US3615554A - Retouchable photographic films for duplicating - Google Patents

Retouchable photographic films for duplicating Download PDF

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Publication number
US3615554A
US3615554A US21500A US3615554DA US3615554A US 3615554 A US3615554 A US 3615554A US 21500 A US21500 A US 21500A US 3615554D A US3615554D A US 3615554DA US 3615554 A US3615554 A US 3615554A
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United States
Prior art keywords
film
parts
swelling agent
photographic film
mat layer
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
US21500A
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English (en)
Inventor
Haruo Takenaka
Teppei Ikeda
Toshiaki Okiyama
Sueo Miyazaki
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
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Filing date
Publication date
Priority claimed from JP4174565A external-priority patent/JPS4939414B1/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3615554A publication Critical patent/US3615554A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
    • 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
    • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
    • 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
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/93—Macromolecular substances therefor
    • 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
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y10S430/109—Polyester
    • 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
    • Y10S430/153—Multiple image producing on single receiver

Definitions

  • a retouchable photographic film for duplicating comprising a polyethylene terephthalate film, a mat layer strongly adhered to one orboth surfaces of the polyester film, an undercoat formed by applying a gelatin-containing disper sion liquor onto the surface of a mat layer, and an emulsion layer containing a photosensitive silver salt'or salts formed on the undercoat, said film being characterized by the use, in the formation thereof, of a swelling agent for the polyester film.
  • FIG. 1 3& 4 44 4 444 44444 4 44 2 o o o o c a FIG. 1
  • the present invention relates to a retouchable photographic film for duplicating comprising a polyethylene terephthalate film which is biaxially oriented and crystallized, hereinafter simply referred to as a polyester film, a mat layer (s) strongly adhered to one or both surfaces of the polyester film, and an emulsion layer containing photosensitive silver salts and being applied to the surface area of one aforementioned mat, whereby an image printed on the photographic film can easily be erased.
  • a photographic film for duplicating comprising a cellulose acetate film, a polyester film and an emulsion layer containing a photosensitive silver salt or salts, the emulsion layer consisting of a mat surface, has also been proposed.
  • a picture printed on such a photographic film for duplicating can be rubbed out with an eraser, the corresponding portion of the film rubbed cannot be retouched for correction.
  • the retouchable photographic film for duplicating prepared in accordance with the present invention is distinguished from conventional recording film and characterized by the advantages that the image formed on the photosensitive layer can be rubbed out and the corresponding portion of the photographic layer rubbed can be retouched for correction, as well as the faculty by which duplication of an image can be achieved.
  • a photographic film comprising a polyester film having thereon a mat layer and an emulsion coating containing a photosensitive silver salt or salts, such that an image formed thereon can be easily erased and the erased portion of the film can be further retouched for correction.
  • Another object of the present invention is to increase the adhesion of a mat layer to a polyester film by incorporating polyester resin into a binder for the mat layer.
  • Still a further object of the present invention is to improve the preservability of a photosensitive material by employing an emulsion of a photosensitive silver salt or salts and to make the photosensitive material free from discoloring.
  • Another object of the present invention is to increase the adhesion between the emulsion coating layer containing a photosensitive silver salt or salts and the mat layer, by providing an intermediate layer composed of gelatin.
  • a further object of the present invention is to increase adhesion between the mat layer and the intermediate layer composed of gelatin by incorporating cellulose nitrate into a binder contained in the mat layer.
  • the swelling agents are selected from among a particular group of such agents, as more fully defined hereinafter, and result in increased hardness as well as increased adhesion between the layers.
  • FIG. 1 is a cross-sectional view showing a first embodiment of the photographic element of this invention
  • FIG. 2 is a cross-sectional view showing another embodiment of the photographic element of the present invention.
  • FIG. 3 is a cross-sectional view showing still another embodiment of the photographic element of the present invention.
  • Polyethylene terephthalate is employed as a supportinghase member to take advantage of its optical, chemical and physical properties which make it suitable as a base material of a photographic film.
  • a copolymerized ester selected from the group consisting of terephthalic acid and isophthalic acid and glycols, is used together with cellulose nitrate mixed therewith.
  • the use of cellulose nitrate improves the adhesion between an intermediate layer composed of gelatin and the mat layer.
  • the adhesion between the mat layer and the polyester film is so increased that they do not separate from the other, even when the duplicating film is touched with a hard pencil at the time of correction.
  • the thickness of the emulsion layer applied is preferably l-lO microns. If it is too thin, poor image contrast results. If it is too thick, the image is difficult to erase.
  • a diam-containing photosensitive liquid is used as a photosensitive mat material, good preservability cannot result and there is a tendency to discoloration, so that a photosensitive silver salt or salts are employed.
  • FIG. 1 shows a normal state of a photographic film comprising a support 1, a mat layer 2, an undercoat 3, and a light-sensitive silver halide emulsion layer 4.
  • FIG. 2 shows a photographic film of the same construction as in Flg. I with the exception that a mat layer 2 is formed on one side of the support opposite to the side having coating layers 2, 3 and 4.
  • FIG. 3 shows a photographic film of the same construction as in Flg. I with the exception that a mat layer 2 is formed on one side of the support opposite to the side having coating layers 2, 3 and 4.
  • FIG. 2 shows a photographic film as in FIG. 2 with the exception that an undercoat 5 of polyester, an undercoat 3 of gelatin and a matted layer 6 of gelatin are applied thereto in place of the mat layer 2, in the order described, to form seven layers including the support 1,
  • the mat layer of the photographic film for duplication may be prepared in accordancewith the method described below.
  • a condensation polyester of at least one dicarboxylic acid selected from the group consisting of terephthalic acid and isophthalic acid and glycols (designated as condensation polyester hereinafter) is dissolved in an organic solvent such as methylene. chloride, ethylene chloride, and trichloroethylene, and the solution is sufficiently blended in a ball mill together with starch, silica and the like added thereto as a matting agent.
  • the use of starch is favorable since it exhibits a white appearance, is free from muddying, and is apt to become fine particles owing to its high degree of dispersion.
  • Cellulose nitrate of lower viscosity is dissolved in acetone, and to the solution is added an agent for swelling a polyester film and having the composition mentioned hereinafter in order to increase the adhesion against the polyester film, after which is further added ethylene chloride and the like to control viscosity.
  • the resulting solution of suitable viscosity for application is mixed with the original liquid mass, above-mentioned, containing copolyester.
  • acetone is most favorable from the point of the stability of the resulting solution.
  • the stability of the solution deteriorates when a solvent having a higher or a lower boiling point than that of acetone is used.
  • the adhesion between a polyester film and the mat layer becomes poor if an agent for swelling the polyester film is not incorporated.
  • the amount of the swelling agent is preferably 3-8 percent, based on the weight of the total solvents.
  • an agent for swelling the polyester film the following are examples: phenol and derivatives thereof such as resorcin, orthochlorophenol, parachlorophenol and cresol; benzoic acid, salicylic acid, esters of salicylic acid, monochloroacetate, trichloroacetate, tn'fluoroacetate, 2- nitropropanol, benzyl alcohol, benzaldehyde, acetonitrile, acetophenone, benzamide, benzonitrile, methyl nicotinate and the like.
  • the thickness of the mat layer after drying is preferably 3-10 microns, most favorably 5-8 microns.
  • the copolyester alone is used as a binder for the mat layer, the adhesion between the mat layer and an undercoat of getatin is poor, and the mat layer is apt to detach from the undercoat of gelatin at the time when an emulsion layer, containing a photosensitive silver salt or salts, is attached to the undercoat.
  • cellulose nitrate By incorporating cellulose nitrate into the copolyester, the adhesion between the mat layer and the undercoat of gelatin is improved, and no detachment is observed.
  • the amount of cellulose nitrate is preferably 5-20 percent based on the weight of the copolyester, and most favorably 8-16 percent.
  • the cellulose nitrate one having the viscosity of %%z seconds is preferred.
  • laminatet layer is coated with an undercoat of gelatin for improving the adhesiveness between the mat layer and an emulsion layer containing a photosensitive silver salt or salts.
  • EXAMPLE l 100 parts by weight of Videne (commercially available copolymer of the system: isophthalic acid-terephthalic acidethylene glycol, manufactured by Good Year Tire & Rubber Company) is dissolved in 900 parts of ethylene chloride, and the solution is blended together with 20 parts of starch and eight parts of silica in a ball mill for 120 hours, to prepare an original liquid mass.
  • Videne commercially available copolymer of the system: isophthalic acid-terephthalic acidethylene glycol, manufactured by Good Year Tire & Rubber Company
  • the mat layer is coated with a liquid composition comprising one part of gelatin, 27 parts of water, 0.3 parts of acetic acid, 24 parts of methanol and 70 parts of ethylene chloride, to thereby form an undercoat of gelatin thereon.
  • an emulsion containing a photosensitive silver salt or salts (previously matted) is applied onto the mat layer on the polyester film, and a gelatin composition previously matted is applied onto the opposite side, on which no mat layer is attached, of the polyester film.
  • the thicknesses of the former and the latter are 3 microns, respectively.
  • EXAMPLE 2 100 parts of Videne dissolved in 900 parts of ethylene chloride is blended together with 15 parts of starch and l0 parts of silica as a matting agent, in a ball mill for 96 hours, to prepare an original liquid mass.
  • the gelatin composition as in the preceding example is applied, to form an undercoat onto the surface of the mat layer on one side of the polyester film for the purpose of increasing the adhesion of an emulsion layer containing a photosensitive silver salt or salts.
  • An emulsion containing a photosensitive silver salt or salts is then applied onto the surface of the undercoat.
  • the thickness of the emulsion layer after drying is 3 microns.
  • An unnecessary portion of a transferred image printed on the photographic film of the present invention can easily be rubbed off by means of a sand rubber wetted with water, and, if necessary, the original image printed can be corrected by retouching the mat layer disclosed.
  • the mat layer is attached to both surfaces of the polyester film, it is natural that both sides of the photographic film are retouched for correction.
  • compositions -7 In 900 parts of ethylene-chloride are dissolved 100 parts of polyester and this mixture added to a solution of 12 parts of RSI/2 nitrocellulose (manufactured by Dainippon Cellophane Co., Ltd. dissolved in a mixture of 100 parts of acetone and 500 parts of ethylenechloride and thereafter stirred. The resulting solution is then coated on polyester film to provide a dry coating layer of 2p. in thickness.
  • compositions 8-10 Compositions 1 1-28
  • 900 parts of ethylene chloride are dissolved 100 parts of polyester. 20 parts of starch and eight parts of silica as a matting agent are then added and the mixture stirred for 120 hours in a ball mill to produce a mother solution.
  • 100 parts of acetone are dissolved 12 parts of RSI/2 nitrocellulose and this solution added to the mother solution.
  • a mixture of 200 parts of a mixture of swelling agents, as set forth above, and tetrachloroethane (1:1) and 500 parts of ethylene chloride are added to said mother solution and stirred to prepare the compositions of examples 1 1-28, respectively.
  • the solutions thus prepared are then coated so as to provide a dry thickness 0f6 [.L.
  • compositions were tested for hardness and adhesion as follows:
  • ADHESION TESTS Polyester films coated with the above compositions are cut into 15 cm. squares and 11 lines at intervals of 1 cm. in each direction are scribed by razor perpendicularly so as to form grooves through said coated layer thus forming squares in Proportion of Coating Stripped from Film Base Adhesion Value A... none B... less than l/SO C... 1/50 to l/lO D... l/IO to 1/5 E... Over 1/5 Values of A or B represent compositions of practical utility. Compositions having a value of C have utility only in limited applications. Compositions having values of D or E are unsuitable for use.
  • PENCIL l-IARDNESS TESTSv These tests were used to show the hardness of the film obtained.
  • the films are considered useful if they are not scratched by a pencil having a hardness of 9H or above, and of limited usefulness if scratched by a pencil having a hardness of 7H.
  • the following coding system was used to indicate the results obtained.
  • the adhesive strength and hardness of the mat layer varies as follows, depending on the identity of the polyester employed: terephthalic acidethyleneglycol-triethyleneglycol terephthalicacid isophthalic acidethyleneglycol isophthalic acid ethyleneglycol-triethyleneglycol.
  • compositions 29-31 Into 900parts of ethylene chloride are dissolved 100 parts of polyester. 20 parts of starch and 8 parts of silica as a matting agent arethen added and the mixture kneaded for 120 hours in a ball mill to form a mother solution. A mixture of 12 parts of RS 1/2 nitrocellulose, 100 parts of acetone, 200 parts of acetone as a swelling agent andSOO parts of ethylene chloride is added to the mother solution and stirred. The resulting solution is coated on the polyester to obtain a coating having a dry thickness of 6 [.L.
  • compositions 32-34 The procedure for preparing the compositions of examples 8-10 is followed, except that instead of acetone as the solvent for cellulose nitrate, an equivalent amount of methylethyl ketone is used.
  • compositions 35 -46 lnto 900 parts of ethylene chloride are dissolved 100 parts of polyester. 20 parts of starch and eight parts of silica as a matting agent are then added and the mixture kneaded for 120hours in a ball mill to form a mother solution. To 100 parts of methylethyl ketone are dissolved RS l/2 cellulose nitrate. 200 parts of the swelling agent (phenol in (3l)-(33), resorcinol in (34-(36). paraohlorophenol in (37-(39), acetone in (40)-(42) tetrachloroethane (lzl) and 500 parts of ethylene chloride are added to the mixture. After stirring it is coated on polyester film in6p. thick after drying.
  • the swelling agent phenol in (3l)-(33), resorcinol in (34-(36). paraohlorophenol in (37-(39), acetone in (40)-(42) tetrach
  • a photographic film for duplicating comprising a polyethylene terephthalate film which is biaxially oriented and crystallized, a mat layer attached onto one side of the film formed by applying thereto a dispersion solution comprising a binding agent composed of a polyester derived from the condensation reaction of glycols with at least one member selected from the group consisting of terephthalic acid and iso-phthalic acid and of cellulose nitrate, at least one agent for swelling the polyester film and one or more organic solvents therefore, the swelling agent being a member selected from the group consisting of phenol and derivatives thereof from the group resorcin, orthochlorophenol, para-chlorophenol and cresol; benzoic acid, salicylic acid, esters of salicylic acid, monochloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-nitropropanal, benzyl alcohol, benzaldehyde, acetonitrile, acetophenone, benzamide,

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
US21500A 1965-07-13 1970-03-20 Retouchable photographic films for duplicating Expired - Lifetime US3615554A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4174565A JPS4939414B1 (xx) 1965-07-13 1965-07-13
US2150070A 1970-03-20 1970-03-20

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252885A (en) * 1977-03-25 1981-02-24 Bexford Limited Polyester coated films using an aqueous polyester dispersion and photographic layer
US6081288A (en) * 1995-11-09 2000-06-27 Fuji Photo Film Co., Ltd. Thermal recording films and method of thermal image recording using the same
WO2013146355A1 (ja) 2012-03-29 2013-10-03 富士フイルム株式会社 熱線遮蔽材および貼合せ構造体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252885A (en) * 1977-03-25 1981-02-24 Bexford Limited Polyester coated films using an aqueous polyester dispersion and photographic layer
US4304851A (en) * 1977-03-25 1981-12-08 Bexford Limited Polyester sublime layers for photographic layers with polyester bases
US6081288A (en) * 1995-11-09 2000-06-27 Fuji Photo Film Co., Ltd. Thermal recording films and method of thermal image recording using the same
WO2013146355A1 (ja) 2012-03-29 2013-10-03 富士フイルム株式会社 熱線遮蔽材および貼合せ構造体

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