JPS63144349A - Developing solution for silver halide photographic sensitive material having improved development accelerating - Google Patents

Abstract

PURPOSE:To suppress the increase of fog and to increase developing speed and effective sensitivity by adding a specified compd. to a developing soln. CONSTITUTION:A compd. represented by formula I is added to a developing soln. In the formula I, each of R1 and R2 is H atom, alkyl, alkoxy or aryl group, R1 and R2 may form a hetero ring contg. N, R1 or R2 and A may form a hetero ring contg. N, R3 is alkyl group, A is alkylene group and (n) is an integer of 0-6. The increase of fog, the deterioration of graininess and the increase of load on environmental pollution are suppressed, the problem of toxicity is solved and developing speed and effective sensitivity are increased.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a development method for silver halide photographic light-sensitive materials, and more particularly, to a color former containing a development accelerator having an improved development accelerating effect. Concerning developers and black and white developers.

[Background of the invention]

In the development process of silver halide photographic light-sensitive materials, it is desired to accelerate the development speed and increase the effective sensitivity of the light-sensitive material without deteriorating its graininess. Many development acceleration methods have been proposed for this purpose. Polyalkylene oxide compounds, such as U.S. Pat.
No. 31,832, No. 2.950,970, No. 3,
No. 291,607, No. 3,495°981, No. 3
, No. 671,247, No. 3,915,710, No. 1
Compounds described in No. 3,996,054, 1,000-onythyl compounds, such as U.S. Pat. No. 3,046,129, U.S. Pat. No. 3,201.242, U.S. Pat. No. .085, No. 1.129,08
The compounds described in No. 8, as well as ammonium, phosphonium or sulfonium type oniwam compounds and polyonium compounds are well known. however,
Furthermore, many of these development accelerators tend to increase fog in photographic images obtained by processing photographic light-sensitive materials, and also tend to coarsen graininess. Furthermore, some of them have the drawbacks of poor solubility in alkaline developing solutions and poor storage stability in developing solutions, and the reality is that very few of these are in practical use. V
Since thioether compound-based development accelerators have a very high stagnation effect, they should be used in cases where all of the silver halide present is developed, such as in color developing solutions for reversal color photographic light-sensitive materials. However, when added to a normal developer, fog increases significantly even in small amounts, making it impossible to obtain an effective increase in sensitivity, and in continuous processing, the concentration of this compound is kept constant. Because it is difficult to do so, it is rarely put into practical use at present.

Furthermore, benol alcohol and thiocyanate are known as development accelerators. However, these compounds have problems with environmental protection and safety.

[Purpose of the invention]

The object of the present invention is, firstly, to provide a developing reed for silver-roddenide photographic light-sensitive materials using a new development accelerator that causes less increase in fog, increases development speed, and effectively increases sensitivity. It is.

Second, continuous processing in which the degree of development accelerator fluctuates
Another object of the present invention is to provide a developer for silver halide photographic materials that can always provide low fog and a desired constant sensitivity.

The third object is to provide a developer for silver halide photographic materials that can increase effective sensitivity without deteriorating graininess.

Fourthly, for silver halide photographic light-sensitive materials with low environmental pollution, which can reduce fog without using development accelerators with high AM pollution such as benol alcohol, and can effectively increase sensitivity and obtain high comma. The purpose is to provide a developer.

Fifth, silver halide photographic sensitizers with low fog, increased sensitivity, and high comma can be obtained without the use of development accelerators such as thiocyanates that may decompose and release cyanide, and which are also low in risk. An object of the present invention is to provide a developer for materials.

[Structure of the invention]

This object of the present invention is achieved by a development guideline for a silver lodenide photographic light-sensitive material whose Vf characteristic is that it contains a compound represented by the following general formula [I].

General formula [I] [wherein R1 and R2 are each a hydrogen atom, an alkyl group,
It represents an alkoxy group, an aryl group, a nitrogen-containing heterocycle in which R3 and R2 may form a ring, or a nitrogen-containing heterocycle in which R1 or R2 and A may form a ring. R3 represents an alkyl group, A represents an alkylene group, and n represents an integer of 0 to 6. ] Hereinafter, the present invention will be explained in detail.

In the above general formula [I], the alkyl group represented by R1 and R2 preferably has 1 to 5 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc., and the alkoxy group is Preferably, it has 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, etc., and examples of the aryl group include a phenyl group, a 4-hydroxyphenyl group, a 4-sulfophenyl group, etc. Examples of the 2-nitrogen heterocycle formed by R and R2 include piperinone ring, morpholine ring, piperidine ring, 1
．． Examples include 4-thianone ring, and R1 or R2 and A
Examples of the nitrogen-containing ring formed by and include a piperidine ring. The alkyl group represented by R1 preferably has 1 to 8 carbon atoms, and includes, for example, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, etc. The alkylene group represented by 6A may be branched, Examples include methylene group, ethylene group, trimethylene group, 2-methyltrimethylene group, 2-methyltetramethylene group, propylene group, 1-methyltetramethylene group, and tetramethylene group.

Next, preferred specific representative examples of the compound represented by the general formula [I] will be shown.

Hereinafter, 100, 1, ノ (1-2) It2N (Cll□:hO-C, II
, (iso)(r −3) 82N(C)I2h
OC, +1゜(1-4) It2N(CIl□
hO-C1+3(1-5) If, N(CI+□
+5O−C2H5(r −6) II□N→CH
2hO-C,il.

(1-7) 112N-0-CJt.

(1-11) II□11-+cl12ho-C
21t.

(1 to 12) +12N-(CII2i0-C1
+1゜(I −13) If2N(CII2hO−
CJt(iso)'(1-14) II2) J-C
1,-0-C21t.

(1-15) )12N-CH2-0-C3)1゜(1-16) It2N-CIICII2-0-C
211°CH.

(+-17) 112N-0-C, II.

(1-20) 11. N-+Cl12hO-C21
t5 Among these compounds represented by general formula [I], (1-2), (I-4
>, (1-5), (+-7), (1-11L (1-1
5) and (+-18) are particularly preferably used.

These compounds are commercially available products (e.g. KOEI CHEM
ICAL CO, LTD, etc.).

The amount of the compound represented by the general formula CI) is 11 parts of the processing solution when added to a color developing solution for ordinary color negative film or color vapor') 0.01~
100 g, particularly preferably in the range of 0.1 to 50 g, and when added to a normal black and white developer or a black and white first developer in the case of reversal color film processing, the amount is 1) per processing 'e, 1r) 0
．． A range of 1 to 30 g is preferred. In addition, in a developer that develops all of the remaining silver halide, such as color development called the second development of reversal color processing, the range of 0.05 to 508 per 11 of the processing solution is preferable.

When applied to a black-and-white developer, the present invention can be applied to a normal black-and-white developer used in the development of black-and-white photographic light-sensitive materials, and a white-silver developer used in the development of silver halide color photographic light-sensitive materials for reversal. It can be applied to all known black and white developers.

These developing solutions can contain various additives that are generally added to black and white developing solutions. Typical additives include 1-phenyl-/t-methyl-4-
Hydroxymethyl-3-pyrazolone, 1-phenyl-3
- Developing agents such as pyrazolidone, metol, and hydroxide, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate, potassium bromide, and 2-methylbenzene. Inorganic or organic inhibitors such as Migzol, methylbenzothiazole, water softeners such as ami/polycarboxylic acids and organophosphates or polyphosphates, surface superstructures consisting of zero amounts of iodides or mercapto compounds. Examples include development inhibitors.

Preferred implementation of the invention! ! In this case, the developer contains at least one of the compounds represented by the following general formulas [II] to [-1].
An embodiment containing the following is preferred. General formula [I]
When the compound represented by formula (II)-(■) is used in combination with the compound represented by general formula (II)-(■), not only can the objects of the present invention be achieved to a higher degree, but also development in an automatic processor with a large air contact area is possible. Another effect is that it also improves the storage stability of the liquid.

General formula (I [) (II) In the formula, A represents a carboxylic acid group, a phosphoric acid group or a salt thereof, X represents a hydroxyl group or a salt thereof, B represents a halogen atom, a hydroxyl group, an alkyl group,
carboxylic acid group, phosphonic acid group, or hydroxyl group,
Represents a salt of a carboxylic acid group or a phosphonic acid group. r and l each represent 0.1 or 2, n represents an integer from 1 to 4, and the theory is °, / General formula CIII) 0tl12 Mushroom R, -C-OH 03H2 (III) In the formula, R, having a substituent having 1 to 5 carbon atoms,
represents an alkyl group or an amide group.

General formula (1’/) OH General formula [V] R.

(IV), (V) where R2, R3, R1, R5 and R6 are each a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, 10R1, -coor<, or represents a substituted or unsubstituted phenyl group.

Further, R7, R8, Rs and R+, respectively represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

Next, preferred representative examples of the compound according to the present invention represented by the general formula (II) will be listed.

(If, -4) (II-3) CII2POith 011zP03il.

(U-5) (II-6) (n-7) (II-81 (II-9) CH2PO,Na2 ([1-10) These compounds are described in U.S. Patent No. f53,632,637 and in the Journal of - It is synthesized by a general synthesis method as described in The American Chemical Society Vol. 89 (1967) p. 837.

Next, typical examples of the compound represented by the general formula (III) and preferably used in the present invention will be listed.

(III-1) 1-hydroxyethylidene-1,1-diphosphonic acid (Iff-2) 1-hydroxypropylidene-1,1-
Diphosphonic acid (I-3) 1,2-nohydroxyethane-1,1-nophosphonic acid (III-4) 1-hydroxybutane-1,1-diphosphonic acid (I-5) 1-hydroxy-2-carboxy- Ethane
1,1-nosulfonic acid (I[l-6) 1-amino-ethylidene-1,1-diphosphonic acid Specific exemplary compounds represented by general formulas (IV) and (V) include 1,2-hydroxybenzene , 4-inpropyl-1,2-hydroxybenzene, 1,2-dihydroxybenzene-3,5-nosulfonef'll, 1.2-
dihydroxybenzene-3,4,5-trisulfonic acid,
1,2-dihydroxybenzene-3,5,6-)disulfonic acid, 1.2.3-trihydroxybenzene, 1,2
．． 3-) dihydroxybenzene-5-carboxylic acid, 1.
2.3-) Lihydroxybenzene-5-carboxymethyl ester, 1.2.3-) Lihydroxybenzene-5
-carboxy-1-propyl ester, 5-t-butyl-1,2゜3-trihydroxybenzene, 2,3-nohydro-a xynaphthalene-6-sulfonic acid, 2,3.8-)
Examples include dihydroxynaphthalene-6-sulfonic acid, but are not limited thereto. Among the above compounds, particularly preferably used compounds include:
1,2-dihydroxybenzene-3゜5-disulfonic acid and its sodium and potassium salts, exemplified compounds (III-1), (II-2) and (II-10) are mentioned, and particularly preferred are , 1,2-nohydro a-xybenzene-3°5-disulfonic acid and its salts (sodium salt, potassium salt).

The compounds of the general formulas (n) to [V] are the developer 1 of the present invention.
It is preferably used in a range of 0.01 to ]Og, more preferably 0.03 to 3g per unit.

General formula (Vl) N-@Afrrj BヰH)3 R'R''R'' Here, R゛, R'' and R゛゛ each represent a hydrogen atom, a hydroxyl group or a lower alkyl group, and l is 0. Represents 1 or 2. [1 and So each represent an integer from θ to 10.

Next, preferred tax table specific examples of the compound represented by the general formula (Vr) will be given.

(■-1) Nf (J12CH2011).

('/l-2) Nmo (C112CIl□0hH)
)(Vl-3) 1(C11,C)lcI+,0
too)! ].

■ H (■-4)　　　　　N+CIl□CFICLOIshun.

H (■-5) N-+C112C112CII201
1):+(Vl -6) N-+CH□CH2C1
hCII20H)i(Vl -7) N-+C11
□CIb0C11, CI! □C) 120! +) (VI
-8) N-(CHCH3ell.O1+).

Among the compounds represented by the above general formula (Vl), compounds particularly preferably used in the present invention include (VI-1
), (Vl-2) and (VI-5).

It is preferable to use these compounds represented by the general formula (VT) in an amount of 0.3 to 50 g per development g. plays especially well.

When the present invention is applied to a color developing solution, the object of the present invention can be effectively achieved by incorporating a combination of an aminocarboxylic acid compound or an amine-7phosphonic acid compound into the developing solution, and furthermore, the purpose of the present invention can be effectively achieved. Crystal precipitation adhering to the inner wall of the tank is also improved.

Therefore, in the present invention, it is preferable to add an amine/carboxylic acid compound or an aminophosphonic acid compound. The aminocarboxylic acid-based compound or the amine-7phosphonic acid-based compound is an amino/compound having at least two or more carboxylic acid groups and an amino/compound having at least two or more phosphonic acid groups, respectively, and preferably the following: General formula [■
] and [■].

General formula [■] General formula [■] In the formula, E is a substituted or unsubstituted fullkylene group, cycloalkylene group, phenylene W, -R,,OR,,0R1
3- or -R13ZR13-, Z is >NR,,
8 or〉N-^6, R3 to RI3 represent a substituted or unsubstituted fullkylene group, ^2 to ^6 each represent a hydrogen atom, -〇]], -C00M or -PO, M2,
In the general formula [■], at least two of ^2 to ^6 are -
COOM or -PO3M2, and at least two of ^2 to ^ in the general formula [■] are -COOI4 or -PO,M2.

M represents a hydrogen atom or an alkali metal atom.

Next, preferred specific examples of the compounds represented by these general formulas [■] and [-l] are listed below.

(Exemplary compounds of the compound represented by the general formula [■]) (■-
1) Ethylenediaminetetraacetic acid (■-2) Noethylenetriaminebentaacetic acid (■-3) Ethylenediamine-N-(β-hydroxyethyl)-N, N', N'
-) Triacetic acid (■-4) Propylenediaminetetraacetic acid (■-5) Triethylenetetraminehexaacetic acid (■-
6) Cyclohexanediaminetetraacetic acid (■-7) 1
．． 2-Noaminopropanetetraacetic acid (■-8) 1.3-
Noaminopropan-2-ol-tetraacetic acid (■-9) Ethyl ethernoamine titraacetic acid (■-
10) Glycol ethernoamine tetraacetic acid (■-11) Ethylenenoamine tetraprobionic acid (■-12) 7-enylenenoamine tetraacetic acid (general formula [
■ Exemplary compound of the compound represented by) (■ -1)
Nitrilotriacetic acid (■-2) Imi7noacetic acid (■-3) Hydroxyethylimi7noacetic acid (■-4) Nitrilotripropionic acid (■-5) Nitrilotrimethylenephosphonic acid (■-6
) Imi7nomethylenephosphonic acid (■-7) Hydroxyethylimi/di/ethylenephosphonic acid (■-8) Nitrilotriacetic acid Tristrium salt These aminocarboxylic acid compounds and aminophosphonic acid Among the series compounds, compounds (■-1), (■22), (■-5), (
■-8), (■-1), (■-3) and (■-5). These compounds represented by formulas (II) to [■] may optionally be used as salts of sodium, potassium, lithium, etc.

The amount of these amine/carboxylic acid compounds and amine-7 phosphonic acid compounds preferably used in the present invention is preferably in the range of 0.1 to 20 g per tL of color development.
Particularly from the viewpoint of the purpose of the present invention, a range of 0.3 to 5 g is particularly preferably used.

A p-phenylenediamine color developing agent is used in the color developing solution of the present invention, and since it is more stable than a free state, it is generally used in the form of a salt, such as a hydrochloride or a sulfate. Further, the 9-7 elendiamine color developing agent is generally about 0.5 to about 30 g per color developer 11.
Use at a concentration of

In the present invention, a particularly useful p-phenylenediamine color developing agent is used because it satisfactorily achieves the object of the present invention and also improves the bleaching stain that occurs during bleach-fixing or bleaching treatment immediately after color development. It is an aromatic primary amine color developer having an amide group having at least one water-soluble group, and particularly preferably a compound represented by the following general formula (ff).

General formula (IX) Ni+2 In the formula, R2 represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group is a linear or branched carbon atom having 1 to 5 carbon atoms.
represents an alkyl group, which may have a substituent, R8
, and RIG represent a hydrogen atom, an alkyl group, or an aryl group, but these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. At least one of RI5 and R16 is an alkyl group substituted with a water group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amide group, a sulfonamido group, or -H
CH2fO)-R+? It is. This alkyl group may further carry a substituted E' group.

In addition, RI7 represents a hydrogen atom or an alkyl group, and this alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and and r each represent an integer of 1 to 5.

Next, typical examples of the compound represented by the above general formula CIX will be listed, but the invention is not limited thereto.

(IX-1) (II-2) (IX-3) Nll□ (TX-4) (IX-6> (IM-7) Nl(.

(IN-8) (rX-9) (IK-10) (L¥-11) H2 (IY-12) '(IX-13) (IM-14) (ff-15) H2 (iX-i6) Nl+ □ These general formulas [! The p-phenylenediamine conductor represented by , benzene disulfonate, etc. can be used.

In the present invention, 1 represented by the general formula [IK]
) - Among the phenylenediamine derivatives, R+5 and zo/
Or R16 is 1++ci! □-)HO)7R, (t, r
and R17 have the same meaning as above. ), the effects of the present invention are particularly well achieved.

It is said that when triadylstilbene-based fluorescence enhancing self-sharpening is used in the color developing solution of the present invention, the effects of the present invention are better exhibited, and the tar characteristics of the light-enhancing solution during storage are further improved. ? It is preferably used in the present invention because it also exhibits a JIJ effect.

The triazylstilbene fluorescent brightener used as a preferred embodiment of the present invention is preferably one represented by the following general formula (X).

General formula (X) In the formula, X, X2, Y, and Y2 are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholif group, an alkoxy group (e.g., methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (e.g. 7eth/oxy, p-sulfo7ethyl7oxy, etc.), alkyl groups (e.g. methyl, ethyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, etc.), ami7 groups, alkylamino7 groups (e.g. methylamino) , ethylami/, propylami/, dimethylami7,
cyclohexylamine/, β-hydroquinethylamino,
) (β-hydroxyethyl)amino/, β-sulfoethylamine 7, N-(β-sulfoethyl)-N'-methylamino 7, N-(β-hydroxyethyl-N'-methylamino, etc.), arylamine 7 groups (For example, Anili/, 0-1l
-1p-sulfoanily7.0-1W-1p-chloro7nilino, 0-1m-19-)ruinono, 0-1 first, p-
6 representing carboxyanili/, 0-1m% p-hydroxyanilino, sulfonaphthylamino, o-1m-19-aminoanili/, 0-1-1p-7, etc.)
M represents a hydrogen atom, potassium atom, sodium atom or lithium atom.

Specifically, the following compounds may be mentioned, but the invention is not limited thereto.

Hereinafter, the margin ゝ・ノ″
It can be synthesized by the usual method described on page 8 (Published in August 2013).

These triadylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per 11 of the color developing solution of the present invention.

The color developing solution according to the present invention contains alkaline compounds commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, and borax. It can also contain various additives such as benol alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citranonic acid, and preservatives such as hydroxylamine or sulfites. It's okay.

The black and white developer It [and the pit of the V color developer is 8.5]
It can be used in the range of 14.0 to 14.0, and preferably 9.0 to 13.0. The p++ of the pretreatment liquid is 0.3 to 14
However, since the pretreatment liquid I) has a desired p++ power i depending on the compound used, it is necessary to find the optimum pH for each by experiment. There is no particular limitation on the processing temperature, but it is generally 20'C.
Processing is carried out at ~60°C, preferably between 30°C and 52°C.

As mentioned above, the present invention can be applied to a color developing solution and a black and white developing solution. Materials included.

The silver halide emulsion contained in these light-sensitive materials may be any of silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, and may be subjected to physical ripening and, if necessary, a sulfur compound. , chemical ripening with gold compounds, etc.

Silver halide emulsions may contain spectral sensitizers (cyanine dyes, 70 cyanine dyes, etc.) and stabilizers (4-hydroxy-6-methyl-1,3,3a, 70 cyanine dyes, etc.) as necessary during the manufacturing process or immediately before coating. hardening agents (e.g. formalin, glyoxal, 2-hydroxy-4,6-fuchloro-3-triazine, mufuchloroic acid, etc.), coating aids (e.g. saponin, Lauryl sulfate, polyethylene oxide, etc.), color couplers, polymer latex, etc. can be added.

Development processing using the developer according to the present invention includes black-and-white negative film, black-and-white reversal film, printing film, χ-ray film, black-and-white aviation film, and black-and-white film. -*ff film, color reversal film color paper, color box film, color reversal film for movies, TV1
f! It can be applied to any processing of general silver halide color photographic materials such as color reversal films.

〔Example〕

The present invention will be described in detail below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support whose surface was coated with a polyethylene layer containing titanium oxide in anatase form as a white pigment was pretreated by corona discharge, and then the following layers were sequentially applied to produce color photographic paper. Had made.

! 11th layer: A silver chlorobromide photographic emulsion containing 15 mol% silver chloride was mixed with 7-hydro 5-methyl-5'-7 toxy 31
It was optically sensitized with 3'-no(3-sulfopropyl)selenocyanine hydroxide, and this was supplemented with 2,5-no-7-butylhydroquinone and α-( as a yellow coupler.
4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-tri7zolidyl)]-]α-bivalyl-2-chloro-5-γ-(2,4-not-t-amylphenoxy)butyl 7mide] to which the acetanilide protect dispersion was added. The coating was applied so that the weight was 28 g/a''.

The second layer is 2-(2'-hydroxy-3',5'-G-t-7'tylphenyl)penztriazole, 2-(
2'H)'Waxy5'-t-butylphenyl)penztriazole, 2-(2-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chloropenztriazole and 2-(2'-hydroquine) A gelatin solution to which a protect dispersion containing a mixture of -3',5'-butylphenyl)-5-chlorobenttriazor was added was applied as an intermediate layer.

Third layer: A silver chlorobromide photographic emulsion containing 25 mol% of silver chloride was added to
Optically sensitized with 3,3'-no(3-sulfopropyl)oxacarbocyanine hydroxide, followed by 2,5-
Di-t-butylhydroquinone, 2,2,4-trimethyl-6-lacryloxy-7-t-octylcoumarone and 1-(2,4.6-) as magenta coupler
+7 90 Lofenyl)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone protected dispersion was added to silver 0.28.

/m2.

Fourth layer: The same liquid as the second layer was applied as an intermediate layer.

5th layer = silver chlorobromide photographic emulsion containing 35 mol% silver chloride -Thiazolinone-2-ylidenecomethyl-3-(3-
Optical sensitization using benzoxacillium hydroxide (sulfopropyl) followed by 2,5-not-t-butylhydroquinone and 2 as cyan coupler.

4-dichloro-3-methyl-6-[γ-(2,4-noamylphenoxy)butylamide)"+7 eth/-el of protect dispersion was added to the coating to give a silver density of 0,214/m2. Established.

6th layer: A gelatin solution was applied as a protective layer.

The silver halide photographic emulsions used in each of the above-mentioned photosensitive layers were prepared by the method described in Japanese Patent Publication No. 46-7772, chemically sensitized with sodium thiosulfate, and 4-hydroxy-6 as a stabilizer. -Methyl-1.

3,3a,7-chitrazaindene was added. In addition, saponin as a coating aid and bis(vinylsulfonylmethyl) ether as a hardening agent were added to the coating solution for all layers.

The color photographic paper made as described above is photo-PA! according to the sensitometry method. The sample was exposed to light and then treated with a treatment liquid having the following treatment steps and treatment liquid composition.

Processing process Color development 33℃ 3 minutes 30 seconds Bleach fixing 33℃ 1 minute 30 seconds Washing with water
30℃ 3 division drying
75-85℃ meter 8 minutes Color developer composition Hydroxylamine sulfate 3g Sodium hexametaphosphate 1.5g Exemplary compound (IX
-1) Sulfate 5g potassium carbonate
30 g lithium sulfate
1.0g potassium sulfite (50% solution)
4ml! central potassium
o, eg potassium chloride
0.5g potassium hydroxide 2.
Add 5g of water to 11 (pH:
10,20) i self-fixer composition ethylenenoamine-tetra vinegar 1' [l 4,0
gAmmonium sulfite (50% solution) 30+
*j! Ammonium thiosulfate (7 oz?8 liquid)
140+nl ammonia water (2896 solution)
30 ml ethylenenoamine-iron(III) tetraacetate
Add 70g water
11 (, II: 6.8) Regarding the addition of a development accelerator to the color developing solution, follow the instructions in 1 to 9 below.
It was classified as a type.

Note that the amount added is per color development filN.

1. D. No development accelerator including the compound represented by general formula [I].

2: Bennol alcohol, which is a known development accelerator as a comparative compound. 3: 5.0 g of exemplified compound (1-5) was added.

4: (1-4) '15:
(1-11) 6: (1-2) #7: (1-7) 8: o (115) 〃9:
(1-18) The obtained photographic properties are shown in Table 16! ! As can be seen from the results in Table I't1, the developer without the addition of a development accelerator has low fog, but the maximum density is extremely low, and the decomposition is also low, meaning that no effective development acceleration effect can be obtained. I know that I can't. Furthermore, developer (2) containing benol alcohol, a known development accelerator, has undesirable characteristics such as slightly high fog and low maximum density, making it difficult to obtain effective sensitivity. In comparison, development a(3) to 9) containing the compound of the present invention exhibits desirable development accelerating effects such as a high maximum density, very low fog, and high opacity.

Example 2 1-Hydroxy-2-11-γ-(2
, 4-note t-7 mil 7/xybutyl) 7 toamide was emulsified and mixed, and 1 green-sensitive silver iodobromide emulsion (containing 5,5 molta 6 silver iodide) was added as a magenta coupler, 1-(2
'． 4',6'-trichlorophenyl)-3-
(2'-chloro3'-(2'',4''-no-L-amyl7e/xyacetamide)anili/]-5-
Hirazolone was emulsified and mixed, and a-benzoyl-[2-chloro-5-α-(dodecyloxycarbonyl)] was added as a yellow coupler to a four-sensitive silver iodobromide emulsion (containing 6.5 mol% silver iodide). A reversal color paper photographic light-sensitive material for photographing was prepared by emulsifying and diconsolidating probyloxycarponinyl]acedoanilide and sequentially coating the mixture on Lennon coated paper.

For emulsification of each coupler, butyl 7-talate and triphrenol phosphate were used as coupler silicate, sorbitan monolaurate and sodium dodecylbenzenesulfonate were used as emulsifiers, and in addition, 1-(p-/nyl-7
Sodium ethylene/oxytrioxyethylene)butane-4-sulfonate and lauric acid ester of sucrose were added as coating aids. Furthermore, a filter layer of yellow Floyd silver containing potassium iodide was placed between the green-sensitive emulsion layer and the blue-sensitive emulsion layer in the sample, and a filter layer of yellow Floyd silver containing potassium iodide was placed between the green-sensitive emulsion layer and the red-sensitive emulsion layer.
An intermediate layer made of gelatin containing dispersed 7-milhydroquinone was provided, and a protective layer mainly made of gelatin was provided on the blue-sensitive emulsion layer.

This silver halide color photographic light-sensitive material is
It was first exposed according to the IJ-method, and then processed in the following processing steps using a processing solution with the following formulation (at 38°C).

Processing step 1st development (black and white development) 38℃ Stop for 2 minutes Bath 38℃ 30 seconds Wash with water 38℃
30 sand color development 38”0
2 minutes wash 3
8℃ 30 seconds bleach-fix solution 38
℃ Wash with water for 3 minutes
Stable bath at 38°C for 2 minutes
38°C, 30 seconds, 11 minutes First developer (black and white development) Composition Tetrapolyphosphoric acid 3.0 Sodium bisulfite 5.0 g 1-phenyl-3-pyrazolidone 0.7 g Anhydrous sodium sulfite 60.0° Hydroquinone
8.0g Sodium carbonate monohydrate 53.0g Potassium bromide
3.0g potassium iodide (0.1%>
44. Om! ! Dinitylene Glyfur
20. Oa+N polyethylene glycol#
400 5,0゜Caustic soda
Add 2.8g water
1r (pH: 9,59) Stop solution composition Sodium acetate 30 g Glacial acetic acid 8. ．． Add 1 water and 1! (pH: 4,0) Color developer (■ Synthetic benol alcohol 12 ml Sodium tetrapolyphosphate 3.0 g Anhydrous sodium sulfite 7.5 g Potassium carbonate
32. Ogα-phosphono-1,
2,4-tricarboxylic acid 2g Potassium bromide 0.3g Potassium iodide (0
,1%) 90. Om (caustic soda
2.3g 3-Methyl-4-7minor N-ethyl-N-β-methanesulfonamide V ethylaniline 11. Og Cogunku R^-10.2g Ethylene glycol Add 20ml water II<pH: 10.7
5) Bleach-fix solution composition Bisthiourea 3.0g Ammonium bromide 50. og ammonia water (28%) 30.0m (ethylenenoaminetetraacetic acid iron ammonium monohydrate 45g ethylenediaminetetraacetic acid disodium dihydrate 2g anhydrous sodium sulfite 10g ammonium thiosulfate), 60.0+n12 glacial acetic acid
6.9a1 Add water
1p (pH: 6.4) Stabilizing solution composition Succinic acid sorg 20 g Fluorescent brightener 1.5R Add water 11 (pH: 4.0) For development processing, use the following for black and white developer. A knife was added and comparative development was performed.

10, no development accelerator was added to the black and white developer 11, including the compound represented by the general formula [I] of the present invention.

11. Comparative compound (known development accelerator) KSCN
2.0g12, exemplified compound (
1-4) 2.0g13, Exemplary Compound (1-5) 2.0g14, Exemplary Compound (1-11) 2. The photographic properties obtained are shown in the second barley.

Table 2 As shown in Table 2, when processed with a developer such as developer 10 that does not contain any developing agent, the fog is very high and the gradient (gamma) is low and effective. It can be seen that it is not possible to obtain the desired sensitivity. In addition, when processing with a developer containing a known thiocyanate as a development accelerator, such as developer 11,
It is true that the development promotion effect is recognized, but the fog is also high, and D
+n a x is also low. Also, the gamma was not satisfactory. However, the developing solutions 12 to 14 containing the compounds of the present invention are ideal in that they have a remarkable development accelerating effect, low fog, and high yield (maximum), and also show desirable values for I understand. It was also found that the granularity of the colored dye after processing was superior to that of black and white developers 10 and 11. There was also no problem with the dye storage property of the coloring dye.

Example 3 Sodium hexametaphosphate in the color developer used in Example 1 was exemplified by compounds (■-1) and (■-2).

(■-8), (■-1), (■-3) and (~1-5)
A color developing solution was prepared using a modified solution and a solution with sodium hexametaphosphate removed, and stored in a glass narrow-mouth bottle with an opening ratio of 10c+a2/1 (the contact area with air for 11 of the developer was 100 m2). )
After storage at room temperature for 20 days, the state of precipitation of crystals on the inner wall of the narrow-necked glass bottle was visually observed.

Further, experiments similar to those in Example 1 were conducted for each of the above color developing solutions.

As a result, regarding photographic properties, when using the compound represented by the general formula [■] or [■], Dmax m
jib high concentration) further increased by 0.03 to 0.04, showing a more favorable effect. Furthermore, the state of adhesion of crystals on the inner glass wall after 20 days of storage is determined by the general formula [■] or [
In the samples to which the compound shown in (2) was added, almost no crystal adhesion was observed, but in the samples to which no compound was added or to the samples using sodium hexametaphosphate, needle-shaped crystals were generated on the inner glass wall and at the developer interface.

Example 4 In fact, 1.5 g/N of sodium hexametaphosphate in the color developer (IjltL) used in Example 1 was added to the illustrative compound (11-2
), ([[-10), (III-1), sodium 1,2-nohydroxybenzene-3,5-disulfonate, sodium 1,2-nohydroxybenzene-3,5,6-)lysulfonate, (Vl-1), (■-2) each 0
．． The developer solution changed to 3 g/l and the developer solution 1e without sodium mexametaphosphate were stored open for one week in a glass beaker with an aperture ratio of 100 cal and 127 e. Using the developer solution after storage, the pond was prepared as in Example 1. A similar experiment was conducted.

As a result, when using the compounds represented by the above general formulas [ll] to (VI), the minimum concentration (Dnin) did not change before and after storage, but when using sodium hexametaphosphate and the compounds, The items excluded are 0 for each
．． 02-0.03 minimum concentration increased.

Other photographic properties were almost the same as in Example 1.

Example 5 The color developing agent in the color developer used in Example 1, exemplified compound NX-1), was mixed with (IM-2) sulfate and! J(tX-
4) A similar experiment was conducted by changing p-toluenesulfonate to 'Ri-, and then using the following developing agents (D-1) sulfate and (D,2) sulfate, respectively. however,
The amount added was the same number of moles as (ff-1).

(o-Jo (D-2) As a result,
When using the compound represented by the general formula (IM) according to the present invention, stain does not occur in the bleach-fixing process, but the other compounds (D-1) and (D-2') have 0.0
Magenta tint of about 2 to 0.04 occurred. Other photographic properties were almost the same as in Example 1.

Example 6 Exemplary compound (X-4) was added to the color developer used in Example 1.
(X -10), (X -13> and (X -14) were added at 28/l each, and an experiment was conducted in the same manner as in Example 1. As a result, the minimum concentration of yellow was 0. 0
It decreased by about 1. Other photographic properties were the same as in Example 1. In addition, for 2 weeks with an opening ratio of 100cm + 2/I,
When we observed the tar generation status after storage at room temperature, we found that the product using the compound represented by the general formula [X] was good with almost no tar generation, but the unused product did not generate much tar. Generation of tar was observed on the surface.

〔Effect of the invention〕

The developer according to the present invention increases fog, worsens graininess,
The increase in pollution load and the problem of toxicity will be reduced or
and has high development speed and effective sensitivity.

Claims (1)

[Scope of Claims] A developer for silver halide photographic materials, characterized by containing a compound represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. ring, or R_1 or R
_2 and A represent a nitrogen-containing heterocycle which may form a ring. R_3 represents an alkyl group, A represents an alkylene group,
n represents an integer of 0 to 6. ]