JPH04247447A - Photosensitive heat sensitive recording material - Google Patents

Abstract

PURPOSE:To obtain good reddish color developing hue and superior raw storage stability by using a combination of a specified diazo compound and a specified coupling component. CONSTITUTION:The recording layer containing as a diazo compound a 1- substituted amino-3-alkoxybenzene-4-diazonium salt, and as the coupling component a mixture of 2 kinds of 2-cyclohexenone derivatives. It is preferred to use this diazo compound in the range of 0.1-2g/m<2> in the recording layer from the viewpoint of the color developing density.

Description

Description: FIELD OF INDUSTRIAL APPLICATION The present invention relates to a recording material utilizing the photosensitivity of a diazo compound (diazonium salt), and more particularly to a red coloring type light and heat sensitive recording material. BACKGROUND OF THE INVENTION Three types of recording materials that utilize the photosensitivity of diazo compounds are known. One type is known as a wet development type, in which a photosensitive layer containing a diazo compound and a coupling component as main components is provided on a support, this material is superimposed on the original, and after exposure, it is processed using an alkaline solution. It is to be developed. The second type is known as a dry development type, which, unlike the wet type, develops with ammonia gas. The third type is known as a heat-developable type, and includes a type that contains an ammonia gas generating agent such as urea that can generate ammonia gas when heated in the photosensitive layer, or a type that contains an ammonia gas generating agent such as urea that can generate ammonia gas when heated, or a type that contains ammonia gas generating agent such as trichloroacetic acid in the photosensitive layer. There are types that contain an alkali salt of an acid that loses its properties as an acid when heated, and types that use a higher fatty acid amide as a coloring aid and activate the diazo compound and coupling component by heating and melting. [0003] In addition to maintenance problems such as the need for replenishing and discarding the liquid because it uses a developing solution and the large size of the device, the wet type also has problems with maintenance, such as the fact that the image is wet immediately after copying, making it difficult to make additions immediately. There are some problems, such as not being able to store images or copied images not being able to withstand long-term storage. In addition, like the wet type, the dry type requires replenishment of developer, requires gas absorption equipment to prevent the generated ammonia gas from leaking outside, and therefore requires larger equipment. There are problems such as the smell of ammonia immediately after copying. On the other hand, unlike the wet and dry types, the heat-developable type has the advantage of maintenance because it does not require a developing solution. Moreover, if the temperature is not controlled to about ±10° C., insufficient development or changes in color tone occur, resulting in an increase in equipment cost. Furthermore, the diazo compound used for such high-temperature development is required to have high heat resistance, but such compounds are often disadvantageous in forming high concentrations. Low temperature development (90°
C to 130° C.), but these had the drawback of decreasing the shelf life of the material itself. As described above, although the thermal development type is expected to have sufficient advantages in terms of maintenance compared to the wet and dry types, the current situation is that it has not yet become the mainstream of diazo recording systems. Now, in order to obtain the desired color density by heating a material in which a layer containing a diazo compound and a coupling component is provided on a support, each component instantly melts, diffuses, and reacts with the coloring dye. It is necessary to generate , but it is preferable to make the system basic during this reaction because it has the effect of accelerating the reaction. Therefore, in order to produce a light- and heat-sensitive recording material having a recording speed that does not pose a practical problem when heated at low temperatures, it is essential to include a basic substance in the coating layer. [0004] On the other hand, it is also essential for light and heat sensitive recording materials to suppress as much as possible the background coloring and the decrease in color density during storage before copying. [0005] As described above, it has a good shelf life,
Although the above-mentioned several attempts have been made to create photosensitive and thermosensitive recording materials with high recording speeds, the current situation is that they have not yet reached the point where they can be put to practical use. [0006] When designing a material that can sufficiently develop color and obtain high density even at low heating temperatures, it is natural that a color reaction may occur even while the material is stored at room temperature before copying. It appears as a phenomenon in which the skin, which should be white, becomes colored. In particular, in the case of red-colored recording materials, slight coloring of the background (fogging) occurs due to high visibility.
But there was a problem with it being noticeable. In order to solve these seemingly incompatible problems, the inventors of the present invention made extensive studies and found that a recording material in which a heat-developable photosensitive layer containing a diazo compound, a coupling component, and a basic substance is provided on a support. , we continued to investigate ways to incorporate the diazo compound into microcapsules, search for basic substances, and how to make microcapsules.
Succeeded in suppressing skin discoloration during pre-storage (Unexamined Japanese Patent Publication No. 2003
-54251). In addition, as a result of studies aimed at improving the storage stability and oil solubility of diazo compounds, we found that 1-substituted amino-
It has been found that 3-alkoxybenzene-4-diazonium salts exhibit excellent performance (Japanese Patent Application No. 169490/1999). Furthermore, as a result of intensive studies on combinations with coupling components, the present inventors discovered that the diazonium salt and the 2-cyclohexenone derivative produce a red pigment with an extremely good hue, leading to the present invention. Problems to be Solved by the Invention Therefore, the first aspect of the present invention
The object of the present invention is to provide a light- and heat-sensitive recording material that provides a good red color hue by using a combination of a specific diazo compound and a specific coupling component. A second object of the present invention is to provide a light and heat sensitive recording material that has excellent storage stability before recording (raw storage stability). [Means for Solving the Problems] The above objects of the present invention are as follows:
In a light and heat sensitive recording material comprising a recording layer containing a diazo compound, a coupling component, and an organic base on a support, the diazo compound is a 1-substituted amino-3-alkoxybenzene-4-diazonium salt, Moreover, the present invention has been achieved using a light and heat sensitive recording material characterized in that the coupling component is a mixture containing two types of 2-cyclohexenone derivatives. Among the diazo compounds according to the present invention, those represented by the following general formula [I] are preferred. General formula [I] [Chemical formula 1] [0011] (In the above formula, R1, R2 and R3 may be the same or different and represent an alkyl group, an aralkyl group, or an aryl group, and these may further include a substituent. (X represents an acid anion.) In the general formula [I], when R1, R2 and R3 have a substituent, the substituent is an alkyl group, an aryl group, a hydroxy group. , an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbamoyl group, an acylamino group, a halogen atom, and a cyano group. R1 , R2 and R3
The total number of carbon atoms is preferably 12 or more from the viewpoint of oil solubility,
In particular, 14 or more is preferred. In the general formula [I], specific examples of the acid anion represented by X include the following examples. Polyfluoroalkylcarboxylic acid having 1 to 9 carbon atoms, polyfluoroalkyl sulfonic acid having 1 to 9 carbon atoms, boron tetrafluoride, tetraphenylboron,
The diazonium salt can also be stabilized by forming a complex using hexafluorophosphoric acid, aromatic carboxylic acid, aromatic sulfonic acid, zinc chloride, cadmium chloride, tin chloride, or the like. The diazo compound according to the present invention has a melting point of 30°C.
The temperature is preferably from 50°C to 200°C, but from the viewpoint of handling, it is preferably from 50°C to 150°C. [0015] Furthermore, since it is used by dissolving it in an appropriate solvent (such as tricresyl phosphate) when it is contained in microcapsules, it is important that it has appropriate solubility in these solvents and low water solubility. preferable. Specifically, it is preferable to have a solubility in the solvent of 5% or more and a solubility in water of 1% or less. The diazo compound according to the present invention is preferably used in the heat-sensitive recording layer in an amount of 0.02 to 3 g/m2, and from the viewpoint of color density, it is preferably used in a range of 0.1 to 2 g/m2. is preferred. Specific examples of the diazo compound according to the present invention are shown below, but the present invention is not limited thereto. [0018] [Formula 2] [Formula 3] [Formula 4] [Formula 4] [0021] etc. The diazo compounds according to the present invention may be used alone or in combination of two or more. Furthermore, the diazo compound according to the present invention and known diazo compounds can be used together depending on various purposes such as hue adjustment. [0023] As the diazo compound that can be used in combination, the following are preferred. 4-Diazo-1-dimethylaminobenzene, 4-diazo-2-butoxy-5-chloro-1-dimethylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-diazo-1-ethylhydroxyethylaminobenzene , 4-diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-tolylmercapto-2, 5-diethoxybenzene, 4-diazo-1-piperazino-2-methoxy-5-chlorobenzene, 4-diazo-1-(N,N-dioctylaminocarbonyl)benzene, 4-diazo-1-(4-tert -octylphenoxy)benzene, 4-diazo-1-(2-ethylhexanoylpiperidino)-2,5-dibutoxybenzene, 4-diazo-1-[α-(2,4-di-tert-amylphenoxy) ) Butyrylpiperidino]benzene, 4-diazo-1-(4-methoxy)phenylthio-2,5-diethoxybenzene, 4-diazo-1-(4-methoxy)
Benzamido-2,5-diethoxybenzene, 4-diazo-1-pyrrolidino-2-methoxybenzene 0024
] Specific examples of acids that form diazonium salts with the above diazo compounds include the following. Polyfluoroalkylcarboxylic acid having 1 to 9 carbon atoms, polyfluoroalkylsulfonic acid having 1 to 9 carbon atoms, boron tetrafluoride, tetraphenylboron, hexafluorophosphoric acid, aromatic carboxylic acid, aromatic sulfonic acid, Furthermore,
The diazonium salt can also be stabilized by forming a complex compound using zinc chloride, cadmium chloride, tin chloride, or the like. The mixture of two 2-cyclohexenone derivatives according to the present invention is two isomers obtained when cyclohexane-1,3-dione is esterified or etherified. From the viewpoint of ease of synthesis and availability of raw materials, the 4-position of the starting material cyclohexane 1,3-dione is preferably an electron-withdrawing group such as a substituted carbonyl group or a cyano group. Therefore, 4-substituted-cyclohexane-1
,3-dione is esterified or etherified to form 4
-Substituted-2-cyclohexenone derivatives and 6-substituted-2-
Cyclohexenone derivatives will be obtained in esterification or etherification mixtures. The molar ratio of the mixture of the 4-substituted-2-cyclohexenone derivative and the 6-substituted-2-cyclohexenone derivative is preferably 0.1:99.9-99.9-0.1, particularly , 1:99 to 99:1 are preferred. The 4-substituted-2-cyclohexenone derivative according to the present invention has a structure in which the double bond at the 2nd position is isomerized to the 3rd position or a diene structure in which the carbonyl group at the 1st position is enolized due to its tautomerism. The 6-substituted-2-cyclohexenone derivative may contain several percent of a diene structure in which the carbonyl group at position 1 is enolized due to its tautomerism. Among the mixtures of two types of 2-cyclohexenone derivatives according to the present invention, a mixture of compounds represented by the following general formulas [II] and [III] is preferred. General formula [II] [Chemical formula 5] (In the above formula, R1, R2 and R3 may be the same or different, and represent a hydrogen atom, an alkyl group,
Represents an aryl group, aralkyl group, substituted amino group, substituted carbonyl group, or cyano group, X1 is a substituted carbonyl group,
It represents a cyano group, and Y1 represents an alkyl group, an aryl group, a substituted carbonyl group, or a substituted sulfonyl group. ) General formula [III] [Chemical formula 6] (In the above formula, R4, R5 and R6 may be the same or different, and represent a hydrogen atom, an alkyl group,
represents an aryl group, an aralkyl group, a substituted amino group, a substituted carbonyl group, or a cyano group, and X2 is a substituted carbonyl group,
It represents a cyano group, and Y2 represents an alkyl group, an aryl group, a substituted carbonyl group, or a substituted sulfonyl group. ) In the general formulas [II] and [III], R
The groups represented by 1, R2, R3, R4, R5 and R6 include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkoxycarbonyl group having 2 to 25 carbon atoms. group, number of carbon atoms 2-2
An alkylcarbonyl group having 5 carbon atoms, an arylcarbonyl group having 7 to 35 carbon atoms, and a cyano group are preferable. At least one of the groups represented by X1 and X2 is an alkoxycarbonyl group having 2 to 25 carbon atoms, an alkylcarbonyl group having 2 to 25 carbon atoms, an arylcarbonyl group having 7 to 30 carbon atoms, A cyano group is preferred. R1 and R2, R2 and R3, R3 and X
1, X1 and Y1, R4 and R5, R5 and R6
, R6 and X2 and R4 and Y2, and R5
and R may be bonded to each other to form a ring containing a heteroatom. Substituents for the substituted carbonyl group and substituted sulfonyl group represented by Y1 and Y2 include a halogen atom,
Preferred are alkyl groups, aryl groups, alkoxy groups, substituted carbonyl groups, substituted amino groups, and heterocyclic residues. These substituents may further have a substituent. The alkyl group and aryl group represented by Y1 and Y2 may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, a substituted carbonyl group, and a substituted amino group. , heterocyclic residues are preferred. These substituents may further have a substituent. [0036] Y1 and Y2 each have 1 to 20 carbon atoms.
alkyl group having 6 to 20 carbon atoms, alkylcarbonyl group having 2 to 20 carbon atoms, 7 carbon atoms
-20 arylcarbonyl group, C2-20 alkylsulfonyl group, C7-20 arylsulfonyl group, C2-20 alkoxycarbonyl group, C2-20 substituted carbamoyl group is preferred. Specific examples of the coupling components according to the present invention are shown below, but the present invention is not limited thereto. [Chemical 7] [Chemical 8] [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 10] [Chemical 10] [Chemical 11] [Chemical 11] [Chemical 12] [Chemical 12] [0044] etc. are mentioned. In the present invention, general formulas [II] and [II
As a coupling component that can be used together with the coupling component represented by [I] for the purpose of hue adjustment, any compound can be used as long as it forms a dye by coupling with a diazo compound in a basic atmosphere. It is. For example, there are so-called active methylene compounds having a methylene group next to a carbonyl group, phenol derivatives, naphthol derivatives, etc. Specific examples include the following, which are used within the range that meets the purpose of the present invention. Resorcin, phloroglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1
-Hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfo-naphthalene, 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-(2,4-di-tert-amylphenoxy)-butanamide]benzamide}phenol, 2,4
-bis-(benzoylacetamino)toluene, 1,3
-bis-(pivaloylacetaminomethyl)benzene [
[0048] The microcapsules used in the present invention are prepared by dissolving a diazonium salt and the same or different compounds that react with each other to produce a polymeric substance in a non-aqueous solvent having a boiling point of 40 to 95°C at normal pressure. After emulsification and dispersion in a hydrophilic protective colloid solution, the system is heated while reducing the pressure in the reaction vessel to distill off the solvent and move the wall-forming substance to the surface of the oil droplet. From the viewpoint of obtaining a good shelf life, it is preferable to use microcapsules that are substantially free of solvent and are produced by proceeding with a polymer production reaction by condensation to form a wall film. Further, in the present invention, the polymeric substance forming the wall of the microcapsule is preferably formed of at least one selected from polyurethane and polyurea. [0049] As the non-aqueous solvent for dissolving the diazonium salt used in the present invention, halogenated hydrocarbons,
Preferably, it is at least one compound selected from fatty acid esters, ketones, and ethers. The same or different compounds which react with each other to form a polymeric substance and which form the walls of the microcapsules used in the present invention are preferably polyurea and urethane, and the corresponding monomers are aromatic or aliphatic isocyanate compounds. selected. The microcapsules containing the diazo compound of the present invention can be polymerized with the corresponding monomer, and the amount of monomer used is such that the average particle size of the microcapsules is 0.3μ to 12μ, the wall thickness is 0.
．． It is determined to be between 01 and 0.3. Further, it is preferable to apply the diazo compound at a rate of 0.05 to 5.0 g/m2. In the present invention, an organic base is added for the purpose of making the system basic during thermal development and promoting the coupling reaction. These organic bases can be used alone or in combination of two or more. Examples of the basic substance include nitrogen-containing compounds such as tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines, and morpholines. In particular, N,N'-bis(3-phenoxy-2-hydroxypropyl)piperazine, N,N'
-bis[3-(p-methylphenoxy)-2-hydroxypropyl]piperazine, N,N' -bis[3-(p
-methoxyphenoxy)-2-hydroxypropyl]piperazine, N,N' -bis(3-phenylthio-2-
hydroxypropyl)piperazine, N,N'-bis[
3-(β-naphthoxy)-2-hydroxypropyl]piperazine, N-3-(β-naphthoxy)-2-hydroxypropyl-N'-methylpiperazine, 1,4-bis{[3-(N-methylpiperazino) -2-hydroxy]
piperazines such as propyloxy}benzene, N-[
3-(β-naphthoxy)-2-hydroxy]propylmorpholine, 1,4-bis[(3-morpholino-2-hydroxy)propyloxy]benzene, 1,3-bis[(
Morpholines such as 3-morpholino-2-hydroxy)propyloxy]benzene, N-(3-phenoxy-2
-hydroxypropyl) piperidine, piperidines such as N-dodecylpiperidine, triphenylguanidine,
Specifically preferred are guanidines such as tricyclohexylguanidine and dicyclohexyl phenylguanidine. In the present invention, it is preferable to use the coupling component in an amount of 0.1 to 30 parts by weight and the basic substance in an amount of 0.1 to 30 parts by weight per 1 part by weight of the diazo compound. In the present invention, in addition to the organic base, a coloring aid may be added for the purpose of promoting the coloring reaction. [0055] Included in the color development aid of the present invention are:
For example, phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, amide compounds, sulfonamide compounds can be added to the photosensitive layer so that thermal development can be carried out quickly and completely with low energy. . These compounds are
It is thought that the melting point of the coupling component or the basic substance is lowered, or the heat permeability of the microcapsule wall is improved, resulting in a high color density. [0056] The coloring aids of the present invention also include heat-melting substances. The heat-melting substance is a substance having a melting point of 50°C to 150°C that is solid at room temperature and melts by heating, and is a substance that dissolves a diazo compound, a coupling component, or a basic substance. Specific examples of these compounds include fatty acid amides, N-substituted fatty acid amides, ketone compounds, urea compounds, esters, and the like. [0057] The coupling component used in the present invention is:
Although it can be used as a solid dispersion together with a water-soluble polymer using a sand mill or the like together with a basic substance, other coloring aids, etc., it is particularly suitable for use in the form of an emulsion together with a suitable emulsifying aid. Preferred water-soluble polymers include water-soluble polymers used when preparing microcapsules (for example, JP-A-59-19
(See No. 0886). In this case, the coupling component, basic substance, and coloring aid are each added in an amount of 5 to 40% by weight based on the water-soluble polymer solution. Preferably, the dispersed or emulsified particle size is 10 microns or less. A free radical generator (a compound that generates free radicals when irradiated with light) used in photopolymerizable compositions is added to the recording material of the present invention for the purpose of reducing yellowing of the background after copying. be able to. Examples of the free radical generator include aromatic ketones, quinones, benzoin, benzoin ethers, azo compounds, organic disulfides, and acyloxime esters. The amount of free radical generator to be added is 0.01 to 5 parts by weight of the diazo compound.
Parts by weight are preferred. Similarly, for the purpose of reducing yellowing, a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as a vinyl monomer) can be used. A vinyl monomer is a compound having at least one ethylenically unsaturated bond (vinyl group, vinylidene group, etc.) in its chemical structure, and has the 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, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and the like. The vinyl monomer is used in an amount of 0.2 to 20 parts by weight per 1 part by weight of the diazo compound. The free radical generator and the vinyl monomer can also be used while being contained in microcapsules together with the diazo compound. In the present invention, in addition to the above materials, acid stabilizers such as citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, and pyrophosphoric acid can be added. The recording material of the present invention is produced by preparing a coating solution containing microcapsules containing a diazo compound, a coupling component, an organic base, and other additives, and coating the solution on a support such as paper or a synthetic resin film. Apply by coating methods such as bar coating, blade coating, air knife coating, gravure coating, roll coating, spray coating, dip coating, curtain coating, etc., and dry to a solid content of 2.5 to 30 g/m.
2 photosensitive layers are provided. In the recording material of the present invention,
The microcapsules, the coupling component, the base, etc. may be contained in the same layer as described in the above method, or a laminated structure in which they are contained in separate layers may be adopted. It is also possible to provide an intermediate layer on the support as described in Japanese Patent Application No. 177,669/1980, and then coat the photosensitive layer. As the support of the present invention, any paper support used for ordinary pressure-sensitive paper, thermal paper, dry or wet diazo copying paper, etc. can be used, as well as neutral paper supports such as alkyl ketene dimer. Neutral paper with a pH of 5 to 9 sized with a sizing agent (described in Japanese Patent Application No. 14281/1982), which satisfies the relationship between Steckigt sizing degree and metric basis weight described in Japanese Patent Application Laid-Open No. 116687/1982, and Paper with a Bekk smoothness of 90 seconds or more, an optical surface roughness of 8 μ or less and a thickness of 30 μm or less as described in JP-A-58-136492.
150μ paper, density 0 as described in JP-A-58-69091
．． 9g/cm3 or less and an optical contact ratio of 15% or more, made from pulp beaten to 400cc or more with Canadian standard freeness (JIS P8121) described in JP-A No. 58-69097. A paper that prevents staining, a base paper made by a Yankee machine described in JP-A No. 58-65695, whose glossy side is used as the coated surface to improve color density and resolution, and a base paper described in JP-A-59-35985. It is also possible to use paper that has been subjected to corona discharge treatment to improve coating suitability. The synthetic resin film used as a support in the present invention can be arbitrarily selected from known materials that do not deform even when heated during the development process and have dimensional stability. Such films include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate film, polystyrene films,
Examples include polypropylene films and polyolefin films such as polyethylene, which can be used alone or in combination. The thickness of the support is
A material having a diameter of 20 to 200 μm is used. When forming an image on the recording material of the present invention,
The following method can be used. One method is to expose a document to light to form a latent image, and then irradiate light onto areas other than the image forming area to fix the image.
This is a method of obtaining a colored image using heat from a thermal pen, thermal head, etc., and then fixing the image by irradiating light onto areas other than the image area. Either method can be preferably used. As light sources for exposure, various fluorescent lamps, xenon lamps,
It is preferable that a mercury lamp or the like be used, and that the emission spectrum of the lamp substantially matches the absorption spectrum of the diazo compound used in the recording material, since areas other than the image forming area can be efficiently fixed by light. Further, in the step of heating and developing the material, a thermal pen, a thermal head, an infrared ray, a high frequency, a heat block, a heat roller, etc. can be used as the heating means. [0065] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Examples Example 1 [Preparation of capsule liquid A of the present invention]: 3.45 parts of 2-hexyloxy-4-N,N-dihexylaminobenzenediazonium hexafluorophosphate and xylylene diisocyanate. 18 parts of trimethylolpropane (3:1) adduct was added to 10 parts of ethyl acetate and dissolved by heating. This diazo compound solution was mixed with polyvinyl alcohol 5.
2 parts dissolved in 58 parts water, 20 parts
The mixture was emulsified and dispersed at ℃ to obtain an emulsion having an average particle size of 2.5μ. Add 100 parts of water to the obtained emulsion and heat to 50°C while stirring.
After 3 hours, a capsule liquid containing a diazo compound in the core substance was obtained. [Preparation of coupler/base emulsion B]: 10 parts of specific compound example (8) of the coupling component of the present invention (mixture ratio: 1:1 in molar ratio), 5 parts of triphenylguanidine, tricresyl phosphate 3 parts were dissolved in 50 parts of ethyl acetate, added to 200 parts of a 15% polyvinyl alcohol aqueous solution, and emulsified and dispersed using a homogenizer. This was kept at 30°C to remove ethyl acetate to obtain emulsion B. The average particle size of the emulsion was 0.5μ. [Preparation of recording material of the present invention]: 50 parts of emulsion liquid B was added to 50 parts of the above capsule liquid A to prepare a coating liquid. This Tofu liquid was applied to a smooth transparent polyethylene terephthalate film (thickness 75 μm) using a coating bar to give a dry weight of 10 g/m2.
The recording material was prepared by drying for a minute. [Color Development and Fixation Test] A test manuscript (a 3 cm diameter circle drawn uniformly black on tracing paper with a 2B pencil) was placed on top of the above recording material and exposed to light using a fluorescent lamp. At this time, a fluorescent lamp whose emission spectrum has a maximum value at 420 nm was used. Next, an image was formed by heating for 3 seconds using a heat block heated to 120°C. An image was also formed when the entire surface was exposed to light using a lamp having an absorption maximum at 420 nm after heating with a heat block previously heated to 120°C. When the density of the colored part was measured using a Macbeth densitometer,
Each was 1.24. Examples 2 and 3 Compound (1) was used instead of compound (8) used in Example 1.
5) (Example 2) and Compound (26) (Example 3) were used to obtain a coupler/base emulsion, but the same operations as in Example 1 were performed to prepare a recording material and form an image. . When the densities of the colored parts were measured using a Macbeth densitometer, they were 1.25 (Example 2) and 1.22 (Example 3), respectively. Examples 4 and 5 In place of 1-dihexylamino-3-hexyloxybenzene-4-diazonium hexafluorophosphate used in Example 1, 1-dibutylamino-3-butoxybenzene-4-diazonium was used. Hexafluorophosphate (Example 4), 1-dioctylamino-3-octyloxybenzene-4-diazonium hexafluorophosphate (
A recording material was prepared and an image was formed by performing the same operations as in Example 1 except that a capsule liquid was obtained using Example 5). When the densities of the colored parts were measured using a Macbeth densitometer, they were 1.23 (Example 4) and 1.22 (Example 5), respectively. Comparative Example 1 Example 1 except that 1-phenyl-3-octyloxycarbonylpyrazoli-5-one was used instead of compound (8) used in Example 1 to obtain a coupler/base emulsion. The same operation as in 1 was performed to form an image. The density of the colored portion was measured using a Macbeth densitometer and was found to be 1.21. Comparative Examples 2 and 3 Instead of 1-dibutylamino-3-butoxybenzene-4-diazonium hexafluorophosphate used in Example 1, 1-morpholino-3-butoxybenzene-4-
Diazonium hexafluorophosphate (Comparative Example 2), 1
-morpholino-2,5-dibutoxybenzene-4-diazonium hexafluorophosphate (Comparative Example 3) was used to obtain a capsule liquid, but the same operation as in Example 1 was performed to form an image. When the densities of the colored parts were measured using a Macbeth densitometer, they were 1.20 (Comparative Example 2) and 1.19 (Comparative Example 3), respectively. Next, the color development hue of the obtained recording material was measured and a comparative test of raw storage stability was conducted. The color hue was measured by visually observing the formed image. The fresh storage stability test was performed by comparing the difference in color density between a thermal recording sheet stored at room temperature and a thermal recording sheet forcedly stored at 60° C. and 30% RH for 72 hours using a hot plate. Changes in color density were measured using a Macbeth reflection densitometer. Table 1 shows the results of coloring hue and coloring density. [Table 1] [0077] These results show that by using the combination of the diazo compound and the coupling component of the present invention, the desired red coloring hue can be obtained, and the raw storage stability of the heat-sensitive recording sheet can be improved. I can see that it is excellent.

Claims (4)

[Claims] Claim 1. A light and heat sensitive recording material comprising a recording layer containing a diazo compound, a coupling component, and an organic base provided on a support, wherein the diazo compound is a 1-substituted amino-3-alkoxybenzene-4- 1. A light and heat sensitive recording material, which is a diazonium salt, and the coupling component is a mixture containing two types of 2-cyclohexenone derivatives. 2. The light and heat sensitive recording material according to claim 1, wherein the mixture is an esterification mixture or an etherification mixture of 4-substituted-cyclohexane-1,3-diones. 3. The light and heat sensitive recording material according to claim 1, wherein one of the mixtures is a 4-substituted-2-cyclohexenone derivative and the other is a 6-substituted-2-cyclohexenone derivative. 4. The light and heat sensitive recording material according to claim 1, wherein the diazo compound is contained in microcapsules.