JPS62166346A - Color image forming method - Google Patents

Abstract

PURPOSE:To form an excellent color image having especially good optical fading stability by image-wisely exposing the silver halide color photographic sensitive material contg. a hardener capable of acting by activating a carboxyl group, and then, effecting a color development of the obtd. material followed by bleaching it for less than the prescribed period. CONSTITUTION:The titled method lies in image-wisely exposing the silver halide color photographic sensitive material contg. the hardener capable of acting by activating the carboxyl group, and then, effecting the color development of the obtd. material followed by practically, bleaching it for >=4min and 15sec. The concrete example of the used hardener capable of acting by activating the carboxyl group is the compd. shown by formula 1. The bleaching period is specified to less than 4min and 15sec, and is preferably, 1-3.5min. The preferable method of reducing the bleaching period is the method of bleaching it in the presence of the specific compd. The representative and concrete example of the bleaching accelerator is the compd. shown by formula 2.

Description

Detailed Description of the Invention (Graduation Field of Application) The present invention relates to a color image forming method using a multilayer silver halide color photographic material (prior art) - g. The basic steps in material processing are color development and desilvering.

That is, the exposed silver halide color photographic material is
Enter the color development process. Here, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. Afterwards, the color photographic material is subjected to a desilvering process.

Here, the dirt generated in the previous step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and removed by a silver ion complexing agent, commonly called a fixing agent.

Therefore, the photographic material that has gone through these steps will only produce a true dye image. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the storage stability of the image. May include. For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing;
Examples include a stop bath that effectively stops the development reaction, an image stabilization bath that stabilizes the image, and a film removal bath that removes the backing layer of the support.

Generally, red blood salt is used as an oxidizing agent in bleaching solutions. However, the disadvantages of bleaching solutions using red blood salts are that the bleaching solution must be replaced when it is exhausted, and that felician ions and their reduced forms are emitted due to overflow during processing and carried into the washing water after bleaching. ferrocyanide ions undergo photochemical oxidation to produce cyanide compounds. These cyanide compounds are highly toxic and cause great harm.

On the other hand, potassium dichromate, ferric salts, persulfates, quinones, copper salts, etc. have traditionally been used as bleaching agents other than red blood salt, but these have the drawbacks of weak oxidizing power and difficulty in handling. have.

In recent years, in color photographic materials, from the viewpoint of quick and simple processing and prevention of environmental pollution, ferric ion complex salts (for example, ferric ion complex salts of aminopolycarboxylic acids, etc., especially EDTA-iron(I[) complex salts) have been used. ) bleaching treatment methods are mainly used.

However, a drawback of the ferric ion complex bleaching bath is that the bleaching blade is weak and it takes a long time for bleaching.

However, the present inventors have found that when a photographic material is exposed to a bleaching bath for a long time, the image storage stability of the photographic material, particularly the photofading resistance, is significantly deteriorated.

In recent years, with the development of technical fields such as TV image conversion processing using viewers, it has become desirable to improve image storage stability, particularly photofading resistance.

(Object of the Invention) The first object of the present invention is to provide a method for forming a color image having excellent image storage stability, particularly excellent photospecimen color stability.

A second object of the present invention is to provide a method for forming color images with good desilvering properties even in short-time processing.

(Structure of the Invention) An object of the present invention is to imagewise expose a silver halide color photographic light-sensitive material containing a hardening agent that acts by activating carboxyl groups, and after color development, to expose the silver halide color photographic material to light for substantially 4 minutes. This could be achieved using a color image forming method characterized by bleaching in 15 seconds or less.

The hardener that acts by activating carboxyl groups in the present invention refers to known inorganic and organic hardeners that react with carboxyl groups in gelatin.

Preferred hardeners in the present invention include the following general formula (1
) to (6) can be mentioned.

General formula (1) In the formula, R1 and R2 are an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a 2-ethylhexyl group, etc.),
An aryl group having 6 to 15 carbon atoms (e.g. phenyl group, naphthyl group, etc.) or an aralkyl group having 7 to 15 carbon atoms (
For example, benzyl group, phenethyl group, etc.), and may be the same or different. It is also preferable that R' and R2 are bonded to each other to form a heterocycle together with the nitrogen atom. Examples of rings that form a ring include a pyrrolidine ring, a piperazine ring, and a morpholine ring. R3 is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, or a carbon number 1 to 1
0 substituents such as alkyl groups. When R3 is an alkoxy group or an alkyl group, these groups may be further substituted, and examples of the substituent include a halogen atom, a carbamoyl group, a sulfo group, and a ureido group. Xe generates anions and becomes a counter ion for the N-carbamoylpyridinium salt. When a sulfo group is included in the substituent of R2, an inner salt may be formed and Xe may not be present. Preferred examples of anions include halide ion, sulfate ion, sulfonate ion, C104es
Examples include BF4e and PFbe.

General formula (2) RI, R2, R3 Oyohi Xe definitions are completely the same as the definitions in set (1).

General formula (3) RI R3 an aralkyl group (e.g. benzyl group, phenethyl group, 3-pyridylmethyl group, etc.), or an aralkyl group having 5 to 20 carbon atoms.
and a phenyl group, a naphthyl group, a pyridyl group, etc., and may be the same or different. Also R1. R2゜R3 and R4 may have a substituent, and examples of the substituent include a halogen atom, a carbon number of 1 to
Examples include an alkoxy group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an N,N-disubstituted carbamoyl group.

It is also preferred that any two of R1, R2, R'' and R4 combine to form a ring.

Examples of R1 and R2 or R3 and R4 bonding together to form a ring together with a nitrogen atom include a pyrrolidine ring, a piperazine ring, a perhydroazepine ring, a morpholine ring, and the like.

Also, R',! Examples of R', or R2 and R4 bonding together to form a ring with two nitrogen atoms and a carbon atom sandwiched between them, include an imidacilline ring, a tetrahydropyrimidine ring, a tetrahydrodiazepine ring, etc. can be given.

X represents a group capable of leaving when the compound represented by the general formula (3) reacts with a nucleophile, and preferable examples include a halogen atom, a sulfonyloxy group, and a 1-pyridinyramyl group. Ye rains anions, halide ions, sulfonate ions, sulfate ions,
C12,04e, BF4e, PFbe, etc. are preferred.

When Ye rains sulfonate ions, X, R',
R”.

It may be combined with R3 or R4 to form an inner salt.

General formula (4) % formula % In the formula, R1 is an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, 2-ethylhexyl group, etc.), a cycloalkyl group having 5 to 8 carbon atoms (e.g., cyclohexyl group, etc.) ), an alkoxyalkyl group having 3 to 1 carbon atoms (eg, methoxyethyl group), or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.). In addition to the groups defined for R1, Rt is preferably a group represented by -R3-N-R'.

θ R3 is an alkylene group having 2 to 4 carbon atoms (for example, ethyl 1/7
M, propylene group, trimethylene group, etc.).

R4 and R5 each represent an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, etc.), which may be the same or different. It is also preferable that R4 and R5 combine to form a heterocycle (eg, pyrrolidine ring, piperazine ring, morpholine ring, etc.) together with the nitrogen atom. R6 is an alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group,
(butyl group, etc.), but substitution is also preferred. Preferred examples of the substituent include substituted or unsubstituted carbamoyl groups and sulfo groups.

Xe produces anions, halide ions, sulfonate ions, sulfate ions, C104e, BF4e,
PFbe and the like are preferred. Further, when R6 is substituted with a sulfo group, an inner salt is formed and Xe may not be present.

General formula (5) In the formula, R1 is an alkyl group having 1 to 1 carbon atoms (e.g., methyl group, ethyl group, butyl group, etc.), or an alkyl group having 6 to 15 carbon atoms (e.g., phenyl group, naphthyl group, etc.). ), or an aralkyl group having 7 to 15 carbon atoms (e.g. benzyl group,
phenethyl group, etc.). These groups may be substituted, and examples of the substituent include carbamoyl group, sulfamoyl group, and sulfo group. R2 and R3 are a hydrogen atom, a halogen atom, an acylamido group, a nitro group,
Substituents such as a carbamoyl group, ureido group, alkoxy group, alkyl group, alkenyl group, aryl group, and aralkyl group may be the same or different. It is also preferred that Rt and R3 combine to form a condensed ring together with the pyridinium ring skeleton.

X represents a group that can be eliminated when the compound represented by the general formula (5) reacts with a nucleophile, and preferred examples include a halogen atom, a sulfonyloxy group, or -〇 P
Examples include groups represented by (OR')2 (R' represents an alkyl group or an aryl group). When X represents a sulfonyloxy group, it is also preferable that X and R1 are bonded.

Ye rains anions, halide ions, sulfonate ions, sulfate ions, C104e, B F4
e-P F h” Natoka Komashi 't'.

Further, when RI is substituted with a sulfo group, an inner salt is formed and ye does not need to be present.

General formula (6) In the formula, RI and R2 are defined as R1. in general formula (1).
The definition of R2 is exactly the same, and R3 is an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, etc.), an aryl group having 6 to 15 carbon atoms (for example, a phenyl group,
naphthyl group, etc.), or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.). Xe is an anion, including halide ion, sulfonate ion, sulfate ion, C10m” 18 F4e
1P Fbe nato is preferred.

As the carboxyl group-activated hardener used in the present invention, in addition to the compounds represented by the general formulas (1) to -6), JP-A-50-38540 and JP-A-5
2-93470, JP-A-56-43353, JP-A-58-113929, U.S. Patent No. 3.321.313
Also preferred are the compounds described in No.

Specific examples of compounds used in the present invention are classified below, but the present invention is not limited thereto.

a, Compounds represented by general formula (1) (For the synthesis method of these compounds, see JP-A-49-5
1945 and JP-A No. 51-59625 for details.

) H-8 H-13 C0 Compounds according to general formula (3) (methods for synthesizing these compounds are described in JP-A-60-225148
I am familiar with the issue bulletin.

X, JP l' b - CH:l CHa 0SOzCFz d, compound according to general formula (4) (methods for synthesizing these compounds are described in JP-A-51-126125
No. 52-48311 for details. )CHs
OCHzCHzN = C= N (Ctlt) *
-N (CH3) z(CHff)2C)l-N=C
=N-(CH2)t-N(CH3)! Peek (CHz) a-3O3e H-26 H-27 1e e, compound according to general formula (5) (methods for synthesizing these compounds are described in JP-A-57-44140, JP-A-57-46538, and JP-B-Sho 58) -50669
I am familiar with the issue. ) I C, H5 f, compound according to the general formula (6) (details of the synthesis method of these compounds can be found in JP-A-52-54427) g, compound described in JP-A-50-38540 ■ C00CzHs h, Compound i described in JP-A-52-93470, compound i described in JP-A-56-43353, JP-A-58-11
Compound ocx described in No. 3929.

The amount of the hardening agent used in the present invention can be selected arbitrarily depending on the purpose. Usually 0.0 for dry gelatin
Proportions ranging from 1 to 20 weight percent can be used. Particularly preferably, the ratio is in the range of 0.05% to 10% by weight.The color image forming method of the present invention includes a multilayer color silver halide sensitive material which is subjected to a color development process, a bleaching process, a fixing process, An image is usually obtained after a water washing process and a stabilization process.

In the present invention, "1: Bleaching in a time of substantially 4 minutes and 15 seconds or less" means the time from when the multilayer color silver halide sensitive material comes into contact with a bleaching solution until it comes into contact with the next processing solution. , the sum of the time in the bleach solution and the time in the air from one bleach solution to the next.

The bleaching treatment time is limited to 4 minutes 15 seconds or less, preferably 1 minute to 3 minutes 30 seconds.

A preferred bleaching time shortening method in the present invention is a method in which bleaching is carried out in the presence of compounds represented by the following general formulas (1) to [■].

General formula (1) General formula (II) 1 ' ll General formula (II [) General formula (IV) General formula (V) N General formula (Vf) General formula [■] R11R [In the above general formula, Q is Heterocycle containing one or more N atoms (
A represents an atomic group necessary to form a 5- to 6-membered unsaturated ring (including those in which at least one 5- to 6-membered unsaturated ring is condensed); (including those to which at least one unsaturated ring is fused);
represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, X and X' represent =S, =O or =NR', R' is a hydrogen atom, and R' is a hydrogen atom, ~6 alkyl groups, cycloalkyl groups, aryl groups, heterocyclic residues (5
(including those with at least one 6-membered unsaturated ring condensed thereto) or an amino group, Y represents /N- or CH-, and Z represents a hydrogen atom, an alkali metal atom, or an ammonium group. , an amino group, a nitrogen-containing hetero or alkyl group, R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (5
~ 6-membered unsaturated ring (including those with at least one condensed thereto) or an amino group, R'', R', R'
, R5, R and R' are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group,
Represents an acyl group, aryl group, or alkenyl group having 1 to 3 carbon atoms. However, R4 and R5 may represent -B-3Z, and R and R', R2 and R3, and R4 and R5 may each be cyclized to form a heterocyclic residue (at least one 5- to 6-membered unsaturated ring (including those condensed thereto) may also be formed.

R6 and R7 are each a group or -(CHz) na SO! - However, when R8 is (CHZ)nsS ()+-, l represents 0 or l. ) G- is an anion, ml to m4 and nl
thru|or R8 each represents the integer of 1-6, and m represents the integer of 0-6. R8 is a hydrogen atom or an alkali metal, and Q' has the same meaning as Q above. D represents a simple bond, an alkylene group or vinylene group having 1 to 8 single primes, and q is 1 to 10
represents an integer. Multiple Ds may be the same or different,
The ring formed with the sulfur atom may be further fused with a 5- to 6-membered unsaturated ring. X' is -COOM', -OH,-
3O, M', -CONH2, SO2N Hz, -N
H,, -3H, -CN, -Co□R'6, -3O□R
16, -〇 R Den 6, N RI 6
Rl Ding, SR+6, -SO3RI6,
-NHCOR", NHS O2R", -〇COR1
6 or -8O□RI6, Y' represents R14R1+ or a hydrogen atom, and m and n each represent an integer of 1 to 10. R”, R”, R”, R”, R” and HiRI 1
1 is a hydrogen atom, a lower alkyl group, an acyl group, or 1
1711 -(C)□X' ■ Represents R12, R" represents a lower alkyl group. RI9 is -NRZ0R2I, QRZ
Z or -3R22, R2° and R'' represent a hydrogen atom or a lower alkyl group, and R1 represents an atomic group necessary to form a ring by linking with RI8. Rzo or R2I
(!: RI8 may be connected to form a ring. M' represents a hydrogen atom or a cation. Note that the general formula (XI)
The compounds represented by (XV) include enolized compounds and salts thereof. ] General formula [■] In the formula, R22~R'' represents an alkyl group having -OR2?, S R28゜ as a substituent, and R27~R3
4 represents a hydrogen atom or an alkyl group, R29 and R30
, R3+ and R3! and Rffff and R34 may be combined to form a heterocycle with a nitrogen atom, Y represents a divalent organic group, X represents an ion, X and y are each O or 1, and 2 is 0 ．． 1. 2. 3 or 4.

The alkyl group represented by R13 to R2h has 1 to 5 carbon atoms in the straight chain portion that connects the nitrogen atom.
Those with a number of 1 to 3 are preferred, and those with a number of 1 to 3 are more preferred. Further, it is preferable that R21 and H2S, and RNA and R26 are the same group. The alkyl group represented by R23 to R26 may be linear or branched, and may have a substituent other than the above-mentioned substituents.

The alkyl group represented by R27 to R34 preferably has 1 to 5 carbon atoms and may have a substituent.

The heterocycle that R29 and R", R" and R", or R33 and R34 may combine to form together with a nitrogen atom may be saturated or unsaturated, preferably 5- to 7-membered. Specific examples include a piperidine ring and a morpholine ring.

Among R23 to RZ6, preferred is -3R2B or R
Specific examples of the alkyl group represented by ``~R26 include the following.

CHzCHzOH -CH2Cl12C1120H CH2CH2OCI+3 -CII20H CHzGHzSH CH2CH2SCI+3 -CHzCHzOCJs -C11□CH25C2H5 -CH2CH2NH2 -CH2CH□N ( CH3) z CHzCONHz CH2CH2ON (C113) z CIIzCSN (Czlls) z H3 " -CHCII□011 Divalent organic compound represented by Y Preferred groups include alkylene, arylene, cycloalkylene, heterocyclic groups, and two or more of these groups directly or -o-, -s
, -so□-, -CO-.

NR35 (R3S is a hydrogen atom, an alkyl group, or
Represents a group. ), -CONR"(R" is synonymous with Ras) or -So! Examples include those bonded via NH-.

The alkylene preferably has 1 to 1 carbon atoms.
Preferred arylenes include phenylene and naphthalene, and preferred cycloalkylenes include 5- to 7-membered arylenes.

The heterocycle may or may not be aromatic.

Examples of the heterocycle include a tetrahydrofuran ring.

The above divalent organic group may have a substituent, and examples of the substituent include halogen, alkyl, hydroxy, 7/L/Doxy, -COOM', -303M'', (M' and M2 are acids, Represents an atom or group necessary to form a salt or ester.) is synonymous with sulfonamide, sulfamoyl, carbonamide, and carba, and p is 0 or 1.) is preferred.

Particularly preferred among Y are -CH, - in the general formula
The terminal part bonded to the group is monoalkylene - aromatic ring group - (the alkylene part is -G
Hz-) or -aromatic ring group-.

Specific examples of the divalent organic group represented by Y include the following.

The ion represented by CHzOClhCHzOCCHz-X is an ion for balancing the charge of the compound of the general formula, and may be a negative ion or a positive ion.

Examples of negative ions include halogen ions, carboxylate ions, sulfonate ions, and nitrate ions, and examples of positive ions include alkali metal ions and ammonium ions.

The bleaching accelerator of the present invention is represented by the general formulas CI) to [■], and typical examples thereof include, but are not limited to, the following.

[Exemplary compounds]

(1-7) (I-8) (I-
9) (1-10)CHzCO
OHC11z (CHzJ zUUUH(I -11
) (I-12) (I-7)
(1-8)CHzCHzCH
zCOOHCHz (CHz) 4COOHI CH2COOHC11□ (C11□), C00II (1
-11) (I -12) (1
-13) (T -14)(
I-15) (1-16
)(1-17) (I-18)
(I-21) (1-22)
CHzcOOH (1-23) (I-24)
CHzCOO)I CH*C
00H(I-25) (I
-26)■ CHzCHzCOOH (I -27) (1-28)
HH (1'-29) (1-30)
HH (I-33) (I-34
)(1-35) (I-36
)(n-1) (n-2)(I
I-3) (II-4) (II
-5) (II -6)(
II-7) (n-8)(
II-9) (n-10
)SS (n −11) (n −
12) (If -13) (
II-14) (n-15)
(II-16) (II-17)
(n −18)ss
5s(n-19) Oll O11(n-
20) (II-21) (n-22) (II-23) (n-24) (II-27) (n-28) HzN C5NHNIIC5NHz (n-29) (II-30) (II-31) ( n-32) (If-33) (n-34) H2N-C5NH(CH2)2NHCS NHz(I
I-35) HzN C3NH(CHz)aN)ICS NHz
(I[-36) HzN C5NH(CHz)sNHcs NHz(
II-37) (n-38) (n-39) (n-40) (n-41) (n-42) (IF-43) (n-44) (II-45) (I[-46) (II-47) (I[-48) (n-49) (n-50) (II-51) (II-52) (II-53) (II-54) 5 1,, +13 (n-55 ) S (II-56) (n-57) (n-58) (n-59) (II-60) (n-61) (n-62) (II-63) (n-64) (If- 65) (II-66) (II-67) CHi N=CS C=N CH3II
II S Na Na (n-68) CzHs N=CS C=N CzHsS II Na Na (II-69) (II-70) (n-71) (n-72) (If-73) (n-74) S (II-75) CHJHCHzCHzNflCSC1l□CHzCHz
COOHI (II-77) (II-78) (n-79) (n-80) (II-81) (II-82) (II-83) (n-84) (II-85) (II-86 ) (II-87) (II-88) (n-89) (TI-90) (nil) (II-92) (II-93) S (n-94) (If-95) (II-96) ■ (n-97) (II-98) (n-99) (n-100) (II-101) (I[-102) (II-103) (II-104) (II-105) (n- 106) (n-107) (n-108) ■ (n-109) (If-110) (ff-111) ' (n-112
)(n −113) (n −11
4) (11-115) (II-
116) (II-117) (
II-118) (If-119)
(If -120) (If -121)
(n −120)S (n −123) (If −
124) (It -125) (
II-126) (n-127)
(n -128) (II -129)
(n -130)S (IT -131) (II -
132) (n -133)
(II-134) (II-135)
(II-135) (If-137)
(II-138) (II
-139) (n -140
)S (IF -14i) (IF -1
42) (II-143) (n-144) N)l (II-145) 1l (If-146) (II-147) H (II-148) (n-149) (n-150) (n- 151) (n-152) (II-153) (II-154) (II-155) (II-156) (II-157) (II-158) (I[[-1) HEN CthCHz SH (III- 2) (III-3) (III-4) (II[-5) HOOC-CH2CH2・5)l (I(r-6) (I[[-7) (I-8) (II[-9)
1h (I[l-10) (II[-11) (I[[-12) (III-13) CH.

(III-14) C112CH2-5H (I[l-15) (I[I
-16) (III-17)
(III-18) (II[-19)
(II[-20)(III-21)
(llll-22)C112
CH2SH (II[-23) (III
-24) (DI -25)
(ll-26) (III-27) CH (I[l-28) (= -29) < m
-30)C1l□-5)l (II[-31) (III
-32) (I[l-33) (I[[-34) (I[l-35) (II[-37) Hs H3 (IV-3) (IV-4) (V-1) (V- 2)I
IN-N
N-N(V-5) (V
-6) (V-7) (V-
8) (V-9) (V-1
0)(V-11) (
V-12) OII
OI+(V-13)
(V −14)OH (V −15) (V −1
6) (V -17) (V
-18) (V -19)
(V-20)SR5H (V-21) (V-22)
(V −23) (V −
24)H (V −25) (V −
26) (V -29) (V
-30) (V -31) (
V-32) (V-33)
(V-34) (V-35)
(V-36) (V-37)
(V-38) (V-40) (V-42) (V-43) (V-4
4) (V -45) (V
-46) (V -47) (
V-48) (V-51)
(V-52) (V-53)
(V-54) (V-55)
(V-56) (V-57)
(V-58) (V-59)
(V-60) (V-61)
(V −62) (V −
63) (V-64)
(V −65) (V −
66) (V -67) (
V-68) (V-69)
(V-70) (V-71)
(V-72) (V-73)
(V-74) (V-75)
(V-76) (V-77)
(V-78)NO3N
H2 (V −79) (V −
80) II NH2MHz (V -81) (V -
82) II NH2CH.

(V −83) (V −
84) II CzHs Czl
b(V -85) (V
-86) II C4119Cl2NH2 (V -87) (V -8
8) II CHzNHz CHzC
HzNHz(V-89)
(V -90) (CHz) Jlh
(CH2)4NH2(V-91)
(V-92)II CHzGHzMHz (C1
l□)3NHK(V-93)
(V -94) (CHz)4NH2MHz (V -95) (V -
96)l NO2Nl2 (V -97) (V -
98) CIl□N11z
C1hCHHzNHz(V-99)
(V -100) (C11□)3NIIZ
(CH2) tNIh(
V −101) (V −
102) H1 2H5 (V -103) (V -
104)l CH2CH2NH2C2H3 (v -105) (v
-106)NH2NH4INH.

(V-115) SH5H SH5t( SH5H S)l 5R(V-123
) (V -124) (V
-125) (V -126
)HH (V −127) (V −
128) (V-129)
(V-130) (V-131)
(V-132) (V-133)
(V -134)NH,SH (V -135) (V -
136) So, INa (V −137) (V −
138) SH5H (V -139) (V -
140) (V-141)
(V-142) (V-143)
(V-144) (V-145)
(V-146) (V-147)
(V −148) (V −
149) (V -150
) (V -151) (V
-152) (V -153)
(V-154) (V-155)
(V -156)SH (V -157) (V -
158) (V-159)
(V -160)S)I (V -161) (V -
162) (V-163)
(V-164) (V-165)
(V-166) (V-167)
(V -168) (V -169
) (V -170) (V
-171) (V -17
2) H (V-173) K (V -174) (V -1
75)H (V -177) (V -
178) SR5R S)I (V -180) (V -
181) SO5H (V -182) (V -1
83) (v-184) N=NH (VI-1) (Vl-2)
(VT-3) (Vl-4) (
Vl-5) (VI-6) (VI-7)
(Vl-8) (VI-9)
(Vl-10) (VI-11) (
VI-12) (VI-13) (VI-1
4) (Vl-15) (Vl-
16) (VI-17) (Vl-18)
(VI-19) (VI-20)
(Vl-21) (Vl-22
) (VI-23) (VI-24)
(VI-25>(Vl-26)
(VI-27) (Vl-28) (V
l-29) (Vl-30)
(Vl-31) (VI-32) (V
I-33) (VI-34) Kuno
- (■-3) (SCH,C)IJHC82CI
(2CH2SO3H) 2H3 (■-16) 1lSCHzCHJCHzCII
zCONILz■ CI.

(■-17) HSCHzCHJHCHzCH
zOH(■-18) H3CH2CHJCH2
CII□OHC,H5 (■-19) 1IscH2cIhNcH2c
112N(CH3)2HI (■-20) HSCHgCHtNCtl□C
IIzOC41zCHzOC1hC0CH.

CHzN(CHzCIhSC)Iz)zCHzN(Cl
l□CIIzOCHz) z(■-10) (H
OCH2CH2)ZNCH2CH20CHICH2N(
C112CH20HhCHtN(CHzGHzSH)z (■-16) C1e (/!eC(le
C1θ CII□N (CHzCIhCNHz)z (■-28) C16C1te (■-32) (■-34) (■-35) ,, +6) 2 (17eH (■-37) (■-38) r r (■ -39) (■-40) (■-42) (■-43) (■-44) (CH35C)12CHZ) JCII zCHzOc
HzCHJ (CHgcHz SCH:l) 2(■-
46) (CH30C)lzGHz)J(CHz)30(C)1
2) 3N (CH, CH20CH3)! (■-47)
(H3CH1CH2)2N(CH2)sN(CH
2CIhSH)Z(■-48) The above compound is described, for example, in British Patent No. 1.138.842,
JP 52-20832, JP 53-28426, JP 53-95630, JP 53-104232, JP 53
-141632, 55-17123, 60-9
5540, U.S. Patent No. 3,232.936, U.S. Patent No. 3,7
No. 72゜020, No. 3,779,757, No. 3,89
It can be easily synthesized by the known technique described in No. 3,858 and the like.

The bleach accelerator of the present invention may be present when bleaching a silver image obtained by development. Bath prior to bleaching (pretreatment solution)
It is also preferable to add it to a silver halide color photographic material and incorporate it into the bleaching bath. In this case, a method may be used in which the silver halide color photographic material is preliminarily contained in the silver halide color photographic light-sensitive material at the time of manufacture, and is made to be present during processing in a bleaching bath.

These bleach accelerators of the present invention may be used alone or in combination.
More than one species may be used in combination, and the amount of the bleach accelerator added to the bleach solution is generally about 0.01 to 1 per IC of the processing solution.
Good results are obtained in the range of 0.00 g.

However, in general, if the amount added is too small, the effect of promoting bleaching will be small, and if the amount added is too large, precipitation may occur and contaminate the silver halide color photographic material being processed. 0 per 11.
05 to 50 g is preferable, and more preferably treatment liquid 11
It is 0.05 to 15 g per serving.

When adding the bleach accelerator of the present invention to a bleach bath, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and add it as necessary. Even if it is dissolved and added using an organic solvent such as methanol, ethanol, or acetone, the bleaching accelerating effect is not affected at all.

When contained in a multilayer silver halide color photographic light-sensitive material, the photographic constituent layer is preferably a silver halide emulsion layer and/or a layer adjacent thereto.

When the compound is used only in the photographic constituent layer and is not added to the processing solution, the amount added is 1 x 10-5 to 5 x 1
The range of 0-"mol/, f is preferable, and 1 x 10-4 to l
More preferred is Xl0-3 mol/d.

Bleach: 3* is an example of the treatment liquid having the above-mentioned bleaching ability.

As the bleaching agent used in the processing solution having bleaching ability, metal complex salts of organic acids are preferred.

As the metal ion constituting the complex salt, iron, copper, and cobalt are preferable, and ferric ion is particularly preferable.

The organic acid is preferably a polyvalent (preferably di- to tetravalent) carboxylic acid, and particularly preferred organic acids include aminopolycarboxylic acids represented by the following general formula ([1) or (rV)]. .

General formula CDI) HOOC/'z Z Ax C00H General formula (I
V) In each of the above general formulas, A, , A, , A3, A4. As and A6 are each substituted or unsubstituted hydrocarbon group, Z is a hydrocarbon group, oxygen atom, sulfur atom, or y N
A? (A? represents a hydrocarbon group or lower fatty acid carboxylic acid).

These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acid represented by the general formula (III) or (IV) or other aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidethylenediamine-N-(β-oxyethyl)-N,N
' , N'-Triacetic acid propylene diamine tetraacetic acid nitrotriacetic acid cyclohexane diamine tetraacetic acid iminodiacetic acid dihydroxyethylglycine ethyl ether diamine tetraacetic acid glycol ether diamine tetraacetic acid ethylene diamine tetraprobionic acid phenylene diamine tetraacetic acid ethylene diamine tetraacetic acid disodium salt ethylene diamine tetraacetic acid Tetra (trimethylammonium)
Salt ethylenediaminetetraacetic acid tetrasodium salt diethylenetriaminepentaacetic acid pentasodium salt ethylenediamine-N-(β-oxyethyl)-N,N
', N'-) diacetate sodium salt propylene diamine tetraacetic acid sodium salt nitrilotriacetic acid sodium salt cyclohexanediamine tetraacetic acid sodium salt The amount of the metal complex salt of the organic acid used is 5 to 400 g per 11 of the processing solution having bleaching ability. Preferably, especially 10-200
g is preferred.

Additives that can be used in the bleach solution include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, among others.

It is also known that pH buffering agents such as borates, acid salts, acetates, carbonates, and phosphates, aminopolycarboxylic acids or their salts, alkylamines, and polyethylene oxides are added to ordinary bleaching solutions. can be added as appropriate.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0.

In combination with the processing steps related to the color image forming method of the present invention, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material and the development treatment is performed using an activator solution.

Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process or a stabilizing process.) Color development process - Bleaching process Constant fixation process ・Pre-hardening process - Color development process Processing process - Stop fixing process - Washing process - Bleaching process Constant fixing process - Washing process - Post-hardening process/Color development process - Washing process - Supplementary color development process - Stop process - Bleaching Treatment process Constant fixation treatment process/Activator treatment process - Bleaching treatment process Constant fixation treatment process The treatment temperature is usually selected in the range of 10°C to 65°C,
The temperature may exceed 65°C. Preferably 25℃
Processed at ~45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylezine amine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as hydrochloric acid, sulfate, p-)luenesulfonate, sulfite, oxalate, benzenesulfonate, etc. I can do it.

These compounds are generally about 0.0% in color developer 11.
A concentration of 1 to 30 g, more preferably about 1 to 15 g per color developer 11 is used.

If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

In particular, the primary aromatic amine color developer used is N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compound examples include N-N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N.

N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3 −
methylaniline-p-)luenesulfone) and the like.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. You may. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
Organic phosphonic acids such as -hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gelcoric acid, 2-phosphonobutane 1. Examples include phosphonocarboxylic acids such as 2.4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount that can be dissolved at least 71 g/j, but for -i it is 70 to 250 g/j! Use with. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

In addition, the bleaching solution and/or fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, ? 1. Potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
Various pH buffering agents such as sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, Organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained.

The pH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5 to 10, preferably 5 to 9.5, most preferably 6 to 9.

The following margin silver halide emulsions include silver halide used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are harvested. The method for producing seed particles and the method for growing them may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, the halide ions and silver ions may be generated by sequentially and simultaneously adding the halide ions and silver ions while controlling the pH and PAR in the mixing pot, taking into consideration the critical growth rate of the silver halide crystals. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, 1,000-onythyl, 1,000-urea, etc. can be present during the growth of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( (including complex salts) selected from
Metal ions can be added to the inside of the particles and/or on the surface of the particles, and by placing them in an appropriate reducing atmosphere, they can be added to the inside of the particles and/or on the surface of the particles. can be given reduction-sensitized nuclei.

The silver halide emulsion may be freed from unnecessary soluble salts after the growth of silver halide grains has finished, or may be left in the silver halide emulsion. D 1s
Closure (hereinafter abbreviated as RD) can be carried out based on the method described in No. 1.7643, Section 2.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

Silver halide grains may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical or plate shapes. In the particles, any ratio of (1001 planes to (111) planes) can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used.

Silver halide emulsions may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. The term "monodisperse emulsion" as used herein refers to one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less. The grain size here follows the above definition. ) may be used alone or in combination.

Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. Namely, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as enhancing dyes. Aggravating pigments may be used alone, or two or more types may be used in combination. Even if the emulsion contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye, along with the sensitizing dye. good.

Exacerbating pigments include cyanine pigment, merocyanine pigment,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process, storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or before the silver halide emulsion is applied after chemical ripening. Compounds known in the art as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are A in section x■ of RD17643.
It is a compound described in .

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The emulsion layer of the photosensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are tetraequivalent, which requires reduction of four molecules of silver ions in order to form one molecule of dye, only two molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical enhancers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with the inhibitor attached directly to the coupling position and those with the inhibitor attached directly to the coupling position.
It is bonded to the coupling position via a valence group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( (referred to as timing DIR couplers and timing DIR compounds). Further, depending on the purpose, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3゜265, No. 506, No. 3.4
No. 08.194, No. 3,551,155, No. 3,
No. 582,322, No. 3.725,072, No. 3
．． 891,445, West German Patent No. 1.547.868, West German Application No. 2.219.917, West German Patent No. 2,261
, No. 361, No. 2゜414.006, British Patent No. 1
, 425,020, JP 51-10783, JP 47-26133, JP 4B-73147, JP 50-
No. 6341, No. 50-87650, No. 50-1233
No. 42, No. 50-130442, No. 51-21827
No. 51-102636, No. 52-82424,
It is described in No. 52-115219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-virazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat. No. 2,600,788, U.S. Pat.
No. 3,311゜476, No. 3,419,39
No. 1, No. 3.519.429, No. 3,558.3
No. 19, No. 3,582.322, No. 3,615.
No. 506, No. 3,834,908, No. 3,891
, 445 West German Patent No. 1,810,464, West German Patent Application (OLS) No. 2,408,665, OLS No. 2,41
No. 7,945, No. 2.418.959, No. 2.4
No. 24,467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 1973
-74027, 49-74028, 49-12
No. 9538, No. 50-60233, No. 50-1593
No. 36, No. 51-20826, No. 51-26541, No. 52-42121, No. 52-58922, No. 5
Examples include those described in Japanese Patent Application No. 3-55122 and Japanese Patent Application No. 110943/1983.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
No. 3,730, No. 2.474.293, No. 2.8
No. 01,171, No. 2,895.826, No. 3,
No. 476.563, No. 3,737,326, No. 3
．． No. 75'8,308, No. 3.893.044, JP-A-47-37425, No. 50-10135, No. 50-25228, No. 50-112038, No. 50-117422, Couplers described in Japanese Patent Application Laid-open No. 58-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate depending on the situation. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent if necessary, and use a stirrer, homogenizer, After emulsifying and dispersing using a dispersion means such as a colloid mill, flow jet mixer, or ultrasonic device.

It may be added to the desired hydrophilic colloid liquid.

A step of removing the low boiling point a solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. ) medium is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate-1, propyl acetate, butyl acetate, butanol, chloroform,
Examples include carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent whitening agents, etc. contain acid groups such as carboxylic acid or sulfonic acid, an alkaline aqueous solution is used. It can also be introduced into hydrophilic colloids as a hydrophilic colloid.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness.
A color anticapri agent can be used to prevent graininess from becoming noticeable.

The color anti-capri agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain an ultraviolet absorber to prevent capri from discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD 1
The compound is a compound described in Section XXI B to D of No. 7643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as fluorescent brighteners are described in RD 17643, item 7.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anine dyes, cyanine dyes, and azo dyes.

A capping agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together. Any capping agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the cloak agent is preferably 0.05μ to 10μ. The amount added is preferably 1 to 300 mg/ba.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 x■.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and improve photographic properties (development acceleration, hardening, aggravation, etc.). Various surfactants can be used for this purpose.

Supports used in the photosensitive material of the present invention include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene phthalate, polycarbonate, and polyamide.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface. It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which are so reactive that if added to the coating solution in advance, they will gel before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but basket coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and dalicidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all of the following examples, the amount added in the silver halide photographic light-sensitive material is expressed per unit unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

Multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) First layer; antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer; Intermediate layer (1,L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
A monodispersed emulsion (emulsion) consisting of AgBr1 containing 6 mol% of Agl and an average grain size (r) of 0.38 μm (emulsion...silver coating amount 1.8 g/+d for 11 moles of sensitizing dye I...ff) 6X10-' molar sensitizing dye...
... 1.0 x 10-' mol cyan coupler (C-1) per 1 mol of silver 0.06 mol colored cyan coupler (CC-1) per 1 mol of silver ...Silver 1
0.003 mol per mole DIR compound (D-1)...0.0015 mol per ml DIR compound 0.002 mol per mol silver 4th layer; High red sensitivity Silver halide emulsion layer (RH-1)
Monodispersed emulsion (emulsion ■) consisting of AgBr1 with an average grain size (r) of 0.15 μm and 7.0 mol% of Agl...Amount of silver coated: 1.3 g/rr
r sensitizing dye ■... 3 x 10-' mol cyan coupler (C-1 )...0.02 mol per 1 mol of silver Colored cyan coupler (CC-1)... 1 silver
0.0015 mol to mole DIR compound (D-2) Old..., 0.001 mol to 1 mole of silver 5th layer; Intermediate layer (1,L,) Same as 2nd layer, gelatin layer .

6th layer; low-temperature green-sensitive silver halide emulsion @ (GL-1
) Emulsion -■... Coated silver amount 1.5g/rr+
Sensitizing dye ■・・・・・・ 2.5×10-' mol sensitizing dye ■・・・ per 1 mole of silver
... 1.2 x 10-' moles per mole of silver Magenta coupler (M-1) ... o, oso per mole of silver
Mol colored magenta coupler (CM-1)...0.009 mol D per 1 mol of silver [R compound (D-1)...0.0010 mol per 1 mol of silver DIR compound (D-3) 0.0030 mol per mol of silver 7th layer; Highly sensitive green-sensitive silver halide emulsion layer (GH-1)
Emulsion - ■... Coated silver 11.4 g/i sensitizing dye ■... 1.5 x 10-' mol sensitizing dye for 1 mole of silver ■...
.... 1.0 x 10-' mole for 1 mole of i.magenta coupler (M-1)...0.0 for 1 mole of i.
20 mol Colored magenta coupler (CM-1)...0.002 mol per mol of silver DIR compound (D-3)...0.0010 mol per mol of silver 8 layers; Yellow Filter N (YC-1) Gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

9th layer; low-temperature blue-sensitive silver halide emulsion layer (BL-1)
Ag containing 5 mol% Agl with an average particle size of 0.48 μm
Monodispersed emulsion (emulsion ■) consisting of Br1... Silver coating amount 0.9 g/% Sensitizing dye ■... 1.3 x 10-' mole yellow coupler (EY-1) per mole of silver ...0.29 per mole of silver
Mole 1st ON: Highly sensitive blue-sensitive emulsion layer (B) I-1) Monodispersed emulsion consisting of AgBr1 with an average grain size of 0.8 μm and containing 115 mol% of 8g (emulsion ■)...Amount of silver coated: 0.5g/ m sensitizing dye■... ill 1.0X10-'Mole yellow coupler (Y-1)...0 per mole of silver
．． 08 mol DIR compound (D-2) 0.0015 mol per 1 mol 11th layer; 1st protective layer (Pro 1) Silver iodobromide (A
gl 1 mol% average particle size 0.07 μm) Silver coating amount 0.5
g/m Gelatin layer containing ultraviolet absorbers UV-1, tlV-2.

12th layer: Gelatin layer containing second protected N (Pro-2) polymethyl methacrylate particles (1.5 μm in diameter) and formalin scavenger (H5-1).

In addition to the above composition, each layer contains a gelatin hardener (H-0
) and surfactants were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide enhancing dye ■; anhydro 9-ethyl-3,3'-di(
3-sulfopropyl)-4,5,4'.

5'-dihenzothiatric luposyanine hydroxide ft? Anhydro 5,5°-diphenyl-9-ethyl-3,3'-di(3-sulfopropyl)
Oxacarbocyanine hydroxide sensitizing dye
3-sulfopropyl) -5,6,5',61-dibenzoxacarbocyanine hydroxide m color sensitive sv; anhydro 3,31-di(3-sulfopropyl) -4,5-benzo-5°-methoxythia Margin below cyanine V-1 H [IV-2 Next, Samples-2 to 6 were prepared in the same manner as Sample-1 except that the gelatin hardening agent H-0 was changed.

The gelatin hardening agent and amount used are shown in Table 1.

Table 1 ``gGel'' is the total amount of Ge attached in ld.
The amount of curing agent relative to the amount of curing agent was expressed as myH number.

A portion of each of the samples Nal to 6 thus prepared was subjected to flat exposure using white light, and then subjected to the following development treatment.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing 3 minutes 15 seconds fixing 6 minutes 30 seconds water? '/c Stabilized for 3 minutes 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37 .5 g enriched sodium
1.2g nitrilotriacetic acid・
Trisodium salt (monohydrate) 2.5 g
Potassium hydroxide 1.0 g Add water to make 1 liter.

[Bleach solution] (BL-1) Ethylenediaminetetraacetic acid iron ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 mf Add water to make 11, and use ammonia water. and adjust to an=6.0.

[Fixer]

Thiosulfate ammonia water 175. Og Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 1 liter, and adjust to pH=6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5 mj
! Konidafukus (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5me water to make 1 liter.

Further, Samples 1 to 6 were treated in the same manner except for the bleaching step time in the treatment step and the addition of a bleaching accelerator to the bleaching solution. The contents of the changes are shown in Table-2.

Table 2: What remains of the treated sample obtained in this way when measured by atomic absorption spectrometry? The amount of I was measured.

On the other hand, the obtained color image was irradiated with xenon light (100,000 lux) for one day using a xenon fade meter.

The color image density was measured before and after xenon light irradiation, and the fastness of the color image to light was evaluated.

The obtained results are shown in Table-3 and Table-4.

The numbers in the table remain! jjf (mg/drd>).

The values in the table are color image retention rate = (color image density after xenon light irradiation/color image density before xenon light irradiation) x 100
(%)showed that.

Table 39 As is clear from the results in Table 4, the present invention has excellent color image stability and furthermore has good desilvering properties.

Patent applicant: Roku Konishi Photo Industry Co., Ltd., agent Patent attorney Takatsuki Hirate Fu K Shufu Seisho (method) % formula % 1. Display of case 1986 Patent application No. 009802 2. Title of invention Color image Formation method 3, relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent -), I′″f″ 3゛°°“) +NthK PJ
5. Date of amendment order: March 25, 1986 6. Subject of amendment: Specification

Claims (1)

[Claims] A silver halide color photographic light-sensitive material containing a hardening agent that acts by activating carboxyl groups is subjected to imagewise exposure and, after color development, is subjected to bleaching treatment in a time of substantially 4 minutes and 15 seconds or less. Characteristic color image forming method.