JPH04121731A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a pressure characteristic and to obviate the staining of a sensitizing screen of this time by adding a compd. having a specific structure before the chemical sensitization of the photosensitive emulsion of photosensitive emulsion layers ends. CONSTITUTION:This silver halide photographic sensitive material is prepd. by adding the compd. of formula I into the photosensitive emulsion of the photosensitive emulsion layers before the emulsion ends the chemical sensitization. The contamination on a sensitizing screen for X-rays is obviated and the dissolving property with lapse of time is improved. In the formula, X denotes OR1 or formula II; R1 denotes a hydrogen atom or the group which can be made into a hydrogen atom by hydrolysis; R2, R3 and R4 respectively denote a hydrogen atom or group which can be substd.; R5, R6 respectively denote a hydrogen atom, alkyl group, aryl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbonyl group, arylcarbonyl group or carbamoyl group; Y is the adsorption accelerating group to a silver halide; L denotes a bivalent combination group; (m) denotes 0 or 1.

Description

[Detailed description of the invention] (Field of industrial application) The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material).
The present invention relates to a technology that eliminates contamination of an X-ray intensifying screen, reduces pressure sensitivity, and improves dissolution properties over time.

(Prior art) In general, photographic materials coated with silver halide emulsions are subjected to various pressures. For example, general photographic negative film may be rolled up in a cartridge or bent when loaded into a camera. , being pulled for frame-by-frame forwarding, or being rubbed against the camera's transport part.

On the other hand, sheet films such as printing sensitive materials and direct medical X-ray sensitive materials are often folded or folded because they are handled directly by humans. Inside, it comes into contact with metal and rubber with strong force.

Furthermore, all types of sensitive materials are subjected to great pressure during cutting and processing.

When various pressures are applied to the photographic material in this manner, pressure is applied to the silver halide grains using gelatin, which is a support (binder) for the silver halide grains, or a polymeric substance as a medium. It is known that when pressure is applied to silver halide grains, blackening or desensitization that does not correspond to the exposure amount occurs, for example, W, B, Mather J, Opt, Soc, ^m,
,” L, 1054 (1948), P. Faelen
sand P, de Smet, Sci, et In
d. Phot, 25. Na5.17B (195
4), P., Faelens, J., Phot, Sc.
i, J, 105 (1954) and others.

Therefore, it is strongly desired to provide a photographic material whose photographic properties are not affected in any way by these pressures. In particular, pressure resistance is a difficult problem for systems with a small amount of binder that can be processed quickly.

In general, there is an unfavorable correlation in that increasing the sensitivity of an emulsion also increases pressure sensitivity.

Additionally, sensitizing dyes promote and exacerbate the caprigenic nature of silver halide grains when subjected to pressure. If a large amount of sensitizing dye is added during color sensitization in an attempt to increase light absorption and increase sensitivity, the blackening phenomenon when pressure is applied will also be significantly worsened. As a means to improve the pressure characteristics against such adverse effects, there are methods such as adding plasticizers such as polymers and emulsions, and reducing the silver halide/gelatin ratio of silver halide grains. Methods are known to prevent particles from reaching the target.

British Patent No. 738,618 describes a heterocyclic compound in British Patent No. 738,618.
No. 38,637 contains alkyl phthalate, No. 73B,
, 639, alkyl esters, and U.S. Pat.
No. 60,404 contains polyhydric alcohol, No. 3,121,
No. 060 discloses a method using carboxyalkylcellulose, JP-A-49-5017 discloses a method using paraffin and a carboxylic acid salt, and JP-B No. 5328086 discloses a method using an alkyl acrylate and an organic acid.

However, the method of adding a plasticizer reduces the mechanical strength of the emulsion layer, so there is a limit to the amount of plasticizer that can be used, and increasing the amount of gelatin slows down the development progress, making it undesirable for a sensitive material for rapid processing. However, it was difficult to achieve sufficient effect.

By the way, as described in U.S. Pat. Because it is large, high optical density can be obtained with a small amount of silver.

Also, due to its large surface area per unit volume,
During spectral sensitization, it is possible to adsorb more sensitizing dyes and the ability to capture incident light is high. It is more preferable to add 100% or more of the above, but as mentioned earlier, the pressure sensitivity increases with the amount added. Furthermore, because of its shape, it is easily deformed by external forces, and the above method cannot achieve a particularly satisfactory state.

(Objective of the present invention) The present invention provides a method for improving pressure properties. It also provides a method that does not stain the intensifying screen at that time. It also has improved dissolution properties over time.

(Means for Achieving the Present Invention) The above object of the present invention is to provide at least one photosensitive emulsion layer on a support, and by the time the chemical sensitization of the photosensitive emulsion is completed, a compound of the following general 2N) can be used. This was achieved using a silver halide photographic material characterized by the addition of .

General formula (R1 represents a hydrogen atom or a group that can be converted into a hydrogen atom by hydrolysis, R2, R3 and R4 each represent a hydrogen atom or a substitutable group, R5 and R6 each represent a hydrogen atom , represents an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbinyl group, an alkylcarbinyl group, or a carbamoyl group, Y is a group promoting adsorption to silver halide, and L is -2 m represents O or /.

Here, the group represented by R1 that can become a hydrogen atom by water decomposition at the cutting edge is, for example, -COR7 (as R7,
Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted/unsubstituted! Represents a plurality of atoms necessary to form a membered ring or a heterocyclic ring which is a membered ring. ).

Examples of substitutable groups for R2, R3 and R4 include halogen atoms (fluorine, chlorine, bromine), alkyl groups (preferably those with carbon numbers of up to 20), and aryl groups (preferably those with carbon numbers of &-20). alkoxy groups (preferably those with a carbon number of ~20), aryloxy groups (preferably those with a carbon number of 2 to -0), alkylthio groups (preferably those with a carbon number of ~20), Arylthia group (preferably) with carbon number z-20), acyl thickness (preferably '?L〈is carbon number 2)
~20), acylamino group (preferably carbon number/
~20 alkanoylamino group, carbon number &-20 benzoylamino group), nitro group, cyano group, oxycarbonyl group (preferably carbon number/~20 alkoxycarbonyl group, FIJEA ~20 aryloxycarbonyl group) ), carhoyasi group, sulfo group, ureido group (preferably an alkylureido group with carbon number/~20, carbon number J −
aryl ureido group of jO), a sulfonamide group (preferably an alkylsulfonamide group having a carbon number of 20 to moyl group, arylsulfamoyl group having z to 0 carbon atoms), carbamoyl group (preferably an alkylcarbamoyl group having 0 to 0 carbon atoms, an alkylcarnoζmoyl group having 20 carbon atoms), acyloxyl group (preferably carbon number/
-20), amino group (unsubstituted amino, preferably an alkyl group with carbon number / - -0, secondary or tertiary amino group substituted with 7 aryl group with 7 to 10 carbon atoms), Carbonate ester group (preferably an alkyl carbonate ester group with a carbon number of up to 0, a carbonate group with a carbon number of 20 to 20), a sulfonyl group (preferably an alkyl sulfonyl group with a carbon number of up to λO, a carbon Arylsulfinyl group with several t-, λO), sulfinyl group (preferably with carbon number/~).

R2, R3, and R4 may be the same or different, and R2, R
If any two of 3> and R4 are substituted on adjacent carbon 7 atoms of the ring, consecutively! ~7
A membered carbocyclic or heterocyclic ring may be formed, and these rings may be saturated or unsaturated.

Specific ring-forming compounds such as cylindrical compounds: hantan, cycloheptane, cycloheptane, cycloheptane, cycloheptane, cycloheptani/, indane, norbornane, noryl, n, 'e:') and the like, and these may further have a substituent.

Further, the total carbon number of R2, R3, and R4 is preferably /~IO.

R5 and R6 are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted arsenulfonyl group, a substituted or unsubstituted 7
R5 represents a lylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted lupamoyl group;
, R6 may be the same or different, or may be linked to form a nitrogen-containing hela 0 ring. (For example, morpholino group, bi is lydino group, pyrrolidino group, imidazolyl group.

Examples of the substituents for R5 and R6 include those listed as substitutable groups for R2, R3 and R4, and +LHy, and hydrogen atoms are particularly preferred for R5 and R6.

It is preferable that X be substituted at the 10000-degree or para-position with respect to the 10R1 group. Among those represented by X, 10R1 is more preferable, and R1 is more preferably a hydrogen atom.

Y is a group that promotes adsorption to silver halide, and L is a divalent linking group. Preferred examples of the adsorption-promoting group to silver halide, where m is O or/and 6°Y, include a thioamide group, a mercapto group, a group having a disulfide bond, or! to t-membered nitrogen-containing heterocyclic groups.

The thioamide adsorption promoting group represented by Y is a divalent group represented by -C-amino, and may be a part of a ring structure, or may be an acyclic temanamide group. good.

Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
No. 030,92j, μ, No. 031,127, Hiromu, O
Za0.207, Dohiro 5.2μ! , No. 037, same, 2
63. ! // issue, bolt 14.2tt, 0/3 issue, and same 1
1,27 tons! t≠ issue, as well as [Research Disclosure J]
Choose from those disclosed in ure) Magazine Volume 7j 1 Ya/Yo/Aj (/Tough wo 2019/Tsunozuki) and Douhei/7 Otsu Volume A/7bu-J (/77R/-Mon) I can do it.

Specific examples of acyclic thioamide groups include thiourido groups, thiourethane groups, dithiocarno; specific examples of cyclic thioamide groups such as mic acid ester groups;
For example, gutiazoline-2-thione, ko-imidasoline-2-thione, cortiohydantoin, rhodanine,
Thiobarbylic acid, tetrazoline, /,
2.4'-triazoline-3-thione, /, 3,1/-
-thiadiazoline-2-thione, /, J, 4'-mxadiazolin-corchion, benzimidacillin-corchion, benzoxazoline-2-thione and (nzoteazoline-λ-thione), and these may be further substituted.

The mercapto group of Y is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (if υ next to the carbon atom to which the -3H group is bonded is a nitrogen atom, a cyclic mercapto group that has a tautomeric relationship with this It has the same meaning as the thioamide group, and specific examples of this group are the same as those listed above).

The j-negative to t-membered nitrogen-containing heterocyclic group represented by Y consists of a combination of nitrogen, oxygen, sulfur, and carbon! An example is a negative or Δ-negative element-containing heterocycle. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazoline, oxazole, thiadiazole, oxadiazole, triazine, and the like.

These may be further substituted with continuous substituents.

Examples of the substituents include those described as substituents for R2, R3, and R4.

Among those represented by Y, preferred are cyclic thioamide groups (i.e., mercapto-substituted nitrogen-containing heterocycles, such as comelkabutothiadiazole group, 3-mercaptothiadiazole group, 2.μ-trianyl group, yo-mercaptotetrazole group, comercapto/ , J , μm
oxadiazole group, comelcabutobenzoxazole group, etc.), or an element-containing heterocyclic group (eg, benzotriazole group, benzimidazole group, indazole group, etc.).

Two or more Y→L Cm groups may be substituted, and may be the same or different.

The divalent linking group represented by L includes C, N, S, 0
An atom or atomic group containing at least one of the following. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -〇-1-S-1-NI(
-1-N=, -C〇-1-SO2- (these groups may have a substituent), etc. alone or in combination.

Specific examples include -CONH-1-NHCONH-1-8O3 positive-1-C
Examples include OO-1.

These may be further substituted with a suitable substituent.

Examples of the substituents include those described as substituents for R2, R3, and R4.

Preferred specific examples of the compound represented by the general formula (1) are shown next, but the scope of the present invention is not limited thereto.

1-/) ■-2) q-ro ■-3) ■-μ) ■-ri■-bu) r-7) I-J') ■-ta) l-1 and ding -//) ■-/ 2) 1-/5 (-/j) H ■-/7) I-/♂ 1-tri■-co0) cl(3δU2NH OH ■-col) ■-23 CH3 Below is the general formula (1 ) will be explained by giving examples of typical synthesis methods.

Synthesis Example Synthesis of Compound I-/ /j-phenylbenztriazole carbonate 23, r
fi (0.1 mol), co(t-aminephenyl)-ethylhydroquine 7! , 29 (0°/l solu), DM
AC/00 was heated in an oil bath under a nitrogen stream.
ectotherm)! The blade was heated and stirred for an hour.

Next, DMAC-t-distilled under reduced pressure and 200 ml of methanol was added, leaving a trace amount of black crystal by-product as an insoluble matter.

Insoluble matter was removed by absorption filtration, methanol was distilled off under reduced pressure, and the resulting reaction mixture was isolated and purified using a silica gel column (chloroform/methanol-4/1). After washing with methanol, the target product 1-11 was purified. Obtained. Yield 14.4 (38,5
%) Melting point: 256-7°C Also, the compound represented by general formula (1) is silver halide 1
per mole l x I O-5 mol to l x 10-1
It is preferably contained in moles of 1×10 to 5×1
The preferred addition amount is in the 0-'' mole range.

Although it is necessary to add the compound of general formula (1) until the end of chemical sensitization of the emulsion, it is particularly preferable to add it at the start of chemical sensitization, before the start of chemical sensitization, or during chemical sensitization.
Among these, the time at the start of chemical sensitization is preferred.

As the sensitizing dye of the present invention, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoholadianine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

The amount of the sensitizing dye added is preferably 80% or more, particularly 100% or more and less than 200% of the saturated adsorption amount on the silver halide grains. 3001Ig or more 2000 per mole of silver halide
It is less than ■, preferably 600 ■ or more and less than 1000 ■.

Specific examples of sensitizing dyes that are effective in the present invention are shown below.

(CH2)4 S Q a Na (CH2)4 O3- O3 8O3H-N(C2H5)3 2H5 (CH2]3 (CH2)3S03K
503-The timing of adding the sensitizing dye of the present invention is as described in U.S. Pat.
As described in No. 66, spectral sensitization is carried out simultaneously with chemical sensitization by adding a sensitizing dye at the same time as a chemical sensitizer, as described in JP-A-5R-I/3. Spectral sensitization can also be performed prior to chemical sensitization as described in No. 2r.
It is also said that it is possible to start the spectral sensitization before the completion of the formation of the oxidized particles precipitate. Furthermore, U.S. Patent No. μ, 22! , adding these target compounds separately as taught in No. 666,
That is, it is also possible to add a portion of these compounds prior to chemical sensitization and the remaining portion after chemical sensitization, as taught in U.S. Pat. It may be carried out at any time during the formation of silver halogenide grains, including the method described above. Of course, the entire amount of the necessary sensitizing dye may be added at the same time as other chemicals when coating. Among these methods, the method described in Japanese Patent Application No. 1986-1-2 (spectral sensitization is performed before chemical sensitization) is particularly preferred for the present invention.

As the tabular photosensitive silver halide emulsion used in the present invention, silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide can be used, but from the viewpoint of high sensitivity. Silver bromide or silver iodobromide is preferred, especially when the legal content is Omo+
%n3 and jmo1% are preferred.

Projected area chamber diameter of the tabular emulsion of the present invention: 410.3 to i, O
0 to ttmz%. j ~/, 7! Preferably it is μm. In addition, the distance between parallel planes (the thickness of the plate is 0.0! μm-0.3 μm, % is 0.1-0.21 μm)
Preferably, the aspect ratio (particle diameter/thickness ratio) is
As for 3 or more and less than 20, especially! It is preferable that it is greater than or equal to r and less than r.

The ascent ratio in the emulsion layer is 50% (area) or more of the total halide grains, preferably 70% or more, particularly preferably 0% or more, based on the proportion of tabular grains having a cross ratio of 3 or more.

The tabular silver halide grains can be produced by appropriately combining methods used in the cancer industry.

In the tabular silver halide emulsion, Funatsu ((ugnac)
and Nya) - (Chateau) "Evolution of the morphology of silver bromide crystals during physical ripening"
"Crystals Dueling Fincal Living]" Science, Engineering, Industry, Fumantogelahui, Volume 33, 75. ! (/ri6), p, /2
/ - / 2 J, Duffin, “Photographic Emulsion Chemistry”
graphic emulsion chemist
ry ) J Focal Pre 7 (Focalp r
es s ), Nini E-ri, 7966, p.
66-p, '72, A, P, H,) Ribery (Trivc
lls, w, F', /C Smith 7 Photographic Jou
rnal), volume to, page 2rj (/9170), etc., but JP-A-Shoj♂-/-7, ri, 2/, JP-A-Sho! Zaichi//J, riλ7, JP-A-Sho sr-//J, ri2
g, can be easily prepared by referring to the method described in US Patent No. 32, No. 20.

In addition, a seed crystal containing 410% or more of tabular grains by weight is formed in an atmosphere with a relatively low pBr value of pf3r/, 3 or less, and silver and parogen solutions are simultaneously added while keeping the pBr value at the same level. Obtained by growing seed crystals under force.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

Tabular...Rogge/Silver oxide grain size is determined by controlling temperature adjustment, selection of solvent type and amount, silver salt used during grain growth, and addition rate of halide! l
lCan be adjusted.

Further, among tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains.

The structure and manufacturing method of the monodisperse hexagonal tabular grains referred to in the present invention are as described in Japanese Patent Application No. 1973, but briefly stated, the emulsion is a silver halide emulsion consisting of a dispersion medium and silver halide grains. The emulsion is an emulsion in which 70 or more of the total projected area of the silver halide grains has a ratio of the length of the side that has the maximum length to the length of the side that follows the minimum length is λ or less. It is a certain hexagonal shape and is occupied by tabular silver halide with two parallel faces as outer surfaces,
Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [the value obtained by dividing the variation (standard deviation) of the grain size expressed by the circular diameter of its projected area by the average grain size] is 20% or less. It has a monodispersity of Preferably, it contains sensitized silver nuclei.

For the present invention, British Patent 6.1! So-called halogen conversion type particles, such as those described in U.S. Pat.

The amount of halogen conversion is 0.2 moI% to λmo1 relative to the amount of silver
%Special VC0.2m01%~0.6mo1% is appreciable.

For silver iodobromide, grains having a structure having a high iodine layer inside and/or on the thorny surface are particularly preferred.

By converting the entire thorny surface of the tabular silver halide grains of the present invention, a silver halide emulsion with higher sensitivity can be obtained.

As a method for halogen conversion, an aqueous solution of 7 JD of halogen, which has a small solubility product with silver and halogen composition, is usually added to the top surface of the particle before halogen conversion. For example, add potassium bromide and 10R potassium iodide aqueous solution to silver chloride or salt-smelling tabular grains, and add 7 JD of potassium iodide aqueous solution to silver bromide or iodobromide tabular grains. cause a conversion. The concentration of the aqueous solution to which these additives are added is preferably thinner, less than 30%, more preferably less than 710% (more preferably less than 710%), and less than 7 molti per minute per 7 mol of chlorogen conversion. It is preferred to add the converted chloride solution at a rate of . Furthermore, a sensitizing dye may be present during the conversion, and silver bromide, silver iodobromide, silver iodide, or silver halide fine particles may be added instead of the aqueous solution during the conversion. You can. Due to the size of these fine particles,
0.2 μm or less, preferably 0.1 μm or less, especially 0.0
It is desirable that the thickness is 6 μm or less. The amount of silver chloride converted is 0.0% of the silver chloride before conversion. ／〜／ m o '1
%%i0,j~0,6mO1% is preferred.

The logen conversion method of the present invention is not limited to any one of the above methods, but may be used in combination depending on the purpose. It is preferable that the iodine content of the different surfaces of the grains before halogen conversion is 11:1 mol % or less. In particular, it is preferable that Jmo is 0.0 and Jmo is 1% or less.

This method is particularly effective in the presence of a silver halide solvent when performing halogen conversion using the above method.

Preferred solvents include thioether compounds, thiocyanates, and fluorinated thioureas. Among them, thioether compounds and thiocyanates are particularly effective, and thioanates have a concentration of 0.5 to 1 mole of silver chloride.
! It is preferable to use 0°2i to 30° f, thioether.

Moreover, in the present invention, % Kaisho 6! -230/3! Ya Tokugan Showa 6
A compound that releases an inhibitor during development, such as those described in /-/bri≠Tata, may be used in combination.

In the process of silver halide grain formation and physical ripening during silver halide production, cadmium salts, zinc salts, lead salts,
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.

Furthermore, so-called silver halide solvents such as thiocyanates, thioether compounds, thiazolidine dithiones, and tetrasubstituted thioureas may be present during grain formation. Among them, thio/anate salts, g-substituted thioureas and thioethers are preferred solvents for the present invention.

As a method for chemically sensitizing the silver halide emulsion used in the present invention, it is recommended to use known methods such as sulfur sensitization, selenium sensitization, reduction sensitization, and gold sensitization. may be used alone or in combination.

Among the noble metal sensitization methods, the gold sensitization method is an alternative method and uses gold compounds, mainly gold complex salts. There is no problem in using complex salts of precious metals other than gold, such as platinum, palladium, and iridium, as goldstone. Specific examples are US patent co, ←tr, ob
No. o, British Patent No. 6/r, No. 067, etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used.

The combined use of sulfur sensitization using thiosulfate and gold sensitization can effectively exhibit the effects of the invention.

As the reduction sensitizer, stannous salts, amines, formamidine sulfine, silane compounds, etc. can be used.

Patent application No. 62-74 for tabular grains used in the present invention.
The vertex development-initiated particles described in t///- are extremely useful.

The chemical sensitization process of the present invention is applied to the photographic emulsion used in the present invention for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and for stabilizing photographic performance. In addition to the silver halide adsorbing substance, various compounds can be used to absorb silver halide. That is, azoles (e.g., benzothiazolium salts, nitroimidazoles, nitro-nitrozimidazoles, chlorobenzimidazoles, bromo-nitroimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.)
; mercapto compounds (e.g. mercaptothiazoles, mercaptobenzothiazoles, mercapto-'nimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.); 5 thioketo compounds such as oxadorinthion; Azaindenes (e.g. triazaindenes, tetraazaindefs (especially hydroxy-substituted (/, j, Ja, 7) tetraazaindenes), pentaa, zaindenes, etc.); benzenethiosulfonic acid, benzenesulfinic acid, Benzene sulfonic acid 7
Also known as antifoggants or stabilizers such as
Additionally, many compounds can be added.

In particular, nitrone and its derivatives described in JP-A-6O-7A74tj and JP-A-60-J'73 Coco, JP-A-Shobo
-Mercapto compounds described in RORI publication, heterocyclic compounds described in JP-A No. 7-76μ736, and complex salts of heterocyclic compounds and silver (e.g. l-phenyl-mercaptotetrazole@)? It can be used conveniently.

In addition to other hydrophilic colloid layers in the photosensitive photographic emulsion layer produced using the present invention (C coating aid, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention and improvement of photographic properties (e.g. Various surfactants may be included for various purposes such as development acceleration, hardening, and sensitization.

For example, saponins (nuteroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyniterene oxide adducts of silicones), sugar Nonionic surfactants such as alkyl ethers; furkylsulfonates, alkylnaphthalene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyltaurifs, null nechosuccinic acid esters anionic surfactants such as sulfoalkylpolyoquine ethylene alkylphenyl ethers; amphoteric surfactants such as alkylbetaines and alkylsulfobetaines; aliphatic or aromatic ψ-class ammonium salts, pyridinium salts, Cationic surfactants such as imidazolium salts can be used.

Among these, saponin, dodecylbenzene disulfonic acid Na
tX, x-ethylhexyl α-sulfosuccinate Na salt, p-octylphenoxyethoxyethoxyethane sulfo/acid Na salt, dodecyl sulfate NafX, triisopropylnaphthalene sulfonate Na salt, N-methyl-oleoyl taurine Na salt, etc. Anion, dodecyltrimethylammonium chloride, N-oleoyl-N', N'
, N'-)riftylammoniodiaminopropane bromide, cations such as dodecylpyridicum chloride, betaines such as N-dodecyl-N, N-dimethylcarboxybetaine, N-oleyl-N, N-dimethylsulfobutylbetaine, Poly(average degree of polymerization n=70) oxyethylene cetyl ether, poly(n=Jj) oxyethylene p-nonylphenol ether, bis(/-poly(
n = 76) I especially like nonions such as oxyethylene-okinko and 4(-di-t-6-terphenyl)ethane! L (can be used.

Perfluorooctaneurphonic acid potassium as an antistatic agent
[, N-propyl-N-perfluorooctane sulfonylglycine Na salt, N-propyl-N-perfluorooctane 2-sulfonylaminoethyloxy(n=j)oxine ethylenebutanesulfonic acid Na salt, N-perfluoro Fluorine-containing surfactants such as octanesulfonyl-N', N', N'-1-limethylammoniodiamine propane chloride, N-perfluorodecanoylaminopropyl-N', N'-dimethyl-N'-carboxyitaine Injection, % Kaisho 60-10? ≠r issue, same 6/ -/ /
J/4 (No. 44, Patent Application No. 6/-/3398', (
Nonionic surfactants described in Ff16/-16066 and the like, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides obtained by doping these with antimony or the like can be preferably used.

In the case of non-invention, U.S. Patent No. I 7210 as a cloak agent
/ issue, 0.270/2! lt! No., same da/gu 2? Tag number, '7396701. Fine particles of organic compounds such as homopolymers of polymethyl methacrylate or copolymers of methyl methacrylate and methacrylic acid starch, and inorganic compounds such as silica, titanium dioxide, sulfuric acid, and barium strontium can be used.

The particle size is 1.0~IOμm, %! μm
It is preferable that

In the coating layer of the photographic material of the present invention, U.S. Patent No. 34t19'! is used as a slipping agent. No. 76, same 4to≠72! In addition to the silicone compounds described in No. R and the colloidal silica described in Japanese Patent Publication No. Sho J6-23/32, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, tantanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention.

Gelatin is generally used as a protective colloid that can be used in the emulsion layer, rP interlayer, and hexagonal protective layer of the light-sensitive material of the present invention, but other hydrophilic Colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose 2, cali-xymethyl cellulose, cellulose ethyl sulfates, etc., sodium alginate, dextran, and starch. Sugar derivatives such as derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

Among these, it is preferable to use dextran or polyacrylamide with an average molecular weight of 50,000 or less together with gelatin. % Gansho 6/-ko/3!03, same 6/-2111
10! 10,000 f! :a Also effective in the present invention.

The photographic emulsions and non-sensitive hydrophilic colloids of the present invention may contain free or organic hardeners.

For example, chromium salts (chromium alum, etc.), aldehydes (
formaldehyde, glitaraldehyde, etc.), N-
Methylol compounds (dimethylol urea, etc.), dioxane derivatives (λ, 3-dihydroxydioxane, etc.), activated vinyl compounds (/.

J, j-triacryloyl-hexahydro-S-triazine, his(vinylsulfonyl)methyl ether, N
, N'-methylenebis-[β-(vinylnulfonyl]propionamide], etc.), active compounds
12+(2<' )chloro-6-hydroquine-5-)
riazine, etc.), mucohalogen acids (such as mucochloric acid), inoxazoles, dialdehyde starch, cococol-6-hydroxytriazinylated gelatin, and the like can be used alone or in combination. Among them, Tokukai Akira! 3-Da/Ko/S same! 3-j7Jj7, same jter 1
62!4t6, Fi6o-rot<tb and U.S. Patent J, 32jr, λF7
The active halides described in this issue are preferred.

N-carbamoylpyridinium salts (e.g., (/-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (e.g., /-(/-chloro-/-pyridinomethylene)pyrrolidiniumconaphthalenosulfonate, etc.) It is also for M.

Polymer hardeners can also be effectively used as hardeners in the present invention.

Examples of the polymeric hardening agent used in the present invention include dialdehyde starch, polyacrolein, and U.S. Patent No. 33 Zoro 0
Polymers that regenerate aldehyde groups, such as the acrolein copolymers described in No. 2, U.S. Pat. No. 3.6J3.171r
No. 3, U.S. Pat.
362. 1'27, Research Day Closure Magazine/7333, etc., a polymer having a dichlorotriazine group, JP-A-66-66J'
! ! - Polymer having an active ester group described in JP-A-Sho! 6-/≠ko! λhiro, US Patent MIG /6
/ 1407, JP-A-54'-1R6033, Research Disclosure Magazine /67jj (/7f), etc. Polymers that regenerate active vinyl groups or groups that become precursors thereof, etc. Polymers having a vinyl group or a group serving as a precursor thereof are preferred, and among them, JP-A-Sho! 6-/4126214, the long group is activated by a vinyl group,
Alternatively, a polymer in which a group serving as a precursor thereof is bonded to the main chain of the polymer is particularly preferred.

The support is preferably polyethylene terephthalate film or cellulose triacetate 7 film.The surface of the support is treated with corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment in order to improve the ε adhesion with the hydrophilic colloid layer. Depending on the method, an undercoat layer made of styrene-butadiene latex, vinylidene chloride latex, etc. may be provided, and a gelatin layer may be further provided on top of the undercoat layer.

Further, an undercoat layer may be provided using a photographic solvent containing a polyethylene swelling agent and gelatin. The adhesion of these undercoat layers to the Vr-hydrophilic colloid layer can be further improved by subjecting them to surface treatment.

As a coating aid for the undercoat layer, an n4 polyethylene oxide type nonionic surfactant can be preferably used.

The emulsion layer of the photographic light-sensitive material of the present invention may contain a plasticizer such as a polymer or an emulsion in order to further improve pressure customization in combination with the effects of the present invention.

A color-forming coupler may also be added to the photographic emulsion layer of the photographic light-sensitive material of the present invention. That is, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) in a color development process is used, for example, as a magenta coupler! - Pyrazolone couplers There are pyrazolopenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, piparoylacetanilides), etc., and cyan couplers include: These include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive ones that develop hydrophobic groups similar to pallast groups in the molecule. The coupler may be either l-equivalent or monoequivalent to silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to the DIR coupler, the product of the campling reaction is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.

There are no particular restrictions on other structures of the emulsion layer of the silver halide photographic material of the present invention, and various additives may be used as necessary. For example, Re5ear
ch Disclosure i Volume 76-λ~ko r
Binders, surfactants, dyes, ultraviolet absorbers, hardeners, coating aids, thickeners, and the like can be used.

The three-dimensional processing of the light-sensitive material of the present invention is, for example, carried out by Research Disclosure.
Any of the known methods and known treatment liquids as described in RD-/76, No. λr-30 (RD-/76≠3) can be applied. This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a color image (color photographic processing), depending on the purpose. Processing temperature is normal/0C
You can choose between so 0C and 1. ! s 0C~3♂
A good range is between 0C.

The developer used in black-and-white photographic processing can contain a developing agent. As a developing agent, dihydroquine/sens (tatoeba hydroquinone), 3-
Pyrazolidones (e.g. /-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-p
-Amine phenols and the like can be used alone or in combination. The developer generally contains other preservatives,
Contains alkaline agents, pH buffering agents, anti-capri agents, etc., and further contains solubilizing agents, color toning agents, surfactants, antifoaming agents, water softeners, hardening agents (e.g. glutaraldehyde) as necessary.
, a viscosity-imparting agent, and the like.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thionanate, organic sulfur compounds whose effectiveness as a fixing agent is known can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

A color developer solution generally consists of an alkaline aqueous solution containing a color developing agent. Color developing agents 12 Known general aromatic amine developers, such as phenylene diamines (for example, ≠
-amino-N, N-diethylaniline, 3-methyl-guamino-N, N-ethylaniline, q-amino-N
-ethyl-N-β-hydroquine ethylaniline, 3-methyl-μ=niamino-N-ethyl-N-β-hydroxyethylaniline 3-methyl-μmamino-N-ethyl-
N-β-methanesulfamide ethylaniline, μm amino-3-methyl-N=ethyl-N-β-methoxyethylaniline, etc.) can be used.

Other books include Photographic Processing Chemistry by P.A. Mason.
graphicProcessingChemis
try, ) (7 Ocalp L/SpocalPres
s, 1966), pages 226-229, U.S. Patent 2,
No. 193.015, No. 2,592,364, JP-A-4
Those described in No. 8-64933 may be used.

The color developer also contains a PH buffer, a development inhibitor, an anti-fogging agent, a water softener, a preservative, and more as necessary.
A solvent, a development accelerator, a carboxylic acid chelating agent, etc. can be added.

Specific examples of these additives include Research Disclosure (RD-17643) and US Patent No. 4,083.
No. 723, West German Open House (OLS) No. 2゜622.950, etc.

(Example) Next, the present invention will be specifically explained.

Example-1 (1) Preparation water of Agl fine particles 2! 0.5 g of potassium iodide and 26 g of gelatin were added thereto, and 80 cc of a silver nitrate aqueous solution containing 40 g of silver nitrate and 80 cc of an aqueous solution containing 39 g of potassium iodide were added over 5 minutes to the solution kept at 35°C while stirring. . At this time, the addition flow rates of the silver nitrate aqueous solution and the potassium iodide aqueous solution were each 8 cc/min at the beginning of the addition, and the addition flow rates were linearly accelerated so that the addition of 80 cc was completed in 5 minutes.

After particles were formed in this manner, soluble salts were removed by a sedimentation method at 35°C.

Next, the temperature was raised to 40°C, 10.5 g of gelatin and 2.56 g of phenoxyethanol were added, and plating was carried out with soluble soda.
H was adjusted to 6.8. The finished amount of the obtained emulsion was 730
The particles were monodispersed Agl fine particles with an average diameter of 0.015 μm.

(2) Preparation water for tabular grains II! , 4.5 g of potassium bromide, 20 g of gelatin.
6g, thioether HO (C8 zs(CHi) 1
Add 2.5 cc of a 5% aqueous solution of s(CHz) to)I into a container kept at 60°C, and add a silver nitrate aqueous solution 3 while stirring.
7cc (3.43g silver nitrate) and 2.97g potassium bromide
33 cc of an aqueous solution containing 0.363 g of potassium iodide was added in 37 seconds using a double jet method. Next, after adding an aqueous solution of 0.9 g of potassium bromide, the temperature was raised to 70°C, and 53 cc of a silver nitrate aqueous solution (4.90 g of silver nitrate) was added to
It was added over a period of minutes. Here, 15 cc of a 25% ammonia aqueous solution was added, and after physical ripening at that temperature for 20 minutes, 14 cc of a 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by a controlled double jet method while maintaining p and Ags at 5. Next, 10 cc of a 2N potassium thiocyanate solution and 0.05 mol % of the AgI fine particles (1) were added to the total amount of silver. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35°C.

In this way, monodisperse tabular fine particles with a total iodine content of 0.31 mol %, an average projected area diameter of 1.10 μm, a thickness of 0.165 μm, and a diameter variation coefficient of 18.5% were obtained.

After this, soluble salts were removed by a sedimentation method.

The temperature was raised to 40°C again, and 35 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate were added as a thickener, and the pH was adjusted to 5.90 and pAg to 8.25 with sodium chloride and silver nitrate solution.

This emulsion was chemically sensitized while being stirred and maintained at 56°C. First, add 0.043■ thiourea dioxide and
Reduction sensitization was performed by holding the sample for 2 minutes. Next 4-
20 μl of hydroxy-6-methyl 1.3,3a,7-chitrazaindene and 500 μl of aggravating dye-A were added. Furthermore, 1.1 g of calcium chloride aqueous solution was added. Subsequently, 3.3+ g of sodium thiosulfate, 2.6 μg of chloroauric acid, and 90 u of potassium thiocyanate were added, and after 40 minutes, 3.3+ g of sodium thiosulfate was added.
Cooled to 5°C.

In this way, preparation of tabular grains 1 was completed.

In the same manner, however, the compounds listed in Table 1 were added simultaneously with thiourea dioxide, and the amount of chloroauric acid was further adjusted to obtain particles 2 to 6.
was prepared.

Sensitizing dye (C1lz)s (Cut)s803
θ SO3Na concentration p411 The following chemicals were added per mole of silver halide of the emulsion to prepare a coating solution.

・2,6-bis(hydroxyamino) 4-diethylamino-1,3゜5-triazine 72 ■ ・Gelatin ・Trimethylolpropane 9g ・Dextran (average molecular weight 39,000) 18.5g ・Sodium polystyrene sulfonate (average Molecular weight 600,000) 1.8g/Hardness 1
1j [J 1. Adjust the amount added so that the 2-bis(vinylsulfonylacetamide) ethane swelling ratio is 225χ Ut+ ・Compound listed in Table 1 (The film thickness of the emulsion layer is 1.5μ) ゛ Tag -1 Surface protective layer Each component was prepared in the following coating amounts.

1 Blood Bean IJL Zakoro 1 cloth ・Gelatin 0.8g/Sodium polyacrylate (average molecular weight 400,000) 0. 0230.0
13 ・C+Js30+CIIzCLOhH0,045・
C+? HssCON(J12CHzSOJaCH,0
,0065 ・CJ+,5OtN+CHzCHtO昂HCffH?
0.003@C11
FI? 5O2N+CH,CH,0±"+CHz) as
OxNaCJt0. 001 g/
Polymethyl methacrylate (average particle size 3.7 μm) 0.087 Proxel 0.0005 (p with NaOH)
Hfli, adjusted to 4) (1) Preparation of dye D-1 for undercoat layer The following dye was ball milled by the method described in JP-A-63-197943.

Water 434 company and 6.7% aqueous solution of Triton X-2000 surfactant (TX-200@) 791ali!
and was placed in a 21 ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) piece 40
0d (2 m diameter) was added and the contents were ground for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO pieces were removed by filtration. When the obtained dye dispersion was observed, the particle size of the pulverized dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter, and the average particle size was 0.37 μm.

Furthermore, by performing a centrifugation operation, dye particles having a size of 0.9 μm or more were removed. Thus dye dispersion D-
I got 1.

(2) Preparation of support A biaxially stretched polyethylene terephthalate film with a thickness of 183 μm was subjected to corona discharge treatment, and a first undercoating liquid having the composition shown below was applied in an amount of 5.5 μm. lcc/rrf
Apply with a wire bar coater so that 17
Dry for 1 minute at 5°C.

Next, a first undercoat layer was provided on the opposite side in the same manner.

The polyethylene terephthalate used contained 0.04 wt% of a dye having the following structure.

A second undercoat liquid having the composition shown below was applied onto the first undercoat layer on both sides, one side at a time, at 150°C using a wire bar coater method on both sides.
Coated and dried.

An emulsion layer and a surface protective layer were coated on both sides of the above-mentioned transparent support by a co-extrusion method, and the amount of coated silver per side was 1.7 g/rrf. (However, the time shown in Table 1 was applied after dissolving the emulsion coating solution at 40°C.

Photographic materials 1 to 12 were thus obtained.

The swelling ratio of the hydrophilic colloid layer was measured after this photographic material had been aged for 7 days under 25"C60%RH conditions. The dry film thickness (a) was determined by scanning the section with a scanning electron microscope. Swollen film layer 0 )) was determined by immersing the photographic material in distilled water at 21°C for 3 minutes, freeze-drying it with liquid nitrogen, and then observing it with a scanning electron microscope.

al For photographic materials, the rate was 225%.

[Each sample of Photographic Materials 101 and 301 to 306 was exposed to light for 0.05 seconds from both sides using Fuji Photo Film's X-Ray Orthoscreen HR-4, and the sensitivity was evaluated. I did it. After exposure, the following processing was performed. The sensitivity is expressed as the ratio of the exposure amount giving a density of 1.0 using photographic sample 101 as a reference in logarithmic form.

<Developer concentrate> Potassium hydroxide 56.6g Sodium sulfite 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbonate
16.7g hou #
10g hydroquinone
83.3g diethylene glycol 4
0g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 22.0g 5-methylbenzotriazole 2g Make 12 with water (
P Hlo, prepared at 60).

<Fixer concentrate> Ammonium 1000 sulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid disodium trihydrate 0.10g Sodium hydroxide 24g Adjust to 11 with water (adjust to pH 5, 10 with acetic acid) Start the development process. At times, each tank of the automatic developer was filled with a processing solution as shown below.

Developing tank: 333 ml of the above developer concentrate, 6611 ml of water
A starter 10W1 containing 1.1 g of potassium bromide and 1.8 g of acetic acid was added to adjust the pH to 10.25.

Fixing tank: 250 m of the above fixer concentrate and 70 m of water Automatic developing machine: 5RX100 manufactured by KONI CA■
1 was modified to increase the film transport speed and dry
The to-dry processing time was 30 seconds. The washing water is run at a rate of 31 times per minute only while the film is passing through.
The rest of the time it was stopped. The replenishment and processing temperatures for the developer and fixer were as follows: 35°C for one-time development, 32°C for fixing, 20°C for washing, and 55°C for drying.

Box border 1 2 (ld/10x12 inches 30d/10x12 inches 31/1 minute Photographic materials 1 to 10, Fuji Photo Film GRENEX
Orthoscreen HR-4 was brought into close contact with both sides using a cassette, and XwA sensitometry was performed. The exposure amount was adjusted by changing the distance between the X-ray tube and the cassette. After exposure, the film was bent at 30° and processed using an automatic processor FPM-9000 (manufactured by Fuji Film Co., Ltd.) using the following developer and fixer. It was evaluated based on the degree of blackening.

O: No practical problem at all.

△: Slight blackening, but within practical tolerance.

×: Blackened and has a practical problem.

Dry to Dry processing time: 24.2 seconds The developer and fixer used had the following compositions.

(Developer) Potassium hydroxide 29g Potassium sulfite 44.2g Sodium hydrogen carbonate 7.5g Boric acid
1.0g diethylene glycol
12g ethylenediaminetetraacetic acid 1
．． 7g 5-methylhensitriazole 0.06g hydroquinone 25g glacial acetic acid
18g triethylene glycol 12g 5-nitroindazole
0.25g 1-phenyl-3-pyrazolidone
2.8g glucuraldehyde (50wt/wt%) 9.86g sodium metabisulfite 12.6g potassium bromide
Add 3.7g water
1. 0j2 (Fixer) Ammonium thiosulfate (70wt/vo1%) 200m ethylenediaminetetraacetic acid disodium dihydrate 0.02g Sodium sulfite 15g Boric acid
10g sodium hydroxide
6.7g glacial acetic acid
15g aluminum sulfate 10g
Add 3.9 g of sulfuric acid (36N) water to make a total volume of 1j2.

(The pH was adjusted to 4.25) After rubbing the sample and a screen with diacetyl cellulose as a protective layer for a certain period of time (24 hours) under the conditions of After irradiation for 1 hour, changes were evaluated visually compared to the originally untreated screen.

O: No change Δ: Slight change (but no practical problem) ×: Change and problem.

As can be seen from Table 1, the samples of the present invention have good pressure resistance and screen stains (and the sensitivity does not change even when dissolved).

Claims (1)

[Scope of Claims] At least one photosensitive emulsion layer is formed on the support, and the photosensitive emulsion is formed by the following general formula (I) before chemical sensitization is completed.
1. A silver halide photographic material, characterized in that it is prepared by adding a compound. General Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, , R_2, R_
3 and R_4 each represent a hydrogen atom or a substitutable group, and R_5 and R_6 each represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, or a carbamoyl group. In the formula, Y is a group promoting adsorption to silver halide, L is a divalent linking group, and m is 0 or 1.