing Co≠~3! r 0c t
Dry for 0 seconds ro 0c
/The ingredients of the announced treatment liquid are as follows.

Color developer water 10
0 Godiethylenetriaminepentaacetic acid 3.07 Sodium sulfite K,oy Potassium bromide O1!2 Potassium carbonate
30.09 to 1-2-(β-methanesulfonamidoethyl)-3-1-methyl-Hiro-aminoaniline
j, 09 sulfate hydroxylamine sulfate μ, 0? Add water 100100O days<rroc
) /l,.

Bleach fixer water 4t
oo Ammonium Gothiosulfate (70% solution) /! Sodium sulfite Iron(III) ethylenediaminetetraacetate Ammonium! 2ethylenediaminetetraacetic acid/uNa! ? add water
/ 000rrdlpH(sroc)
The same measurements as in Examples 70 and 70 were carried out, and the same results were obtained.

(Example ≠) In Example /, the compound i described in the main text as a green-sensitive sensitizing dye -(2)-/ -f3)-/-(51,/
-(7)-No(3)1.2-141, λ-(6) also obtained the same results as Sample 7 of Example/.

(Effects of the Invention) According to the present invention, since the sensitivity of the green-sensitive layer to argon laser light is sufficiently higher than the sensitivity of the blue-sensitive layer, the effect of preventing color mixture is remarkable.

Further, according to the present invention, photographic power S with excellent sharpness can be obtained.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Showa t/year/month/day f

Claims (1)

[Claims] (1) In a color light-sensitive material having at least a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support, the spectral sensitivity of the green-sensitive emulsion layer is 500 nm or more. A color photosensitive material having a peak at 530 nm and containing tabular grains having an average aspect ratio of 5 or more in at least one of the red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers.