JPH0534860A - Photosensitive and thermosensitive recording material - Google Patents

Abstract

PURPOSE:To provide the photosensitive and thermosensitive recording material high in transparency of a color developing layer, small in coloring of the surface of the recording material with lapse of time, and using a diazo compound and a coupling component. CONSTITUTION:A layer formed on a support contains a 2-cyclohexanone derivative having an aryl group substituted at the position 5 and having the total carbon number of >=15, represented, preferably, by formula I, the diazo compound, and an organic base. In formula I, each of R1-R3 is, independently, H, alkyl, aryl, aralkyl, substituted amino or carbonyl, cyano, or halogen; Ar is an aromatic ring; and R is alkyl, aryl, or substituted carbonyl or sulfonyl or silyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material utilizing the photosensitivity of a diazo compound (diazonium salt), and more particularly to a red color type light and heat sensitive recording material.

[0002]

2. Description of the Related Art As recording materials utilizing the photosensitivity of diazo compounds, three types are known. One is a type known as wet development type, in which a photosensitive layer containing a diazo compound and a coupling component as a main component is provided on a support, and this material is superposed on an original document and exposed to an alkaline solution. It is to develop. The second is a type known as a dry development type, which is different from the wet type in that development is performed with ammonia gas. The third type is known as heat development type, which contains a type of ammonia gas generating agent such as urea that can generate ammonia gas when heated in the photosensitive layer and trichloroacetic acid in the photosensitive layer. There are a type containing an alkali salt of an acid that loses its properties as an acid by various heating, and a type utilizing activation of a diazo compound and a coupling component by heating and melting using a higher fatty acid amide as a color-forming aid.

The wet type requires a replenishment and disposal of a liquid because it uses a developing solution, maintenance problems such as a large size of the apparatus, and since it is moist immediately after copying, it is possible to quickly add to it. There are some problems such as not being present or the copied image being intolerable to long-term storage. Also, the dry type requires replenishment of the developing solution like the wet type,
In addition to the fact that a gas absorption facility is required to prevent the generated ammonia gas from leaking to the outside, and thus the device becomes larger, there are problems such as the smell of ammonia immediately after copying. On the other hand, unlike the wet type and dry type, the heat development type has an advantage in maintenance because it does not require a developing solution, but all the conventionally known types have a high development temperature of 150 ° C to 200 ° C. However, if the temperature is not controlled to about ± 10 ° C., the development cost may be insufficient or the color tone may change, resulting in a high apparatus cost. Further, the diazo compound used for such high temperature development also needs to have high heat resistance, but such a compound is often disadvantageous for forming a high concentration. Low temperature development (90 ° C
Although many attempts have been made at ˜130 ° C., there has been a drawback that the shelf life of the material itself is shortened. As described above, the heat-development type is not yet dominated by the mainstream of the diazo recording system, though the merit in maintenance is expected enough compared with the wet type and the dry type.

In order to obtain a desired color density by heating a material having a layer containing a diazo compound and a coupling component on a support, each component is instantly melted, diffused and reacted by heating. It is necessary to generate a color-developing dye, but it is preferable to make the system basic during this reaction because it has the effect of promoting the reaction. Therefore, in order to prepare a light and heat sensitive recording material having a recording speed at which heating at a low temperature does not cause a significant obstacle in practical use, it is an essential requirement to incorporate a basic substance in the coating layer.

On the other hand, for the light and heat sensitive recording material, the surface (background) of the recording material becomes colored during storage before copying,
It is also an essential requirement to prevent the color density from decreasing.

With such a good shelf life,
In addition, although the above-mentioned several attempts have been made to prepare a light and heat sensitive recording material having a high recording speed, the present situation is that it has not yet been put to practical use.

When a material is designed so that a sufficient color can be obtained even if the heating temperature is low, a coloring reaction may naturally occur during storage at room temperature before copying. It appears as a phenomenon in which the background, which must be white, is colored. In particular, in the case of a red-coloring type recording material, the visibility is high, so slight background coloring (fogging)
But there was a problem that it stood out. In order to solve this seemingly incompatible problem, the inventors of the present invention have made extensive studies, and as a result, in a recording material provided with a heat-developable photosensitive layer containing a diazo compound, a coupling component and a basic substance on a support. , Including the inclusion of the diazo compound in a microcapsule, further searching from the viewpoint of basic substances, how to make microcapsules, etc.
Succeeded in suppressing background coloring during pre-storage. (JP-A-2-54251) However, cyclohexane-1,3-which is the coupling component described in the above patent.
It was found that the dione derivative actually has low oil solubility and the storage stability of the recording material after emulsification and dispersion is not so good, and it was necessary to develop a coupling component with improved stability of the dispersion.

[0008]

Therefore, the first aspect of the present invention
It is an object of the invention to provide a light and heat sensitive recording material in which the transparency of the color forming layer is improved by using a coupling component having an improved oil solubility. A second object of the present invention is to provide a light and heat sensitive recording material with less background fog.

[0009]

The above objects of the present invention are as follows.
In a light and heat sensitive recording material having a recording layer containing a diazo compound, a coupling component and an organic base on a support, the coupling component is a 2-cyclohexenone derivative having a total carbon number of 15 or more. Was achieved by a light and heat sensitive recording material.

Among the 2-cyclohexenone derivatives according to the present invention, from the viewpoint of the coupling activity with the diazo compound, the 3-cyclohexenone derivative has a substituent bonded to the 3-position via a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. Preferably. In particular, the substituent at the 3-position preferably has a substituent bonded via an oxygen atom.

Of the 2-cyclohexenone derivatives according to the present invention, compounds represented by the following general formula (I) are preferable. The 2-cyclohexenone derivative according to the present invention may contain the general formula (II) or (III) which is a tautomer. General formula (I)

[0012]

[Chemical 1]

General formula (II)

[0014]

[Chemical 2]

Formula (III)

[0016]

[Chemical 3]

In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a substituted amino group, a substituted carbonyl group,
A cyano group and a halogen atom, Ar represents an aromatic ring, and R represents an alkyl group, an aryl group, a substituted carbonyl group, a substituted sulfonyl group, and a substituted silyl group. More preferably, the groups represented by R ₁ , R ₂ and R ₃ in formula (I) are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom. Preferred are an alkoxycarbonyl group having 2 to 25 carbon atoms, an alkylcarbonyl group having 2 to 25 carbon atoms, an arylcarbonyl group having 7 to 35 carbon atoms, and a cyano group. The aromatic ring represented by Ar may have a substituent, and the substituent is preferably an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a halogen atom, a substituted amino group, an alkylthio group or an arylthio group. Particularly, an alkyl group, an alkoxy group and an alkylthio group are preferable.

Of the aromatic rings represented by Ar, a benzene ring,
A naphthalene ring, a pyridine ring, a pyrimidine ring and the like are preferable. Particularly, a benzene ring and a naphthalene ring are preferable.

The group represented by R in the general formula (I) may have a substituent, and when R is an alkyl group, an aryl group, a substituted carbonyl group or a substituted sulfonyl group, the substituent is A halogen atom, an alkyl group, an aryl group, an alkoxy group, a substituted carbonyl group, a substituted amino group and a heterocyclic residue are preferable, and when R is a substituted silyl, an alkyl group and an aryl group are preferable. The substituents of these alkyl groups and aryl groups may further have a substituent.

More preferred R is 1 to 2 carbon atoms.
0 alkyl group, C 6-30 aryl group, C 2-20 alkylcarbonyl group, C 7-20 arylcarbonyl group, C 2-20
And an alkylsulfonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a substituted carbamoyl group having 2 to 20 carbon atoms are preferable. Particularly, an alkylcarbonyl group having 2 to 15 carbon atoms, an arylcarbonyl group having 7 to 15 carbon atoms, an alkoxycarbonyl group having 2 to 15 carbon atoms, and a substituted carbamoyl group having 2 to 15 carbon atoms are preferable.

Of the 2-cyclohexenone derivatives according to the present invention, for example, when R is a substituted carbonyl group, it can be selectively obtained by esterifying a cyclohexane-1,3-dione derivative. As the esterification method, (1) a method in which a cyclohexane-1,3-dione derivative is allowed to act with a carboxylic acid halide under basic conditions, (2)
Cyclohexane-1,3-dione derivative under acidic conditions
There is a method of using a carboxylic acid. in particular,
The method (1) (the following formula) is mild and preferable.

[0022]

[Chemical 4]

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

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

[0028]

[Chemical 9]

And the like.

The 2-cyclohexenone derivative according to the present invention may be used alone or in combination of two or more kinds.

The diazo compound and the coupling component contained in the photosensitive layer in the present invention are brought into contact with each other by heating and react with each other to develop a color, and the diazo compound is a light of a specific wavelength before the color development reaction. A photodegradable compound is used which decomposes upon receiving. The photodecomposable diazo compound as used in the present invention mainly refers to an aromatic diazo compound, and more specifically, refers to an aromatic diazonium salt, a diazosulfonate compound, or a diazoamino compound. Usually, the photolysis wavelength of a diazo compound is said to be its absorption maximum wavelength. It is also known that the maximum absorption wavelength of the diazo compound changes from about 200 nm to about 700 nm depending on its chemical structure. ("Photodecomposition and Chemical Structure of Photosensitive Diazonium Salt" by Takahiro Tsunoda and Nobuo Yamaoka Journal of the Photographic Society of Japan 29 (4) 197-205 (1965)) That is, when a diazo compound is used as a photodegradable compound, Decomposes with light of a specific wavelength depending on the chemical structure. Further, by changing the chemical structure of the diazo compound, the hue of the dye after the reaction can be changed even when the coupling reaction with the same coupling component is carried out.

The diazo compound is a compound represented by the general formula (IV). General formula (IV)

[0033]

[Chemical 10]

In the formula, Ar represents a substituted or unsubstituted aromatic ring, N ₂ represents a diazonium group, and X represents an acid anion.

Specific examples of the diazo compound used in the present invention include the followings.

4-diazo-1-dimethylaminobenzene, 4-diazo-2-butoxy-5-chloro-1-dimethylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-diazo-1-ethylhydroxy Ethylaminobenzene, 4-diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-toluylmercapto -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-ditert-amylphenoxy) butyrylpiperidino] benzene, 4-diazo-1- (4-methoxy) phenylthio-2,5-diethoxybenzene, 4- Diazo-1- (4-methoxy) benzamide-2,5-diethoxybenzene, 4-diazo-1-pyrrolidino-2-methoxybenzene

Specific examples of the acid forming the diazonium salt with the diazo compound include the followings.

Polyfluoroalkylcarboxylic acid having 1 to 9 carbon atoms, polyfluoroalkylsulfonic acid having 1 to 9 carbon atoms, tetrafluoroboric acid, tetraphenylboric acid, hexafluorophosphoric acid, aromatic carboxylic acid,
Aromatic sulfonic acid, zinc chloride, cadmium chloride,
It is also possible to stabilize the diazonium salt by forming a complex compound using tin chloride or the like.

In the present invention, a diazo compound having a different photolytic wavelength or a different photolytic rate can be used to provide a multicolor recording material.

The microcapsules used in the present invention are
After emulsifying and dispersing in a hydrophilic protective colloid solution a solution in which a diazonium salt and the same or different compound that reacts with each other to form a polymeric substance are dissolved in a non-aqueous solvent having a boiling point of 40 to 95 ° C. under normal pressure, While reducing the pressure in the reaction vessel and raising the temperature of the system to distill off the solvent, the wall forming substance is moved to the surface of the oil droplet, and the polymer formation reaction by polyaddition and polycondensation is allowed to proceed on the surface of the oil droplet to form a wall film. From the viewpoint of obtaining a good shelf life, it is preferable that the microcapsules are substantially free of a solvent and are produced by forming

Further, in the present invention, the polymer substance forming the walls of the microcapsules is preferably formed of at least one selected from polyurethane and polyurea.

As the non-aqueous solvent for dissolving the diazonium salt used in the present invention, a halogenated hydrocarbon,
It is preferably at least one compound selected from fatty acid esters, ketones and ethers.

The same or different compounds that react with each other to form a polymer substance forming the wall of the microcapsule used in the present invention are polyurea and urethane, preferably aromatic or aliphatic isocyanate compounds as the corresponding monomers. To be selected. The microcapsules containing the diazo compound of the present invention can polymerize corresponding monomers, but the amount of the monomers used is such that the average particle diameter of the microcapsules is 0.3 μ to 12 μ, and the wall thickness is 0.01 to 0. It is decided to be .3. The diazo compound is preferably applied in an amount of 0.05 to 5.0 g / m ² .

In the present invention, the coupling component which can be used together with the coupling component represented by the general formula (I) for the purpose of adjusting the hue and the like forms a dye by coupling with a diazo compound in a basic atmosphere. Any compound is possible as long as it is one.

For example, there are so-called active methylene compounds having a methylene group next to a carbonyl group, phenol derivatives, naphthol derivatives and the like. Specific examples thereof include the followings, which are used in a range consistent with the object 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-sulfonylnaphthalene, 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

In the present invention, an organic base is added for the purpose of making the system basic during heat 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.

[0048] Especially, 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- (beta Nafutokishi ) -2-Hydroxypropyl] piperazine,
N-3- (beta Nafutokishi) -2-hydroxypropyl -N ^'- methylpiperazine, 1,4-bis {[3- (N
-Methylpiperazino) -2-hydroxy] propyloxy} benzene and other piperazines, N- [3- (βnaphthoxy) -2-hydroxy] propylmorpholine,
Morpholines such as 1,4-bis [(3-morpholino-2-hydroxy) propyloxy] benzene and 1,3-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, N- (3-phenoxy) Specifically, piperidines such as 2-hydroxypropyl) piperidine and N-dodecylpiperidine, and guanidines such as triphenylguanidine, tricyclohexylguanidine, and dicyclohexylphenylguanidine are specifically preferable.

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 with respect to 1 part by weight of the diazo compound.

In the present invention, in addition to the organic base, a color forming auxiliary agent can be added for the purpose of promoting the color forming reaction.

Included in the color forming aid of the present invention are:
For example, a phenol derivative, a naphthol derivative, an alkoxy-substituted benzene, an alkoxy-substituted naphthalene, a hydroxy compound, an amide compound, a sulfonamide compound can be added to the photosensitive layer so that a rapid and complete thermal development can be performed with low energy. .. These compounds are
It is considered that the melting point of the coupling component or the basic substance is lowered, or the heat permeability of the microcapsule wall is improved, and as a result, high color density is obtained.

The color forming aid of the present invention also includes a heat-meltable substance. The heat-fusible 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.

The coupling component used in the present invention is
It can be used by solid-dispersing it together with a water-soluble polymer by a sand mill or the like together with a basic substance, other color-forming aid, etc., but it is particularly excellent for the purpose of forming an emulsion with a suitable emulsification aid. Preferred water-soluble polymers include water-soluble polymers used when preparing microcapsules (for example, JP-A-59-19).
0886). In this case, the coupling component, the basic substance, and the color-forming aid are added to the water-soluble polymer solution in an amount of 5 to 40% by weight, respectively. The dispersed or emulsified particle size is preferably 10 μm or less.

To the recording material of the present invention, a free radical generator (a compound capable of generating a free radical upon irradiation with light) used in a photopolymerizable composition or the like for the purpose of reducing yellowing of the background after copying is added. be able to. Examples of the free radical generator include aromatic ketones, quinones, benzoin, benzoin ethers, azo compounds, organic disulfides, acyloxime esters and the like. The amount of addition of the free radical generator is 0.01 to 1 part by weight of the diazo compound.
5 parts by weight is preferred.

Similarly, for the purpose of reducing yellowing, a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as vinyl monomer) can be used. The vinyl monomer is a compound having at least one ethylenically unsaturated bond (vinyl group, vinylidene group, etc.) in its chemical structure and has a chemical form of a monomer or a prepolymer. Examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic polyhydric alcohols, and amides of unsaturated carboxylic acids with aliphatic polyhydric amine compounds. The vinyl monomer is used in a proportion of 0.2 to 20 parts by weight with respect to 1 part by weight of the diazo compound.

The free radical generator and the vinyl monomer may be used together with the diazo compound in microcapsules.

In the present invention, in addition to the above materials, citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. can be added as an acid stabilizer.

For the recording material of the present invention, a coating solution containing microcapsules containing a diazo compound, a coupling component, an organic base, and other additives is prepared, and coated on a support such as paper or a synthetic resin film. To a solid content of 2.5 to 30 g / m by coating and drying by a coating method such as bar coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, curtain coating.
Providing ² photosensitive layers. In the recording material of the present invention, microcapsules, coupling components, bases and the like may be contained in the same layer as described in the above method, or may have a laminated structure in which they are contained in different layers. You can also It is also possible to apply the photosensitive layer after providing the intermediate layer described in Japanese Patent Application No. 177669/1984 on the support.

As the support of the present invention, any paper support used for ordinary pressure-sensitive paper, heat-sensitive paper, dry type or wet type diazo copying paper, etc. can be used as well as neutral ones such as alkyl ketene dimer. Neutral paper having a pH of 5 to 9 sized with a sizing agent (as described in Japanese Patent Application No. 55-14281), satisfying the relationship between Steckigt sizing degree and metric basis weight described in JP-A-57-116687, and Paper having a Beck's smoothness of 90 seconds or more, an optical surface roughness described in JP-A-58-136492 of 8 μm or less, and a thickness of 30 to 30.
150 μ paper, paper having a density of 0.9 g / cm ³ or less as described in JP-A-58-69091 and an optical contact ratio of 15% or more, Canadian standard freeness (JP-A-58-69097) Paper which is made from pulp that has been beaten to 400 cc or more in accordance with JIS P8121) to prevent soaking of the coating liquid. It is also possible to use a paper having improved resolving power, a paper described in JP-A-59-35985, which has been subjected to corona discharge treatment to have improved coating suitability.

The synthetic resin film used as the support in the present invention can be arbitrarily selected from known materials which do not deform even when heated in the developing process and have dimensional stability. Examples of such a film include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate films, polystyrene films, polypropylene films, polyolefin films such as polyethylene, and the like, which may be used alone or in combination. Can be used. The thickness of the support is 20 to 200 μm.

When an image is formed on the recording material of the present invention,
The following method can be used. One is a method of exposing a document to form a latent image, and then irradiating light to a portion other than the image forming portion to fix the latent image.
In this method, a colored image is obtained by heat from a hot pen, a thermal head or the like, and then the area other than the image area is irradiated with light to fix the image. Either method can be preferably used. As a light source for exposure, various fluorescent lamps, xenon lamps, mercury lamps, etc. are used, and the fact that the emission spectrum is almost the same as the absorption spectrum of the diazo compound used in the recording material makes it possible to efficiently use the components other than the image forming portion. It is preferable because it can be fixed by light. In the step of heating and developing the material, a heating pen, a thermal head, an infrared ray, a high frequency wave, a heat block, a heat roller or the like can be used as a heating means.

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

Synthesis Example Synthesis Example 1 5- (2-tetradecyloxy) phenyl-cyclohexane-1,3-dione 40.0 g, triethylamine 1
0.6 g was dissolved in 100 ml of acetonitrile, and 12.5 g of pivaloyl chloride was slowly added dropwise under ice cooling. After completion of dropping, the mixture was stirred at the same temperature for 1 hour, and the reaction mixture was poured into 500 ml of water. The precipitated crystals were filtered and recrystallized with alcohol to obtain 43.6 g of compound (5). (Yield = 90%, mp = 30 to 31 ° C.)

Synthesis Example 2 Compound (6) (42.6 g) was obtained by following the same procedure as in Synthesis Example 1, except that 9.9 g of methyl chloroformate was used instead of using pivaloyl chloride. It was (Yield = 93%, mp = 55-56 ° C.)

Synthetic Example 3 Instead of using pivaloyl chloride in Synthetic Example 1, 11.3 g of N, N-dimethylcarbamic acid chloride was used.
The reaction was performed in the same manner as in Synthesis Example 1 except that was used to obtain 41.4 g of the compound (7). (Yield = 88%, mp =
38-40 ° C)

Synthesis Example 4 Instead of using 5- (2-tetradecyloxy) phenyl-cyclohexane-1,3-dione in Synthesis Example 2, 5- (2-tetradecyloxy) phenyl-4-
The reaction was performed in the same manner as in Synthesis Example 2 except that 41.4 g of methyl-cyclohexane-1,3-dione was used to obtain 40.1 g of compound (11). (Yield = 85%, mp.
= 41 to 43 ° C)

Synthesis Example 5 Instead of using 5- (2-tetradecyloxy) phenyl-cyclohexane-1,3-dione in Synthesis Example 2, 5- (2-tetradecyloxy) phenyl-4-
Methyl-4-methoxycarbonyl-cyclohexane-
Synthesis Example 2 except that 47.6 g of 1,3-dione was used
The same reaction was carried out as in the above to obtain 44.0 g of the compound (31).
(Yield = 83%, mp = 44-45 ° C.)

[0068]

【Example】

Example 1 [Preparation of capsule liquid A of the present invention]: 4-morpholino
3.45 parts of 2,5-dibutoxybenzenediazonium hexafluorophosphate and 18 parts of xylylene diisocyanate and a trimethylolpropane (3: 1) adduct were added to 10 parts of ethyl acetate and dissolved by heating. A solution of this diazo compound was prepared by adding 5.2 parts of polyvinyl alcohol to 58 parts of water.
The mixture was mixed with an aqueous solution dissolved in a part and emulsified and dispersed at 20 ° C. to obtain an emulsion having an average particle size of 2.5 μ. 100 parts of water was added to the obtained emulsion and heated to 50 ° C with stirring,
After a lapse of time, a capsule liquid containing a diazo compound as a core substance was obtained.

[Preparation of Coupler / Base Emulsion B]: 10 parts of the compound (5) of the present invention, 5 parts of triphenylguanidine, and 3 parts of tricresyl phosphate were dissolved in 50 parts of ethyl acetate to prepare a 15% polyvinyl alcohol aqueous solution 200. In addition to the parts, the mixture was emulsified and dispersed by a homogenizer. This was kept at 30 ° C. to remove ethyl acetate to obtain an emulsion B. The average particle size of the emulsion was 0.5μ.

[Preparation of Recording Material of the Present Invention]: 50 parts of the above-mentioned capsule liquid A was added with 50 parts of emulsion B to prepare a coating liquid. This and the lid solution were applied to a smooth and transparent polyethylene terephthalate film (thickness 75 μm) using a coating bar so that the dry weight was 10 g / m ² , and the temperature was 50 ° C. 1
A recording material was prepared by drying for a minute.

[Coloring and Fixing Test] A test original document (tracing paper with a circle having a diameter of 3 cm painted uniformly in black with a 2B pencil) was overlaid on the recording material and exposed with a fluorescent lamp. At this time, the fluorescent lamp used a lamp having a maximum value at 420 nm. Next, an image was formed by heating for 3 seconds with a heat block heated to 120 ° C. The formed image developed a reddish color. Also, when the image was previously exposed to a lamp having an absorption maximum at 420 nm after being heated by a heat block heated to 120 ° C., the formed image developed a reddish color.
When the density of the color-developed portion was measured with a Macbeth densitometer, they were 1.23, respectively.

Example 2 A recording material was prepared in the same manner as in Example 1 except that a coupler / base emulsion was obtained by using Compound (6) instead of Compound (5) used in Example 1. Created and imaged. The formed image developed a reddish color, and when the density of the color-developed portion was measured with a Macbeth densitometer, it was 1.25.

Example 3 Instead of the compound (5) used in Example 1, the compound (1
0) was used to obtain a coupler / base emulsion but in Example 1
The same operation as above was performed to prepare a recording material and form an image. The formed image developed a reddish color, and when the density of the color-developed portion was measured with a Macbeth densitometer, it was 1.22.

Example 4 Instead of the compound (5) used in Example 1, the compound (1
Example 1 except that a coupler / base emulsion was obtained using 1).
The same operation as above was performed to prepare a recording material and form an image. The formed image developed a reddish color, and when the density of the color-developed portion was measured with a Macbeth densitometer, it was 1.24.

Example 5 Instead of the compound (5) used in Example 1, the compound (1
Example 1 except that a coupler / base emulsion was obtained using 3).
The same operation as above was performed to prepare a recording material and form an image. The formed image developed a reddish color, and when the density of the color-developed portion was measured with a Macbeth densitometer, it was 1.25.

Comparative Example 1 Instead of the compound (5) used in Example 1, 5,5-dimethyl-cyclohexane-1,3-dione (Comparative Example 1)
An image was formed in the same manner as in Example 1 except that a coupler / base emulsion was obtained by using. The formed image developed a reddish color, and when the density of the color-developed portion was measured with a Macbeth densitometer, it was 1.20.

Comparative Example 2 Instead of the compound (5) used in Example 1, 5-phenyl-4-methoxycarbonyl-cyclohexane-1,3 was used.
An image was formed in the same manner as in Example 1 except that the coupler / base emulsion was obtained using dione. The formed image developed a reddish color, and when the density of the color-developed portion was measured with a Macbeth densitometer, it was 1.19.

Next, the storage properties of the obtained recording materials were compared with the fog on the background. Shelf life test is 40 ℃, 90%
It was carried out by observing the transparency of the material left for 1 day under the condition of RH. When the storability is poor, it is not suitable as a recording material because it is observed as cloudy. Further, the fog test on the background part was performed by measuring the density of the background part with a Macbeth densitometer. The respective results are shown in Table 1.

[0079]

[Table 1]

From these results, it is understood that the coupling component of the present invention is excellent in the storage stability and stability of the emulsion and the prevention of fog on the background part.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Kamikawa 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd.

Claims (4)

[Claims] 1. A light and heat sensitive recording material comprising a support and a recording layer containing a diazo compound, a coupling component and an organic base, wherein the coupling component is a 2-cyclohexenone derivative having a total carbon number of 15 or more. The light and heat sensitive recording material is characterized by: 2. The light and heat sensitive recording material according to claim 1, wherein the coupling component is a 2-cyclohexenone derivative having a substituted aryl group at the 5-position. 3. A coupling component having an alkyl group, an aryl group or an alkoxy group at the 4- and / or 6-positions
The light and heat sensitive recording material according to claim 1, which is a cyclohexenone derivative. 4. The light and heat sensitive recording material according to claim 1, wherein the diazo compound is contained in microcapsules.