JPH02949A - Heat development type copying material - Google Patents

Abstract

PURPOSE:To lower the texture coloring (fogging) density and the degradation in color forming density during preservation prior to copying by providing a photosensitive layer contg. specific org. bases. CONSTITUTION:A diazo compd. is incorporated into a microcapsule which contains substantially no solvent and at least one kind of the org. bases expressed by the formulas I-IV are incorporated as the basic material therein. In the formulas I, II, R1-R4 and R6 respectively denote hydrogen, <=18C alkyl, etc.; R5 denotes lower alkylene, phenylene, etc. In the formulas III, IV, Y denotes a monovalent group; R7, R8 respectively denote an alkyl group, aryl group, etc.; R9, R10 respectively denote alkyl, alkoxy, aryl thio group, etc. The performances of the good shelf life, i.e. the low texture coloring (fogging) density and the small degradation of the color forming density during the preservation prior to copying are obtd. in this way.

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a copying material in which a diazo compound (diazonium salt) is encapsulated in microcapsules, and particularly to a copying material having a good shelf life. <Prior Art> There are three types of copying materials that utilize the photosensitivity of diazo compounds. The first type is known as a wet development type, in which a photosensitive layer containing a diazo compound and a coupling component as main components is provided on a support, and this material is superimposed on the original and exposed to light ff!
It is developed using a caustic solution. The second type is known as a dry development type, which differs from the wet type in that development is performed using 7 ml gas. The third type is known as a heat-developable type, and is a type that contains a 7-mmon-7 gas generating agent such as urea that can generate 7-mmon-7 gas by heating in the photosensitive layer. A type that contains an alkali salt of an acid that loses its properties as an acid when heated, such as trichloroacetic acid, and uses higher fatty acid 7-amide as a coloring aid to activate the diazo compound and coupling component by heating and melting. There are different types. In addition to maintenance problems such as the need for replenishing and discarding the developer as it uses a developer and the large size of the device, the wet type also has problems with maintenance, such as the fact that it is wet immediately after copying, making it difficult to make additions immediately. There are several problems such as copy images not being able to withstand long-term storage. In addition, the dry type requires replenishment of developer like the wet type, requires gas absorption equipment to prevent the generated 7mm gas from leaking outside, and therefore requires larger equipment. To,
There are problems such as the smell of ammonia immediately after copying. On the other hand, unlike the wet and dry types, the heat-developable type has the advantage of maintenance because it does not require a developing solution. Moreover, if the temperature is not controlled to about ±10<6>C, insufficient development may occur or the color tone may change, resulting in an increase in the cost of the apparatus. Furthermore, the diazo compound used for such high-temperature development is required to have high heat resistance, but such compounds are often disadvantageous for high-temperature formation. Low temperature development (906C~130°C
) have been attempted, but they have the drawback of decreasing the shelf life of the material itself. As described above, although the thermal development type is expected to have sufficient advantages in terms of maintenance compared to the wet and dry types, the current situation is that it has not yet become the mainstream of diazo copying systems. Now, in order to obtain the desired color density by heating a material in which a layer containing a diazo compound and a coupling component is provided on a support, each component instantly melts, diffuses, and reacts with the coloring dye. It is necessary to generate , but it is preferable to make the system basic during this reaction because it has the effect of accelerating the reaction. Therefore, in order to produce a heat-developable copying material that has a copying speed that does not pose a practical problem when heated at low temperatures, it is essential to include a basic substance in the coating layer. On the other hand, for heat-developable copying materials, it is also essential to suppress as much as possible the background coloring and the decrease in color density during storage before copying. Although several attempts have been made to create heat-developable copying materials that have a good shelf life and a high copying speed, the current situation is that they have not yet reached the point where they can be put to practical use. . If we design a material that can sufficiently develop color and obtain a high concentration even at low heating temperatures, it is natural that a color reaction may occur even while it is stored at room temperature before copying. This appears as a phenomenon in which the bare skin becomes colored. In order to solve this incompatible problem, the present inventors made extensive studies and found that diazotized
Discovered that one basic solution for copying materials provided with a heat-developable photosensitive layer containing a diazo compound, a coupling component, and a basic substance is to incorporate the diazo compound into microcapsules. did. However, although this alone can considerably suppress background discoloration during storage before copying, it is insufficient, and the phenomenon of decrease in color development degree still cannot be suppressed. For this purpose, the present inventors newly searched for basic substances,
We continued to study from the viewpoint of how to make microcapsules, etc., and arrived at the present invention. Therefore, a first object of the present invention is to provide a copying material that can obtain high color density even by low-temperature development. A second object of the present invention is to provide a copying material that has a good shelf life, that is, has a low background coloring (fog) density during storage before copying, and a small decrease in color density. A third object of the present invention is to provide a copying material which exhibits excellent long-term preservation of copy images (lower decrease in color density and smaller increase in background density when stored in bright and dark places). A fourth object of the present invention is to provide a copying material with excellent water resistance, chemical resistance, and abrasion resistance. A fifth object of the present invention is to provide a copying material that has a simplified layer structure and is easy to manufacture. A sixth object of the present invention is to provide a simple and easy-to-maintain image forming method that uses the copying material described above and combines a latent image forming process by exposure and a developing process by heating. Means for Solving the Problems> The above aspects of the present invention provide a copying material in which a heat-developable photosensitive layer containing a diazo compound, a coupling component, and an organic base is provided on a support. Thermal development characterized in that the compound is contained in microcapsules substantially free of solvent, and the organic base is at least one compound represented by the following general formulas [1) to (IV). Achieved by mold copying material. General formula (1) General formula (11) In general formula (1), [11], R, R2R, R,
and R6 may be the same or different and each represents hydrogen, alkyl having 18 or less carbon atoms, cyclic alkyl, aryl, 7-ralkyl, 7-mino, alkyl-7-mino, acyl, acylamino, carbamoyl, or a heterocyclic residue. Represents O, NH or a single bond. ) represents. The aryl group in the formula is lower alkyl, alkoxy, nitro, acyl,
It may have a substituent more widely than acyl 7-mino, 7-mino, alkyl 7-mino or halogen. General formula (Ill) General formula (IV) In the general formulas (Ill) and (IV), Y represents a monovalent group, including a substituted or unsubstituted alkyl group, an aryl group, a 7-mido group, and an ester. monovalent groups, including ureido groups, sulfonyl groups, ether groups, carbamoyl groups, and thioether groups. R7R8 may be the same or different, and each represents an alkyl group, an aryl group, or a 7-ralkyl group, each of which may have a substituent. Also, R7 and R
6 may be connected to each other to form a ring, and in that case, the connected ring may contain a betero atom. Rg, Rh
. may be the same or different and each represents a substituted or unsubstituted alkyl, aryl, 7ralkyl, alkoxy, aryloxy, alkylthio, or arylthio group. The diazo compound and the coupling component contained in the photosensitive layer of the present invention develop color when they come into contact with each other when heated, and the diazo compound decomposes when exposed to light of a specific wavelength before the coloring reaction. Photodegradable compounds are used. The photodegradable diazo compound as used in the present invention mainly refers to aromatic diazo compounds, and more specifically refers to aromatic diazonium salts, diazosulfonate compounds, and diazo-7mino compounds. It is generally said that the photodecomposition wavelength of a diazo compound is its maximum absorption wavelength. Also, the maximum absorption wavelength of diazo compounds varies from around 200 nm to 7Q depending on their chemical structure.
It is known that it changes up to about Qnm. (“Photodecomposition and chemical structure of photosensitive diazonium salts” by Takahiro Tsunoda and Ao Yamaoka, Journal of the Photographic Society of Japan 29 (4) pp. 197-205 (
1965)) That is, when a diazo compound is used as a photodegradable compound, it is decomposed by light of a specific wavelength depending on its chemical structure. Furthermore, by changing the chemical structure of the diazo compound, the hue of the dye after the reaction can be changed even when the same coupling component is used for the coupling reaction. A diazo compound is a compound represented by the general formula ArN2X. (In the formula, Ar represents a substituted or unsubstituted aromatic ring%
N represents a diazonium group, and X represents an acid 7 anion. ) In the present invention, a multicolor heat-developable copying material can be obtained by using diazo compounds having different photodecomposition wavelengths or different photodecomposition rates. Specific examples of the diazo compound used in the present invention include the following examples. 4-Diazo-1-dimethyl 7-minobenzene, 4-diazo-2-butoxy-5-riO-1-dimethyl 7-minobenzene, 4-diazo-1-methylbenzylaminobenzene 4-diazo-1-ethylhydroxyethylaminobenzene , 4-diazo-1-diethyl 7minor 3-methoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene,
4-Diazo-1-tolylmercapto-2,5-jethoxybenzene, 4-diazo-1-piperazino-2-methoxy-5-chlorobenzene, 4-diazo-1-(N,N
-dioctyl7minocarbonyl)benzene, 4-diazo-1-(4-tert-octylphenoxy)benzene, 4-diazo-1-(2-ethylhexanoylpiperidino)-2゜5-dibutoxybenzene, 4 -Diazo-1-
(2,5-di-tert-7milphenoxyα-butanoylpiperidino)benzene, 4-diazo-1-(4-
methoxy)phenylthio-2,5-jethoxybenzene, 4-diazo-1-(4-methoxy)benz7 mido2
．． 5-Jethoxybenzene. 4-Diazo-1-pyrrolidino-2-methoxybenzene Specific examples of the acid that forms a diazonium salt with the above diazo compound include the following examples. Cn F 2n*+ COOH (n is an integer from 1 to 9)
,C. F2+l+IS03H (m is an integer from 1 to 9)
, boron tetrafluoride, tetraphenylboron, hexafluorophosphoric acid, aromatic carboxylic acid, aromatic sulfonic acid. Metal halides (zinc chloride, cadmium chloride, tin chloride)
etc.) The microcapsules used in the present invention have a
After emulsifying and dispersing a solution of a diazonium salt and the same or different compounds that react with each other to produce a polymeric substance in a non-aqueous solvent with a boiling point of 95°C in a hydrophilic protective colloid solution, the reaction vessel is reduced in pressure. By increasing the temperature of the system while distilling off the solvent, the wall-forming substance is transferred to the oil droplet surface, and a polymer production reaction by polyaddition and polycondensation proceeds on the oil droplet surface to form a wall film. Preferably, the substantially solvent-free microcapsules are produced. The nonaqueous solvent for dissolving the diazonium salt used in the present invention is preferably at least one compound selected from halogenated hydrocarbons, fatty acid esters, ketones, and ethers, and forms the walls of microcapsules. It is preferable that the polymeric substance is formed from at least one selected from polyurethane and polyurea. The non-aqueous solvent having a boiling point of 40° C. or more and 95° C. or less at normal pressure used in the present invention is preferably used in an amount of 5 to 100 parts by weight per 10 parts by weight of the diazonium salt as the solute. Specific examples of the nonaqueous solvent used in the present invention are listed below, but the present invention is not limited thereto. (
) indicates the boiling point at normal pressure. acetone (56), iso7 methyl methyl ether (91
), isobutyl methyl ketone (94). Methyl isobutyrate (92), ethyl isobutyl ether (
79), ethyl isopropyl ether (54), ethylpropyl ether (64). t”-7 mil chloride (86), ethylene chloride (84). Isobutyl chloride (69), butyl chloride (7B). Ethylidene chloride (57), propyl chloride (48). Methylene chloride (42), ethyl formate (54). ). Propyl formate (81), chloromethyl methyl ether (59), methyl chloroformate (71), ethyl acetate (7
7), methyl acetate (57), carbon tetrachloride (77), 1.
1-Dichloropropane (86). Trichlorethylene (87), methyl propionate (8
0), propyl ether (91), methyl chloroform (74), chloroform (61) The microcapsules of the present invention are characterized in that they do not substantially contain non-aqueous solvents. developed a method for quantifying the nonaqueous solvent contained in these microcapsules by the following method, and defined the term "substantially free" in the present invention. The microcapsules of the present invention are rarely used as a capsule liquid alone, but are generally used in a manner in which a coating liquid is prepared together with a coupler and a base, coated and dried, and then present in a film of a copying material. Therefore, the amount of non-aqueous solvent contained in the coating film, which was present at several percent in the capsule liquid stage, was below the detection limit. Microcapsule liquid produced by the production method of the present invention 0.
19 was weighed into a 20 cc volumetric flask, methanol was added to make the volume exactly 20 cc, and the mixture was left for 30 minutes. 2 CC of the methanol solution was measured using a microsyringe and injected into a gas chromatograph mass spectrometer (Hitachi M-808). Column is TENAX 3mmφ
X1m was used. Quantification was performed using the m/z peak depending on the solvent to be measured. (For example, in the case of ethyl acetate, the peak of m/Z" 43 + in the case of methylene chloride, 84 was used.) According to this measurement method, the microcapsule liquid of the present invention contains 0.01 to 3.00% non-containing material. The aqueous solvent was contained.The same or different compounds that react with each other to produce a polymeric substance forming the walls of the microcapsules used in the present invention are preferably polyurea or urethane, and the corresponding monomers are aromatic or The microcapsules containing the diazo compound of the present invention can be polymerized with the corresponding monomer, and the amount of monomer used is selected from aliphatic isocyanate compounds with an average particle size of 0°3 μm to 3 μm. 12μ, wall thickness 0.01~0.
3. Moreover, the diazo compound has 0.
05 to 5.09/m" is preferable. The coupling component used in the present invention is one that forms a dye by coupling with a diazo compound in a basic atmosphere, and has a methylene group next to a carbonyl group. There are so-called active methylene compounds, phenol derivatives, naphthol derivatives, etc., with the following specific examples: resorcin, phloroglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphthoic acid. Morifolinop Pill 7mide, 1.5-
Dihydroxynaphthalene, 2.3-dihydroxynaphthalene, 2.3-dihydroxy-6-sulfanylnaphthalene, 2-human Oxy-3-naphthoic acid morpholinopropyl 7mide, 2-bitroxy-3-naphthoic acid octylamide, 2-hydroxy- 3-naphthoic acid 7nylide, benzoyl 7cetonylide, 1-phenyl-3-methyl-5
-pyrazolone, 1-(2,4,6-trichlorophenyl)-3-7nilino-5-pyrazolone, 2-[3-α-(
2,5-di-tert-amylphenoxy)-butane 7
Midobenzamide] phenol, 2,4-bis-(benzoyl7cetamino)toluene, 1,3-bis-(pivaOyl7cetaminomethyl)benzene These coupling components can be used alone or in combination of two or more. You can also obtain any hue as needed. In the present invention, organic bases represented by general formulas (1) to (IV) are added for the purpose of making the system basic during thermal development and promoting the coupling reaction. These organic bases can be used alone or in combination of two or more, and depending on the purpose, they can also be used in combination with basic substances other than the general formulas (1) to (IV). These basic substances are preferably poorly water-soluble or water-insoluble substances that generate alkali upon heating. Basic substances include inorganic and organic ammonium salts, 7mide, urea, thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, indoles, imidazoles, imidacillins, triazoles, and morpholines. , piperidines, heptamines, formamidines, pyridines, and other nitrogen-containing compounds. These basic substances are 2
More than one species can be used in combination. Specific examples of the organic bases represented by formulas (1) to (IV) included in the present invention are shown below, but the present invention is not limited thereto. Phenylguanidine, 1,3-diphenylguanidine,
1,3-di-0-tolylguanidine, 1゜3-di-p-
Methoxyphenylguanidine, 1-dimethyl-3-phenylguanidine, 1-benzoyl-3-phenylguanidine, 1-benzyl-3-phenylguanidine, 1.2
．． 3-triphenylguanidine, 1,1,3-triphenylguanidine, 1,2-dibenzoyl-3-phenylguanidine, 1,3-diphenyl-2-cyclohexylguanidine, 0-tolyl biguanide, p-di(1 ,3-
diphenylguanidino) diphenyl. Di(phenylg7dinino)ethane, di(triphenylg7dinino)methane, 1,3-dicyclohexylguanidine, 1.2.3-)dicyclohexylguanidine,
N,N'-bis(3-phenoxy-2-hydroxypropyl)piperazine. N, N″-bis(3-(p-methylphenoxy)
-2-hydroxypropyl)piperazine, N,
N'-bis(3-(p-methoxyphenoxy)-2-hydroxypropyl)piperazine, N, N'
-bis(3-phenylthio-2-hydroxypropyl)
Piperazine, N, N″-bis[3-(β-naphthoxy)-2-hydroxypropylcopiperazine. N-3-(β-naphthoxy)-2-hydroxypropyl-N′-methylbiperazine, N-(3-( β-naphthoxy)-2-hydroxy)propylmorpholine, 1.4-
Bis[(3-morpholino-2-hydroxy)propyloxy]benzene. 1.3-bis((3-morpholino-2-hydroxy)propyloxy)benzene, 1.4-bis((3-(N-
Methylpiperazino)-2-hydroxy)propyloxy)benzene In the present invention, the coupling component is 0.1 to 30 parts by weight, and the basic substance is 0.
．． It is preferable to use it in a proportion of 1 to 30 parts by weight. In the present invention, in addition to the organic base, a coloring aid may be added for the purpose of promoting the coloring reaction. The coloring aids of the present invention include, for example, phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, and hydroxy compounds in the photosensitive layer so that thermal development can be carried out quickly and completely with low energy. , amide compounds, and sulfonamide compounds can be added. These compounds are thought to lower the melting point of the coupling component or the basic substance, or to improve the thermal permeability of the microcapsule wall, resulting in a high color density. The coloring aids of the present invention also include thermofusible substances. The heat-melting substance is a substance having a melting point of 50°C to 150°C that is solid at room temperature and melts by heating, and is a substance that dissolves a diazo compound, a coupling component, or a basic substance. Specific examples of these compounds include fatty acid amides, Nl-converted fatty acid amide, ketone compounds, urea compounds, esters, and the like. The coupling component, basic substance, and other coloring aids used in the present invention are preferably used after being solidly dispersed together with a water-soluble polymer using a sand mill or the like. Preferred water-soluble polymers include water-soluble polymers used when preparing microcapsules (for example, Japanese Patent Application Laid-Open No. 1986-1999).
190886). In this case, the coupling component, the basic substance and the coloring aid are each added in an amount of 5 to 40% by weight based on the water-soluble polymer solution. Preferably, the dispersed particle size is 10 microns or less. A free radical generator (a compound that generates free radicals when irradiated with light) used in photopolymerizable compositions can be added to the copying material of the present invention for the purpose of reducing yellowing of the background after copying. . As free radical generators, aromatic ketones,
Examples include quinones, benzoin, benzoin ethers, 7zo compounds, organic disulfides, and acyloxime esters. The amount of the free radical generator to be added is preferably 0.01 to 5 parts by weight per 1 part by weight of the diazo compound. Similarly, for the purpose of reducing yellowing, a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as a vinyl monomer) can be used. Vinyl monomers have at least one ethylenically unsaturated bond (vinyl group, vinylidene group, etc.) in their chemical structure.
It is a compound that has the chemical form of a monomer or a prepolymer. Examples thereof include unsaturated carboxylic acids and their salts, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohols, and 7-mides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds. The vinyl monomer is used in an amount of 0.2 to 20 parts by weight per 1 part by weight of the diazo compound. The free radical generator and the vinyl monomer can also be used while being contained in microcapsules together with the diazo compound. In the present invention, in addition to the above materials, citric acid is used as an acid stabilizer.
Tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. can be added. The copying material of the present invention is prepared by preparing a coating solution containing microcapsules containing a diazo compound, a coupling component, an organic base, and other additives, and coating it on a support such as paper or a synthetic resin film with a bar. A photosensitive layer having a thickness of 2.5 to 309/m" is provided by coating and drying by a coating method such as , blade coating, F-knife coating, gravure coating, O-ru coating, spray coating, or dip coating. Copying material of the present invention In this case, the microcapsules, the coupling component, the base, etc. may be contained in the same layer as described in the above method, or may have a laminated structure in which they are contained in separate layers.Also, Patent application 1984 on the support
It is also possible to apply the photosensitive layer after providing an intermediate layer as described in the specification of No. 177669 and the like. As the support of the present invention, any paper support used for ordinary pressure-sensitive paper, thermal paper, dry or wet diazo copying paper, etc. can be used, as well as neutral sizing agents such as alkyl ketene dimer. Neutral paper with a pH of 5 to 9 (described in Japanese Patent Application No. 55-14281) sized by paper with an optical surface roughness of 8μ or less and a thickness of 30 to 150μ as described in JP-A No. 58-136492, a paper with a density of 0.99/2 as described in JP-A-58-69091 am
Paper with an optical contact ratio of 3 or less and an optical contact ratio of 15% or more, JP-A-5
Canadian Standard Freeness (JIS) as described in No. 8-69097
P8121) Paper made from valves beaten to 4000C or higher to prevent coating liquid from seeping in, JP-A-58
-65695, the glossy side of base paper made by a Yankee machine is used as the coating surface to improve the color density and resolution, and the base paper described in JP-A-59-35985 is subjected to corona discharge treatment to improve coating suitability. Improved paper can also be used. Further, the synthetic resin film used as a support in the present invention can be arbitrarily selected from known materials that do not deform even when heated during the development process and have dimensional stability. Examples of such films include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate films, polystyrene films, polypropylene films, and polyolefin films such as polyethylene. Alternatively, they can be used by laminating them together. The thickness of the support is 20 to 200
μ is used. The following method is preferred for forming an image on the copying material of the present invention. In the first step of performing exposure corresponding to the image of the original to form a latent image on the photosensitive layer and fixing areas other than the image forming area by light irradiation, various types of fluorescent lamps, xenon lamps, etc. can be used as the light source for exposure. Mercury lamps are used,
It is preferable that this emission spectrum substantially matches the absorption spectrum of the diazo compound used in the copying material, since areas other than the image forming area can be efficiently optically fixed. Further, in the second step of heating and developing the entire surface of the photosensitive layer of the material with a heating means, the heating means may include a thermal pen,
A thermal head, infrared rays, high frequency, heat block, heat roller, etc. can be used. <Effects of the Invention> As detailed above, the copying material of the present invention contains a diazo compound in microcapsules that do not substantially contain a solvent, and has general formulas [1] to (IV) as a basic substance. By containing at least one organic base represented by the following, it is possible to achieve a good shelf life, that is, a low background coloring (fogging) concentration and a small decrease in color density during storage before copying. Ta. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples. <Example>

[Preparation of capsule liquid A of the present invention] =1-morpholino-
3.45 parts of 2,5-dibutoxybenzene-4-diazonium hexafluorophosphate and xylylene diisocyanate and trimethylolpropane (3:1) adduct 1
8 parts were added to 10 parts of ethyl acetate and dissolved by heating. This diazo compound solution was mixed with an aqueous solution containing 5.2 parts of polyvinyl alcohol dissolved in 58 parts of water, and emulsified and dispersed at 20°C to obtain an emulsion having an average particle size of 265 μm. 100 parts of water was added to the obtained emulsion and heated to 50°C while stirring, and after 3 hours, a capsule liquid containing the diazo compound in the core substance was obtained. This reactor was heated with a water pump for 40 minutes.
It was maintained under reduced pressure of 0 mm89 to 500 mmH9. The amount of ethyl acetate in the capsule liquid was determined using the measurement method described above.
．． A value of 62% was obtained. (Preparation of comparative capsule liquid B) = 1-morpholino-2,5
- 3.45 parts of dibutoxybenzene-4-diazonium hexafluorophosphate and 18 parts of an adduct of xylylene diisocyanate and trimethylolpropane (3:1) were added to a mixed solvent of 6 parts of tricresyl phosphate and 5 parts of ethyl acetate. and heated to dissolve. This diazo compound solution was mixed with an aqueous solution containing 5.2 parts of polyvinyl alcohol dissolved in 58 parts of water, emulsified and dispersed at 20°C, and the average particle size was 2.
．． A 5μ emulsion was obtained. 100 parts of water was added to the obtained emulsion and heated to 50°C while stirring, and after 3 hours, a capsule liquid containing the diazo compound in the core substance was obtained. (Preparation of coupler/base dispersion C of the invention): 10 parts of 2-human Oxy-3-naphthoic acid anilide and 1.2.3
-), 10 parts of Riphenylg7nidine were added to 200 parts of a 5% polyvinyl alcohol aqueous solution, and dispersed in a sand mill for about 24 hours. A dispersion C having an average particle size of 3 μm was obtained. . Preparation of coupler/base dispersion of the invention): Dispersion C
was prepared in the same manner except that N,N″-bis(3-phenoxy-2-humanOoxypropyl)piperazine was used instead of 1.2.3-triphenylguanidine. (Comparative dispersion) Preparation of E) Bidispersion C was prepared in the same manner except that ste7lylamine was used instead of triphenylguanidine. (Preparation of copying material F of the present invention) As described above. 050 parts of the dispersion liquid and 10 parts of the 40% calcium carbonate dispersion liquid were added to 50 parts of the obtained capsule liquid A to prepare a coating liquid.The coating liquid was dried on smooth high-quality paper (759/m") using a coating bar. It was applied to a weight of 109/m" and dried at 50°C for 1 minute to prepare copying material F. [Preparation of copying material G of the present invention]: When preparing copying material F, a dispersion liquid was used. Copying material G was prepared in exactly the same manner as F except for the above. (Preparation of comparative copying material H): Copying material G was prepared in exactly the same manner as F except that dispersion E was used when preparing copying material F. [Preparation of Comparative Copying Material 1]: Copying Material 1 was prepared in exactly the same manner as Copying Material F except that capsule liquid B was used. [Comparative Copying Material J] Creation]: When creating copy material G,
Copy material J was prepared in exactly the same manner as G except that capsule liquid B was used. [Preparation for comparison copy material]: When preparing copy material H,
Copying material K was prepared in exactly the same manner as H except that capsule liquid B was used. Test manuscript on copying material F-K (a circle with a diameter of 3 cm painted evenly black on tracing paper with a 2B pencil)
was placed on top and exposed to fluorescent light. At this time, a fluorescent lamp whose emission spectrum has a maximum value at 420 nm was used. Next, an image was formed by heating for 3 seconds using a heat block heated to 120°C. In the same way,
The temperature of the heat block was also tested at 100°C and 160°C. Also, to test shelf life, 4
After being stored at 06C 90% RH for 24 hours, it was exposed to light in the same manner and developed at 120°C. A 24 hour storage test was also conducted at 60°030%RH. The densities of the colored parts and background parts of the samples obtained in each test were measured using a Macbeth densitometer. Table 1 shows the results of tests at different heating temperatures, and Table 2 shows the results of the pre-copy storage test. In the above table, the * mark indicates a sample tested as a comparative example for the present invention.

Claims (1)

[Scope of Claims] 1) A copying material in which a heat-developable photosensitive layer containing a diazo compound, a coupling component, and an organic base is provided on a support, wherein the organic base has the following general formula [I] to [IV
A heat-developable copying material comprising at least one compound represented by the formula: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In general formulas [I] and [II], R_1, R_2,
R_3, R_4 and R_6 may be the same or different and each represents hydrogen, alkyl having 18 or fewer carbon atoms, cyclic alkyl, aryl, aralkyl, amino, alkylamino, acyl, acylamino, carbamoyl, or a heterocyclic residue. R_5 is lower alkylene, phenylene, naphthylene or ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, X is lower alkylene, SO_2, S_2, S, O
, NH or a single bond. ) represents. The aryl group in the formula may have a substituent selected from lower alkyl, alkoxy, nitro, acyl, acylamino, amino, alkylamino or halogen. General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In general formulas [III] and [IV], Y represents a monovalent group. In addition to substituted or unsubstituted alkyl groups and aryl groups, amide groups, ester groups, ureido groups, sulfonyl groups,
Included are monovalent groups including ether groups, carbamoyl groups, and thioether groups. R_7 and R_8 may be the same or different and represent an alkyl group, an aryl group, or an aralkyl group, each of which may have a substituent. Further, R_7 and R_8 may be connected to each other to form a ring, and in that case, a heteroatom may be included in the connected ring. R_9,
R_1_0 may be the same or different, and each represents substituted or unsubstituted alkyl, aryl, aralkyl,
Represents an alkoxy, aryloxy, alkylthio, or arylthio group. 2) The diazo compound is contained in microcapsules, and the microcapsules are heated under normal pressure of 40 to 95°C.
After emulsifying and dispersing a solution of a diazonium salt and the same or different compounds that react with each other to produce a polymeric substance in a non-aqueous solvent with a boiling point of By raising the temperature of the oil to move the wall-forming substance to the surface of the oil droplet, and proceeding with the polymer production reaction by polyaddition and polycondensation on the surface of the oil droplet to form a wall film, a microorganism that is substantially free of solvent is formed. The heat-developable copying material according to claim 1, which is produced by a method for obtaining capsules. 3) The heat-developable copying material according to claim 2, wherein the polymeric substance is formed of at least one selected from polyurea and polyurethane. 4) With respect to the copying material according to claim 1,
A first step of forming a latent image on the photosensitive layer by exposing it to light corresponding to the image of the original, and fixing the area other than the image forming portion by light irradiation; and after the first step, the entire surface of the photosensitive layer of the copying material is covered. An image forming method comprising a second step of heating and developing with a heating means.