US3779775A - Light-sensitive materials - Google Patents

Light-sensitive materials Download PDF

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Publication number
US3779775A
US3779775A US00092878A US3779775DA US3779775A US 3779775 A US3779775 A US 3779775A US 00092878 A US00092878 A US 00092878A US 3779775D A US3779775D A US 3779775DA US 3779775 A US3779775 A US 3779775A
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US
United States
Prior art keywords
light
mixtures
sensitive
cellulose
sensitive material
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
US00092878A
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English (en)
Inventor
T Chiba
T Yonezawa
J Kobayashi
G Akashi
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.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
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 Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3779775A publication Critical patent/US3779775A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • 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
    • Y10S430/163—Radiation-chromic compound

Definitions

  • ABSTRACT 'substance and a binder present in the pores of said layer is disclosed.
  • the present invention relates to a light-sensitive material. More particularly, the present invention relates to a light-sensitive material which is simple to make low in production costs and is high in resolving power, and which is abrasion-proof, water-proof, chemically resistant and weather-proof.
  • the present invention comprises a light-sensitive material in which the production cost is low, in which the resolving power is excellent and which is water-proof, abrasion-proof, chemically resistant and weatherproof.
  • the light-sensitive material is obtained by forming firstly a porous plastic layer and then forming or filling a light-sensitive substance such as silver halide in the pores of the plastic layer.
  • lightsensitive substances such as light-sensitive silverhalides, diazo light-sensitive substances, ferrous ammonium citrate-red prussiate light-sensitive substances, organic halides such as carbon tetrabromide or its derivative, diphenylamine or its derivative light-sensitive substances, quinone diazide derivatives, leuco compunds-organic halogen generating agent lightsensitive substances, photochromic dyes, compounds which change color with pH and are capable of being transformed into an acid or base by radiation of light, and the like, are filled into plastic layers having a number of pores of from 0.1 to several microns in diameter.
  • the light-sensitive substance is silver halide
  • the silver grains are formed in the pores after exposure and development.
  • the light-sensitive material of the invention is better from an abrasion-proof and water-proof standpoint in comparison with prior art light-sensitive materials.
  • the abrasion-proof characteristics can further be raised, if desired, by treating the material with a solvent thus to close the pores.
  • phase-separation process as shown in the following Examples as well as a known process employing the foaming action of foaming agents and high pressure gases as in the production of foamed styrols or ure thane foam rubbers can be used, but the former is more suitable for obtaining fine pores.
  • any supporting material such as paper, plastics, metals, glass and synthetic papers can be used.
  • Suitable silver halides which can be used are silver chloride, silver bromide, silver iodobromide and the like, depending on the end use.
  • One feature of the invention is the formation of silver halide in the presence of the binder such as organic hydro colloid, for example, gelatin, gum arabic, polyvinyl alcohol, methyl cellulose, ethyl cellulose and the like in the pores of plastics.
  • the binder such as organic hydro colloid, for example, gelatin, gum arabic, polyvinyl alcohol, methyl cellulose, ethyl cellulose and the like in the pores of plastics.
  • Another feature of the invention comprises treating the surface of the light-sensitive material with a solvent for the plastics, after development thereby closing the pores and resulting in stable water-proof, chemically resistant weather-proof developed image.
  • a solvent for the plastics methylene chloride or ethyl acetate is suitable particularly in the TAC-DAC system of Example l, hereinafter set forth.
  • vinyl chloride type resins are used as the plastic layer, a solvent such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and butyl acetate is suitable.
  • Plastic materials suitable for forming the pores are as follows:
  • TAC/cellulose acetate Butyrate i. Triacety] cellulose (TAC)/ diacetyl cellulose (DAC) 95:5-5:95 :25-25:75 ii. TAC/nitrocellulose (NC) do. Do. iii. NC/DAC do. Do. iv. PVC-AC/PVC-AC1vinylchloride-vinyl acetate copolymers (PVC-AC) differing in mixing composition: 92:8-821l8 50:50-75:25 by weight] :10-10:90 75:25-25:75 v. TAC/cellulose propionate do. Do. vi. TAC/cellulose acetate Butyrate do. Do. vii.
  • Styrol do.
  • Do. viii Polyurethane rubber do.
  • Do. ix. Polyvinyl alcohol alone do.
  • TAC and DAC in a weight ratio of 3:2 were dissolved in a mixed solvent of methylene chloride/methanol to give a concentration of 5 percent by weight.
  • water corresponding to 7 percent by weight of the solution was added to the resulting solution and, directly before phase-separation, coated onto a water-proof paper of l 10 p. in thickness to give a thickness of 10p. on a dry basis followed by drying.
  • the thus-obtained coating was a TAC-DAC layer having pores of about 0.3a.
  • Solution A Aqueous Solution of 3 percent Silver Nitrate and 0.l percent gelatin Solution
  • B Aqueous Solution of 30 percent Potassium Bromide Solution
  • C Aqueous Solution of 20 percent Potassium Bromide and 2 percent Potassium Bichromate
  • the above-described solutions were prepared and coated in the order of Solution A Solution B Solution C using a reverse roll type coating machine. During the coating, application of ultrasonic waves promoted the permeation of the solution in the pores. Silver bromide was formed in the form of fine grains in the pores of the foregoing porous plastic layer by the reaction of Solution A with Solutions B and C. A sheet having light sensitive characteristics was obtained.
  • EXAMPLE 2 The same procedure as described in Example 1 was repeated except that TAC and DAC in a weight ratio of 1:1 were dissolved in a mixed solvent of methylene chloride/methanol to give a concentration of 4.5 percent by weight. A light-scnsitive material was obtained.
  • EXAMPLE 3 NC and DAC in weight ratio of 1:1 were dissolved in a mixed solvent of methylene chloride/methanol/isopropanol to give a concentration of 3 percent by weight and mixed with vigorous agitation with water corresponding to 6.5 percent by weight of the total of the solution.
  • NC-DAC layer had pores ranging from 0.6 to 1.8; ⁇ . as determined using an electron microscope of the scanning type.
  • Solution D Aqueous Solution of 45 percent AgNO 0.8 percent Gum Arabic Solution
  • E Aqueous Solution of 2 percent KBr, 1
  • EXAMPLE 4 To the porous plastic layer obtained by the method of Example 3 was applied a light-sensitive solution of the ferrous ammonium citrate-red prussiate type for blue print under action of ultrasonic waves and dried to obtain a light-sensitive material.
  • the light-sensitive material of the invention is a completely novel light'sensitve material.
  • a water-proof, abrasion-proof, weather-proof and chemically-resistant light-sensitive material having excellent resolving power consisting essentially of a support having coated thereon a fine porous plastic layer containing a light-sensitive substance and a binder therefor distributed in the fine pores of said layer, said fine pores having a diameter of from 0.1 to 1.8 microns, said porous plastic layer being formed by a process which consists essentially of:
  • plastic materials which differ in their affinity for water in a solvent therefor to form a solution
  • said plastic materials are selected from the group consisting of triacetyl cellulose/diacetyl cellulose mixtures, triacetyl cellulose/nitrocellulose mixtures, nitrocellulose/diacetyl cellulose mixtures, vinyl chloride-vinyl acetate copolymer/vinyl chloride-vinyl acetate copolymer mixtures differing in the vinyl-chloride-vinyl acetate weight ratios, triacetyl cellulose/cellulose propionate mixtures and triacetyl cellulose/cellulose acetate butyrate mixtures,
  • a water-proof, abrasion-proof, weather-proof and chemically-resistant light-sensitive material having excellent resolving power consisting essentially of a support having coated thereon a fine porous plastic layer containing a non-silver salt light-sensitive substance and a binder therefor distributed in the fine pores of said layer, said fine pores having a diameter of from 0.1 to 1.8 microns, said porous plastic layer being formed by a process which consists essentially of:
  • plastic materials which differ in their affinity for water in a solvent therefor to form a solution
  • said plastic materials are selected from the group consisting of triacetyl cellulose/diacetyl cellulose mixtures, triacetyl cellulose/nitrocellulose mixtures, nitrocellulose/diacetyl cellulose mixtures, vinyl chloride-vinyl acetate copolymer/vinyl chloride-vinyl acetate copolymer mixtures differing in the vinyl chloride-vinyl acetate weight ratios, triacetyl cellulose/cellulose proprionate mixtures and triacetyl cellulose/cellulose acetate butyrate mixtures,
  • a water-proof, abrasion-proof, weather-proof and chemically-resistant light-sensitive material having excellent resolving power consisting essentially of a support having coated thereon a fine porous plastic layer consisting essentially of a light-sensitive substance and a binder therefor distributed throughout the fine pores of a plastic material selected from the group consisting of triacetyl cellulose/diacetyl/cellulose mixtures, triacetyl cellulose/nitrocellulose mixtures, nitrocellulose/- diacetyl cellulose mixtures, polyvinyl chloride/vinyl aeetate copolymer mixtures, triacetyl cellulose/cellulose propionate mixtures and triacetyl cellulose/cellulose acetate butyrate mixtures, the pores of said plastic layer having a diameter of from 0.3 to 1.8 microns, said porous plastic layer being formed by a process which consists essentially of:
  • the components of the first three of the recited mixtures being present in weight ratios of from 95/5 to 5/95, the components of the last three mixtures being present in weight ratios of from 90/10 to l0/90,
  • the light-sensitive substance is selected from the group consisting of a light-sensitive silver halide, a diazo light-sensitive substance, at light-sensitive substance comprising an organic halide and diphenyl amine or its derivative, a quinone diazide derivative, a leuco compound organic halogen generating lightsensitive substance, a photochromic dye and a compound changing color with a pH change and capable of being transformed into an acid or base on radiation of light.
  • non-silver salt light-sensitive substance is a ferrous ammonium citrate-red prussiate compound.
  • binder is an organic hydrocolloid

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
US00092878A 1969-11-26 1970-11-25 Light-sensitive materials Expired - Lifetime US3779775A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44094928A JPS4925896B1 (enrdf_load_stackoverflow) 1969-11-26 1969-11-26

Publications (1)

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US3779775A true US3779775A (en) 1973-12-18

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Family Applications (1)

Application Number Title Priority Date Filing Date
US00092878A Expired - Lifetime US3779775A (en) 1969-11-26 1970-11-25 Light-sensitive materials

Country Status (5)

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US (1) US3779775A (enrdf_load_stackoverflow)
JP (1) JPS4925896B1 (enrdf_load_stackoverflow)
CA (1) CA952757A (enrdf_load_stackoverflow)
DE (1) DE2058243A1 (enrdf_load_stackoverflow)
GB (1) GB1320937A (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049846A (en) * 1976-06-11 1977-09-20 American Optical Corporation Photochromic plastic materials
US4187111A (en) * 1977-05-31 1980-02-05 Bell Telephone Laboratories, Incorporated Sensitized porous bodies useful for producing thick refractive index recordings
WO1980001614A1 (en) * 1979-02-02 1980-08-07 Eastman Kodak Co Imaging elements containing microvessels and processes for forming images therewith
US4366235A (en) * 1981-02-17 1982-12-28 Polaroid Corporation Photosensitive element and method of preparing same
US4374190A (en) * 1978-09-28 1983-02-15 Am International, Inc. Erasable intermediate diazo-type paper
US4375507A (en) * 1980-09-08 1983-03-01 Eastman Kodak Company Imaging with nonplanar support multicolor filter elements
US4387154A (en) * 1980-09-08 1983-06-07 Eastman Kodak Company Receivers with nonplanar support elements
US4387146A (en) * 1980-09-08 1983-06-07 Eastman Kodak Company Multicolor filters with nonplanar support elements

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US53815A (en) * 1866-04-10 Process and composltions-for printing photographic pictures
US235831A (en) * 1880-12-21 Hermann w
US705643A (en) * 1901-11-26 1902-07-29 Otto Buss Casein photographic film and process of making same.
US1599147A (en) * 1923-09-04 1926-09-07 Schmidt Henry Duplex blue-print paper
US2017853A (en) * 1932-05-27 1935-10-22 Oxford Varnish Corp Method of patterning artificial leather or oil cloth and similar band-forming fibrous material
US2305169A (en) * 1937-03-16 1942-12-15 Lierg Friedrich Process of producing sensitive silver halide-colloidal aggregates
US2699392A (en) * 1951-12-12 1955-01-11 Gen Aniline & Film Corp Vesicular prints and process of making same
US2893867A (en) * 1955-11-07 1959-07-07 Ici Ltd Compositions for use in the manufacture of light-sensitive photographic materials
US2939009A (en) * 1956-02-01 1960-05-31 Jack M Tien Thermotransfer duplicating process
US3061453A (en) * 1959-08-03 1962-10-30 Polaroid Corp Process for incorporating photographic reagents in a photographic element using a common solvent and a preferential solvent
US3072481A (en) * 1957-09-17 1963-01-08 Ncr Co Light sensitive element and process for recording images thereon
US3214274A (en) * 1960-10-19 1965-10-26 Mitsubishi Paper Mills Ltd Manufacture of photographic materials
US3216882A (en) * 1960-12-05 1965-11-09 Nalco Chemical Co Porous plastic film
US3235381A (en) * 1962-10-25 1966-02-15 Union Carbide Corp Three-dimensional photograph and light sensitive element for preparing same
US3264134A (en) * 1964-04-13 1966-08-02 Grace W R & Co Polyurethane latex containing a water soluble alcohol
US3272629A (en) * 1962-01-25 1966-09-13 Nashua Corp Photosensitive diazotype materials
US3421932A (en) * 1965-12-16 1969-01-14 Mobay Chemical Corp Method and apparatus for preparing cellular polyurethane plastics
US3661589A (en) * 1970-02-18 1972-05-09 Norman T Notley Interfacial vesicular print materials and methods of preparation

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US53815A (en) * 1866-04-10 Process and composltions-for printing photographic pictures
US235831A (en) * 1880-12-21 Hermann w
US705643A (en) * 1901-11-26 1902-07-29 Otto Buss Casein photographic film and process of making same.
US1599147A (en) * 1923-09-04 1926-09-07 Schmidt Henry Duplex blue-print paper
US2017853A (en) * 1932-05-27 1935-10-22 Oxford Varnish Corp Method of patterning artificial leather or oil cloth and similar band-forming fibrous material
US2305169A (en) * 1937-03-16 1942-12-15 Lierg Friedrich Process of producing sensitive silver halide-colloidal aggregates
US2699392A (en) * 1951-12-12 1955-01-11 Gen Aniline & Film Corp Vesicular prints and process of making same
US2893867A (en) * 1955-11-07 1959-07-07 Ici Ltd Compositions for use in the manufacture of light-sensitive photographic materials
US2939009A (en) * 1956-02-01 1960-05-31 Jack M Tien Thermotransfer duplicating process
US3072481A (en) * 1957-09-17 1963-01-08 Ncr Co Light sensitive element and process for recording images thereon
US3061453A (en) * 1959-08-03 1962-10-30 Polaroid Corp Process for incorporating photographic reagents in a photographic element using a common solvent and a preferential solvent
US3214274A (en) * 1960-10-19 1965-10-26 Mitsubishi Paper Mills Ltd Manufacture of photographic materials
US3216882A (en) * 1960-12-05 1965-11-09 Nalco Chemical Co Porous plastic film
US3272629A (en) * 1962-01-25 1966-09-13 Nashua Corp Photosensitive diazotype materials
US3235381A (en) * 1962-10-25 1966-02-15 Union Carbide Corp Three-dimensional photograph and light sensitive element for preparing same
US3264134A (en) * 1964-04-13 1966-08-02 Grace W R & Co Polyurethane latex containing a water soluble alcohol
US3421932A (en) * 1965-12-16 1969-01-14 Mobay Chemical Corp Method and apparatus for preparing cellular polyurethane plastics
US3661589A (en) * 1970-02-18 1972-05-09 Norman T Notley Interfacial vesicular print materials and methods of preparation

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049846A (en) * 1976-06-11 1977-09-20 American Optical Corporation Photochromic plastic materials
US4110244A (en) * 1976-06-11 1978-08-29 American Optical Corporation Photochromic plastic material
US4187111A (en) * 1977-05-31 1980-02-05 Bell Telephone Laboratories, Incorporated Sensitized porous bodies useful for producing thick refractive index recordings
US4374190A (en) * 1978-09-28 1983-02-15 Am International, Inc. Erasable intermediate diazo-type paper
WO1980001614A1 (en) * 1979-02-02 1980-08-07 Eastman Kodak Co Imaging elements containing microvessels and processes for forming images therewith
EP0014572A3 (en) * 1979-02-02 1981-05-13 Eastman Kodak Company Imaging elements containing microvessels and processes for forming images therewith
US4362806A (en) * 1979-02-02 1982-12-07 Eastman Kodak Company Imaging with nonplanar support elements
US4375507A (en) * 1980-09-08 1983-03-01 Eastman Kodak Company Imaging with nonplanar support multicolor filter elements
US4387154A (en) * 1980-09-08 1983-06-07 Eastman Kodak Company Receivers with nonplanar support elements
US4387146A (en) * 1980-09-08 1983-06-07 Eastman Kodak Company Multicolor filters with nonplanar support elements
US4366235A (en) * 1981-02-17 1982-12-28 Polaroid Corporation Photosensitive element and method of preparing same

Also Published As

Publication number Publication date
CA952757A (en) 1974-08-13
DE2058243A1 (de) 1971-06-09
GB1320937A (en) 1973-06-20
JPS4925896B1 (enrdf_load_stackoverflow) 1974-07-04

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