JPS58205150A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness of a color image, its reproducibility, etc., by adding to a color photographic sensitive material a specified coupler capable of releasing a development inhibitor on reacting with the oxidation product of a developing agent. CONSTITUTION:The objective silver halide color photographic sensitive material is obtained by adding to a silver halide emulsion layer as least one of couplers represented by formulae I -IV in which A is a coupler residue; R1 is H, halogen, alkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, or the like; R2 is H, alkyl, alkenyl, aralkyl, cycloalkyl, or the like; Z is benzotriazole or a hetero ring having thio; L is a divalent group having a bond released in a color developing bath; Y is optionally substd. 1-10C alkyl or alkenyl or cycloalkyl, or the like; k is 0 or 1; n, m is 1 or 2; l is 1 or 2.

Description

Detailed Description of the Invention Yumei Moto is a photographic coupler, JJia, which is an ILT kite that can react with the oxidation products of the boundary culvert and release the boundary 1# inhibitor.
Coupler (iJevelopment Lnhibi
This invention relates to a cuff-released photosensitive material containing torReleasing C'upler)2.

Silver halide color photographic material Nk is used to create color dust images.
The oxidized aromatic-grade amine type Kafu image agent and the coupler react to form indophenol.

Indaniline, indamine, azomethane/1phenocypsin, and phenazine are used to produce the pigments that are present, resulting in the formation of no pigment.

In this method, the subtractive color method is usually used for the color change, and the halogenated coffee shavings are selectively exposed to light, green, and red, resulting in a yellow color.

Magenta and cyan color image forming agents are used. To form a yellow color image, one example is 7 fluacetanilide, or a dibensoylmethane thread coupler, and to form a magenta color image, bilanron is mainly used. and lanlohenzimidazole, cyanoacetophenone or Q11ndazolone couplers are used, and phenolic thread couplers such as phenol or 2L-11 phthols are mainly used to form cyan images.

Normally, color photographic light-sensitive materials are roughly divided into two types: the outer type method, in which the coupler is placed in a box, and the inner type method, in which each photosensitive layer of the coupler JT light-sensitive material contains an independent function. be done. In the latter case, one dye (1k M
The resulting coupler was added to the halogenated steel emulsion. Couplers that are weighted in the emulsion must be non-diffusive in the emulsion binder matrix.

Now, when developing, it corresponds to 11 degrees of both types.
It is known that a compound r releasing an inhibitor τ can be included in the photographic S& source material. This compound is generally ri
Reacts with the oxidation products of the coloring agent.

A representative example of the types that release dust 1-inhibitors is the so-called L)lK coupler, in which a group is introduced into the active position of the coupler that has the ability to create a boundary effect when released from the active position. It has been known. Lllf(, Turnip.

The coloring agent combines with the oxidation products of the light coloring agent to form a pigment and releases a borderline inhibitor.

As a υlR coupler, U.S. Patent No. 3. λ27゜! ! No. J, 70/, 71.39f, 3,6/s,
rot No. 3,617. Compounds described in λri No. 1, etc., and these compounds [further improved versions published in the U.S.
The compound described in No. 3 is known.

The D1 coupler is used for purposes such as improving the sharpness of the color due to the edge effect and improving the re-positioning due to the 1N force, as in the case of the upper rudder.

Although the known IJLR couplers have a certain degree of performance τ, it has been desired to further improve the performance. In particular, when the #L dan suppressant released during color development with Koyo's 1JIR coupler diffuses into the processing solution of Kansei Materials Co., Ltd., it accumulates in the processing solution.

The problem was that the treatment solution exhibited an inhibitory effect τ.

In the method of continuously processing Taisetsu photosensitive materials, that is, the processing method used commercially, it is important to always obtain a constant gradation. I had to deal with contamination of the processing solution due to a lot of trouble.

I tried to solve this problem, or tried some measures like a immersion chamber in the past, but all of them had their drawbacks.
Not traced. For example, the convenient t' of the aia coupler
The way to limit the time is to replace the current one with a new one.

Orui decides that it is a new method to acquire the particle milk cup f-, the photosensitive material -Cy&B, the Kangen layer work 9Rtk, and the term 1y side J market cutting τ. These methods reduce the photographic properties of the μDIR coupler, and also have the disadvantages of reducing the photographic properties of the μDIR coupler.

The υlK coupler of the present invention is an improvement on the root of the above-mentioned problems. 1, that is.

The purpose of Akira Motoya is to provide a material that has been developed to facilitate the use of couplers in the water-VL site 111 and to improve the color image quality.

The second object of the present invention is to use a new one coupler, and the third object of the present invention is to use a new one coupler. If you use it, the color developing solution 1 will be contaminated.

Surikoto vL-Mel provides a color photographic material that has been subjected to a processing method that continuously reuses a color developing solution.

These objects of the present invention ζ, -t, general formula (Il sword) et al.
The coupler paste shown in [2] also contains at least one halogenated complex emulsion containing t% mold, and a color photographic effect was achieved using the material.

- Formula (1) General formula (11) General formula [臘] General formula (iVJ In the above formula [1) = -b (~], Aid turn 7- residue w'1 ip1... Above formula (1) zh
(fV) is bonded to the # elementary atom of A at the coupling position γ.

R is Mizumiko, Haroken Mako, Aryaru group.

Alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylfumino group, ureido group, 77-group, nitro group, sulfonami F group, sulfamoyl group, carbamoyl group.

Aryl group, carpho group, sulfo group, cycloalkyl M, flucansulfonyl group, arylsulfonyl group,
The symbol represents a fluor group.

2 is a hydrogen atom, an alkyl group, or an alkenyl group.

Represents an aralkyl group, a cycloalkyl group, or an aryl group.

Z is a hensitriazole group (/, , + is also connected to A via a linking moiety at the 3-position); t sign) r expression.

Ld ester bond, wonton ii 5 units, etc. Coloring #1. +
e Represents a divalent group containing 2 bonds that can be easily dispersed.

Is Y carbon? Substituted alkyl groups from i/ to io (6m groups include halogen groups, cyano groups, alkanesulfunyl groups,
Nitro group, sulfamoyl group, alcoquine sulfonyl group, carbamoyl group, aryloxycarbamoyl group, alcoquine group + urethane group, anru group, acylamino group, acyluoquine group.

N-alkylcarbamoyl group, N-alkylsulfamoyl-attached or heterocyclic group (containing a quadrant atom, oxygen atom, ioc atom r as a hetero extension member or a monocyclic or condensed ring of 6jj rings, for example, a pyridyl group, quinolyl group, furyl group, imidazolyl, benzothiazolyl group, birazolylokipzolyl group), homogeneous xt
b/gara IO alkenyl group, 7-chloroalkenyl group, cycloalkyl group (these alkenyl groups.

The cycloalkenyl group and the cycloalkyl group may further have a substituent, and the substituents mentioned above for the alkyl group are selected.

Heterocyclic group (selected from the Bedero ring L9 in which 11 of the alkyl groups mentioned above is a substituent) or an unsubstituted aryl group with carbon ρ6 and 10 (as a substituent e-alkyl group or N is an alkyl group) (Selected from the substituents mentioned above.) [Expression.

□ K represents O or /Q.

n:i;'jhnl represents an integer τ of -f:g/or λ.

When tf'iix or mttiv expression t is 2, approximately 1 is formed into a fused ring and the compound represented by the general formula (1) is oxidized to form a colored dust. The coupling with +lk and the leaving group released serve as precursors to antipalpitation agents. This dust monk suppresses the cup precursor to the sun and the furnace#
1. The wound inhibitor eZ÷L-Y)n'2 is released. child·/
The inhibitor diffuses into the emulsion layer and some of it flows out into the color developing solution. "Z-(-L-'r)n that leaked into the processing solution is L
In other words, Z and Y are cleaved, and a compound with a water-soluble group attached to Z and having low development inhibiting properties remains in the developer. During the treatment, compounds with anti-social behavior are not accumulated and can be reused repeatedly, and the light-sensitive material is exposed to light (L). It is now possible to use an IR coupler containing -1-.
・.

The yellow color image 11-forming coupler residues colored by A include piparoylacetanilide type, benzoylacetanilide type, malondiamide type, dibenzoylmethane type,
Benzothyanyl acetamide type, malonnis del heptanamide type, benzothianyl lylacetamide, benzoxoxypropylene lylacetamide, benzoxiazolylacetate-1-malonodiester, pensimitanlylacetamide type or benzimida Noryl acetate type coupler 1 & 1, US 1, 1, 1, ♂ Δ′θ, 1, Henarotsuka rlt, dobmid or heterocycle 11, acerade, lead 1, 1, 2, 1, 2, 3, 3, 4, 5, 4, 5, 4, 5, 4, 5, 4, 5, 4, 5, 5, 4, 5, 4, 5, 4, 5, 4, 5, 4, 5, 4, 5, 4, 5, 4, 5, 4, 5, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , . Mokukuni t + 3 + 77' + ” ” 'M% UK waiting plan/.

ti j y, t 7/ @, =i
%1(uLS)x, t.

3.0 Tata 1 Japan 1 Public Special Hit 60-/3, 731 Dirty Research Disclosure τ-/6737 #
: There are 1jflL coupler residues derived from acyl 7cetamides.

Examples of the magenta color aiM forming coupler group represented by A include Okin-Kohirasolin, Biranro [/,
ra) Benzimitanol bales, cyanoacetophenone type Kab 2-residues, -ranlotriazole nuclei, etc. are preferred.

As the 777-color 1lII monomer-forming Kapun residue represented by A, phenol 91 or α-su7toll nucleus is preferred.

Third, when the coupler combines with the oxidized form of the dust-scarring compound, it releases the boundary 1 group inhibitor, and therefore, the effect as a LIIR coupler is the same even if no dye R is actually formed.

Coupler residues of this type, represented by f, include Norihiro Kiyama, Oj2.273, 4μ, oir♂.

Hiroshi/issue, 3,63λ, 34L1 machine 3. Rij♂, 7
No. 23 or No. 3. Coupler residues from 80 companies are included.

Examples of the heterocyclic thio group represented by Z include a tetrano'lylteo group and a pensthiazolylthio group.

Pensimimesolylthio group, triazolylthio group.

1゛mitanolylthio group etc. are included.

An example of the ni group represented by is the following τ.

+C1-t) -COO-+Ck-12YC(JUC
H2CH2SO□-p This 4 In the above formula, R3 represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an aryl group, or an alkenyl group, and k
L+ri hydrogen atom, halogen atom, nitro group, gray thread number/
~Otsu's alkoxy ζ alkyl-Ik [Representation *
pr/'i0 D' G) iG 7:z table.

Among the coupler residues represented by A, those represented by the general formula 1:d and 4f are particularly strange.

- is represented by the formula (1 general formula [νl]), where Rs is an aliphatic group, an aromatic 'IIk group, or a heterocyclic a
iτ and ks each represent a hydrogen atom or an aliphatic radical, and 7 represents a radical group, a heterocyclic group, or an aromatic group.

The aliphatic groups represented by R5, H, and 6 and R7 each have carbon numbers/-, and ZJ is I11 or Muden-1.
may be cyclic, and the most unscrupulous substituents on fatty leather include flukoxy groups, aryloxy groups, amino groups, anrulamino groups, and haloken atoms, even if they themselves have substituents in their history. good. Specifics of useful aliphatic groups Jj
914 can be expressed as a first-order error: isoproyl group,
Inbutyl group.

tert-fuchiru! ii. Methyl 4. Isoamyl group.

tert-amyl group, l,/-dimeterphther group.

/, /-dimetelha-kyfur ah /+i-genalhexyl group, dotesyl group, hexadecyl group, ophtatefur group, cyclohexyl group, λ-methothencyinobrovir a
, -Z-; enoquine imbrovir group.

2-p-tert-butylphenoxyimprobyl group,
Examples include α-aminoinpropyl group, α-(diethylamino)inpropyl group, α-(tsuccinimide)1-sobropyl group, α-(phthalimide9-impropyl group), α-(benzenesulfonamitocaisopropyl group), and the like.

If R5oAhirua is a Taniya aromatic group (phenyl group in the ox) t, v1゛, '3! The y group leader will work even if he makes a direct decision. Aromatic group 4 such as phenyl group is a halogen atom, nitro group, cyano group, calphoquine group, alkyl group having 3 or less carbon atoms, f-alkyl group, brukoxy group, alkoxycarbonyl group, alkoxycarbonyl fumino group. This combined alkyl group has a fluorine group in the chain. Even if an aromatic group such as shin is added, it is still small.

Phenyl group U'! ;-aryloki77, 7 arylokynecarbonyl group, arylcarbamoyl group, aryl abatto group, arylsulfamoyl group, arylsulfo/amide group, arylureido group etc. =<, the aryl group of the substituent has one or more alkyl groups with a total number of carbon atoms of 1S-
It has been changed to %L.

If R52 engineering R7 is a double purple block group, then the heterocyclic group is seven,! ? One of the carbon atoms forming the shadow is replaced with the carbon atom of the carbonyl of the decyl group or the fluorine atom of the amide group, which forms the alpha acylacetamide. Examples of such a heterocyclic ring include nao7ene, furan, biran, virol, pyrazole, hirin/, pyrazine, hirimin, pyridazine, indolino, imitasol, and thiazole.

Examples include ox7zole, triane/, thia7azi7, and oxazino. Even if you put a J substitute on the lucid without doing this, it is still the same.]8 For the s, Re, of the covalent substituent n represented by the general formula [1] 7 are attached to each other, and either one is a divalent group; it is a symmetrical or asymmetrical coupler.

The couplers that can be used in the present invention are limited to 11th-order compounds.
It's not a sign.

(Oノ()1 Cu2(,:1-i2C()zc 2Hs(ro)

UU()bl 02 (15! (16) The turnip-aFi of the present invention can generally be synthesized according to the reaction formula shown below.

In the formula, n represents the same meaning as the group already defined, and X represents a halogen atom or hydroxyl substituted at the coupling position of the coupler. represents a group. When X is a halogen atom, X' is a hydroxy group, and when X is a hydroxy group, X' is a halogen atom. It is a group that can be converted into However, if the helmet has a functional group that can be used in the third step, the second step is not necessary, and the conversion of the functional group in the second step may require two or three steps instead of one step, and it may be converted to W'. be.

Next, a typical synthesis example of the photographic coupler of the present invention will be shown below.

Synthesis fft (1) Synthesis of the example coupler (1) can be synthesized using the synthesis route shown below.

α Step ■ Preparation of compound (1) 3λ2 of λ-(N-ethyltrifluoroacetamide)
Hiro Menalu - Nitrophenol 2! 00 Add scales to acetonitrile and add to the solution without stirring Ll;l/
1. ! 9 of triethylamine and 6λ of 2 of λ-bihariru-2-chloro[λ-chloro5-(Hiro-(2,Hiro-G'tert-amyl)phenoquine 1 phthylamide] acetanilide were added.This solution tλ,j After heating under reflux for an hour, streaking was performed under reduced pressure.The remaining -74 ml of Loo was dissolved in methanol, and 1109 ml of sodium hydroxide was added thereto.

It was dripped with a solution dissolved in water. Dripping A1 reaction temperature #-
1: Cooled with water to maintain the temperature below 0C. After stirring for 1 hour, the gravel @# was pressurized with λ000 ice water containing ≠CO directly τ. Precipitated solid ethyl acetate 't' reconstituted +
L,6r,byv-formed 8911 (1) k Obtained Step ① Preparation of coupler (5) λg of compound (1) attended in Step ① was suspended in ethyl 392 〇〇-. A 221v saturated sodium carbonate aqueous solution was applied to this at a temperature below the temperature range. After stirring for 20 minutes, the oil layer was separated. This liquor 1/C2A9 (
≠-Phenoxy(sulfonylphenyl)tetrazolylnaocarphonyl chloride was added with triethylamine at step 79. After stirring for 1 hour, the precipitated crystals were split and the cap was tied. ◇ Using an eluent mixed with hexane and ethyl monoate, τλ, column □ filled with silica gel R, 0092: 9 chromatography I did this. #bL target coupler ♂ was added to Norakunyoung containing product r.

Elemental analysis C"H Calculated value 62.12 6.0/ 10.21 夾'jj
H16=, air r, Tata lθ, J (7 synthesis examples (2
) Synthesis of Example Uncoupler (16) This coupler can be synthesized by following the synthesis route shown below.

cu2 C41 (glnl (1) PA CFi0 combined in a three-lobe flask @ C1) 6, the 9. Improper tool 700mk, iron vIj709. Ammonium chloride J, j? Mix and heat under stirring to reflux (7 oz.).

Add 70 mQf of water to the mixture and allow to react for an additional 2 hours.

Reaction completed t1! ,、Dip out the filtrate every day, add half of the filtrate with a fang, add it to the water, and wash it with water. Recrystallize with acetonitrile to form compound N+)vjj?
Obtained.

Step ■ Compound (If) k33' was added to a flask containing 111 mol of phosphoric acid imide and ImQ (2% mol) of λ00rnQ. Mix gold with ethanol and heat reflux #LL on a bath for 25 hours.

After cooling, (it is pressed down and placed in water, the shoulder-contact layer τ
The mixture was extracted with ethyl acetate. The mixture was removed under reduced pressure, and the remaining chloroform and ethyl acetate were separated using a silica gel column.

Compound (+++) was produced by yielding the product under pressure of 100 fft.
Compound vIJ(lii) / 9t Dimenal Sulfoxide λ00m9. Defrost, stir, and cool in ice water.

Sodium holohydride /, /9 (λ (7% excess)
I added a little bit of . After further reacting at room temperature for 30 minutes, one reaction mixture was added to ice water and extracted with ethyl acetate.

Washed with water and dried in 111'.

The resulting residue was separated through a silica gel column using a mixed solvent of chloroform and ethyl acetate. The desired compound was obtained by condensation of raw hx, phthalate, and fracnylon.

Compound (1v) was used in the next step of the reaction without further preparation of γL or more.

Stage ■ -3 of coupler (16)! Proof of Tetokuhydrofuran (T)lI! ') to compound (IV)6. 3. Dissolve the ffr bath and stir while flowing the Y mixture gas/λmQ. Go'-Carphonyl-(Hiro-Feno-Cycarphonyl)-Phenyl-Yo-Mercaptotetrazole 'l' hF Elution (/mol/1THk
7 drops (adjusted to '). After further stirring at room temperature for 3 hours, reaction mixture C was added to ice water and extracted with ethyl acetate. After drying the Shichikishishi, dry-paint it on a vertical pressure plate, and then mix the remaining residue with a mixture of ether and hexane. Il↓Crystallized colorless coupler (16) Force xjy attended 1° Elemental analysis CHN Calculation 1 shift 77-276. λ/♂, j≠actual value 67
．． 6 ta 6.3 gu 1,3 n so U, ff1 Nj (3)
Synthesis of Exemplary Coupler (18) The water coupler can be synthesized by following the synthetic route shown below. Step ■ Polishing compound (1) ! '-(Hiro-(λ,44-di-tert-amyl)phenoxy1 bunalamide acetanilide tμ!t and 0'-hydroxy7
Add 36 g of potassium benzyl alcohol mr and N,N-dimethylformamide JOOmη and stir at 60=C for 6 hours. To the reaction mixture, add 74 ethyl acetate and add 2 tons of water.
I washed it with water. After washing the oil layer with 77N of diluted saline, the water was washed several times with l to make it neutral. The ethyl butyrate layer was used in the next step to make the silk pongee leaves and kezugi which were dried with anhydrous sodium phosphate.

Step ■ Preparation of compound (it) Compound 9(1)j/9't chloroform u- prepared in Step ■
00wK#IP#shita. A drop of phosphorus trichloride of 1000/4f was added. After the temperature was lowered, the water was stirred for 14 hours and poured into the water. Washed with water and dried with calcium chloride. L9 chromatography was carried out on a 00911-coated column with silica fiber using the remaining chloroform from cotton milling and acetic acid ethyl (c/)rx as an eluent. Object (il) Function included in '319's oily substance 1-Samurai Ta・Shinkai ■ 369's! -720,000 sulfonylbenzotriazole potassium sulfonate and the compound (11) obtained in step ①, 7N, were mixed with ~-dimethylformamide 200m#! 00(:,
The mixture was stirred for 4 cf. Add il acetate t to the reaction mixture.
/, washed with water using IIJ water bottle. After washing the oil layer with t/N of diluted hydrochloric acid, the water was purified and returned to water until it became neutral. The ethyl acetate layer was dried with anhydrous sodium sulfate.
kMI, iron oak τ fN sweetening medium of chloroform and ethyl acetate was used as bath solution, and silica gel j00r? 'f: Chromatography was performed using a packed column. Generate*Kit 7 Luxion / 39 Coupler (
18) It's f-4.

Elemental content +J, CI-1N Calculated value 6, 60 4.4/ 7.46 Calculated value 69. J, l 6. AJ 7.71 The couplers according to the present invention are roughly divided into Finscher type couplers, which have carboxyl groups, hydroxyl groups, and sulfo groups, and hydrophobic type couplers. Traditionally known. The addition method or dispersion method of Kabu 2 to the preparation and the addition method of adding it to the hydrophilic colloid are applied to the Ceratene No. 10g/Kasho emulsion. An example is a high-grade shoulder bath piece -- dibutyl 7-thalerate, tricresyl phosphate, wax, esters of 7, and a coupler to disperse them. An example is woodland. Togai No. 3
The method described in Ohiro, Ri 32, Souko, 3-λ, No. 027, etc. 114 low-grade organic baths or water baths
A method of mixing and dispersing yukake and coupler.

In addition, it can be used in conjunction with a striped boiling point shoulder machine bathing cup to disperse the coupler. No. 911, U.S. Patent No. c, J'0/,
/ No. 70, No. 2. Iv/, /7/, No. 2. The method described in Rihiro and 3 to'wyl. If the coupler itself has a sufficiently low melting point of 9 or Q (for example, 7J0C or less), the coupler that should be used with it, such as fine sand or sen, can be used in combination with color F, Kabushi sword 1 anchor seed, coupler, etc. to disperse it. how to. For example, Germany % 1st, /'13
The description in No. 1707 etc. is applicable.

As a dispersion aid, 1 commonly used anionic surfactants (for example, sodium alkylbenzene sulfonate,
So/um di-octyl sulfosuccinate, dotesyl W & sodium, alkylnaphthalene sulfone natri, wam, Fisher type Kabufu, etc.) Zwitterionic surfactants (for example, hetetratesyl, N-N dipolyethylene alpha betaine, etc.) f Nonionic interfacial bleaching agents (for example, sorbitan, monolaflate, etc.) are used.

The #additional strength of the coupler of the present invention is 0.0/-107 moles per mole of the halogenated complex. Preferably it is 0.1 to 5 mol.

The emulsion used in the present invention is a zeftin-halogenated emulsion containing silver chloride, bromide, tK, and their mixed halogenated compounds. Derived tough water e colloid a,
Geranan and cellulose! conductor.

Alginic acid bottle koji water-based synthetic polymers include polyvinyl alcohol, polyvinyl hyloridone, polystyrene sulfonic acid, and plasticizers and polymer latexes such as polymethyl methacrylate and polyethyl to improve the dimensional stability of the film. Acrylate etc. are used. A commonly used chemical sensitization method is used for the halogenated milk removal used in the present invention. ψIJ is the first US patent.

3 Tata, 01f3, No. ko, jri 7, IjTb No. ℃, jri "y, yir" 7.
S gold sensitization method, U.S. Patent No. 22 μm 7,160, No. λ,
j2/, No. 125 contains the reduction sensitization method and rice special plan ^/, 6 pieces 3. Hiroshi No. 2.

No. 2,4L10.612, US Pat. a<go, 060
No. 2. jA6, 2ψjW and IJko, yo66°)6
A sensitization method using Yuhikinosho ion or a combination thereof described in No. 3 can be applied.

The spectral sensitization method normally used for color light-sensitive materials is also applicable, and 4+:b*3Ph at 6°.An example of commonly used stabilizers is lyhydroxy-/.3.3a.7-titrazaindene derivatives. , anti-cuff cutting.

For example, application aids such as mercapto compounds, citriazole derivatives, tILII compound, acupuncture, and sensitizers, such as Japanese Patent No. Co., J7/, A13, No. 1.

21#, No. 226, No. 2.33<A, Onium derivatives such as μ-class ammonium doves marked in No. 1tz4L,
U.S. License No. λ, 70g, No./62, No. λ.

531.13λ, first! 33,! P5FO issue,
3rd, λ/117. /9'/ issue, #3. /! I, ≠ is Hirogo.

The polyalkylene oxide conductor recorded in
If you include it, it will become sharp. In addition, dyes for preventing dyeing and elements for improving color photosensitive materials according to the present invention may include a filter layer, a mordant color layer, and a gradual color layer containing a hydrophobic dye. can.

The photosensitive emulsion a1 used in the present invention is applied to various patterned objects. For example, cellulose acetate film, polyethylene terephragm 7-1 lum.

Polyethylene 77i lume, polybrobylene lume.

Glass dry plates, baryta paper, resin/2mm paper, and synthetic paper are used.

The light-sensitive materials riI3@commonly used conductors such as Buffelen-Diamin conductors and/or aminophenol conductors, etc., and the light-sensitive materials riI3@commonly used conductors such as τ, and the light-colored liquid (translucent pH value ~ Used in the range of 13)? Use this to process the current experience. ... Diphenylenediamine derivatives that can be used are one example (p・amine・N-ethyl・N−/・(/tansulfo”amide ether)−m −) luidine sesquilate “ruanito motsuno \itrate, diethylamino・p
9. Phenyldiamine heptasulfate, p-amino N=N-diethyl-m-toluidine hydrochlorite h p-amino to enal 1 μm hydroxyenalaniline sesquisulfate monohydrate, etc.9. Two-negative photosensitive materials, color negative photosensitive materials for movies, oak paper, and dust liquids for instant color photosensitive materials are used. For example, Tokko Sho≠j'−Jj7μ? No., U.S. Clock 3,6 Rij, Nig3 No., Betsuko Shoq7-2≠343, Special Public Shoj/-37531
No. d pi resistance.

Also)i, 1xordun-3@ihe t3ri
tissue journal of rhotogra
phy'/ri! 1 year/month/j8 publication 111 pages ~:/
Published on January 2, 1955 by Hirogu OR~Yarij6ki January 6% Published by Lambda Sada~etc. Written by M. Horwitz Same story / Hirotsu dco in 1960 Published by Nihon Gen 2/ Page 2~sE, Ijehre
Author: same magazine published on March 1, 2015, 12λ, 6j
Year! Published on the 7th of March 3rd, 6th, Yaj, 1Veech, the same magazine / " / JV sheep μ / 13 Usumaru / r Kosada ~ and German Patent Publication Specification No. λ, λEl, 01 / issue etc. lol In this article, the color development process of Ruby Group '2-2 & Sakaizawa is used.This example is specifically exemplified. It will be easier to understand how to apply the techniques of the present invention.

Example 1 A multilayer color light-sensitive material was prepared on a cellulose triacetate film support, comprising each layer having the composition shown in Section F.

1st @: Antihalation layer (AHL) Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer (ML) Gelatin layer containing an emulsified dispersion of λ・j-di-t-oftelha・f-droquinone 3rd layer: First red-sensitive emulsion layer (RLl) Silver iodobromide emulsion (silver iodide: j morch) --- Silver coating amount 1.7 f/m
2 Sensitizing dye I...AX/per mole of silver
0 mole sensitizing dye 1...1.3X10 per mole of silver
Molar coupler A...O, O4c per mole of silver Molar coupler C...Q, 003 per mole of silver
mole of the above compound (1)... 1 mole of silver (2 to o
, ooo6 mole Third layer: Red-sensitive emulsion layer (RL2) Silver iodobromide emulsion (silver iodide: reference mole %)...Silver coating amount l, reference y /
m2 sensitizing dye I...JXlo per mole of silver
Molar sensitizing dye■・・・-・per mole of silver/, 2X10
Molar coupler: o, ooz for 1 mole of silver Molar coupler C: Xo, ooi4 for 1 mole of silver
J molar layer: Intermediate layer (ML) Layer same as the second layer: 1st II emulsion layer (GLl) Silver iodobromide emulsion (silver iodide: molar %) --- Coated silver amount t, sf/m2 Sensitizing dye Summer...JX/0 mol per mole of silver Sensitizing dye ■...1XlO mol coupler B per mole of silver... O, Oj moles per mole of silver Coupler M...O, oor moles per mole of silver The above compound (1)...1 mole of silver (2 to o
, oois mole 7th layer: First green-sensitive emulsion layer (GL2) Silver iodobromide emulsion (silver iodide: 5 moles 4) --- Coated silver amount / , 6
? / m2 Sensitizing dye I...2.3 x 10 moles per mol of silver Sensitizing dye ■...Q, r x 10 per mol of silver
Molar coupler B: 0.02 mol per mol of silver Coupler M: 0.003 mol per mol of silver 1st layer: Yellow filter * (YFL) 1= in gelatin aqueous solution A seratene layer comprising yellow colloidal silver and an emulsified dispersion of j-di-t-octylhydroquinone.

Second layer: First blue-sensitive emulsion layer (B L 1 ) Silver iodobromide emulsion (silver iodide: 6 moles)...Amount of coated silver
1.617m2 coupler Y
...0.2j mol per 1 mol of silver Compound (1): o, oos mol per 1 mol of silver 1st O layer: 1st blue-sensitive emulsion layer (BL2 ) Silver iodobromide (silver iodide: 6 moles)...Coated silver amount 1.12/m2 Coupler Y...0.06 moles per 1 mole of silver /layer: Protected l11 (PL) Polymethylmethanoacrylate particles (diameter approx. 7゜jμ)
Apply a gelatin layer containing.

In addition to the above composition, a gelatin hardening agent and a surfactant were added to each layer.

The sample prepared as described above was designated as sample 10/.
C. Sample 10
2-103; Produced in the same manner as sample 10/ except that compounds (2) and (6) were added in equal amounts to (1) instead of compound (1) in sample toi.

Sample to Hiro; Sample 10/Compound +ll of April 2D
IR-coupler D-t was prepared in the same manner as sample ivt except that the same amount of 1/co as in (1) was used.

DI instead of compound (1) of sample 1ota sample 10/
R coupler D-4 was exploded in the same manner as sample ioi except that an amount equivalent to 1/co of (1) was used.

Comparison DIR coupler-2 Compound sensitizing dye used to prepare the sample ■: Anhydro j -j'-dichloro-3.
3'-di(r-sulfopropyl)-9-ethyl-theacarbocyanine hydroxide pyridinicum salt sensitizing dye IN=Anthrotorethyl-3-37-di~(r-sulfopropyl)-μ・j- μ′=! '-dibenzothiacarbocyanine hydroxide triethylamine salt sensitizing dye I'-anhydro-9-ethyl-j-1'-dichloro-3,3'-di(r-sulfopropyl)oxacarbocyanine nato IJum salt sensitization Dye ■: Anhydro=j-6・j′・6′-tetrachloro-/-1′-diethyl-3・3′-di(j-[β-(r-sulfoboxy)ethoxy]ethylimidazolocarbon Anine hydroxide sodium salt coupler A coupler B α coupler C H The obtained samples toi to ios were processed into 3!mm size films and wedge exposed. This was done in a liquid tank.

1. Color ring II...3 minutes/j seconds, bleaching...
・・・・・・6 minutes 30 seconds 3, wash with water・・・・・・・・・
・3 minutes/j seconds≠, fixing...6 minutes 30 seconds, washing with water...3 minutes lj seconds 6, stable...
......3 minutes/j paper The composition of the processing solution used in each step is as follows Color developer Sodium nitrilotriacetate 7.02 Sodium sulfite φ, θf Sodium carbonate 30. Of potassium bromide
1. ≠2 hydroxylamine sulfate
β-hydroxyethylamino)-1-methyl-aniline sulfate Hiroshi, jy add water ti bleaching solution ammonium bromide i4o, oy aqueous ammonia (it%) cojr, 0ml ethylenediamine-tetraacetic acid sodium iron salt /30? glacial acetic acid
Add 14cm 1 water
Ill Fixer Tetrapolyrin M-=Thorium 2. Of sodium sulfite ≠, Of ammonium thiosulfate (yo%) / 7 j, 0m7
Tribisulfite sodium tricum μ, 61 water was added /1 Stable liquid formalin r, o,,1 water was added /1 Further, the overflow of the developer was recycled by the following method and reused.

Playback processing is done using a patch method. First, the perflow solution was put into an electrodialysis tank and electrodialysis was performed so that the KBr was 0.7f/11 or less.

This liquid contains the sodium nitrilotriacetate, sodium sulfite, sodium carbonate, potassium bromide, hydroquineluamine sulfate, Hiroshi-(N-ethyl-N
-β-hydroxyethylamino)-λ-methyl-aniline sulfate was added to adjust the pH to to and os, and the solution was reused as a replenisher. 〇 Supplementary light was carried out at a rate of 311/m2 of treatment.

Table 1 shows the decrease in sensitivity when the method of performing the regeneration process once when the overflow liquid reaches /l is repeated to times.

From the results in Table 1, samples 10/, toco, and 103 had almost no decrease in sensitivity, whereas samples p/0≠ and lOS had a large decrease in sensitivity. This means that compounds (1), (2), (
Even if the leaving group in 6) flows into the color developing solution, it decomposes into a photographically unaffected compound, so it does not accumulate in the developing solution like other non-degradable leaving groups. This indicates that the product can be recycled and used repeatedly.

Example Samples 101 and 10 used in Example 1! A 3 m/m x 1 x film was exposed to light, and the development process of Example 1 was carried out at a speed of 7170 m in an SL developer tank. The data comparing the sensitivity of the successful part and the sensitivity of the after-treatment part of the processed film are shown in Table 1. From the results in Table 3, Sample 10/~/No 3 is Sample 10 Hiro~10.
There is less decrease in sensitivity compared to 4. This JL is compound D-i
The leaving group of , D-2 flows out into the developer solution and exhibits a development moat suppressing effect when accumulated, but the leaving group of compound (box 2) (61 shows a negative effect after flowing out into the developer solution). This shows that it is decomposed into a compound that is photographically transparent.

Claims (1)

[Claims] The following general formula (IJ, (II), [:nl)]
Among the couplers shown in the formula, at least -t containing a halokunkai emulsion 1 is said to have a characteristic force 2-Yoma l & original material General formula ■] General formula (IIJ General formula (Ill) In the above formulas [1゛] to [~], A represents a coupler residue, which is bonded to the mole element Ip at a coupling position, and R1 is a hydrogen atom, /.Rokun atom.Alkyl group, alkenyl group, aralkyl group, alkoxy group , γ-rucosulfonyl group, anilino group. Acylamino group, Waleido group, cyano group, nitro group, sulfonamide group, sulfamodyl group, carbamoyl group,
Aryl group, carpho group, sulfo group, cycloalkyl group, alkanesulfonyl group. Represents an arylsulfonyl group or an acyl group. kL2 is the actual size of hydrogen, alkyl group, alkenyl group. represents an acryl group, a cycloalkyl group, or an aryl group. B is a benzotriazole group (/+2 is linked to A at the 3rd position through an Ayu moiety;)) or a hetero group (B;));
b) Its part τ is connected to A through 1) tray representation. L is a bivalent base 1 cm including the hearth cleavage in the party-colored priest's bath shell.
Table A, C. Is N the number of carbon atoms/1 to 10 ￥ Italian Al 1,000 or carbon?
Substituted or substituted fluorenyl group, cycloalkenyl group, cycloalkyl group, heteroaryl group, or aryl group having 6 to 10 carbon atoms [Table 1]. k represents 0 or /. n and m are each lmayt-ri-xytx1. . It represents lbal or ko, and when t is 2, make a block with two R1 and make t.