JPS61273535A - Photographic element - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic element high in sensitivity and small in fog by incorporating a specified compound in at least one of silver halide emulsion layers formed on a support. CONSTITUTION:At least one of silver halide emulsion layers formed on the support contains one of compounds represented by general formulae I-IV in which Y<-> is a counter ion; P is 0 or a positive integer for balancing ion charges; each of X1-X8 is H, alkyl, or aryl, and each combination of X1 and X2, X3 and X4, X5 and X6, and X7 and X9 are not simultaneously H; each of R1, R5 and R6 is H or optionally substd. hydrocarbon group; R2, R4 are each H or optionally substd. hydrocarbon group; and R7 is H or a quaternary group. Compounds especially useful for the photographic purpose are those represented by formula IV in which R7 is alkyl and R6 is methyl.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photographic element, and more specifically, a silver halide photographic element containing a five-membered ring compound containing tellurium and nitrogen in the same ring, or a salt thereof. Regarding elements.

[Conventional technology]

Five-membered ring compounds containing oxygen, sulfur, selenium, and other oxygen group elements and nitrogen in the same ring or salts thereof [chalcogenazoles] have been widely used in the field of silver halide photography. It has been used, for example, as a core of polymethine dyes, antifoggants or stabilizers, nucleating agents, latent image stabilizers and speed or contrast enhancing additives.

In particular, it is desired that the sensitizing dye appropriately expands the sensitive wavelength range of silver halide grains and further increases the photosensitivity in this wavelength range. It is known that photosensitivity can be increased by increasing the size of silver halide grains, but the graininess of the resulting image may be noticeable, or a large amount of silver may be required to obtain an image of the same density. There is a problem. The history of improvements in silver halide photographic elements is a history of higher image quality and higher image quality, and techniques for obtaining higher sensitivity and improved image quality are always desired. Sensitivity and image quality, especially graininess, are mutually exclusive, and sacrificing one can improve the other. This means that one improved technology can be used to improve the other.
For example, if sensitization techniques allow smaller particles to be sensitized to the same level as larger particles sensitized by conventional techniques, granularity will be improved. Therefore, sensitizing dyes capable of sensitizing halide grains to higher sensitivity are being sought after for increasing the sensitivity and image quality of silver halide photographic elements.

On the other hand, high-sensitivity technology is usually accompanied by an increase in fog.
As silver halide grains become more sensitive to 25C, there is a need for a technique that does not reduce sensitivity or increase fog. Conventionally known antifoggants have too weak antifogging ability and require a large amount of addition in order to obtain effective properties. Although the performance is good, there are drawbacks such as desensitization, and improvements are desired.

[Object of the present invention]

A first object of the present invention is to provide a silver halide photographic element with high sensitivity.

A second object of the present invention is to provide new sensitizing dyes for obtaining highly sensitive silver halide photographic elements.

A third object of the present invention is to provide a silver halide photographic element with reduced fog.

A fourth object of the present invention is to provide a new antifoggant for obtaining silver halide photographic elements with reduced fog.

[Configuration of the present invention]

The object of the present invention is to provide a support having at least one silver halide emulsion layer and a compound represented by the following general formula CI), (n), (I [[) or [IV]]. Achieved by photographic elements.

In the formula, XI, Xt, X3. X#, XSI X6. X? and X6 each represent a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), an aryl group (e.g., phenyl group, naphthyl group, etc.) (provided that X,
and XZ, X3 and X4. X, and each represents a hydrogen atom or a hydrocarbon moiety that may have a substituent (for example, each group such as alkyl or aryl), R, l represents a hydrocarbon moiety that may have a substituent (for example, alkylidene), R2 and R4 represent a hydrogen atom or a hydrocarbon moiety that may have a substituent (e.g., each group such as alkyl or aryl), and t represents a hydrogen atom or a quaternized substituent (e.g., an alkyl or sulfo group). represents each group (such as alkyl).

In the above formulas (1) to (IV) and the following formulas, X1 to Xll
When R represents an aryl group, the aryl group includes a halogen atom, hydroxy group, amino group, alkoxy group, alkyl group, aryl group, alkylthio group, cyano group, cycloalkyl group, carbamoyl group, alkoxycarbonyl group. Substituents such as the following can be introduced.

General formula (n) can form a merocyanine dye represented by the following general formula (V) by R5.

In the formula X3. X4 represents a hydrogen atom, an alkyl group, or an aryl group, respectively (however, X and X4 are never hydrogen atoms at the same time).

R4 is an alkyl group or an aryl group, E is an acidic nucleus, L+ and Lx are each independently a methine bond, n is 0.1
or 2.

Preferred compounds of general formula (V) are represented by general formula (Vl).

Xs, Xs, Ra, E and n have the same meanings as in the general formula (V).

The acidic nucleus E can take the form of any conventional merocyanine acidic nucleus. Typically, E consists of a methylene moiety attached, either directly or via a methine linkage, to a carbonyl, sulfo or cyano group at one resonance extreme. Unlike the cyanine dye nucleus, the acidic nucleus E
need not be a heterocycle, or even a ring.

In a preferred form, E can be represented by the following formula: in which m represents O or 1, D is a cyano, sulfo or carbonyl group and D' is a methine substituent, which can be of the form can be taken together with D to complete a 5- or 6-membered heterocyclic ring containing ring atoms selected from the group consisting of carbon, nitrogen, oxygen and sulfur.

When E is an acyclic group, i.e. when D and D' are independent groups, E is selected from among groups such as malononitrile, alkylsulfonylacetonitrile, cyanomethyl benzofuranyl ketone or cyanomethyl phenyl ketone. You can choose. In the preferred ring form of E, D and D' together complete the nucleus: 2
-pyrazolin-5-one, virazoliden-3,5-dione, imidacillin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazoline-4-
one, 2-oxazolin-5-one, 2-thioxazolidine-2,4-dione, isoxazolin-5-one,
2-thiazolin-4-one, thiazolidin-4-one,
Thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-
1,3-dione, thiophene-3-one, thiophene-
3-1,1-dioxide, indolin-2-one, indolin-3-one, indacillin-3-one, 2-oxoindacillinium, 3-oxoindacillinium, 5
．． 7-thioxo6,7-cyhydrothiazolo(3,2-
a) Pyrimidine, cyclohexane-1,3-dione, 3
．． 4-dihydroisoquinolin-4-one, 1,3-dioxane-4゜6-dione, barbylic acid, 2-thiobarbital acid, chroman-2,4-dione, indacillin-
2-one or pyrido(1,2-a)pyrimidine-1,
3-dione core. Common ring substituents are contemplated.

-ffi formula (mV) is a general formula that can form a cyanine dye represented by the following general formula [■] by Rh.
■] In the formula, Xq and X* represent a hydrogen atom, an alkyl group, and an aryl group, respectively. (However, Xy and Xs are never hydrogen atoms at the same time.) R7 and R8 independently represent quaternized substituents, L+, Lx,
Ls, R4 and Ri each independently represent a methine group, n is 0.1 or 2, m is O or 1, Q is an atomic group that completes the nucleus of the basic azolinylidene or azinylidene heterocycle, Y- represents a counter anion, and P represents O or a positive integer for balancing the ionic charge.

As is clear from the above formula, this cyanine dye is one of the quaternized tellurium azolium salts of the formula (rV), which has a substituent R1 at the 2-position and has been carefully considered. The tellurium azolium nucleus has already been described above. Although this nucleus could be characterized as a tellurium azolium nucleus or a tellurium azolinylidene nucleus, for convenience we will use the former designation, but for consistency we will refer to the remaining nuclei as azolinylidene or azinylidene nuclei.

In general, any conventional aprinylidene or azinylidene nucleus satisfying formula (■) can be used in combination with the tellurium azolium nucleus.

It is particularly contemplated that Q can be selected from: benzotelluriazolinylidene, naphthothyl! Rarethoquinolinylidene, 2- or 4-pyridylidene, imidazopyridylidene, 2- or 4-quinolinylidene, 1- or 3-intolylidene, penzoquinolinylidene, thiazoloquinolinylidene, imidazoquinolinylidene, 3H-intolylidene, 1H or 3H-benzintolylidene, oxazolinylidene, oxazolidinylidene, penzoxazolinylidene, naphthoxazolinylidene, oxadiazolinylidene, thiazolidinylidene, phenanthrothiazolinylidene, acenaphthothiazo Linylidene, thiazolinylidene, penzothiazolinylidene, naphthothiazolinylidene, tetrahydropenzothiazolinylidene,
Dihydronaphthothiazolinylidene, thiadioxazolinylidene, selenium azolinylidene, selenium azolinylidene, penzoselen azolinylidene, naphthoselen azolinylidene, selenium adiazolinylidene, birazolylidene, intrilidene, imidazolidinylidene , penzimidazolinylidene, naphthoimidazolinylidene, diazolinylidene, tetrazolinylidene, and imidazoquinoxalinylidene cores. This nucleus can be substituted in any conventional manner consistent with formula (■). R11
can be, for example, any conventional quaternized group and can be selected from any of the various forms of R1 mentioned above. The cyanine dye is represented by the following general formula (IX).

In the formula, Xヮ+ Xll+ n+ Y- and P represent the same meanings as in the above general formula [■].

R1 and R6 are independently optionally substituted alkyl groups with sulfo, and Q' is an atomic group completing the basic azolinidene or azinylidene nucleus which may include a benzo or naphtho ring moiety.

In certain preferred forms, R7 and R6 are sulfo- or sulfato-substituted hydrocarbon (eg, alkyl or aryl) substituents containing 1 to 6 carbon atoms, such as 1. A sulfomethyl, sulfatomethyl, sulfoethyl, sulfatoethyl, sulfopropyl, sulfatopropyl, sulfobutyl, sulfatobutyl, sulfophenyl, or sulfatophenyl substituent.

In the general formula (IV), R6 can form a rhodacyanine dye represented by the following general formula (X).

General formula (X) In the formula, W is an oxygen atom, a sulfur atom, or a selenium atom.

Or >N-R" is X?, XI is each a hydrogen atom,
Hail alkyl groups and aryl groups. (However>(?,X
* cannot be a hydrogen atom at the same time. ) R7 and R
11 is an alkyl group, R9 and R'' each independently represent an alkyl group, an aryl group, or an aryl group, Lx, Lt, La, and R each independently represent a methine group, m and r are O or 1 , S is 0.1 or 2, Q is the atomic group that completes the nucleus of the basic azolinidene or azinylidene heterocycle, Y- is the counter anion, P is O or a positive integer to balance the ionic charge. represents.

It is particularly contemplated that Q can be selected from: benzotelluriazolinylidene, naphthotellurium azolinylidene, 2- or 4-pyridylidene, imidazopyridylidene, 2- or 4-quinolinylidene, 1- or 3
- intrilidene, penzoquinolinylidene, thiazoloquinolinylidene, imidazoquinolinylidene, 3H-intolylidene, IH or 3H-benzinylidene, oxazolinylidene, oxazolidinylidene, penzoquinolinylidene, naphtho Oxazolinylidene, oxadiazolinylidene, thiazolidinylidene, phenanthrothiazolinylidene, acenaphthothiazolinylidene, thiazolinylidene, penzothiazolinylidene, naphthothiazolinylidene, tetrahydrobenzothiazolinylidene, Dihydronaphthothiazolinylidene, thiadioxazolinylidene, selenium azolinylidene, selenium azolinylidene,
Penzoselen azolinylidene, naphthoselen azolinylidene, selenium azolinylidene, birazolylidene, intrilidene, imidazolidinylidene, penzimidazolinylidene, naphthoimidazolinylidene, diazolinylidene, tetrazolinylidene, and imidazoquinoxalinylidene The core of.

For details, R', R”+ Lll Lz+ L31 L
lll and ri are each the groups described above in the general formula [■].

The alkyl group represented by R''l and R10 includes, for example, unsubstituted alkyl groups such as methyl group and ethyl group, substituted alkyl groups such as methoxyethyl group and phenylmethyl group, and examples of the aryl group include phenyl group. .

Particularly preferably, general formula (X) is represented by the following formula.

In the formula: X”, X”l Lll L41 Ls+
R'l R'', R'IW, Q and m each have the same meaning as in general formula (X).

In another preferred form, the cyanine dye used in the photographic elements of this invention can be represented by the following general formula (XI).

X in the ceremony? +Xs represents a hydrogen atom, an alkyl group, and an aryl group, respectively. (However, X9.
, Ls, R4 and Ri each independently represent a methine group, n is 0.1 or 2, m is 0 or 1, Q is an atomic group completing the basic heterocyclic azolinylidene or azinylidene nucleus, Y- represents a counter anion, and P represents O or a positive integer for balancing the ionic charge.

With the exception of the form of the azolinylidene or azinylidene ring completed by Q, the various components of formula (XI) can be selected in the same way as described above with respect to formula (■), so that
I won't explain it again. In its optimal form, Q in formula (XI)
is selected from among the cores of pyrrolilidene, intrilidene, carboazolilidene, benzintolylidene, pyrazolylidene, indasylylidene, and pyrrolopyridinylidene. Again, common ring substituents consistent with formula (X) are contemplated. R? and R11 are optimally sulfo- or sulfato-substituted hydrocarbon substituents, as described above.

Next, specific representative examples of compounds represented by the above general formula (1), (% formula % ((X) and (XI)) used in the present invention will be given. It is not limited.

[Exemplary compound of general formula (I [[)] [Example compound of general formula (I)] [Example compound of general formula (II)] tus [Example compound of general formula [■]] (CHg) 5sOsθ CHzCToCHSOse H3 [ [Illustrative compounds of general formulas [■] and (IX)] (■-3) ■-4) (Vl-6) CH2
CH25O3e (■-9) (■-10) (■-11) (■-12) (■-15) (■-18) (■-19) (■-20) (■-21) CJ=n Je C
HzCHzCOOH (■-22) (■-23) (■-25) (■-26) [Exemplary compounds of general formula (X)] (X-3) so, e CCHt) s ■ so, e (X-6 ) 03e (X-8) CtHs CtHS H3 (X-10) [Exemplary compounds of general formula (XI)] No. 757.767, Journal of the Chemical Society, 19
63.5712 5717 (J, Ches, Soc,
, 1963゜5712-5717), Pharmaceutical journal volume 68,
191-194 (1948) and the like.

Moreover, the above general formula (II), (IV), (V)
, (Vl).

Compounds used in the present invention represented by [■), (IX) and (X) are described, for example, in Journal of the American Chemical Society, Vol. 61.

1875-1889 (1945) (J, As+
, Che-, Soc, , Dan-e, 1B75-1889
(1945)) or Cyanine Dice and Related Compounders by F.M. Harma (
Those skilled in the art can synthesize the product by referring to the method described in (Published by Inter Science Publishers, 1964).

Next, specific synthesis examples will be shown, but other compounds represented by the above general formula can also be synthesized according to the synthesis method below.

(Synthesis example) 2-methyl-4-phenyltetrazole (Exemplary compound I
II-I) The inside of the reaction vessel system was completely replaced with nitrogen, and 18 g of dehydrated acetonitrile and 20 g of α-bromoacetophenone were added thereto.
Add g. Add 2.5 g of phosphorus oxychloride and replace the inside of the system with nitrogen. Hydrogenated tellurium (Journal) generated from aluminum telluride and hot water through a gas introduction pipe
of American Chemical Society J
, Am, Chem, Soc, ) 7L429 (194
9)) to react by heating on a water bath.

The reaction solution is subjected to steam distillation to remove unreacted components.

Subsequently, the remaining reaction solution is made alkaline and subjected to steam distillation again to distill out the basic components. This water root is extracted with ether and dried using anhydrous magnesium.

The ether phase was distilled off to obtain a viscous yellow oil.

Crystallize from isopropanol to obtain colorless prism crystals.

Yield 1.4g, melting point 56-61℃2-(5
-2-(3-methyl-4-phenyl-2(3H)tellazoliden)ethylidene)4-oxo-2-thioxo-1
, 3-thiazolidin-3-yl)ethanesulfonic acid (Exemplary Compound V-10) 2-acetamidovinyl-3-methyl-4-phenyltellazolium trifluoromethanesulfonate 2.9 g and 3-β-sulfoethyl rhoda Dissolve 1.2 g of nin in 30 mβ of absolute ethanol, add 2 g of triethylamine, and heat under reflux for 15 minutes. The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol.

Yield: 0.81 g.

Maximum absorption wavelength in methanol solution: 546 nm.

2-(5-chloro-2-(3-(3-methyl-4-phenyl-2(3H)tellazoliden)-1-probenylidene)-3-benzooxazolio)ethanesulfonic acid inner salt (exemplary compound ■- 7) Dissolve 13.5 g of 2-methyl-4-phenyltetrazole in 80 sJ of dichloromethane, add 9.0 g of methyl-trifluoromethanesulfonate, stopper tightly, and leave at room temperature for 1 week. Precipitated crystals are collected by filtration, followed by 120 sJ of acetic anhydride. Suspend in mlt.

Add 19.6 g of diphenylformamidine and heat under reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried. Yield: 15.1 g, Crude product: 2.9 g
was dissolved in 20ml of m-cresol and 2-(5-chloro-
1.4 g of 2-methyl-3-benzooxazolio)ethanesulfonic acid inner salt and 1 g of triethylamine are added, and the mixture is heated and stirred at 110° C. for 15 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Add acetone and stir to crystallize. The precipitate is collected by filtration and washed with ethanol.

It was purified by recrystallization from a mixed solvent of chloroform-methanol (1:2).

Yield: 0.54 g.

Maximum absorption wavelength in methanol solution: 601 nm.

The dyes described above can be applied in any application in which otherwise corresponding dyes containing other chalcogen atoms are used. The dyes used as compounds of this invention are incorporated into silver halide photographic elements in a preferred application. The location and concentration of the dye depends on the photographically useful function sought to be achieved. Silver halide emulsion layer 1
or when it imagewise absorbs actinic radiation that passes through 2 or more, thereby reducing the scattered radiation, the dye
It can be located behind the above silver halide emulsion layer. In other words, the dye can be used as an anti-haleysilane dye.

The compounds of the invention can be incorporated into interlayers or overcoating layers to function as filter dyes.In a preferred application, when the compounds of the invention are used as dyes, they can be incorporated directly into the silver halide emulsion. . Dyes can increase photographic sharpness by blocking and absorbing actinic radiation that would otherwise be reflected between particles.

In other words, the compounds of the invention can take the form of interparticulate sorbents.

A highly preferred utility of the compounds of this invention as dyes is to increase the wavelength of the spectral response of silver halide grains to exposing radiation.

In such applications, the dye is typically adsorbed to the surface of the silver halide grains. Additionally, the dye can also function to reduce the sensitivity of the silver halide grains in the spectral region of inherent or native sensitivity. This can be a desirable feature in addition to spectral sensitization, or increases the difference between the sensitized and intrinsic sensitivity of the emulsion, as is desirable for minus-blue recording emulsions in color photography. This can be a desirable feature in combination with spectral sensitization. It is specifically contemplated that the dyes as compounds of this invention may be used as spectral sensitizers in both surface and internal latent image-forming emulsions.

The latter emulsion offers the advantage of a more favorable dye concentration desensitization relationship, i.e., allowing the dye as a compound of the invention to be directly deposited, i.e., more dye is not required to reach the desensitization level. Those substituents can be selected to increase electron capture when used in combination with surface fogging silver halide emulsions used in forming images. As mentioned above, ultraviolet, blue, green, red and infrared absorbing dyes according to the invention are contemplated.

However, dyes with absorption maxima at wavelengths of 500 nm and longer are particularly advantageous.

The compounds of the invention need not necessarily be in the form of dyes. A large number of chalcogenazolium anti-capri agents and stabilizers are known in the art, and the compounds of the present invention can be used as substitutes therefor while still achieving the benefits of the present invention.

A particularly useful class of compounds for photographic purposes is the class of compounds represented by formula (■) above, in which R7 is an alkynyl substituent and R& is a methyl substituent.

Here, R1 is preferably an alkynyl group having 3 to 5 carbon atoms and most preferably a propargyl group or a 2-butynyl group. R
h is preferably -0. determined from electron-withdrawing properties.
It is a methyl group which may have a substituent having a Panot's sigma value more positive than 2.

These compounds can be used in combination with internal latent image-forming emulsions to directly form positive images. It is valid. Therefore, when the compounds of this invention are used as nucleating agents, they are present in the photographic element prior to imagewise exposure.

Moreover, it is preferable to interpose an adsorption-promoting moiety as at least one of X and X, or a part thereof.

Useful adsorption-promoting groups include thioamide groups, such as oxythioamide groups, dithioamide groups, and thiourido groups. ``This compound can also be used to increase photographic sensitivity. In this case, a compound is adsorbed onto the surface of the light-sensitive silver halide grains in the surface latent image-forming emulsion, and preferably contains a thioamide group.

Nucleating agents in which the tellurium-containing heterocycle of the present invention is bonded directly or via an intervening bonding group to the nucleating moiety of hydrazine and hydrazine derivatives (e.g., hydrazide and hydrazone alkyl) can also be used to form internal latent image-forming silver halide grains. It can be adsorbed to the surface.

Additionally, hydrazines and their hydrazide derivatives are useful in surface latent image forming negative working emulsions to increase contrast to very high levels.

In yet another embodiment, the compounds of the present invention can be used to promote latent image retention while still achieving the effects of the present invention. A useful group of latent image-retaining additives that are useful in photographic elements according to the present invention are those in which RS is represented by II.CHJ.CHtC.CR.

In the formula, R" is a hydrogen atom or a methyl group, and Rlj is,
Hydrogen or an alkyl group, preferably having 1 to 6 carbon atoms.

The compounds of the present invention contain 10'''I per mole of silver halide.
A mole to 1 mole is added.

When the compound of the present invention is used as an antifoggant, it is added to at least one of the constituent layers of a light-sensitive material, preferably a silver halide emulsion layer. The amount added is a power value that changes as appropriate depending on the type of compound and the layer to which it is added, and is difficult to define unambiguously, but it is generally 10-" per mole of silver halide.
The amount ranges from 1 mol to 1 mol, and the more preferable range is 10-6 to 10-3 per mol of silver halide.
It is a mole.

When the compounds of the present invention are used as sensitizing dyes, each mol.
-"mol, preferably lXl0-'mol-2,5xt
o-'' mol, particularly preferably 4.times.10-' mol-1.times.

The compounds used in the present invention can be added to the emulsion as sensitizing dyes by methods well known in the art. For example, these sensitizing dyes can be dispersed directly in the emulsion, or they can be dispersed in pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone,
or a mixture thereof, or diluted with water, or dissolved in water, and added to the emulsion in the form of these solutions, and the sensitizing dye is added to the emulsion. This may be done at any time during the emulsion manufacturing process, but preferably during or after chemical ripening.

The silver halide emulsions used in the photographic elements of this invention include:
Any silver halide used in conventional silver halide emulsions can be used, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Also, while considering the critical growth rate of silver halide crystals, adjust the pH in the mixing vessel of halide ions and silver ions.

It may also be produced by sequentially and simultaneously adding pAg while controlling it. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

In the process of forming and/or growing the grains, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts (complex salts containing). A metal ion is added using at least one selected from complex salts containing
Alternatively, these metal elements can be contained on the surface of the particles, and by placing them in a suitable reducing atmosphere, reduction/multiplying nuclei can be provided inside the particles and/or on the back surface of the particles.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left as they are contained. When removing the salts, Research Disc
It can be carried out based on the method described in No. 17643.

The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

Silver halide grains used in silver halide emulsions may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or irregular crystal shapes such as spherical or plate shapes. It can be something you have. In these particles, (100)
Any ratio between the plane and the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5 μm or less, and particularly preferably 3 μm or less.

The silver halide emulsion of the present invention may have any grain size distribution. Emulsions with a wide grain size distribution may be used, or emulsions with a narrow grain size distribution may be used alone or in combination.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or to maintain stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the art as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsion
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

When gelatin is used as a binder for a silver halide emulsion, the jelly strength of the gelatin is not limited, but it is preferably 250 g or more (value measured by baggy method).

The photographic emulsion layer and other hydrophilic colloid layers of the photographic element of the present invention may be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. Can be done. The hardening agent can be added in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

Plasticizers can be added to the silver halide emulsion layers and/or other hydrophilic colloid layers of the photographic elements of this invention to increase flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the photographic element of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

The emulsion layer of the photographic element of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-phenylenediamine derivative, aminophenol derivative, etc.) during color development to form a dye. A dye-forming coupler is used.

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers can be combined with oxidized forms of developing agents to produce development accelerators, bleaching accelerators, developing agents, silver halide solvents, toning agents, hardener capri agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments, such as spectral sensitizers and desensitizers, can be included. Colored couplers that have a color correction effect on these dye-forming couplers, or D that releases development inhibitors during development to improve image sharpness and image graininess.
An IR coupler may also be used. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. In place of the DIR coupler, which may be a dye-forming compound, a DIR compound is used which reacts with the coupler or in combination with the oxidized form of the developing agent to form a colorless compound and at the same time releases a development inhibitor. Good too.

A colorless coupler that undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent if necessary, and stir with a surfactant in a hydrophilic binder such as an aqueous gelatin solution.
After emulsifying and dispersing using a dispersion means such as a homogenizer, colloid mill, flow jet mixer, or ultrasonic device,
It may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the photographic element of the present invention, causing color turbidity and deterioration of sharpness. A color anti-capri agent can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

Image stabilizers can be used in the silver halide photographic elements of this invention to prevent degradation of the dye image.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photographic element of the present invention contain an ultraviolet absorber to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

Formalin scavengers can be used to prevent degradation of magenta dye-forming couplers and the like by formalin during storage of the photographic element.

In the photographic elements of this invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a mordant such as a cationic polymer.

Compounds that change developability, such as development accelerators and development retardants, and bleach accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the photographic elements of the present invention. Compounds that can be preferably used as development accelerators are listed in Research, Disclosure + - (Re5earch Di
Section XXI B-D of No. 17463
The development retardant is a compound described in Section XXI of No. 17643, Section E. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The photographic emulsion layer of the photographic element of the present invention may contain polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urethane derivatives, urea derivatives, imidazole derivatives, and the like.

In the photographic element of the present invention, an optical brightener can be used for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable.

Photographic elements of the invention can be provided with auxiliary layers such as filter layers, antihalation layers, and/or anti-irradiation layers. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the photographic element of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together.

A lubricant can be added to reduce the sliding friction of the photosensitive material.

Antistatic agents can be added to the photographic elements of this invention for antistatic purposes. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for.

The photographic emulsion layer and/or other hydrophilic colloid layer of the photographic elements of this invention may include coatability-improving, antistatic, slippery-improving,
Various surfactants can be used for the purpose of emulsification dispersion, prevention of adhesion, and improvement of photographic properties (development acceleration, film hardening, sensitization, etc.).

Supports used in the photographic elements of this invention include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc., and reflective layers on these films. Includes flexible supports, glass, metal, ceramics, etc.

The photographic element of the present invention can be produced directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, or to improve the adhesion, antistatic properties, dimensional stability, body abrasion properties, etc. of the support surface. It may be applied through one or more subbing layers to improve hardness, antihalation, frictional properties, and/or other properties.

Thickeners may be used in coating the photographic elements of this invention to improve coating properties. Also, for example, as a hardening agent,
For substances that have a fast reactivity and may cause gelation before coating if added to the coating solution in advance, it is preferable to mix them using a static mixer or the like immediately before coating.

In preparing the photographic elements of this invention, the silver halide emulsion layers and other protective colloid layers were prepared by Research Disclosure.
e) It can be applied by the method described in Section A of XV of No. 17463 and dried by the method described in Section B of the same.

The photographic elements of this invention can be exposed with electromagnetic radiation in the region of the spectrum to which the constituent emulsion layers are sensitive. Light sources include natural light (sunlight), Dungesten electric lamp, fluorescent lamp,
Light emitted from phosphors excited by mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, T-rays, α-rays, etc. , any known light source can be used.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. However, exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

Any known method can be used for developing the photographic element of the present invention. This development process may be either a process for forming a silver image (black and white development process) or a process for forming a color image, depending on the purpose. If an image is to be produced by the reversal method, a black and white negative development step is first carried out, and then a color development process is carried out by applying white exposure or processing with a bath containing a fogging agent.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods, such as a spray method in which the processing solution is supplied in the form of a spray, or contact with a carrier impregnated with the processing solution, are also used. A web method, a method of viscous development processing, etc. may be used.

The black and white development process includes, for example, a development process, a fixing process, and a water washing process. Alternatively, a developing agent or its precursor may be incorporated into the sensitive material, and the developing process may be carried out using only an alkaline solution.

A development process using a lithium developer as a developer may be performed.

The color development process includes a color development process, a bleaching process, a fixing process, and if necessary, a water washing process, or a stabilization process accompanied by water washing. Instead of a liquid treatment process,
A bleach-fixing process can be carried out using a one-bath bleach-fix solution, or a monobath process can be carried out using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be carried out in one bath. You can also do that.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, an activator treatment step in which a color developing agent or its precursor is contained in the material and development is performed with an activator solution may be performed instead of the color development treatment step, or an activator treatment step may be performed in place of the monobath treatment. The beta treatment, bleaching and fixing treatments may be carried out simultaneously. Representative treatments among these treatments are shown below. (These treatments are carried out as a final step, for example, either a water washing process or a stabilization process accompanied by a water washing process.) Color development process - Bleaching process Constant fixation process Color development process - Bleach-fixing process/Pre-hardening process - Neutralizing process - Color development process - Stop-fixing process - Washing process - Bleaching process Constant coloring process - Washing process - Post-hardening process/Color development Development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process / Monobath process / Activator process - Bleach-fixing process / Activator process - Bleach process Constant fixation Processing process In addition to these treatments, there is a method in which developed silver produced by color development is bleached with halogen, and then color development is performed again, and various intensification treatments (amplification) described in JP-A-58-154839. Processing may be performed using a developing method that increases the amount of produced dye, such as processing).

[Embodiments of the invention]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example-1 Silver halide grains were precipitated by a double jet method, physically ripened by a conventional method, desalted, and further chemically ripened by a gold sensitization method and a sulfur sensitization method, followed by iodization. l!
A silver iodobromide emulsion containing 6 mol % was obtained. The average diameter of the silver halide grains contained in this emulsion was 0.55 μl. One pupil of this emulsion contained 0.57 mol of silver halide and 900 g of gelatin binder.

Furthermore, 4-hydroxy-6-methyl-1,3,3a,
20 m of a 1.0% by weight aqueous solution of 7-chitrazaindene
It was stabilized by adding l.

1 km of this emulsion was weighed into a pot and heated to 40°C to dissolve it. Then, predetermined amounts of methanol solutions of the sensitizing dye according to the present invention and the comparative sensitizing dye were added and mixed and stirred. A coating aid and a hardening agent were added to each of these emulsions, and the resulting emulsions were coated on a cellulose triacetate film base to a dry film thickness of 5 μm and dried to obtain samples of light-sensitive materials.

These samples were exposed to light using a sensitometer using a tungsten light source. After exposure, 2
The strip was developed at 0° C. for 3 minutes, stopped, fixed, washed with water and dried to obtain a strip with a black and white image.

The density of each developed sample was measured using an optical densitometer to measure sensitivity and fog. The optical density reference point for determining the sensitivity was the fog +0.2 point.

Dye for developer composition comparison (A) thL; tls (L; HzJ
tslJs - Dye for Comparison (B) The results obtained are shown in Tables 1 to 3. Note that the sensitivity is a relative value with the sensitivity (So) when using a comparative dye being 100.

As is clear from Table 1, Table 2, Table 3, and Tables 1 to 3, the photographic element of the present invention has a lower capri and higher sensitivity than the comparative photographic elements having approximately the same photosensitive wavelength.Example-2 Iodination A silver iodobromide emulsion containing 6 mol % of silver was chemically ripened by a conventional method to obtain an average grain size of 0.9 μm.

An emulsion containing 0.60 mol/kg of silver salt and 10 g/kg of gelatin was obtained. This emulsion 1 pupil was heated to 40°C, and 500 g of an emulsion of cyan coupler D described below was added. The emulsion of coupler D was prepared by adding 3 ethyl acetate to 100 g of coupler D.
00 tag and dibutyl butare) to dissolve it, add sodium dodecylbenzenesulfonate, and use a homogenizer to emulsify and disperse in 1 ml of a 10% aqueous gelatin solution. To this emulsion were added predetermined amounts of methanol solutions of the sensitizing dye according to the present invention and the comparative sensitizing dye, and the mixture was mixed and stirred.

Additionally 4-hydroxy-6-methyl-1,3,3a.

20 va of 1.0 wt% aqueous solution of 7-chitrazaindene
The emulsion completed by adding n to stabilize it, and further adding a coating aid and a hardening agent, was coated on a cellulose triacetate film base at a coated silver amount of 5 g/rrf, dried, and a sample was prepared. Obtained.

This film sample was subjected to light wedge exposure using a photosensitive needle having a light source with a color temperature of 5400° and a red filter attached to the light source. After exposure, the following formulation was developed, bleached, fixed, and dried, and the density of the developed cyan dye image was measured, and the sensitivity and capri were measured. The optical density reference point for determining the sensitivity was the point of Capri +0.20.

In addition, the sensitivity is 1 the sensitivity (SO) when using the comparative dye.
Coupler D expressed as a relative value to 00 Development processing recipe 1, color development 3 minutes 15 seconds (38°C) 2, bleaching
White 6 minutes 30 seconds 3, water washing 3 minutes 15 seconds 4, fixation 6 minutes 30 seconds 5, water washing 3 minutes 15 seconds 6, stabilization 3 minutes 15 seconds The composition of the processing liquid used in each step is as follows. be.

Color Developer Bleach Fixer Stabilizer (Comparative Dye D) (Comparative Dye E) As is clear from Tables 4 and 5, the photographic elements of the present invention have approximately the same photosensitive wavelength. Example 3 with low fog and high sensitivity compared to comparative elements Each of the constituent layers described below was coated on polyethylene coated paper in order from the support side to prepare a sample of a multilayer color light-sensitive material.

First layer...Blue-sensitive emulsion layer The blue-sensitive silver chlorobromide emulsion layer (containing 1190 mol% bromide) contains the following yellow coupler dissolved and dispersed in 400 g of gelatin and dibutyl phthalate per mol of silver halide. Contains 0.2 mol per mol of silver halide, and the amount of silver is 40
This layer is coated so that the thickness is 0 m/nf.

Second layer: Intermediate layer This is a gelatin layer containing 2.5-di-t-octylhydroquinone and is coated at a gelatin content of 1.5 g/rd.

Third layer...Green-sensitive emulsion layer The green-sensitive silver chlorobromide emulsion layer (containing tB bromide 80 mol%) is
500 g of gelatin per mole of silver halide and 0.2 mole of 2,5-di-
0.05 mol of t-octylhydroquinone per mol of magenta coupler, 1.4-di-octyloxy-2,
Contains 0.3 mol of 5-di-t-amylbenzene per mol of magenta coupler, and has a silver content of 500 μ/mole.
This is a layer coated so that it becomes rrl.

4th layer: 2,5-di-t dissolved and dispersed in intermediate layer dibutyl phthalate
- Octylhydroquinone at 30 μ/d and 2-(benzotriazol-2-yl)-4 as a UV absorber.
, 6-di-t-butylphenol at 0.7s/rrl, and the coated gelatin is 1.5g/rrl.
This is a layer coated to give +d.

5th Layer: Red-Sensitive Emulsion Layer A red-sensitive silver chlorobromide emulsion layer ( bromide (containing 70 mol%) contains 500 g of gelatin per mol of silver halide and 0.2 mol of the following cyan coupler dissolved and dispersed in dibutyl phthalate per mol of silver halide, and the amount of silver is This layer was coated to give a ratio of 450 .mu./a.

6th layer: Intermediate layer A gelatin layer containing 0.4 g/rtf of the above-mentioned ultraviolet absorber dissolved and dispersed in dibutyl phthalate.A layer coated with gelatin at a concentration of 1.5 g/rrl. .

Seventh layer: Protective layer This is a gelatin layer coated so that the amount of gelatin is 1.5 g/rrl.

(Yellow coupler) (Magenta coupler) (Cyan coupler) l The silver halide emulsions in each of the above photosensitive layers are
It was prepared by the method described in Japanese Patent No. 7772, and chemically sensitized using sodium periosulfate pentahydrate, and 4-hydroxy-6-methyl-1,3,
3a, 7-chitrazaindene was added, as well as a hardener and a coating aid.

These samples were subjected to light wedge exposure using a photosensitive layer having a light source with a color temperature of 5400 DEG and an I red filter attached to the light source. After exposure, the following formulation was developed, bleached and fixed, washed with water, and then dried, and the density of the colored dye image was measured.
Sensitivity and fog were measured.

The optical density standard for determining the sensitivity was a point of Capri +0.20.

The obtained results are shown, and the sensitivity is shown as a relative value with the sensitivity (So) of the sample using the comparative dye being set as 100.

Standard processing steps (processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2]
] Bleach-fixing 33°C 1 minute 30 seconds [3] Washing 25-30°C 3 minutes [4] Drying 75-80°C approximately 2 minutes Processing solution composition (color developer tank solution) (bleach-fix tank solution) (for comparison) Dye F) (Comparative Dye G) As is clear from Tables 6 and 7, the photographic element of the present invention has lower fog (, sensitivity is high.

Example 4 A compound of the present invention or a comparative compound was added as an antifoggant to the emulsion used in Example 1, and then coated and dried in the same manner as in Example 1 to obtain a sample. The sample was exposed and developed in the same manner as in Example 1, and the sensitivity and fog of the obtained strip were measured, and the results are shown in Tables 8 and 9.

The sensitivity is the sensitivity of the sample without antifoggant (So)
is the relative sensitivity with 100.

As is clear from Tables 8 and 9, in the photographic element of the present invention, the addition of the compound of the present invention reduces fog and does not result in a corresponding decrease in sensitivity.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent Patent attorney Takatsuki Shite Tsuzuki Shufu Seisho (Method) % formula % 2. Name of the invention Photographic element 3. Relationship with the person making the amendment Patent applicant address Tokyo Shinjuku-ku Nishi-Shinjuku 1-26-2 Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Megumi Ide, student 4, agent 6, subject of amendment Specification, part 1 7, content of amendment

Claims (1)

[Scope of Claims] A photographic element characterized by having at least one silver halide emulsion layer on a support and a compound represented by the following general formula [I], [II], [III] or [IV]. . General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Y^- is the counter ion, P is 0 or a positive integer to adjust the ion charge, X_1, X_2, X_3, X
_4, X_5, X_6, X_7 and X_8 each represent a hydrogen atom, an alkyl group, an aryl group (However,
_8 cannot be a hydrogen atom at the same time. ), R_1, R_5 and R_6 each represent a hydrogen atom or a hydrocarbon moiety that may be substituted, R_3 represents a hydrocarbon moiety that may be substituted, and R_2 and R_4 each represent a hydrogen atom or a hydrocarbon moiety that may be substituted. R_7 represents a hydrogen atom or a quaternized substituent.