Source: http://www.google.es/patents/US4753862?dq=flatulence
Timestamp: 2013-05-24 10:55:58
Document Index: 669599690

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60']

Patente US4753862 - Light-sensitive material containing silver halide, reducing agent ... - Google PatentesB�squeda Im�genes Maps Play YouTube Noticias Gmail Drive M�s » B�squeda avanzada de patentes | Historial web | Iniciar sesi�n B�squeda avanzada de patentesPatentesA light-sensitive material comprising a light-sensitive layer which contains silver halide, a reducing agent and a polymerizable compound provided on a support, characterized in that the light-sensitive layer further contains a triazenesilver having the following formula: ##STR1## in which Ar is an aryl...http://www.google.es/patents/US4753862?utm_source=gb-gplus-sharePatente US4753862 - Light-sensitive material containing silver halide, reducing agent, polymerizable compound and triazenesilver N�mero de publicaci�nUS4753862 ATipo de publicaci�nConcesi�n N�mero de solicitud07/018,370 Fecha de publicaci�n28 Jun 1988 Fecha de presentaci�n24 Feb 1987 Fecha de prioridad24 Feb 1986 InventoresKozo SatoSoichiro Yamamoto Cesionario originalFuji Photo Film Co., Ltd. Clasificaci�n de EE.UU.430/138430/254430/920430/353430/619430/919430/203430/281.1430/253 Clasificaci�n internacionalG03F7/004G03F7/028G03C1/498 Clasificaci�n cooperativaG03C1/49809G03F7/0285 Clasificaci�n europeaG03F 7/028BG03C 1/498BReferenciasCitas de patentes (2)Otras citas (2) Citada por (8)Enlaces externosUSPTO Cesi�n de USPTO EspacenetLight-sensitive material containing silver halide, reducing agent, polymerizable compound and triazenesilverUS 4753862 A Resumen A light-sensitive material comprising a light-sensitive layer which contains silver halide, a reducing agent and a polymerizable compound provided on a support, characterized in that the light-sensitive layer further contains a triazenesilver having the following formula: ##STR1## in which Ar is an aryl group or a heterocyclic group, each of which may have one or more substituent groups; R is a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic group, each of which may have one or more substituent groups; L is a ligand; and n is 0, 1 or 2. Image-forming methods utilizing the light-sensitive materials are also disclosed.
We claim: 1. In a light-sensitive material comprising a light-sensitive layer which contains silver halide, a reducing agent and an ethylene unsaturated polymerizable compound provided on a support, the improvement wherein the light-sensitive layer further contains a triazenesilver having the following formula: ##STR10## in which Ar is an aryl group or a heterocyclic group, each of which may have at least one substituent group; R is a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic group, each of which may have at least one substituent groups; L is a ligand; and n is 0, 1 or 2.
2. The light-sensitive material as claimed in claim 1, wherein each of Ar and R in the formula independently is an aryl group which may have at least one substituent group; and n is 0.
3. The light-sensitive material as claimed in claim 1, wherein the triazenesilver is contained in an amount of from 1 to 1,500 mole % based on the silver halide in the light-sensitive layer.
4. The light-sensitive material as claimed in claim 1, wherein the light-sensitive layer further contains a color image forming substance.
5. The light-sensitive material as claimed in claim 1, wherein the ethylene unsaturated polymerizable compound is dispersed in the light-sensitive layer in the form of oil droplets, and silver halide and the triazenesilver are contained in the oil droplets.
6. The light-sensitive material as claimed in claim 1, wherein the ethylene unsaturated polymerizable compound is contained in microcapsules which are dispersed in the light-sensitive layer, and silver halide and the triazenesilver are contained in the microcapsules.
7. An image-forming method which comprises: imagewise exposing a light-sensitive material comprising a light-sensitive layer provided on a support wherein the light-sensitive layer contains silver halide, a reducing agent, an ethylene unsaturated polymerizable compound and a triazenesilver having the following formula: ##STR11## in which Ar is an aryl group or a heterocyclic group, each of which may have at least one substituent group; R is a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic group, each of which may have at least one substituent group; L is a ligand; and n is 0, 1 or 2, to form a latent image of the silver halide; and simultaneously or thereafter heating the light-sensitive material to polymerize the polymerizable compound within the area where the latent image of the silver halide has been formed.
8. The image-forming method as claimed in claim 7, wherein after heating the light-sensitive material, the light-sensitive material is pressed on an image-receiving material to transfer the obtained image to the image-receiving material.
9. The image-forming method as claimed in claim 7, wherein the triazenesilver is contained in an amount of from 1 to 1,500 mole % based on the silver halide in the light-sensitive layer of the light-sensitive material.
10. The image-forming method as claimed in claim 7, wherein the triazenesilver functions as a precursor of a polymerization initiator.
11. A image-forming method which comprises: imagewise exposing a light-sensitive material comprising a light-sensitive layer provided on a support wherein the light-sensitive layer contains silver halide, a reducing agent, an ethylene unsaturated polymerizable compound and a triazenesilver having the following formula: ##STR12## in which Ar is an aryl group or a heterocyclic group, each of which may have at least one substituent group; R is a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic group, each of which may have at least one substituent group; L is a ligand; and n is 0, 1 or 2, to form a latent image of the silver halide; and simultaneously or thereafter heating the light-sensitive material to polymerize the polymerizable compound within the area where the latent image of the silver halide has not been formed.
12. The image-forming method as claimed in claim 11, wherein after heating the light-sensitive material, the light-sensitive material is pressed on an image-receiving material to transfer the obtained image to the image-receiving material.
13. The image-forming method as claimed in claim 11, wherein the triazenesilver is contained in an amount of from 1 to 1,500 mole % based on the silver halide in the light-sensitive layer of the light-sensitive material.
14. The image-forming method as claimed in claim 11, wherein the triazenesilver functions as a precursor of a polymerization initiator.
An improved image forming method employing a dry process is described in Japanese Patent Provisional Publication Nos. 61(1986)-69062 and 61(1986)-73145 (the contents of both publications are described in U.S. Pat. No. 4,629,676 and European Patent Provisional Publication No. 0174634A2). In this image forming method, a recording material (i.e., light-sensitive material) comprising a light-sensitive layer containing a light-sensitive silver salt (i.e., silver halide), a reducing agent, a cross-linkable compound (i.e., polymerizable compound) and a binder provided on a support is imagewise exposed to form a latent image, and then the material is heated to polymerize within the area where the latent image of the silver halide has been formed. The above method employing the dry process and the light-sensitive material employable for such method are also described in Japanese Patent Provisional Publication Nos. 61(1986)-183640, 61(1986)-188535 and 61(1986)-228441 (the content of the three publications are shown in U.S. Pat. Ser. No. 827,702).
Further, Japanese Patent Provisional Publication No. 61(1986)-260241 (corresponding to U.S. Patent Ser. No 854,640) describes another image forming method in which the polymerizable compound in a portion where a latent image of the silver halide has not been formed is polymerized. In this method, when the material is heated, the reducing agent functions as polymerization inhibitor in the portion where a latent image of the silver halide has been formed, and the polmerizable compound in the other portion is polymerized.
In the light-sensitive material employed in these image forming method, the reducing agent which functions as a polymerization initiator (or a precursor thereof) shows a tendency to be gradually decomposed in the storage. Therefore, it is important to improve the preservability of the light-sensitive material.
SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material which is improved particularly in the preservability.
Another object of the invention is to provide a light-sensitive material which gives an image having high contrast.
There is provided by the present invention a light-sensitive material comprising a light-sensitive layer which contains silver halide, a reducing agent and a polymerizable compound provided on a support, characterized in that the light-sensitive layer further contains a triazenesilver having the following formula: ##STR2## in which Ar is an aryl group or a heterocyclic group, each of which may have one or more substituent groups; R is a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic group, each of which may have one or more substituent groups; L is a ligand; and n is 0, 1 or 2.
heating the light-sensitive material either simultaneously with or after the imagewise exposure to polymerize the polymerizable compound within the area where the latent image of the silver halide has been formed (or the area where the latent image of the silver halide has not been formed).
The light-sensitive material of the invention is characterized in that the light-sensitive layer contains therein the above triazenesilver.
The triazenesilver functions as a precursor of a polymerization initiator in the light-sensitive material of the invention. The triazenesilver of the invention is a thermally very stable compound and hence shows extremely reduced tendency to be decomposed with the passage of time. Therefore, the triazenesilver can be stably kept in the light-sensitive material until it is reduced in a development process to release the triazene compound. Thus, the light-sensitive material of the invention has excellent preservability.
In the above-mentioned light-sensitive material, a hydrazine derivative, which functions as a precursor of the polymerization initiator was preferably used singly or in combination with the other reducing agent. But it is difficult to preserve the hydrazine derivative in a long term. In addition to the excellent preservability, the light-sensitive material of the invention employing the triazenesilver in place of the hydrazine derivative can give an improved clear image having high contrast as that employing the hydrazine derivative gives.
DETAILED DESCRIPTION OF THE INVENTION The triazenesilver employed in the present invention has the following formula: ##STR3## in which Ar is an aryl group or a heterocyclic group, each of which may have one more more substituent groups; R is a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic group, each of which may have one more more substituent groups; L is a ligand; and n is 0, 1 or 2.
Examples of the aryl groups which constitute the Ar include phenyl and naphthyl. The heterocyclic group which constitutes the Ar preferably contains a heteroring condensed with an aromatic ring, or contains a heteroring having a aromaticity. Examples of the heterocyclic group include pyridyl, thiazolyl and benzothiazolyl. Examples of the substituent groups which may be attached to the Ar include an aryl group, an alkyl group (preferably containing 1-5 carbon atoms), an alkoxy group (preferably containing 1-5 carbon atoms), an alkylthio group (preferably containing 1-5 carbon atoms), carboxyl, an alkoxycarbonyl group (preferably containing 2-6 carbon atoms), carbamoyl, sulfamoyl, an alkylsulfonyl group (preferably containing 1-5 carbon atoms), cyano, hydroxyl, nitro and a halogen atom. These substituent groups except carboxyl, cyano, hydroxyl, nitro and a halogen atom may also have one or more substituent groups.
R in the above formula is a monovalent group selected from the group consisting of an alkyl group (preferably containing 1-5 carbon atoms), a cycloalkyl group (preferably containing 5-7 carbon atoms), an aralkyl group (e.g., benzyl), an aryl group and a heterocyclic group. Each of the aryl group and the heterocyclic group individually has the same meaning as that of the Ar. The Ar and the R may be identical or different from each other. Example of the substituent groups which may be attached to the R is the same as that of the Ar.
There is no specific limitation with respect to the ligand (L) except that it contains an atom having affinity to silver (e.g., oxygen, nitrogen, sulfur). Examples of the ligand include alcohols, ethers, amines, nitrogen-containing heterocyclic compounds (e.g., pyridine), hydroxycarboxylic acids, aminocarboxylic acids and water. Concrete examples of the ligand include water, methanol, ethanol, ethylene glycol, propylene glycol, glycollic acid, lactic acid, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N-(2-hydroxyethyl)ethylenediamine, N,N'-dimethylethylenediamine, ammonia, glycine, alanine, o-phenylenediamine, pyridine, picoline, collidine, lutidine, 2-aminopyridine, 2-hydroxypyridine, 2,2'-dipyridyl-1,10-phenanthroline.
The "n" is 0, 1 or 2. The value of "n" can be determined by the nature of the triazenesilver and its preparation. When the triazenesilver is prepared in a following general way, "n" is 0.
The triazenesilver of the invention is reduced to form a triazene compound in a development process in which a latent image center functions as catalyst. The formed triazene compound can be easily decomposed upon heating to release a free radical which is supposed to function as a polymerization initiator, and which is different from behavior of the triazenesilver. The formation of the free radical by the thermal decomposition of the triazene compound is described in C. Walling, "Free Radicals in Solution", pp. 518, John Wiley & Sons, Inc., (1957).
Examples of the triazenesilver which are preferably used in the invention will be described hereinafter. ##STR4##
The triazenesilver can be used singly or in combination of two or more compounds.
The triazenesilver can be prepared according to a known manner, for instance, by the following process.
A triazene compound can be prepared by diazotizing aniline or its derivatives and treating the resulting compound with an amine in an excessive amount. The triazene compound can react with a silver salt (e.g., silver nitrate, silver acetate) in an adequate medium (e.g., water, alcohol, pyridine) to obtain the triazenesilver. When a water soluble binder (e.g., gelatin) is previously contained in the reaction medium, uniformly fine particles of the triazenesilver can be obtained. Further, when an adequate ligand is containd in the reaction medium and the molar ratio of the ligand to the triazenesilver is adjusted, the triazenesilver to which the ligand is coupled can be obtained.
Examples of the preparation of the triazenesilver are described in Ann., Vol. 137, pp. 55 and J. Am Chem. Soc., Vol. 63, pp. 78.
The amount of the triazenesilver in the light-sensitive layer preferably ranges from 1 to 1,500 mole % based on the silver halide, and more preferably ranges from 10 to 1,000 mole %.
The total silver content (including the silver halide, the triazenesilver and an organic silver salt which is one of optional components) in the light-sensitive layer preferably is in the range of from 0.1 mg/m.sup.2 to 10 g/m.sup.2. The silver content of the silver halide in the light-sensitive layer preferably is not more than 1 g/m.sup.2, more preferably in the range of from 1 mg to 500 mg/m.sup.2.
The reducing agent employed in the light-sensitive material has a function of reducing the silver halide and/or function of accelerating or restraining a polymerization of the polymerizable compound. Examples of the reducing agents having these functions include various compounds, such as hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, sulfonamidopyrazolotriazoles, α-sulfonamidoketones, hydrazines, etc. Depending on the nature or amount of the reducing agent, the polymerizable compound in either a portion where a latent image of the silver halide has been formed or a portion where a latent image of the silver halide has not been formed can by polymerized. In the developing system in which the polymerizable compound in the portion where the latent image has not been formed is polymerized, 1-phenyl-3-pyrazolidone is preferably employed as the reducing agent.
Examples of these reducing agents include pentadecylhydroquinone, 5-t-butylcatechol, p-(N,N-diethylamino)phenol, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenylsulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2-(N-butylcarbamoyl)-4-phenylsulfonylaminonaphtol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol, 1-acetyl-2-phenylhydrazine, 1-acetyl-2-(p- or o-aminophenyl)hydrazine, 1-formyl-2-(p- or o-aminophenyl)hydrazine, 1-acetyl-2-(p- or o-methoxyphenyl)hydrazine, 1-lauroyl-2-(p- or o-aminophenyl)hydrazine, 1-trityl-2-(2,6-dichloro-4-cyanophenyl)hydrazine, 1-trityl-2-phenylhydrazine, 1-phenyl-2-(2,4,6-trichlorophenyl)hydrazine, 1-{2-(2,5-di-tert-pentylphenoxy)butyloyl}-2-(p- or o-aminophenyl)hydrazine, 1-{2-(2,5-di-t-pentylphenoxy)butyloyl}-2-(p- or o-aminophenyl)hydrazine pentadecylfluorocaprylate salt, 3-indazolinone, 1-(3,5-dichlorobenzoyl)-2-phenylhydrazine, 1-trityl-2-[{(2-N-butyl-N-octylsulfamoyl)-4-methanesulfonyl}phenyl]hydrazine, 1-{4-(2,5-di-tert-pentylphenoxy)butyloyl}-2-(p- or o-methoxyphenyl)hydrazine, 1-(methoxycarbonylbenzohydryl)2-phenylhydrazine, 1-formyl-2-[4-{2-(2,4-di-tert-pentylphenoxy)butylamide}phenyl]hydrazine, 1-acetyl-2-[4-{2-(2,4-di-tert-pentylphenoxy)butylamido}phenyl]hydrazine, 1-trityl-2-[{2,6-dichloro-4-(N,N-di-2-ethylhexyl)carbamoyl}phenyl]hydrazine, 1-(methoxycarbonylbenzohydryl)-2-(2,4-dichlorophenyl)hydrazine and 1-trityl-2-[{2-(N-ethyl-N-octylsulfamoyl)-4-methanesulfonyl}phenyl]hydrazine.
The amount of the reducing agent in the light-sensitive layer preferably ranges from 0.1 to 1,500 mole % based on the amount of silver (contained in the silver halide, the triazenesilver and an organic silver salt).
There is no specific limitation with respect to the polymerizable compound, and any known polymerizable compounds including monomers, oligomers, and polymers can be contained in the light-sensitive layer. In the case that heat development (i.e., thermal development) is utilized for developing the light-sensitive material, the polymerizable compounds having a relatively higher boiling point (e.g., 80 hardly evaporated upon heating are preferably employed. In the case that the light-sensitive layer contains a color image forming substance, the polymerizable compounds are preferably cross-linkable compounds having plural polymerizable groups in the molecule, because such cross-linkable compounds favorably serve for fixing the color image forming substance in the course of polymerization hardening of the polymerizable compounds.
The polymerizable compounds can be used singly or in combination of two or more compounds. Further, compounds formed by bonding a polymerizable group such as a vinyl group or a vinylidene group to a reducing agent or a color image forming substance are also employed as the polymerizable compounds. The light-sensitive materials employing these compounds which show functions as both the reducing agent and the polymerizable compound, or of the color image forming substance and the polymerizable compound, are included in embodiments of the invention.
The amount of the polymerizable compound for incorporation into the light-sensitive layer preferably ranges from 5 to 1.2.times.10.sup.5 times (by weight) as much as the amount of silver halide, more preferably from 10 to 1
The polymerizable compound is preferably dispersed in the form of oil droplets in the light-sensitive layer. A light-sensitive material in which the polymerizable compound is dispersed in the form of oil droplets is describbed in Japanese Patent Application No. 60(1985)-218603. Other components in the light-sensitive layer, such as silver halide, the reducing agent, the color image forming substances may be also contained in the oil droplets. A light-sensitive material in which silver halide is contained in the oil droplets is described in Japanese Patent Application No. 60(1985)-261888.
The oil droplets of the polymerizable compound are preferably prepared in the form of microcapsules. There is no specific limitation on preparation of the microcapsules. The light-sensitive material in which the oil droplets are present in the form of a microcapsule is described in Japanese Patent Application No. 60(1985)-117089. There is also no specific limitation with respect to the shell material of the microcapsule, and various known materials such as polymers which are used in the conventional microcapsules can be employed as the shell material. The mean particle size of the microcapsule preferably ranges from 0.5 to 50 μm, more preferably 1 to 25 μm, most preferably 3 to 20 μm.
Examples of the dyes and pigments (i.e., colored substances) employable in the invention include commercially available ones, as well as various known compounds described in the technical publications, e.g., Yuki Gosei Kagaku Kyokai (ed.), "Handbook of Dyes" (in Japanese, 1970) and Nippon Ganryo Gijutsu Kyokai (ed.), "New Handbook of Pigments" (in Japanese, 1977). These dyes and pigments can be used in the form of a solution or a dispersion.
Examples of the substances which develop to give a color in contact with other components include various compounds capable of developing a color through some reaction between two or more components, such as acid-base reaction, oxidation-reduction reaction, coupling reaction, chelating reaction, and the like. Examples of such color formation systems are described in Hiroyuki Moriga, "Introduction of Chemistry of Speciality Paper" (in Japanese, 1975), 29-58 (pressure-sensitive copying paper), 87-95 (azo-graphy), 118-120 (heat-sensitive color formation by a chemical change) or in MSS. of the seminar promoted by the Society of Kinki Chemical Industry, "The Newest Chemistry of Coloring Matter--Attractive Application and New Development as a Functional Coloring Matter", 26-32 (June 19, 1980). Examples of the color formation systems specifically include a color formation system used in pressure-sensitive papers, etc., comprising a color former having a partial structure of lactone, lactam, spiropyran, etc., and an acidic substance (developer), e.g., acid clay, phenol, etc.; a system utilizing azo-coupling reaction between an aromatic a diazonium salt, diazotate or diazosulfonate and naphthol, aniline, active methylene, etc.; a system utilizing a chelating reaction, such as a reaction between hexamethylenetetramine and a ferric ion and gallic acid, or a reaction between a phenolphthalein-complexon and an alkaline earth metal ion; a system utilizing oxidation-reduction reaction, such as a reaction between ferric stearate and pyrogallol, or a reaction between silver behenate and 4-methoxy-1-naphthol, etc.
There is no specific limitation with respect to the sensitizing dyes, and known sensitizing dyes used in the conventional art of photography may be employed in the light-sensitive material of the invention. Examples of the sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These sensitizing dyes can be used singly or in combination. Combinations of sensitizing dyes are often used for the purpose of supersensitization. In addition to the sensitizing dyes, a substance which does not per se exhibit spectral sensitization effect or does not substantially absorb visible light but shows supersensitizing activity can be used. The amount of the sensitizing dye to be added generally ranges from about 10.sup.-8 to about 10.sup.-2 mol per 1 mol of silver halide.
When the heat development is employed in the use of the light-sensitive material, an organic silver salt is preferably contained in the light-sensitive material. It can be assumed that the organic silver salt takes part in a redox reaction using a silver halide latent image as a catalyst when heated to a temperature of 80 case, the silver halide and the organic silver salt preferably are located in contact with each other or close together. Examples of organic compounds employable for forming such organic silver salt include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or an α-hydrogen atom, imino group-containing compounds, and the like. Among them, benzotriazoles are most preferable. The organic silver salt is preferably used in an amount of from 0.01 to 10 mol., and preferably from 0.01 to 1 mol., per 1 mol. of the light-sensitive silver halide. Instead of the organic silver salt, an organic compound (e.g., benzotriazole) which can form an organic silver salt in combination with an inoganic silver salt can be added to the light-sensitive layer to obtain the same effect. The light-sensitive material employing an organic silver salt is described in Japanese Patent Application No. 60(1985)-141799 (corresponding to U.S. Pat. Ser. No. 879,747).
Various image formation accelerators are employable in the light-sensitive material of the invention. The image formation accelerators have a function to accelerate the oxidation-reduction reaction between a silver halide (and/or an organic silver salt) and a reducing agent, a function to accelerate emigration of an image forming substance from a light-sensitive layer to an image-receiving material or an image-receiving layer, or a similar function. The image formation accelerators can be classified into inorganic bases, organic bases, base precursors, oils, surface active agents, hot-melt solvents, and the like. These groups, however, generally have certain combined functions, i.e., two or more of the above-mentioned effects. Thus, the above classification is for the sake of convenience, and one compound often has a plurality of functions combined.
The thermal polymerization initiators employable in the light-sensitive material preferably are compounds that are decomposed under heating to generate a polymerization initiating species, particularly a radical, and those commonly employed as initiators of radical polymerization. The thermal polymerization initiators are described in "Addition Polymerization and Ring Opening Polymerization", 6-18, edited by the Editorial Committee of High Polymer Experimental Study of the High Polymer Institute, published by Kyoritsu Shuppan (1983). Examples of the thermal polymerization initiators include azo compounds, e.g., azobisisobutyronitrile, 1,1'-azobis(1-cyclohexanecarbonitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis(2-methylbutyronitrile), and azobisdimethylvaleronitrile; organic peroxides, e.g., benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tertbutyl hydroperoxide, and cumene hydroperoxide; inorganic peroxides, e.g., hydrogen peroxide, potassium persulfate, and ammonium persulfate; and sodium p-toluenesulfinate. The thermal polymerization initiators are preferably used in an amount of from 0.1 to 120% by weight, and more preferably from 1 to 10% by weight, based on amount of the polymerizable compound. In a system in which the polymerizable compound located in a portion where the latent image has not been formed is polymerized, the thermal polymerization initiators are preferably incorporated into the light-sensitive layer. The light-sensitive material employing the thermal polymerization initiators is described in Japanese Patent Provisional Publication No. 61(1986)-260241 (corresponding to U.S. Ser. No. 854,640).
Examples and usages of the other optional components which can be contained in the light-sensitive layer are also described in the above-mentioned publications and applications concerning the light-sensitive material, and in Research Disclosure Vol. 170, No. 17029, 9-15 (June 1978).
The light-sensitive material employing the heating layer is described in Japanese Patent Application No. 60(1985)-135568 (corresponding to U.S. Pat. Ser. No. 868,385 and European Patent Provisional Publication No. 203613A). Examples and usage of the other auxiliary layers are also described in the above-mentioned publications and applications concerning the light-sensitive material.
Polymers having a principal chain consisting essentially of a hydrocarbon chain substituted in part with hydrophilic groups which contain, in their terminal groups, -OH or nitrogen having a lone electron-pair are preferably introduced into the polymerizable compound prior to the preparation of the light-sensitive composition. The polymer has a function of dispersing silver halide or other component in the polymerizable compound very uniformly as well as a function of keeping thus dispered state. Further, the polymer has another function of gathering silver halide along the interface between the polymerizable compound (i.e., light-sensitive composition) and the aqueous medium in preparation of the microcapsule. Therefore, using this polymer, silver halide can be easily introduced into the shell material of the microcapsule.
The triazenesilver can be incorporated into an aqueous medium, such as the silver halide emulsion, the emulsion of the polymerizable compound, and the coating solution to prepare the light-sensitive material of the invention. The triazenesilver can be directly added to the aqueous medium. The silver halide emulsion containing the triazenesilver can be also prepared by adding a soluble silver salt to the mixture of a soluble halogen salt and a triazene compound, or by adding a soluble halogen salt to the triazensilver for the in situ formation of the silver halide by reaction of halide ion with the part of silver ions of the triazensilver.
Alternatively, the triazenesilver can be incorporated into the polymerizable compound (including the light-sensitive composition) to prepare the light-sensitive material of the invention. The triazenesilver in the form of solid particles can be directly added to the polymerizable compound, or dispersed in an adequate hydrophobic medium prior to the addition to the polymerizable compound.
Various exposure means can be employed in the image-wise exposure, and in general, the latent image on the silver halide is obtained by imagewise exposure to radiation including visible light. The type of light source and exposure can be selected depending on the light-sensitive wavelengths determined by spectral sensitization or sensitivity of silver halide. The original image can be either monochromatic image or color image.
Heating in the heat development process can be conducted in various known manners. The heating layer which is arranged on the light-sensitive material can be used as the heating means in the same manner as the light-sensitive material described in Japanese Patent Application No. 60(1985)-135568. Heating temperatures for the development process usually ranges from 80 100 The heating time is usually from 1 second to 5 minutes, and preferably from 5 seconds to 1 minute.
During the above development process, a polymerizable compound in a portion where a latent image of the silver halide has been formed or in a portion where a latent image of the silver halide has not been formed is polymerized. In a general system, the polymerizable compound in a portion where the latent image has been formed is polymerized. If a nature or amount of the reducing agent is controlled, the polymerizable compound in a portion where the latent image has not been formed can be polymerized in the same manner as the light-sensitive material described in Japanese Patent Provisional Publication No. 61(1986)-260241 (corresponding to U.S. Patent Ser. No. 854,640).
The light-sensitive material can be used for monochromatic or color photography, printing, radiography, diagnosis (e.g., photography for CRT of diagnostic device using supersonic wave), copy (e.g., computer-graphic hard copy), etc.
EXAMPLE 1 Preparation of silver halide emulsion In 1,000 ml of water were dissolved 20 g of gelatin and 3 g of sodium chloride, and the resulting gelatin solution was kept at 75 the gelatin solution, 600 ml of an aqueous solution containing 21 g of sodium chloride and 56 g of potassium bromide and 600 ml of an aqueous solution containing 0.59 mole of silver nitrate were added simultaneously at the same feed rate over a period of 40 minutes to obtain a silver chlorobromide emulsion having cubic grains, uniform grain size distribution, a mean grain size of 0.35 μm and a bromide content of 80 mole %.
The emulsion was washed for desalting and then subjected to chemical sensitization with 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene at 60 the emulsion was 600 g.
Preparation of silver benzotriazole emulsion In 3,000 ml of water were dissolved 28 g of gelatin and 13.2 g of benzotriazole, and the solution was kept at 40 To the solution was added 100 ml of an aqueous solution of 17 g of silver nitrate over 2 minutes. Excessive salts were sedimented and removed from the resulting emulsion by pH-adjustment. Thereafter, the emulsion was adjusted to pH 6.30 to obtain a silver benzotriazole emulsion. The yield of the emulsion was 400 g.
Preparation of dispersion of triazenesilver Commercially available diphenyltriazene was purified by recrystallzation from n-hexane to obtain pure diphenyltriazene having a melting point of 95
To a mixture of 16.7 g of silver nitrate and 200 ml of methanol was added 23.7 g of pyridine. To the mixture was further added portionwise a solution at 20 dissolved in 100 ml of methanol, and the resulting mixture was stirred for 30 minutes at 20 orange sediment, and the sediment was washed with methanol. The resulting sediment was recrystallized from pyridine to obtain 22 g of the following triazenesilver (a) [diphenyltriazenesilver] in the form of yellowish orange needle-like crystals. The decomposition point of the triazenesilver (a) was 226 ##STR5##
To 200 ml of 1% aqueous solution of gelatin was added 10 g of the triazenesilver (a), and the resulting mixture was ground for 30 minutes using a Dynomill to obtain a dispersion of the triazenesilver (a).
Preparation of light-sensitive composition In 100 g of trimethylolpropane triacrylate was dissolved 0.40 g of the following copolymer, 6.00 g of Paragascript Red I-6-B (produced by Ciba Geigy) and 2 g of Emulex NP-8 (tradename, preduced by Nippon Emulsion Co., Ltd.). ##STR6##
To 18.00 g of the resulting solution were added 3.5 g of the silver halide emulsion, 3.0 g of the silver benzotriazole emulsion and 5.0 g of the dispersion of the triazenesilver (a). To the solution was further added a solution in which 1.22 g of the following reducing agent is dissolved in 1.80 g of methylene chloride, and the mixture was stirred at 15,000 r.p.m. for 5 minutes to obtain a light-sensitive composition. ##STR7##
Preparation of light-sensitive microcapsule To 10.51 g of 18.6% aqueous solution of Isobam (tradename, produced by Kuraray Co., Ltd.) was added 48.56 g of 2.89% aqueous solution of pectin. After the solution was adjusted to a pH of 4.0 using 10% sulfuric acid, the light-sensitive composition was added to the resulting solution, and the mixture was stirred at 7,000 r.p.m. for 2 min. to emulsify the light-sensitive composition in the aqueous medium.
To 72.5 g of the aqueous emulsion were added 8.32 g of 40% aqueous solution of urea, 2.82 g of 11.3% aqueous solution of resorcinol, 8.56 g of 37% aqueous solution of formaldehyde, and 2.74 g of 8.76% aqueous solution of ammonium sulfate in this order, and the mixture was heated at 60 C. for 2 hours while stirring. After the mixture was adjusted to a pH of 7.0 using 10% aqueous solution of sodium hydroxide, 3.62 g of 30.9% aqueous solution of sodium hydrogen sulfite was added to the mixture to obtain a dispersion containing light-sensitive microcapsules.
Preparation of light-sensitive material To 10.0 g of the light-sensitive microcapsule dispersion were added 1.0 g of 1% aqueous solution of the following anionic surfactant and 1.0 g of 10% solution (solvent: water/ethanol=50/50 as volume ratio) of guanidine trichroloacetate to prepare a coating solution. ##STR8##
The coating solution was uniformly coated on a polyethyleneterephthalate film (thickness: 100 μm) using a coating rod of #40 to a wet thickness of 70 μm and dried at about 40 material (A).
EXAMPLE 2 Preparation of dispersion of triazenesilver Each of the dispersions of the following triazenesilvers (b) to (d) was prepared in thhe same manner as in Example 1. ##STR9##
Preparation of light-sensitive composition Light-sensitive compositions were prepared in the same manner as in Example 1 except that each 5.0 g of the above dispersions of the triazenesilvers (b) to (d) was used in place of 5.0 g of the dispersion of the triazenesilver (a).
Preparation of light-sensitive microcapsule Dispersions of light-sensitive microcapsule were prepared in the same manner as in Example 1 except that the above light-sensitive compositions were used.
Preparation of light-sensitive material Light-sensitive materials (B) to (D) were prepared in the same manner as in Example 1 except that the above light-sensitive microcapsules were used.
Preparation of image-receiving material To 125 g of water was added 11 g of 40% aqueous solution of sodium hexametaphosphate, and were further added 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% slurry of calcium carbonate, followed by coarsely dispersing in a mixer. The coarse dispersion was then finely dispersed in a dynamic dispersing device. To 200 g of the resulting dispersion were added 6 g of 50% latex of SBR (styrene-butadiene rubber) and 55 g of 8% aqueous solution of polyvinyl alcohol, and the resulting mixture was made uniform.
The mixture was then uniformly coated on an art paper having a weight of 43 g/m.sup.2 to give a layer having a wet thickness of 30 μm and dried to obtain an image-receiving material.
Evaluation of light-sensitive material Each of the light-sensitive materials prepared in Examples 1 and 2 was imagewise exposed to light using a tungsten lamp at 200 lux for 1 second and then heated on a hot plate at 130 the exposed and heated light-sensitive materials was then combined with the image-receiving material and passed through press rolls under pressure of 350 kg/cm.sup.2. The image-receiving material was then separatted from the light-sensitive material. The density of the magenta positive image obtained on the image-receiving material was measured using Macbeth reflection densitometer.
Further, after each of the light-sensitive materials was preserved at 40 the obtained image was measured.
The results are set forth in Table 1. In Table 1, "0 day" is referred to as the image which has been formed immediately after the preparation of the light-sensitive material and "5 days" is referred to as the image which has been formed after the material was preserved at 40 days.
TABLE 1______________________________________Light- Tri-    0 day          5 daysSensitive  azene-  Maximum   Minimum                           Maximum MinimumMaterial  silver  Density   Density                           Density Density______________________________________(A)    (a)     1.41      0.26   1.36    0.24(B)    (b)     1.36      0.23   1.34    0.23(C)    (c)     1.34      0.18   1.32    0.19(D)    (d)     1.42      0.25   1.38    0.22______________________________________
It is apparent from the results in Table 1 that each of the light-sensitive materials using the triazenesilver forms an improved positive image which has a high maximum density and a low minimum density. It is also apparent that each of the light-sensitive materials has excellent preservability.
Citas de patentes Patente citada Fecha de presentaci�n Fecha de publicaci�n Solicitante T�tuloUS413722619 Dic 197730 Ene 1979Gaf Corporation3,3-(1,1'-Biphenyl-2,2'-diyl)-1-(4-methylphenyl)-1-triazeneUS44657634 May 198314 Ago 1984Ciba Geigy AgProcess for the production of photographic color images by the silver dye bleach processOtras citasReferencia1J. Kosar, Light Sensitive Systems, Photo polymerization processes, 4/65, pp. 175 180.2J. Kosar, Light-Sensitive Systems, Photo polymerization processes, 4/65, pp. 175-180. Citada por Patente citante Fecha de presentaci�n Fecha de publicaci�n Solicitante T�tuloUS493325616 May 198812 Jun 1990Fuji Photo Film Co., Ltd.Image-forming method employing light-sensitive material having microcapsules and fine polymer particles and image-receiving materialUS507379127 Jul 199017 Dic 1991Canon Kabushiki KaishaImage forming deviceUS538423821 Ene 199424 Ene 1995Minnesota Mining And Manufacturing CompanyPositive-acting photothermographic materialsUS543610814 Jun 199425 Jul 1995Polaroid CorporationThermographic image-recording materialsUS566303212 Ene 19942 Sep 1997Canon Kabushiki KaishaPhotosensitive composition containing photosensitive and heat developable element and polymer element and image-forming method utilizing the sameEP1315034A111 Nov 200228 May 2003EASTMAN KODAK COMPANY (a New Jersey corporation)Core/shell silver donors for photothermographic systems comprising an oxidatively more reactive shellEP1315035A111 Nov 200228 May 2003Eastman Kodak CompanyCore/shell silver donors for photothermographic systems comprising an oxidatively less reactive shellWO1994014620A116 Dic 19937 Jul 1994Polaroid CorporationThermographic image-recording materialGirarImagen originalP�gina principal de Google - Sitemap - Descargas masivas de USPTO - Pol�tica de privacidad - Condiciones de servicio - Acerca de Google Patentes - Danos tu opini�nDatos proporcionados por IFI CLAIMS Patent Services©2012 Google