US3811894A - Photosensitive aluminum plate and process for preparing the same - Google Patents

Photosensitive aluminum plate and process for preparing the same Download PDF

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Publication number
US3811894A
US3811894A US00068091A US6809170A US3811894A US 3811894 A US3811894 A US 3811894A US 00068091 A US00068091 A US 00068091A US 6809170 A US6809170 A US 6809170A US 3811894 A US3811894 A US 3811894A
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Prior art keywords
aluminum
photosensitive
plate
compound
percent
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US00068091A
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English (en)
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T Yonezawa
A Shirai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/77—Photosensitive materials characterised by the base or auxiliary layers the base being of metal

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  • ABSTRACT A photosensitive plate comprising an aluminum support containing from 0.05 to 1.0 percent by weight copper and having thereon a finely porous oxide layer formed by the anodization of said support, said oxide layer carrying a photosensitive material, is disclosed. A process forpreparing the photosensitive aluminum plate is also disclosed.
  • the invention relates to a photosensitive plate using anodized aluminum as a support. More particularly, this invention relates to a photosensitive aluminum plate having on an aluminum alloy an anodized finely porous oxide layer carrying in the fine pores a photosensitive material such as silver halide, and the like. This invention also relates to the process for preparing the photosensitive plate.
  • An object of the present invention is to provide a photosensitive plate which is high in its photographic properties, is inexpensive to manufacture and can be manufactured under mild anodizing conditions.
  • Aluminum is a metal which is relatively inexpensive, easily workable because of its excellent ductility, light and easily handled due to its low specific gravity, silver in color and beautifuL'and corrosion resistant because it easily reacts with oxygen in the air forming a stable oxide film.
  • Use of aluminum has recently progressed rapidly because of these advantages.
  • aluminum is low in hardness'(soft) and easily damaged (scratches and dents) and because the oxide film which is naturally produced is generally from 5 X to 1.5 X 10" mm in thickness, corrosion occasionally occurs in an unusual manner.
  • a method of anodizing aluminum has been devised to overcome such disadvantages and, since the aluminum oxide film produced thereby minimizes the scratching and corroding of aluminum, the abovementioned defects have been eliminated.
  • an oxide film is formed on the surface of the aluminum.
  • the oxide film is composed of a unit cell which is a hexagonal post perpendicular'to the metallic surface. In the central part of the hexagonal post a pore exists.
  • the sizes of the cell and the pore vary depending upon the conditions of film formation.
  • the .present inventors have found that, when preparing a photosensitive plate from, in addition to pure aluminum, a binary alloy of Al-Mg, Al-Cu, Al-Mn, Al-Sn, Al-Fe, Al-Zn, and the like, and a ternary alloy based on two binary alloys by the method described below and creating an image thereon, aspecific range of copper content is extremely effective for improving the color in the image areas and the non-image areas. That is, it has been found that if the copper content is increased within a certain range the developed silver image is increased in neutral black optical density to a greater extent and the aluminum oxide film in the non-image I areas is colored to a lesser ex-tent by anodizing.
  • the volume of a pore of 'y in diameter which is given as a function of the pressure by the following formula can be determined from the change of the volume of BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
  • the drawing shows the relationship graphically of the pore diameter and the volume percentage in aluminum oxide film.
  • TABLE 2 TABLE4 Amount of Silver in Conditioned Material and Developing Efficiency Amount of Silver After Before Developing Material Development Development Efficiency 17 T4 (mg/100cm) (mg/100cm) ml 0 6.5 16.3 0.39 H-l4 7.8 l6.7 0.47 ,H-l8 7.8 I6.4 0.47
  • Table 3 shows that the higher the copper content the higher is the developing efficiency (the production efficiency of reduced silver). Although the reason is not completely understood, it is believed that the movement to the right in the following relationship is probably varied depending upon the stereo structure of the pore.
  • the effective range of the copper content is from 0.05 to 1.0 percent and the preferred content is from 0.12 to 0.30 percent.
  • the anodizing in the present invention is carried out Amount of Sum on he mm Before a d as described in the specification of U.S. Pat. No.
  • n 1 a e oevelopmcm and Developing Emciency 2,766,199 using a solution of a mlxture of oxalic acid and an oxalate of an alkali metal such as sodium oxa- Afier Developing late and potassium oxalate as an electrolyte and passing Sample Development Development Efficiency an electric current of 0.5 to 5 amp/dm therethrough while maintaining the temperature of the liquid at from m 0 v (mg/100mm (mg00cm,) 17M 40 to at pH of from l to 5.
  • the electric current A 5.8 14.7 0.39 used at this point can be either DC or a mixture of DC 2 3% 8-23 and AC.
  • An aqeuous solution of sulfuric acid, chromic acid, or phosphoric acid, and the like can be used as the electrolyte.
  • the anodized aluminum plate is immersed into an aqueous solution of silver nitrate and a hydrophilic colloid, or such liquid can be coated on the aluminum plate.
  • Suitable hydrophilic colloids are polyvinyl alcohol, methyl cellulose, gum arabic, gelatin, and the like.
  • the concentration of the silver nitrate is from 30 to 50 percent and that of hydrophilic colloid is from 0.1 to 0.5 percent.
  • oxidizing agent such as ferricyanates of alkali metal, bichromates, chromate,-
  • the anodized plate can be treated with the above described oxidizing agents, and these oxidizing agents can be used together with the alkali halide or a silver salt of the above described oxidizing agentscan be used together with silver nitrate.
  • the reflection concentration of the image is higher in comparison with that of a conventional material 1 100 (American Aluminum Association) having a 0.02 percent copper content.
  • the reflection concentration of the image is one obtained by exposing a plate through a fi1- ter of 0.85 in concentration for seconds by a Quick Copy Printer (made by the Fuji Photo Film Co., Ltd.) and treating it with an Alphoto Processor.
  • the present invention is characterized in that a sufficient image density can be obtained even by treatment under mild conditions of anodizing since a high image density can be obtained when the copper content is within the specific range as described above.
  • the present invention has the advantages that a photosensitive plate high in photographic ability can be manufactured cheaply. under mild anodizing conditions.
  • the aluminum alloy can be manufactured using conventional methods. One method will be summarized as follows.
  • the desired quantity of copper is added to aluminum of 99.5 percent in purity and an ingot is made therefrom. After a homogenizing treatment (540C X 4 hr.) the ingot is cold-rolled or hot-rolled to obtain a plate having the desired thickness. At this point, addition of a trace amount of manganese, magnesium, silicon, iron, and the like, other than copper, does not affect reversely on the photosensitive plate.
  • a quinone diazaido derivative such as diazo salicylic acid, a leuco compound such as 4,4-tetra-methyldipheny1methane, Michlers hydrol, Michlers hydromethylether, but-(4,4- bis-dimethylamine benzhydryl) ether, 4,4-tetramethyl diaminodiphenyl methyl benzoate, tetramethyl benzidine, crystal violet lactone, crystal violet carbinol base, and the like and an organic halogen generator such as C8,, and a photochromic dye, for example, the 1,3,3- trimethylindolinobenzospiropyrans, the 1,3,3- trimethylindolino-B-naphthospiropyrans, the
  • the present invention can be conducted by the methods described in the present specification and by methods well known in the photographic art similar to the use of silver halide.
  • the plate thus obtained was exposed under a negative film, developed in a photographic developer, fixed, and washed with water, and, thereafter, was intensified with a golden intensifier, and, if necessary, was dyed, and finally was sealed in a hot solution of nickel salt or boiling water for filling up the pores to obtain a distinct photo copy which is higher in contrast.
  • the photographic image so obtained is characterized by being particularly fast to light and weather.
  • this plate before toning had an image density corresponding to the copper content of 0.16
  • Solution 5 Silver Nitrate Gelatin Concentrated Nitric Acid Distilled Water After squeezing the excess liquid from the surface of the oxide film and drying it, the oxide film was immersed into the following solution (Solution 6) for 60 seconds:
  • the plate before intensification had an image density corresponding to a copper content of 0.l6 percent in Table 5.
  • EXAMPLE 3 Material H-l8 (corresponding to C in the Table and the Drawing) having a copper content of 0.50 percent was electrolyzed in each of the liquid compositions and in the same manner as in Example 1 and the liquid was impregnated into the pore.
  • the plate so obtained had an image density corresponding to the copper content of 0.50 percent in Table 5.
  • EXAMPLE 4 After anodizing material H-l4 (corresponding to A in the Table and the Drawing) having a copper content of 0.16 percent under the same condition as used in Example with the liquid consisting of the following compositions I (l) Ethyl Cellulose 5 g Ethyl Alcohol 20 cc Toluene 20 cc Carbon Tetrabromide 2 g and (2) J-Dibcnzyl Amino-7- diethylamino-florane 2 g Ethylene Dichloride 10 cc aluminum support containing therein, from 0.05 to l .0 I percent by weight of copper, and having thereon, a
  • said oxide layer carrying a photosensitive material and said photosensitive material further being characterized as having filled the pores of said finely porous oxide layer
  • said aluminum support consisting of (l) aluminum
  • photosensitive material is selected from the group consisting of a silver halide; a diazo compound; ammonium iron citrate and a red prussiate; an organic halogen compound and diphenylamine; a compound changing color depending .upon the pH and a compound converted to an acid or base upon light irradiation; a quinone diazaido derivative; a leuco compound and an organic halogen generator; and a photochromic dye.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
US00068091A 1969-08-29 1970-08-31 Photosensitive aluminum plate and process for preparing the same Expired - Lifetime US3811894A (en)

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JP44068410A JPS499977B1 (es) 1969-08-29 1969-08-29

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JP (1) JPS499977B1 (es)
DE (1) DE2042834C3 (es)
FR (1) FR2059365A5 (es)
GB (1) GB1298896A (es)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961962A (en) * 1973-11-29 1976-06-08 Fuji Photo Film Co., Ltd. Photomask material and method for producing same
US4047956A (en) * 1975-11-17 1977-09-13 E. I. Du Pont De Nemours And Company Low coating weight silver halide element and process
US4092169A (en) * 1971-03-01 1978-05-30 Fuji Photo Film Co., Ltd. Anodized aluminum photographic plates with silver bromide in pores of oxide layer, and process of manufacture thereof
US4242438A (en) * 1974-09-06 1980-12-30 Fuji Photo Film Co., Ltd. Photomask material
US4331479A (en) * 1974-12-27 1982-05-25 Fuji Photo Film Co., Ltd. Process of using light-sensitive o-quinone diazide material to make aluminum oxide nameplate
US4387156A (en) * 1981-02-04 1983-06-07 Minnesota Mining And Manufacturing Company Imageable film containing a metal oxide opacifying layer
US4672022A (en) * 1984-07-13 1987-06-09 Hoechst Aktiengesellschaft Radiation-sensitive printing plates with base which consists of an aluminum alloy having iron and manganese
CN106191957A (zh) * 2016-08-29 2016-12-07 深圳天珑无线科技有限公司 一种铝合金表面处理方法及该方法得到的感光变色铝合金
CN108396354A (zh) * 2018-03-18 2018-08-14 天津孚信阳光科技有限公司 一种适于阳极氧化技术的光致变色染色液及染色工艺
CN109487319A (zh) * 2019-01-03 2019-03-19 江苏兴甬铝业科技有限公司 一种铝合金的感光表面处理方法及铝合金工件

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1160880A (en) * 1979-02-02 1984-01-24 Keith E. Whitmore Imaging with nonplanar support elements
CH645409A5 (de) * 1980-09-08 1984-09-28 Schenk & Co Verfahren zum faerben von oxydschichten von aluminium oder aluminiumlegierungen mit organischen verbindungen.

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092169A (en) * 1971-03-01 1978-05-30 Fuji Photo Film Co., Ltd. Anodized aluminum photographic plates with silver bromide in pores of oxide layer, and process of manufacture thereof
US3961962A (en) * 1973-11-29 1976-06-08 Fuji Photo Film Co., Ltd. Photomask material and method for producing same
US4242438A (en) * 1974-09-06 1980-12-30 Fuji Photo Film Co., Ltd. Photomask material
US4331479A (en) * 1974-12-27 1982-05-25 Fuji Photo Film Co., Ltd. Process of using light-sensitive o-quinone diazide material to make aluminum oxide nameplate
US4047956A (en) * 1975-11-17 1977-09-13 E. I. Du Pont De Nemours And Company Low coating weight silver halide element and process
US4387156A (en) * 1981-02-04 1983-06-07 Minnesota Mining And Manufacturing Company Imageable film containing a metal oxide opacifying layer
US4672022A (en) * 1984-07-13 1987-06-09 Hoechst Aktiengesellschaft Radiation-sensitive printing plates with base which consists of an aluminum alloy having iron and manganese
CN106191957A (zh) * 2016-08-29 2016-12-07 深圳天珑无线科技有限公司 一种铝合金表面处理方法及该方法得到的感光变色铝合金
CN106191957B (zh) * 2016-08-29 2019-01-04 深圳天珑无线科技有限公司 一种铝合金表面处理方法及该方法得到的感光变色铝合金
CN108396354A (zh) * 2018-03-18 2018-08-14 天津孚信阳光科技有限公司 一种适于阳极氧化技术的光致变色染色液及染色工艺
CN109487319A (zh) * 2019-01-03 2019-03-19 江苏兴甬铝业科技有限公司 一种铝合金的感光表面处理方法及铝合金工件

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Publication number Publication date
DE2042834A1 (de) 1971-03-25
DE2042834C3 (de) 1978-05-24
FR2059365A5 (es) 1971-05-28
JPS499977B1 (es) 1974-03-07
DE2042834B2 (de) 1977-09-15
GB1298896A (en) 1972-12-06

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