US3816132A - Heat-developable light-sensitive materials - Google Patents

Heat-developable light-sensitive materials Download PDF

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Publication number
US3816132A
US3816132A US00343867A US34386773A US3816132A US 3816132 A US3816132 A US 3816132A US 00343867 A US00343867 A US 00343867A US 34386773 A US34386773 A US 34386773A US 3816132 A US3816132 A US 3816132A
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United States
Prior art keywords
heat
material according
silver salt
developable light
light
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Expired - Lifetime
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US00343867A
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English (en)
Inventor
T Higuchi
Y Takegawa
T Matui
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Oriental Photo Industrial Co Ltd
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Oriental Photo Industrial 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49881—Photothermographic systems, e.g. dry silver characterised by the process or the apparatus

Definitions

  • the present invention relates to a heat-developable light-sensitive material. More particularly, the invention relates to a heat-developable light-sensitive material containing no silver halide, the sensitivity and image densities of which have been highly improved by subjecting the material to a suitable heat pre-treatment.
  • a system comprising an organic silver salt, a reducing agent, a binder and an acidic stabilizer is exposed to the pattern of an image and then heat-developed to obtain only a faint gray image on slight turbid yellow back. It is also described therein that no practically advantageous image density could be obtained even by changing exposure conditions and heat-developing conditrons.
  • a heat-developable lightsensitive material capable of producing an effective image density can be obtained by forming a single layer or multilayers containing a silver salt of long chain fatty acid, an organic reducing agent and an organic carboxylic acid, preferably on a support, and then subjecting the same to a heat pretreatment under proper heating conditions to impart an excellent light sensitivity to said material, which can never be obtained without such heat pre-treatment.
  • the silver salt of long chain fatty acid which is hardly dissociated at ambient temperature may be partially thermally dissociated to release silver ion.
  • the resulted silver ion may form a neutral silver aggregate which is capable of acting as sensitivity speck in the successive exposure step.
  • the dissociated silver ion forms a sensitivity speck according to the above assumed mechanism.
  • the first coating layer comprising a silver salt of long chain fatty acid and an organic carboxylic acid dispersed in a binder material is provided on a support made of such materials as paper, etc. Then, the surface of the layer is treated with a treating solution containing a reducing agent and thereafter dried. However, at this step, the product hardly has any image-forming property. Then, it is subjected to a heat pre-treatment for a proper time at a temperature, at which a part of the silver salt in the system may be dissociated. Thus, an excellent light sensitivity is obtained. The lightsensitive material thus obtained is exposed to the pattern of an image and then heat-developed at a temperature higher than that of the heat pre-treatment. By this treatment, a silver image is formed selectively in the exposed portion by the action of the reducing agent contained therein. As the energy source for the exposure, ultraviolet rays or another radiation energy may be used in addition to visible rays.
  • the light-sensitive material of the present invention hardly has light-sensitivity before the heat pretreatment and, therefore, it may be exposed to ordinary indoor lights for a short time. Further, by adding mercury salts which will be described below as antifoggant, the light-sensitivity prior to the heat pretreatment can be inhibited completely. Namely, no particular light-intercepting means is required at the time of packing, storage or transportation, if the material is passed through a heating roll or subjected to another heat pre-treatment immediately before the material is to be introduced in a successive exposure device.
  • the sensitivity imparted to the material by the heat pre-treatment is not substantially extinguished as time elapses. This property is utterly different from the phenomenon that the sensitivity caused by the electric charge extinguishes as time elapses in electrophotography.
  • the sensitivity is inclined to be gradually extinguished if the material is placed in an atmosphere containing vapor of a solvent which is capable of swelling and dissolving the coated material. Therefore, for preventing the reduction of the sensitivity, it is preferred to avoid the use of atmosphere of a solvent such as trichloroethylene, toluene, acetone and alcohol. On the contrary, for promoting the reduction of sensitivity intentionally, the material may be exposed to the atmosphere of such solvents.
  • silver salts used in the present invention there may be mentioned silver salts of organic acids or silver salts of organic compounds containing imide group or mercapto group. Particularly, those which are hardly deteriorated or darkened at room temperature under indoor light are silver salts of long chainfatty acids such as silver behenate, silver stearate, silver palmitate, silver myristate, silver laurate. silver oleate and silver hydroxystearate. Silver salts of fatty acids having 18 24 carbon atoms arepreferable.
  • aromatic compounds substituted with hydroxyl group- Particularly effective compounds are hydroquinone, methylhydroquinone, chlorohydroquinone, bromohydroquinone, catechol, pyrogallol, methylhydroxynaphthalene, aminophenol, 2,2- methylene-bis(6-tert.-butyl-4-methylphenol), 4,4- butylidene-bis(6-tert.-butyl-3-methylphenol),4,4- thiobis-(6-tert.-butyl-2-methylphenol), etc.
  • amino compounds such as N,N"-diethyl-pphenylenediamine and N-phenyl-N"-isopropyl-pphenylenediamine are also effective.
  • bisnaphthol reducing compounds described in U.S; Pat. No. 3,672,904 (French Patent No. 2,090,923; Belgian Patent No. 766,589) are also effective. Those compounds may be used singly or in combination.
  • Suitable organic carboxylic acids used in the present invention are aliphatic monocarboxylic acids, aliphatic unsaturated monocarboxylic acids, dicarboxylicacids and aromatic carboxylic acids.
  • capric acid lauric'acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, linolic acid, oleic acid, succinic acid, adipic acid, sebacic acid, benzoic acid, cinnamic acid, salicyclic acid, 'p-hydroxybenzoic acid, 2,6- dihydroxybenzoic acid, phthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, diphenic acid, 5,5 -methylene-bis-salicyclic acid, tetrachlorobenzoic acid and-tetrabromobenzoic acid.
  • long chain fatty acids having 18 to 24 carbon
  • Optimum temperature range and heating time of the heat pre-treatment which is one of characteristic fea tures of the present invention depend on the kinds of silver salt of long chain fatty acid, organic reducing agent and organic carboxylic acid used.
  • this heat pre-treatment it is desirable that as much as the amount of heat should be supplied to the material within the limit of substantially causing no fog on the material, that is, the change in optical density of the surface of the material during the heat-pre-treatment being less than 0.].
  • the heat treatment can be carried out at a temperature of 50 200C.
  • the heat pretreatment should be effected at 70 120C for a short period of time. For example, when a system comprising a combination of silver behenate,
  • heatingroll heating plate or hot air at the time of drying or at a suitable time after the drying but before the exposure.
  • the light-sensitive material of the present invention may be added with a toning agent, anantifoggant etc., depending upon the kinds of silver salt or reducing agent used.
  • a toning agent anantifoggant etc.
  • phthalazinone and derivates thereof described astoning agents for heat sensitive reproducing paper containing a silver salt of long chain fatty acid in US. Pat. No..3,080,254 are effective toning agents.
  • cyclic imides disclosed in U.S. Pat. No. 3,672,904 . are also effective toning agents.
  • Mercury salts described in US. Pat. No. 3,589,903 are effective as antifoggant, storage stabilizer and toning agent.
  • White pigments such as zinc oxide, titanium dioxide, etc. have effects of improving whiteness of the back (non-image part) and also of improving image density and apparent sensitivity.
  • the light-sensitive material of the present invention can be sensitized by incorporating therein a spectral sensitizing dye selected from the class consisting of cyanines, merocyanines oxonols and acridines. Though it is said that Acridine Yellow have nosensitizing effect to silver halides, it can also be used in the present invention.
  • a binder may be preferably incorporated in the lightsensitive material of the present invention.
  • binders there may be metioned polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, polyvinyl pyrrolidone, ethylcellulose, cellulose acetate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol and. gelatin.
  • a support or a base there is preferably used'a support or a base. Any material which is stable against heating may be used.
  • Suitable supports or bases are films of synthetic resins such as polyethylene terephthalate, poly- 1 carbonate and cellulose acetate; foils of metals such as 2,2-methylene-bis(6-tert.-butyl-4-methylphenol) and behenic acid is employed as in Example 3 which will be given below,-it is preferred to carry out the heat treatment at 80C for 5 3.0 seconds or at 100C for l a 5 seconds. Heating for a longer period of time is undesirable, since it causes fog.
  • a preferred heat pre-treatment comprises heating the surface of a support which was coated with a dispersion of a silver salt of long chain fatty acid and an organic carboxylic acid in a suitable binder and treated with a solution of a reducing agent in a suitable solvent,
  • Optimum ratio of the components of the present invention depends upon the kinds of silver salt of long chain fatty acid, reducing agent and organic carboxylic acid used. In general, it is proper to use 10 0.01 part by weight of an organic reducing agent and 10 0.01 part by weight of an organic carboxylic acid per 1 part by weight of a silver salt of long chain fatty acid. Preferably, l l/10 mole of an organic reducing agent and 10 l/l0 mole of an organic carboxylic acid are used per mole of a silver salt of long chain fatty acid.
  • Example 1 Silver behenate 17 g -Continued Behenic acid 13 g Polyvinyl butyral 40 g Heat pre- Density Tolu 350 l Sample treatment Sensitivity Dm Df Dm-Df Ethanol 350 ml 5 N0. temperature l 0.08 0.08 Then, the second coating solution containing a re- 2g 8-32 8-82 8 ducing agent of the following composition was applied 4 s0 7 liOO 0:08 0:92 by using a roll coater and dried at a temperature below 10 5 H 50C. Amount of the coating was 1.0 g per m of the base after drying.
  • Example 2 Coating compositions were prepared in the same manner as in Example 1, except using an equimolar amount of sebacic acid in place of behenic acid and 23 g of N-phenyl-N-isoprop yl-p-phenylene-diamine in place of hydroquinone reducing agent in the second coating liquid. These coating compositions were applied to the same base paper in the same manner as in Example 1. After heat pre-treatment, exposure and heat development in the same manner as in Example 1, a dark brown positive image was obtained. Suitable heating conditions of the heat pre-treatment and heat development in this case were 80C for 5 seconds and and 100C for 5 seconds, respectively.
  • EXAMPLE 3' A heat developable light-sensitive material was prepared in the same manner as in Example 1, except that the second coating solution of the following composition was used. The amount of the coating was 2.5 g per m of the base after drying.
  • EXAMPLE 4 The first coating dispersion and the second coating solution of the following compositions were applied to a photographic base paper in this order and then dried.
  • EXAMPLE 5 The first coating dispersion and the second coating solution of the following compositions were applied to a photographic base paper in this order and then dried.
  • Example l 100 Parts of the first coating dispersion used in Example l were prepared. The following components were added and dissolved thereto successively, immediately before the application.
  • the thus resulting coating solution was applied to a photographic base paper and dried. After heat pretreatment, exposure and heat development in the same manner as in the preceding example, a black positive image could be obtained.
  • a heat-developable light-sensitive material comprising a silver salt of long chain fatty acid, an organic reducing agent and an organic carboxylic acid, to which a heat-pretreatment was effected so as to impart to the material an image-forming ability by activation.
  • a heat-developable light-sensitive material according to claim 1 in which said heat-pretreatment was effected at a temperature of 50 to 200C.
  • a heat-developable light-sensitive material according to claim 1, in which aspectral sensitizing dye selected from the class consisting of cyanines, merocyanines, oxonols and acridines is incorporated in the material.
  • a process for the preparation of heatdevelopable light-sensitive materials which comprises the steps of providing a first coating layer comprising a dispersion of a silver salt of long chain fatty acid and an organic carboxylic acid on a support, then treating the surface of the layer with a solution containing an organic reducing agent, drying the same and subjecting it to a heat pretreatment at a temperature of 50 200C in order to dissociate a part of the silver salt.
  • a process for forming an image which comprises the steps of applying a radiation energy to the material according to claim 1 in a pattern of the image for exposure and then heat-developing the same.
  • a reproducing material comprising a silver salt of long chain fatty acid, an organic reducing agent and an organic carboxylic acid which is light inactive before it is subjected to heat-pretreatment.
  • a process for imparting light-sensitivity in which the material according to claim-l4 is subjected to heat- 9 10 pretreatment to convert the material to a light-sensitive according to claim 14 in a pattern of the image, exposone. ing the whole surface to radiation energy and then 16.
  • a process for forming an image which comprises heat-developing the same. the steps of applying a thermal energy to the material

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  • 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)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00343867A 1972-03-27 1973-03-22 Heat-developable light-sensitive materials Expired - Lifetime US3816132A (en)

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JP47030568A JPS5129819B2 (US08124317-20120228-C00026.png) 1972-03-27 1972-03-27

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JP (1) JPS5129819B2 (US08124317-20120228-C00026.png)
BE (1) BE797364A (US08124317-20120228-C00026.png)
FR (1) FR2177962B1 (US08124317-20120228-C00026.png)
GB (1) GB1420868A (US08124317-20120228-C00026.png)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985565A (en) * 1974-07-12 1976-10-12 Eastman Kodak Company Photothermographic, composition using a phenolic leuco dye as a reducing agent
US4030931A (en) * 1974-05-17 1977-06-21 Fuji Photo Film Co., Ltd. Heat developable light-sensitive material
US4038083A (en) * 1972-04-27 1977-07-26 Agfa-Gevaert N.V. Photothermographic recording sheet
US4039334A (en) * 1974-11-15 1977-08-02 Fuji Photo Film Co., Ltd. Thermally developable light-sensitive material
US4113496A (en) * 1975-12-16 1978-09-12 Asahi Kasei Kogyo Kabushiki Kaisha Dry image forming material
DE2931920A1 (de) * 1978-08-11 1980-02-21 Asahi Chemical Ind Bilderzeugungsverfahren und vorrichtung hierfuer
US4327176A (en) * 1979-11-09 1982-04-27 Asahi Kasei Kogyo Kabushiki Kaisha Dry image forming material
US4332889A (en) * 1980-05-23 1982-06-01 Asahi Kasei Kogyo Kabushiki Kaisha Post-activation type dry image forming material
US4820617A (en) * 1986-04-28 1989-04-11 Oriental Photo Industrial Co., Ltd. Heat-developable photosensitive material
US4857439A (en) * 1988-04-04 1989-08-15 Eastman Kodak Company Photothermographic element and process
US4893148A (en) * 1986-09-04 1990-01-09 Asahi Kasei Kogyo Kabushiki Kaisha Method for storing dry silver salt roll film for rotary type microphotography and rotary type microphotography camera system
US5968714A (en) * 1996-03-14 1999-10-19 Agfa-Gevaert Sensitivity-increasing recording process for a photosensitive thermally developable photographic material

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5151933A (ja) * 1974-11-01 1976-05-07 Fuji Photo Film Co Ltd Netsugenzokankozairyo
JPS52169067U (US08124317-20120228-C00026.png) * 1976-06-15 1977-12-22
JPS5327027A (en) * 1976-08-26 1978-03-13 Asahi Chemical Ind Dry picture forming method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3764329A (en) * 1972-01-17 1973-10-09 Minnesota Mining & Mfg Heat activated dry silver

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2700610A (en) * 1952-11-04 1955-01-25 Suchow Lawrence Photothermographic composition
NL273128A (US08124317-20120228-C00026.png) * 1961-01-03
FR1411286A (fr) * 1963-08-26 1965-09-17 Minnesota Mining & Mfg Feuille de copie
US3667958A (en) * 1970-04-09 1972-06-06 Eastman Kodak Co Photosensitive and thermosensitive elements,compositions and processes
DE2020939C3 (de) * 1970-04-29 1978-11-02 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches Aufzeichnungsmaterial

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3764329A (en) * 1972-01-17 1973-10-09 Minnesota Mining & Mfg Heat activated dry silver

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038083A (en) * 1972-04-27 1977-07-26 Agfa-Gevaert N.V. Photothermographic recording sheet
US4030931A (en) * 1974-05-17 1977-06-21 Fuji Photo Film Co., Ltd. Heat developable light-sensitive material
US3985565A (en) * 1974-07-12 1976-10-12 Eastman Kodak Company Photothermographic, composition using a phenolic leuco dye as a reducing agent
US4039334A (en) * 1974-11-15 1977-08-02 Fuji Photo Film Co., Ltd. Thermally developable light-sensitive material
US4113496A (en) * 1975-12-16 1978-09-12 Asahi Kasei Kogyo Kabushiki Kaisha Dry image forming material
US4287295A (en) * 1978-08-11 1981-09-01 Asahi Kasei Kogyo Kabushiki Kaisha Image forming method and apparatus therefor
DE2931920A1 (de) * 1978-08-11 1980-02-21 Asahi Chemical Ind Bilderzeugungsverfahren und vorrichtung hierfuer
US4327176A (en) * 1979-11-09 1982-04-27 Asahi Kasei Kogyo Kabushiki Kaisha Dry image forming material
US4332889A (en) * 1980-05-23 1982-06-01 Asahi Kasei Kogyo Kabushiki Kaisha Post-activation type dry image forming material
US4820617A (en) * 1986-04-28 1989-04-11 Oriental Photo Industrial Co., Ltd. Heat-developable photosensitive material
US4893148A (en) * 1986-09-04 1990-01-09 Asahi Kasei Kogyo Kabushiki Kaisha Method for storing dry silver salt roll film for rotary type microphotography and rotary type microphotography camera system
US4857439A (en) * 1988-04-04 1989-08-15 Eastman Kodak Company Photothermographic element and process
US5968714A (en) * 1996-03-14 1999-10-19 Agfa-Gevaert Sensitivity-increasing recording process for a photosensitive thermally developable photographic material

Also Published As

Publication number Publication date
BE797364A (fr) 1973-07-16
FR2177962A1 (US08124317-20120228-C00026.png) 1973-11-09
GB1420868A (en) 1976-01-14
FR2177962B1 (US08124317-20120228-C00026.png) 1977-02-04
JPS4897523A (US08124317-20120228-C00026.png) 1973-12-12
DE2315233A1 (de) 1973-10-11
JPS5129819B2 (US08124317-20120228-C00026.png) 1976-08-27
DE2315233B2 (de) 1977-05-26

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