JPH0133355B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a light and heat sensitive composition that records by heating and fixes non-recorded areas by irradiation with light, and more particularly relates to a light and heat sensitive composition that is capable of high sensitivity thermal recording and has excellent storage stability. It is related to. In recent years, with the development of information and communications, the demand for hard copy technology has increased, and various methods have been developed. Among these, the thermal recording method, which records electrical information by converting it into heat using a thermal head, has the advantages of being able to make the device smaller and lighter, and can perform noiseless recording. It is becoming more and more used. Conventionally, the so-called "3M type" paper, which uses a reaction between an organic acid metal salt and a reducing agent, and the so-called "NCR type" paper, which uses a reaction between a leuco dye and an oxidizing agent, have been used as thermal recording paper. . However, since these materials cannot fix the recording, they develop color when reheated. There was a problem in that the color developed or disappeared due to the adhesive solvent, cellophane tape, or ink. In addition, NCR type thermal paper in particular had the disadvantage that the color would fade if the recording sample was exposed to light for a long period of time. This is because leuco dyes generally have poor light resistance. In order to solve these drawbacks, it is necessary to use a reaction system that can be fixed and produces a dye with better light resistance when heated. In order to achieve this goal, an attempt was made to record by reacting a diazonium salt and a coupler by heating to form an azo dye, and then fixing by photodegrading the diazonium salt in the non-recording area by irradiation with light. be. Such a reaction system applies the so-called heat development diazo system. The thermal development diazo method is a well-known technique in the field of diazo photography, and has the advantage of eliminating ammonia odor during wet processing and development, which is a drawback of wet diazo photography and dry diazo photography. In the thermal development diazo method, the original written on transparent paper and the thermal development diazo paper are placed on top of each other, and the diazonium salt in the non-document areas is decomposed by exposing the original side to light. By heating at 100 to 200° C. for several seconds to several tens of seconds, the diazonium salt in the written portion of the manuscript reacts with the coupler, thereby obtaining a positive azo dye recorded image corresponding to the manuscript.
When such a heat-developable diazo paper is used as a heat-sensitive recording paper, a heat-writing process is first carried out, followed by a fixing operation, and the order of heating and exposure is reversed from that of heat-developable diazo photography. Here, since heating is performed by a thermal head in an extremely short time of several milliseconds, a thermal sensitivity that is superior to that of the thermal development diazo method is required. The history of the heat development diazo method is not so new; patent applications have been filed since the 1940s, and various proposals have been made. However, the reason why the thermal development diazo method has not become widespread to this day is mainly due to the insufficient storage stability of the recording paper. In addition, when trying to improve storage stability, there was a dilemma in that the color development properties deteriorated. The following methods have been proposed for realizing heat-developable diazo paper. US Pat. No. 2,653,091, US Pat. No. 3,157,503, and Japanese Patent Publication No. 51-40,455 describe attempts to use trichloroacetic acid, which is a thermally decomposable acidic substance, or an alkali salt of trichloroacetic acid.
In other words, when these substances are thermally decomposed by heating, the acidic atmosphere of the system is destroyed, and the system is changed to a basic atmosphere by the action of basic substances added to the same system, or alkalis generated by thermal decomposition. The aim is to induce a diazo coupling reaction. However, in order to decompose trichloroacetic acid by 90%, thermogravimetric analysis (TGA) is required.
According to the paper, it is necessary to heat up to about 140℃, and the thermal sensitivity is insufficient for these systems to be used as thermal paper. Similarly, if we estimate the thermal decomposition rate of trichloroacetic acid at room temperature using TGA (see AENewkirk: Analytical
Chemistry, 32 , No. 12, ^1558- ( ¹⁹⁶⁰ )) is obtained), and this value requires 3 to naturally decompose up to 50% of the total amount. This means that it only takes about a day, and it is clear that long-term storage stability is not guaranteed. Further, British Patent No. 1092293 describes an attempt to create a basic atmosphere by coexisting a substance such as urea in the system as a developer and using ammonia gas generated by decomposition of urea by heating. However, when the degradability at room temperature was similarly examined using the above-mentioned TGA method, it took only about 20 days for 10% decomposition, and the shelf life of this system is not guaranteed. Furthermore, British Patent No. 909491 proposes the use of a urea-based developer and a thermally decomposable acidic substance, but similarly, storage stability is not guaranteed, and heat sensitivity is limited to heating above 120°C. This is necessary and the purpose of the present invention cannot be realized. Also, U.S. Patent No. 2217189 and No.
No. 2,680,062 proposes the use of diazosulfonate, which is a diazonium salt that has no coupling ability at room temperature. However, diazosulfonate does not have coupling ability unless it is heated to 140°C or higher, so it is insufficient in terms of thermal sensitivity. In addition, diazosulfonate generally has extremely low photodegradability, so there is a problem in that the photofixability is extremely poor. Furthermore, in US Pat. No. 3,076,707, it is proposed to use a eutectic adduct of bisphenol and amine or a clathrate compound of urea and amine as a developer, but the thermal sensitivity is 150 to 180°C. 5 seconds, which does not allow the purpose of the present invention to be achieved. Further, US Pat. No. 3,135,607 proposes using a quaternary ammonium compound as a developer and causing a diazo coupling reaction using ammonia gas generated by heating. However, the thermal sensitivity was extremely inadequate at 177°C for 15 seconds. Many attempts have been made to generate couplers that thermally decompose substances that have no coupling ability at room temperature. In U.S. Patent No. 937160, α-
120 using tertiary ester of pyrrole carboxylic acid
It states that color development occurs at ℃. However, azo dyes formed from a pyrrole compound and a diazonium salt often have a shallow color tone, and there are problems such as the recorded image being easily discolored. Special Public Service 1977-
No. 11952 proposes the use of γ-resorcinic acid derivatives. However, the thermal decomposition temperatures of these compounds are generally high, ranging from 160 to 210°C, and are insufficient in terms of thermal sensitivity. As described above, a system that utilizes the thermal decomposition properties of materials cannot realize a system that satisfies the thermal sensitivity and storage stability required for thermal recording paper. British Patent No. 815005 proposes coating a diazonium salt and a coupler separated by a wax layer without using a developer. However, such a system that does not use a developer cannot fully satisfy the thermal sensitivity required by the present invention. Further, US Pat. No. 3,202,510 proposes the use of hexamethylenetetramine or urea microencapsulated with wax or the like as a developer. However, since hexamethylenetetramine is a sublimable substance, it acts on the diazonium salt and coupler through the diaphragm during storage, causing background fog. Further, as mentioned above, in the case of urea, ammonia gas generated by thermal decomposition that proceeds at room temperature acts on the coloring layer through the diaphragm. The specification of Japanese Patent Publication No. 49-2614 states that a heat-developable diazo paper with excellent thermal sensitivity and storage stability can be realized by using microcapsules of high-boiling liquid amines as a developer. However, microcapsules with liquid as their core material have the problem that they are easily destroyed by mechanical stimulation, pressure bonding, and the like. Also, special public service 53-27604
No., JP-A-54-28616 discloses a system in which a diazonium salt and a coupler are coated in a layer, and an imidazole compound or an imidazoline compound is coexisting therein to melt the coupler layer and create a salty atmosphere, thereby improving thermal sensitivity. The company says it will be able to create heat-developable diazo paper with excellent storage stability. However, for example, benzimidazole has a high melting point of 170°C, so it exhibits extremely insufficient thermal sensitivity of 126°C for 40 seconds. Furthermore, although imidazole, which has a relatively low melting point of 90°C, provides better thermal sensitivity, it is thought to have problems with storage stability. In other words, when the thermal decomposition of imidazole at room temperature is investigated using the TGA method mentioned above, the time required for 10% decomposition is about 4 months, and the diazonium salt is contained in the diazonium salt by the very small amount of thermally decomposed basic gas generated at room temperature. This is because coloring occurs at the interface between the layer and the layer containing the coupler. Further, in this system, since the developer component is not particularly partitioned, it is difficult to coexist the diazonium salt and the coupler in the same layer, and it is necessary to coat them in separate layers. For this reason, there is a problem that the thermal sensitivity is inferior to that of systems coexisting in the same layer. The present invention is characterized by using a fine powder of a basic substance which has a relatively low melting point and is stable against thermal decomposition as a developer. The object of the present invention is to realize a photosensitive and thermosensitive composition. Table 1 shows the developer used in the present invention. Since all of these materials are basic substances, they can effectively form a basic atmosphere especially at temperatures near their melting points, and can couple the diazonium salt and coupler to form an azo dye. All of these substances are also stable against thermal decomposition;
As shown in Table 1, the time required for 10% decomposition is much longer than that of conventionally used urea and imidazole, and it has excellent storage stability. Moreover, by using it as a fine powder, the storage stability is further improved. There are two methods for using it as a fine powder: That is, there are two methods: one is to use the powder as a dispersion by pulverizing it by a method such as a ball mill, and the other is to use it as microcapsules. The photosensitive and thermosensitive composition obtained in the present invention contains a basic substance isolated from the diazonium salt and the coupler in a non-contact state, that is, a diazonium salt and the coupler are provided with a diaphragm layer or a partition wall of a microcapsule so that the basic substance can be isolated from the diazonium salt and the coupler. It is configured so that there is no contact with the

[Table] The structure is as shown in Figure 1 or Figure 2. In FIG. 1, diazonium salt, coupler,
A layer 12 consisting of an acid stabilizer for preventing coupling at room temperature and other additives is applied, and a developer layer 14 is applied via a barrier layer 13. The developer layer contains fine developer powder. The layer 12 may be coated on a precoated layer provided on the base paper 11, or may be coated using a suitable binder. The solvent used for coating the barrier layer 13 must not be the same as that for the layer 12. The developer layer 14 is suitably coated using a suitable binder, and the solvent used in this case must not be one that dissolves the layer 13. Waxes and various synthetic resins can be used as the partition wall material. It is also appropriate to add a pigment or the like to each layer to prevent staking with the head. In FIG. 2, 21 includes a base material, 22 includes a microencapsulated developer, and 23 includes a diazonium salt, a coupler, an acid stabilizer, other additives, a staking inhibitor, and the like. Microcapsulation of the developer can be carried out by various methods, and suitable methods include an in situ polymerization method, a melt dispersion cooling method, a Wuerster method, and a spray drying method. Waxes and various synthetic resins can be used as wall materials for microencapsulation. The thermal sensitivity of the composition obtained according to the present invention is determined by the melting point of the developer and the basicity of the developer. That is, the stronger the basicity and the lower the melting point, the greater the developing effect. Regarding the developer listed in Table 1,
1.3-diphenylguanidine, 3-amino-1H-
1.2.4-Triazole (hereinafter referred to as 3-amino-triazole) has a slightly high melting point but is strongly basic, and also has 2.6-pyridine-di-methanol, 3-amino-triazole,
Hydroxy-pyridine, 2,2'-di-pyridylamine, and 4,4'-di-pyridylmethane are somewhat weakly basic, but because of their low melting points, they all have excellent developing effects. Further, when these developers are used in combination, the melting point is lowered due to the melting point depression phenomenon, and further improvement in thermal sensitivity can be realized. Further, when utilizing the melting point reduction by mixing, compounds other than the developer mentioned above can also be used. At this time, the compound used for mixing must not react with the developer. It is also desirable that the material be stable against thermal decomposition. Such compounds include acrylamide (melting point: 84℃), nicotinamide (melting point: 123℃), 2-phenylimidazole (melting point: 148℃), isonicotinamide (melting point: 123℃),
Sodium diethyldithiocarbamate (155℃), sodium diethyldithiocarbamate (90℃), 3-amino-pyridine (58℃),
4-dimethylaminopyridine (109℃), 6-
Amino-2,4-lutidine (same, 64℃), 2-piperazine-methanol (same, 69℃), piperazine hexahydrate (same, 45℃), 1,3-di-piperidylpropane (same, 67℃), 4- Phenyl-pyridine (same, 70
), γ.γ′-di-pyridyl (same, 72°C), 2-hydroxy-pyridine (same, 105°C), o-tolyl-bi-guanide (same, 142°C), 2-amino-5- Chloro-3-picoline (69°C), 2-amino-thiazole (92°C), 2,3-diamino-pyridine (115°C), N,N'-diphenylformamidine (140°C) ), 2-phenyl-imidazoline,
Potassium malonate, o-phenylenediamine (same, 101℃), 2.6-tolylenediamine (same,
105℃), 1.8-diamino-octane (same, 62℃),
1.9-diaminooctane (same, 38℃), guanidine carbonate (same, 197℃), nitrosoguanidine, guanidine sulfate, guanidine hydrochloride (same, 184℃), nitroguanidine, guanidine sulfamate (same,
128℃), aminoguanidine sulfate, aminoguanidine bicarbonate, triethylamine hydrochloride, diethylamine hydrochloride, dimethylamine hydrochloride, dicyandiamide (same, 208℃), benzidine (same, 126℃),
Phenylhydrazine hydrochloride, P-toluenesulfonylhydrazide, hydrazobenzene, isonicotinic acid hydrazide (same, 173°C), 4,4'-di-thiomorpholine, indole, 1,2,3-benztriazole (same, 100°C) , P-toluenesulfonamide, benzamide, α-cyanoacetamide, triphenyltetrazolium chloride, 2-amino-pyridine, piperazine hydrochloride, 6-amino-2-picoline (same, 39°C), 2-amino-2-methyl- 1.3
-propanediol, 4,4'-styrene dianiline, 5-nitro-2-amino-thiazole, 6-
Aminomercaptobenzothiazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, piperidinium pentamethylene dithiocarbamate, 2-methylindole (same, 60°C), benzamidine hydrochloride (same, 171)
℃), 2.2'-dipyridine (same temperature, 71℃), sodium malonate, 2-aminopyrimidine (same temperature, 128℃),
m-Toluylene diamine (98℃), m-amino-diphenyl (125℃), P-toluidine (43℃), ammonium phthalate, malonamide,
Piperazine (109℃), tolylene-3,4-diamine (89℃), 1,8-diamino-naphthalene (62℃), P-phenylenediamine (142℃)
℃), 2.6-dichloropyridine (dichloropyridine, 88℃), 2.6-
Diamino-pyridine (116℃), α-picolineamine (106℃), 6-amino-3-picoline (33℃), 2-amino-4-picoline (99℃)
℃), 2.5-diphenyloxazole (same temperature, 73℃),
2-piperidine ethanol (same, 39℃), N-hydroxypiperidine (same, 38℃), 4-pyridinemethanol (same, 57℃), m-phenylenediamine (same, 65℃), 1.3-diamino-2 -Hydroxypropane (44℃), P-piperidinoacetophenone (85℃), 4-piperidino-piperidine (65℃), tetramethylpyrazine (85℃)
), sodium citrate, 2-amino-5-picoline (same, 77°C), 2-amino-4-ethylpyridine (same, 67°C), 2.5-diaminopyridine sulfite, 2-amino-3.5-dichloro Pyridine (same as
74°C), 2-amino-3.5-dichloro-4-picoline (129°C), 2.2'-dimethyl-3-aminopropanol (100°C), 2-cyano-6-methyl-pyridine (72°C) ), 3-cyano-5-methyl-pyridine (same, 84°C), 3.5-dicyanopyridine (same, 113°C), 2,6-dicyano-pyridine (same,
123℃), etc. Compounds that do not lower the melting point and are used simply to adjust thermal sensitivity include sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium chloride, ammonium sulfate, ammonium thiocyanate, ammonium acetate, ammonium phosphate, and hydrogen carbonate. Examples include salts such as ammonium, sodium oxalate, potassium tartrate, sodium hydrogen carbonate, sodium P-toluenesulfonate, sodium methanesulfonate, sodium stearate, sodium formate, sodium acetate, potassium acetate, and the like. The diazonium salt used in the present invention is one that can couple with a coupler in a basic atmosphere to form an azo dye. The following gave good results: P-diazo-N-ethyl, N-
Hydroxyethylaniline chloride zinc chloride,
P-diazo-N,N-diethylaniline chloride zinc chloride, P-diazo-N,N-dimethylaniline chloride zinc chloride, P-diazo-N-benzyl-N-ethylaniline chloride zinc chloride,
4-Diazo-N,N-diethylaniline fluoroborate, 4-benzamido-2.5-diethoxybenzeneazonium chloride zinc chloride, 4-methoxy-6-benzamido-m-toluidine-diazonium chloride zinc chloride, sulfuric acid-4-diazo -diphenylamine, 1-diazo-3-naphthol-4-sulfonic acid soda, 1-diazo-2-
Sodium naphthol-4-sulfonate, 2-methoxy-4-morpholinobenzenediazonium chloride zinc chloride, 4-morpholino-2.5-dibutoxybenzenediazonium chloride zinc chloride, 4
-P-methoxybenzamide-2.5-diethoxybenzenediazonium chloride zinc chloride, 2-
N,N-diethyl-m-toluidine-diazonium fluoroborate, 6-morpholino-m-toluidine-diazonium fluoroborate, sodium 2-diazo-1-naphthol-4-sulfonate, 2-diazo-1-naphthol-5- Sodium sulfonate, 4-diazo-4'-methoxy-diphenylamine chloride. The coupler used in the present invention is any that couples with a diazonium salt in a basic atmosphere to form a dye. Such couplers include resorcinol, catechol, phloroglucin, o-hydroxybiphenyl, α-naphthol, 1.5-di-hydroxynaphthalene, 2.3-di-
Hydroxynaphthalene, 2.7-di-hydroxynaphthalene, sodium 1-hydroxynaphthalene-4-sulfonate, NW acid, sodium 2-hydroxynaphthalene-4-sulfonate, sodium 2-hydroxynaphthalene-6-sulfonate,
Schiefuric acid, 3-hydroxynaphthalene-3.6
-sodium di-sulfonate, R acid, potassium 2-hydroxynaphthalene-6.8-di-sulfonate,
G acid, sodium 2.3-dihydroxynaphthalene-6-sulfonate, sodium 2.7-dihydroxynaphthalene-3.6-disulfonate, sodium 1.8-dihydroxynaphthalene-3.6-di-sulfonate (disodium chromotrope) ,
Acetoacetanilide, dimedone, 3-methyl-
5-pyrazolone, 1-phenyl-3-methyl-5
-Pyrazolone, 2-hydroxy-3-naphthoic acid-morpholinopropylamide, 2-hydroxy-
3-naphthoic acid-o-toluidinoamide, 4-methoxy-1-naphthol, 2-hydroxy-3-
Naphthoic acid methyl ester, 2-hydroxy-
3-naphthoic acid-o-aniside, 2-hydroxy-3-naphthoic acid-amide-anilide, 2-hydroxy-3-naphthoic acid-α-naphthylamide,
2-Hydroxy-3-naphthoic acid m-xylidine, 2-hydroxy-3-naphthoic acid m-nitroanilide, 2-hydroxy-3-naphthoic acid-
β-naphthylamide, 2-hydroxy-3-naphthoic acid-hydroxyethylamide, 2-hydroxy-3-naphthoic acid amide, 2-hydroxy-3-naphthoic acid amide
-Naphthoic acid-P-methoxybenzamide, 2-
Hydroxy-3-naphthoic acid-m-nitro-benzamide, 2-hydroxy-3-naphthoic acid-P
-Chlorbenzamide, 2-hydroxy-3-naphthoic acid-o-ethoxybenzamide, 2-hydroxy-3-naphthoic acid-2.5-di-methoxybenzamide, 2-hydroxy-3-naphthoic acid-
2-Methyl-4-chloro-benzamide, 2-hydroxy-3-naphthoic acid-3-chloro-4.6-
Di-methoxy-benzamide and the like are suitable. Further, as the coupler, an image of any tone can be obtained by using not only the above-mentioned couplers alone but also two or more kinds of couplers. For example, P
-Diazo-N-ethyl-N-hydroxyethylaniline chloride The pigments produced by coupling zinc chloride with sodium 2,3-di-hydroxynaphthalene-6-sulfonate and acetoacetanilide are purple and yellow, respectively, and together they are almost black. form an image. A suitable acid stabilizer is added to prevent coupling between the diazonium salt and the coupler at room temperature. In the present invention, since the developer is separated from the diazonium salt and the coupler by a suitable diaphragm, a less acidic stabilizer can be used, and there is no need to add a large amount. . Suitable examples of such acid stabilizers include tartaric acid, citric acid, oxalic acid, boric acid, and phosphoric acid. Other additives that can be added include reducing agents that prevent coloration through oxidation after photodecomposition of the diazonium salt, such as thiourea, ascorbic acid,
Allyl isothiocyanate, etc. are added. Zinc chloride is also added as a stabilizer for the diazonium salt. In addition, as a solubilizing agent for Kuplar, alkali metal salts or alkaline earth metal salts of organic acids such as sodium citrate, calcium citrate, magnesium citrate, sodium tartrate, calcium tartrate, and calcium gluconate, caffeine,
Sodium 1,3,6-naphthalene trisulfonate and the like can also be added. Furthermore, guanidine sulfate, pentaerythritol, etc., which contribute to promoting thermal color development, can also be added. The barrier wall material used to isolate the developer is one that can effectively protect the developer from diazonium salts and couplers even if it is thin, and it melts and softens at 50 to 110°C when heated to protect the developer from diazonium salts. microcrystalline wax, montanic acid wax, montanic acid ester, oleic acid amide, stearic acid amide, lauric acid amide, ethylene bisstearic acid amide, paraffin. waxes, such as polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, linear saturated polyester, methacrylic acid ester, ethylene-vinyl acetate graft polymer, ethylene-vinyl acetate copolymer, polystyrene epoxy resin, 1.2- Synthetic polymeric compounds such as polybutadiene are suitable. A detailed explanation will be given below based on examples. Examples 1 to 23 A solution having the following composition was prepared and coated on high-quality paper that had been precoated with finely powdered silica and polyvinyl acetate emulsion to produce a dry diazo drying paper. Water 100 parts P-diazo-N-ethyl, N-hydroxyethylaniline chloride Zinc chloride 2 parts Sodium 2.3-di-hydroxynaphthalene-6-sulfonate 3 parts Tartaric acid 4 parts Thiourea 5 parts Zinc chloride 4 parts A diaphragm layer was provided by applying a solution having the following composition. PVC-vinyl acetate copolymer (Denkavinyl #1000AS polymerization degree 320) 10 parts Toluene 100 parts The coating amount was 10 g/m ² . Next, a developer layer was provided on the diaphragm layer using the developer combinations shown in Table 2. That is, in each example, natural rubber gasoline was added to 10 parts of the developer listed in Table 1 or a mixed developer (1:1), or a mixture of a developer and another compound (1:1). Solution (product name Esdyne No. 153)
A developer dispersion liquid was prepared by adding 100 parts and pulverizing this in a ball mill. This liquid was applied onto the diaphragm layer at 3 g/m ² . The resulting composition was heated at a constant temperature for 5 seconds at 100 g/cm ²
The thermal sensitivity was measured by pressing it against a heating plate at a pressure of . All compositions formed purple dye images with a maximum O.D of 1.0 or more. Table 2 shows the temperature that gives a density of 1/2 of the maximum density as the coloring temperature. Both are 100
This indicates that color development occurs at temperatures below ℃. Furthermore, each composition could be fixed by leaving it for one hour under room light or by exposing it to an ultraviolet fluorescent lamp for several seconds. Furthermore, the obtained composition was stored at 20 to 25°C and a relative humidity of 30 to 60%, shielded from light. The initial concentration is 0.15 to 0.20 for all compositions, and the relationship between the standing time and concentration is

【table】

[Table] Preservability was measured by examining the relationship. The storage period is defined as the point in time when the initial concentration is doubled.Table 2
The results were obtained. All exhibited storage stability for one year or more. Examples 24 to 29 Developer microcapsules were prepared by the melt-dispersion cooling method in the following manner. silicone oil 100
Add 0.5 g of developer pulverized to an average particle size of 50 μm and 1.5 g of wax to cc, and heat and stir at 80 to 90°C. The microcapsules formed by rapid cooling in an ice water bath were filtered, washed with a solvent such as hexane, and collected. Table 3 summarizes the developer and microcapsule wall material used in each example. Five parts of the microcapsules thus obtained were added to the following solution to prepare a coating solution. Water 100 parts P-diazo-N,N-diethylaniline chloride Zinc chloride 2 parts Sodium 2.7-di-hydroxynaphthalene-3.6-di-sulfonate 3 parts Citric acid 5 parts Thiourea 5 parts Zinc chloride 4 parts Polyvinyl alcohol 2 parts Finely powdered silica 10 parts All of the compositions formed by coating this dispersion on high-quality paper formed purple dye images with an O.D of 1.0 or more when heated at 100° C. for 5 seconds. In addition, when recording was attempted using a thermal printer, all compositions formed dye images with a resolution of 5 lines/mmO.D1.0 or more. After recording, the non-recorded areas could be fixed by exposure for one hour under room light or for several seconds under an ultraviolet fluorescent lamp. In addition, the storage stability of all samples was over 1 year.

[Table] Examples 30 to 34 Developer microcapsules were prepared by the spray drying method in the following manner. Average particle size of 30μ in 10% methylene chloride solution of vinyl chloride-vinyl acetate copolymer
Disperse 10 g of the developer crushed into m. This was sprayed into an atmosphere at 50° C. using a conventional spray drying device, and the methylene chloride was evaporated to form a film of vinyl chloride-vinyl acetate copolymer on the surface of the developer. The obtained microcapsules were spherical with an average particle size of 35 μm, and a complete coating was formed. Table 4 shows the developer used in each example.
Five parts of the microcapsules thus obtained were added to the following solution to prepare a coating solution. Water 100 parts P-diazo-N,N-diethylaniline fluoroborate 2 parts Disodium chromotrope 3 parts Oxalic acid 2 parts Thiourea 5 parts Zinc chloride 4 parts Polyvinyl alcohol 2 parts Finely powdered silica 10 parts The composition formed by coating on paper is printed with a thermal printer at a resolution of 7 lines/mmO.
A blue image with a D1.0 or higher was obtained, and it could be fixed with high sensitivity using indoor light or an ultraviolet fluorescent lamp. composition

[Table] The shelf life of all items could be guaranteed for one year or more. Examples 35 to 39 In Examples 30 to 34, microcapsules could be prepared by using microcrystalline wax instead of the vinyl chloride-vinyl acetate copolymer and toluene instead of methylene chloride. By using the obtained microcapsules in the same manner as in Examples 30 to 34, it was possible to obtain a photosensitive and thermosensitive composition with excellent thermal sensitivity and storage stability. Examples 40 to 44 Developer microcapsules were prepared by the Wuerster method in the following manner. A developer pulverized to an average particle size of 30 μm is suspended in a fluidized air bed of a Wu¨ster process device, and a 10% methylene chloride solution of a vinyl chloride-vinyl acetate copolymer is sprayed onto the surface of the developer. A coating of bicopolymer was formed. As the developer, any of the systems shown in Table 4 could be used. A coating solution was prepared by adding 5 parts of the obtained microcapsules to the following solution. Water 100 parts P-diazo-N-ethyl, N-hydroxyethylaniline chloride Zinc chloride 1 part Acetoacetanilide 1 part Tartaric acid 5 parts Thiourea 5 parts Zinc chloride 4 parts Polyvinyl alcohol 2 parts Finely powdered silica 10 parts The composition formed by coating on paper was printed with a thermal printer at a resolution of 7 lines/mm and O.
A black image with D1.0 or higher was formed. Furthermore, it was possible to fix with high sensitivity using indoor light or an ultraviolet fluorescent lamp.
The shelf life of all compositions could be guaranteed for one year or more. Examples 45-49 Microcapsules were prepared in Examples 40-44 using microcrystalline wax instead of the vinyl chloride-vinyl acetate copolymer and toluene instead of methylene chloride. By using the obtained microcapsules in the same manner as in Examples 40 to 44, thermal sensitivity and
A photosensitive and thermosensitive composition with excellent storage stability could be obtained. As explained above, in light and heat sensitive compositions containing diazonium salts and couplers,
1.3-diphenylguanidine, 3-amino-triazole, 2.6-pyridine-dimethanol, 3-
Hydroxypyridine, 2,2′-dipyridylamine,
4.4'-Dipyridylethane can be melted by heating to effectively create a basic atmosphere capable of coupling the diazonium salt and coupler, and these materials are extremely stable against thermal decomposition at room temperature. Since the composition does not thermally decompose and generate basic gas during storage, a photosensitive and thermal composition with excellent heat sensitivity and storage stability can be obtained, and it can be used as a fixable thermal recording paper or a thermally developable diazo paper. It has the advantage that it can be applied as

[Brief explanation of drawings]

1 and 2 show cross-sectional views of the photosensitive and heat-sensitive composition obtained by the present invention. DESCRIPTION OF SYMBOLS 11... Base material, 12... Layer containing diazonium salt and coupler, 13... Partition layer, 14... Developer layer, 21... Base material, 22... Microencapsulated developer, 23... Diazonium Layer containing salt and katsupular.

Claims (1)

[Claims] 1. Contains a diazonium salt, a coupler, and a basic substance, increases a basic atmosphere by heating, and forms a recorded image by reacting the diazonium salt and the coupler to form an azo dye; In a light- and heat-sensitive composition system containing a diazonium salt and a coupler dispersed in the same layer, the diazonium salt can be decomposed by light irradiation so that no recorded image is formed even if the non-recorded portion is heated. 1.3-diphenylguanidine, 3-
Amino-1H-1.2.4-triazole, 2.6-pyridine-dimethanol, 3-hydroxypyridine,
A photosensitive and thermosensitive composition characterized in that one or a mixture of two or more fine powders of 2.2'-dipyridylamine and 4.4'-dipyridylethane is used in isolation from the diazonium salt and coupler in a non-contact state. thing. 2 As basic substances in the above system, 1,3-diphenylguanidine, 3-amino-1H-1.2.4-
triazole, 2,6-pyridine-dimethanol,
A mixture of one or more fine powders of 3-hydroxypyridine, 2.2'-dipyridylamine, and 4.4'-dipyridylethane and one or more compounds that do not react with these developers. 2. The photosensitive and thermosensitive composition according to claim 1, characterized in that the diazonium salt and the coupler are used in isolation in a non-contact state.