JPH04194842A - Photosensitive and heatsensitive recording material - Google Patents

Abstract

PURPOSE:To provide an excellent red coloring color phase by a method wherein a recording layer containing a diazo compound, a coupling compound, and an organic base is formed on a carrier, the diazo compound is 1-substitutional amini-3-alkoxybenzene-4-diazonium salt, and the coupling component is a 2- cyclohexenone derivative. CONSTITUTION:A substance expressed by a formula is preferable as a diazo compound. In a formula, when R1, R2, and R1 have a substitutional group, an alkyl group and an aryl group are listed as the substitutional group. CnF2n+1COOH (n is an integral number of 1 - 9) and CmF2m+1SO3H (m is an integral number of 1 - 9) are listed as an example of acid of acid anion indicated by X<->. From a point of view of coupling activity of a 2-cyclohexenone derivative, it is desirable that a substitutional group combined through a hetero atom, such as oxygen, nitrogen, and sulfure, is provided in a third rank. It is desirable in terms of availability that a sixth rank is substituted with an electron attractive group, such as a substitutional carbonyl group and a cyano group.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a recording material that utilizes the photosensitivity of a diazo compound (diazonium salt), and particularly to a red-coloring type light and heat sensitive recording material.

<Prior Art> Three types are known as recording materials that utilize the photosensitivity of diazo compounds. 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 developed with an alkaline solution. 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 by heating in the photosensitive layer, and a type that contains trichloroacetic acid in the photosensitive layer. There are types that contain alkaline salts of acids that lose their acid properties when heated, and types that utilize higher fatty acid amides as coloring aids to activate diazo compounds and coupling components by heating and melting. .

In addition to maintenance problems such as the need for replenishing and discarding the developer as it uses a developer and the large size of the device, there are also problems with the wet type, such as the fact that it is too wet to make changes immediately after copying. have some problems. 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 thermal development type does not require a developer and has the advantage of maintenance, but all conventional types require a high development temperature of 1506C to 2006C. Moreover, if the temperature is not controlled to about ±10° C., insufficient development or change in color tone occurs, 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
Although many attempts have been made to increase the temperature at temperatures between 130° C. and 130° C., they have the drawback of decreasing the shelf life of the material itself. As described above, although the thermal development type is expected to have sufficient advantages in terms of maintenance compared to the wet and dry types, the current situation is that it has not yet become the mainstream of diazo 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, heating causes each component to instantly melt, diffuse, and
Although it is necessary to react to produce a coloring dye, it is preferable to make the system basic during this reaction since this 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.

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.

Although the above-mentioned several attempts have been made to create photosensitive and thermosensitive recording materials that have a good shelf life and a high recording speed, the current situation is that they have not yet reached the point where they can be put to practical use.

If we design a material that can sufficiently develop color and obtain high density even at low heating temperatures, it is natural that a color reaction may occur even while it is stored at room temperature before copying, and the material must be white. This appears as a phenomenon in which the bare skin becomes discolored. In particular, in the case of red-coloring type recording materials, there is a problem in that even slight coloring (fogging) of the background becomes noticeable due to high visibility. In order to solve this incompatible problem, the inventors of the present invention made extensive studies and found 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, and succeeded in suppressing background discoloration during storage before copying ( Japanese Patent Publication No. 2-5425
No. 1). Furthermore, as a result of studies aimed at improving the storage stability and oil solubility of diazo compounds, it was discovered that 1-substituted amino-3-alkoxybenzene-4-diazonium salts exhibited excellent performance (Japanese Patent Application No. 169490/1999). issue). Furthermore, as a result of intensive study on combinations with coupling components, the present inventors found that the diazonium salt produces a good red pigment with a hue similar to that of a 2-cyclohexenone derivative. It's arrived.

Accordingly, a first 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 to Solve the Problems> The above-mentioned aspects of the present invention are, in a light and heat sensitive recording material in which a recording layer containing a diazo compound, a coupling component, and an organic base is provided on a support. is a 1-substituted amino-3-alkoxybenzene-4-diazonium salt, and the coupling component is a 2-cyclohexenone derivative.

Among the diazo compounds according to the present invention, those represented by the following general formula (1) are preferred.

(In the above formula, R, , R, and R3 may be the same or different and represent an alkyl group, an aralkyl group, or an aryl group, and these may further have a substituent, and X- is an acid represents an anion.) In general formula (1), R,, R,
When R3 has a substituent, examples of the substituent include an alkyl group, an aryl group, a hydrocyanyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an acyloxy group, and a carbamoyl group. , an acylamino group, a halogen atom, a cyan group, and the like.

The total number of carbon atoms in R, R, and R1 is preferably 12 or more, particularly preferably 14 or more, from the viewpoint of oil solubility.

In general formula (1), specific examples of the acid anion represented by X- include the following examples.

C, F, , C○OH (n is an integer from 1 to 9), C.

F, ..., S○+H (m is an integer of 1 to 9), tetraphnohyboron, tetraphenylboron, hexafluorophosphoric acid, aromatic carboxylic acid, aromatic sulfonic acid.

Furthermore, the diazonium salt can be stabilized by forming a complex compound using zinc chloride, cadmium chloride, tin chloride, or the like.

The diazo compound according to the present invention has a melting point of 30'C to 20'C.
0°C is preferable, but 50°C for handling reasons.
Preferably, the temperature is between 150°C and 150°C.

In addition, since it is used by dissolving it in a suitable solvent (for example, tricresyl phosphate) when it is contained in microcapsules, it is preferable that it has suitable solubility in these solvents and low water solubility. 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 contains 0.02
It is preferable to use it in the range of ~3 g/m', and from the point of view of color density, it is preferable to use it in the range of 0.1 to 2 q/m'.

Specific examples of the diazo compound according to the present invention are shown below, but the present invention is not limited thereto.

Examples include.

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 aspects such as hue adjustment.

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-dinothylaminobenzene, 4-diazo-1-methylhencylaminobenzene 4-diazo-1-ethylhydroxyethylamino Hensen, 4-siacy 1-diethylamino-3-methoxyhenzene, 4-diazo 1-morpholinobenzene, 4-siacy 1-morpholino-2,5-dibutoxybenzene.

4-diazo-1-tolylmercapto-2,5-jethoxybenzene, 4-diazo-1-piperazino-2-methoxy-5-chlorohenzene, 4-diazo-1-(N,
N-dioctylaminocarbonyl)benzene, 4-diazo-1(4-tert-octylphenoxy)henganese. 4-Diazo-1-(2-ethylhexanoylpiperidino)-2,5-dibutoxybenzene, 4-diazo-1-
(2,5-di-tert-amylphenoxy-α-phthanoylpiperidino)benzene, 4-diazo-1-(4-
methoxy)phenylthio-2,5-jethoxybenzene, 4-diazo-1-(4-methoxy)benzamide-2
, 5-diethoxyhenzene, 4-diazo-1-pyrrolidino-2-methoxyhenzene Specific examples of acids that form diazonium salts with the above-mentioned diazo compounds include the following examples.

c, F+-++ co OH (n is an integer from 1 to 9), C7F I, ..., IS OI H (m is an integer from 1 to 9), boron tetrafluoride, tetraphenylboron, hexafluorophosphoric acid , aromatic carboxylic acids, aromatic sulfonic acids.

Furthermore, the diazonium salt can be stabilized by forming a complex compound using zinc chloride, cadmium chloride, tin chloride, or the like.

From the viewpoint of coupling activity with a diazo compound, the 2-cyclohexenone derivative according to the present invention should have a substituent bonded via a heteroatom such as an oxygen atom, a silicon atom, or a sulfur atom at the 3-position. is preferred. In particular, it is preferable that the substituent at the 3-position has a substituent bonded via an oxygen atom.

Among the 2-cyclohexenone derivatives according to the present invention, those in which the 6-position is substituted with an electron-withdrawing group such as a substituted carbonyl group or a cyan group are preferred from the viewpoint of ease of synthesis and availability of raw materials. .

Among the 2-cyclohexenone derivatives according to the present invention, a compound represented by Funato (11) below is preferred.

The 2-cyclohexenone derivative according to the present invention may contain the general formula (Ill) or (1), which is a tautomer.

(Il+) (1■) (In the above formula, R,, R, and R may be the same or different, and include a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a substituted amine group, a substituted carbonyl group, a cyano (R4 represents a substituted carbonyl group, cyano group, R represents an alkyl group, aryl group, substituted carbonyl group, substituted sulfonyl group, substituted silyl group.) More preferably, in -Funenin (11), R, , R, and R3 have a hydrogen atom and a carbon atom number of 1.
~10 alkyl group, aryl group having 6 to 20 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyl group having 2 to 25 carbon atoms, 7 carbon atoms
-35 arylcarbonyl groups and cyan groups are preferred.

R6 is an alkoxycarbonyl group having 2 to 25 carbon atoms,
Preferred are alkylcarbonyl groups having 2 to 25 carbon atoms, arylcarbonyl groups having 7 to 30 carbon atoms, and cyan groups.

The group represented by R in general formula (11) may have a substituent, and when R is an alkyl group, an aryl group, a substituted carbonyl group, or a substituted sulfonyl group, examples of the substituent include a haloken atom and an alkyl group. , aryl group, alkoxy group,
Substituted carbonyl groups, substituted amino groups, and heterocyclic groups are preferable, and when R is substituted nitrogenyl, alkyl groups and aryl groups are preferable. The substituents of these alkyl groups and aryl groups may further have a substituent.

More preferable examples of R include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 30 carbon atoms (7)71J-JI4, an alkylcarbonyl group having 2 to 20 carbon atoms, and an alkyl group having 7 to 20 carbon atoms.
20 arylcarbonyl group, an alkylsulfonyl group having 2 to 20 carbon atoms, an arylsulfonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted carbamoyl group having 2 to 20 carbon atoms, preferable. Particularly preferred are alkylcarbonyl groups having 2 to 15 carbon atoms, arylcarbonyl groups having 7 to 15 carbon atoms, alkoxycarbonyl groups having 2 to 15 carbon atoms, and substituted carbamoyl groups having 2 to 15 carbon atoms.

The 2-cyclohexenone derivative according to the present invention can be easily obtained by esterifying a cyclohexane-1,3-dione derivative.

The esterification method is (1) cyclohexane-1,
Examples include a method in which a 3-dione derivative is reacted with a carboxylic acid halide under basic conditions, and (2) a method in which a cyclohexane-1,3-dione derivative is reacted with a carboxylic acid under acidic conditions. In particular, method (1) is mild and preferred.

Next, specific examples of the coupling component according to the present invention are shown below, but the present invention is not limited thereto.

Examples include.

In the present invention, coupling components that can be used for the purpose of hue adjustment, etc. together with the coupling component represented by general formula (11) include those that form a dye by coupling with a diazo compound in a basic atmosphere. Any compound is possible.

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 molyporinopropylamide, 1,5-
Dihydroxynaphthalene, 2.3-dihydroxynaphthalene, 2.3-dihydroxy-6-sulfonylnaphthalene, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3- naphthoic acid anilide, pencylacetonilide, 1-phenyl-3-methyl-5
-pyrazolone, 1-(2,4,6-drichlorophenyl)-3-anilino-5-pyrazolone, 2-[3-α-(
2,4-di-tert-amylphenoxy)-butanamidobenzamide]phenol, 2,4-his-(benzoylacetamino)toluene, 1,3-his-(pivaloylacetaminomethyl)benzene Used in the present invention The microcapsules are stored under normal pressure □40. After emulsifying and dispersing a solution of a diazonium salt and the same or different compounds that react with each other to produce a polymeric substance in a non-aqueous solvent with a boiling point of ~95°C in a hydrophilic protective colloid solution, the reaction vessel is removed. The wall-forming substance is transferred to the surface of the oil droplet while the system is heated under reduced pressure to distill off the solvent, and a wall film is formed by proceeding with polymer production reactions through polyaddition and polycondensation on the surface of the oil droplet. From the viewpoint of obtaining a good shelf life, it is preferable to use microcapsules which are produced by stirring and are substantially free of solvent.

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.

The nonaqueous solvent for dissolving the diazonium salt used in the present invention is preferably at least one compound selected from halogenated hydrocarbons, fatty acid esters, ketones, and ethers.

The same or different compounds that react with each other to produce a polymeric substance forming the walls of the microcapsules used in the present invention are preferably polyurea or urethane, and the corresponding monomers are selected from aromatic or aliphatic isocyanate compounds. Ru. 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 and the wall thickness is 0.01 to 0. ．．
3. The diazo compound is still 0.
05-5. It is preferable to apply the coating at Og/m'.

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. Basic substances include tertiary amines, piperidines, piperazines, amidines, formamidines,
Examples include nitrogen-containing compounds such as pyrins, guanidines, and morpholines.

In particular, N,N-his(3-phenoxy-2-
hydroquinepropyl)piperazine, N,N'-HisC3-(p-methylphenoxy)-2-hydroxypropylcopiperazine, N,N-His[3-(p-
methoxyphenoxy)-2-hydroxypropylcopiperazine, N,N-bis(3-phenylthio-2
-Hydroxypropyl)piperazine, N, N-
His[3-(β-naphthoxy)-2-hydroxypropylcopiperazine, N-3-(β-naphthoxy)-2-hydroxypropyl-N-methylbiperazine, 1,4-
Piperazines such as his([3-(N-methylpiperazino)-2-hydroxy]propyloxy)henzen, N
-[3-(β-naphthoxy)-2-hydroxy]propylmorpholine, 1,4-his[(3-morpholino-2-
Morpholines such as hydroxy)propyloxy]benzene, 1,3-bis[(3-morpholino-2-hydroxy)propyloxy]henzen, N-(3-phenoxy-2-hydroxypropyl)piperidine, N-dodecylpiperidine, etc. Specifically, guanidines such as piperidines, triphenylguanidine, tricyclohexylguanidine, and dicyclohexylphenylguanidine are preferable.

In the present invention, the coupling component is 0.1 to 30 parts by weight and the basic substance is 0.1 to 30 parts by weight per 1 part by weight of the diazo compound.
．． It is preferable to use it in a proportion of 1 to 30 parts by weight.

In the present invention, in addition to the organic base, a coloring aid may be added for the purpose of promoting the coloring reaction.

The coloring aids of the present invention include, for example, phenol derivatives, naphthol derivatives, alkoxy-substituted hempins, alkoxy-substituted naphthalenes, and hydroxy compounds in the photosensitive layer so that thermal development can be carried out quickly and completely with low energy. , amide compounds, and sulfonamide compounds can be added. These compounds are thought to lower the melting point of the coupling component or the basic substance, or to improve the thermal permeability of the microcapsule wall, resulting in a high color density.

The coloring aids of the present invention also include thermofusible substances.

The heat-melting substance is a substance that is solid at room temperature and has a melting point of 50°C to 150°C 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.

The coupling component used in the present invention includes a basic substance,
It can also be used as a solid dispersion with a water-soluble polymer using a sand mill etc. together with other coloring aids, etc.
It is particularly suitable for use in emulsions with appropriate emulsification aids.

Preferred water-soluble polymers include water-soluble polymers used when preparing microcapsules (see, for example, JP-A-59-190886). In this case, the coupling component, the basic substance and the coloring aid are added in an amount of 5 to 40% by weight, respectively, based on the water-soluble polymer solution. The dispersed or emulsified particle size is 1
It is preferable that it be 0u or less.

A free radical generator (a compound that generates free radicals when irradiated with light) used in photopolymerizable compositions can be added to the recording material of the present invention for the purpose of reducing yellowing of the background after copying. Ru. As free radical generators, aromatic ketones,
Examples include quinones, hengeine, benzoin ethers, azo compounds, organic disulfides, and acyloxime esters. The amount of the free radical generator to be added is preferably 0.01 to 5 parts by weight per 1 part by weight of the diazo compound.

Similarly, for the purpose of reducing yellowing, a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as a hinyl monomer) can be used.

Hinyl monomer is a chemical structure with at least one ethylenically unsaturated bond (hinyl group, hnylidene group, etc.)
It is a compound that has the chemical form of a monomer or a 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 hinyl 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 by being contained in microcapsules together with the cyanogen compound.

In the present invention, in addition to the above materials, citric acid is used as an acid stabilizer.
Tartaric acid, oxalic acid, boric acid, phosphoric acid, birophosphoric acid, etc. can be added.

The recording material of the present invention can be 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. - Coating and drying by coating methods such as coating, blade coating, air knife coating, graphia coating, roll coating, spray coating, day knob coating, curtain coating, etc. to form a light absorbing layer of 2.5 to 30 g/m' . The recording material of the present invention has a laminated structure in which the microcapsules, the coupling component, and the base may be contained in the same layer as described in the above method, or in separate layers. It can also happen. It is also possible to provide an intermediate layer on the support, as described in Japanese Patent Application No. 1159-177669, and then apply 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, and in addition, neutral sizing agents such as alkyl ketene dimers can be used. Sized neutral paper with a pH of 5 to 9 (described in Japanese Patent Application No. 55-14281), which satisfies the relationship between Steckigt sizing degree and metric basis weight described in JP-A No. 57-116687, and has Hetsk smoothness. 90 seconds or more paper, paper with an optical surface roughness of 8μ or less and a thickness of 30 to 150μ as described in JP-A-58-136492, density 0.9 g/cm as described in JP-A-58-69091
Paper with an optical contact ratio of 15% or more, JP-A No. 5
Canadian Standard Freeness (JIS) as described in No. 8-69097
Paper made from valves beaten to 400cc or more with P8121) to prevent coating liquid from seeping in, JP-A-58
-65695, the glossy side of base paper made by a Yankee machine is used as the coating surface to improve the color density and resolution, and the base paper described in JP-A-59-35985 is subjected to corona discharge treatment to improve coating suitability. Improved paper can also be used.

The synthetic resin film used as a support in the present invention can be arbitrarily selected from known materials that do not deform even when heated during the development process and have dimensional stability. Examples of such films include polyester films such as polyI ethylene terephthalate and polyphthelene terephthalate, cellulose derivative films such as cellulose triacetate films, polystyrene films, polypropylene films, and polyolefin films such as polyethylene. It can be used by pasting them together. The thickness of the support is 20 to 200
μ is used.

When forming an image on the recording material of the present invention, the following method can be used. One is to expose the original to light to form a latent image, and then irradiate light onto areas other than the image forming area to fix the image.The other is to develop color using heat from a thermal pen, thermal head, etc. In this method, after an image is obtained, areas other than the image area are irradiated with light to fix the image. Either method can be preferably used. Various types of fluorescent lamps, xenon lamps, mercury lamps, etc. are used as the light source for exposure, and the fact that this emission spectrum almost matches the absorption spectrum of the diazo compound used in the recording material is that
This is preferable because it allows efficient optical fixation of areas other than the image forming area. Further, in the step of heating and developing the material, a thermal pen, a thermal head, an infrared ray, a high frequency, a heat flock, a heat roller, etc. can be used as the heating means.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1> 5-phenyl-4-methoxycarbonyl-cyclohexane-1,3-dione 24.6 g, triethylamine 10
．． Dissolve 6g in 100ml of acetonitrile and cool with water.
12°59 of pivaloyl chloride was slowly added dropwise.

After the dropwise addition was completed, the mixture was stirred at the same temperature for 1 hour, and the reaction mixture was diluted with 50% water.
A digit at 0m1. The separated crystals were filtered and recrystallized with alcohol to obtain compound (8) 29. I got s9.

(Yield -89%, m, 'p, = l l 5-11
7°C) Synthesis Example 2> Compound (9) 27. 4g was obtained.

(Yield = 90%, m, p, = 78-79°C)
Synthesis Example 3> In Synthesis Example 2, 5-(2-tetradecyloxyphenyl)-4-methoxycarbonyl-1,3 was used instead of using 5-funiny-methoxycarbonyl-cyclohexane-1,3-dione. -The reaction was carried out in the same manner as in Synthesis Example 2, except that 45.89% of the dione was used, and compound (15) was obtained.
43,9(] was obtained.

(Yield I = 85%, m, p, = 63-64 °C) <Synthesis Example 4> Instead of using 5-phenyl-4-meth:dicarbonyl-cyclohexane-1,3-dione in Synthesis Example 2 5-(4-dodecyl-3-methoxyphenyl)-4-methoxycarbonyl-1,3-dione 46.0
The reaction was carried out in the same manner as in Synthesis Example 2 except that 9 was used to obtain 44.09 of compound (26).

(Yield -85%, m,, p, = 79-81°C) Synthesis Example 5> In place of using 5-phenyl-4-methoxycarbonyl-cyclohexane-1,3-dione in Synthesis Example 1, 5- (2-decyloxy-1=naphthyl)-4-methoxycarponyl-1,3-dione 45.2 g, 1 year old except that 11.39 g of N,N-dimethylcarbamic acid chloride was used instead of pivaloyl chloride The reaction was carried out in the same manner as in [Synthesis Example] to obtain compound (22) 48. I got ec.

(Yield = 93%, m, p, = 79-81 °C) <Example 1> [Preparation of capsule liquid A of the present invention] ~2-hexyl: t
*3.45 parts of C4N,N-dihexylaminobenzenediazonium hexafluorophosphate and 18 parts of an adduct of xylylene diisocyanate and trimethylolpropane (3:1) were added to 10 parts of ethyl acetate and dissolved by heating. This diazo compound solution was mixed with an aqueous solution containing 5.2 parts of borihinyl alcohol dissolved in 58 parts of water, emulsified and dispersed at 20°C, and the average particle size was 2.
A 5μ emulsion was obtained. 100 parts of water was added to the obtained emulsion and heated to 50°C while stirring, and after opening at 3 o'clock, a capsule liquid containing a diazo compound in the core substance was obtained.

[Preparation of coupler/base emulsion B] Two 10 parts of the coupling component specific compound example (8) of the present invention, 5 parts of triphenylguanidine, and 3 parts of tricresyl phosphate were mixed with 5 parts of ethyl acetate.
0 parts, 15% polyhinyl alcohol aqueous solution 20 parts
In addition to 0 parts, the mixture was emulsified and dispersed using a homogenizer. This is 3
Emulsion B was obtained by removing ethyl acetate while maintaining the temperature at 0°C.

The average particle size of the emulsion was 0.5μ.

[Preparation of recording material of the present invention]; The above capsule liquid A50
850 parts of the emulsion was added to prepare a coating solution. Spread this splashing liquid onto a smooth, transparent polyethylene terephthalate film (
75 μm) using a coating bar, dry weight 1
It was coated at a concentration of 0 g/m' and dried at 50°C for 1 minute to prepare a recording material.

[Test of Color Development and Fixation] A test manuscript (a circle with a diameter of 3 cm painted uniformly black on a tracing paper using a 2B pencil) was placed on top of the recording material and exposed to light using a fluorescent lamp. At this time, a fluorescent lamp having an extremely thick emission spectrum of 420 parts m was used. Next, an image was formed by heating for 3 seconds using a heat flock heated to 120°C. Also, first +
An image was also formed when the entire surface was exposed to light using a lamp having an extremely thick absorption at 420 parts m after heating with a heat block heated to 20°C. When the density of the colored portion was measured using a Maches densitometer, it was 1.24.

<Example 2.3> Instead of compound (8) used in Example 1, compound (1
5) (Example 2) and Compound (25) (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. . The densities of the colored parts were measured using a Maches densitometer and were 1.25 (Example 2) and 1.22 (Example 3), respectively.

<Example 4.5> Instead of 1-dioctylamino-3-hexyloxybenzene-4-diazonium hexafluorophosphate used in Example 1, 1-cyphthylamino-3-butoxybenzene-4-diazonium hexafluorophosphate was used. Fluorophosphate (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 density of the colored portion was measured using a Macbeth densitometer, they were 123 (Example 4) and 1°22 (Example 5), respectively.

<Comparative Example 1> Same as Example 1 except that 1-phenyl-3-octyloquine luponylvirazoli-5-one was used instead of compound (2) used in Example 1 to obtain a coupler/base emulsion. The image was formed by performing various operations. The density of the colored portion was measured using a Maches densitometer and was found to be 1.21.

<Comparative Example 2.3> Instead of 1-dibutylamino-3-phthoxyhenzene-4-diazonium hexafluorophosphate used in Example 1, 1-morpholino-3-phthoxyhenzene-4 was used. −
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 density of the colored part was measured using a Maches densitometer, it was 1.20 (comparative example 2) and 1.1, respectively.
9 (Comparative Example 3).

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 raw storage stability test was performed using a thermosensitive recording sheet stored at room temperature and at 60°.
A comparison was made based on the difference in color density between thermosensitive recording sheets that were forcibly stored under conditions of C130% RH for 72 hours using a hot plate.

Changes in coloring density were measured using a Maches reflection densitometer.

Table 1 shows the results of coloring hue and coloring density.

These results show that by using the combination of the diazo compound and the coupling component of the present invention, the desired red color hue can be obtained, and the heat-sensitive recording sheet has excellent shelf life.

[Table 1]

Claims (1)

[Scope of Claims] 1) A light and heat sensitive recording material in which a recording layer containing a diazo compound, a coupling component, and an organic base is provided on a support, wherein the diazo compound is a 1-substituted amino-3-alkoxybenzene. - A light and heat sensitive recording material which is a 4-diazonium salt and wherein the coupling component is a 2-cyclohexenone derivative. 2) The light and heat sensitive recording material according to claim 1, wherein the diazo compound according to claim 1 is contained in microcapsules.