JP3197719B2 - Image forming method and copy material used therefor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a heat-developable copying material, and more particularly to an image forming method characterized in that a copied image is formed by heat generated by absorbing infrared light. .

[0002]

2. Description of the Related Art The present invention relates to an image forming method in which a latent image is formed on a recording layer by exposing the copying material to an image of a document and then the entire recording layer is heated by a heating means to develop the image. It relates to a forming method. The latent image formed on the recording layer by exposure is a negative image corresponding to whether the photosensitive organic substance used for the recording layer is activated or inactivated by light irradiation on the labeling organic substance. Or a positive image. A labeling organic substance that chemically or physically distinguishes between a photosensitive organic substance and a photolysis product of the photosensitive organic substance causes a reaction, a phase change, a substance permeability change, and the like by adding thermal energy to a conventional system. It was known as a group of compounds. Therefore, when assembling a recording system using the above change, the less heat energy required, the cheaper and smaller the system becomes. However, the heating means conventionally used or proposed is a method in which a heat source is brought into contact with the recording layer, and the amount of heat transfer becomes non-uniform due to the degree of close contact. Unevenness occurs in the color density. As means for preventing this, an excessive amount of heat is given to obtain a uniform color density, or a large pressure is applied to increase the adhesion between the heat source and the recording layer. This is an obstacle to assembling an inexpensive and small system, and in fact, if used for a long time, deposits from the material accumulate on the heat source part and a good copy image cannot be obtained. And many other inconveniences, including failures.

[0003] The above-mentioned problem is caused by the thermal development of a copying material in which a thermal head as a heat source is brought into close contact scanning with the surface of a thermosensitive recording material having a thermosensitive coloring layer provided on a support to transfer heat energy directly to the thermosensitive coloring layer. A similar phenomenon occurs in a thermal recording method for recording a color image based on exactly the same principle as the method. For example, if a facsimile or printer is used for a long period of time, the thermal head will be worn and may be destroyed in some cases, or the components of the thermal recording material may adhere to the surface of the thermal head during recording,
It is widely known that a correct recorded image cannot be obtained due to the adhesion between the thermal head and the surface of the recording material, and its solution is of interest.

In a thermal recording method using a thermal head, in order to solve the above-mentioned problems, it is necessary to use a laser beam as a heat source to perform thermal recording at high speed and high density without contacting the thermal recording material. In addition to the proposals, many proposals have been made in relation to the above in order to make the heat-sensitive recording material efficiently absorb the laser beam. However, when a substance having an absorption wavelength matching the laser oscillation wavelength is added to the heat-sensitive recording layer, the light absorbing substance to be added needs to have almost no absorption in the visible region. In general, light-absorbing substances that do not have absorption in the visible region are many in inorganic compounds, most of which have low light-absorbing efficiency and are far from practical, and when organic compounds are used as light-absorbing substances, Although high absorption efficiency can be obtained, most compounds also absorb in the visible light region, so that the background portion is colored. (For example, JP-A-50-2361
7, JP-A-54-121140, JP-A-57-11-11
090, JP-A-58-56890, JP-A-58-9
4494, JP-A-58-134791, JP-A-58
145493, JP-A-59-89192, JP-A-60-205182 and JP-A-62-56195.

In particular, in an image forming method in which the entire recording layer is heated as in the present invention, the problem becomes much more difficult than in the above-described system in which the heated portion is considerably small. Even if it is applied to a mold copying material and an image forming method using the same, it is quite insufficient as a means for solving the current problems.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a heat development system which is simple, compact, easy to maintain, and capable of keeping the apparatus cost low. An object of the present invention is to provide an image forming method capable of obtaining a good copied image.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive organic substance, a photochemical reaction product of the photosensitive organic substance, and a labeling organic substance capable of chemically or physically distinguishing those substances on a support. And an image forming method for forming an image using a copying material provided with a photosensitive and heat-sensitive recording layer containing an infrared light absorbing substance capable of absorbing infrared light and converting it into heat, as an essential component. This was achieved by an image forming method characterized by irradiating and developing.

In the present invention, a photosensitive organic substance, a labeling organic substance capable of chemically or physically distinguishing the photosensitive organic substance and its photochemical reaction product, and an infrared ray are absorbed on a support to absorb heat. A copying material provided with a light- and heat-sensitive recording layer containing an infrared light absorbing substance which can be converted is superimposed on a document, and the recording layer is exposed to ultraviolet light through the document. In the recording layer, a portion corresponding to the non-recording portion of the document is exposed to a larger amount of ultraviolet light than a portion corresponding to the recording portion, so that the photosensitive organic material in the portion is decomposed (at the same time, the photochemical As a result, a distribution of the presence of the photosensitive organic substance corresponding to the image of the original document is generated, and the distribution can be recorded by identifying the distribution of the presence of the organic substance for labeling. Then, the light sensitivity of the exposed copy material
When the entire surface of the thermal recording layer is irradiated with infrared rays and developed,
An image is formed.

The representative copy material included in the present invention will be described in detail. In the present invention, a diazo compound is included as the photosensitive organic substance. The diazo compounds include the following compounds, but the present invention is not limited thereto. "Photodegradation and chemical structure of photosensitive diazonium salts" (Takahiro Tsunoda and Ao Yamaoka, Photographic Society of Japan 2
9 (4) 197-205 (1965)) and JP-A-2-12-1
And diazo compounds, aromatic diazonium salts, diazosulfonate compounds and diazoamino compounds described in US Pat.
-Diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-toluylmercapto-2,5-diethoxybenzene, 4-diazo-1-piperazino-2-
Methoxy-5-chlorobenzene, 4-diazo-1- (2
-Ethylhexanoylpiperidino) -2,5-dibutoxybenzene, 4-diazo-1- (4-methoxy) phenylthio-2,5-diethoxybenzene, 4-diazo-1
-(4-methoxy) benzamide-2,5-diethoxybenzene, 4-diazo-1-pyrrolidino-2-methoxybenzene and the like. Specific examples of the acid forming a diazonium salt with the diazo compound include C _n F _{2n + 1} COOH
(N is an integer of 1 to 9), C _m F _{2m + 1} SO ₃ H (m is 1 to 9)
9), boron tetrafluoride, tetraphenyl boron,
Hexafluorophosphoric acid, aromatic carboxylic acid, aromatic sulfonic acid, metal halides (zinc chloride, cadmium chloride, tin chloride, etc.) are exemplified.

The diazo compound used in the present invention reacts with a coupling component described later to form a desired hue, and is decomposed when receiving light of a specific wavelength before the reaction, so that the coupling component no longer acts. It is a photo-decomposable diazo compound that no longer has a coloring ability. The hue in this coloring system is determined by the diazo dye formed by the reaction between the diazo compound and the coupling component. Therefore, the color hue can be easily changed if the chemical structure of the diazo compound is changed or the chemical structure of the coupling component is changed as is well known, and almost any color hue can be obtained depending on the combination. .

In the present invention, the organic substance for labeling the diazo compound is an organic compound capable of forming an azo dye by a coupling reaction with the diazo compound. The coupling component used is one that forms a dye by coupling with a diazo compound in a basic atmosphere.
There are a so-called active methylene compound having a methylene group next to the carbonyl group, a phenol derivative, a naphthol derivative, and the like. Specific examples thereof include the following. Resorcin, phloroglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2
-Naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy- 3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid anilide, benzoylacetonilide, 1-phenyl-3-methyl-5-
Pyrazolone, 1- (2,4,6-trichlorophenyl)
-3-anilino-5-pyrazolone, 2- [3-α-
(2,5-di-tert-amylphenoxy) -butanamidobenzamide] phenol, 2,4-bis- (benzoylacetoamino) toluene, 1,3-bis- (pivaloylacetoaminomethyl) benzene and the like It is. Details of these coupling components are described in JP-A-62-1466.
No. 78. These coupling components can be used alone or in combination of two or more, and any color can be obtained as required.

When a combination of a diazo compound and a coupling component is used in the present invention, a coupling reaction is likely to occur in a basic atmosphere, and thus a basic substance may be added as a color-forming aid. As the basic substance, a water-insoluble or hardly soluble basic substance or a substance which generates an alkali by heating is used. Examples thereof include inorganic and organic ammonium salts, organic amines, amides, ureas and thioureas and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles , Morpholines, piperidines, amidines, foliamazines, pyridines and the like. Specific examples thereof are described in, for example, JP-A-61-291183.
No. etc. These basic substances can be used in combination of two or more.

In the present invention, the coupling component is preferably used in an amount of 0.1 to 30 parts by weight, and the basic substance is preferably used in an amount of 0.1 to 30 parts by weight, based on 1 part by weight of the diazo compound.

The color-forming aid of the present invention includes:
In addition, a phenol derivative, a naphthol derivative, an alkoxy-substituted benzene, an alkoxy-substituted naphthalene, a hydroxy compound, an amide compound, or a sulfonamide compound may be added to the photosensitive layer so that thermal development is performed quickly and completely with low energy. it can. These compounds are
It is considered that the melting point of the coupling component or the basic substance is reduced, or the heat permeability of the microcapsule wall is improved, so that a high color density can be obtained.

The coloring aid of the present invention also includes a heat-meltable substance. The heat-meltable substance is a substance that is solid at room temperature and melts by heating and has a melting point of 50 ° C to 150 ° C, 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, N-substituted fatty acid amides, ketone compounds, urea compounds, esters and the like.

In the present invention, a photo-oxidizing agent is contained as the photosensitive organic substance. These compounds are available from Photo
o. Sci. Eng. 5,98 (1961), Shoko 4
Examples thereof include carbon tetrabromide, N-bromosuccinimide, tribromomethylphenylsulfone, azide polymer, 2-azidobenzoxazole, benzoylazide, and the like. 2-azidobenzimidazole, 3-ethyl-1-
Methoxy-2-pyridothiacyanine perchlorate, 1
Principle is applied to photocrosslinkable photosensitive resins such as -methoxy-2-methylpyridinium-p-toluenesulfonate, 2,4,5-triarylimidazole dimer, benzophenone, p-aminophenylketone, polynuclear quinone, thioxanthenone Compounds known as organic photochromic materials such as photocrosslinking agents, for example, vinyl cinnamate, coumarin, anthracene, 2-methyl-5-vinylpyridine, and spiropyrans, triphenylmethane dyes , Anils, azobenzenes, tetrachlorodihydronaphthalenes, benzylpyridines and the like. Lophine dimer compounds or organic halogen compounds are also included.

In the present invention, the labeling organic for the photooxidant has one or two hydrogen atoms, and is removed and, in some cases, added with additional electrons to form a color forming layer to form a dye. It contains various leuco dyes. Aminotriarylmethane described in U.S. Pat. No. 3,445,234,
Examples include aminoxanthene, amino-1,9-dihydroacridine, aminophenoxazine, aminodihydrophenazine, leucoindamine, hydrazine, phenethylaniline and the like.

The photosensitive organic substance of the present invention further contains a photopolymerization initiator. As a typical photopolymerization initiator,
Aromatic ketones (eg, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, thioxanthone, fluorenone, acridone, etc.), benzoin and benzoin ethers (eg, benzoin methyl ether) Benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether, etc.), 2,4,5-triarylimidazole dimers (eg, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, (P-methoxyphenyl) -4,5-diphenylimidazole dimer, etc.),
Polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylsulfone, etc.), JP-A-53-13342
No. 8, JP-B-57-1819, JP-B-57-6096
And the compounds described in U.S. Pat. No. 3,615,455, and S-triazine derivatives having a trihalogen-substituted methyl group described in JP-A-58-29803 (for example,
2,4,6-tris (trichloromethyl) -S-triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, etc.), JP-A-59-1893.
No. 40 organic peroxides (for example, ditertiary butyl diperoxyisophthalate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, α,
α'-bis (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 3,3 ',
4,4'-tetra- (tert-butylperoxycarbonyl) benzophenone and the like, U.S. Pat.
No. 530, the organic boron compounds described in EP 0223587 (for example, tetramethylammonium salt of triphenylbutyroborate, tetrabutylammonium salt of triphenylbutylborate, tri (P-methoxyphenyl) )
Butyl borate tetramethylammonium salt), other diaryl iodonium salts, iron allene complexes, and other well-known photopolymerization initiators in the art can be usefully used.

In the present invention, the organic substance for labeling with respect to the photopolymerization initiator may be an electron-accepting and polymerizable vinyl monomer as long as it is a compound containing an electron-accepting group and a vinyl group in the molecule. Examples of such a compound include methacryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-63-173682 and acryloxyethyl ester which can be synthesized by a similar synthesis method, and JP-A-59-83693. , 60-1415
Nos. 87 and 62-99190, esters of hydroxymethyl-containing benzoic acid and hydroxymethylstyrene, hydroxystyrenes described in European Patent No. 29323, JP-A-62-167077 and JP-A-62-16777.
N of zinc halide described in JP-A-2-16708
Compounds that can be synthesized with reference to a vinylimidazole complex, a developer monomer described in JP-A-63-317558, and the like can be used.

In the present invention, these electron-accepting and polymerizable vinyl monomers are polymerized by exposure to ultraviolet light, become high molecular weight, are resistant to diffusion, and can react with the electron-donating colorless dye in the heating step. Disappears. On the other hand, the monomer that has not been exposed to ultraviolet light can diffuse in the recording layer in the heating step and react with the electron-donating colorless dye. Accordingly, these electron-accepting and polymerizable vinyl monomers react with the electron-donating colorless dye in inverse correlation with the amount of exposure to ultraviolet light to form a coloring dye. Examples of the electron-donating colorless dye include known triphenylmethanephthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leuco-lamin compounds, rhodamine lactam compounds, and triphenylmethane compounds. And various compounds such as triazene compounds, spiropyran compounds, and fluorene compounds. Specific examples of phthalides are described in US Reissued Patent Specification No. 23
No. 024, U.S. Pat.
No. 491112, No. 349116 and No. 35
No. 09174 and specific examples of fluorans are described in U.S. Pat. Nos. 3,624,107, 3,627,787 and 36.
No. 41011, No. 3462828, No. 36813
No. 90, No. 3920510, No. 3959571
And specific examples of spirodipyrans are described in US Pat.
Nos. 71,808 and pyridine and pyrazine compounds are described in U.S. Pat. Nos. 3,775,424 and 38,538.
No. 69, No. 4,246,318 and specific examples of fluorene compounds are described in Japanese Patent Application No. 61-240989.

In addition to those included in the color-forming aid of the present invention, a phenol derivative, a naphthol derivative, an alkoxy-substituted benzene, an alkoxy-substituted naphthalene may be contained in the photosensitive layer so that rapid and complete thermal development can be performed with low energy. , A hydroxy compound, an amide compound, a sulfonamide compound. These compounds are
It is considered that the melting point of the coupling component or the basic substance is reduced, or the heat permeability of the microcapsule wall is improved, so that a high color density can be obtained.

The coloring aid of the present invention also includes a heat-fusible substance. The heat-meltable substance is a substance that is solid at room temperature and melts by heating and has a melting point of 50 ° C to 150 ° C, 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, N-substituted fatty acid amides, ketone compounds, urea compounds, esters and the like.

The microcapsules containing the diazo compound and the electron-donating colorless dye of the present invention can be prepared by an interfacial polymerization method, an internal polymerization method, an external polymerization method, for example, as described in JP-A-59-19088.
No. 6 can be prepared. Polyurea and polyurethane which form the walls of the microcapsules can be obtained by polymerizing the corresponding monomers by the method described above. The amount of the monomers used is 0.3 μm to 12 μm in average particle size of the microcapsules, It is determined to be 0.01 to 0.3. Further, the diazo compound is 0.05 to
It is preferable to apply 5.0 g / m2.

The microcapsules containing the diazo compound and the electron-donating colorless dye of the present invention can react with the diazo compound in a non-aqueous solvent having a boiling point of 40 ° C. or more and 95 ° C. or less at normal pressure to convert a high molecular substance. After dispersing and emulsifying the resulting solution of the same or different compound in a hydrophilic protective colloid solution, the system is heated while the pressure in the reaction vessel is reduced, and the non-aqueous solvent is distilled off to form a wall-forming substance on the oil droplet surface. And the microcapsules substantially free of solvent produced by forming a wall film by causing a polymer formation reaction by polyaddition and polycondensation on the surface of the oil droplet to achieve a good shelf life. Is particularly preferred.

The compound forming the polymer substance is added inside the oil droplet or outside the oil droplet. Specific examples of the polymer substance include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer and the like. Preferred polymeric substances are polyurethanes, polyureas, polyamides, polyesters, polycarbonates, and particularly preferred are polyurethanes and polyureas. Two or more polymer substances can be used in combination.

Specific examples of the hydrophilic protective colloid include gelatin, polyvinylpyrrolidone, and polyvinyl alcohol. For example, when polyurea is used as a capsule wall material, a polyisocyanate such as a diisocyanate, a triisocyanate, a tetraisocyanate, or a polyisocyanate prepolymer, a polyamine such as a diamine, a triamine, or a tetraamine, and an amino group are used. The microcapsule wall can be easily formed by reacting a prepolymer, piperazine or a derivative thereof, a polyol, or the like containing at least one of them with an interfacial polymerization method in an aqueous solvent. Further, for example, a composite wall composed of polyurea and polyamide or a composite wall composed of polyurethane and polyamide is heated using, for example, a polyisocyanate and an acid chloride or a polyamine and a polyol after adjusting the pH of an emulsifying medium to be a reaction liquid. Can be adjusted. Details of the method for producing the composite wall composed of polyurea and polyamide are described in JP-A-58-66948.

The core substance of the microcapsule used in the present invention may contain an infrared light absorbing substance. They may be contained outside the microcapsules or in the microcapsule wall. It may be contained in two or more places at the same time.

The coupling component, basic substance, and other color-forming aids used in the present invention are preferably used as a solid dispersion with a water-soluble polymer by a sand mill or the like. Preferred water-soluble polymers include water-soluble polymers used when preparing microcapsules (for example,
JP-A-59-190886). In this case, a diazo compound, a coupling component,
The color-forming aid is added so as to be 5 to 40% by weight. The size of the dispersed particles is preferably 10 μm or less.

The infrared light absorbing substance used in the present invention will be described in detail. As the infrared light absorbing substance used in the present invention, even in the aqueous solution state, even if it is colored with the absorption maximum wavelength also in the visible light region, except for the water content of the aqueous solution, when dried, the dye It is preferable to use a dye whose absorption maximum wavelength in the visible light region shifts to the longer wavelength side, that is, shifts to the infrared region due to association of the dyes. When such a dye is added to the recording layer, even if it is colored at the time of application, it becomes colorless after the recording layer is dried, so that the background of the recording material can be made white or nearly colorless. In addition, the absorption efficiency of infrared light can be improved.

[0030]

Embedded image

In the formula, Z ¹ and Z ² are non-metallic atoms for forming a ring, R ¹ and R ² are alkyl groups, R ³ and R
⁵ is a hydrogen atom or an atom necessary to form a 5-membered ring by linking, R ⁴ is a hydrogen atom or a monovalent group, and X ⁻ is an anion.

[0032]

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In the formula, Z is a group of non-metallic atoms for forming a benzene ring, a naphthalene ring or a heteroaromatic ring, T is an atom necessary for forming a 5- or 6-membered ring, and Q is N and C To form a 5-, 6- or 7-membered ring,
L is a trivalent linking group formed by linking 5 or 7 methine groups by a conjugated double bond, and X ^- is an anion.

[0034]

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In the formula, R is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or a benzene ring condensed with a pyridine ring, R ¹ and R ² are a hydrogen atom, an alkyl group or an aryl group, and Z is a terminal. It is an atomic group having a nitrogen atom or an oxygen atom necessary for completing conjugation with the nitrogen atom of the pyrocholine nucleus.

[0036]

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In the formula, Z ¹ and Z ² are linked to each other to form a ring, or may be the same or different alkyl, aryl or alkenyl groups, and Q is a nitrogen atom or a substituted or unsubstituted group. Methine groups, R ¹ , R ² and R
³ is an alkyl group, an aryl group or an alkenyl group in which at least one of these groups is linked to L to form a ring or may be the same or different, L is a substituted or unsubstituted methine group, or A trivalent group in which 3, 5, or 7 are linked to form a conjugated double bond;
G atomic group necessary for forming a 5 or 6-membered ring, X ^-
Is an anion.

[0038]

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In the formula, Z ¹ and Z ² are an atomic group necessary for forming a nitrogen-containing heterocyclic ring, Z ³ is a divalent hydrocarbon group required for forming a 5- or 6-membered ring, R ¹ And R ² are a hydrogen atom or an alkyl group, A is an oxygen atom, a sulfur atom, an imino group or a divalent organic residue, l, m and n are 0 or 1, p and q
Is 0, 1 or 2.

[0040]

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In the formula, L is a methine group or a trimethine chain or a pentamethine chain in which these are linked by a conjugated double bond, E is an oxygen atom, a sulfur atom, NR ⁴ , R ¹ and R ⁴
Are linked to each other to form a ring, or may be the same or different, and may be an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an amino group, a hydrazino group or a diazenyl group, and R ² is a hydrogen atom , An alkyl group,
Aryl group, alkenyl group, alkynyl group or heterocyclic group, R ³ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group and a salt thereof, an alkyl group,
An aryl group, an alkenyl group, an alkynyl group, a heterocyclic group or a substituent linked by an oxygen atom, a sulfur atom, a nitrogen atom, or a carbonyl group.

[0042]

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Where R¹, R^TwoAnd R^ThreeIs a hydrogen atom,
Alkyl group, halogen atom or oxygen atom, sulfur atom, nitrogen
Linked by an atom, carbonyl group, or sulfonyl group
A substituent, n is 0 to 3, R^FourAnd R^FiveAre connected to each other
Or may be the same or different from each other
Hydrogen, alkyl or aryl, R⁶And R ⁷
Represents an alkyl group, an alkoxy group, a halogen atom, an acyl group
Mino group, alkoxycarbonylamino group or ureido
Group, X is cyano group, acyl group, alkoxycarbonyl
Group, carbamoyl group or sulfonyl group, Ar is aryl
Or a heteroaryl group.

[0044]

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Wherein R ¹ and R ² are an alkyl group, an aryl group, a cycloalkyl group or a hetaryl group, R ³ ,
R ^4, or R ^5, R ⁶ and R ⁷ are two of these optional to form an aliphatic ring or a heterocyclic ring of 5- to 7-membered bonded to each other,
Or a hydrogen atom, an alkyl group, an aryl group, a hetaryl group, a halogen atom,
A cyano group or a substituent connected by an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, or a sulfonyl group, Y is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom or a phosphorus atom, and A and Z are each independently , the atoms necessary to form an aliphatic ring or a heterocyclic ring (provided that atoms necessary to Y to form a Z cyclic structure in the case of nitrogen or phosphorus atom), n is 0 to 2, X ^- is It is an anion.

[0046]

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In the formula, R is an alkyl group, cycloalkyl
Group, aryl group or hetaryl group, R ¹, R^Two, R^Three,
R^FourAnd R^FiveMeans that any two of these are linked together
Form a 7-membered aliphatic or heterocyclic ring, or
Hydrogen atom, alkyl group,
Reel group, hetaryl group, halogen atom, cyano group or
Oxygen atom, sulfur atom, nitrogen atom, carbonyl group, sulfo
A substituent connected by a nyl group. A is -CO
R⁶, -CO_TwoR⁶, -CONHR⁶, -CON
(R ⁶)_Two, -SO_TwoR⁶, -SO_TwoNHR⁶, -SO
_TwoN (R⁶)_Two, -SR⁶Or -CN, and B is -N
HR⁶, -N (R⁶)_Two, -OR⁶, -SR⁶Or R ⁶
Or A and B are bonded to each other or R
^ThreeOr R^FourAnd a 5- to 7-membered aliphatic or heterocyclic ring
May be formed. R⁶Is an alkyl group, cycloalkyl
Group, aryl group or hetaryl group, Y is a 5- or 6-membered ring
An atom necessary for formation, Z is a 5- to 7-membered aliphatic ring or
The atomic group necessary for forming an elementary ring, n is 0-5.

[0048]

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Where R¹, R^Two, R^ThreeAnd R^FourAre these
Any two of which are bonded to each other to form a 5- to 7-membered aliphatic ring or
Form an elementary ring or are the same or different
Hydrogen, alkyl, aryl, hetaryl
Group, hydroxy group, halogen atom, cyano group or oxygen atom
Atom, sulfur atom, nitrogen atom, carbonyl group, sulfonyl group
Or a substituent linked by^Five, R⁶,
R⁷Or R⁸And a 5- to 7-membered aliphatic ring or
It may form a ring. R^Five, R⁶, R⁷, And R ⁸Is
Any two of these are joined together to form a 5- to 7-membered aliphatic ring
Or form a heterocyclic ring or are the same or different
Hydrogen atom, alkyl group, cycloalkyl
Group, aryl group or hetaryl group, n and m are 1 to 4
It is.

[0050]

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In the formula, R is a hydrogen atom, an alkyl group, an aryl group, a hetaryl group, a halogen atom, a cyano group or a substituent linked by an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, or a sulfonyl group; An atomic group forming a 7- to 7-membered nitrogen-containing heterocyclic ring, aromatic ring or fused ring;
It is.

The infrared light absorbing substance used in the present invention has a wavelength longer than the absorption maximum wavelength of the aqueous solution of the dye by at least 50 nm from the viewpoint of increasing the whiteness of the background of the copy material and increasing the absorption efficiency of the infrared light. And 700 to 1300 nm
Is preferably contained in the recording layer in a state having an absorption maximum wavelength in the range.

The above-mentioned conditions can be attained by a method of adsorbing an infrared light absorbing substance on non-photosensitive silver halide fine particles, a method of dissolving and emulsifying and dispersing the light absorbing substance in a high boiling point oil, And a method in which the substance is present as an aggregate (also referred to as an aggregate). Among these methods, from the viewpoint of the suitability for producing a copy material, a method in which an infrared light absorbing substance is dissolved in water to form an aqueous solution, and then the water is removed and the aggregate is present in the recording layer is preferable.

In the copying material of the present invention in which the photosensitive organic substance is a diazo compound, a free radical generator (freed by light irradiation) used in a photopolymerizable composition or the like for the purpose of reducing yellowing of the background after copying is used. Compounds that generate groups) can be added. As the free radical generator, aromatic ketones, quinones, benzoin, benzoin ethers, azo compounds,
Organic disulfides, acyl oxime esters and the like can be mentioned. The amount to be added is preferably 0.01 to 5 parts by weight of the free radical generator per 1 part by weight of the diazo compound.

Similarly, for the purpose of reducing yellow coloring, a polymerizable compound having an ethylenically unsaturated bond (hereinafter, referred to as a vinyl monomer) can be used. The vinyl monomer is a compound having at least one ethylenically unsaturated bond (vinyl group, vinylidene group, etc.) in its chemical structure, and has a chemical form of a monomer or prepolymer. Examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohols, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds. The vinyl monomer is used in an amount of 0.2 to 20 parts by weight based on 1 part by weight of the diazo compound. It is preferable that the free radical generator and the vinyl monomer are used in a microcapsule together with a diazo compound.

The copying material of the present invention is prepared by preparing a coating liquid containing a microcapsule containing a diazo compound or the like, a coupling component, a coloring aid, an infrared light absorbing substance and other additives, and forming a paper or a synthetic resin. Bar coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, etc. on a support such as a film, for example, Yuji Harazaki, “Coating Engineering” 25
Coating and drying by a coating method that can be selected from the methods described on page 3 (published by Asakura Shoten, 1987)
A recording layer of ３０30 g / m ² is provided.

In the copying material of the present invention, a photosensitive organic substance, a photochemical reaction product of the photosensitive organic substance, a labeling organic substance capable of chemically or physically distinguishing those substances, and a heat absorbing infrared light infrared light absorbing substance which can be converted to the Ru contained in the same layer. In addition, to apply the recording layer liquid safely and uniformly, and to maintain the strength of the coating film,
In the present invention, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, starches,
Gelatin, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide, polystyrene and its copolymer, polyester and its copolymer, polyethylene and its copolymer, epoxy resin, acrylate and methacrylate-based resin and its copolymer, polyurethane Resins, polyamide resins and the like can be used together with the microcapsules.

Further, on a support, JP-A-61-549 was used.
After providing the intermediate layer described in the specification of No. 80 or the like, the recording layer can be applied.

As the support of the present invention, any paper support used for ordinary pressure-sensitive paper, thermal paper, dry or wet diazo copy paper, etc., and neutral supports such as alkyl ketene dimer can be used. Neutral paper having a pH of 6 to 9 sized with a sizing agent (described in Japanese Patent Application No. 55-14281), satisfying the relationship between the Stechig sizing degree and the metric basis weight described in JP-A-57-116687, and Paper having a Beck smoothness of 90 seconds or more, an optical surface roughness described in JP-A-58-136492 of 8 μ or less, and a thickness of 30 to
Paper having a density of 0.9 g / cm ³ or less and an optical contact ratio of 15% or more described in JP-A-58-69091; and a Canadian standard freeness described in JP-A-58-69097. Paper made from pulp beaten to 400 cc or more according to JIS P8121) to prevent the infiltration of the coating solution, and the glossy surface of the base paper made by the Yankee machine described in JP-A-58-65695 was used as the coated surface, and the color density and Paper having improved resolution, paper obtained by subjecting a base paper described in JP-A-59-35985 to corona discharge treatment to improve coating suitability, and the like can also be used.

Further, the synthetic resin film used as a support in the present invention can be arbitrarily selected from well-known materials which are not deformed by heating in the developing process and have dimensional stability. Examples of such a film include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate film, polystyrene films, polypropylene films, polyolefin films such as polyethylene, polyimide films, polyvinyl chloride films, and polyvinyl chloride films. Vinylidene film, polyacryl film, polycarbonate film and the like,
These can be used alone or bonded together, or can be used by bonding to one or both sides of a paper support. . As the thickness of the support, 10 to 200
μ is used.

The support used in the present invention comprises a heat-resistant treatment,
Those subjected to an antistatic treatment are preferred. In the present invention, in order to prevent the recording layer from peeling from the support,
Before applying the recording layer on the support, it is preferable to provide an undercoat layer on the support.

In the recording layer of the copy material of the present invention, the infrared light absorbing substance capable of absorbing infrared light and converting it into heat is present at any one or more of the inside, outside and inside the microcapsule. When it is contained, the infrared light absorbing substance absorbs the irradiated infrared light and converts its energy into heat energy. As a result, the microcapsules are heated to become material-permeable, and the internal pressure is increased. As a result, the reactants inside and outside the microcapsules come into contact with the microcapsule wall to develop color.

To form an image on the copy material of the present invention,
The following method is preferred. In the process of superimposing a heat-developable copy material and a document and exposing the copy material recording layer to UV light through the document, various fluorescent lamps, xenon lamps, mercury lamps and the like are used as an exposure light source. It is preferable that the absorption spectrum substantially coincides with the absorption spectrum of the photosensitive organic substance used in the copying material. Next, in the step of irradiating the whole surface of the recording layer with infrared rays for development, an infrared light source used preferably has an intense spectrum at 650 nm to 1300 nm, such as an infrared lamp or a xenon flash. Of course, it is also possible to use an infrared laser.

[0064]

According to the present invention, since the recording layer can be heated by non-contact means such as infrared light irradiation to form an image, it is simple, compact, easy to maintain, and low in cost. Equipment can be designed.

[0065]

The following examples are provided to further clarify the effects of the present invention, but the present invention is not limited thereto. In the examples, "%"
Means “% by weight” unless otherwise specified.

Example 1 (Preparation of Microcapsule Solution) 1-morpholino-2,5-dibutoxybenzene-4 was used as a diazonium salt compound.
3.45 parts of diazonium hexafluorophosphate and 18 parts of an adduct of xylylene diisocyanate and trimethylolpropane (3: 1) as microcapsule wall material were added to 10 parts of ethyl acetate, and dissolved by heating. A solution of this diazo compound was prepared by adding 5.2 parts of polyvinyl alcohol to 58 parts of water.
The resulting mixture was mixed with the aqueous solution dissolved in the mixture and emulsified and dispersed at 20 ° C. to obtain an emulsion having an average particle size of 2.5 μm. 100 parts of water was added to the obtained emulsion, and the mixture was heated to 60 ° C. while stirring,
After 2 hours, a capsule solution containing the diazo compound in the core substance was obtained. During this reaction, the vessel was kept at 100 mmH with a water jet pump.
g-130 mmHg under reduced pressure.

0.1 g of this microcapsule solution was added to 20 c
The sample was weighed into a volumetric flask (c), methanol was added to make exactly 20 cc, and then left for 30 minutes. Weigh 2 cc of the methanol solution with a microsyringe and use a gas chromatograph mass spectrometer (M-80B, Hitachi, Ltd.).
Was injected. The column used was TENAX 3 mmφ × 1 m. Quantification was performed using the m / z peak of ethyl acetate = 43 m / z, and the content of ethyl acetate in the capsule solution was 0.87
% Values were obtained.

(Preparation of Coupling Component Dispersion) As a coupling component, 10 parts of 2-hydroxy-3-naphthoic acid anilide and 10 parts of triphenylguanidine were added to 200 parts of a 5% aqueous polyvinyl alcohol solution, and dispersed by a sand mill for about 24 hours. Thus, a dispersion having an average particle size of 3 μ was obtained.

(Preparation of Infrared Light Absorbing Dye Solution) 1 g of an infrared light absorbing dye represented by the following formula was dissolved in distilled water to make 100 g. Upon dilution with a concentration of 10 ⁻⁵ M and measurement with a Shimadzu spectrophotometer, the maximum absorption wavelength was 710 nm. 10 g of this 1% by weight aqueous solution is mixed with 50 g of 10% by weight of polyvinyl alcohol (saponification degree 98%, polymerization degree 1700).
And stirred for 1 hour.

[0070]

Embedded image

(Preparation of Copying Material) 50 parts of a capsule solution of a diazo compound, 50 parts of a dispersion of a coupling component and triphenylguanidine, and infrared light absorbing dye solutions 30 and 4
10 parts of a 0% calcium carbonate dispersion was added to obtain a coating solution. This coating solution was applied to smooth high-quality paper (75 g / m ² ) using a coating bar so as to have a dry weight of 10 g / m ² , and dried at 50 ° C. for 1 minute to prepare a copy material.

A test manuscript (a tracing paper having a circle of 3 cm in diameter uniformly painted black with a 2B pencil) was overlaid on the copying material and exposed with a fluorescent lamp. At this time, a lamp having an emission spectrum of a fluorescent lamp having a maximum value at 420 nm was used.

Then, a TP-MA manufactured by 3M Corporation equipped with a thermofax lamp of 120 V and 1350 W was used.
It passed through KERMODEL 4550 at a speed of 5 cm / sec. When the density of the color-developed portion and the background portion of the obtained sample was measured with a Macbeth densitometer, the color-developed density and the background density were 1.28 and 0.14, respectively.

For comparison, when the same copy material exposed to a fluorescent lamp was heated for 3 seconds by a heat block heated to 120 ° C., the color density and the background density were each 1.
26, 0.13.

Further, in order to test the shelf life, the film was stored at 40 ° C. and 90% RH for 24 hours, exposed in the same manner, and developed at each temperature. A 24-hour storage test at 60 ° C. and 30% RH was also performed. The density of the color-developed portion and the background portion of the sample obtained by each test was measured with a Macbeth densitometer. As a result, the samples under the former condition were 1.25 and 0.14, respectively, and the samples under the latter condition were 1.23 and 0.13, respectively.

[Example-2] (Preparation of microcapsule liquid) 3 parts of leuco crystal violet, 2,2'-bis- (o-chlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole 3 parts, tribromomethylphenylsulfone 0.6 part,
0.4 parts of 2,5-di-t-octylhydroquinone and 24 parts of a 75% ethyl acetate solution of xylylenediisocyanate trimethylolpropane adduct were mixed with methylene chloride 22 parts.
And tricresyl phosphate in a mixed solvent of 24 parts. This solution was added to 63 parts of an aqueous 8% polyvinyl alcohol solution, and emulsified and dispersed at 20 ° C. to obtain an emulsion having an average particle size of 1 μm. 100 parts of water was added to the obtained emulsion, and stirring was continued at 40 ° C. for 3 hours. Thereafter, the temperature was returned to room temperature and filtration was performed to obtain a capsule dispersion liquid.

Next, 30 parts of 1-phenylpyrazolidin-3-one (phenidone A) was added to 4% of polyvinyl alcohol.
Dispersed in a horizontal sand mill in addition to 150 parts of the aqueous solution,
A phenidone A dispersion having an average particle size of 1 μ was obtained.

(Preparation of Infrared Light Absorbing Dye Solution) 1.3 g of an infrared light absorbing dye represented by the following formula was dissolved in distilled water.
g. When the solution was diluted to a concentration of 10 ^-5 M and measured with a Shimadzu spectrophotometer, the maximum absorption wavelength was 650 nm. 10 g of this 1% by weight aqueous solution is treated with 10% by weight of polyvinyl alcohol (saponification degree 98%, polymerization degree 1700) 5
0 g and stirred for 1 hour.

[0079]

Embedded image

Next, 240 parts of the above capsule dispersion liquid, 180 parts of the above phenidone dispersion liquid, 50 parts of the infrared light absorbing dye solution 50
Coating solution prepared by mixing 20 parts of a 20% silica (Syloid 404, manufactured by Fuji Devison Chemical Co., Ltd.) dispersion and 10 parts of a 3% aqueous solution of polyethylene glycol lauryl ether on a high quality paper (basis weight: 76 g / m ² ). Apply with a rod so that the solid application amount becomes 10 g / m ² ,
To obtain a recording material.

The recording material was exposed to a fluorescent light in the same manner as in Example 1, and the image density of the exposed portion was measured with a Macbeth densitometer to obtain a value of 1.26. When the sample after the image formation was left in a bright room for 6 hours, the density of the non-image portion became 1.24, and it became impossible to distinguish the image from the non-image portion. Therefore, the same TP-MAK as in the first embodiment is used.
Thermal development was performed using ERMODEL 4550, and the density of the image portion and the non-image portion when the sample after the heat treatment was left in a bright room for 6 hours was measured. At this time, the image density was 1.25, and the density of the non-image portion was 0.16.

Example 3 (Preparation of Electron-donating Colorless Dye Capsule) Electron-donating colorless dye 2-anilino-3-methyl-6-N-ethyl-N-
9 parts of butyl-aminofluorane were dissolved in 17 parts of ethyl acetate, and 20 parts of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 parts of Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. 8%
Was added to a mixture of 42 parts of phthalated gelatin and 1.4 parts of a 10% sodium dodecylbenzenesulfonate solution.
The emulsion was dispersed at 20 ° C. to obtain an emulsion. 14 parts of water and a 2.9% aqueous solution of tetraethylenepentamine 7 were added to the obtained emulsion.
2 parts were added, and the mixture was heated to 60 ° C. with stirring, and after 2 hours, contained an electron-donating colorless dye in the core and had an average particle size of 0.5 μm.
m of capsule liquid was obtained.

(Preparation of emulsion of photocurable composition) Photopolymerization initiator 2,2'-bis- (o-chlorophenyl) -4,
4 parts of 4 ', 5,5'-tetraphenylbiimidazole,
Polymerizable electron-accepting compound 2 was added to a mixed solution of 0.6 parts of tribromomethylphenylsulfone and 6 parts of isopropyl acetate.
8 parts of -chloro-4- (5'-methacryloyloxypentamethyleneoxycarbonyl) phenol were added. This solution was added to a mixed solution of 15 parts of a 13% aqueous solution of gelatin and 2 parts of a 2% aqueous solution of sodium dodecylbenzenesulfonate, and emulsified at 10,000 rpm for 5 minutes with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain a photocurable solution. An emulsion of the composition was obtained.

(Preparation of Coating Solution for Photosensitive Layer) 4 parts of a colorless dye-donating dye capsule, 12 parts of an emulsion of a photocurable composition and 12 parts of a 15% aqueous gelatin solution were mixed to prepare a coating solution for a photosensitive layer. Prepared.

(Preparation of Coating Solution for Protective Layer) 4.5 parts of 10% gelatin aqueous solution, 4.5 parts of distilled water, 3 parts of 2% sodium dodecylbenzenesulfonate aqueous solution, Snowtex N
1 part with each other to prepare a coating solution for a protective layer.

(Support) A double-sided undercoated polyethylene terephthalate synthetic paper E68L (manufactured by Toray Industries, Inc.) was used.

(Preparation of photosensitive / thermosensitive recording material) A coating solution for a photosensitive / thermosensitive layer was coated on a support using a coating bar so that the dry weight of the coating layer was 8 g / m ^2.
Dry at 0 ° C. for 10 minutes. Further, a coating liquid for a protective layer was further applied thereon by using a coating bar so that the dry weight of the applied layer was 2 g /
m ² and dried at 30 ° C. for 10 minutes to obtain a sample of Example 3.

The resulting photosensitive and heat-sensitive recording material was exposed to ultraviolet light from a 2000 W high-frequency lighting type ultra-high pressure mercury lamp (Printer P627GA manufactured by Dainippon Screen Co., Ltd.) through a lithographic film developed. After that, 120V, 1350W
5cm / sec to 3M TP-MAKE MODEL 4550 equipped with a thermofax lamp
When the film was passed at a speed of c, a clear image was obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-53-34515 (JP, A) JP-A-1-295253 (JP, A) JP-A-3-72358 (JP, A) JP-A-4- 331186 (JP, A) JP-A-5-116450 (JP, A) JP-A-5-124337 (JP, A) JP-A-5-124338 (JP, A) JP-A-5-124339 (JP, A) JP-A-5-124340 (JP, A) JP-A-63-213841 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/52 G03C 1/675 G03F 7/004 505

Claims (1)

(57) [Claims] 1. A photosensitive organic substance, a photochemical reaction product of the photosensitive organic substance, a labeling organic substance capable of chemically or physically distinguishing those substances, and a heat absorbing infrared light on a support. Copying material provided with a light and heat sensitive recording layer containing an infrared light absorbing substance as an essential component that can be converted into
An image forming method comprising the steps of: exposing the copying material by irradiating ultraviolet rays through a document; and irradiating the entire surface of the photosensitive and heat-sensitive recording layer of the exposed copying material with infrared rays for development.