JPH06308660A - Photosensitive and heat sensitive recording material - Google Patents

Abstract

PURPOSE:To provide a photosensitive and heat sensitive recording material capable of obtaining a recorded image remarkably superior contrast to conventional ones. CONSTITUTION:The photosensitive and heat sensitive recording material has a photosensitive and heat sensitive layer on a support, and it is characterized by comprising in this layer microcapsules enclosing at least an electron donative dye precursor capable of developing color by oxidation and a photo-oxidizing agent capable of reacting with this precursor to form the dye, other microcapsules enclosing a reducing agent capable of inactivating the photooxidizing agent, a diazo compound capable of reacting with a coupler by heating and developing a hue other than the hue developed by that dye precursor, and the coupler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light and heat sensitive recording material, and in particular, it is subjected to imagewise exposure and then uniform heat development, or imagewise heat recording and then uniform exposure to give a colored background. The present invention relates to a light and heat sensitive recording material capable of obtaining a colored image having a high contrast and a hue different from that of the background color.

[0002]

2. Description of the Related Art A thermal recording method is widely used in the field of facsimiles, printers, etc. because it has the advantages that it does not require development, it is easy to handle, the recording device is simple and inexpensive, and there is little noise during recording. Recently, development of a heat-sensitive recording material that can be used for OHP and the like has been advanced (Japanese Patent Laid-Open No. 63-22).
No. 735 and Japanese Patent Laid-Open No. 4-101885).

In this case, the contrast of the image is determined by the white color of the screen and the color density of the color-developing portion of the heat-sensitive layer. It is difficult to perform thermal erasing with high sensitivity, and therefore, especially OHP
In such use, there is a drawback that a sufficient image contrast cannot be obtained.

[0004]

By the way, if the chances of another substance coming into contact with the surface such as OHP increases, the non-image portion is colored and the image quality is apt to deteriorate. Therefore, for such use, it is desired to use a photo-fixable diazo heat-sensitive recording material (for example, JP-A-4-290788). On the other hand, a non-silver salt light-sensitive material that develops color by light is also known.

The inventors of the present invention have made extensive studies as to the advantages of combining heat-coloring, light-coloring, and light-fixing. As a result, by further combining the light-sensing system of diazo with a light-coloring system, the contrast is extremely excellent. The inventors have found that an image can be obtained and have reached the present invention. Therefore, a first object of the present invention is to provide a light and heat sensitive recording material capable of obtaining an image excellent in contrast, which has never been seen before. A second object of the present invention is to provide a light and heat sensitive recording material suitable especially for OHP.

[0006]

The above objects of the present invention are a light and heat sensitive recording material having a light and heat sensitive layer on a support, wherein the light and heat sensitive layer has at least an oxidative color-forming electron donating property. Microcapsules containing together a dye precursor and a photo-oxidizing agent capable of absorbing light and reacting with the dye precursor to form a dye, a reducing agent capable of inactivating the photo-oxidizing agent, It is achieved by a light and heat sensitive recording material containing a microcapsule containing a diazo compound that develops a color by reacting with a coupler when heated, in a hue different from that of the electron-donating dye precursor, and a light and heat sensitive recording material containing the coupler. It was

In the light and heat sensitive recording material of the present invention, the light and heat sensitive layer when not exposed or thermally recorded is white, but when exposed to light, it is encapsulated in microcapsules together with the electron-donating dye precursor. When the photo-oxidizing agent is activated, it reacts with the electron-donating dye precursor to develop color, and the exposed part is colored, and at the same time, the diazo compound contained in the other microcapsule undergoes photolysis and is no longer heated. Even if it is done, it will not develop color.

Therefore, if the entire surface of the light and heat sensitive layer is uniformly heated after imagewise exposure and recording, each microcapsule that isolates the photo-oxidizing agent and the diazo compound becomes substance permeable, and While the oxidizing agent is inactivated by contact with the reducing agent, the diazo compound develops color by contacting with the coupler, so that the image is heat-fixed and the unexposed area (background area) is colored in the exposed area. Color in a different hue from the hue.

On the contrary, when image-wise thermal recording is performed first, each microcapsule containing the diazo compound and the photo-oxidizing agent becomes substance-permeable, and the heated portion is colored by the contact between the diazo compound and the coupler. Since the photo-oxidizing agent is contacted with the reducing agent to be deactivated, the photo-oxidizing agent no longer reacts with the electron-donating dye precursor to form a color even when irradiated with light. After thermal recording in this way, when the entire surface of the light and heat sensitive layer is exposed uniformly, the unheated part (background part) is colored in a different hue from the image part due to reaction between the electron-donating dye precursor and the photo-oxidizing agent. At the same time, since the diazo compound is also photodecomposed (photofixation), color is no longer developed even if heat is further applied.

Then, the contrast of the obtained image is
It is determined by the hue and density of the non-image area (background) and the hue and density of the image area. Therefore,
From the viewpoint of image contrast, it is preferable that the spectral absorption region of the dye formed in the background and the spectral absorption region of the dye formed in the image area do not overlap. Examples of preferable combinations of hues include combinations of blue and orange, black and orange or yellow, blue and red, and the like.

From the standpoint of obtaining a particularly good quality image, a layer containing an electron-donating dye precursor (hereinafter, this layer is referred to as a photo-coloring layer).
And a layer containing a diazo compound (hereinafter, referred to as a thermal color-developing layer) are preferably provided in multiple layers. As long as the two layers are substantially transparent, their vertical relationship is arbitrary, and an intermediate layer may be provided between these layers. However, if an opaque support is used, it is necessary to place a transparent layer on top. In this case, the lower layer may be an opaque layer.

In the present invention, the electron-donating dye precursor has one or two hydrogen atoms which form a dye by adding an additional electron or by removing the electron to form a dye. Means a reduced dye. In the present invention, among such electron-donating dye precursors,
Select one that is substantially colorless or light colored.

The oxidatively coloring electron-donating dye precursor used in the photocoloring system in the present invention is, for example, US Pat. No. 3,44.
No. 5,234, and specific examples thereof include:
(1) aminotriarylmethane, (2) aminoxanthene, (3) aminothioxanthene, (4) amino-
9,10-dihydroacridine, (5) aminophenoxazine, (6) aminophenothiazine, (7) aminodihydrophenazine, (8) aminodiphenylmethane,
(9) Leuco damine, (10) aminohydrocinnamic acid (cyanoethane, leucomethine), (11) hydrazine, (12) leucoin digoid dye, (13)
Amino-2,3-dihydroanthraquinone, (14) tetrahalo-p, p'-biphenol, (15) 2- (p
-Hydroxyphenyl) -4,5-diphenylimidazole, (16) phenethylaniline and the like can be mentioned.

Of these electron-donating dye precursors,
The compounds of (1) to (9) develop color by losing one hydrogen atom to give a dye, while those of (10) to (16) lose two hydrogen atoms to form a dye. Of these, aminotriarylmethane is particularly preferable in the present invention. Such aminotriarylmethane has been reported in detail in JP-A-1-227145.

The photo-oxidizing agent used in the present invention is activated by irradiation with light and reacts with the electron-donating dye precursor to form a colored pigment. Such photo-oxidants are
It is an inactive compound until it is exposed to actinic rays such as visible rays, ultraviolet rays, infrared rays and X-rays.

Specific examples of such a photo-oxidizing agent include US Pat. Nos. 3,042,515 and 3,502,4.
No. 76, carbon tetrabromide, halogenated hydrocarbons such as N-bromosuccinimide and tribromomethylphenyl sulfone, azide polymer described on page 55 of Abstracts of Spring Meeting of the Photographic Society of Japan 1968, USA Azide compounds such as 2-azidobenzoxazole, benzoyl azide and 2-azidobenzimidazole described in US Pat. No. 3,282,693, US Pat. No. 3,61.
3'Ethyl-1-methoxy- described in 5,568.
2-pyridothiacyanine perchlorate, 1-methoxy-2-methylpyridinium-p-toluenesulfonate, 2,4 described in JP-B-62-39,728.
Mention may be made of lophine dimer compounds such as 5-triarylimidazole dimers, benzophenones, p-aminophenyl ketones, polynuclear quinones, thioxanthenones and mixtures thereof.

In the present invention, the ratio of the photo-oxidizing agent to the electron-donating dye precursor used is preferably mixed in a molar ratio of 10: 1 to 1:10, and particularly 2: 1. It is preferable to mix in a ratio of ˜1: 2. In the present invention, a stabilizer such as a sensitizer for a photo-oxidizing agent or an antioxidant may be further added to the microcapsule for use. These additives are described in detail in JP-A-1-227145.

The reducing agent used in the present invention is a so-called free radical scavenger that traps free radicals generated from the activated photo-oxidizing agent, and has a function of deactivating the oxidizing action of the photo-oxidizing agent. is there. Therefore, even if the light and heat sensitive recording material is irradiated with an actinic ray after heating, the electron-donating dye precursor is no longer oxidized by the photo-oxidizing agent.

The above free radical scavenging substance can be appropriately selected and used from known substances. Specifically, for example, as described in US Pat. No. 3,042,515, an organic compound having a hydroxyl group on a benzene ring and at least another hydroxyl group or an amino group existing at another position of the benzene ring is used. Reducing agents (for example, hydroquinone and its derivatives, catechol, resorcinol, hydroxyhydroquinone, pyrologricinol and aminophenols such as o-aminophenol and p-aminophenol):

Cyclic phenylhydrazide compounds described in JP-B-62-39,728, such as 1-phenylpyrazolidin-3-one (phenidone A), 1-phenyl-4-methylpyrazolidine-3- On (phenidone B), 1-phenyl-4,4-dimethylpyrazolidine-
3-one (dimezone), 3-methyl-1- (p-sulfophenyl) -2-pyrazolin-5-one and 3-methyl-1-phenyl-2-pyrazolin-5-one;

The guanidine compounds described in JP-A-57-132,141, such as 1-3-diphenylguanidine, phenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, 1- Benzylidene-guanidinoamino; alkylenediamine compounds such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine; hydroxyamine compounds such as diethanolamine and triethanolamine.

However, the phenyl group of the cyclic phenylhydrazide is o-, m- and p-methyl, p-trifluoromethyl, m- and p-chloro, m- and p-bromo,
substituted with p-fluoro, o-, m- and p-methoxy, p-ethoxy, p-benzyloxy, p-butoxy, p-phenoxy, 2,4,6-trimethyl and 3,4-dimethyl, etc. Is also good.

The 4-position on the heterocyclic group of cyclic phenylhydrazide may be substituted with bis-hydroxymethyl, hydroxymethyl and methyl, dimethyl, dibutyl, ethyl and benzyl. Further, the 5-position on the heterocyclic group of cyclic phenylhydrazide may be substituted with dimethyl, methyl or phenyl.

The reducing agents may be used alone or in combination of two or more kinds. Further, any reducing substance capable of acting on an oxidizing agent to lose its oxidizing ability can be used without being limited to the above reducing agent. The amount of reducing agent used is a photo-oxidizing agent.
Although it can be used in the range of 1 to 100 mol per mol, 1 to 10 mol is generally sufficient.

The photodecomposable diazo compound used in the present invention is mainly an aromatic diazo compound, and more specifically, an aromatic diazonium salt, a diazosulfonate compound,
Examples thereof include diazoamino compounds. Of these, the diazonium salt is particularly preferably used in the present invention from the viewpoint of photosensitivity.

The diazonium salt is a compound represented by the general formula Ar—N ₂ ⁺ X ⁻ (wherein Ar represents an aromatic moiety, N ₂ ⁺ represents a diazonium salt, and X ⁻ represents an acid anion). These have various maximum absorption wavelengths depending on the position and type of the substituent of the Ar portion.

Specific examples of the diazo compound used in the present invention include 4- (N- (2- (2,4-di-tert-
Amylphenoxy) butyryl) piperazino) benzenediazonium, 4-dioctylaminobenzenediazonium, 4- (N- (2-ethylhexanoyl) piperazino) benzenediazonium, 4-dihexylamino-2
-Hexyloxybenzenediazonium, 4-N-ethyl-N-hexadecylamino-2-ethoxybenzenediazonium, 3-chloro-4-dioctylamino-2-
Octyloxybenzenediazonium ,;

2,5-Dibutoxy-4-morpholinobenzenediazonium, 2,5-octoxy-4-morpholinobenzenediazonium, 2,5-dibutoxy-4-
(N- (2-ethylhexanoyl) piperazino) benzenediazonium, 2,5-diethoxy-4- (N- (2
-(2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium, 2,5-dibutoxy-4-tolylthiobenzenediazonium, 3-
(2-octyloxyethoxy) -4-morpholinobenzenediazonium and the like. In the present invention, these hexafluorophosphate salt, tetrafluoroborate salt, and 1,5-naphthalenesulfonate salt are particularly useful because they have low solubility in water and are soluble in organic solvents.

The coupler which reacts with the diazo compound used in the present invention to produce a color upon heating includes resorcin, phloroglucin and 2,3-dihydroxynaphthalene-6-.
Sodium sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-
Dihydroxy-6-sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3
-Naphthoic acid ethanolamide, 2-hydroxy-3-
Naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid-N-dodecyloxypropylamide, 2-hydroxy-3-naphthoic acid tetradecylamide;

Acetanilide, acetoacetanilide,
Benzoylacetanilide, 2-chloro-5-octylacetoacetanilide; 1- (2-tetradecanooxyphenyl) -2-carboxymethylcyclohexane-3,
5-dione, 1-phenyl-3-methyl-5-pyrazolone, 1- (2'-octylphenyl) -3-methyl-5
-Pyrazolone, 1- (2 ', 4', 6'-trichlorophenyl) -3-benzamido-5-pyrazolone, 1-
(2 ', 4', 6'-trichlorophenyl) -3-anilino-5-pyrazolone, 1-phenyl-3-phenylacetamido-5-pyrazolone and the like can be mentioned. Specific examples of suitable couplers include compounds represented by the following chemical formulas 1 to 7.

[0031]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

Of these, the couplers of Chemical Formula 1 are brown, the couplers of Chemical Formula 2 are orange, the couplers of Chemical Formulas 3, 6 and 7 are red, the couplers of Chemical Formula 4 are maroon, and the couplers of Chemical 5 Is a purple type. Two or more of these couplers may be used in combination. The basic substance that accelerates the reaction between the diazonium salt and the coupler includes an inorganic or organic basic compound as well as a compound that decomposes upon heating to release an alkaline substance.

Representative ones are organic ammonium salts,
Organic amines, amides, urea and thiourea, their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines,
Examples thereof include nitrogen-containing compounds such as piperidines, amidines, formazines and pyridines.

Specific examples thereof include tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine; allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea; 2
-Benzylimidazole, 4-phenylimidazole,
2-phenyl-4-methylimidazole, 2-undecylimidazoline, 2,4,5-trifuryl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-
Imidazoline, 2-phenyl-2-imidazoline;

1,2,3-triphenylguanidine,
1,2-dicyclohexylguanidine, 1,2,3-tricyclohexylguanidine, guanidine trichloroacetate; N, N'-dibenzylpiperazine;4,4'-dithiomorpholine, morpholinium trichloroacetate; 2
-Aminobenzothiazole, 2-benzoylhydrazinobenzothiazole and the like. These may be used in combination of two or more.

In the present invention, from the viewpoint of improving the transparency of the light and heat sensitive layer, and from the viewpoint of raw storability (prevention of fog) such as preventing contact between the photo-oxidizing agent and the reducing agent and the diazo compound and the coupler at room temperature, the above-mentioned conditions The photo-oxidizing agent, the electron-donating dye precursor, and the diazo compound are each encapsulated in microcapsules before use.

From the viewpoint of improving the transparency of the light- and heat-sensitive layer, the reducing agent and the coupler are dissolved in an organic solvent that is sparingly soluble or insoluble in water, and then this is necessary as well as having a water-soluble polymer as a protective colloid. Accordingly, it is preferable to use it in the form of a dispersion obtained by further mixing with an aqueous phase containing a surfactant and emulsifying and dispersing. The organic solvent used in this case is
It can be appropriately selected from the high boiling point oils.

Among the preferred oils, in addition to esters, dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene, dimethylbiphenyl, diethylbiphenyl, diisopropylbiphenyl, diisobutylbiphenyl, 1-methyl-1-dimethylphenyl-1 are preferred.
-Phenylmethane, 1-ethyl-1-dimethylphenyl-1-phenylmethane, 1-propyl-1-dimethylphenyl-1-phenylmethane, triallylmethane (for example, tritoluylmethane, toluyldiphenylmethane), terphenyl compound, Examples thereof include alkyl compounds, alkylated diphenyl ethers (eg propyl diphenyl ether), hydrogenated terphenyls (eg hexahydroterphenyl), diphenyl ethers and the like.

Of these, it is particularly preferable to use the esters from the viewpoint of the emulsion stability of the emulsion dispersion.
Examples of the esters include phosphates (eg, triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, cresyl diphenyl phosphate), phthalates (dibutyl phthalate, 2-ethylhexyl phthalate,
Ethyl phthalate, octyl phthalate, butylbenzyl phthalate), dioctyl tetrahydrophthalate, benzoic acid ester (ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate);

Abietic acid esters (ethyl abietic acid, benzyl abietic acid), dioctyl adipate,
Isodecyl succinate, dioctyl azelate, oxalate (dibutyl oxalate, dipentyl oxalate), diethyl malonate, maleate (dimethyl maleate, diethyl maleate, dibutyl maleate), tributyl citrate, sorbate ( Methyl sorbate, ethyl sorbate, butyl sorbate), sebacate ester (dibutyl sebacate, dioctyl sebacate);

Ethylene glycol esters (formic acid monoesters and diesters, butyric acid monoesters and diesters, lauric acid monoesters and diesters, palmitic acid monoesters and diesters, stearic acid monoesters and diesters, oleic acid monoesters and diesters), triacetin , Diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, borate esters (tributyl borate, tripentyl borate) and the like. Among these, the use of tricresyl phosphate alone or in combination is preferable because the emulsion dispersion stability of the color developer is particularly good.

It is also possible to use the above oils in combination, or to use in combination with other oils. In the present invention, an auxiliary solvent may be added to the above organic solvent as a low boiling point dissolution aid. As such an auxiliary solvent, for example, ethyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like can be mentioned as particularly preferable ones.

The water-soluble polymer to be contained as a protective colloid in the aqueous phase mixed with the oil phase containing these components is appropriately selected from known anionic polymers, nonionic polymers and amphoteric polymers. However, polyvinyl alcohol, gelatin, cellulose derivatives and the like are preferable.

Further, as the surfactant to be contained in the aqueous phase, an anionic or nonionic surfactant which does not cause precipitation or aggregation by acting on the protective colloid is appropriately selected and used. You can Preferred surfactants include sodium alkylbenzene sulfonate, sodium alkylsulfate, dioctyl sodium sulfosuccinate, polyalkylene glycol (eg, polyoxyethylene nonylphenyl ether), and the like.

The emulsified dispersion of the present invention comprises a means used for ordinary fine particle emulsification such as high speed stirring and ultrasonic dispersion of an oil phase containing necessary components and an aqueous phase containing a protective colloid and a surfactant. It can be easily obtained by using and mixing and dispersing. The value of the ratio of the oil phase to the water phase (oil phase weight / water phase weight) is preferably 0.02 to 0.6, and particularly preferably 0.1 to 0.4.
If it is 0.02 or less, the amount of the aqueous phase is too large to be diluted and sufficient color developability cannot be obtained, and if it is 0.6 or more, the viscosity of the liquid is increased, which causes inconvenience in handling and a decrease in coating liquid stability.

Any of an interfacial polymerization method, an internal polymerization method and an external polymerization method can be adopted for producing the microcapsules used in the present invention. In particular, the electron donating dye precursor and the photo-oxidizing agent are particularly preferable. , Or, after emulsifying the core substance containing the diazo compound in an aqueous solution in which a water-soluble polymer is dissolved,
It is preferable to employ an emulsion polymerization method in which a wall of a polymer substance is formed around the oil droplet. The reactant forming the polymer substance is added inside the oil droplet and / or outside the oil droplet.

Specific examples of the polymeric substance include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer,
Examples thereof include styrene-acrylate copolymer. Preferred polymeric substances are polyurethanes, polyureas, polyamides, polyesters and polycarbonates, particularly preferably polyurethanes and polyureas. Two or more polymer substances can be used in combination. Specific examples of the water-soluble polymer include gelatin, polyvinylpyrrolidone, polyvinyl alcohol and the like.

For example, when polyurea is used as the capsule wall material, polyisocyanates such as diisocyanate, triisocyanate, tetraisocyanate and polyisocyanate prepolymer, polyamines such as diamine, triamine and tetraamine, and amino groups are used. The microcapsule wall can be easily formed by reacting a prepolymer containing two or more of the above, piperazine or a derivative thereof, a polyol and the like with an interfacial polymerization method in an aqueous solvent.

Further, for example, the composite wall composed of polyurea and polyamide or the composite wall composed of polyurethane and polyamide is added, for example, by using polyisocyanate and acid chloride or polyamine and polyol, after adjusting the pH of the emulsifying medium as the reaction liquid. It can be prepared by warming. For details of the method for producing a composite wall composed of these polyurea and polyamide, see JP-A-58-6.
6948.

Further, a metal-containing dye, a charge control agent such as nigrosine or any other additive substance may be added to the microcapsule wall used in the present invention, if necessary. These additive substances can be contained in the wall of the capsule at the time of forming the wall or at any other time.
In addition, a monomer such as a vinyl monomer may be graft-polymerized or these polymers may be attached in order to adjust the chargeability of the capsule wall surface, if necessary.

Further, a sensitizer may be added in an emulsified state or a solid dispersed state in order to swell the microcapsule wall during heating. The sensitizer may be selected from those referred to as plasticizers for polymers used as microcapsule walls, and those having a melting point of 50 ° C. or higher, preferably 120 ° C. or lower, and solid at room temperature can be used. For example,
When the wall material is made of polyurea or polyurethane, a hydroxy compound, a carbamic acid ester compound, an aromatic alkoxy compound, an organic sulfonamide compound, an aliphatic amide compound, an arylamide compound and the like are preferably used.

When a mixed solution of the emulsion dispersion and the microcapsule solution prepared as described above (hereinafter referred to as a light- and heat-sensitive layer coating solution) is applied on a support, a known water-based or organic solvent-based coating solution is used. The coating means described below is used. When the heat-sensitive layer is a single layer, all the necessary components are added to the light- and heat-sensitive coating liquid and applied, but as described above, when the photo-coloring layer and the heat-coloring layer are applied in multiple layers, the same procedure is performed. It goes without saying that the coating liquid for each layer may be prepared and each layer may be provided by the means described later.

Methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, starches, gelatin, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide are used as binders in order to apply the coating liquid safely and uniformly and to maintain the strength of the coating film. , Polystyrene and its copolymers, polyester and its copolymers, polyethylene and its copolymers, epoxy resins, acrylate and methacrylate resins and their copolymers, polyurethane resins, polyamide resins, etc. together with microcapsules. You can also

In order to produce the light and heat sensitive recording material of the present invention, a coating solution containing the above binder and other additives is prepared in the above coating solution, and the coating solution is prepared on a support such as paper or synthetic resin film. Bar coating, blade coating, air knife coating,
Coating and drying are carried out by a coating method such as gravure coating, roll coating coating, spray coating or dip coating to provide a light and heat sensitive layer having a solid content of 2.5 to 25 g / m ² . The light and heat sensitive layer thus provided has extremely good transparency.

The support used in the present invention may be transparent or opaque, but when it is used as a light and heat sensitive recording material for OHP, a transparent support is used. The transparent support preferably has high transparency and dimensional stability that does not deform even when heated during thermal recording. The thickness of the support is 10 μm to 200 μm.

Examples of such a transparent support 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 films, and polyimides. Examples of the film include a film, a polyvinyl chloride film, a polyvinylidene chloride film, a polyacrylic film, and a polycarbonate film, and these can be used alone or in combination.

On the other hand, examples of the opaque support of the recording material include paper, synthetic paper, aluminum vapor deposition base, and the above-mentioned transparent support coated with a pigment or the like. As the paper used for the support, neutral paper having a heat extraction pH of 6 to 9 sized with a neutral sizing agent such as alkyl ketene dimer (described in JP-A-55-14281) is used.
It is advantageous in terms of storage stability over time. In order to prevent the coating liquid from penetrating into the paper and to improve the contact between the thermal recording head and the thermal recording layer, the Steckigt sizing degree / (meter basis weight) ² ≧ 3 described in JP-A No. 57-116687. Papers with × 10 ^-3 and Beck's smoothness of 90 seconds or more are advantageous.

The optical surface roughness described in JP-A-58-136492 is 8 μm or less and the thickness is 40 to 7.
5 μm paper, 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-58-69097, Canadian standard drainage described in JP-A-58-69097. Paper made from pulp that has been beaten to 400 cc or more in accordance with JIS P8121, and coated with a glossy surface of base paper made by a Yankee machine as described in JP-A-58-65695. A surface for improving color density and resolution, JP-A-59-3598
The paper described in JP-A No. 5-5, which is obtained by subjecting the base paper to a corona discharge treatment to improve the coating suitability, is also used in the present invention and gives good results. In addition to these, any of the supports generally used in the field of heat-sensitive recording paper can be used as the support of the present invention.

In the present invention, an undercoat layer is provided on the support before coating a coating solution containing microcapsules or the like on the support for the purpose of preventing the entire light- and heat-sensitive layer from peeling off from the support. Is desirable. For the undercoat layer, an acrylic ester copolymer, polyvinylidene chloride, SBR, aqueous polyester, etc. can be used,
The film thickness is preferably 0.1 to 0.5 μm. The coating amount is preferably 1 to ²⁰ g / m ² , and particularly 3 to 1
It is preferably 0 g / m ² .

The undercoat layer may deteriorate the recording image quality when the undercoat layer swells due to the water contained in the coating solution when the coating solution such as the light and heat sensitive layer is applied thereon. Therefore, it is desirable to cure with a hardener. Such hardeners are described in detail in JP-A-2-111585.

Further, it is desirable to activate the surface of the support by a known method before applying the undercoat layer.
As a method of activation treatment, etching treatment with acid,
Flame treatment with a gas burner, corona treatment, glow discharge treatment, or the like is used, but from the viewpoint of cost or simplicity, US Pat. Nos. 2,715,075 and 2
The corona discharge treatment described in No. 846,727, No. 3,549,406, No. 3,590,107 and the like is most preferably used.

The layer of the light and heat sensitive recording material of the present invention which comes into contact with the thermal head is provided with silica, barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide for the purpose of preventing sticking to the thermal head and improving writability. , Pigments such as calcium carbonate and fine powders such as styrene beads and urea-melamine resin can be added.
In order to maintain the transparency of the recording layer, a protective layer mainly for the purpose of preservability and thermal head suitability may be provided on the recording layer by a known method, and the above fine powder may be added to the protective layer. preferable.

Details of the protective layer are described, for example, in "Paper Pulp Technology Times" (1985, September issue), pages 2 to 4. In the present invention, together with the above-mentioned protective layer conventionally used, or instead of those protective layers,
A silicone resin (JP-A-4-316885) or a protective layer mainly containing colloidal silica and silica-modified polyvinyl alcohol (JP-A-2-153781) may be provided. As a result, the suitability for a thermal head can be remarkably improved and the water resistance can be remarkably improved without impairing the transparency of the recording layer.

The silicone resin used in the protective layer may be any one having a siloxane bond as the main chain.
Alkyl group, phenyl group, carboxyl group, vinyl group,
It may be substituted with a nitrile group, an alkoxy group, a chlorine atom or the like. Further, together with the silicone resin, melamine resin, phenol resin, acrylic resin, polyester resin, epoxy resin, fluororesin, nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate, vinylidene fluoride,
Other non-aqueous resins such as chlorinated rubber may be used together.

Waxes and metal soaps may be added to the protective layer to prevent sticking. The amount of these used is 0.2 to 7 g / m ² . If necessary, a layer having the same composition as the protective layer may be provided as an intermediate layer between the photo-coloring layer and the thermo-coloring layer from the viewpoint of improving the adhesiveness between the layers. A back layer may be provided on the back surface of the support for the purpose of preventing curling or improving the writability of the back surface. In the present invention, a perforation may be provided so that the light and heat sensitive recording material can be smoothly transported in the recording apparatus.

The light source for exposure for forming an image on the light and heat sensitive recording material produced as described above of the present invention is not particularly limited, and may be natural light, artificial light, monochromatic light, non-coherent light or Either coherent light or the like can be used. However, in order to form an appropriate image, it is necessary to select a light source having an appropriate light wavelength and light density corresponding to the photo-oxidizing agent used. Such a light source and the like are described in detail in JP-A-1-227145. Further, as a light source for photolysis of the diazo compound, various light sources which emit light of a desired wavelength can be used, for example, various fluorescent lamps, xenon lamps, xenon flash lamps, mercury lamps of various pressures, and for photography. Various light sources such as a flash and a strobe can be used.

[0067]

As described in detail above, in the light and heat sensitive recording material of the present invention, an electron donative dye precursor capable of oxidative coloration, a photo-oxidizing agent, a reducing agent, and a different color are used in the light and heat sensitive layer. Since it contains a diazo compound and a coupler that develop color occasionally, it is possible to obtain a colored recorded image which is excellent in contrast and suitable for OHP and which is different from the background hue by one heating and exposure.

[0068]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Example 1. Preparation of capsule liquid A (electron-donating dye precursor and photo-acid agent)
Manufactured by Leuco Crystal Violet 3.0 parts, as photo-oxidizing agent 2,2'-bis- (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole 3.0
Parts, 0.6 parts of tribromomethylphenyl sulfone and 0.4 parts of a compound represented by the following chemical formula 8 (photo-oxidizing agent), 22 parts of methylene chloride, 24 parts of tricresyl phosphate, xyliresin isocyanate / trimethylolpropane Of 1
/ 3/3 adduct (75 wt% ethyl acetate solution) [Takenate D-110N (trade name of microcapsule wall agent manufactured by Takeda Pharmaceutical Co., Ltd.)], mixed in a liquid of 24 parts to an aqueous solution of 8 wt% polyvinyl alcohol. After adding 100 parts of distilled water to the aqueous solution, the mixture was emulsified and dispersed at 20 ° C. to obtain an emulsion dispersion having an average particle size of 1 μm.

The obtained emulsified dispersion was stirred at 40 ° C. for 3 hours, encapsulated, returned to room temperature and filtered to obtain a capsule liquid A.

[Chemical 8]

Preparation of reducing agent emulsion dispersion A 2,5-dioctylhydroquinone 6 parts, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane 2
Parts, t-octylhydroquinone 2 parts and tricresyl phosphate 1 part were dissolved in ethyl acetate 10 parts. The resulting solution was mixed with an aqueous solution obtained by mixing 50 parts of an 8 wt% polyvinyl alcohol aqueous solution and 2 parts of a 2 wt% sodium dodecylbenzenesulfonate aqueous solution, and using an ace homogenizer (manufactured by Nippon Seiki Co., Ltd.), 10 , 0
Emulsified at 00 rpm for 10 minutes at room temperature, average particle size 0.5
A μm reducing agent emulsion dispersion was obtained.

Preparation of Capsule Liquid B (Diazo Compound) 3.4 parts of diazo compound represented by the following chemical formula 9, 6 parts of tricresyl phosphate, 12 parts of methylene chloride, 18 parts of trimethylolpropane trimethacrylate, xylylene diisocyanate A solution obtained by mixing 24 parts of 1/3 adduct of nato / trimethylolpropane (Takenate D-110N: trade name of capsule wall material manufactured by Takeda Pharmaceutical Co., Ltd.),
8 wt% polyvinyl alcohol aqueous solution (PVA217
E: trade name of Kuraray Co., Ltd.) 63 parts and distilled water 100
The parts were mixed into a mixed aqueous solution.

[Chemical 9]

The obtained aqueous solution was used with an ace homogenizer (trade name of Nippon Seiki Co., Ltd.) for 10,000
The mixture was emulsified at 0 rpm and 20 ° C. to have an average particle size of 2 μm, reacted at 40 ° C. for 3 hours, cooled to 20 ° C.,
100 ml of Urban Light IR-120B (trade name of Rohm and Haas) was added, and the mixture was stirred for 1 hour and then filtered to obtain a capsule liquid B.

Preparation of Emulsion Dispersion B (Coupler / Base) 14 parts of coupler represented by the following Chemical formula 10, 6 parts of triphenylguanidine (base), 14 parts of color forming auxiliary represented by the following chemical formula 11, tricresyl A solution prepared by mixing 10 parts of phosphate and 20 parts of ethyl acetate was mixed with polyvinyl alcohol 4
It is mixed with 170 parts by weight of an aqueous solution, and then 1 using an ace homogenizer (trade name of Nippon Seiki Co., Ltd.)
The emulsion was emulsified at 20,000 rpm and 20 ° C. for 5 minutes to obtain an emulsified dispersion B having an average particle diameter of 0.5 μm.

[0075]

[Chemical 10]

[Chemical 11]

Preparation of coating liquid A (photochromic layer coating liquid) Coating liquid A was prepared by mixing 9 parts of capsule liquid A and 6 parts of emulsified dispersion liquid A. Preparation of coating liquid B (thermochromic layer coating liquid) A coating liquid B was prepared by mixing 4.9 parts of the capsule liquid B, 0.2 part of a 5% by weight hydroquinone aqueous solution, and 3.7 parts of the emulsified dispersion liquid B.

Preparation of Light and Heat Sensitive Recording Material The coating solution B thus obtained was coated on a 170 μm thick transparent polyethylene terephthalate (PET) support in a solid content of 3 parts.
A thermochromic layer was formed by coating and drying so as to be g / m ² . Next, the coating liquid A was added on the layer in a solid content of 7 g /
After coating and drying so as to have m ² to form a photo-coloring layer, a protective layer coating solution having the composition shown in Table 1 below is further added in a solid content of 2
A protective layer was formed by coating and drying so as to be g / m ² to prepare a light and heat sensitive recording material of the present invention.

[0078]

[Table 1] Composition of coating liquid for protective layer ──────────────────────────────────── Silica-modified polyvinyl alcohol 1 part by weight (solid content) (R2105: Kuraray Co., Ltd. product name) colloidal silica 1.5 parts by weight (solid content) (Snowtex 30: Nissan Chemical Co., Ltd. product name) Zinc stearate emulsion 0.02 Parts by weight (solid content) (Hydrin Z-7: trade name manufactured by Chukyo Yushi Co., Ltd.) Paraffin wax 0.02 parts by weight (solid content) (Hydrin P-7: trade name manufactured by Chukyo Yushi Co., Ltd.) ─── ──────────────────────────────────

Image Recording Test The obtained light and heat sensitive recording material was exposed through a document using a Recopy Super Dry 100 type for 1 minute, and then 12
Using a heat roller at 0 ° C., heat fixing was performed at a speed of 450 mm / min to obtain a recorded image. When the density of the image part and the density of the non-image part (background part) of the obtained recorded image were measured using a Macbeth transmission densitometer, the density of the image part was 0.9 in terms of the red filter density and that of the non-image part. The density was 0.4 with a blue filter.

When the obtained image record was projected using OHP, the projected image had a blue background and a yellow image portion.
It was a good image with excellent contrast. Also, first,
80m using a thermal head (manufactured by Kyocera Corporation)
When an image was recorded with J / mm ² energy, and then exposed for 1 minute using Recopy Super Dry 100 type, the heat-recorded portion developed blue color, the background portion developed yellow color, and again, the contrast. An excellent image could be obtained. When the recorded image thus obtained was projected using OHP, the projected image was a good image with a yellow background and a blue image portion and excellent contrast.

Example 2. Instead of the two layers of photo-coloring layer and thermo-coloring layer formed in Example 1, 7 parts of coating liquid A and coating liquid B3
A heat-sensitive recording material was prepared in exactly the same manner as in Example 1 except that one layer of the light- and heat-sensitive recording layer was formed by using the coating liquid containing the mixed parts, and an image was recorded in exactly the same manner as in Example 1. , O
When an image was projected using HP, a good projected image excellent in contrast and substantially the same as in Example 1 was obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 1/52 9019-2H 6956-2H B41M 5/18 112

Claims (2)

[Claims] 1. A light and heat sensitive recording material having a light and heat sensitive layer on a support, wherein the light and heat sensitive layer absorbs at least an electron-donating dye precursor capable of oxidative coloration, and the dye precursor. A microcapsule containing a photo-oxidizing agent capable of reacting with the body to form a dye together, a reducing agent capable of deactivating the photo-oxidizing agent, and a hue different from that of the electron-donating dye precursor. A light- and heat-sensitive recording material comprising a microcapsule containing a diazo compound which reacts with a coupler to generate a color upon heating, and the coupler. 2. A light- and heat-sensitive layer, at least a microcapsule containing both an oxidatively colorable electron-donating dye precursor and a photo-oxidizing agent, and a reducing agent are dissolved in an insoluble or sparingly soluble organic solvent in water. A layer obtained by applying and drying a coating liquid consisting of an emulsified dispersion that has been emulsified and dispersed, microcapsules containing a diazo compound, and an emulsified dispersion after dissolving the coupler in an organic solvent that is insoluble or sparingly soluble in water. 2. The light and heat sensitive recording material according to claim 1, wherein the light and heat sensitive recording material is a layer formed by applying multiple layers of a coating liquid comprising the emulsified dispersion prepared above and drying the coating liquid.