JPS62229132A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having high sensitivity and less tendency for generating fog by specifying the component of compds., the shape and the used amount of the silver halide particle contd. in the silver halide emulsion. CONSTITUTION:At least one of the silver halide emulsion layers contain at least one kind of the compds. shown by formula I and at least one kind of the compds. shown by formula II. The silver halide emulsion layer contains at least 40% of the silver halide particle on the weight or particle number basis. The silver halide particle has substantially cube or 14 polyhedron form particle and the roundish apex on the crystal surface. In the formula, R1 and R2 are each a substd. or an unsubstd. alkyl, alkenyl or aryl group, R3 is hydrogen atom, a lower alkyl or an aryl group, R4 and R6 are each a substd. or an unsubstd. lower alkyl group. R5 and R7 are each a lower alkyl group or a hydroxy alkyl group, etc., X1<-> and X2<-> are each an anion, Z1-Z4 are each a non-metallic atom group necessary for forming a substd. or an unsubstd., benzene ring, (n) is 1 or 2.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a silver halide photographic material.

In particular, it relates to a silver halide photographic light-sensitive material that is highly sensitive, has low fog, is resistant to safelight exposure, and has good storage stability.

[Conventional technology]

In recent years, with the development of photographic technology, there has been a strong desire for higher sensitivity of silver halide photographic materials.

For example, high-speed camera shutters, rapid processing of color and black and white photographic paper, electronics and simplification in the printing industry, reduction of X-ray exposure dose in the medical field, etc. This is sensitization.

Taking the field of medical X-ray photography as an example, the conventional 450nm
From the regular type, which was sensitive to wavelengths in the 540 to 550 nm wavelength range, ortho-sensitized photosensitive materials of the ortho type that are sensitive to the wavelength range of 540 to 550 nm have come into use. Those sensitized in this manner have a wider photosensitive wavelength range and a higher sensitivity. Therefore, the amount of X-rays to which they are exposed can be reduced, and the effects on the human body etc. can be reduced.

Various research and developments have been carried out in the past regarding enhancement techniques for photographic emulsions, and many useful methods have been discovered. There is. However, although this technology is an extremely useful means of sensitization, there are still many unresolved problems, such as insufficient sensitivity depending on the type of photographic emulsion used, and storage of photographic emulsions after sensitization. However, there are still problems such as the sensitivity is not sufficient and the color fades over time, color staining occurs, and exposure to the conventionally used safelight causes fogging.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to achieve low capri and high sensitivity without affecting other photographic performance, and to provide a safe camera that is conventionally used. An object of the present invention is to provide a silver halide photographic material that is not easily exposed to light and has good storage stability.

[Structure and operation of the invention]

As a result of intensive research, the present inventors have found that, in a photographic light-sensitive material having at least one silver halide emulsion layer on a support, in at least one of the emulsion layers, the following general formula (I) is present. and at least one compound represented by the following general formula (1'l), and the silver halide emulsion layer contains substantially cubic or 14 A silver halide photographic light-sensitive material characterized in that silver halide grains, which are hedral grains and have rounded apexes on the crystal surface, are contained in a small amount by weight or number of grains (both 40%). , found that this can be achieved.

General formula (1) R1 and R2 are each substituted or unsubstituted alkyl group,
an alkenyl group or an aryl group, at least R3 and R
Any one of 2 is a sulfoalkyl group or a carboxyalkyl group.

R3 is a hydrogen atom, a lower alkyl group or an aryl group, Xl- is an anion 2, . 22 is a group of nonmetallic atoms necessary to complete a substituted or unsubstituted Hensen ring, n is 1 or 2 (however, when forming an inner salt, n-
1).

General formula (II) R,R.

Ra and Rh are substituted or unsubstituted lower alkyl groups; R5 and R'l are lower alkyl groups, hydroxyalkyl groups, sulfoalkyl groups, and carboxyalkyl groups; X2- is an anion Z3. Z4 is a group of nonmetallic atoms necessary to complete a substituted or unsubstituted Hensen ring, n is 1 or 2 (however, when forming an inner salt, n-
1).

- The compound represented by the general formula (I) (Il) functions as a sensitizing dye, and according to the present invention, the dye represented by the general formula (I) and the -r formula are added to the emulsion as described above. By incorporating the dye represented by [1], it becomes possible to sensitize a photographic emulsion to a high sensitivity without the drawbacks of conventional methods, and the object of the present invention can be achieved.

The present invention will be explained in more detail below.

First, the sensitizing dye represented by general formula (I) will be described.

In general formula (I), the substituted or unsubstituted alkyl group for R, R, specifically includes lower alkyl groups such as methyl, ethyl, n-propyl or butyl. be able to. R,,
Examples of the substituted alkyl group for R include vinylmethyl as a vinylalkyl group, and 2-hydroxyethyl, 4-hydroxyethyl as a hydroxyalkyl group.
2- as an acetoxyalkyl group such as hydroxybutyl
Acetoxyethyl, 3-acetoxybutyl, etc., carboxyalkyl groups such as 2-carboxyethyl, 3-carboxypropyl, 2-(2-carboxyethoxy)ethyl, etc., sulfoalkyl groups such as 2-sulfoethyl, 3-
Examples include sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, and the like. As the alkenyl group of R,, R, allyl,
Examples include butynyl, octenyl, and oleyl, and examples thereof include those with substituents. Further R,
, R2, substituted or unsubstituted aryl groups include, for example, phenyl, carboxyphenyl, and the like. However, as described above, at least one of RI+R2 is a sulfoalkyl group or a carboxyalkyl group.

In general formula (1), R3 represents a hydrogen atom, a lower alkyl group, or an aryl group, and examples of the lower alkyl group include groups such as methyl, ethyl, propyl, and butyl.

Examples of aryl groups include, for example, phenyl groups. A substituent may be bonded to these.

Examples of the anions represented by X and - in formula (1) include chlorine ion, bromide ion, iodide ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonate ion, and ethylsulfate ion. can be mentioned.

Next, typical examples of the compound represented by the general formula (1) will be given, but the present invention is not limited thereto.

Compound Examples In the following formula [■], examples of the lower fulkyl groups of Ra and Rb include methyl, ethyl, propyl, butyl and the like. Examples of substituted argyl groups include the groups exemplified for R, and R in formula [■].

Examples of lower alkyl groups for R5 and R7 are the same as Ra and Rh.

Examples of the hydroxyalkyl group, sulfoalkyl group, and carboxyalkyl group for Rs and Rq include the groups exemplified for R+ and Rz in formula [■].

Examples of the anion of X2- include those exemplified as Xl- in the formula.

Typical specific examples of the compound represented by the formula [] are listed below.Of course, the present invention is not limited to these examples either.

(Compound Examples) The total amount of the compounds represented by formulas (1) and (II) of the present invention can be in the range of 5 to 600 cm per mole of silver halide. In particular, 10 to 450 square meters is preferable.

These dyes used in the present invention can be synthesized by various methods, for example, easily synthesized by known methods.

These sensitizing dyes can be added to silver halide photographic emulsions by dissolving them in water-miscible organic solvents such as methanol and ethanol.

These sensitizing dyes may be added to the photographic emulsion at any time during the emulsion manufacturing process, but it is particularly preferable to add them immediately before or during the second ripening, immediately before or during the ripening, or after the ripening.

Furthermore, if it is added after ripening, before adding the pigment,
Preferably, potassium iodide is added afterwards or at the same time.

Next, the emulsion layer in the present invention containing at least one compound represented by the general formula (t) (II) as described above will be explained.

At least 40% of the silver halide grains contained in this silver halide layer are substantially cubic or tetradecahedral grains, and the apex of the crystal surface is rounded. .

The proportion of silver halide grains contained in the emulsion layer in the present invention is 40% by weight based on all silver halide grains.
or more, preferably 60% or more.

As described above, the silver halide grains of the present invention are substantially cubic or tetradecahedral, and the apexes of the crystal grain surfaces of the silver halide grains are rounded.

Here, "substantially" means that it does not preclude the inclusion of other shapes to the extent that they do not interfere with the effect of the cubic or tetradecahedral shape.

Further, the degree to which the apex of the crystal grain surface is rounded is arbitrary, and may be slightly rounded.

Such a method of rounding the surface vertices of silver halide grains is widely known (for example, US Pat. No. 32,711).
Organic thioethers described in JP-A No. 57, JP-A No. 3531289, JP-A No. 3574628, JP-A-5.11019 and JP-A No. 54-158917, etc.;
-82408, 55-77737 and 55-2
1,000 urea derivatives described in various publications such as No. 982, silver halide solvents having an oxygen or sulfur atom and a nitrogen atom and a thiocarbonyl group described in JP-A-53-144319, and JP-A-53-144319. Examples include imidazoles, sulfites, and thiocyanates described in JP-A-54-100717, and silver halide solvents such as potassium halide described in JP-A-59-178447.

Further, the silver halide grains according to the present invention may be used alone, or two or more types of grains may be mixed.

The size of the silver halide grains used in the present invention is 0.2
~8.0 μm is preferred. Particularly preferably 0.3 to 1.
It is 5 μm.

Furthermore, the silver halide grains of the present invention have a diameter of 0.7 μm.
It is preferable to contain 35% or more of the following particles. Particularly preferably, the content is 50% or more.

The size distribution of the silver halide grains used in the present invention may be monodisperse or polydisperse, but monodisperse is preferable. Here, monodisperse means that 95% of the particles are ±4 of the number average particle diameter.
It is a dispersion system whose size falls within 0%. Here, the number average particle diameter is the number average diameter of the projected area diameter of particles.

In the practice of the present invention, when an emulsion layer is provided in addition to the emulsion layer of the present invention, the size distribution of the silver halide grains may be monodisperse or polydisperse.

The composition of silver halide in the photographic emulsion used in the present invention is arbitrary, and examples include silver chloroiodobromide, silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodide, etc. Silver oxide may be used, but silver iodobromide is preferable in terms of high sensitivity. Among these, this average silver iodide content is 0.5 to 20 mol%
Preferably, silver iodobromide in an amount of 1 to 8 mol % is particularly preferable.

Although the internal structure of the silver halide grains used in the present invention is arbitrary, core-shell structures with different silver halide compositions are preferred. Examples of these include
No. 1415, No. 46-19024, No. 49-2165
No. 7, JP-A-58-95736, JP-A No. 5B-12652
No. 6, No. 58-127920, No. 59-52237, No. 58-181037, No. 59-177535,
Examples include those described in No. 59-178447.

Particularly preferred is that the silver iodide content of at least one adjacent layer is as high as the layer inside the grain, preferably 20
These are silver halide grains having a structure in which the amount is greater than mol %.

Further, silver halide grains having localized portions in which silver iodide is localized at a high concentration of 20 mol % or more can be preferably used.

It is preferable that such a high concentration silver iodide localized portion of 20 mol % or more is located as far inside as possible from the outer surface of the grain, and in particular, the localized portion is present at a distance of 0.01 μm or more from the outer surface. It is preferable to do so.

Furthermore, the localized portion may exist in a layered manner inside the particle, or may have a core-shell structure, with the entire core serving as the localized portion. In this case, 0.0 from the outer surface
It is preferable that part or all of the grain core part, excluding the shell part having a thickness of 1 μm or more, is a localized part with a silver iodide concentration of 20 mol % or more.

Note that the concentration of silver iodide in the localized portion is preferably in the range of 30 to 40 mol%.

In the present invention, from the inside of the particle (preferably from the outer wall of the particle)
．． As a method for forming localized areas of high concentration silver iodide of at least 20 mol % on the inside of grains separated by 01 μm or more, it is preferable to use seed crystals, but methods that do not use seed crystals are preferable. It may be.

If seed crystals are not used, a reaction phase containing protected gelatin (
Since there is no silver halide that can serve as growth nuclei in the mother liquor (hereinafter referred to as mother liquor) before the start of ripening, first, silver ions and halide ions containing high concentration iodide ions of at least 20 mol% are supplied to generate growth nuclei. Let it form. Then, additional supply is continued to grow particles from the growth nuclei.

Thereafter, it is coated with silver halides such as silver iodobromide, silver chloroiobromide, silver chlorobromide, silver bromide, and silver chloride.

Preferably, 0.018 m or more from the outer surface, especially 0.018 m or more, especially 0.018 m or more from the outer surface.
Particularly preferably, the shell portion having a thickness of 1 to 0.5 μm is silver iodobromide containing 10 mol% or less of silver iodide,
It is formed from less than mol% of silver iodobromide.

More preferably, the shell portion is formed of silver halide (usually silver bromide) that does not contain silver iodide.

If seed crystals are used, at least 20 mol% of the seed crystals alone
The above silver bromide may be formed and then covered with a shell layer. Alternatively, the amount of silver iodide in the seed crystal is set to 0 or within the range of 10 mol % or less, and at least 20 mol % or more of silver iodide is formed inside the grain in the step of growing the seed crystal, and then the shell It may be coated with a layer.

The latter having a multiple structure is preferable in the present invention. This is because it is easier to obtain a monodispersed emulsion.

Furthermore, a halogen substitution method may be used as a method for forming the layer of the localized portion.

The halogen substitution method can be carried out, for example, by adding an aqueous solution of an iodine compound after the internal core is formed. For details, see U.S. Pat. No. 2,592,250, U.S. Pat.
This can be carried out by the method described in Japanese Patent No. 127549 and the like.

As mentioned above, it is preferable that the emulsion used in the present invention be a monodisperse emulsion. By making the emulsion a monodisperse emulsion in this way, aggravating treatments such as chemical sensitization can be sufficiently performed, and the emulsion has a very high Sensitivity can be changed, and high contrast can be achieved with at least less softening caused by sensitization.

To prepare a monodisperse emulsion, first, grain growth of crystals is performed. Regarding grain growth, regarding the addition of silver ions and halide solutions, both may be performed alternately in time series.
It is preferable to use the so-called double jet method.

The supply of silver ions and halide ions is necessary and sufficient for the growth of only existing grains, without dissolving the existing crystal grains as the crystal grains grow, and conversely not allowing the generation and growth of new grains. The critical growth rate to supply silver halide,
Alternatively, the growth rate is increased continuously or stepwise within the allowable range. This increasing method is described in Japanese Patent Publication No. 48-36890, Japanese Patent Publication No. 52-16364, and Japanese Patent Application Laid-Open No. 55-142329.

Although this critical growth rate varies depending on the temperature pi(, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, intergrain distance, crystal habit, or type and concentration of protective colloid, etc.) can be easily determined experimentally by methods such as microscopic observation of emulsion particles suspended in a liquid phase and turbidity measurement.

In order to obtain the above-mentioned monodisperse emulsion, it is particularly preferable to use seed crystals and grow grains by supplying silver ions and halide ions using the seed crystals as growth nuclei.

The wider the particle size distribution of this seed crystal, the wider the particle size distribution after particle growth. Therefore, in order to obtain a monodisperse emulsion, it is preferable to use particles with a narrow particle size distribution at the seed crystal stage.

A particularly preferred method for preparing the silver halide grains used in the present invention is to use the above-mentioned double jet method, with a layer having a silver iodide content of 20 mol % or more having a pAg of 7.3±0.2, and a subsequent shell layer having a pAg of 9. .3±0.2, with p/Ig being preferably 9.7 or higher in the latter half of the preparation, that is, during the period corresponding to the formation of the shell layer. That is, a preferred method is to increase the pHg gradually or instantaneously when the amount of silver used in the preparation is 1/2, and the pag is 9.7 or more at the end of mixing.

Furthermore, the amount of silver is between 2/3 and 9/10, and 9Ag is 9.
A method in which the pAg is gradually or instantaneously increased from 0±0.2 and the pAg at the end of mixing is 9.7 or more is preferable.

More preferably, a method in which the pHg at the end of mixing is 10.1 or more is preferred.

Silver halide emulsions are usually chemically sensitized on their grain surfaces, and this method can also be employed in the present invention. For chemical sensitization, for example, ``Die Grundlagen der Fotografisodien Prozesse Mint Silber Halogennieden'' edited by H. Freezer, Akademisosche Verlagsgesellschaft
ser stitch eGrundlagen der Ph
otographischen Prozessemi
t Silherhalogeniden (Aka
demischeVerlagsgesellscha
The method described in f t (196B) pages 675-734 can be used.

The amount of coated silver is arbitrary, but preferably 1000 to 15000 μ/-, more preferably 20
00mlt/r/ or more and 10000mg/rd or less.

Further, photosensitive layers containing the silver halide grains of the present invention may be present on both sides of the support.

As the emulsion binder or protective colloid in the photographic light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

The emulsion in the photographic material of the present invention may contain various compounds for the purpose of preventing capri or stabilizing the photographic performance during the manufacturing process, storage or photographic processing of the photographic material.

Antifoggants or stabilizers particularly preferably used in the present invention include the following general formula (FIT), (IV) [
V], (Vf), and nitrone compounds.

In addition to the above-mentioned antifoggants, Japanese Patent Application Laid-Open No. 57-747
The antifoggants described in No. 38, No. 58-217928 are particularly preferably used.

H TVE OT( (V) (wherein, R11 is the same or different hydrogen atom, halogen atom, hydroxyl group, alkyl group which may have a substituent, an aralkyl group which may have a substituent, a substituted an alkoxy group which may have a group, an acyl group which may have a substituent, a carboxymethyl group which may have a substituent, -COOMg or -5O,M group, M group is a hydrogen atom,
Represents an alkali metal atom or an ammonium group. ), RI21 R11, R14 represent -COOM group or -8o3M group, nI+n2+ is 1 to 3, n is 1
or represents an integer of 2, and n 2 + n 4 represents 0 or 1. However, both n and n4 are never 0.

General formula (Vl) Z (, -3M Z represents an atomic group necessary to form a 5- or 6-membered heterocycle consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom.

Moreover, this heterocycle may be bonded. For example, tetrazole, triazole, imidazole, thiadiazole, oxadiazole, oxazole, benzthiazole, benzimidazole, benzoxazole, purine,
There are azaindene, tri-tetra-pentapyridine, and pyrimidine.

Further, these heterocycles may be substituted with an alkyl group, an alkoxy group, a carboxy group, a sulfo group, a hydroxyl group, an amino group, a nitro group, a halogen atom, a carbamoyl group, an alkylthio group, a mercapto group, or the like. Preferred among these are compounds in which Z is tetrazole, triazole, thiadiazole, benzimidazole, or benzthiazole, and most preferred are thiadiazole compounds. In the formula, M represents a hydrogen atom, a -NH4 group, or an alkali metal atom.

As a specific representative example of the compound represented by the general formula (Ill) that can be used in the present invention, m-(1)
Tl1- (2)H
OOC01+ +100c
OH1[1-(3)
I[I-(4)0OH ITI-(5) I-(
6) [[1-(7) I
TI-(8)0■ COOH 11r-(9) I-(10)
Cool C00HI
TI-(11) I[I-
(12) COOHC0OH ■-(13) II[-'
H4) 111- (15)
II[-(16) 1[[-(17)
1II- (1B) 111- (19)
lll-(20)03H 1[[-(21) I[I-(22
) SOJH4SO3NH4' m-(25) III-(26> Specific representative examples of the compound represented by the general formula (IV) include the following.

■-(1) IV-(2) TV-(3)
IV-(4)O3K Moreover, as specific representative examples of the compound represented by the general formula (V), there are the following.

V-(1) V-(2) 110.3 V-(3) V-(5) V-(6) V-
(7) V-(8)111+ v-(9) v-(10)N
Il, O, S Preferred specific examples of the compound represented by the general formula (Vl) include the following.

Vr-(]) N -□ N Vl-(2) N □ N Vl-(3) N -□ N Vl-(4) N -N VT-(5) Vl-(6) Vl-(7) Vl -(8)Vr-
(9) Vl-(10) Vl-(11
) Vl-(12) Vl-(13)
Vl-(14)SO□NHz Vl-(15) Vl-(16)
Vl-(17) Vl-(1B
)Vl-(19) Vl-(20)Vl-(
21) Vl-(22) Vr-(23)
Vl-(24) Vl-(25)
Vl-(26) Vl-(27)
VI-(2B)Vl-(29) Compound 1 contains 5X10-8 to 5XIO per mole of silver.
It can be preferably used by adding -'' moles.

There are also various nitrone compounds that can be used as antifoggants or stabilizers.

For example, the Journal of the Chemical Society (J
internal of the chemical 5o
It is possible to use a nitrone compound or an inorganic acid salt or an organic acid salt of a nitrone compound represented by the following structural formula [■] or [■] described in No. 1, pp. 824-825 (193B). Specific examples include chlorates, bromates, perchlorates, hydrosulfides, and acetates of the above-mentioned nitrone compounds.

Structural formula [■] Others: JP-A-60-122,936, JP-A No. 60-11
The following compounds shown in No. 7.240 can also be used.

Furthermore, a compound represented by the following general formula (B) can also be used.

General formula (B) In the formula, X represents a sulfur atom or =N R24, and R
21, R2□, R23+ R24 represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocycle. However, if R24 is a hydrogen atom, R21~
RZ3 represents something other than a hydrogen atom. Also, R2I and R
2□, R22, RZa, and R23 to R24 may be bonded to each other to form a ring.

In general formula (B), a substituted or unsubstituted alkyl group refers to a substituted or unsubstituted linear alkyl group (a substituted or unsubstituted branched alkyl group such as a methyl group, an ethyl group, or an n-octyl group). (isopropyl group, isobutyl group, 2
-ethylhexyl group, t-butyl group, etc.), substituted or unsubstituted cycloalkyl group (cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), substituted or unsubstituted aryl group means substituted or unsubstituted phenyl group,
The substituted or unsubstituted heterocycle representing a naphthyl group or the like represents a substituted or unsubstituted 3-pyridyl group, 2-furyl group, 2-benzothiazolyl group, or the like.

Here, the substituents in RlI, Rt□, R23 and RlI4 include a halogen atom, a nitro group, a cyano group,
Alkoxy group, carbamoyl group, sulfamoyl group, carboxy group, alkoxycarbonyl group, sulfo group, amide group, sulfonamido group, hydroxy group, sulfonyl group, sulfinyl group, sulfenyl group, mercapto group, amino group, ureido group, aminocarbonyl Examples include an oxy group, an alkoxycarbonylamino group, an aryl group, and a heterocycle, and one or more of them may be present.

Furthermore, RlI, Rffi2+ Rag, RZa, and R
23 and R14 may be bonded to each other to form a ring (for example, a 5-membered ring or a 6-membered ring).

Specific examples of the mesoionic triazolium compound of general formula (B) that can be used are shown below, but the compounds that can be used in the present invention are limited to these specific examples B-(1) B-(2) B- (3) B-(4) B-(5) B-(6) B-(7> B-(8) B-(9) B-(10) B-(11) Cβ Photographic light-sensitive material of the present invention The photographic emulsion layer or other hydrophilic colloid layer may contain coating aids, antistatic agents, slippery improvement, emulsion dispersion, adhesion prevention, and photographic property improvement (e.g. development acceleration,
Various surfactants may be included for various purposes such as high contrast, sensitization, etc.

In addition, a physical property improver can be used, such as a polymer latex made of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, etc., and the like.

The photographic emulsion used in the present invention includes a compound obtained by addition copolymerizing glycidol and ethylene oxide to a phenol aldehyde condensate (for example, JP-A-51-5
6220), lanolin-based ethylene oxide adducts and alkali metal salts and/or alkaline earth metals (for example, those described in JP-A-53-145022), water-soluble inorganic chlorides, and capping agents (such as those described in JP-A-53-145022), Kaisho 54-
69242), an addition condensate obtained by addition-condensing glycidol and ethylene oxide to a phenol aldehyde condensate, and a fluorine-containing succinic acid compound (JP-A-52-1049)
An antistatic agent such as No. 40) can be added.

Antistatic agents particularly preferably used in the present invention include:
Those represented by the following general formula (IX) (X) (XI) (XH) can be mentioned.

-X' General formula (rX) R-L -(CHzCHzO)m-HC In the formula, R represents a substituted or unsubstituted alkyl group, alkenyl group, or aryl group, and It represents an alkyl group or (CHzCHzO)m H, and m represents an integer of 2 to 50. ] General formula (X) [In the formula, R, 11 and R311 represent a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, an alkoxy group, or a phenyl group, and R33 represents a hydrogen atom, a methyl group or an α -represents a furyl group, n and m
represents an integer from 2 to 50. ] General formula (XI) +1as In the formula, Ra& and R3 are substituted or unsubstituted alkyl group, aryl group, alkoxy group', halogen group,
Represents an acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group.

In the general formula, the substituents on the phenyl ring may be asymmetrical.

R34 and R35 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R34 and R3S
+ R36 and R37 and R36 and Rff9 may be linked to each other to form a substituted or unsubstituted ring.

nl + nl + n3 and n4 are average degrees of polymerization of ethylene oxide, and are numbers from 2 to 50.

Moreover, m is an average degree of polymerization, and is a number from 2 to 50.

General formula (Xll) Rf -A, -(CHzCHzO)ns -B-E
In the formula, Rf represents a substituted or unsubstituted alkyl group, alkenyl group, or aryl group having 1 to 30 carbon atoms and partially or entirely substituted with a fluorine group.

B represents an alkenylene group, an alkylene group or an arylene group. Also, it is not necessary.

E represents a water-soluble group and a hydrogen atom, and n5 represents a number of O to 50.

A1 is 10- group, -8- group, -COO- group, -R,. group (here, R1° represents a hydrogen atom or a substituted or unsubstituted alkyl group).

Compounds represented by the general formula (IX) used in the present invention include compounds represented by the following general formula.

[General formula]

(IX)-(A) R-0-(CHiCHgO)m -Hm=2~50R is an alkyl group that may have an unsaturated bond, preferably has 4 to 22 carbon atoms, and hydrogen is substituted with fluorine. It's okay.

(IX) -(B) R31 and R3□ may be the same or different, and each represents a hydrogen atom, a halogen atom, a carboxyl group, an acyl group, an alkoxycarbonyl group, an alkyl group, a substituted alkyl group, an alkoxy group, or a phenyl group. represent. Hydrogen may be substituted with fluorine.

(IX) -(C) RS (CHzCHzO) m Hm= 2~50
R is an alkyl group that may have an unsaturated bond, preferably has 4 to 22 carbon atoms, and hydrogen may be substituted with fluorine.

IX) -(D) R■ m=2-50 R31 is an alkyl group, preferably one with 1-20 carbon atoms, R3□ is a hydrogen atom, an alkyl group (1-20 carbon atoms)
, represents a fluorine-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl group or a -(cutcoto) m -H group.

([X) -(E) zz 21C-N 11 ゝ\-(-CHzco to -)-T-Hm
=-2 to 50 R31 is an alkyl group, preferably one having 1 to 20 carbon atoms, Rag is a hydrogen atom, an alkyl group (having 1 to 20 carbon atoms)
, represents a fluorine-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a -(C112C1!20) m --H group.

CIX) -(F) R31CO(CIhCtlzO) m HI30 m-2 to 50R3I represents an alkyl group, preferably one having 4 to 22 carbon atoms.

Among these compounds represented by the general formula (IX), particularly preferred compounds in the present invention include the following.

[Exemplary compounds]

(IX)-(1) Cal(I+ -〇-(CI□CII
□O)s H(IX) (2) Ca1(+y
O(C1lzCt120) to H(■)-(3)
C, □11□s O(CIlzClhO) q H
(IY) (4) C+3Hz70 (CIIz
CRzQ) to H(rX) (5) CIbf
■nz O (CIhCH20) to HCIX)
(6) Cl1lH370 (CIhCH20) +
s H(IX) (7) H(CF2CF2)5 0
(CIIzCllzO) to H(IX)
(8) CI(2Cj! CIC12CH2C1I□0
- ※※-(CIhCH20)s -H (ff) -(9) CIX)-(10) (IX)-(12) (IX)-(13) (IX) -(1,1) [)-( 15) (rX)-(16) (IX)-(17) (IX)-(19) r7! (IX)-(20)C, □Hzs S (CI
hCH20)+s H(IX) (21) C
+1lHs? S (CH2C1I□0)ts
H(rX)-(22)C,. ■１□＋S
(CHzCHgO)s H(IX) (
28) CsL +C0NII (C1l.C
Il□O)s HCTX) (33) C3
H17CO(CII□CII□0) to Hll (IX) (34) Cl5H33C-0(CH2
C) 120) 3°-Hll (IX) -(35) c,. Hg+CO(C1hC
tLzO) +. -Hll Next, typical specific examples of the compound represented by the general formula (X) will be shown.

[Exemplary compounds]

X-(3) X-(5) n+: r12 =30! 20m+:m2
=15 X-(6) x-(7) X-(9) X-(10) X= (11) X-(14) OCI+.

'--0-(-CH2Cl(,0)-r HX-(15
) C4I+.

X-(16) X-(17) X-(20> Specific examples of the compound represented by the general formula (XI) (X11) used in the present invention include the following.

XI-(1) XI-(2) XI-(3) XI-(4) xr-(5) XTI-(1) Xn-(2)
XIT-(4) Furthermore, the photographic light-sensitive material of the present invention is disclosed in JP-A-57-104
925 and 5El]6233 and the like can be used.

In the photographic light-sensitive material of the present invention, an inorganic or organic hardener is added to the photographic emulsion layer and other hydrophilic colloid layers. Water-insoluble or
Dispersions of soluble synthetic polymers can be included.

The photographic emulsion used in the present invention may contain a compound represented by the following general formula (XIV) in order to suppress deterioration of the image quality of photographic images due to rapid development processing at high pH and high temperature. .

General formula (X IV) [In the above general formula, A' and B' each represent a group of nonmetallic atoms necessary to form a heterocycle, and X is an anion (for example, (1, Br, Ca2- 9CH, SOa-, etc.) First, to explain the compound (XTV), the compound (
the nonmetallic atomic group A and/or B or a lower alkyl group necessary to form a heterocycle of the compound represented by XTV); n represents 2 or 3; ] is preferable. Representative examples of compounds CX, IV) include the following compounds.

Moa. [Exemplary compound] CX IV-1) (X IV-2) (
XTV-3) (XIV-4) (XIV-5) (, For this purpose, water-soluble dyes may be included.

In particular, the photographic emulsion used in the present invention may contain magenta and/or yellow filter dyes to improve sharpness.

The following substances can be exemplified as substances that can be preferably used in the present invention.

) U311 Ki CHi CC=Cl1 CC1j13II I
II II)U, NaIN(C2H5)a"C Among the above dye compounds, any one can be selected depending on the purpose of use, but particularly preferred compounds include those included in the following general formula (A). Examples include those with a structure that

General formula (A) However, R61+ RbN in the formula is an alkyl group having 1 to 7 carbon atoms, a carboxyl group, an alkoxycarbonyl group,
an alkylaminocarbonyl group, an amino group, an acylamino group or a trifluoromethyl group; M is a hydrogen atom, an alkali metal atom, or an ammonium group; n is 1 or 3;

Furthermore, in the present invention, in order to increase the power of irradiation light, it is preferable that particles of 0.7 μm or less be contained in an amount of 35% or more. Particularly preferably, the content is 50% or more.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color-forming coupler that forms color through oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) during color development processing. It may also contain a compound that absorbs water. It may also be a color I coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR colored coupler). In addition to the DIR coupler, the coupling reaction product may include a colorless DIR camping compound which is colorless and releases a development inhibitor.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

The light-sensitive material of the present invention uses hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives,
It may also contain ascorbic acid derivatives.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. The order of these layers can be selected arbitrarily as needed. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. .

In the photographic light-sensitive material of the present invention, the rotated emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various known coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. U.S. Patent 2,681.
No. 294, No. 2,76L791, No. 3,526,5
The method described in No. 28 is an advantageous method.

The support may be a cellulose ester film such as cellulose triacetate film, a polyester film such as polyethylene terephthalate film, or α-
Paper coated with an olefinic polymer is preferred.

In addition, as a support, JP-A No. 52-104913,
No. 59-19941, No. 59-19940, No. 59
It is preferable to use the subbing treatment described in No. 18949.

The silver halide emulsion of the present invention is applicable not only to black-and-white photosensitive materials such as direct or indirect X-ray photosensitive materials, lithographic photosensitive materials, and photosensitive materials for black-and-white photography, but also to color photosensitive materials such as color negative photosensitive materials, color reversal photosensitive materials, and color paper. It can also be used for materials etc.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure (Research D 1sc-
1osure) No. 1.76, pages 25-30 (RD-
Any of the known methods and known treatment liquids, such as those described in 17643), can be applied.

This photographic processing may be either photographic processing that forms a silver surface image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose.

Exposure for the photographic emulsion of the present invention varies depending on the state of optical sensitization, purpose of use, etc., but may include tungsten, fluorescent lamp, mercury lamp, arc lamp, xenon, sunlight, xenon flash, cathode ray tube flying spot, laser light, electronic Various types of light sources can be used as appropriate, such as X-rays, X-rays, and fluorescent screens for X-ray photography.

In addition to normal exposure times of /1000 to 100 seconds, xenon flash, cathode ray tube, and laser light
Short-time exposure of /10' to 1/109 seconds can be applied.

〔Example〕

Examples of the present invention will be described below. It should be noted that, as a matter of course, the present invention is not limited to the following examples.

Example 1 A polydisperse emulsion (1-1) with 12 mol% of Ag inside the grains and an average grain size of 0.62 ms as shown in Table 1 was prepared by a forward mixing method.
was prepared.

In addition, emulsions 1-2 to T shown in Table 1 were prepared as follows.
-8 was prepared.

Silver iodide 2 with an average grain size of 0.3 μm was produced using the double jet method while controlling the temperature at 60°C, pAg=8, and pH=2.0.
, 0 mol % of silver iodobromide (A) was obtained. In this emulsion, the incidence of twin grains was 1% or less in terms of number, as determined by electron micrographs.

Using this emulsion (A) as a seed crystal, it was grown as follows.

That is, this seed crystal (A>) was dissolved in a solution 8.51 containing protected gelatin and optionally ammonia kept at 40°C, and the pH was further adjusted with acetic acid. Ammoniacal root ion aqueous solution was added by double jet method.In this case, pH and EA
g was changed as needed depending on the silver iodide content and crystal habit.

That is, the pH was changed from 9 to 8, the pAg was kept at 9.0, and the cubic crystal emulsion 1-2 shown in Table 1 was changed to 1 pAg.
1.0 to produce octahedral emulsion r-3. In this emulsion, 95% of the grain size is a layer with a silver iodide content of 2 mol %, and the outer layer is a shell of pure silver bromide.

Next, I) After controlling Ag to 7.3 and flH to 9.7 to form a layer with a silver iodide content of 35 mol%, the pH was changed from 9 to 8 and pAg was adjusted to 11.0. octahedral emulsion T-4 was prepared while the pAg was maintained at 9.0 and cubic emulsion 1-5. 1-6 was prepared.

Here, emulsion 1-. Regarding 6, after mixing, 1 bromide!
10 g of potassium bromide was added per mole to give a pAg of 11.5, and the mixture was aged for 5 minutes to round off the apex of the particle surface.

In addition, in Emulsion T-7 and Emulsion 1-8 shown in Table 1, the apexes of the grains were rounded in the following manner. That is, emulsion 1-
Up to 95% of the grain size for Emulsion 7 and up to 90% of the grain size for Emulsion 1-8 were prepared in the same manner as Emulsion 1-5, and a potassium bromide solution was added through a nozzle over 8 minutes. , the PAg was lowered to 11.0, and the mixing was completed 3 minutes after the addition of potassium bromide, thereby rounding off the tops of the particles.

The grain size of these eight types of emulsions is 0.6 μm'. Further, the silver iodide content of the entire grain is about 2 mol %.

Among the above emulsions, emulsions 1-6 to 1-8 are emulsions of the present invention containing silver halide grains that are substantially cubic or tetradecahedral grains with rounded apexes on the crystal surface.

Sensitizing dye (A) (Sensitizing dye of the present invention) Sensitizing dye (B) (Sensitizing dye of the present invention) Sensitizing dye (C) (Comparative sensitizing dye) Compound (D) CH3CC=CHCCCH2 X / \ / N N 503Ti5O3H Compound (E) 1100C-C--C=Cll-CH=Cll-C-C
-CO'O■N N 5O3H5OaH Tests f:tIT-1 to -16 shown in Table 2 were prepared using the above emulsions T-1 to I-8.

t, I to each emulsion obtained as described above.
L. After removing excess water-soluble salts by a coagulation precipitation method, ammonium thiocyanate, chloroauric acid, and hypo were added to perform gold-sulfur sensitization. After completion of sensitization, 4-hydroxy-6-methyl-1+ 3.3 a.

7-Chitrazaindene was added. After that, potassium dichloride was added to the emulsions of samples rl-1 to 1it-8 shown in Table 2.
) 15 mg was added. In addition, for the emulsions I+-9 to 11-16 shown in Table 2, the enhancing dye (0) was added to 18
Added 0 ■. (Here, the amount of dye is I7 silver halide 1
The amount is per mole. , ) As inhibitors, Exemplified Compound II+ -(23), (VT)-], the compound of structural formula (■), other usual stabilizers, hardeners, coating aids, and Exemplified Compound XrV After adding -4, this emulsion was coated on the next base (support) as follows. That is, a copolymer consisting of three types of polymers, 1-50 wt% of glycidyl methacrylate, 104% of methyl acrylate, and 40 wt% of butyl methacrylate, was prepared at a concentration of 10 wt%.
The copolymer aqueous dispersion obtained by diluting it so that X-2, Xl-2, X11-1 and a gelatin protective layer containing usual matting agents, coating aids and hardeners were uniformly coated on both sides and dried to obtain sensitometric samples.

Wedge exposure was performed on each sample at 3.2 CMS, and XD
-90 processing solution was used for 90 seconds to determine the sensitivity of each sample.

Sensitivity is determined by calculating the reciprocal of the amount of light required to increase the blackening density by 0 months by exposure, and is expressed as a relative value with the sensitivity of mn-2 in Table 2 as 100.

Furthermore, the stability against safelight was tested using the silver halide photosensitive material prepared as described above. That is, each sample of tlhTl-1 to ■-16 was exposed to a 20W light source and a safe light using a Sakshi Th4A Safelight C filter under the light source at a distance of 1 m for 1 hour, and after being left, 1 full sample was treated in the usual manner. Fog due to safelight and residual color after treatment were visually measured. The results are shown in Table 2.

Safelight properties are indicated by the difference in density between each sample and those processed without safelight exposure.
In addition, color staining was expressed in three levels, starting from the one with the least amount of staining. 1 indicates the least color contamination, and 3 the most.

Further, a surrogate test was conducted on the storage stability of the silver halide photographic materials of samples n-1 to -16 prepared as described above. That is, the above sample emulsion was heated at 55°C, 20% r, h, and 55%
%r, h, for 3 days. 23℃ for 3 days, 5
A comparison sample was made that was stored at 5% r,h. Thereafter, they were processed in the same manner as in Example 1, and fog was measured for each. The measured value was expressed as the difference in fog between the sample stored at high temperature and the comparison sample.

The results are shown in Table 2.

As shown in Table 2, the sample floor 116 to which the present invention is applied
．． It can be seen that n-7 and If-8 had good safelight properties, good color retention, and improved storage stability while maintaining low fog and high sensitivity. Among them, samples IT-7 and n-8
was found to be highly sensitive.

Note that the above sample Th1l-6, H-7°H to which the present invention is applied
-8 are all silver halide grains according to the present invention.
00% content.

Example 2 Emulsion 1-1 used in Example 1 was prepared with an average grain size of 0.
．． A 9μ polydisperse emulsion was obtained. Hypo, the sensitizing dye (C), ammonium thiocyanate, and chloroauric acid were added to this emulsion in this order to carry out dye sensitization.Then, the same additives as in Example 1 were added, and the same coating samples 1 to 1 were added. I got it. Further, this polydisperse emulsion was subjected to dye sensitization in the same manner as samples IT-1 to IT-118 of Example 1 to obtain a similar coated sample (IV-2).

Next, 1.0
Three types of emulsions were obtained: 5μ, 0.80μ, and 0.55μ. Thereafter, dye sensitization similar to coating sample IV-1 was applied, and Table 3
A coating sample IV-3 similar to the mixed coating sample rv-i was obtained at the ratio shown in . Coated sample (2)-4 was obtained by adding the compounds (D) and (E) to the emulsion of coating sample (2) and then adding the same additives as above to obtain a similar coated sample. Furthermore, 1, 05μ, 0.
Three types of emulsions, 80μ and 0.55μ, were subjected to the same dye sensitization as coating sample TV-2 and mixed in the proportions shown in Table 3 to obtain a similar coating sample (rv-5).

Next, in the same manner as Emulsion 1-8 used in Example 1, three types of emulsions with average grain sizes of 1.05 μ, 0.75 μ, O, , 55 μ were obtained. A similar coated sample (I
V-6) was obtained.

Next, in the same manner as emulsion r-8 used in Example 1, the average grain size was 1. Three types of emulsions were obtained: OO/N, 0.65m, and 0.48μ. This emulsion was subjected to dye sensitization similar to coating sample Tl-1, and coating sample [V
-7 was applied to compound (D) (E) in the same manner as sample TV-4.
was added to obtain a similar coated sample (IV-8). In addition, 1,00 μ, 0.6 prepared in the same manner as coating sample I-8
Three types of emulsions, 5μ and 0.48μ, were subjected to the same dye sensitization as coating sample IV-2 to obtain coating sample TV-9. Further, dye sensitization was carried out in the same manner as in coating sample 1-9, and compound (r) (E) was added in the same manner as in coating sample rV-4 to obtain a similar coating sample 2-10.

The jj sharpness of 10 types of OT samples obtained, coated samples rv-i to -10, was evaluated using MTF. In other words, 0.
An MTF chart containing a lead square wave of 8 to 10 lines/mm was placed in close contact with the back side of the front side of a fluorescent screen, Sakura Hi-Ortho Screen KS (manufactured by Konishiroku Photo Industry Co., Ltd.), and X-rays were irradiated so that the density of the portion not shielded by Char 1 was approximately 1.0 on both sides.

After developing in the same manner as in Example 1, the recorded rectangular wave pattern was measured using a Sakura Microdensitometer M-5 model (manufactured by Konishiroku Photo Industry Co., Ltd.). In addition, the aperture size at this time is 300 μ in the parallel direction of the rectangular wave.
The magnification was 20x at 25μ in the orthogonal direction.

The obtained MTF value is representative of the spatial frequency 2.0 line 1
Indicated by a value of 1. The MTF values of IV-1 to TV-10 are shown in Table 3.

In addition, for each sample of coating samples 1 to rV10, Example 1
Wedge exposure was performed in the same manner as in Example 1, and then the same processing as in Example 1 was performed to determine the sensitivity, which is shown in Table 3. The sensitivities in Table 3 are the values when the sensitivity of sample IV-1 is taken as 100.

As described above, it was found that the coating samples TV-5, TV-6, and -9 of the present invention had better sharpness than rV-1 and TV-2. In particular, sample TV-9 was obtained by using at least 50% of the particles of the present invention, particularly particles with an average particle size of 0.70μ or less, and by using the dye of the present invention, compound (D), which is a filter dye, (E ) was found to improve the sharpness even without using.

In addition, the above-mentioned samples IV-5, rV-6, ■-
9 contains silver halide grains according to the present invention.
It contains 0%.

Example 3 Coating sample IV-9 used in Example 2 and the following comparative sample ■
-11, the relative sensitivity, safelight property, and storage stability (20% r, h, -3 days) were investigated in the same manner as in Example 1.

Comparative sample (1)-11 was obtained by the same procedure as emulsion 1-1 to obtain an emulsion with an average grain size of 0.90μ, and by the same procedure as emulsion 1-8 to obtain an emulsion with an average grain size of 1.90μ. Two types of emulsions (emulsions containing grains having the characteristics of the present invention) with Oθμ and 0.48μ were obtained, and each emulsion was mixed with 5:
It was obtained by blending at a mixing ratio (weight) of 1:2. Other conditions are the same as in ①-9 above. This comparative emulsion ■-11 contains silver halide grains of the present invention in a weight ratio of 3.
Since it is 7.5% and less than 40%, it is a sample outside the present invention.

Table 4 shows the test results for samples ■-9 and IV-11.
Shown below.

As is clear from Table 4 in Ic), in Sample 1-11, which is a comparative example outside the scope of the present invention, the effect of particles having the characteristics of the present invention is I-membered, and the effect of particles not having the characteristics is You can see that it mainly appears.

〔Effect of the invention〕

According to the present invention, a silver halide photographic material with low fog and high sensitivity can be realized without affecting other photographic properties, and the material is sensitive to safelight. It also has the advantage of good storage stability.

Claims (1)

[Scope of Claims] A photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the emulsion layers contains at least one compound represented by the following general formula (I). seeds and at least one compound represented by the following general formula (II), and the silver halide emulsion layer contains:
A silver halide photograph characterized by containing at least 40% by weight or number of grains of silver halide grains that are substantially cubic or tetradecahedral grains and have rounded apexes on the crystal surface. photosensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_1 and R_2 are each substituted or unsubstituted alkyl group, alkenyl group, or aryl group, and at least R_
Either of 1 and R_2 is a sulfoalkyl group or a carboxyalkyl group. R_3 is a hydrogen atom, a lower alkyl group, or an aryl group; When forming an inner salt, n=
1). General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_4 and R_6 are substituted or unsubstituted lower alkyl groups, R_5 and R_7 are lower alkyl groups, hydroxyalkyl groups, sulfoalkyl groups, carboxyalkyl groups, X^-_2 is an anion Z_3, Z_4 is a group of nonmetallic atoms necessary to complete a substituted or unsubstituted benzene ring, n is 1 or 2 (however, when forming an inner salt, n=
1).