Fuji Photo Film Company, Limited

Masanao Hinata

Akira Sato

Haruo Takei

Akira Ogawa

Tadashi Ikeda

Atsuo Iwamoto

Yuji Mihara

Keisuke Shiba

Jun Hayashi

Masanaga Ohki

Keiichi Adachi

Tadao Shishido

Reiichi Ohi

Nobuaki Miyasaka

Hirotetu Kato

Kenji Takahashi

Seiiti Kubodera

Yasushi Oishi

Masao Takano

Junichi Matsuyama

Hartuo Takei

Mitsuo Iwamoto

Akiro Sato

A silver halide photographic emulsion selectively spectrally sensitized, particularly to red light, with a combination of at least one sensitizing dye represented by general formula (I): ##STR1## wherein Z.sup.1 and Z.sup.2 each represents the atoms necessary to form a benzothiazole nucleus or a benzoselenazole nucleus, R.sup.1 and R.sup.2 l each represents an alkyl group or a substituted alkyl group, wherein at least one of R.sup.1 or R.sup.2 should represent a sulfo group-containing substituted alkyl group, a carboxyalkyl group or a hydroxyalkyl group, R.sup.3 represents an alkyl group, X.sub.1 represents an acid anion, and m represents 1 or 2, wherein m equals 1 when the dye forms an intramolecular salt (betaine-like structure); at least one sensitizing dye represented by general formula (II): ##STR2## wherein Z.sup.3 represents a sulfur atom or a selenium atom, Z.sup.4 represents the atoms necessary to form a benzothiazole nucleus, a benzoselenazole nucleus, a naphtho[1,2-d]thiazole nucleus or a naphtho[1,2-d]selenazole nucleus, R.sup.4 and R.sup.5 each represents an alkyl group or a substituted alkyl group, wherein at least one of R.sup.4 or R.sup.5 should be a sulfo group-containing substituted alkyl group, a carboxyalkyl group or a hydroxyalkyl group, R.sup.6 represents an alkyl group, an aryl group, a furyl group or a thienyl group, X.sub.2 represents an acid anion, and n represents 1 or 2, wherein n equals 1 when the dye forms an intramolecular salt (betaine-like structure), and at least one benzimidazolothiacarbocyanine dye, which exhibits increased color reproducibility, high sensitivity and reduced residual coloration.

Silver halide photographic emulsion

A silver halide photographic emulsion spectrally sensitized with a sensitizing combination of at least one sensitizing dye represented by General formula (I), at least one sensitizing dye represented by General formula (II) and at least one sensitizing dye represented by General formula (III): ##STR1## wherein Z.sup.1 and Z.sup.2 each is the atoms necessary to form a benzothiazole nucleus or a benzoselenazole nucleus, R.sup.1 and R.sup.2 each is an alkyl group or a substituted alkyl group, wherein at least one of R.sup.1 and R.sup.2 is a substituted alkyl group having a sulfo group, R.sup.3 is an alkyl group, X.sub.1 is an acid anion and m is 1 or 2 and when the dye forms an intermolecular salt (betaine like structure), m is 1; ##STR2## wherein Z.sup.3 is a sulfur atom or a selenium atom, Z.sup.4 is the atoms necessary to form a benzothiazole nucleus, a benzoselenazole nucleus, a naphtho[1,2-d]thiazole nucleus or a naphtho[1,2-d]selenazole nucleus, R.sup.4 and R.sup.5 each is an alkyl group or a substituted alkyl group, wherein at least one of R.sup.4 and R.sup.5 is a substituted alkyl group having a sulfo group, R.sup.6 is an alkyl group, an aryl group, a furyl group or a thienyl group, X.sub.2 is an acid anion and n is 1 or 2, and n is 1 when the dye forms an intermolecular salt (betaine like structure); wherein Z.sup.5 is the atomic group necessary to complete a naphthothiazole nucleus, Z.sup.6 is the atomic group necessary to complete a benzimidazole nucleus, R.sup.7 and R.sup.8 each is an alkyl group or a substituted alkyl group, where at least one of R.sup.7 and R.sup.8 is a carboxyalkyl group or a substituted alkyl group having a sulfo group, X.sub.3 is an acid anion, and p is 1 or 2, and p is 1 when the dye forms an intermolecular salt.

Photographic silver halide emulsions

A method of spectrally sensitizing a photographic light-sensitive emulsion where a water-soluble solution, prepared by dissolving a methine dye having at least one water-soluble group in water in the presence of a 'Red Shift Compound', as hereinafter defined, is added to a photographic light-sensitive emulsion to provide a photographic light-sensitive emulsion spectrally sensitized with increased sensitizing efficiency and with reduced fog. The disadvantages caused by the use of high organic solvent contents are avoided and photographic light-sensitive emulsions suitable for high-speed coating are obtained.

Method for spectrally sensitizing photographic light-sensitive emulsions

Silver halide radiographic sensitive materials comprising at least one silver halide photographic emulsion layer on a support, which are used according to a process which comprises exposure to radiation from a fluorescent intensifying screen which emits light having a maximum emission in the green spectral range by excitation with radiation wherein at least 1/2 of the emission energy is in the wavelength range of above about 400 nm, and carrying out development of the exposed sensitive material to form radiographic images, wherein said silver halide sensitive materials contain below about 8.6 g of silver per square meter and said at least one silver halide photographic emulsion layer contains a combination of at least one dye represented by formula (I) and at least one dye represented by formula (II): ##STR1## wherein A.sub.1 and A.sub.2 each represents a hydrogen atom or a halogen atom; A.sub.3 and A.sub.4 each represents a hydrogen atom, a halogen atom, an alkoxy group or a phenyl group; B.sub.1, B.sub.2, B.sub.3 and B.sub.4 each represents a hydrogen atom, a halogen atom or an alkoxy group; R, R.sub.1 and R.sub.2 each represents an alkyl group and at least one of R.sub.1 and R.sub.2 represents a sulfoalkyl group or a carboxyalkyl group; R.sub.0 represents a hydrogen atom or a lower alkyl group, R.sub.3 and R.sub.4 each has the same meaning as R.sub.1 and R.sub.2 ; X.sub.1 represents an anion; m and n each represents an integer of 1 or 2, but m and n are 1 when the dye forms an inner salt; and X.sub.2 represents an anion.

Radiographic silver halide sensitive materials

A silver halide photographic emulsion containing at least one sensitizing dye represented by the following general formula (I), ##STR1## in which Z represents an atomic group necessary for forming a benzoxazole nucleus or a naphthoxazole nucleus; R.sub.1 represents an aliphatic group; R.sub.2 represents an alkyl group, an allyl group or an aryl group; R.sub.3 represents a 2-(2-hydroxyethoxy)-ethyl group, a 2-(2-acyloxyethyoxy)-ethyl group, an N-(N,N-dialkylaminoalkyl)carbamoylalkyl group, an N-(N,N,N-trialkylammoniumalkyl)carbamoylalkyl group or an N,N,N-trialkylammoniumalkyl group; X represents an acid anion; and n represents 0 or 1.

A supersensitized silver halide photographic emulsion containing a cyan coupler and, in combination, at least one of the sensitizing dyes represented by the following general formula (I) and at least one of the sensitizing dyes represented by the general formula (II): ##STR1## WHEREIN W.sup.1 and W.sup.2 each represents a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom, an alkoxycarbonyl group, an acyl group or an aryl group; R.sup.1 and R.sup.2 each represents a sulfoalkyl group; R.sup.3 represents an alkyl group or an allyl group; X.sub.1 represents an acid anion; and m is 1 or 2, m being 1 in the case that the dye forms an inner salt of a betaine-like structure; ##STR2## wherein Z.sup.1 and Z.sup.2 each represents an atomic group required for forming a benzothiazole nucleus, a benzoselenazole nucleus, a .beta.-naphthothiazole nucleus or a .beta.-naphthoselenazole nucleus; R.sup.4 and R.sup.5 each represents an aliphatic group and at least one of R.sup.4 and R.sup.5 represents a carboxyalkyl group or a sulfoalkyl group; R.sup.6 represents an alkyl group, an aryl group, a thienyl group or a furyl group; X.sub.2 represents an acid anion; and n is 1 or 2, n being 1 in the case that the dye forms an inner salt of a betaine-like structure.

A silver halide photographic emulsion containing at least one sensitizing dye represented by the following general formula (I), ##STR1## in which Z represents an atomic group necessary for forming a benzoxazole nucleus or a naphthoxazole nucleus; R.sub.1 represents an aliphatic group; R.sub.2 represents an alkyl group, an allyl group or an aryl group; R.sub.3 represents an alkoxycarbonylalkyl group, an alkoxyalkyl group, an N-(N,N-dialkylaminoalkyl)carbamoylalkyl group, an N-(N,N,N-trialkylammoniumalkyl)carbamoylalkyl group or an N,N,N-trialkylammoniumalkyl group, with R.sub.2 being a phenyl group where R.sub.3 is an alkoxycarbonylalkyl group; X represents an acid anion; and n represents 0 or 1.

A silver halide photographic emulsion containing at least one spectral sensitizing dye represented by formula (I) ##STR1## wherein Z is an atomic group necessary for completing a 5- or 6-membered heterocyclic ring, R.sub.1 is an aliphatic group, R.sub.2 is an aliphatic group having an alkylthio group or an aliphatic group having two alkoxy groups on the same carbon atom, R.sub.3 is an aryl group, an alkyl group or an alkenyl group, R.sub.4 is a hydrogen atom, an alkyl group or an aryl group, and m and n are 1 or 2.

Silver halide photographic emulsions

A supersensitized silver halide photographic emulsion which contains at least one dye of the formula: ##STR1## wherein Z.sup.1 represents the atoms necessary to complete a benzisoxazole ring; Q.sup.1 represents the atoms necessary to complete a 2-thiooxazolidine-2,4-dione ring, a rhodanine ring or a 2-thiohydantoin ring; and R.sup.1 represents an aliphatic group, in combination with at least one cyanine dye or merocyanine dye which contains no benzisoxazole ring.

Spectrally sensitized silver halide photographic emulsion

An improved silver halide photographic light-sensitive material comprising a support having coated thereon at least one photographic emulsion layer containing a dicarbocyanine dye having two heterocyclic nuclei which are 5- or 6-membered nitrogen-containing nuclei and which are connected to each other at the carbon atom in the 2- or 4-position thereof through a pentamethine chain, which can be substituted in the meso-position, a nitrogen atom of one nitrogen-containing heterocyclic nucleus of said carbocyanine dye being substituted by a sulfo- or carboxy-containing alkyl group, and a nitrogen atom of the other nitrogen-containing heterocyclic nucleus being substituted by an aralkyl group or an aryloxyalkyl group, with the proviso that said aralkyl and aryloxyalkyl groups are not substituted by a sulfo group or a carboxyl group.

Silver halide photographic light sensitive material

A silver halide photographic emulsion containing at least one sensitizing dye of the following general formula (I) and at least one sensitizing dye of general formulae (II) and/or (III), in an amount effective to achieve supersensitization: ##STR1## wherein V.sup.1 and V.sup.2, which may be the same or different, each represents a hydrogen atom, halogen atom, trifluoromethyl, cyano, carboxy, alkoxycarbonyl, aminosulfonyl or alkylsulfonyl; W.sup.1 and W.sup.2, which may be the same or different, each represents a hydrogen atom, halogen atom, alkyl, alkoxy, hydroxy, acyloxy or phenyl; R.sup.1 represents alkyl or substituted alkyl; R.sup.2 and R.sup.3, which may be the same or different, each represents alkyl or substituted alkyl, and at least one of R.sup.2 and R.sup.3 represents 1 or 0; substituted alkyl containing a carboxy or sulfo radical; R.sup.4 and R.sup.5, which may be the same or different, each has the same meanings as R.sup.1 ; X.sup.- represents an acid anion; and m represents ##STR2## wherein V.sup.3 and V.sup.4, which may be the same or different, each has the same meaning as V.sup.1 and V.sup.2 ; W.sup.3 and W.sup.4, which may be the same or different, each has the same meaning as W.sup.1 and W.sup.2 ; R.sup.6 has the same meaning as R.sup.1 ; R.sup.7 and R.sup.8, which may be the same or different, each has the same meaning as R.sup.2 and R.sup.3 ; X.sup.- represents an acid anion; and n represents 1 or 0; ##STR3## wherein W.sup.5 and W.sup.6, which may be the same or different, each has the same meaning as W.sup.3 and W.sup.4 ; R.sup.10 and R.sup.11, which may be the same or different, each has the same meaning as R.sup.2 and R.sup.3 ; R.sup.9 represents an alkyl group; X.sup.- represents an acid anion; and p represents 1 or 0.

Direct-positive process utilizing a supersensitized silver halide

In a process for forming radiographic images which comprises exposing a photograhic sensitive material comprising a support and at least one silver halide photographic emulsion layer to radiation from a fluorescent intensifying screen to form a latent image and thereafter developing the same, the improvement which comprises the fluorescent intensifying screen having a maximum emission wavelength in the range of about 500 to about 570 nm and a distribution such that at least about 1/2 of the emission energy is at a wavelength of above about 400 nm, and said silver halide photographic emulsion layer contains at least one sensitizing dye represented by formula (I) and at least one sensitizing dye represented by formula (II): ##STR1## WHEREIN R.sub.o represents an alkyl group and R.sub.1 and R.sub.2 each represent an alkyl group but at least one of R.sub.1 and R.sub.2 represents a sulfoalkyl group, X represents an anion, and m represents an integer of 1 or 2, and m = 1 when the dye forms an inner salt; ##STR2## wherein Z represents the group of atoms necessary to complete a benzoxazole nucleus, R.sub.3 represents an alkyl group, and Q represents the group of atoms necessary to complete a 2-thioimidazolidine-2,4-dione nucleus.

Radiographic process and sensitive material for the same

A silver halide photographic emulsion spectrally sensitized in the relatively shorter wavelength region ranging from blue to green with a supersensitizing combination of at least one sensitizing dye represented by the general formula (I) ##STR1## WHEREIN Z.sup.1 represents the atoms necessary to form a benzimidazole ring, an oxazole ring, a benzoxazole ring or a naphthoxazole ring; Z.sup.2 represents the atoms necessary to form a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring or a naphthoselenazole ring; R.sup.1 and R.sup.2 each represents an aliphatic group containing up to 8 carbon atoms, which may be unsubstituted or substituted, and the carbon chain of which may be interrupted with an oxygen atom or a sulfur atom; R.sup.3 represents an alkyl group containing up to 3 carbon atoms, an aryl group or an aralkyl group; X.sup.1 represents an acid anion; and m represents 1 or 2, wherein m equals 1 when the dye forms an intramolecular salt; and at least one dye selected from the group consisting of a simple merocyanine and a dimethinemerocyanine dye, or with a supersensitizing combination of at least one sensitizing dye represented by the general formula (I) as defined above and at least one sensitizing dye represented by the general formula (II) ##STR2## wherein Z.sup.3 represents the atoms necessary to form a 5- or 6-membered heterocyclic ring; Q represents the atoms necessary to form a rhodanine ring, a thiohydantoin ring or a 2-thioxazolidinedione ring; R.sup.4 represents an aliphatic group containing up to 4 carbon atoms, which may be unsubstituted or substituted and the carbon chain of which may be interrupted by an oxygen atom or a sulfur atom; R.sup.5 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group; and n represents 1 or 2.

A silver halide photographic emulsion spectrally sensitized with a combination of sensitizing dyes consisting essentially of at least one sensitizing dye represented by the following general formula [I] and at least one sensitizing dye represented by the following general formula [II] in supersensitizing amounts: ##STR1## wherein R.sup.1 and R.sup.2 each is an alkyl group, R.sup.3 is an alkyl group, X.sub.1 is an acidic anion, m is 1 or 2, and m is 1 when the dye forms an intramolecular salt (betaine-like structure). ##STR2## WHEREIN Z.sup.1 is a sulfur atom or a selenium atom, Z.sup.2 is an atomic group necessary to form a benzothiazole ring, a benzoselenazole ring, a naphtho[1,2-d]thiazole ring or a naphtho[1,2-d]selenazole ring, R.sup.4 and R.sup.5 is an alkyl group, R.sup.6 is an alkyl group, a phenyl group, an aralkyl group, a furyl group or a thienyl group, X.sub.2 is an acidic anion, n is 1 or 2, and n is 1 when the dye forms an intramolecular salt (betaine-like structure).

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Minami-ashigara, Japan

Masanao Hinata