US3909270A - Dichroic reversible photosensitive materials - Google Patents

Dichroic reversible photosensitive materials Download PDF

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Publication number
US3909270A
US3909270A US392302A US39230273A US3909270A US 3909270 A US3909270 A US 3909270A US 392302 A US392302 A US 392302A US 39230273 A US39230273 A US 39230273A US 3909270 A US3909270 A US 3909270A
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United States
Prior art keywords
alkali metal
ion
crystal
alkali
accordance
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Expired - Lifetime
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US392302A
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English (en)
Inventor
Yasuo Kishi
Toshiaki Yokoo
Terutoyo Imai
Keiichi Kanatani
Takehito Yazaki
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National Institute of Advanced Industrial Science and Technology AIST
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Director Of Agency Of Ind Scie
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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
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

  • This invention relates to dichroic reversible photosensitive materials and a method for the preparation thereof. More particularly, it concerns dichroic reversible photosensitive materials which consist of the crystals of an alkali metal halide which contain an alkali metal ion having smaller ion radius than that of the alkali metal in said alkali metal halide and also one or more kinds of other metal ions than alkali metal ion which possess an ability to act as an electron trap; which have M-center, and a method for the preparation therof.
  • the M-center oriented to the direction of 1 l), e.g., that of sodium fluoride shows a maximum absorption band at 505 mp. to the light polarized to the direction of (l and an absorption band at 340 M,u. to the light polarized to the direction of (1 1 0).
  • the band at long wave length side between two absorption bands is called as the first absorption band and one at short Wave length side as the second absorption band.
  • M-center possesses a property of being not reoriented by the light of first absorption band but reoriented by the light of second absorption band to the direction of polarization, e.g., the M-center oriented to the direction of (1T0) is reoriented to the direction of (1 l0) by irradiation of the light at second absorption band polarized to the direction of (110). Accordingly, it will be possible to write and read an information in using such property of M-center.
  • the crystals having M-center will possess a capacity of an analogue record for voluntary pattern such as characters, figures and the like as well as of a digital record as mentioned above. They will, therefore, be usable for a photosensitive material as equivalent to photographic 'films. Furthermore, a great advantage to use M-center as above is that crystals having M-center become a reversible photosensitive material which is capable of recording and erasing an information repeatedly. Therefore the crystals'are promising as a memory element.
  • a reversible photosensitive material which consists of the crystals of an alkali metal halide intermixed with one kind of a specific metallic cation in which M-center is formed, and as a result of further studies on using a new theory developed by them, have succeeded to obtain new dichroic reversible photosensitive materials having a remarkably improved photosensitivity which consist of the crystals of an alkali metal halide intermixed with one kind of alkali metal ion having smaller ion. radius than the alkali metal in said alkali metal halide used as the base mate- I rial and one or more kinds of metal ions other than the alkali metal ion which possess an ability to act as an electron trap, which have M-center.
  • the alkali metal halide crystal to be used as the base material of this invention means the crystals of salts of an alkali metal such as lithium, sodium, potassium, rubidium or cesium, with a halogen such as chlorine, bromine, fluorine or iodine.
  • the most preferred example of the alkali metal halide may be sodium fluoride.
  • Preferred examples may be sodium chloride, sodium bromide, potassium chloride, potassium fluoride, potassium bromide, lithium fluoride, rubidium fluoride, rubidium bromide and the like.
  • cesium fluoride, cesium bromide, sodium iodide and the like may be mentioned as other examples to be used in this invention.
  • the alkali metal ion in the compound producing an alkali metal ion having smaller ion radius than that of the alkali metal in the alkali metal halide means, for instance, lithium ion to sodium ion, or sodium or lithium ion to potassium ion or the like.
  • the compound producing an alkali metal ion having smaller ion radius than that of the alkali metal in the alkali metal halide is one producing an alkali metal ion as mentioned above, preferably a halide compound of the same kind of halogen as that of the alkali metal halide used.
  • the metal ion in the compound producing metal ion other than the alkali metal ion which possesses an ability to act as an electron trap means the ion derived from metals as mentioned below.
  • an alkali earth metal such as beryllium, magnesium, calcium, strontium or barium.
  • a metal belonging to the group I B of the periodic table such as copper or silver.
  • a metal belonging to the group II B of the periodic table such as zinc, cadmium or mercury.
  • a metal belonging to the group III B of the periodic table such as gallium, indium or thallium.
  • a transition metal such as iron, cobalt, nickel, titanium, vanadium, chronium or magnesium.
  • a rare earth metal such as samarium or europium.
  • the compound producing metal ion other than alkali metal ion which possesses an ability to act as an electron trap means the compound producing the metal ions as mentioned above.
  • Preferable one is a halide compound of the same kind of halogen as that of the alkali metal halide to be used.
  • an appropriate amount of alkali metal halide crystal is firstly melted, e,g., in a melting pot or bath, to which are added one kind of compound producing alkali-metal ion and one or more kinds of compounds producing metal ions and melted. Crystals are grown and isolated in accordance with a conventional method, e.g., Kyropoulos method. See, e.g.,
  • the addition amount of each of the compound producing alkali metal ion and the compounds producing metal ion may be about 0.00001 10.0 molar percentage to the crystals of alkali metal halide as the base material, preferably about 0.1 2.0 molar percentage.
  • the addition amount of each of the compounds is increased over the above figure, it will be meaningless, because an amount to be practically intermixed with the alkali metal halide crystal depends upon a coefficient of segregation of the crystals used.
  • applying /cm- Next, M-center is formed in the resulting crystals by a conventional method. As its examples may be mentioned a method for applying, an electron beam, X-ray or 'y-ray, an electrolytic coloring method and the like.
  • M-center it is desired to make M-center at a concentration as high as possible, preferably a concentration of about l cm 18 cm.
  • concentration as high as possible, preferably a concentration of about l cm 18 cm.
  • alkali metal halide crystal there are various combinations of the alkali metal halide crystal, another alkali metal ion and other metal ions as the components of the materials in this invention.
  • sodium fluoride as the alkali metal halide crystal, there may be mentioned as follows.
  • NaF Li Ag NaF Li Pd NaF Li Mg, NaF Li Be, NaF Li Sr, NaF Mg Cr, NaFzLi-Mg-Cr, NaFzLi-Ag-Be-Cr, NaF Li Tl Mg Ni, etc.
  • potassium chloride as the base material, there may be mentioned as follows.
  • KCl Nu Ag KCl Li Ag, KCI Na Mg, KCl Li Be, KCl Li Sr, KCl Na Mg -Cr, KClzLi-Mg-Cr, KCl:Na-Fe-Mg, KClzLi-Cr-Be-Ag, KCI2Na-Ag-Be-Cr, KCl Nu Tl Mg Ni etc.
  • M-center will migrate one latice length and combine with another M-center or F- center to form other color centers during repeated writings and eliminations, by which the M-center disappeares.
  • the crystals to be obtained by this invention have few such possibility, because at least two kinds of impure materials which have a different action to each other are fixed in the crystals. Therefore, they will be usable as a photosensitive material having a long life, i.e., a reversible photosensitive mate rial.
  • the crystals of this invention may be cleaved to make a thin plate which can be used as a reversible ultramicrofiche, to which a graphic description is copied through a polarizer. Besides, they may be used as an optical storage element for optical memory system, the material for pattern information filing system and the like.
  • a dichroic reversible photosensitive material which consists of an alkali metal halide crystal having M-centers, said crystal containing an alkali metal ion having a smaller ion radius than that of the alkali metal in said alkali metal halide and one or more metal ions which possess the ability to act as an electron trap selected from the group consisting of alkali earth metal ions and transition metal ions.
  • alkali metal halide crystal is crystal of sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, lithium fluoride, rubidium bromide, cesium fluoride or cesium bromide.
  • crystal contains said alkali metal ion and said alkali earth metal ions or a mixture of said alkali earth metal ions and transition metal ions.
  • alkali earth metal ion is an ion of beryllium, magnesium, calcium, strontium or barium.
  • transition metal ion is an ion of iron, cobalt, nickel, titanium, vanadium, chromium or magnesium.
  • the alkali metal halide crystal is sodium fluoride crystal
  • the alkali metal ion having smaller ion radius than that of tha alkali metal of said alkali metal halide is lithium ion
  • the metal ion other than alkali metal ion which possesses an ability to act as as electron trap is magnesium ion.
  • the alkali metal halide crystal is sodium fluoride crystal
  • the alkali metal ion having smaller ion radius than that of the alkali metal of said alkali metal halide is lithium ion
  • the metal ion other than alkali metal ion which possesses an ability to act as as electron trap is beryl lium ion.
  • the alkali metal halide crystal is sodium fluoride crystal
  • the alkali metal ion having smaller ion radius than that of the alkali metal of said alkali netal halide is lithium ion
  • the metal ion other than alkali metal ion which possesses an ability to act as an electron trap is strontium ion.
  • the alkali metal halide crystal is sodium fluoride crystal
  • the alkali metal ion having smaller ion radius than that of the alkali metal of said alkali metal halide is lithium ion
  • the metal ions other than alkali metal ion which possess an ability to act as an electron trap are magnesium ion and chromium ion.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US392302A 1972-08-31 1973-08-28 Dichroic reversible photosensitive materials Expired - Lifetime US3909270A (en)

Applications Claiming Priority (1)

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JP7286608A JPS5031824B2 (enrdf_load_stackoverflow) 1972-08-31 1972-08-31

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0375534A3 (en) * 1988-12-20 1990-11-28 Fujitsu Limited Photomask and manufacturing method therefor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5550518B2 (enrdf_load_stackoverflow) * 1973-11-26 1980-12-18

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3580688A (en) * 1968-02-26 1971-05-25 Irwin Schneider Information storage with optic materials
US3720926A (en) * 1971-03-31 1973-03-13 I Schneider Information storage using m color centers in alkali fluorides
US3761267A (en) * 1971-03-10 1973-09-25 Eastman Kodak Co Photographic element containing monodispersed unfogged dye sensitizedsilver halide grains metal ions sensitized internally and the use theeof in reversal process
US3814601A (en) * 1972-07-21 1974-06-04 I Schneider Grainless photographic medium and method of making same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3580688A (en) * 1968-02-26 1971-05-25 Irwin Schneider Information storage with optic materials
US3761267A (en) * 1971-03-10 1973-09-25 Eastman Kodak Co Photographic element containing monodispersed unfogged dye sensitizedsilver halide grains metal ions sensitized internally and the use theeof in reversal process
US3720926A (en) * 1971-03-31 1973-03-13 I Schneider Information storage using m color centers in alkali fluorides
US3814601A (en) * 1972-07-21 1974-06-04 I Schneider Grainless photographic medium and method of making same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0375534A3 (en) * 1988-12-20 1990-11-28 Fujitsu Limited Photomask and manufacturing method therefor
US5147742A (en) * 1988-12-20 1992-09-15 Fujitsu Limited Photomask and fabrication of the same

Also Published As

Publication number Publication date
JPS5031824B2 (enrdf_load_stackoverflow) 1975-10-15
JPS4948329A (enrdf_load_stackoverflow) 1974-05-10

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