US3772029A - Light-sensitive imaging materials - Google Patents
Light-sensitive imaging materials Download PDFInfo
- Publication number
- US3772029A US3772029A US00763005A US3772029DA US3772029A US 3772029 A US3772029 A US 3772029A US 00763005 A US00763005 A US 00763005A US 3772029D A US3772029D A US 3772029DA US 3772029 A US3772029 A US 3772029A
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- United States
- Prior art keywords
- light
- compound
- oxidizing agent
- process according
- oxidizing
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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
- G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
Definitions
- the lightsensitive copying papers for silver halide diffusion transfer process are markedly high in sensitivity but are expensive due to complexity in steps for the production thereof, and operations for the development thereof are also complex.
- the diazo copying papers are low in cost but, in developing the papers, a high concentration alkali developer or an ammonia gas strong in irritating odor should undesirably be used. Moreover they are poor in storability since diazo compounds are hydrophilic, in general, and hence are susceptible to temperature variation.
- the electrophotographic copying papers have such drawbacks that the copying step thereof is markedly complex and the machine to be used for the copying thereof is quite expensive. Accordingly, there have been desired copying papers for business which can overcome the above-mentioned drawbacks, and which are high in light sensitivity, simple to use so as to require no particular skill, low in cost and high in quality.
- the present invention comprises .a light-sensitive printing material containing a photo-activator capable of yielding a free radical by action of light, and a normally oxidizable compound which develops a distinct color change upon oxidation, but which loses its colordeveloping ability by action of said free radical. That is, when the light-sensitive printing material in accordance with the present invention is subjected to contact printing by application of light, the free radical released by the photo-activator at portions which have been exposed to light brings about a photochemical reaction corresponding to the degree of exposure, though no substantial change in appearance of the material is observed.
- the free radical reacts with the oxidizable, color-developing compound to produce, in direct proportion to the degree of exposure a form of that compound which is to a greater degree incapable of oxidizing to effect a color change; for example, an undimerized form of compound.
- the oxidizable color-developing compound is left unchanged in inverse proportion to the degree of exposure and remains, in the light-sensitive layer, as a posiposi image, though the image is not clearly visible to the eye. This positive image, when treated with such oxidizing agents develops a distinct color change to form a clear image.
- the photo-activators and oxidizable, colordeveloping compounds employed in the present invention are not particularly complex, as shown below, and are easily obtainable. Furthermore, they are low in cost.
- o-nitro-a,a,a-tribromoacetophenone m-nitro-a,a,a-tribromoacetophenone, p-nitro-a,a,a-tribromoacetophenone, 01,0:,a-tribromacetophenone, a,a,a-m-tetrabromoacetophenone, a,a,a-tribroms-3,4-dichloroacetophenone, a,a,a-p-tetrabromoacetophenone, and a,a,a,a,a,a-hexabromo-p-diacetylbenzene.
- 2-w-bromomethylisoquinoline 4-m,m,m-tribromomethylpyrimidine, 4-phenyl-6-w,unw-tribromomethylpyrimidine, 2-m,w,w-trichloromethyl--nitrobenzothiazole, 1-phenyl-3-w,w,w-trichloromethylpyrazole, w,w,w-tribromolepidine-bromomethylate, a-cu,m-dibromomethyl-4-chloropyridine, l-methyl-2-chloromethylbenzimidazole, and 2,5-di-tribromomethyl-3,4-dibrornothiophene.
- a sample 20 mg. of a sample is dissolved in 2 cc. of water or an organic solvent such as acetone or methanol.
- a filter paper is impregnated with the thus formed solution and is then dried. Subsequently, the paper is dipped in an aqueous solution containing 1-5 percent of potassium ferricyanide. If, in the above case, the filter paper undergoes a change in color, the sample compound may be used in the present invention. However, said compound should further pass the following test: 005g. of the said compound and 0.l5g. of hexabromodimcthyl sulfone are dissolved in 5cc. of an organic solvent such as acetone or methanol.
- the solution is applied to a baryta paper, and is than dried. Subsequently, the paper is exposed to ultraviolet light and is then treated with an oxidizing agent. If, in this case, the difference between exposed portions and unexposed portions is sufficient to form an image, the said compound can be effectively used in the present invention.
- Typical of oxidizable compounds which are useful in the present invention are the compounds shown below. However, compounds usable in the present invention are not limited only to these.
- the light-sensitive material according to the present invention contains, as main components, at least one photo-activator and oxidizable, color-developing compound as mentioned above, and may further be incorporated with color toners, oxidation accelerators, sensitizers and the like.
- the optimum weight ratio of photo-activator to oxidizable, color-developing compound is 3 l, but may be suitably varied depending on the kind of compounds employed.
- Effective as the sensitizers may be any of those which are usable for light-sensitive silver halide photographic materials, such as xanthene dyes, eg erythrosine and eosine, and cyanine dyes (including derivatives).
- the light-sensitive printing materials of the present invention may be prepared by dissolving the compo-' nents mentioned above in water or suitable solvents and applying the solutions onto supports, followed by drying.
- high molecular weight compounds which are soluble in solvents and excellent in filmforming ability, may be used as binders.
- high molecular weight compounds suitable for the above purposes are vinyl acetate-maleic anhydride copolymers, methyl vinyl ether-maleic anhydride copolymers, ethylene-maleic anhydride copolymers, vinyl pyrrolidone, ethylene glycol polymer, and gelatine.
- the solvents for the aforesaid components may be suitably selected taking dangerousness, drying property and workability into consideration.
- Usable as volatile solv vents other than water are alcohols such as methanol,
- ketones such as acetone and methylethylketone
- aromatic hydrocarbons such as benzene, toluene and xylene
- halogenated hydrocarbons such as methylene chloride and trichloroethylene, tetrahydrofuran, dimethylformamide, and cyclohexane.
- Procedures for preparing the light-sensitive printing materials of the present invention are as follows:
- the photoactivator, the oxidizable, color-developing compound and desired additives are dissolved or dispersed in a solution containing the binder component.
- the resulting solution or dispersion is applied onto a support according to such a coating method as dipping, doctor or reverse roll method, followed by drying.
- the above operations may be effected under a yellow safety lamp.
- the components in the form of fine powders may be rubbed in a support, or may be added when using paper supports, during the paper-making process.
- As supports various plastics films, papers and glass plates may be used. Baryta papers and plasticcoated papers are particularly useful and exceptional positive images good in resolution and high in intensity can be obtained with these materials.
- any light source may be effectively used which emits a light having a wave length of about 3,4005,000 A, since the light-sensitive printing material of the present invention is sensitized with a light having a wave length within said range.
- the present lightsensitive material can be printed according to front copying using ultraviolet light, reflex copying using daylight, and enlarge-copying using a tungsten lamp.
- a commercially available diazo copying machine (with a mercury lamp) can be used as it is; in the case of reflex copying,
- an exposing apparatus for diffusion transfer copying paper can be used; and in the case of enlarge copying, a photographic enlarger or a slide projector can be used.
- the light-sensitive printing material bearing the lightformed latent image is then subjected to developing treatment with an oxidizing agent, whereby a distinct color change is obtained and the latent image becomes a permanently visible image.
- an oxidizing agent usable in said developing treatment may be any of those which, in general, quickly bring about oxidation reactions and which do not decolor dyes formed by the oxidation.
- Particularly preferable oxidizing agents are those which have not themselves colored or which are only slightly colored.
- Typical examples of useful oxidizing agents are potassium bichromate, sodium bichromate, ammonium bichromate, chromic anhydride (chromium trioxide), potassium permanganate, potassium ferricyanide, sodium ferricyanide, ferric chloride, potassium chlorate, potassium nitrate, nitric acid, hydrogen peroxide, sodium peroxide, barium peroxide, lead peroxide, lead nitrate, sodium nitrate, sodium chlorate, potassium peroxide, cupric chloride, potassium persulfate, ammonium persulfate, sodium hypochlorite, zinc permanganate, sodium permanganate, barium permanganate, ozone, bromine, chlorine and iodine.
- the said materials are ordinarily treated for about -30 seconds with the oxidizing agents in the form of solutions in water, aqueous alkaline solutions or aqueous acidic solutions, or in the form of gases.
- the concentration of the aqueous oxidizing solution varies depending on the kind of the oxidizing agent, but is preferably from 1 to percent by weight.
- concentration of the aqueous oxidizing solution varies depending on the kind of the oxidizing agent, but is preferably from 1 to percent by weight.
- an aqueous solution containing 1 percent of potassium ferricyanide sufficiently displays oxidizing ability.
- Example 1 In a state shielded from direct light, I g. of 4- methoxy-a-naphthol and 3 g. of tribromomethyl sulfone were dissolved in cc. of methanol. The solution was applied to a photographic baryta paper in an amount of 30 cc. per square meter and was dried at room temperature to obtain a light-sensitive printing material. The thus obtained light-sensitive material was closely contacted with a photographic positive and was exposed for 5 seconds to a tubular 800 w high pressure mercury lamp at a distance of 5 cm. The exposed material was dipped for 10 seconds in a developer prepared by dissolving 5 g.
- Example 2 In a state shielded from direct light, I g. of lmethoxy-4-amino-naphthalenesulfate and 3 g. of hexabromodimethyl sulfone were dissolved in an acetonemethanol l I) mixed solvent. The solution was applied according to an ordinary procedure onto a I50 g. baryta paper in an amount of 30 cc.
- Example 3 In place of the l-methoxy-4-amino-naphthalenesulfate used in Example 2, the equivalent amount of 4- ethoxy-a-naphthol was employed to form a solution. The solution was applied onto a paper, which had been surface-treated with polyvinyl alcohol, to prepare a light-sensitive printing material.
- This light-sensitive material was subjected to the same exposure and developing treatment as in Example 1, whereby a clear image was obtained.
- the light-sensitive material of this example is for the posiposi process, and therefore it gives a negative image when a negative is used as original and forms a positive image when a positive is used as original.
- Example 4 In a state shielded from direct light, 1 g. of 2,4- dibromo-a-naphthol and 3 g. of hexabromodimethyl sulfone were dissolved in 100 cc. of an acetonemethanol (1 z mixed solution containing 2 percent of ethylene glycol polmer resin.
- Example 4 Example 4 was repeated, except that tribromomethylphenyl sulfone was used in place of the hexabromodimethyl sulfone, whereby a clear, deep blue image was obtained.
- Example 6 In a state shielded from direct light, lg. of 4-methoxya-naphthol and 3 g. of hexabromomethyl sulfone were dissolved in 100 cc. of an acetone-methanol (l 1) mixed solution containing 2 percent of vinyl acetatemaleic anhydride copolymer resin. The solution was further charged with 0.5 cc. of a methanol solution containing 2 percent of Acridine Orange. The solution is applied to a 150 g. photographic baryta paper in a proportion of 30 cc. per square meter and was then dried to obtain a light-sensitive printing material. To this light-sensitive material was projected for 1 minute a 35 mm. microfilm, using a 300 w slide projector at a distance of 50 cm, and then the same developing treatment as in Example 1 was effected to obtain a clear, blue, enlarged image.
- l 1 acetone-methanol
- Example 7 Example 1 was repeated, except that indoxyl was used in place of the 4-methoxy-a-naphthol, to prepare a light-sensitive printing material. This light-sensitive material was exposed in the same manner as in Example l and was then developed in an atmosphere of iodine gas, whereby a blue image was obtained.
- An imaging process comprising:
- exposing irnagewise to light material comprising a support and a coating thereon of light-sensitive composition consisting essentially of l an organic a-naphthol; 4-acetamino-a-naphthol; fiihiocyano a-naphthol; and 4-methylthio-a-naphthol; and thereby irnagewise forming said free radical in reactive association with said normally oxidizable compound in said composition, thus irnagewise rendering said compound incapable of normal color-changing oxidation; and
- An imaging process comprising:
- exposing irnagewise to light material comprising a support and a coating thereon of light-sensitive composition consisting essentially of (1) an organic halogen-containing photoactivator capable of forming a free radical by action of light and (2) a compound normally oxidizable to effect a distinct color change therein, said normally oxidizable compound being selected from the group consisting of indoxyl; -bromo-indoxyl; thiaindoxyl; 5- chloro-7-methyl-thiaindoxyl; 4-methyl-6-bromothiaindoxyl; and thereby irnagewise forming said free radical in reactive association with said normally oxidizable compound in said-composition, thus irnagewise rendering said compoundincapable of normal color-changing oxidation; and
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- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
Claims (7)
- 2. The process according to claim 1 wherein said treating step comprises contacting said material with a fluid oxidizing agent.
- 3. The process according to claim 2 wherein said oxidizing agent comprises a solution of an oxidizing compound.
- 4. The process according to claim 2 wherein said oxidizing agent is a gas.
- 5. An imaging process comprising: a. exposing imagewise to light material comprising a support and a coating thereon of light-sensitive composition consisting essentially of (1) an organic halogen-containing photoactivator capable of forming a free radical by action of light and (2) a compound normally oxidizable to effect a distinct color change therein, said normally oxidizable compound being selected from the group consisting of indoxyl; 6-bromo-indoxyl; thiaindoxyl; 5-chloro-7-mEthyl-thiaindoxyl; 4-methyl-6-bromo-thiaindoxyl; and thereby imagewise forming said free radical in reactive association with said normally oxidizable compound in said composition, thus imagewise rendering said compound incapable of normal color-changing oxidation; and b. treating said material thus exposed with an oxidizing agent, whereby said normally oxidizable compound situated in the unexposed portions of said composition, and thus remaining normally oxidizable, is oxidized to yield said distinct color change, thereby providing a visibly distinct image.
- 6. The process according to claim 5 wherein said treating step comprises contacting said material with a fluid oxidizing agent.
- 7. The process according to claim 6 wherein said oxidizing agent comprises a solution of an oxidizing compound.
- 8. The process according to claim 6 wherein said oxidizing agent is a gas.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6211467 | 1967-09-28 |
Publications (1)
Publication Number | Publication Date |
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US3772029A true US3772029A (en) | 1973-11-13 |
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Application Number | Title | Priority Date | Filing Date |
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US00763005A Expired - Lifetime US3772029A (en) | 1967-09-28 | 1968-09-26 | Light-sensitive imaging materials |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4368254A (en) * | 1979-08-20 | 1983-01-11 | Vannikov Anatoly V | Non-silver light-sensitive composition |
US5565287A (en) * | 1991-08-16 | 1996-10-15 | Eastman Kodak Company | Migration imaging with dyes or pigments to effect bleaching |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB957192A (en) * | 1959-10-15 | 1964-05-06 | Agfa Ag | A method and material for the production of photographic images |
US3490907A (en) * | 1964-04-15 | 1970-01-20 | Kalle Ag | Negative working printout reproduction material comprising ferrocene and method of use |
-
1968
- 1968-09-26 US US00763005A patent/US3772029A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB957192A (en) * | 1959-10-15 | 1964-05-06 | Agfa Ag | A method and material for the production of photographic images |
US3490907A (en) * | 1964-04-15 | 1970-01-20 | Kalle Ag | Negative working printout reproduction material comprising ferrocene and method of use |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4368254A (en) * | 1979-08-20 | 1983-01-11 | Vannikov Anatoly V | Non-silver light-sensitive composition |
US5565287A (en) * | 1991-08-16 | 1996-10-15 | Eastman Kodak Company | Migration imaging with dyes or pigments to effect bleaching |
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Legal Events
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AS | Assignment |
Owner name: CHEMICAL BANK, A BANKING INSTITUTION OF, NEW YORK Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING AS Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: CHEMICAL BANK, A BANKING INSTITUTION OF NY. Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIA Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 |