JPS6346458A - Method for processing silver halide color reversal reflex printing photosensitive material - Google Patents

Abstract

PURPOSE:To prevent the deterioration of sensitivity and fogging by incorporating a specified heterocyclic compound in the reversal reflex printing photosensitive material and processing it with a color developing solution containing an organic thioether compound. CONSTITUTION:The silver halide color reversal reflex printing photographic sensitive material having blue-sensitive, green-sensitive, and red-sensitivelayers contains the compound represented by formula I in which M is H, a cation, or a group protecting an alkali-cleavable mercapto group; Z is an atomic group necessary to form a 5- or 6-membered unsaturated hetero ring. This photosensitive material is processed with the color developing solution containing as a promoter the organic thioether, for example, represented by formula II is which R41 is 1-5C alkylene, and each of m and n is 1, 2, or 3, thus permitting deterioration of sensitivity and fog to be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide color inverse reflection printed light-sensitive material, and in particular, a halogenated silver halide color inversion-reflection printed photosensitive material that does not cause low sensitivity or high noise and prevents fogging. This invention relates to a silver color reverse reflection printed photosensitive material.

(Prior Art) A color inversion reflective print photosensitive material is made by coating three types of silver halide emulsion layers, each with different sensitivities to red, green, and blue light, on a reflective support. Yes, T, H
James, ed., The Theory of.
The Photographic Poetry
theory of the Photo-graph
ic Process)”, μth edition, page 33,
Macmi 1lan: Published by Macmi 1lan (1
As described in 977), as a development process,
First development in which black-and-white development is performed, a step in which the silver halide that was not developed in the first development is covered with light or a chemical method to make it developable, color development in the presence of a coupler, and halogenation of the developed silver It refers to a color photographic material that undergoes processing consisting of a bleaching process to restore silver and a fixing process to dissolve and remove it.

Normally, the processing of color reversal reflective print photosensitive materials is black and white development (first development) → washing → reversal exposure - color development → washing →
It is carried out in the following steps: drifting, fixing, washing, and drying. In this process of black and white development and color development, a silver halide solvent is contained in order to impart a development accelerating effect through dissolution physical development.

Furthermore, since color reversal reflective print photosensitive materials require a larger amount of development processing than reversal photosensitive materials for direct photography, the development processing time is set to be shorter (for example, the development processing time for color reversal photosensitive materials is Manufactured by Fuji Photo Film ■, CR-
The first development time and color development time are both 6 minutes in the s Otsu processing, while the first development time is 75 minutes in the company's RP-303 processing, which is a development processing for color reverse reflection print sensitive materials.
color development is i3s seconds. ) The silver halogenide emulsion used also has high development activity because development is completed in a short time. Therefore, color reverse reflection print photosensitive materials tend to generate capri during development processing.

On the other hand, as a method for preventing the generation of capri during development processing in silver halide photosensitive materials, for example, mercaptobenzothiazole (British Patent No. 76g≠O1, British Patent No. 1
Hiro 7!7 Otori No., Tokukai Sho Taco 10 Otsu No. 7, Tokukai Shoj
Otsu-72 Hiroj No. 1, etc.), /-Phenyl-! -Mercaptotetrazoles (Belgium Patent No. 67/, Kou 02, U.S. Pat. No. 3.2 Tata, No. 97, U.S. Pat. No. 3,374,31)
No. 0, No. 3.1. /! , l, /l, No. 3,07
/.

≠No. 6j, No. 3. ≠20. l, No. 64, No. 2゜4
t03.927, Tokukai Showyu (:)-374L31. No., JP-A-Sho JG-TA J7. ! r etc.), benzotriazole without mercapto group (British Patent No. 1/2, 06
), U.S. Pat. /! 7
．． ! No. 09, No. 3,012. Ofg No., German Patent No. 1. /7, 7/2, etc.), benzimidazoles having no mercapto group (US Pat. No. 3,137., t7r, US Pat. No. 3, /411).

ot No. 4, same No. 3. ! //, 1. t3, British Patent No. 2
71.4'73 No. 1. J4I-≠,! 4tg issue,
Same No. 3, 1111. Ott No. 3. ta //, 663
German Patent No. 7 (#, 41211, German Patent No. 6.3)
! , 71. No. 2.20! , No. 332, etc.) is added to the light-sensitive material or to the processing solution.

However, when these known anti-capri agents are applied to color reverse reflection print photosensitive materials, some lack the ability to suppress fog, while others are highly effective in suppressing capri, but Since it strongly adsorbs to silver, it has the disadvantage of greatly reducing sensitivity by inhibiting development.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a color inversion-reflection print photosensitive material which does not have a decrease in sensitivity and is prevented from fogging during development.

(Means for Solving the Problems) The present inventors have conducted extensive research in order to develop a silver halide color reverse reflection print photosensitive material that satisfies these demands, and have developed a silver halide color photosensitive material. The reverse reflection print photosensitive material contains only 2 to 3 nitrogen atoms and carbon atoms! It has been found that by including a mercapto compound having a negative to 6-membered unsaturated heterocycle, the occurrence of fog can be significantly reduced without suppressing sensitivity.

The present invention has been developed based on this knowledge.

That is, the present invention provides a silver halide color reverse reflection print light-sensitive material having at least each of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support, in which a compound represented by the following - coating material CI) is used. At least one of them is represented by the general formula (I), where M represents a hydrogen atom, a cation, or a protecting group for a mercapto group that can be cleaved with an alkali, and Z represents a group necessary to form a J-negative to 6-membered unsaturated heterocycle. Represents a group of atoms.

The unsaturated heterocycle consists of only carbon atoms and 2 or 3 nitrogen atoms, may have a substituent, or may be fused with a benzene ring.

Next, the compound represented by the general formula CI) will be explained.

M is a hydrogen atom, a cation (e.g., sodium ion, potassium ion, ammonium ion, etc.) or a protecting group for a mercapto group that can be cleaved with an alkali (e.g., −〇(J
/ , -e(J(JR', -I::HOHtsuC(JR
/, -CHCH□CN.

-CH2Cl-42S (J2C1 (3 etc. However, 1t'
represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, etc.).

Z represents an atomic group necessary to form a negative to 6-membered unsaturated heterocycle. This j- to 6-membered unsaturated heterocycle consists only of carbon atoms and 2 or more and 3 or less nitrogen atoms.

Further, this petero ring may have a substituent or may be condensed with a benzene ring.

Among the j-negative to 6-membered unsaturated heterocycles of the present invention consisting only of carbon atoms and nitrogen atoms, those having two nitrogen atoms include imidazole, pyrazole, pyridazine, pyrimidine, pyrazine, and partially hydrogenated products thereof. , and their condensates with benzene rings.

Examples of three nitrogen atoms are l, 2. ≠-triazole, /, 3. IA-) riazole, l, 31j-) riazine, /, 2. Examples include ≠-triazine, partially hydrogenated products thereof, and condensates thereof with a benzene ring.

Preferred among these nitrogen-containing heterocycles are those containing three nitrogen atoms, and the most preferred are /,! ,
It is a μ-triazole ring.

These rings also include alkyl groups (e.g. methyl group, ethyl group, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc.), alkenyl groups (e.g. allyl group, etc.), aralkyl groups (e.g. benzyl group, phenethyl group, etc.). ), aryl groups (e.g. phenyl group, naphthyl group, p-acetamidophenyl group, p-carboxyphenyl group, m-hydroxyphenyl group, p-sulfamoylphenyl group, p-acetylphenyl group, O-meth)oxyphenyl group , 2. ≠-diethylaminophenyl group, λl-dichlorophenyl group), alkylthio group (e.g. methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (e.g. phenylthio group, naphthylthio group, etc.), aralkylthio group (e.g. benzylthio group) group), acylamino group (e.g. acetylamino group,
propionylamino group, butyrylamino group, benzoylamino group, phenylacetylamino group, etc.), alkoxycarbonyl-substituted alkyl group (e.g. methoxycarbonylethyl group, etc.), sulfo group or its salt (e.g. -8O3H, -8O3Na), Hydroxyalkyl group (e.g. hydroxymethyl group, hydroxyethyl group, etc.), carboxyl group, hydroxyl group, amino group,
halogen (e.g. -0, -Br, -I, etc.),
-861 groups (Mit, full meaning as mentioned above)
.

It may be replaced with, etc.

Preferred specific examples of the compounds represented by (1) are shown below, but the compounds are not limited to these.

H aη (JH (g) (JH H H Qυ (branch)) The compound represented by the general formula (I) of the present invention exhibits an effect even if it is contained in a layer that does not contain a silver halide emulsion. A greater effect is obtained when the compound is incorporated into a layer containing silver oxide.In that case, it is desirable that the compound of the present invention is exclusively absorbed into the surface of the halogen nitride T11 grains at a rate of 1%. Although it is desirable to add the compound of the present invention to the silver halide emulsion in advance, it may also be added to the coating solution containing the silver halide emulsion immediately before coating. May be added at the time of formation.

The amount of the compound of the invention used is - from lo-5 to 'io' mole per mole of silver halide in the membrane, preferably from lo-4 to 'io' mole, preferably from lo-4 to
It is in the range of 10-2 moles.

The same compound of the present invention may be added to two or more different layers, or two or more different types may be added to the same layer.

The "reflective support" used in the present invention refers to one that enhances the total reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

Pair: light fk The emulsion layer of the photographic light-sensitive material used in the present invention may contain any of silver halides including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. It's okay.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal structures such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical shapes. It may be one with crystal defects such as twin planes or a composite form thereof. Also, mixtures of particles of various crystal forms may be used.

The grain size of the silver halide may be fine grains of less than about 0.1 micron, dog-sized grains with projected area diameters up to about 10 microns, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. An emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 776, A17&≠3 (17g/February), 22~
．． Page 23, “Engineering, Emulsion Manufacturing (Emulsion Pr.
117, A/R 7/4 (/97
9 years//month), you can follow the method described on page z≠.

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

Glafkides, Chimie et Ph
ysiquePhotographyque Pau
``Photographic Emulsion Chemistry'' by Duffin, published by Focal Press (G, F, D
uf fin, Photo-graphic
Emu, l5ion Chemistry (Foca
"Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L,
Zelikman et al., Makinga
nd Coating Photographic
Emulsion.

It can be prepared using the method described in Focal Press, Iri 6≠), etc. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a tin halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. For more information,
For example, Photographic Science and Engineering rIJk A ◆ , -19, U , sk
: -Qt-: -. 2. cormorant. AEngin
earing) Volume 6, pp. 717-745 (15'1
2); Journal of Photo-grap Science
hic5science), vol. 72, 2412-.
2j/page (/ri64L), U.S. Patent No. 3. Otsu! ! , 35
'μ and British Patent No. 1. U/J, No. 7I1.1.

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

No. 717, Japanese Patent Publication No. Shoj/-/2340, Japanese Patent Publication No. Shoj3-r
21t01, JP-A Showj3-/414c3/RI, JP-A-J≠-100717 or JP-A-Showu μm/! ;
! Physical ripening can also be carried out in the presence of thioethers and thione compounds described in No. 1121 and the like. Even with this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution can be obtained.

Monodisperse emulsions that can be used in the present invention include silver halide grains having an average grain diameter of greater than about 0,000 microns, and at least greater than 1% by weight of the average grain diameter
Within ≠θ%: Una emulsion is typical. Furthermore, the average particle diameter is between 0.13 and 2 microns, and at least 9
At least % weight or (number of particles)! All emulsions containing silver halide grains in a range of 20% of the average grain diameter can be used. A method for producing such an emulsion is described in U.S. Patent No. 3. Tough≠, t2r, same No. 3. Oh dear, 32μ
No. 1 and British Patent No. 1. It is described in μ/3,7 R issue. Also, Tokukai Sho≠r-rtoo issue, same! ! -37C)
1.7, 5i-r3゜ri 7, same jJ-/37/3
No. 3, J4-Hiro♂ No. 321, J-Hiro-Tata Hirori No. 3,
same! Monodisperse emulsions such as those described in #-3763 evening issue and JR-T Tata 3g issue can also be preferably used.

The aspect ratio! Tabular grains such as those described above can also be used in the present invention, but these grains have a
Due to its large surface area, it is very prone to fogging in the developer. Therefore, when using tabular grains with an aspect ratio of 5 or more, the projected area of the grains is less than 0% of the total projected area of the silver halide grains present in the same layer.
The following is desirable.

These tabular grains are described by Gutoff, Photography Science and Engineering.
, Photographic 5science and
Engineering), Volume 144, 2≠t
~ Kota page 7 (/? 70 years); US Patent No. ≠, Ko 3≠.

22 Otsu issue, same μ, 1 iti4L, 'sio issue, same hiro, ≠
No. 33, θ≠g, 4≠, 4t3, No. 520 and British Patent No. 2,1/2,717.

It is also possible to use particles whose crystal shape is controlled by using a sensitizing dye or some mild additives in the particle formation process.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are based on British Patent No. 1.0 Core, /
≠6, U.S. Patent No. 3. jor, otr issue, same,,C
,41,t4(,177 and patent application 1986-,!≠g
It is disclosed in No. 4L62 and the like.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are described in U.S. Patent No. μ, oqt.
i-, tir41. No., same≠, lguco, rioo no., samehiro, hiro39.3! ;3, British Patent No. 2,03♂, 7 Octopus, US Patent No. ≠, 3≠ri, 622, Dohiro,! '? !
,≠7g issue, same≠.

Hiro 33, 30/issue, same lA, ≠63.0 and 7, same J,
l, JA, No. 762, 32g! λ, No. 067, Tokukai Sho! It is disclosed in No./12j≠O, etc.

Furthermore, chemical ripening is applied to the crystal surface to form photosensitive nuclei (Ag2S).

It is also possible to use a grain structure having a so-called internal latent type grain structure in which silver halide is further grown on the periphery after forming silver halide (Ag n % Au, etc.).

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

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

Furthermore, a direct reversal emulsion may be used. The direct reversal emulsion may be of the noradiation type, the latent type, the photofogging type, the type using a nucleating agent, etc., or a combination of these may be used.

In order to remove 'soluble silver salts from the emulsion before and after physical ripening, Nudel water washing, 70-cure precipitation method, ultrafiltration method, etc. are used.

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

Additives used in such processes are described in Research Disclosure-ya/74 Hiro J (1979/1979) and 4117/A (2/1979), and the relevant sections are listed below. They are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Discs a-Jar, and their locations are shown in the table below.

1 Chemical sensitizer Page 23 6q Sub right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer,
i3-2 hiro page 1st page right column ~ super sensitizer
6μ page right column 4 Brightener 2≠page 5 Antifogging agent 2μ～2≠page 64L page right column and stabilizer 6 Original absorbent, film 2≠～color page 2≠right column～Ilter dye ( , to left column UV absorber 7 Stain inhibitor Co! page right column 6zo page left to right column 8 Dye image stabilizer 2 ≠ page 9 Hardener 26 page 47/page left column 10
Binder page 26 Same as above 11 Plasticizing lubricant page 27 6! Q Right column 12 Coating aids, Table 26, page 7 Same as above Surface activator 13 Static prevention Page 27 Same as above stop agent Various color couplers are used in the present invention. A specific example thereof is described in the patent described in the aforementioned Research Disclosure &176≠3, ■-C-G. As dye-forming couplers, the three primary colors of the subtractive color method (
That is, couplers that give yellow, -magenta and cyan) by color development are important, and specific examples of diffusion-resistant, hydrophobic, pro-equivalent or f'iλ-equivalent couplers can be found in the aforementioned Research Disclosure i/71p≠ 3, ■
- In addition to the couplers described in the patents described in C and 9,
The following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
1. -07,210, No. 2゜! 7! , θ! No. 7 and No. 3,261. ! It is described in rOA issue etc.

The use of two-equivalent yellow couplers is preferred for the present invention, and is disclosed in U.S. Pat. ≠μ7.
Octopus R, same No. J! 733. ! 0/No. and Hiroshi No. 0,
02λ.

Oxygen atom separation type yellow coupler described in GXO issue etc. or Tokuko Sho! ! -/θ73, U.S. Patent μ, 4toi, ij1, U.S. Patent No. ≠, 321, . 02≠ issue, 几D-/♂0!3 (Iri 7 year ψ month), British patent No. 1
．． ≠No. 21,020, West German Application Publication No. 2,21 Ri, Ri 1
No. 7, No. 2,271/,! ! .

No. 1, No. 2.32P, J-17 and No. 2゜μ
A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 33,112. Especially α−
Pivaloylacetanilide couplers are desirable because they provide excellent color fastness, particularly light fastness and color hue.

Examples of the magenta coupler that can be used in the present invention include hydrophobic couplers having a pallast group, indacylon-based modi- or cyanacetyl-based couplers, preferably Fij-pyrazolone-based and pyrazoloazole-based couplers. ! -Pyrazolone couplers are preferably those in which the 3-position is substituted with an arylamine group or an acylamino group from the viewpoint of the hue and color density of the special color dye, and representative examples thereof include U.S. Pat. Same No. 2, 3eJ, No. 703,・
Same 2nd. too, No. 711, No. 2. Or, j73, same No. 3.062, 6I3, same No. 3. /j2.196
No. 3 and No. 3 of the same. '? J&, No. 0/j, etc. Two cars! - As a leaving group for pyrazolone couplers, US Patent No. 3IO.

Particularly preferred are the nitrogen atom leaving groups described in US Pat. Further, the pyrazolone couplers having a ballast group described in European Patent No. 73°AJG can provide high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. /-
C) C/1λ, 4t)) Riazoles, Research Disclosure Ya2hiro 220 (/rihiro June) and JP-A-Sho tO-33! ! Pyrazolotetrazoles described in No. 2 and Research Disclosure, Jf6ul
jjjO (/ri r4c4t month) and JP-A-Sho-tO-μ34
Examples include the pyrazolopyrazoles described in No. 12. U.S. patent cylinder ≠, in terms of low yellow side absorption of color dye and light fastness! Imidazo (/
,,2-b) Pyrazoles are preferred, and European Patent Co., Ltd.
pyrazolo (/, j-b) (/,
, 2. ≠] Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include naphthol and phenolic couplers that are hydrophobic and diffusion-resistant. μ7≠.

2, No. 2, No. 3, preferably U.S. Pat.

Typical examples include dicarium naphthol couplers of the oxygen atom dissociation type, which are described in Iμ6,326, IMU, 12r, 233, and IMU, λrit, No. 200. Further, specific examples of phenolic couplers include US Pat.
, 36 Ri, Ri 2, No. 2. roi, /7/, No. 2,772,162, No. J, r5'j, r2G, etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is an alkyl group having an ethyl or higher group at the meta position of the phenol nucleus described in U.S. Pat. No. 3,772,002. A phenolic cyan coupler having U.S. Pat. No. 2,772,142,
Same No. J, m.

3eJ issue, same issue, /2A, Jri issue 6, same issue ≠.

J3≠, No. 0/I, No. 327.173, West German Patent Publication No. 3,32, No. 72, and European Patent Application No. 12/1
, El, ko described in No. 1, etc.,! -Diacylamino-substituted phenolic couplers and U.S. patent cylinders 3. ≠≠A
, A22, No. 333, Tatata No., μ, 41
j/,! It has a phenylureido group at the 2-position as described in No. J and No. μ, ≠ No. 27,767, and! −
It is a phenolic coupler acid having an acylamino group in the position.

Dye-forming couplers may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are:
US Patent Tube 3. t, tzi, rλ0 and Hiroshi the same, o
Ro, No. xii. Examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Pat. No. 44,367,212.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil droplet dispersion method in water. It can be mentioned as follows. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 17.00 or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or Finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.
No. 2,027, etc.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

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

No. 363, West German Patent Application ((JLS) No. 11 RTL-/
.

No. 27μ and No. 2. Jμ/, No. 230, etc. have been published.

The light-sensitive materials produced using the present invention can be used as color-capturing inhibitors or color-mixing inhibitors such as hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, and colorless couplers. , sulfonamidophenol derivatives, etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include no-idokuquinones, t-hydroxychromans, t-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzene, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. It is mentioned as. Further, metal complexes substituted for (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
It is desirable to appropriately provide auxiliary layers such as a protective layer, an intermediate layer, a filter layer, a cushioning prevention layer, and a pack layer.

In the processing of the color reverse reflection printed photosensitive material of the present invention,
Black and white development (first development), reversal, color development, bleaching, and fixing steps are performed, respectively.

Known developing agents can be used in the first developer used in the present invention. As developing agents, dihydroxybenzenes (for example), idroquino/), 3-pyrazolidones (for example, /-phenyl-3-virazolido/),
), amine phenols (e.g. N-methyl-p-amine phenol), /-phenyl-3-pyrazoli/s,
Ascorbic acid and as described in U.S. Pat. No. OA7,172/2. ! , a heterocyclic compound in which a μm tetrahydroquinoline ring and an intrene ring are condensed can be used alone or in combination.

In addition, the black and white developer used in the present invention may include preservatives (e.g., sulfites, bisulfites, etc.), buffers (e.g., carbonates, boric acid, borates, alkanolamines),
Alkaline agents (e.g. hydroxides, carbonates), solubilizing agents (
For example, polyethylene glycol, these esthetics'
), pH adjusters (e.g. organic acids such as acetic acid), sensitizers (e.g. quaternary ammonium salts), development accelerators, surfactants, toning agents, antifoaming agents, hardening agents, viscosity imparting agents. etc. can be contained.

The first developer used in the present invention preferably contains a compound that acts as a silver halide solvent. Sulfite, which is usually added as a preservative, plays this role. The sulfite and other usable silver halide solvents include specifically KSCN, Na5CN, KS
(J Na25 (J3.2 3% K S (J Na252U5, K2S2O5
, 225 to Na, S, (J, etc.) - Particularly preferred among these compounds is KS (, "N.

If the amount of these silver halide solvents used is too small, the progress of development will be delayed, and if it is too large, the silver halide emulsion will be covered with gold, so there is a preferable amount to use, but it is difficult to determine the amount. can be easily accomplished by a person skilled in the art.

For example, 5CN- is o, oos~0.0 per developer/l.
Preferably it is 2 mol, especially OOO/~o, oir mol, and S,'- is o, os~1 mol, especially 0. /
~0. Preferably it is J' moles.

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast;
Preferably, the range is from about r,j to about //,j.

In the reversal step, the reversal may be performed by light irradiation, or a fog bath may be used. A known fogging agent can be contained in Caprace 1.

+: &b Honfue l tin ion - Arinakata phosphorus - vinegar salt (Ukokoku Patent No. 3.1./7, 2g 2 Ming Mfi book), stannous ion organic phosphonocarboxylic acid acetate (Special Publication Showa! 4) -3
．． 2t/1. (British Patent Nos. I, 2O).

stannous ion complex salt borohydride compounds such as (U.S. Patent No. 2.?rμ, J67 specification);
Heterocyclic amine borane compounds (British Patent No. 1,0//,0
boron compounds such as No. 00 Moe Saisho). The pH of this fogging bath (reversal bath) ranges over a wide range from acidic to alkaline, preferably from 2.3 to 10S, and particularly preferably from 3 to 10S. be.

The color developer used in the present invention has the composition of a general color developer containing an aromatic primary amine developing agent. A preferred example of the aromatic primary amine color developing agent is p-phenylenediamine i1 as shown below. N,N-diethyl-p-phenylenediamine, ko-amino-diethylaminotoluene, 2-amino-J--(N-ethyl-N-laurylamino)toluene, ≠-[N-ethyl-
~-(β-hydroxyethyl)aminecoaniline, 2-
Methyl-≠-[N-ethyl-N-(β-hydroxyethyl]amine]aniline, N-ethyl-N-(β-methanesulfamidoethyl)-3-methyl-Hiro-aminoaniline, N-1,2 -amine-!-diethylaminophenylethyl)methanesulfonamide, N,N-dimethyl-p
-Phenylenediamine, US Patent 36J6! O issue details, same 3 otsuri 162! ≠-amino-3-methyl-N-ethyl-he-methoxyethylaniline, ≠-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline and μm amino-3-methyl-
N-ethyl-N-β-duthoxyethylaniline and salts thereof (e.g. sulfate, hydrochloride, sulfite, p-toluene/
sulfonate, etc.) are preferred representative examples.

Further, it is preferable to contain an organic thioether compound in order to impart a development accelerating effect to the color developing solution.

Particularly preferred are compounds represented by general formulas (IIa) to (nc), in which Ab0 General formula (■a) HO+1 is also 41-8"7("4□-(JH-Fukudai(Il
b) (G1 (J-1 also -8R, -(J-R4□)
20 General Formula (IIC) Here, m and n represent integers of 1 to 3, R and 几. □ represents an alkylene group (for example, methylene group, ethylene group, butylene group, etc.) whose carbon number is 1.

Among the general formulas (■), the most preferred book is 几.

is an ethylene group.

Preferred specific examples of the compounds represented by -fukudai (If) are shown below, but the invention is not limited thereto.

(II-/) f((JCH2(,'H2SCH2CH2S(,'H2
C) 12 (JH(II--2) (ll-3) H(JCH□CH□5eH2CH2(CH□CH□(J
CH2(,”I-1□(,X;H2C112SCH2C
020H(■-μ) (■-riH(JCH□C1(25C)42CH2(JH(■-6
) )1(J(,'H20H□5C)12CH2SCH2e
)12S c)i□e)12(J)1(n-7) H(Jet(2CH2CH2CH2SC)12C1(2
When the compound CH2C:H2(J)1-Fukudai (n) is added to a color developing solution, the amount added is preferably jX/0-'moh to jX/0- per 1 liter of developer. '
% mol, more preferably /Xl0-'mol~koX10-'
It is a mole.

Any other development accelerator can be added to the color developing solution if necessary. For example, US Pat.

Specification of Hiro No., Special Publication Akihiro≠-ta J03, U.S. Patent 3
47/2≠ Various pyridinium compounds and other cationic compounds represented by the specification of No. 7, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, and the Publications, U.S. Pat.
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in No. 7 specification, Japanese Patent Publication No. 4 LμmPsoy, Belgian Patent No. 6-211.2
Organic solvents and organic amines, ethanolamine, ethylenediamine, jetanolamine, etc. listed in the No. 1, as well as F, A, Mason (L.

F., A. Mason), “Photographic Processing Chemistry”
icProcessing Chemistry)”
, pages ao to 4t3 (7 Orcal Press, /ri6
6) can be used.

Although Hensyl alcohol can be contained in the color developing solution in order to enhance its development activity, it is preferable not to contain it from the viewpoint of pollution burden and safety.

The color developer may also contain other known developer component compounds. For example, alkali agents, buffering agents, etc. include caustic soda, caustic potash, soda carbonate, potassium carbonate,
Tertiary phosphate or potassium, potassium metaborate, borax, etc. are used alone or in combination.

Color developing solutions usually contain sulfites, which are used as preservatives.
For example, sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite) or hydroxylamine can be added.

Furthermore, the color developing solution contains amino acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and l,3-propylenediamine-cooltetraacetic acid. Polycarboxylic acids can be included as water softeners.

Competing couplers and compensating developers can also be added to the color developer.

Citraj 7e, J611, H2 as a competitive coupler
etc. are useful.

As a compensating developer, p-aminophenol, N-benzyl-p-aminephenol, l-phenyl-3-pyrazolidone, etc. can be used.

The pH of the color developing solution is preferably in the range of about J'-/J. The temperature of the color developing solution is selected within the range of 2o'C to 70'C, but preferred are JOoC, 1, O'C:.

It is.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As bleaching agents, compounds of polyvalent metals such as iron (lit), cobalt l'), chromium l), copper ([I), peracids, quinones, nitrone compounds, etc. are used. For example, ferricyanide, iron dichromate, iron (
organic complex salts of lfI) or Kobal)(I[I), such as ethylenediaminetetraacetic acid, nitrilotriacetate, /, 3
-Aminopolycarboxylic acids such as diamino-2-propatoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (III
) Sodium and iron(III) ethylenediaminetetraacetate
) Ammonium is particularly useful. Aminopolycarboxylic acid iron(III) complexes are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or fixing solutions, U.S. Patent 30≠2!20
No. specification, 324c194! , No. specification, Tokko Sho tt.
Various additives can also be added, including the bleaching accelerators described in Z-trot, Japanese Patent Publication No. 4Lj-rlrJt, and the like.

The fixing bath of the present invention contains 3oy71 ammonium salt, sodium salt, and potassium salt of thiosulfate as a fixing agent.
-2oo? In addition, stabilizers such as monosulfites and isomeric bisulfites, hardeners such as potassium alum, acetates, borates, phosphates, carbonates, etc.
t-i buffer, etc. may be included. The pH of the fixer is 3
~10, more preferably! It is ~ri.

It is also desirable to provide a washing bath or a rinsing bath between each treatment step.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

(Example 1) A color photographic material was prepared by applying the following layers from the first layer to the first layer on a paper support laminated on both sides with polyethylene. The coating side of the seventh layer of polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amount in units of 9/m are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (antihalation layer) Black colloidal silver ・・・・・・・・・0.
0/gelatin ・・・・・・・・・
・0.2 second layer (low sensitivity red sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (+S and 4) (silver iodide 3.! morch, average grain size 0.7μ)
・・・・・・Silver 0. /! gelatin
, −, −−−−−−/ , 0 Cyan coupler (bitter 3) ・・・・−・・・・0. JO anti-fading agent (screen 2) ・・・・・・・・・0. /j coupler solvent (Ao 18 and Sawa 1) ・・・・・・・・・0.0
6 Third layer (high sensitivity red sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (axes 5 and 4) (silver iodide r, o molti, average grain size 0.7μ)
・・・・・・Silver 0.10 gelatin
・・・・・・・・・0. ! 0 Cyan coupler (Yellow 3) ・・・・・・・・・0.10 Anti-fading agent (Kan 2) ・・・・・・・・・o, or coupler solvent (Yellow 18 and So 1) ・・・...0.0
2nd μ layer (intermediate layer) Yellow: 10-ide silver, 0.02 gelatin, i, o.

Color mixing prevention agent (+X4) ・・・・・・・・・
o, or color mixing inhibitor solvent (dinner X3)...
...o, it polymer latex (+6) ...
...O, aOth! Layer (Low sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with a green sensitizing dye (bone 12) (silver iodide 2.jmolar, average grain size O 1μμ)
・・・・・・Silver 0.20 gelatin
......0.70 Magenta coupler (+XX) ...Old -0, <20 Anti-fading agent A (+to) ...0.0! Anti-fading agent B (+9) ' ・・・・・・・・・
O, OS anti-fading agent C (-xs)...
...0.0 cocoupler solvent (+7) ...
...O, ir 6th layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (+XZ) (silver iodide J, j morch, average grain size O9 ri μ)
・・・・・・Silver O0λO gelatin
・・・・・・・・・0.70 magenta coupler (4-11) ・・・・・・・・・O,ILLO
Anti-fading agent A (+xo) ・・・・・・・・・
0.0! Anti-fading agent B (+9) ・・・・・・
...O, OS anti-fading agent C (+s) ...
...0.0 coupler solvent (supper 7) ・
・・・・・・・・・0. /j 7th layer (yellow filter single layer) Yellow colloid) "Silver---------・-0, J O Gelatin ・・・・・・・・・／, O
O color mixing inhibitor (-ax4) ・・・・・・・・・
・・o, o4 color mixing inhibitor solvent (+X3) ・・
...0.2 μth g layer (low sensitivity blue sensitivity N) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (+ta) (silver iodide!, J' morch, average grain size O1jμ)
・・・・・・Silver o, it gelatin
・・・・・・・・・0.10 Yellow coupler (+t S ) ・・・・・・・・・0.20 Coupler solvent (+18) ・・・・・・・・・o
, or 7th layer (high sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with a blue sensitizing dye (bitter 16) (silver iodide 2.! morch, average grain size/, μμ)
...eo, 2゜gelatin
・・・・・・・・・o3゜yellow coupler (
+X S ) ・・・・・・・・・0.20 Coupler solvent (4xa) ・・・・・・・・・o, o
r1st O layer (ultraviolet absorbing layer) Gelatin ・・・・・・・・・1.
Sunset UV absorber (+x 9)...
...7.0 UV absorber solvent (-+XS) ・
・・・・・・・・・0.30 color mixture prevention agent (formerly 17)
・・・・・・・・・0.0g 11th layer (protective layer) Gelatin ・・・・・・・・・/,
The compounds used here are as follows: Sake 1
Dioctylphthalate appetizer 22-(,2-hydroxy-j-sec-butyl-
r-tithylphenyl)benzotriazole 32-[α-(2,≠-di-t-amylphenoxy)butyramide]-μ,I,-dichloro-y-ethylphenol 4j,j'-dichloro-3 ,3'-di(3-sulfobutyl)-terethylthiacarbonyl cyanine Na
salt + s)'J ethylammonium-3-(x-(2-(J
-(J-sulfopropyl)nando(/, 2-d)thiazoline-coylidenemethyl)-/-butenyl)-3-naphtho(/, 2-d)thiazolino]propanesulfonate-x:6 Polyethyl acrylate 7 Phosphoric acid trioctyl ester"+ 8 2.41-t-hexylhydroquinone ÷ 9 Di(2-hydroxy-j-1-butyl-!-
methylphenyl)methane★ 10 3,3.3',,3'-tetramethyl-! .

6, 6′-tetrapropoquine-7゜/′-bisspiroindane 11 / −(2,≠,6-dolichlorophenyl)-j-(2-chloro-yo-tetradecanamide)anilino Kobirazolino! -On Kaoru 126. J'-diphenyl-terethyl-3゜3'
-Disulfopropyloxacarbocyanine Na salt +131J-0-cresyl ester +14 2. μ
m di-t-octylhydroquinone 15 α-piparoyl-α-[(λ, 4L-dioxo-7-benzyl-!-ethoxyhydantoin-3-
IL) - Coke Loco! -(α-2,l-dioxo-1
-amylphenoxy)butanamine]acetanilide 16) ethyl ammonium 3-(2-(3-benzylrhodanine-! -IJ Thea) -3-benzoxazolinyl]propanesulfonate 17 Ko, Hiroji 5ec- Octylhydroquinone + 181J phosphoric acid trinonyl ester≠ 19 yo-chloro-2-(2-hydroxy-3-
1-Butyl-1-1-octyl)phenylbenztriazole + 2oi, 4L-bis(hinylsulfonylacetamido)ethane sample prepared by filtration? Sample ioi was used as a comparison sample from now on.

In sample 10/, the fifth layer (low-sensitivity green-sensing layer) was
A sample was prepared in exactly the same manner as Sample/Ql except that the compound shown in was added. The sample number is also shown in Table/.

The obtained sample was exposed to a light source at 3200°, and the illuminance of the exposed surface was j
Exposure was performed under OOlux with white light through a centometric wedge and then processed as follows.

A long time ago Compound J/ Aroma compound! 2 [Processing process] First development (black and white development >3r'ci,,'iz" water washing Jr'CI, '30" reversal exposure 7 ooLux or more l" or more color development
3r ”C=tirn water washing 3PC Hiro!〃Bleach fixing 3
r"c 2.'oo"Wash 3
r'c 2. 'ls'' [Processing solution composition] 1st developer NitriloN, N, N-)rimethylenephosphonic acid, pentasodium salt 0.62 Diethylenetriaminepentaacetic acid, pentasodium salt Hiroshi, O potassium sulfite 30. Of thiocyanic acid Potassium / 21 potassium carbonate
Jl, 0? Hydroquinone monosulfonate potassium salt Koz, oy diethylene glycol /j, 0gol-phenyl-Hiro-
Hydroxymethyl-Hiro-Methyl-3 One pyrazolidone λ, Oy Potassium bromide 0.1? Potassium iodide z, o Add water
/1 (pH 2,70) Color developer benzyl alcohol /j, 011 diethylene glycol 12. oIIij3.6-
ditear i,r-octanediol 0,2f nitrilo-
N N N-) Rimethylenephosphonic acid pentasodium salt □, jf Diethylenetriaminepentaacetic acid pentasodium salt 2.02 Sodium sulfite K, oy Potassium carbonate
Ko! , o Tahydrokyfluamine sulfur HtM 3. o y to one ethyl N-(β
-methanesulfonamidoethyl) -3-methylder-aminoaniline sulfate! , o1 potassium bromide. ,jy diiopotassium
! , add 0+g water
/1 (pHIo, 4AO) Bleach-fix solution λ-mercapto 1,31 μm triazole /, Of ethylenediaminetetratradic acid disodium dihydrate j, Of ethylenediaminetetratradic acid Fe(II) ammonium monohydrate to , oy Sodium sulfite /j, 09 Sodium thiosulfate (700 fl liquid) Ho, o, 13 Glacial acetic acid
J, add 0.1 water
/1 (pH+, to) After the above-mentioned processing, the characteristic curve of the green-sensitive emulsion layer is determined by self-registered density measurement using a green filter, and this is the difference between the maximum density (Dmax) value and the minimum value of the green-sensitive emulsion layer. concentration(
Dmin) value was determined. Furthermore, (Dmax+Dmin
)/-2f, the sensitivity was determined from the reciprocal of the concentration value t-4l-ffi amount. Dmax of each sample.

Table 1 shows the relative sensitivity of each sample when the sensitivity of sample ioi is 6ioo.

Since this is a color reversal process, if the degree of emulsion fogging is large, the Dmax value will decrease.

The degree of fogging is large in sample 10/. Samples containing compounds (51) and (52) iox~lO! Although the occurrence of fog can be significantly suppressed, the sensitivity is significantly lowered, which is not preferable. Compound of the present invention (/, 2.7~
io, i2. is, ko! , 2t)/II
-/30, the decrease in sensitivity was extremely small and the occurrence of fogging could be significantly suppressed, giving very favorable results.

(Example 2) Table 3 shows the results of an experiment conducted in the same manner as in Example 1 except that benzyl alcohol was removed from the color developer during the processing step. Since the benzyl alcohol has been removed from the color developer, the activity of the color developer has decreased. Therefore, Dma in Example 1
In this example, the Dmax value is reduced compared to x.

However, in this example, the increase in emulsion fog was Dm
This corresponds to a decrease in the ax value.

From Table 3, sample 7 containing compound (52) or (52)
02 to 106, the occurrence of fogging was significantly suppressed,
A significant decrease in sensitivity is undesirable. Compound of the present invention (1
12,7~10,12,/! , 2, and samples iit and 13o, in which the additives were added, had extremely small decreases in sensitivity and significantly suppressed the occurrence of fog, giving very favorable results.

(Example 3) A sample was prepared by changing the fifth layer (low-sensitivity green-sensing layer) and the second layer (high-sensitivity green-sensing layer) to those with the following composition in Sample 10/ in Example/Middle. 30/. What are the ingredients below? /m2 unit indicates fc coating amount. Regarding silver halide, the coating amount is shown in terms of tin.

No.! Layer (Low sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*/, ri (silver iodide 2.! morch, average grain size 0.4tμ)
...Old...Silver 0. /.

Gelatin ・・・・・・・・・・・・
0.70 magenta coupler ($, 2/) ・・・ Old -0, 3j anti-fade agent A (*, 10) ・・・・・・
......0. /.

Coupler solvent (*7) ・・・・・・・・・・・・
o, is layer (high-sensitivity green-sensitive layer) silver iodobromide emulsion spectrally sensitized with green-sensitizing dye (*/, silver iodide 3.0%, average grain size 0.9) ′μ)
・・・・・・・・・Silver o, i.

Gelatin...River...0.
70 magenta coupler (*,!/) ・・・・・・・・・
・・0.3j anti-fading agent (*10) ・1 Old...
... o, i.

Coupler solvent (*7) ・・・・・・・・・・・・
0. /Yo*,! /Nia-chloro-6-methyl-co[/
-Methyl-λ-(2-octyloxy-yo-(ni-octyloxy-j-t-octylbenzenesulfonamido)ethyl]-/H-pyrazolo(l, r-b) [/,,!
.

In Gutsu-triazole sample 30/, the th! A sample was prepared in exactly the same manner as Sample 30/, except that the compound shown in Table 1 was added to the layer. The sample number is also shown in the table.

The obtained sample was exposed and developed in the same manner as in Example No. Dmax and sensitivity were determined. The values are shown in the table below.

table! Therefore, the degree of fogging in sample 30/ is large. In samples 302 to 30j to which compound (j/)(tx) was added, the occurrence of fogging could be significantly suppressed, but the sensitivity was significantly lowered, which is not preferable. Sample 3 added with the compound of the present invention
/I to 330, the decrease in sensitivity was extremely small and the occurrence of fogging could be significantly suppressed, giving very favorable results.

(Example G) In the implementation example 3, force 2 during the processing process - from the developer,
The experiment was carried out in the same manner as in Example 3, except that the benzyl alcohol was removed, and the results are shown to you.

From Table 6, compound (!/) Mayu added (!2) and t samples 302-30! Although the occurrence of fog is significantly suppressed, the sensitivity is significantly lowered, which is undesirable. In Samples 31/-330 to which the compound of the present invention was added, the decrease in sensitivity was extremely small and the occurrence of fogging was significantly suppressed, which was a very favorable result.

Claims (1)

[Scope of Claims] A silver halide color reverse reflection print light-sensitive material having at least one layer each of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support, comprising a compound represented by the following general formula (I). 1. A method for processing a silver halide color reverse reflection print photosensitive material, which comprises processing a silver halide color reverse reflection print photosensitive material containing at least one of the above with a color developing solution containing an organic thioether compound. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, M represents a hydrogen atom, a cation, or a protecting group for a mercapto group that is cleaved with an alkali, and Z represents a 5- or 6-membered unsaturated heterocycle. represents the atomic group required to form . The unsaturated heterocycle consists of only carbon atoms and 2 or 3 nitrogen atoms, may have a substituent, or may be fused with a benzene ring.