JPH0623828B2 - Photo elements - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sensitizing dye having a 5-membered heterocyclic nucleus having a nitrogen atom and a tellurium atom as ring-constituting atoms sandwiching a carbon atom (hereinafter referred to as tellurium-containing sensitizer). The present invention relates to a silver halide photographic element containing a sensitizing dye, and more particularly to a silver halide photographic element having an improved dry fog.

[Prior art]

The tellurium-containing sensitizing dye containing tellurium with respect to oxygen, sulfur and selenium as an oxygen group element is useful for a silver halide photographic element because of its great bathochromic effect. 78444 and 60-78445. However, it has been found that silver halide photographic elements containing said sensitizing dyes are susceptible to fog (dry fog) during the rapid drying process that is widely practiced in the industry in recent years. Dry fogging becomes more noticeable than when the drying process is slow.

It is considered that this phenomenon is generally caused by the fact that the silver halide grains are distorted due to the pressure applied to them because the dispersion medium of the silver halide grains, such as gelatin, is rapidly contracted by being dried in a short time.

In the industry, rapid drying not only allows for high speed, high volume coating of photographic elements, but also eliminates the instability of keeping photographic elements too wet.
Furthermore, since it is rapidly dried, simultaneous coating of multiple layers is possible. Therefore, the occurrence of dry fogging in rapid drying is a major problem to be improved.

Conventionally, as a method of preventing dry fogging, a method of adding polyhydric alcohols, U.S. Patent Nos. 2960404 and 3520694,
No. 3619198, No. 3650759, etc. However, with the above method, it is not only difficult to prevent the dry fogging by the tellurium-containing sensitizing dye, but also the tackiness of the film is caused by the addition of the polyhydric alcohol, which is not preferable.

[Purpose of the present invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic element containing a tellurium-containing sensitizing dye, which causes little dry fog even in rapid drying.
The purpose of is to provide a method of making the photographic element.

[Configuration of the present invention]

The object of the present invention has been achieved by the following. That is, at least one silver halide emulsion layer and a sensitizing dye having a 5-membered heterocyclic nucleus having a nitrogen atom and a tellurium atom as a ring-constituting atom sandwiching a carbon atom as at least one basic nucleus are provided on a support. A silver halide photographic element containing the photographic element, wherein the photographic element is hardened with a hardening agent represented by the following general formula [I] or [II] or a vinyl sulfone hardening agent. Achieved by silver photographic elements. However, in the present invention, a photographic element which is a photothermographic material is excluded. This is because the heat-developable light-sensitive material is not effective in preventing rapid drying fog even with the above structure. [Wherein R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an —OM group (M is a monovalent metal atom), and a —NR′R ″ group (R ′ and R ″ are each hydrogen. Atom, alkyl group, aryl group) or -NHCO
R represents a hydrogen atom (R is a hydrogen atom, an alkyl group, or an aryl group), and R ₂ is a group having the same meaning as R ₁ except the chlorine atom. ] General formula [II] [Wherein, R ₃ and R ₄ are each a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group or an —OM group (M is 1
(Valent metal atom). Q and Q'are each -O
A linking group selected from —, —S—, and —NH—, and L represents an alkylene group or an arylene group. l and m represent 0 or 1, respectively.

In the present invention, rapid drying means, for example, a gelatin-silver halide emulsion layer coated on a film support after coating,
The water content of the sum of each layer such as the gelatin-containing protective layer is based on its average dry weight, that is, When expressed in percentage, the time until reaching the water content near the critical water content of 200% or less (end of constant rate drying process) is within 5 minutes. It is preferably within 3 minutes, more preferably within 1 minute.
This drying time is preferably 10 seconds or more in relation to the coating solution set.

The vinyl sulfone type hardener used in the present invention is a compound having at least two vinyl sulfonyl groups in the molecule. For example, an aromatic type compound as described in German Patent 1100942, JP-B-44. -29622, alkyl compounds bonded with a hetero atom as described in JP-A-47-25373, sulfonamides, ester compounds as described in JP-B-47-8736, JP-A-49-24435 1,3,5-tris [β- (vinylsulfonyl) -brovionyl] -hexahydro-s-triazine as described in JP-A-51-44164 or an alkyl compound as described in JP-A-51-44164 .

Typical specific examples thereof are shown below, but the present invention is not limited to these.

H-1 _{H-2 O (CH 2 CH} 2 SO 2 CH = CH 2) 2 H-3 NH (CH 2 CH 2 SO 2 CH = CH 2) 2 H-4 H-5 H-6 H-7 _{H-8 CH 3 C (CH} 2 OCH 2 SO 2 CH = CH 2) 3 H-9 C (CH 2 OCH 2 SO 2 CH = CH 2) 4 H-10 N (CH 2 CH 2 OCH 2 SO 2 CH = CH _{2) 3} H-11 H-12 _{H-13 C 2 H 5 C} (CH 2 SO 2 CH = CH 2) 3 H-14 C 8 H 17 C (CH 2 SO 2 CH = CH 2) 3 H-15 _{H-16 (CH 2 = CHSO} 2 CH 2) 3 CCH 2 Br H-17 (CH 2 = CHSO 2 CH 2) 2 CHCH (CH 2 SO 2 CH = CH 2) 2 H-18 (CH 2 = CHSO 2 CH ₂ ) ₃ CCH ₂ OCH ₂ C (CH ₂ SO ₂ CH = CH ₂ )
₃ H-19 C (CH ₂ SO ₂ CH = CH ₂ ) ₄ H-20 _{H-21 (CH 2 = CHSO} 2 CH 2) 3 CCH 2 SO 2 CH 2 CH 2 Cl H-22 The vinyl sulfone type hardener in the present invention is a compound having at least 3 vinylsulfonyl groups in the molecular structure in addition to the above exemplified compounds, for example, exemplified compound [H-5].
To [H-22] include a reaction product obtained by reacting a compound having a group capable of reacting with a vinyl sulfone group and a water-soluble group such as diethanolamine, thioglycolic acid, sarcosine sodium salt and taurine sodium salt.

Next, the general formula [I] or [II] used in the present invention is used.
The compound represented by will be described in detail.

In the general formulas [I] and [II], the alkyl group, alkoxy group and alkylthio group represented by R ₁ include
An alkyl group having 1 to 3 carbon atoms can be mentioned,
For example, methyl group, ethyl group, methoxy group, ethoxy group,
Examples include methylthio group and ethylthio group.

The M representing a monovalent metal atom -OM group represented by R ₁
Are, for example, sodium, potassium, ammonium and the like. Further, the alkyl group represented by R ′ and R ″ of the —NR′R ″ group is an alkyl group having 1 to 3 carbon atoms, for example, methyl group, ethyl group and the like. And the aryl group includes a phenyl group.

Further, the alkyl group and the aryl group represented by R of the —NHCOR group represented by R ₁ have the same meanings as the alkyl group and the aryl group represented by R ′ and R ″, respectively.

R ₂ is a group having the same meaning as R ₁ described above except for a chlorine atom as described above.

Next, the groups represented by R ₃ and R ₄ are the same as the groups represented by R ₁ above.

Examples of the alkylene group represented by L include alkylene groups having 1 to 3 carbon atoms, such as methylene group and ethylene group. Examples of the arylene group include a phenylene group.

Next, typical examples of the hardener according to the present invention represented by the above general formulas [I] and [II] will be described.

(I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) (I-9) (II-1) (II-2) (II-3) (II-4) (II-5) (II-6) (II-7) (II-8) (II-9) To add the vinyl sulfone-based hardener according to the present invention and the hardener represented by the general formula [I] or [II] to a silver halide emulsion layer or other constituent layers, water or a water-miscible agent is added. It may be dissolved in a solvent (for example, methanol, ethanol, etc.) and added to the coating liquid for the above-mentioned constituent layers. The addition method may be either a batch method or an in-line method. The addition timing is not particularly limited, but it is preferably added immediately before coating.

These hardeners are 0.5-100 mg / g coated gelatin,
Preferably, 2.0 to 50 mg is added.

The sensitizing dye according to the present invention is a sensitizing dye having a 5-membered heterocyclic nucleus having a nitrogen atom and a tellurium atom as ring-constituting atoms sandwiching carbon atoms as at least one basic nucleus, and having an unsaturated bond in the ring. Depending on the bonding state with the nitrogen atom, various structures can be taken, but as typical ones, there are those having a tellurazole ring nucleus, a tellurazoline ring nucleus, a tellurium azolium ring nucleus, and a tellurium azolinium ring nucleus.

Among these, the following general formulas [I] to [IV] are preferable.
It is shown by.

General formula [I] General formula (II) General formula (III) General formula (IV) In the formula, R ₁ and R ₂ are each (i) a hydrogen atom or an optionally substituted monovalent group, and at least one is an optionally substituted alkyl group or aryl group, and preferably each is ,
A hydrogen atom or an alkyl group which may be substituted,
Or, an aryl group, at least one of which is an alkyl group or an aryl group which may be substituted.

(Ii) A group of atoms that jointly completes a ring (preferably 5 to 6 members) fused to a ring containing tellurium and nitrogen, and preferably an aromatic ring fused directly to the ring containing tellurium and nitrogen. Alternatively, it is an atomic group that completes an aromatic ring fused to a non-aromatic ring fused to the ring containing tellurium and nitrogen.

R ₃ and R ₆ are each a hydrogen atom or an optionally substituted hydrocarbon part, R ₁ is a hydrogen atom, an optionally substituted hydrocarbon part or an amino group, and R ₅ is an optionally substituted hydrocarbon part. , R ₇ represents a hydrogen atom or a quaternized substituent, Y ⁻ represents a counter ion, p represents 0 or a positive integer for matching the ionic charge.

R ₃ and R ₇ together with R ₂ may complete a 5-6 membered fused heterocycle.

R ₃ is a fused heterocycle (preferably 5 to ₅₎ in cooperation with R ₄ or R 5.
6 members) may be completed.

R ₇ together with R ₆ may complete a fused heterocycle (preferably 5-6 membered).

To Y representing the ion ^- As the halogen atom (chlorine, bromine and each atom of iodine, etc.) and sulfonic acids (methanesulfonic acid, trifluoromethanesulfonic acid and p- toluenesulfonic acid, etc.)
Each anion such as is typical.

The ring completed by R ₁ and R ₂ is typically an aromatic 5- or 6-membered ring such as benzene, naphthalene, thiophene, benzothiophene furan, benzofuran and pyridine.

These rings may be substituted. As the substituents, hydroxy, hydroxyalkyl groups (eg, groups such as hydroxyethyl, hydroxypropyl, etc.), alkyl groups (eg, groups such as methyl, ethyl, isopropyl, t-butyl, etc.), alkoxy groups (eg, methoxy, ethoxy, etc.) β-
Each group such as methoxyethoxy, γ-carboxypropyloxy, etc.) aryloxy (for example, each group of phenoxy, ρ-chlorophenoxy, etc.), aryl group (for example, ρ-tolyl, phenyl, m-hydroxyphenyl, ρ-hydroxyphenyl, 2 -Hydroxynaphthyl, etc.), halogen atoms (e.g., chlorine, fluorine, bromine, etc.), trifluoromethyl group, amino group (e.g., dimethylamino group, diethylamino group, etc.), cycloalkyl group (e.g., A cyclohexyl group), a cyano group, a carba, a moyl group (for example, a carbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-diethylcarbamoyl group or the like), an alkoxycarbonyl group (for example, an ethoxycarbonyl group), and an alkylthio group (for example, methylthio). Basis)
Each group such as

Examples of the ring in which R ₂ and R ₃ , R ₂ and R ₇ , R ₃ and R ₄ , and R ₃ and R ₅ are bound to each other and fused with a heterocycle containing tellurium include the following.

R ₃ is preferably an optionally substituted aryl group or an alkyl group, an alkenyl group, an alkynyl group, R ₄ is preferably an optionally substituted aliphatic hydrocarbon, and R ₅ is preferably substituted. Is an optionally substituted aliphatic hydrocarbon, and R ₆ is preferably an optionally substituted aliphatic hydrocarbon.

The description of the above general formulas [I] to [IV] is as follows.
The same applies to each general formula described later.

It is in the form of a tellurium azolium ring at one resonance extremity, and at the second resonance extremity it is in the form of a tellurium azollidene, since the basic nucleus of the sensitizing dye according to the invention, such as the tellurium azolium ring, preferably forms part of the chromophore. Rearrange to a ring.

In a particularly preferred form, at least one of the sensitizing dyes of the present invention is a polymethine dye containing a tellurium azolium ring. Such dyes include cyanine and merocyanine dyes. Dyes are most commonly present,
It can contain two nuclei linked via a methine bond. These dyes are sometimes referred to as simple cyanines or merocyanines to distinguish them from those containing 3 or more nuclei called complex cyanine or merocyanine dyes. In addition to the above, these polymethine dyes for use in the photographic elements of the present invention can take the form of hemicyanine, styryl, neomycin, azacyanine, and allopralcyanine dyes. Such dyes are direct analogues of conventional dyes in these classes, the difference being that the presence of a divalent tellurium atom in at least one chalcogen azolium nucleus instead of another divalent chalcogen. is there.

The general formula [II] can form a merocyanine dye represented by the following general formula [V] by R ₅ .

General formula [V] In the formula, R ₁ , R ₂ and R ₃ have the same meaning as in the general formula [II], and the same ones are exemplified.

Further, R ₃ may cooperate with L ₁ to complete a 5- or 6-membered fused heterocycle.

E represents an acidic nucleus, L ₁ and L ₂ each represent an optionally substituted methine bond, and n represents 0, 1 or 2.

Examples of the fused heterocycle formed by R ₃ and L ₁ in combination include the following.

The acidic nucleus E represented by E in the general formula [V] and the following formulas can take the form of any ordinary acidic merocyanine nucleus.

E is an acyclic group In the formula, R ^a , R ^b , R ^c and R ^d are each a monovalent substituent, and are alkyl groups (for example, methyl group, ethyl group, octyl group, dodecyl group, sec-octyl group, etc.), aryl groups (for example, and a heterocyclic group (for example, a benzofuryl group).

When E is a cyclic group, Etc. can be selected.

Preferred compounds of the general formula [V] are represented by the general formula [VI] [VI ']
It is shown in [VI ″].

General formula [VI] R ₁ , R ₂ , R ₃ , n and E have the same meaning as in the general formula [V].

General formula [VI '] R ₁ , R ₂ , R ₃ and E have the same meanings as in the general formula [V], and R ⁽¹⁾ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aralkyl group, and a cyano group. Or, together with R _3, it represents an atomic group forming a 5- or 6-membered ring. R ⁽²⁾ and R ⁽³⁾ represent a hydrogen atom and an alkyl group, respectively.

General formula [[VI ″] R ₁ , R ₂ , R ₃ and E have the same meanings as in the general formula [V], and R ⁽⁴⁾ is a hydrogen atom, alkyl (for example, each group such as methyl and ethyl),
It represents an alicoxy (eg, each group of methoxy, ethoxy, etc.), aryloxy (eg, phenoxy group), aryl (eg, phenyl group), aralkyl (eg, benzyl group) and cyano group.

R ⁽⁴⁾ and R ₃ may together form a 5- or 6-membered ring.

R ⁽⁵⁾ , R ⁽⁶⁾ and R ⁽⁷⁾ are a hydrogen atom, alkyl (for example, groups such as methyl, ethyl and propyl), aralkyl (for example, groups such as benzine and phenethyl), aryl (for example, phenyl group). , Heterocycle (for example, groups such as thienyl and furyl), alkyloxy (for example, groups such as methoxy and ethoxy), aryloxy (for example, phenoxy group),
It represents a cyano group, amino (for example, each group of dimethylamino, anilino, etc.), alkyloxy, alkylthio (for example, methylthio group), arylthio (for example, phenylthio group), and an acidic nucleus. However, R ⁽⁴⁾ , R ⁽⁵⁾ , R ⁽⁶⁾ , and R ⁽⁷⁾ are not all hydrogen atoms.

k is 0 or 1.

k is 0 or 1.

The general formula [IV] can form a cyanine dye represented by the general formula [VIII] by R ₆ .

General formula [VIII] In the formula, R ₁ , R ₂ and R ₇ have the same meaning as in the general formula [IV]. R ₇ is preferably a quaternized substituent, R ₈ represents a quaternized substituent, and R ₇ may cooperate with L ₁ to complete a 5-6 membered fused heterocycle.

In a particularly preferred form, the compounds according to the invention are cyanine dyes. These dyes can be symmetric and thus contain at least two identical tellurium azolium nuclei or can be asymmetric, in which case the nuclei can each be different tellurium azolium nuclei, or at least one It can be a combination of one tellurium azolium nucleus and one or more conventional basic heterocyclic cyanine dye nuclei. The nuclei are attached via methine bonds, which can consist of a single methine group or a chain of methine groups. As mentioned above, the tellurium azolium ring can generate an absorption shift due to the bathochromic effect, so that a smaller number of methine groups can be used to absorb longer wavelength electromagnetic radiation. However, methine linkages of up to 13 or more consecutive methine groups can be incorporated into the dye, if desired.

L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each independently represent a methine group which may be substituted, n is 0, 1 or 2, m is 0 or 1 and Q is a basic azolinidene or azinilidene. The group of atoms that completes the nucleus of the heterocycle, Y ^- p, has the same meaning as in formula [IV].

Further, the substituents of L _{1 to} L ₅ may combine to form a ring.

The fused heterocycle formed by combining R ₇ with R ₂ or L ₁ includes
For example:

In the general formula [VIII] and each of the following formulas, R ₇ and R ₈ in a certain optimum form are substituted hydrocarbons containing 1 to 6 carbon atoms (for example, alkyl or aryl groups)
Is.

Representative examples of the substituent include sulfo, sulfato, carboxy, hydroxycarbamoyl, cyano, imino succinate, trimethylsilyl, alkoxy, and sulfo-substituted alkoxy.

Specifically, sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfophenyl, sulfatomethyl, sulfatoethyl, sulfatopropyl, sulfatobutyl, sulfatophenyl, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyphenyl , Hydroxyethyl, hydroxypropyl, carbamoylmethyl, carbamoylethyl, carbamoylpropyl, carbamoylbutyl, carbamoylphenyl, cyanoethyl, cyanopropyl, iminoethyl succinate, iminopropyl succinate, trimethylsilylethyl, methoxyethyl, methoxypropyl, sulfoethoxyethyl, etc. Each group is representative.

As is clear from the above formula, this cyanine dye is a kind of quaternized tellurium azolium salt of the formula [IV] although the structure of the substituent R _{6 at} the 2-position is complicated. The tellurium azolium nucleus has already been mentioned above. This nucleus could be characterized as a tellurium azolium nucleus or a tellurium azolinylidene nucleus, but for convenience the former notation of the nucleus is used, but for consistency the rest of the nuclei are called azolinylidene or azinilidene nuclei.

In general, any azolinidene or azinilidene nucleus satisfying formula [VIII] can be used in combination with the tellurium azolium nucleus. It is especially conceivable that Q can be selected from the following: benzotelluazolinylidene, naphthotelluazolinylidene, 2- or 4-
Pyridylidene, imidazopyridylidene, 2- or 4-
Quinolinylidene, 1- or 3-isoquinolinylidene,
Benzoquinolinylidene, thiazoloquinolinylidene, imidazoquinolinylidene, 3H-indolylidene, 1H or 3H-benzindolylidene, oxazolinylidene,
Oxazolidinylidene, Benzoxazolinylidene, Naphthoxazolinylidene, Oxadiazolinylidene, Thiazolidinylidene, Phenanthrothiazolinylidene, Acenaphthothiazolinylidene, Thiazolinilidene, Benzothiazolinylidene, Naphthothia Zolinylidene, tetrahydrobenzothiazolinylidene, dihydronaphthothiazolinylidene, thiadioxazolinylidene, selenium azolidinylidene, selenium azolinylidene, benzoselenium azolinidene, naphthoselenazolinylidene, selenium asiazolid Niridene, pyrazolidene, imidazolidinylidene,
Nuclei of imidazolidinylidene, benzimidazolinylidene, naphthoimidazolinylidene, diazolinilidene, tetrazolinilidene, and imidazoquinoxalinilidene.
This nucleus can be substituted in any conventional manner consistent with formula [VIII]. R ₈ can be, for example, any conventional quaternizing group, and can be selected from any of the various forms of R ₇ described above.

In a preferred form, the cyanine dye of the present invention satisfying the general formula [VIII] is represented by the following general formula [IX].

General formula [IX] In the formula, R ₁ , R ₂ , n, m, Y ⁻ and p are represented by the general formula [VII
Synonymous with I].

R ₇ and R ₈ are independently optionally substituted alkyl and aryl groups, and Q is a group of atoms that completes the basic azolinidene or aziridinene nucleus, which may include a benzo or naphtho ring moiety. .

In another preferred form, the cyanine dye of the present invention satisfying the general formula [VIII] is represented by the following general formulas [X] and [XI].

General formula [X] General formula (XI) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , Q, Y ⁻ , M and P have the same meanings as in the general formula [VIII].

R ^{(8) to} R ⁽¹⁰⁾ are each a hydrogen atom, alkyl (for example, each group such as methyl, ethyl, and propyl), aralkyl (for example, each group such as benzine and phenethyl), aryl (for example, phenyl group), hetero group (for example, (Cenyl, furyl, etc.), alkyloxy (eg, methoxy, ethoxy, etc.), allooloxy (eg, phenoxy group), cyano group, amino (eg, dimethylamino, anilino, etc.), alkyloxy, alkylthio ( For example, methylthio group), arylthio (for example, phenylthio group) groups and acidic nuclei.

n'represents 0 or 1, and n "represents 1 or 2.
When n ′ + n ″ ≦ 2, all of R ^{(8) to} R ⁽¹⁰⁾ and R ₁₀ and R ₁₁ are not hydrogen atoms.

R ₁₀ and R ₁₁ are a hydrogen atom, alkyl (for example, groups such as methyl and ethyl), alkoxy (for example, groups such as methoxy and ethoxy), aryloxy (for example, phenoxy group), aryl (for example, phenyl group), aralkyl ( For example, a benzyl group) and a cyano group.

R ₁₀ and R ₁₁ may together form a 5- or 6-membered ring. R ₁₂
Represents a hydrogen atom or an alkyl group (eg, methyl group), and R ₁₃ represents a hydrogen atom or an alkyl group (eg, methyl group).

In another preferred form, the cyanine dye used in the photographic element of the present invention is represented by the following general formula [XIII] besides the general formula [VIII].

General formula (XIII) R ₁ and R ₂ have the same meaning as in the general formula [IV], and R ₇ , R ₈ and L ₁ ~
L ₅ , Y ⁻ , p, m and n have the same meanings as in the general formula [VIII].

The ring which R ₁ may form with R ₂ or L ₁ is represented by the general formula [VII
The ones mentioned in [I] are mentioned.

Except for the form of the azolinidene or azinilidene ring completed by Q, the various components of formula [XIII] can be selected as described above for formula [VIII].

In the most optimal form, Q of formula [XIII] is selected from the pyrrolidene, indolylidene, carboazolylidene, benzindolilidene, pyrazolylidene, indazolylidene, and pyrrolopyridinylidene nuclei.

Again, ordinary ring substituents consistent with formula [XIII] are contemplated.

R ₇ and R ₈ optimally represent substituted alkyl and aryl substituents, respectively, as described above.

The tellurium-containing sensitizing dyes of the present invention can be used as spectral sensitizers in both surface and internal latent image forming emulsions. The latter emulsion offers the advantage of enabling a more convenient dye concentration desensitization relationship, ie more dye is needed to reach the desensitization level. When the tellurium-containing sensitizing dyes of this invention are used in combination with surface fog silver halide emulsions used in directly forming positive images, their substituents can be selected to enhance electron capture. As mentioned above, the dyes according to the invention which absorb in the UV, blue, green, red and infrared are conceivable. However, dyes that have absorption maxima at wavelengths of 500 nm and longer are particularly advantageous.

The sensitizing dye according to the present invention is used in a silver halide emulsion in an amount of 1 × 10 ^-8 mol to 5 mol per mol of silver halide.
× 10 ^-3 mol, preferably 1 × 10 ^-6 mol to 2.5 × 10 ^-3 mol, particularly preferably 5 × 10
It is used in the proportion of ^-6 mol to 1 x 10 ^-3 mol.

When the above sensitizing dye is added to the silver halide emulsion, the dye may be directly dispersed in the above emulsion, or it may be dissolved in a suitable solvent such as a single solvent or a mixed solvent such as methanol, ethanol and dimethylformamide. It may be added to the emulsion afterwards. The silver halide emulsion may be added at any time during the process for producing the light-sensitive material, but it is generally preferable to add it to the silver halide emulsion during the second ripening or immediately after the second ripening.

NO.8 NO.9 NO.10 NO.11 NO.12 NO.13 NO.14 NO.15 NO.16 NO.17 NO.18 NO.19 NO.20 NO.21 NO.22 NO.23 NO.24 (VII-13) NO.25 NO.26 NO.27 NO.28 NO.29 NO.30 NO.31 NO.32 NO.33 NO.34 NO.35 NO.36 NO.37 NO.38 NO.39 NO.40 NO.41 NO.42 NO.43 NO.44 NO.45 NO.46 NO.47 NO.48 NO.49 NO.50 NO.51 NO.52 NO.53 NO.54 NO.55 NO.56 NO.57 NO.58 NO.59 NO.60 NO.61 NO.62 NO.63 NO.64 NO.65 NO.66 NO.67 NO.68 NO.69 NO.70 NO.71 NO.72 NO.73 NO.74 NO.75 NO.76 NO.77 NO.78 NO.79 NO.80 NO.81 NO.82 NO.83 NO.84 NO.85 NO.86 NO.87 Compound 1 NO.88 NO.89 NO.90 The sensitizing dye of the present invention can be prepared by referring to the following patents and documents.

British Patent Nos. 625245, 654690, 841119, French Patent 757767, U.S. Patent No. 1846302, 2345094
No. 2369646, No. 2387883, No. 2385815, No. 24783
66, 2610121, 2238231, 2213995, 250
3776, 2734900, JP-A-47-9678, 60
-78445, Journal of the American Chemicals-Society, Vol. 67, 1875-1889 (1945),
F. M. Hama, Cyanine Soybean And Relayed Compounds (published by Inter Science Publishers in 1964), Vol. 68, 191-194 (1948) Next, specific synthetic examples are shown above. Other compounds represented by the general formula can also be synthesized according to the following synthetic method.

[Synthesis Example 1] 4- [2- (5,6-dihydro-2H-4H-tellurazolo [5,4,3-i, j]]
Quinoline 2-ylidene) ethylidene] -5-oxo-2-thioxo-1,3-thiazolidin-1-ylacetic acid (exemplary compound NO18) 2-acetanilidovinyl-5,6-dihydro-4H-telrazolo [5,4, 4.6 g of 3-i, j, quinolinium chloro salt and 1.9 g of 3-carboxymethyl rhodamine are dissolved in 50 m of absolute ethanol, 2 g of triethylamine is added, and the mixture is heated under reflux for 15 minutes.
The reaction solution is allowed to cool, further cooled sufficiently in an ice bath for crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by repeating recrystallization from methanol. Yield 1.4g Absorption maximum wavelength 550nm in methanol solution [Synthesis example 2] 3- [2- (3- (5,6-dihydro-2H, 4H -Terrazolo 〔5,4,3-i,
j] quinoline-2-ylidene) -1-propenyl) -1-naphtho [1,2-d] thiazolio] propanesulfonic acid inner salt (exemplified compound NO24) 5,6-dihydro-2-methyl-4H-telrazolo 3.2 g of [5,4,3-i, j] quinolinium chloro salt is suspended in 30 m of acetic anhydride, 3.8 g of diphenylformamidine is added, and the mixture is heated under reflux for 10 minutes. After cooling, isopropyl ether is added for dilution, and the precipitate is collected by filtration, washed with ethyl acetate and dried.

Yield 3.3 g 2.3 g of crude product was dissolved in 20 m of m-cresol to give 3- (2-methyl
1-naphtho [1,2-d] thiazolio) propanesulfonic acid inner salt 1,6 g and triethylamine 2.0 g were added for 20 minutes 11
Heat and stir at 0 ° C.

After cooling, add isopropyl ether to dilute and discard the supernatant. Acetone is added and the mixture is stirred for crystallization, and the precipitate is collected by filtration and washed with ethanol.

The crude product is purified by repeating recrystallization from chloroform and methanol (1: 1).

Yield 0.56 g, melting point 300 ° C., absorption maximum wavelength in methanol solution 607 nm [Synthesis example 3] 2- [5-2- (3-methyl-4-phenyl-2 (3H) telrazolidene)
Ethylidene)] 4-oxo-2-thioxo-1,3-4thiazolidin-3-yl) ethanesulfonic acid (exemplary compound NO28) 2-acetamidovinyl-3-methyl-4-phenylterrazolium trifluoromethanesulfonate 2.9 g and 3-β-sulfoethylrhodamine 1.2 g are dissolved in absolute ethanol 30 m, triethylamine 2 g is added, and the mixture is heated under reflux for 15 minutes. The reaction solution is allowed to cool, further cooled sufficiently in an ice bath for crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by repeating recrystallization from methanol Yield 0.81 g Absorption maximum wavelength in methanol solution 546 nm [Synthesis example 4] 2- (5-chloro-2- (3- (3-methyl-4) -Phenyl-2 (3H) telrazolidene) -1-propenylidene) -3-benzoxazolio) ethanesulfonic acid inner salt (Exemplified compound NO33) 2-Methyl-4-phenyltetrazole 13.5 g was dissolved in dichloromethane 80 m to give methyltrifluoride. Add 9.0 g of methanesulfonate and seal tightly, and leave at room temperature for 1 week.

The precipitated crystals are collected by filtration and then suspended in 120 m of acetic anhydride.

Add 19.6 g of diphenylformamidine and heat to reflux for 10 minutes. After cooling, isopropyl ether is added for dilution, the precipitate is collected by filtration, washed with ethyl acetate and dried.

Yield 15.1 g 2.9 g of the crude product was dissolved in 20 m of m-cresol, and 1.4 g of 2-(-5-chloro-2-methyl-3-benzoxazolio) ethanesulfonic acid inner salt and 1 g of triethylamine were added and the mixture was added for 15 minutes. Heat and stir at 110 ° C.

After cooling, add isopropyl ether to dilute and discard the supernatant. Acetone is added and the mixture is stirred for crystallization, and the precipitate is collected by filtration and washed with ethanol.

The product was recrystallized from a chloroform-methanol (1: 2) mixed solvent for purification.

Yield 0.54 g Absorption maximum wavelength 601 nm in methanol solution [Synthesis Example 5] Bis-3,8-3 ', 10-trimethylene telluracarbocyanine iodo salt (exemplified compound NO43) 2,3-trimethylene benzoterrazolium iodide 4 g of salt and 1.5 g of ethyl orthoformic acid ester were added to 30 m of pyridine.

Triethylamine was added, and the mixture was heated under reflux for 15 minutes and allowed to cool and crystallize.

The precipitate was collected by filtration and washed with ethanol to obtain 1.0 g of a crude product.

The product was purified by repeating recrystallization from methanol.

Yield: 0.6 g, melting point: 300 ° C or higher, absorption maximum wavelength in methanol: 627 nm [Synthesis example 6] 5- [2- (3-ethyl-6-methyl-2 (3H) benzothiazolidene)
Ethylidene] -3-phenyl-2-thio-terrazolidine-2,4
-Dione (exemplified compound NO48) 2- (2-acetanilidovinyl) -3-ethyl-6-methylbenzothiazolium iodo salt (4.5 g) and 3-phenyl-2-thio-terrazolidine-2,4-dione (2 g) Dissolve in 30m of ethanol. Add 2 g of triethylamine and heat to reflux for 10 minutes, then cool.

The precipitated crude product is filtered and washed with ethanol.

Recrystallization from methanol gives orange-red crystals.

Yield 1.2 g Absorption maximum wavelength 531 nm in methanol solution [Synthesis example 7] 4- [5-hydroxy-3-methyl-4- (3- (4-oxo-3-phenyl-2-thioxoterrazolidinidene)) -1-propenyl)
Pyrazolyl] benzenesulfonic acid potassium salt (Exemplified compound NO53) 3-phenyl-2-thio-terrazolidine-2,4-dione 1.0 g and 4- (3-acetanilidoalilidene) -3-methyl-1- (P-sulfo 2.1 g of phenyl) -5-pyrazolone is dissolved in 10 m of dimethylformamide, 1 g of triethylamine is added, and the mixture is stirred. After 4 hours, add 50 m of water, dilute and acidify with diluted hydrochloric acid.

The precipitate is collected by filtration and washed with methanol.

The crude product is dissolved in a methanol solution containing 1 or 2 equivalents of triethylamine, and 2 equivalents of potassium acetate is added for crystallization for purification.

Yield 1.3 g [Synthesis Example 8] 2- (5- (2- (3-methyl-2 (3H) thieno [2,3-d] telrazolidene) ethylidene) -4-oxo-2-thioxo-1,3- Thiazolidin-3-yl) ethanesulfonic acid (Exemplary compound NO56) 2-acetanilidovinyl-3-methyl-thieno [2,3-d] terrazolium trifluoromethanesulfonate 2.6 g and
1.2 g of 3-β-sulfoethyl rhodanine in 50 m of absolute ethanol
, 2 g of triethylamine is added, and the mixture is heated under reflux for 15 minutes. The reaction solution is allowed to cool, further cooled sufficiently in an ice bath for crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol. Yield 0.85g Absorption maximum wavelength in methanol solution 562nm [Synthesis example 9] 3,3 'dimethyl-thieno [2,3-d] telluracarbocyanine trifluoride. Rhomethanesulfonic acid (Exemplary compound NO61) 12.5 g of 2-methyl-thieno [2,3-d] telrazole was dissolved in 100 m of dichloromethane, 9.0 g of methyltrifluoromethanesulfonate was added, and the container was sealed and left at room temperature for 1 week.

The precipitated crystals are collected by filtration and then suspended in 120 m of acetic anhydride.

Add 19.6 g of diphenylformamidine and heat to reflux for 10 minutes. After cooling, isopropyl ether is added and diluted. The precipitate is collected by filtration, washed with ethyl acetate and dried.

Yield 14.8 g 2.6 g of crude product was dissolved in 20 m of m-cresol and 2,3-dimethyl-thieno [2,3-d] telrazolium trifluoromethanesulfonate 2.0 g and triethylamine 2.
Add 0 g and heat and stir for 15 minutes at 110 ° C.

After cooling, add isopropyl ether and dilute to discard the supernatant. Addition of acetone [Synthesis example 10] 2- (5- (2- (5-fluoro-3-methyl-2 (3H) benzotelrazolidene) ethylidene) 4-oxo-2-thioxo-1,3-thiazolidine 3-yl) ethanesulfonic acid (Exemplified compound NO62) 2-acetanilidovinyl-5-fluoro-3-methylbenzoterrazolium trifluoromethanesulfonate 2.8 g and
0.95 g of 3-carboxymethyl rhodamine to absolute ethanol 3
Dissolve in 0 m, add 2 g of triethylamine and heat to reflux for 20 minutes.

The reaction solution is allowed to cool and then sufficiently cooled in an ice-water bath to crystallize and the precipitated crystal is collected by filtration.

The crude product is purified by repeating recrystallization from methanol.

Yield 0.6 g Absorption maximum wavelength 547 nm in methanol solution [Synthesis Example 11] Anhydro 3- [2- (3- (5-fluoro-3-methyl-2 (3H) benzotelrazolidene] -1-propenyl) -5 -Methoxy-3-benzoselenazolio] propanesulfonic acid inner salt (Exemplified compound NO69) 13.1 g of 5-fluoro-2-methylbenzotellurazole was dissolved in 100 m of dichloromethane, 9.0 g of methyltrifluoromethanesulfonate was added, and the mixture was sealed at room temperature. Leave for 2 weeks.

The precipitated crystals are collected by filtration and then suspended in 100 m of acetic anhydride.

Add 19.6 g of diphenylformamidine and heat to reflux for 10 minutes. After cooling, isopropyl ether is added and diluted. The precipitate is collected by filtration, washed with ethyl acetate and dried.

Yield 8.3 g 2.8 g of crude product was dissolved in 20 m of m-cresol, and 1.7 g of 3- (5-methoxy-2-methyl-3-benzoselenazolio] propanesulfonic acid inner salt and 2 g of triethylamine were added and 110 minutes for 15 minutes. Heat and stir at ℃.

After cooling, isopropyl ether was added to dilute, the supernatant was discarded, and acetone was added. Exemplified compound NO72) 2,3,5-Trimethylbenzotelrazolium-trifluoromethanesulfonate 4.2 g and 3- (5-chloro-2- (2methylthio-1-propenyl) -3benzothiazolio) propanesulfonic acid Intramolecular 3.8 g of salt is added to 30 m of pyridine, 2 g of triethylamine is added, and the mixture is stirred at 40 ° C. The dye that has precipitated is collected by filtration and washed with methanol.

Recrystallization and purification from a mixed solution of 2,2,3,3-tetrafluoropropanol and methanol gave 0.74 g of the desired product.

Absorption maximum wavelength 595 nm in methanol solution [Synthesis example 13] 5- (4- (3-ethyl-5-methyl-2 (3H) telrazolidene) -2-methyl-2-butenylidene) -4-oxo-2-thioxo -1,3-thiazolidin-3-ylacetic acid (Exemplified compound NO76) 2- (3-acetanilidemethylene-2-butenyl) -3-ethyl-
5.9 g of 5-methylbenzotelrazolium iodo salt and 1.9 g of 3-carboxymethylrhodamine are added to 80 m of ethanol. Triethylamine (3 g) was added, and the mixture was heated under reflux for 30 minutes and cooled with ice to acidify acetic acid for precipitation.

The crude product is dissolved in methanol containing triethylamine by heating, allowing to cool, and acidifying with acetic acid for crystallization.

It was collected by filtration and washed with ethanol to obtain 1.2 g of the desired product.

Absorption maximum wavelength 608 nm in methanol solution The silver halide emulsion used in the photographic element of the present invention comprises
As the silver halide, any of those used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride can be used.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by adding halide ions and silver ions successively and simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained.

During the production of the silver halide emulsion, the grain size, grain shape, grain size distribution and grain growth rate of the silver halide grains can be controlled by using a silver halide solvent, if necessary.

The silver halide grains include cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (complex salt containing) and iron salt (in the process of forming and / or growing the grain). By adding a metal ion using at least one selected from the group consisting of (complex salt containing), these metal elements can be contained inside the particles and / or on the surface of the particles, and by placing in a suitable reducing atmosphere, Reduction sensitization nuclei can be provided inside the grain and / or on the surface of the grain.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. The removal of the salts can be performed according to the method described in Research Disclosure 17643.

The silver halide grains used in the silver halide emulsion may be those having a uniform silver halide composition distribution within the grain, or may be core / shell grains having a different silver halide composition between the inside and the surface area of the grain. .

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

The silver halide grains used in the silver halide emulsion may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. You may have one. In these particles, {100}
Any ratio of the plane to the {111} plane can be used.
Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (the grain size represents the diameter of a circle having 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. An emulsion having a wide grain size distribution may be used, or an emulsion having a narrow grain size distribution may be used alone or in combination of several kinds.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, a sulfur sensitization method, a selenium sensitization method, a noble metal sensitization method using a gold or other noble metal compound can be used alone or in combination.

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

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
During coating, during chemical ripening for the purpose of preventing fogging during storage or during photographic processing, or for maintaining stable photographic performance, at the end of chemical ripening, and / or after the end of chemical ripening, until the silver halide emulsion is coated. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsion
As for, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other macromolecules, other proteins, sugar derivatives, cellulose derivatives,
A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a single or copolymer can also be used.

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

The photographic emulsion layer of a photographic element using the silver halide emulsion of the present invention, and other hydrophilic colloid layers, include one or more hardeners that crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in an amount capable of hardening the photosensitive material to the extent that it is not necessary to add the hardener to the processing liquid.
It is also possible to add a hardening agent to the processing liquid.

A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of a photographic element using the silver halide emulsion of the present invention for the purpose of increasing flexibility.

A photographic emulsion layer or other hydrophilic colloid layer of a photographic element using the silver halide emulsion of the present invention contains a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. Can be made.

In the color development processing, the emulsion layer of the photographic element of the present invention undergoes a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative or aminophenol derivative) to form a dye. Dye forming couplers are used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each 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, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Further, these dye-forming couplers need only reduce 4 molecules of silver ions in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ions even if they are 4 equivalents. Either of two equivalence may be used. The dye-forming coupler includes a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener fog agent, an anti-fogging agent, a chemical sensitizer, by coupling with an oxidized product of a developing agent. Compounds that release photographically useful fragments, such as spectral sensitizers, and desensitizers can be included. A colored coupler which has a color correction effect on these dye-forming couplers, or a development inhibitor which is released upon development to improve image sharpness and image graininess.
An R coupler may be used in combination. At this time, it is preferable that the DIR coupler is of the same type as that of the dye formed from the dye-forming coupler used in the same emulsion layer, if the color turbidity is not noticeable. It may form a dye. Instead of the DIR coupler, a DIR compound which, in combination with or in combination with the coupler, reacts with an oxidized product of a developing agent to form a colorless compound and simultaneously releases a development inhibitor may be used.

A colorless coupler capable of undergoing a coupling reaction with an oxidized product of an aromatic primary amine developer but not forming a dye may be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR couplers, DIRs that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, antifoggants, UV absorbers,
Among the fluorescent whitening agents, various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method can be used for the hydrophobic compound, which is the chemical structure of the hydrophobic compound such as coupler. It can be appropriately selected according to the above. The oil-in-water emulsification dispersion method can be a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point of about 150 ° C. or higher and a high boiling point organic solvent, and / or an aqueous solution. With a water-soluble organic solvent, and using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, a stirrer, homogenizer, colloid mill, flowgit mixer,
It may be added to the target hydrophilic colloid layer after emulsifying and dispersing using a dispersing means such as an ultrasonic device. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

Dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, and brightening agents having an acid group such as carboxylic acid and sulfonic acid, an alkaline aqueous solution. It can also be introduced as a hydrophilic colloid.

Dissolving a solvent in which a hydrophobic compound is used alone or in combination with a high boiling solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic surfactants can be used.

Between the emulsion layers (the same color-sensitive layers and / or different color-sensitive layers) of the photographic element of the present invention, the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or deterioration of sharpness. Alternatively, a color antifoggant can be used to prevent the graininess from being conspicuous.

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

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

A hydrophilic colloid layer such as a protective layer and an intermediate layer of the photographic element of the present invention contains an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of a light-sensitive material due to friction and the like and to prevent deterioration of an image by UV light. May be included.

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

In the photographic element of the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a mordant such as a cationic polymer.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the photographic element of the present invention, a compound which changes the developability such as a development accelerator and a development retarder and a bleaching accelerator can be added. A compound that can be preferably used as a development accelerator is Research Disclosure 17463.
No. XX43, Item XXI to No. D, and the development retarder is the compound, No. 17643, Item XXI, Item E. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The photographic emulsion layer of the photographic element of the present invention comprises a polyalkylene oxide or a derivative thereof such as an ether, an ester or an amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound, for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may include a urethane derivative, a urea derivative, an imidazole derivative, and the like.

Fluorescent brighteners can be used in the photographic elements of the present invention for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous.

The photographic elements of this invention can be provided with auxiliary layers such as filter layers, antihalation layers, and / or antiirradiation layers. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained.

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 gloss of the light-sensitive material, improving writing properties, and preventing sticking of the light-sensitive materials to each other.

A lubricant can be added to reduce the sliding friction of the light-sensitive material.

An antistatic agent intended for antistatic purposes can be added to the photographic elements of the present invention. 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 emulsion layer and / or
It may be used in a protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated with respect to the support.

The photographic emulsion layer and / or the other hydrophilic colloid layer of the photographic element of the present invention may have an improved coatability, antistatic property, improved slipperiness,
Various surfactants can be used for the purpose of emulsion dispersion, prevention of adhesion, improvement of photographic characteristics (acceleration of development, hardening, sensitization, etc.).

The supports used in the photographic elements of the present invention include cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride,
Films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate, polycarbonate, polyamide,
These films include flexible supports provided with a reflective layer, glass, metal, pottery, and the like.

The photographic element of the present invention is, if necessary, subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, and then directly or on the support surface adhesiveness, antistatic property, dimensional stability, abrasion resistance, It may be applied via one or more subbing layers to improve hardness, antihalation properties, friction properties, and / or other properties.

Thickeners may be used in coating the photographic elements of the invention to improve coatability. Also, like hardeners,
It is preferable to use a static mixer or the like to mix immediately before coating for those that cause gelation before coating because of its rapid reactivity when added to the coating solution in advance.

In making the photographic elements of this invention, the silver halide emulsion and other protective colloid layers are coated by the method described in Research Disclosure 17463 XV A, and dried by the method B. can do.

The photographic elements of this invention can be exposed using electromagnetic waves in the spectral region of which the emulsion layers of which they are sensitive. As the light source, natural light (sunlight), tungsten 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, χ rays, γ rays, α rays, etc. Any of the known light sources, such as, can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, exposure of 100 nanoseconds to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, exposure longer than 1 second is also possible. The exposure may be performed continuously or intermittently.

Any known method can be used for the development processing of 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 development process for forming a color image, depending on the purpose. Steps are followed by white exposure or by processing in a bath containing a fog agent for color development. [Alternatively, silver dye bleaching may be used in which a dye is contained in the light-sensitive material, a black-and-white development processing step is performed after exposure to form a silver image, and this is used as a bleaching catalyst to bleach the dye.

Each processing step is usually carried out by immersing the light-sensitive material in the processing solution, but other methods, for example, a spray method of supplying the processing solution in the form of a spray, a web for carrying out processing by contacting with a carrier impregnated with the processing solution A method, a method of performing viscous development processing, or the like may be used.

As the black and white development processing, for example, a development processing step, a fixing processing step, and a water washing processing step are performed. Further, the developing agent or its precursor may be incorporated in the light-sensitive material, and the developing treatment step may be carried out only with the alkaline solution. A development process using a lith developer as a developer may be performed.

As color development processing, a color development processing step, a bleaching processing step, a fixing processing step, a washing processing step if necessary, or a stabilization processing step accompanied by a washing processing is performed, but a processing step using a bleaching solution and fixing Instead of the treatment process using liquid,
A bleach-fixing treatment step can be carried out using a 1-bath bleach-fixing solution, or a mono-bath processing step using a 1-bath development bleach-fixing solution which can carry out color development, bleaching and fixing in a 1-bath is carried out. You can also

In combination with these processing steps, a total hardening processing step, a neutralization step thereof, a stop fixing processing step, a post-hardening processing step and the like may be performed. In these treatments, instead of the color development processing step, a color developing agent or its precursor may be contained in the material and the development processing may be performed by an activator solution, or an activator processing step may be performed instead of the monobath processing. It may be performed at the same time as the beta treatment and the bleaching and fixing treatments. A typical process is shown among these processes. (These treatments are, for example, either a washing treatment step or a stabilizing treatment step accompanied by a washing treatment step as the final step.) • Color development processing step-bleaching processing step-fixing processing step-Color development processing step -Bleaching and fixing process-Pre-hardening process-Neutralization process-Color development process-
Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplementary color development process-Stopping process-Bleaching process- Fixing process step ・ Mono bath processing step ・ Activator processing step-bleach fixing step-Activator processing step-bleaching step-fixing step Other than these processing, developed silver generated by color development is bleached again and then again. Processing may be carried out using a method of performing color development or a developing method for increasing the amount of dye formed, such as various types of force treatment (amplification) described in JP-A-58-154839.

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 the double jet method, physically ripened by a conventional method, desalted, and then chemically ripened by the total sensitizing method and the sulfur sensitizing method. % Silver iodobromide emulsion was obtained. The average diameter of silver halide grains contained in this emulsion was 0.6 μm. 1 kg of this emulsion contains 0.60 mol of silver halide and 880 g of gelatin binder. 4-hydroxy
Stabilization was performed by adding 20 m of a 1.0 wt% aqueous solution of -6-methyl-1,3,3a, 7-tetraguindene.

1 kg of this emulsion was weighed into a pot and heated to 40 ° C. to dissolve. Then, 20 m each of 0.5% methanol solutions of the sensitizing dye according to the present invention and the comparative sensitizing dye were added and mixed and stirred. To each of these emulsions, a small amount of α-resorcylic acid and diethylene glycol, a coating aid, and a hardener (15 mg / 1 g
Gelatin) was added to the finished emulsion and coated on a cellulose triacetate film base to a dry film thickness of 5μ. Then, as a normal drying method, the film heat transfer coefficient was 10 Kcal at a dry bulb temperature of 24 ° C and a wet bulb temperature of 18 ° C. / m ² hr Approx. 1 depending on the condition
Those that took time to dry, and as a rapid drying method, a dry-bulb temperature of 30 ℃, a wet-bulb temperature of 24 ℃, and a film heat transfer coefficient of 70Kcal / m ² hr ℃
It took about 5 minutes to prepare a dried product.
These samples were subjected to wedge exposure with green light, developed with a developer having the following composition at 20 ° C. for 3 minutes, stopped, fixed and washed with water and dried to obtain strips having black and white images. .

The density and fog of each developed sample were measured using an optical densitometer. The reference point of the optical density for which the sensitivity was determined was the point of fog +0.2.

Developer composition However, the relative sensitivity is 100% for the quick drying sample of test No. 1.
Is the value.

Comparative dye (D-1) Comparative Hardener (A-1) Comparative Hardener (A-2) As is clear from Table 1, the dry fog caused by the dye of the present invention is prevented by using the hardener of the present invention. Therefore, it has been revealed that in the combination of the present invention, a photographic element having high sensitivity can be achieved without causing fog in drying power even when subjected to rapid drying.

Example-2 A silver iodobromide emulsion containing 7 mol% of silver iodide was chemically ripened by a conventional method to obtain an emulsion having an average grain size of 1.0 μm, a silver salt of 0.60 mol / Kg emulsion and a gelatin of 70 g / Kg emulsion. It was 1 Kg of this emulsion was heated to 40 ° C. and 500 g of the following cyan coupler D emulsion was added. The emulsion of the coupler D is the coupler D
300 g of ethyl acetate and 100 m of dibutyl butarate in 100 g
Add and dissolve, add sodium dodecylbenzene sulfonate, and use a homogenizer to add 10% gelatin aqueous solution 1 kg.
The one obtained by emulsifying and dispersing therein was used. 0.5% each of the sensitizing dye according to the present invention and the comparative sensitizing dye are added to this emulsion.
A methanol solution (30 m) was added and mixed and stirred.

Furthermore, 20m of a 1.0% by weight aqueous solution of 4-hydroxy-6-methyl-1,3,3a, 7, -tetrazaindene is added to stabilize it, and further a coating aid and a hardener (15mg / 1g gelatin). Was added to the cellulose triacetate film base so that the coated silver amount would be 5 gr / m ² , and dried in the same manner as in Example 1 to obtain a sample. This film sample was subjected to optical wedge exposure using a sensitometer having a light source with a color temperature of 5400 ° K and a red filter attached to the light source. After exposure, the following formulation was developed and bleached, fixed and dried to produce a cyan dye. The density of the image was measured to measure sensitivity and fog. The reference point of the optical density for which the sensitivity was determined was the point of fog +0.20.

Coupler D Development recipe 1. Color development 3 minutes 15 seconds (38 ° C) 2. Bleach 6 minutes 30 seconds 3. Washing with water 3 minutes 15 seconds 4. Fixation 6 minutes 30 seconds 5. Washing with water 3 minutes 15 seconds 6. Stabilization 3 minutes 15 seconds The treatment liquid composition used in each step is as follows.

Color developer Bleach Fixer Stabilizer Comparative dye (D-2) Hardener for comparison (A-3) Hardener for comparison (A-4) However, the relative sensitivity is 100% for the quick drying sample of test No. 1.
Is the value.

As is clear from Table 2, even in a photographic element containing an emulsion of a coupler, rapid drying fog caused by the dye of the present invention can be prevented by selecting the hardener of the present invention. .

Example 3 Seven layers of the following constituent layers were simultaneously coated on a polyethylene-coated paper on a support 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 90 mol% of silver bromide) contains 400 g of gelatin per mol of silver halide and the following yellow coupler dissolved and dispersed in dieptyl phthalate. It is a layer containing 0.2 mol per mol of silver halide and coated so that the amount of silver is 400 mg / m ² .

Second layer ... Intermediate layer A gelatin layer containing 2,5-di-t-octylhydroquinone, which is a layer coated so as to have a coating gelatin of 1.5 g / m ² .

3rd layer: Green-sensitive emulsion layer A green-sensitive silver chlorobromide emulsion layer (containing 80 mol% of silver bromide) was prepared by dissolving 500 g of gelatin per mol of silver halide and the following magenta dispersed in diptylphthalate. The coupler is 0.2 mol per mol of silver halide, the 2,5-di-t-octylhydroquinone is 0.05 mol per mol of the magenta coupler, 1,4-
This is a layer containing di-octyloxy-2,5-di-t-amylbenzene in an amount of 0.3 mol per mol of the magenta coupler and coated so that the amount of silver was 500 mg / m ² .

4th layer ... Intermediate layer 2,5-di-t-octylhydroquinone dissolved and dispersed in diptylphthalate 30 mg / m ² and 2- (benzotriazol-2-yl) -4,6- as UV absorber This is a gelatin layer containing 0.7 mg / m ^{2 of} di-t-butylphenol, which was coated so that the coated gelatin was 1.5 g / m ² .

Fifth layer Red-sensitive emulsion layer A red-sensitive silver chlorobromide emulsion layer (silver bromide 80) was prepared by adding a predetermined amount of each of the sensitizing dye according to the invention and the comparative sensitizing dye shown in Table 3 to a methanol solution. (Mole% content) contains gelatin of 500 gr per mol of silver halide and the following cyan coupler dissolved and dispersed in dioctyl phthalate in an amount of 0.2 mol per mol of silver halide so that the silver amount becomes 500 mg / m ^2. Is the layer applied to. However, sensitizing dye is 4 mg / m ²
Was added.

6th layer ... Intermediate layer Gelatin layer coated gelatin containing 0.4 g / m ^{2 of} the above UV absorber dissolved and dispersed in diptyl phthalate is 1.5 g /
It is a layer applied to have a size of m ² .

Seventh layer ... Protective layer This is a gelatin layer coated so that the amount of gelatin is 1.5 g / m ² .

(Yellow coupler) (Magenta coupler) (Cyan coupler) The silver halide emulsion in each of the above light-sensitive layers is described in JP-B-46-7.
Preparation by the method described in Japanese Patent No. 772 and chemical sensitization with sodium theosulfate pentahydrate, respectively, and 4-hydroxy-6-methyl-1,3,3a, 7-tetra Zaindene was added, and further a hardener (20 mg / 1 g gelatin) and a coating aid were added.

Seven layers were simultaneously coated with a slide hopper type multilayer coating machine, and then dried in the same manner as in Example-1.

These samples were subjected to optical wedge exposure with a red filter attached to the light source using a sensitometer having a light source with a color temperature of 5400 ° K. After the exposure, the following formulation was developed, bleach-fixed and washed with water, and then dried, and the density of the color dye image was measured, and the sensitivity and fog were measured. The optical density standard for determining the sensitivity was set at 0.80.

The results obtained are shown in Table 3.

Paper treatment Standard treatment process (treatment temperature and treatment time) (1) Color development 38 ° C 3 minutes 30 seconds (2) Bleach fixing 33 ° C 1 minute 30 seconds (3) Washing treatment 25-30 ° C 3 minutes (4) Drying 75 ~ 80 ℃ About 2 minutes Processing solution composition (color development tank solution) (Bleaching and fixing tank liquid) However, the relative sensitivity is 100% for the quick drying sample of test No. 1.
Is the value.

However, HX-1 was prepared by reacting the hardener H-19 of the present invention with taurine at a ratio of 1: 1 (weight ratio), and dissolving them in a 1% aqueous phenylylcarbamoylated gelatin solution to give tetra (vinylsulfonylmethyl) methane. It was made to be 3% by weight.

Comparative dye (D-3) As is clear from Table 3, even in the multilayer color light-sensitive material, it has been clarified that the dry fog caused by the sensitizing dye of the present invention in rapid drying is prevented by selecting the hardener of the present invention. .

Example-4 Sensitizing dyes NO.7, NO.14, N shown in Table-1 of Example-1
Example-1 except that NO.74, NO.57, NO.49, and NO.21 were used instead of O.18 and NO.19, and the following D-4 was used instead of the comparative dye D-1. The same operation as above was performed, and the obtained results are shown in Table-4.

Comparative dye (D-4) However, the relative sensitivity is 100% for the quick drying sample of test No. 1.
Is the value.

As is clear from Table 4, the rapid drying fog caused by the sensitizing dye containing a tellurium atom is a high sensitivity which is an advantage of the sensitizing dye containing a tellurium atom by selecting the hardener of the present invention. Can be kept low while maintaining.

Example-5 NO.36 and NO.68 were used instead of the sensitizing dyes NO.1 and NO.39 shown in Table-2 of Example-2, and the following D- was used instead of the comparative dye D-2. The same operation as in Example-2 was carried out except that 5 was used, and the obtained results are shown in Table-5.

Comparative dye (D-5) However, the relative sensitivity is 100% for the quick drying sample of test No. 1.
Is the value.

As is clear from Table 5, the rapid drying fog caused by the sensitizing dye containing a tellurium atom is an advantage of the sensitizing dye containing a tellurium atom, which is an advantage of selecting a hardener of the present invention. Can be kept low while maintaining.

Example-6 NO.45 and NO.79 were used instead of the sensitizing dyes NO.10 and NO.40 shown in Table-3 of Example-3, and the following D- was used instead of the comparative dye D-3. The same operation as in Example-3 was carried out except that 6 was used, and the obtained results are shown in Table-6.

Comparative dye (D-6) However, the relative sensitivity is 100% for the quick drying sample of test No. 1.
Is the value.

As is apparent from Table-6, the rapid drying fog caused by the sensitizing dye containing a tellurium atom is a high sensitivity which is an advantage of the sensitizing dye containing a tellurium atom by selecting the hardener of the present invention. Can be kept low while maintaining.

Comparative Example A photothermographic material sample 101 of Example-1 described in JP-A-61-264334 was prepared. That is, a benzotriazole silver emulsion was prepared as follows. 28 g of gelatin and 13.2 g of benzotriazole were dissolved in 3000 m of water, and the solution was stirred at 40 ° C. A solution prepared by dissolving 17 g of silver nitrate in 100 m of water was added to this solution over 2 minutes.

The pH of this benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion with a yield of 400 g.

Also, a silver halide emulsion was prepared as follows. Well-mixed gelatin aqueous solution (20 ml of gelatin in 1000 m of water)
g and sodium chloride 3g, kept at 75 ℃)
A 600 m aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 600 m of water) were simultaneously added at a constant flow rate for 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μ was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-
Add 60 mg of 6-methyl-1,3,3a, 7-tetrazaindene to 60
Chemical sensitization was performed at ° C. The yield of emulsion was 600 g.

On the other hand, a gelatin dispersion of the dye-donor was made as follows. 5 g of cyan dye-providing substance (A), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, 10 g of tri-iso-nonyl phosphate
Was weighed, ethyl acetate (30 m) was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution and 100 g of a 10% solution of lime-processed gelatin were mixed by stirring and then dispersed by a homogenizer for 10 minutes at 10,000 rpm.

(A) In addition, a photosensitive coating material was prepared as follows.

a) Silver benzotriazole emulsion 10 g b) Photosensitive silver chlorobromide emulsion 15 g c) Dispersion of dye-donor substance 25 g d) 5% aqueous solution of the following compound 5 m e) 10% methanol solution of benzenesulfonamide
5m f) 4-methylsulfonylphenylsulfonyl guanidine acetate 10% aqueous solution 15mg g) 0.04% methanol solution of the following sensitizing dye 4.5m sensitizing dye The above a) to g) are mixed and a thickener (polystyrene-p-
Sodium sulfonate) and water were added to make 100 m. This solution was applied on a polyethylene terephthalate film having a thickness of 180 μm to a wet film thickness of 50 μm.

The following protective layer coating composition was prepared.

Protective layer coating composition h) 10% gelatin 400g i) 4-methylsulfonylphenylsulfonyl guanidine acetate (10%) aqueous solution 240m j) Hardener (4%) aqueous solution of the following structural formula 50m CH ₂ = CH-SO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH = CH ₂ was mixed, and a thickener and water were added to make 1000 m.

This coating composition was coated on the above-mentioned photosensitive coating material, further coated at a thickness of 30 μm, and dried to prepare a photosensitive material 101.

However, as for the drying after application, both a sample dried by the normal drying method and a sample dried by the rapid drying method were prepared in the same manner as in Example-1.

The sample dried by the normal drying method was designated as sample 101A, and the sample dried by the rapid drying method was designated as sample 101B. The samples 101A and 101B were subjected to the same exposure, heat development and transfer to a dye fixing material as described in the publication as follows.

That is, the sample prepared as described above was imagewise exposed at 2000 lux for 10 seconds using a tungsten bulb and a SC-50 filter.

Then, it was uniformly heated for 30 seconds on a heat block heated to 140 ° C.

On the other hand, a dye fixing material was prepared as follows. Poly (methyl acrylate-co-N, N, N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate to vinylbenzylammonium chloride is 1:
1) Dissolve 10 g in 200 m of water and use 10% lime-processed gelatin
Mix uniformly with 100 g. This mixed solution was placed on a paper support laminated with polyethylene in which titanium dioxide was dispersed,
A wet film thickness of 90 μm was applied uniformly. This sample was dried and used as a dye fixing material having a mordant layer. Next, after supplying 20 m of water per 1 m ² to the film surface side of the dye fixing material, the heat-treated samples 101A and 101B were superposed on the fixing material so that the film surfaces were in contact with each other.

After heating for 6 seconds on a heat block at 80 ° C., the dye fixing material was peeled off from the light-sensitive material, and a cyan image was obtained on the fixing material. This is a Macbeth reflective densitometer (RD
-519) was used to measure the concentration.

Table 7 shows the relative sensitivity values and fog values of the samples 101A and 101B thus obtained.

As is clear from Table 7, in the photothermographic material, the improvement effect on the prevention of rapid drying fog is small.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kiyoshi Yamashita Kiyoshi Yamashita No. 1 Sakura-cho, Hino-shi, Tokyo Inside Konishi Roku Photo Industry Co., Ltd. (56) Reference JP-A-61-264334 (JP, A)

Claims (1)

[Claims] 1. A support having at least one silver halide emulsion layer and a 5-membered heterocyclic nucleus having a nitrogen atom and a tellurium atom as ring-constituting atoms sandwiching a carbon atom as at least one basic nucleus. In a silver halide photographic element containing a dye, the photographic element is represented by the following general formula [I]
Alternatively, a silver halide photographic element characterized by being hardened with a hardener represented by [II] or a vinyl sulfone hardener. However, photographic elements which are photothermographic materials are excluded. General formula [I] [Wherein R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an -OM group (M is a monovalent metal atom), and a -NR'R "group (R 'and R" are each hydrogen. Atom, alkyl group, aryl group) or -NHCO
R represents a hydrogen atom (R is a hydrogen atom, an alkyl group, or an aryl group), and R ₂ is a group having the same meaning as R ₁ except the chlorine atom. ] General formula [II] [In the formula, R ₃ and R ₄ are each a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group or an —OM group (M is 1
(Valent metal atom). Q and Q'are each -O
A linking group selected from —, —S—, and —NH—, and L represents an alkylene group or an arylene group. l and m represent 0 or 1, respectively. ]