US3790376A - Electron beam recording material - Google Patents

Electron beam recording material Download PDF

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Publication number
US3790376A
US3790376A US00177761A US3790376DA US3790376A US 3790376 A US3790376 A US 3790376A US 00177761 A US00177761 A US 00177761A US 3790376D A US3790376D A US 3790376DA US 3790376 A US3790376 A US 3790376A
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United States
Prior art keywords
electron beam
recording material
sensitivity
recording
film
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Expired - Lifetime
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US00177761A
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English (en)
Inventor
M Hashiue
H Yamashita
N Sekikawa
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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
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G03F7/0295—Photolytic halogen compounds
    • 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
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G03C1/732—Leuco dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/143—Electron beam

Definitions

  • ABSTRACT A highly sensitive electron beam recording material is obtained by adding to the system of N-vinylcarbazole and tetrabromornethane in a hydrophilic binder an additive of a leucomethylene blue having the formula CH3 S /CH:1
  • alkyl or alkoxyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
  • the present invention relates to a recording material suitable for directly recording image information by electron beam, that is, a material for recording an electron beam having high sensivity which is easily treated.
  • a recording material having a high sensitivity to the electron beam is required. If the electron beam sensitivity of the recording material is low, defects in the convergence of the electron beam, in the accumulation of electric charge and in the writing-in rate occur. If the electron beam sensitivity of a recording material is low, an electron beam having a high electronic current density is required. When recording an image by a scanning electron beam focused into a small spot on a recording material with an electron beam having a large electric current it is difficult to focus into a microscopic spot and, accordingly, it is not suitable for recording of high density information. If the electronic current density is high, the electric charge of the incident electrons accumulates on the recording material to deteriorate the image quality.
  • Neopan SS a highly light sensitive negative film, made by Fuji Photo Film Co., Ltd.
  • Type ST an electron microscopic film made by Fuji Photo Film Co., Ltd.
  • the latter has a high sensitivity reversely of about 5 times that of the former.
  • Kalvar film made by Kalvar Corp.
  • a diazo sensitive material made by Ricoh Company Ltd.
  • the energy carried by the former is only several electron volts, while the energy carried by the latter can be raised according to the accelerating voltage and, within the usually used region thereof, it is in the range of from several kiloelectron volts to several ten kiloelectron volts.
  • thesearch for a material with a high sensitivity to an electron beam must be made from a standpoint quite different from that for a search for a material with a high photosensitivity.
  • silver halidegelatin photographic emulsion As a recording material for electron beams, silver halidegelatin photographic emulsion has been used widely so far. It is truethat this kind of recording material has high sensitivity to electron beams, but they have such defects that photographic treatment thereof is by a wet process and troublesome.
  • recording materials made of diazo compounds or those of drysilver process and the like used for electron beam recording whose treatments are of dry process and simple. However, these materials have such a defeet as is known widely, that they all have low sensitivity when compared with the recording materials using a silver halide-gelatin photographic emulsion.
  • hydrophilic binder having a filmforming ability means gelatin, polyvinyl alcohol. carboxymethyl cellulose, starch, casein, gum arabic, hydroxyethyl cellulose, polyvinyl pyrrolidone and the like.
  • additive means non-substituted or substituted benzoyl or naphthoyl leucomethylene blue having the following general formula:
  • R represents a phenyl or naphthyl group which may be substituted by a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having I to 4 carbon atoms.
  • a weight ratio of leucomethylene blue to N- vinylcarbazole is l/l00,000 to 1/10, more preferably l/l0.000 to l/l,0O0.
  • the weight ratio of tetrabromomethane to N- vinylcarbazole is l/5O to 50 more preferably l/5 to 5.
  • the weight ratio offilm-forming polymer to the sum of N-vinylcarbazole and tetrabromomethane is H100 to and more preferably, l/lO to 20.
  • a conventional photographic support is used such as baryta paper, resin-coated paper, cellulose acetate film, polyethylene terephthalate film and the like.
  • EXAMPLE 1 4 g. of gelatin was swollen in 1-5 ml of water and dissolved at 40-50 C. 2.5 g, of N-vinylcarbazole were then added and stirred at a high spped using a homogenizer at atem e enas C t al ixenq it perselThereafter, 2.5 g. of tetrabromomethane and 3 mg. of benzoyl leucomethylene blue were added and again in the same way emulsified and dispersed to prepare an emulsion. The resulting emulsion was coated onto baryta paper used for photography with a rod and dried at room temperature ina dark place to prepare a recording material.
  • the recording material thus obtained was placed inside an electron microscope at the position for the sensitive materal.
  • the electron microscope had an accelerating voltage of KV and the material was then irradiated with the electron beam.
  • the term the-position for the sensitive material means the position where the photographic film or the photographic dry plate is placed when usually taking an electron microscopephotograph.
  • the electron beam intensity was changed within the range of from l X 10 ampere/cm to l X l0" amphere/cm
  • the time of exposure was changed within the range of from I to 100 seconds.
  • the recording material was immediately taken out of the electron microscope and exposed to a 300 watt flood lamp through a red filter (which transmits light of wavelength longer than about 600 mu) for 2 seconds at a distance of 40 cm. from the lamp. This recording material was then kept at a temperature of C for about 10 seconds.
  • the characteristic curve of the response of this recording material to the irradiation with the electron beam is given by curve No. 1.
  • the amount of the irradiation by the electron beam in units of coulomb/em isplotted as the abscissa and the visual reflection density as the ordinate.
  • This red safety lamp is a 20 watt tungsten electric lamp covered with Fuji safe light glass No. 2B, which is kept away at a distance of more than 1.5 m. during the operation.
  • EXAMPLE 4 The procedure d e s eribed in Example I was carried out using 3.2 mg. of the additive naphthoyl leucomethylene blue instead of 3 mg. of benzoyl leucomethylene blue to prepare a recording material which was treated in the similar way.
  • COMPARISON EXAMPLE 1 A recording material which consists of N- vinylcarbazole and tetrabromomethane and which uses gelatin as a binder was prepared according to the procedure described in Example 1 without adding the additive benzoyl leucomethylene blue.
  • the recording material was prepared in the following way. 4 g. of gelatin were swollen in 15 ml of water and heated to 40-50 C to dissolve. 2.5 g. of N- vinylcarbazole were then added and stirred at a high speed using a homogenizer at a temperature of 70-72" C to emulsify and disperse. Thereafter, 2.5 g. of tetrabromomethane were added and again in the same way emulsified and dispersed to prepare an emulsion. The resulting emulsion was coated onto baryta paper used for photography with a rod and dried at room temperature in a dark place to prepare the recording material.
  • COMPARISON EXAMPLE 2 The procedure described in Comparison ExampleT was carried out using polyvinyl alchohol (GOHENOL GL-03, made by The Nippon Synthetic Chemical Industry Co., Ltd.) instead of gelatin to prepare a recording material.
  • the response characteristics of there: cording material prepared by Comparison Example 2 with respect to the electron beam are about the same as that of the recording material prepared by Comparison Example 1, but the sensitivity of the former is about ten times that of the latter.
  • COMPARISON EXAMPLE 3 Among recording materialsusing a gelatin photographic emulsion, the characteristic curve of MINI- COPY film (made by Fuji Photo Film Co., Ltd. emulsion number 77534-348-05) in the irradiation with the electron beam is given by curve No. 3 in the FIGURE. For this case only, the visual diffuse transmission density was plotted as the ordinate.
  • the irradiation condition of the electron beam was that the accelerating voltage was 50 KV, the electron beam intensity on the Mctol (Monol) 1.0 g. Anhydrous sodium sulfite 75.0 g. Hydroquinone 9.0 g. Sodium carbonate H O 29.0 g. Potassium bromide 6.0 g.
  • the exposure with ultraviolet light was carried out by using a Uniarc, made by Ushio Denki Co., Ltd. as a source of ultraviolet light by placing the sample at a distance of about 70 cm. from the mercury lamp and exposing it for 10 seconds.
  • the recording material prepared by this invention has the advantages that it has a high sensitivity to an electron beam and that the subsequent treatment thereof is a completely dry process.
  • An electron beam recording material having a high sensitivity to electron beams comprising a support having thereon a layer consisting essentially of a hydrophilic film-forming polymer binder, N-vinylcarbazole, tetrabromomethane and leucomethylene blue having the following formula:
  • R is selected from the group consisting of a phenol group and a naphthyl group wherein each may be substituted by a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon'atoms wherein the weight ratio leucomethylene blue/N-vinylcarbazole varies from l/l000 to l/lO; wherein the weight ratio tetrabromomethane/N-vinylcarbazole varies from l/50 to 50/1 and wherein the weight ratio hydrophilic film-forming polymer binder/sum of N-vinylcarbazole and tetrabromomethane varies from l/lOO to 20/1.
  • hydrophilic film-forming polymer binder is selected from the group consisting of gelatin, polyvinyl alcohol, carboxymethyl cellulose, starch casein, gum arabic, hydroxyethyl cellulose and polyvinyl pyrrolidone.
  • An electron beam recording material as claimed in claim 1 where said support is selected from the group consisting of baryta paper, resin-coated paper, cellulose acetate film and polyethylene terephthalate film.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00177761A 1970-09-03 1971-09-03 Electron beam recording material Expired - Lifetime US3790376A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45077408A JPS495462B1 (enrdf_load_stackoverflow) 1970-09-03 1970-09-03

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US3790376A true US3790376A (en) 1974-02-05

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US (1) US3790376A (enrdf_load_stackoverflow)
JP (1) JPS495462B1 (enrdf_load_stackoverflow)
BE (1) BE772149A (enrdf_load_stackoverflow)
DE (1) DE2144284A1 (enrdf_load_stackoverflow)
GB (1) GB1312746A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923521A (en) * 1973-01-31 1975-12-02 Horizons Inc Ultraviolet holdback of nonsilver photosensitive systems by incorporating therein certain organic additives
US3936307A (en) * 1972-08-03 1976-02-03 Matsushita Electric Industrial Co., Ltd. Light and heat sensitive composition for producing a colored transfer complex image
US4386154A (en) * 1981-03-26 1983-05-31 Minnesota Mining And Manufacturing Company Visible light sensitive, thermally developable imaging systems
US4460677A (en) * 1981-03-26 1984-07-17 Minnesota Mining And Manufacturing Company Visible light sensitive, thermally developable imaging systems
EP0170188A1 (en) * 1984-07-31 1986-02-05 The Hilton - Davis Chemical Company Novel phenothiazines, preparation thereof and use thereof in electrochromic recording systems

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3147117A (en) * 1961-05-26 1964-09-01 Horizons Inc Process of forming print-out images from light sensitive organic amine compositions
US3342604A (en) * 1964-09-28 1967-09-19 Horizons Inc Non-silver photosensitive printout compositions
US3525616A (en) * 1964-12-10 1970-08-25 Kalle Ag Light sensitive combination of a halogen hydrocarbon,a leuco triaryl methane dye and an n-vinylcarbazole
US3560211A (en) * 1967-09-22 1971-02-02 Horizons Research Inc Light sensitive leuco dye systems containing no molecular oxygen therein

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3147117A (en) * 1961-05-26 1964-09-01 Horizons Inc Process of forming print-out images from light sensitive organic amine compositions
US3342604A (en) * 1964-09-28 1967-09-19 Horizons Inc Non-silver photosensitive printout compositions
US3525616A (en) * 1964-12-10 1970-08-25 Kalle Ag Light sensitive combination of a halogen hydrocarbon,a leuco triaryl methane dye and an n-vinylcarbazole
US3560211A (en) * 1967-09-22 1971-02-02 Horizons Research Inc Light sensitive leuco dye systems containing no molecular oxygen therein

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3936307A (en) * 1972-08-03 1976-02-03 Matsushita Electric Industrial Co., Ltd. Light and heat sensitive composition for producing a colored transfer complex image
US3923521A (en) * 1973-01-31 1975-12-02 Horizons Inc Ultraviolet holdback of nonsilver photosensitive systems by incorporating therein certain organic additives
US4386154A (en) * 1981-03-26 1983-05-31 Minnesota Mining And Manufacturing Company Visible light sensitive, thermally developable imaging systems
US4460677A (en) * 1981-03-26 1984-07-17 Minnesota Mining And Manufacturing Company Visible light sensitive, thermally developable imaging systems
EP0170188A1 (en) * 1984-07-31 1986-02-05 The Hilton - Davis Chemical Company Novel phenothiazines, preparation thereof and use thereof in electrochromic recording systems

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Publication number Publication date
DE2144284A1 (de) 1972-03-30
GB1312746A (en) 1973-04-04
BE772149A (fr) 1972-01-17
JPS495462B1 (enrdf_load_stackoverflow) 1974-02-07

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