US3847613A - Silver halide photosensitive materials for color photography - Google Patents

Silver halide photosensitive materials for color photography Download PDF

Info

Publication number
US3847613A
US3847613A US00325338A US32533873A US3847613A US 3847613 A US3847613 A US 3847613A US 00325338 A US00325338 A US 00325338A US 32533873 A US32533873 A US 32533873A US 3847613 A US3847613 A US 3847613A
Authority
US
United States
Prior art keywords
group
emulsion layer
sensitive emulsion
silver halide
lower alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00325338A
Other languages
English (en)
Inventor
N Fujimori
K Sakazume
S Ito
E Sakamoto
K Mine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Application granted granted Critical
Publication of US3847613A publication Critical patent/US3847613A/en
Assigned to KONICA CORPORATION reassignment KONICA CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: KONISAIROKU PHOTO INDUSTRY CO., LTD.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group

Definitions

  • ABSTRACT A silver halide photosensitive material for color photography providing excellent color reproducibility is disclosed which comprises a support and at least three emulsion layers supported thereon; said layers being a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer; the blue-sensitive emulsion layer containing a sensitizing dye represented by the following formula:
  • Y and Y each stand for a non-metallic atomic group necessary for forming a nitrogencontaining heterocyclic ring nucleus selected from the group consisting of pyrroline, thiazoline, thiazole, benzothiazol, naphthothiazole, selenazole benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxozole, imidazole, benzimidazole, pyridine, and quinoline, which heterocyclic ring nucleus may be substituted by a halogen atom, a lower alkyl group, a lower alkoxy group, or an aryl group, which group may be substituted by a halogen atom, a lower alkyl group or alower alkoxy group; R stands for a lower alkyl group, a hydroxyalkyl group, or a sulfoalkyl group; R is a hydrogen atom or a lower al
  • This invention relates to a silver halide photosensitive material for color photography. More particularly, it 5 emulsion layer:
  • sitive material for color photography which includes a blue sensitive emulsion layer sensitized by a spectral sensitizer.
  • a primary object of this invention to provide a coupler-containing, silver halide, photosensitive material for color photography having excellent color reporducibility, which comprises a blue sensitive emulsion layer sensitized by sensitizing dyes free of the afore mentioned defects.
  • the compounds of the present invention are preferafi l? f ff bly added to the emulsions in the form of solutions in (19) s s 427 a watermiscible organic solvent such as methanol or u ethanol.
  • the addition of such compounds may be effected at any desired point during the preparation of the emulsions. In general, however, it is preferable that N N they be added just after the chemical ripening or chemr y n onmogmoncmso w ical sensitization.
  • the compounds are incorporated in H an amount of 0.01 to 0.5 g per mole of silver halide, alwe though the preferred amount can vary depending on 382 the kind of additiye and silver halide emulsion.
  • the blue sensitive layer may contain a compound which can react with an oxide of a color developer containing a primary amino group to form a ycllow dye.
  • the coupler is preferably incorporated into the emulsion as an aqueous alkalisolution or as a solution in a high or low boiling point organic solvent.
  • photographic additives such as stabilizers, film-hardening agents, pl-ladjusting agents, viscosityincreasing agents, coating assistants and color stain preventive agents in thephotosensitive material.
  • Synthetic and natural high molecule compounds such as gelatin, casein and polyvinyl alcohol can be used singly or in combination as a binder.
  • the silver halide may, for example, be silver chloride
  • the silver halide photosensitive material according to this invention can achieve a good balance in photographic characteristics between the red, green and blue sensitive layers even in high-temperature, high-speed development. It is also one of the advantages of this invention that the silver halide photographic material is freer from spot-like fog than the photographic material of the prior art. Spot-like fog often arises during development according to prior art'and is believed to result from a small quantity of fine metal stuck to the surface of the photosensitive material during its preparation,
  • Example 1 Composition of Coupler Dispersion Coupler 100 g Dibutyl phthalate lOO ml Ethyl Acetate 300 ml 5% Aqueous solution of Alkano'l B (manufactured by Du Pont) 150 ml 6% Aqueous solution of gelatin 500 ml Then, a stabilizer, a film-hardening agent, a coating assistant and a pH-adjusting agent were-added to the emulsion to form a red sensitive emulsion.
  • a green sensitive emulsion was prepared by using a sensitizing dye, anhydro-5,5-diphenyl-3,3'- disulfopropyl-9-ethyl-oxacarbocyanine hydroxide in an amount of 0.l5g per mole of the silver halide and, as a coupler, l-( 2,4,6-trichloro-phenyl -[3-(2,4-di-tertiary-amylphenoxyacetamide)benzamid]-5-pyrazolone in an amount of 60g per mole of the silver halide.
  • a color negative emulsion of silver bromideiodide containing 4.5 mole percent of silver iodide was chemically ripened and divided into seven portions. From these seven portions of the emulsion, seven kinds of blue sensitive emulsions were prepared by adding compounds (7), (9) or 14) of this invention individually in g 7 an amount of 0.00g, 0. 10g or 0.l5g per mole ofthfe silamt-halide; Aft r.-thq..ts. tins mtXt ts w e.
  • g per mole of silver halide of 4-dodecylbenzoyl-Z'-methoxyacetoanilide was incorporated as a yellow coupler into each mixture in the form of a cow pler dispersion.
  • the dispersion was prepared in the same manner as the above described red and green sensitizing emulsions. Then a stabilizer, a film-hardening agent, a coating assistant and a pH-adjusting agent were incorporated into each of the resulting compositions.
  • a photographic film was prepared by coating on a cellulose triacetate film base.
  • An anti halation layer, a red sensitive emulsion layer, a gelatin film layer, a green sensitive layer, a colloidal silver-containing yellow filter layer, a blue sensitive and a gelatin protective layer were successively coated on the base in that order.
  • the relative blue light sensitivity of the blue sensitive emulsion layer and the degree of the residual coloration were measured and the results are shown in Table l.
  • the relative sensitivity is expressed as a relative value based on the blue light sensitivity (100) of the sample'( 1) containing no sensitizing dyes, and the degree of the residual coloration is expressed as a value of the complementary color concentration at the nonimage area.
  • Table l readily be-understood that the samples containing the.
  • Belgian Pat. No. 738,921 )1 compounds of this invention exhibit not only a low degr'ee of the residual coloration but also a high blue light sensitivity and are thus particularly suitable as sensitizing dyes for blue sensitive emulsion.
  • Example 2 A color reversable emulsion of silver iodidebromide containing 5 mole of silver iodide was chemically ripened and 0.15g per mole of silver halide of anhydro 5,- 5-disulfopropyl-9-ethyl-thiacarbocyane hydroxide was added as a sensitizing dye to the emulsion in the form of a methanol solution. Then 50g per mole of 4-chlorol-hydroxy-2-n-octylnaphthamide was added as a cyan coupler in the form of a dispersion prepared in the same manner as in Example 1, the resulting was well mixed and dispersed. A stabilizer, a film-hardening agent, a coating assistant and a pl-l-adjusting agent,
  • a green sensitive emulsion was prepared by employing, as a sensitizing dye, anhydro-5,5'-diphenyldisulfopropyl-9-ethyl-oxacarbocyanine hydroxide in an amount of 0.15g per mole of the silver halide and, as a magenta coupler, l-(3-carboxyphenyl)-3-(4- stearoylaminophenyl)-5-pyrazolone in an amount of 6X52, 9 sf es lterba jsie ⁇ N f S I Comparative dye B (disclosed in the specification of Pat. No. 3,480,434):
  • the Immediate Test data were obsinsstwlisn l1ifhbl Prep Samples were tested
  • the Test after Preservation data were obtained when the samples were tested after they had been maintained at high temperature (50C) and high humidity relative humidity 80 percent for 2 days.
  • the relative sensitivity is expressed as a relative value based on the sensitivity in the Immediate Test" of the sample containing no sensitizing dye in the blue sensitive layer.
  • Emulsion layer Emulsion Luyer Emulsion Layer Kind Amount Dmax Dmin r Dmax Dmin r Dmux Dmin r 8 0.06 1.90 3.3 0.05 2.10 3.4 0.03 2.12 9 comparative colorant (A) 0.10 3.2 0.07 1.85 3.3 0.05 2.10 3.4 0.0. 2.12 10 comparative colorant (A) 0.20 3.1 0.08 1.91 3.3 0.05 2.10 3.4 0.03 2.12
  • Example V V dltcllons Ve.ry ia f y lsblowebr According to the procedures of Example 1, various a C ear Image 0 no C0 Ora can silver halide color negative photosensitive materials tamed. Moreover, even when high-temperature, highwe re prepared as follows.
  • Color Development Treatment samples they were maintained at a temperature of C.. and a relative humidity of percent for 2 days. They were then exposed tolight and subjected to the color development in the same manner as described above to obtain the color negative image.
  • the blue light sensitivity of the blue sensitive layer and the residual coloration were determined and the results are shown in Table 4. 1n the Table, the 1mmediate Test data were obtained from the fresh samples and the Test after Preservation" data were obtained from samples which had been stored under the high temperature and high humidity conditions as de Table 4 scribed above.
  • the relative sensitivity is a relative value based on the value (100) of the sensitivity in the 1mmediate Test of the sample containing no sensitizing dye in the blue sensitive layer, and the residual coloration is expressed in terms of the value of the complementary color concentration of the non-image area.
  • silver halide photosensitive material prepared in accordance with this invention is far superior to silver halide photosensitive materials without any sensitizing dye as well as those materials using prior art comparable dyes.
  • the high-temperature development treatment is applied, a higher blue light sensitivity is attained, and, even afterstorage under high temperature and high humidity conditions, the reduction in sensitivity is extremely slight and a sufficient sensitivity is retained.
  • the degree of the residual coloration is low, resulting in a very clear image.
  • the spectrophotography was conducted on the same samples as described above to examine the spectral sensitivity curves of blue sensitive emulsion layers. The results are shown in FIGS. 1 and 2.
  • broken line (1) is the spectral sensitivity curve of the blue sensitive emulsion layer of sample (23) having compound (3) of this invention therein in an amount of 0.15g per mole of silver halide.
  • Solid line (2) is the spectral sensitivity curve of the blue sensitive emulsion layer of sample 17) containing no sensitizing dye.
  • broken line (3) is the spectral sensitivity curve of sample (25) having compound (14) of this in- Sample dye Added and Its Amount (g per mole Immediate Test Test after Preservation No. of silver halide)
  • the bluesensitive emulsion layer containing a sensitizing dye represented by the following formula:
  • Y and Y each stand for a non-metallic atomic group necessary to form a nitrogen-containing heterocyclic ring nucleus selected from the group consisting of pyrroline, thiazoline, thiazole, benzothiazol, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxozole, imidazole, benzimidazole, pyridine, and quinoline, which nucleus 'maybe substituted by a halogen atom, a lower 14 alkyl group, a lower alkoxy group, or an aryl group, which group may in turn be substituted by halogen, lower alkyl or lower alkoxy; R stands for lower alkyl, hydroxyalkyl, or sulfoalkyl; R is hydrogenor lower alkyl, A designates alkylene,
  • each of said layers contains a coupler.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00325338A 1972-01-24 1973-01-22 Silver halide photosensitive materials for color photography Expired - Lifetime US3847613A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP47008300A JPS5037538B2 (fr) 1972-01-24 1972-01-24

Publications (1)

Publication Number Publication Date
US3847613A true US3847613A (en) 1974-11-12

Family

ID=11689290

Family Applications (1)

Application Number Title Priority Date Filing Date
US00325338A Expired - Lifetime US3847613A (en) 1972-01-24 1973-01-22 Silver halide photosensitive materials for color photography

Country Status (4)

Country Link
US (1) US3847613A (fr)
JP (1) JPS5037538B2 (fr)
DE (1) DE2303204A1 (fr)
GB (1) GB1366623A (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976492A (en) * 1974-07-25 1976-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions
US3985563A (en) * 1974-09-09 1976-10-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3986878A (en) * 1974-09-04 1976-10-19 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3988155A (en) * 1974-09-04 1976-10-26 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4018610A (en) * 1974-07-26 1977-04-19 Fuji Photo Film Co., Ltd. Supersensitized silver halide photographic emulsion
FR2379577A1 (fr) * 1977-02-02 1978-09-01 Polaroid Corp Colorants de thiacyanine-betaine pour la sensibilisation au bleu d'emulsions photographiques
US4147547A (en) * 1975-03-29 1979-04-03 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
US4818671A (en) * 1986-07-31 1989-04-04 Konishiroku Photo Industry Co., Ltd. Rapidly processable silver halide color photosensitive material
US4828969A (en) * 1985-05-01 1989-05-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material
US5024928A (en) * 1988-07-19 1991-06-18 Minnesota Mining And Manufacturing Company Silver halide multilayer color reversal photographic material having improved color reproducibility
US5047311A (en) * 1984-05-29 1991-09-10 Mitsubishi Paper Mills Ltd. Panchromatic silver halide photographic element
US5250544A (en) * 1990-07-10 1993-10-05 Adir Et Compagnie New piperidine tetrahydropyridine and pyrrolidine compounds
US5460928A (en) * 1994-04-15 1995-10-24 Eastman Kodak Company Photographic element containing particular blue sensitized tabular grain emulsion
US5474887A (en) * 1994-04-15 1995-12-12 Eastman Kodak Company Photographic elements containing particular blue sensitized tabular grain emulsion
US5576157A (en) * 1994-04-15 1996-11-19 Eastman Kodak Company Photographic element containing emulsion with particular blue sensitivity
US5582960A (en) * 1995-02-17 1996-12-10 Eastman Kodak Company Photographic print material
US20090247579A1 (en) * 2006-02-21 2009-10-01 Cancer Research Technology Limited 2-[3h-thiazol-2-ylidinemethyl]pyridines and related compounds and their use

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5180224A (ja) * 1975-01-07 1976-07-13 Konishiroku Photo Ind Harogenkaginkaraashashinkankozairyo
JPS51106426A (ja) * 1975-03-17 1976-09-21 Konishiroku Photo Ind Senkorokoyoharogenkaginshashinnyuzai
JPS599900B2 (ja) * 1975-03-29 1984-03-06 コニカ株式会社 ハロゲンカギンカラ−シヤシンカンコウザイリヨウ
JPS537233A (en) * 1976-07-08 1978-01-23 Mitsubishi Paper Mills Ltd Multicolor photographic material having improved blue sensitive layer
JPS5650325A (en) * 1980-07-07 1981-05-07 Fuji Photo Film Co Ltd Silver halide photographic emulsion
JPS59116645A (ja) * 1982-12-13 1984-07-05 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
EP0197202B1 (fr) * 1985-04-09 1990-04-18 Agfa-Gevaert N.V. Procédé photographique d'inversion par transfert par diffusion de complexes d'argent
JP2700794B2 (ja) * 1988-02-24 1998-01-21 コニカ株式会社 ハロゲン化銀写真感光材料
US5439789A (en) * 1993-05-11 1995-08-08 Fuji Photo Film Co., Ltd. Methine compound and silver halide photographic material comprising the same
DE19841985A1 (de) * 1998-09-03 2000-03-09 Schering Ag Dialkylsulfonsäure- und Dialkylcarbonsäure-Derivate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2170803A (en) * 1934-08-11 1939-08-29 Eastman Kodak Co Photographic sensitizing dyes and their preparation
US2231659A (en) * 1939-05-09 1941-02-11 Eastman Kodak Co Polymethine dye intermediates
US2921067A (en) * 1957-04-03 1960-01-12 Eastman Kodak Co Method of making carbocyanine and merocarbocyanine spectral sensitizing dyes
US3149105A (en) * 1961-09-14 1964-09-15 Eastman Kodak Co Novel synthesis of cyanines and merocyanines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2170803A (en) * 1934-08-11 1939-08-29 Eastman Kodak Co Photographic sensitizing dyes and their preparation
US2231659A (en) * 1939-05-09 1941-02-11 Eastman Kodak Co Polymethine dye intermediates
US2921067A (en) * 1957-04-03 1960-01-12 Eastman Kodak Co Method of making carbocyanine and merocarbocyanine spectral sensitizing dyes
US3149105A (en) * 1961-09-14 1964-09-15 Eastman Kodak Co Novel synthesis of cyanines and merocyanines

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976492A (en) * 1974-07-25 1976-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions
US4018610A (en) * 1974-07-26 1977-04-19 Fuji Photo Film Co., Ltd. Supersensitized silver halide photographic emulsion
US3986878A (en) * 1974-09-04 1976-10-19 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3988155A (en) * 1974-09-04 1976-10-26 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3985563A (en) * 1974-09-09 1976-10-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4147547A (en) * 1975-03-29 1979-04-03 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
FR2379577A1 (fr) * 1977-02-02 1978-09-01 Polaroid Corp Colorants de thiacyanine-betaine pour la sensibilisation au bleu d'emulsions photographiques
US4250244A (en) * 1977-02-02 1981-02-10 Polaroid Corporation Thiacyanine betaine blue sensitizing dyes
US5047311A (en) * 1984-05-29 1991-09-10 Mitsubishi Paper Mills Ltd. Panchromatic silver halide photographic element
US4828969A (en) * 1985-05-01 1989-05-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material
US4818671A (en) * 1986-07-31 1989-04-04 Konishiroku Photo Industry Co., Ltd. Rapidly processable silver halide color photosensitive material
US5024928A (en) * 1988-07-19 1991-06-18 Minnesota Mining And Manufacturing Company Silver halide multilayer color reversal photographic material having improved color reproducibility
US5250544A (en) * 1990-07-10 1993-10-05 Adir Et Compagnie New piperidine tetrahydropyridine and pyrrolidine compounds
US5278185A (en) * 1990-07-10 1994-01-11 Adir Et Compagnie Piperidine, Tetrahydropyridine and pyrrolidine compounds
US5460928A (en) * 1994-04-15 1995-10-24 Eastman Kodak Company Photographic element containing particular blue sensitized tabular grain emulsion
US5474887A (en) * 1994-04-15 1995-12-12 Eastman Kodak Company Photographic elements containing particular blue sensitized tabular grain emulsion
US5576157A (en) * 1994-04-15 1996-11-19 Eastman Kodak Company Photographic element containing emulsion with particular blue sensitivity
US5582960A (en) * 1995-02-17 1996-12-10 Eastman Kodak Company Photographic print material
US20090247579A1 (en) * 2006-02-21 2009-10-01 Cancer Research Technology Limited 2-[3h-thiazol-2-ylidinemethyl]pyridines and related compounds and their use

Also Published As

Publication number Publication date
DE2303204A1 (de) 1973-08-16
JPS4878930A (fr) 1973-10-23
GB1366623A (en) 1974-09-11
JPS5037538B2 (fr) 1975-12-03

Similar Documents

Publication Publication Date Title
US3847613A (en) Silver halide photosensitive materials for color photography
US4469785A (en) Light-sensitive silver halide color photographic material
US3672898A (en) Multicolor silver halide photographic materials and processes
EP0127081A2 (fr) Matériel photographique couleur d'inversion sensible à la lumière
US4791053A (en) Silver halide photographic material
US4863846A (en) Silver halide photographic light-sensitive material
US3822136A (en) Silver halide light-sensitive supersensitized materials
EP0683427B1 (fr) Colorants sensibilisateurs pour le bleu substitués par des hétérocycles
US3672897A (en) Silver halide color photographic light-sensitive material
US4717648A (en) Process for processing a color reversal photographic light-sensitive material
US5126237A (en) Silver halide light-sensitive photographic material
US4925780A (en) Direct positive silver halide light-sensitive color photographic material
US3580724A (en) Light-sensitive supersensitized silver halide color photographic emulsions
JP3421408B2 (ja) フランもしくはピロール置換された色素化合物を含むハロゲン化銀写真要素
US3713828A (en) Multi-layer color photographic silver halide light-sensitive materials
US4889796A (en) Silver halide photographic emulsion
DE3525900A1 (de) Verfahren zur entwicklung von photographischen farbumkehrmaterialien
US4970141A (en) Silver halide photographic emulsion
JPS59111641A (ja) ハロゲン化銀写真感光材料
US4863844A (en) Gold and sulfur sensitized silver halide light-sensitive photographic material
US4517284A (en) Light-sensitive silver halide photographic material
JP2929511B2 (ja) ハロゲン化銀カラー写真感光材料
US3480434A (en) Sensitizer for blue-sensitive emulsions
JPS58107533A (ja) ハロゲン化銀カラ−写真感光材料
US4900656A (en) Silver halide color photographic material

Legal Events

Date Code Title Description
AS Assignment

Owner name: KONICA CORPORATION, JAPAN

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:KONISAIROKU PHOTO INDUSTRY CO., LTD.;REEL/FRAME:005159/0302

Effective date: 19871021