JPH03274180A - Photosensitive thermal recording material - Google Patents

Abstract

PURPOSE:To improve the luminance and saturation of an image by microencapsulating any one of diazo compound and coupler and by providing at least one transparent photosensitive thermal layer of the other of them as an emulsion dispersant on a support having a mirror reflection or class II diffuse reflection metal layer. CONSTITUTION:An application liquid containing a microcapsule involving one of diazo compound and coupler, a dispersant emulsion-dispersing the other of them, a binder and other additives is prepared, applied onto a mirror reflection or class II diffuse reflection support by an application method such as bar application and dried thereafter to form at least one thermal layer with 2.5-25g/m<2> solid part. A metal thin film layer having reflection characteristics can be formed as a laminate on a substrate or laminated into a support. As further methods for providing the metal thin film layer, a vacuum evaporation, sputtering method, ion plating method, electrodeposition method, electroless plating, etc., are used to provide one or two layer of metal thin film or more on a predetermined substrate. As the substrate for the support, there are used, e.g. synthetic resin film, paper, RC-paper, synthetic paper, etc.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a light and heat sensitive recording material that provides images with a three-dimensional effect, and in particular has excellent image brightness, saturation, gradation reproducibility in dark areas, sharpness, etc. This invention relates to light and heat sensitive recording materials.

(Prior Art) Light and heat sensitive recording materials have been known in which a light and heat sensitive layer containing a diazo compound and a coupler is provided on a support. That is, this type of recording material uses a photodegradable diazo compound and coupler in combination with a heat-fusible material, and when heated, the diazo compound and coupler undergo a coupling reaction to develop color. It also takes advantage of the fact that the diazo compound can be decomposed by exposure to light in the photodegradation wavelength range of the diazo compound, thereby preventing color development and fixing the diazo compound. Therefore, optical recording can be performed on the above recording material by image-wise exposure to light in the above wavelength range and then heating above the melting point of the thermofusible material; conversely, after thermal recording, the recording layer Thermosensitive recording can be performed by exposing the entire surface to light. Therefore, when the above-mentioned recording material is used as a heat-sensitive recording material, unlike the leuco color-forming heat-sensitive recording material, the recorded image after fixing does not develop unnecessary color on the background, etc., and the recording stability is improved. It has an excellent feature.

In addition, the thermal recording method has the following advantages: (1) development is not required; (2)
When the support is paper, the quality of the paper is similar to that of ordinary paper, (3) it is easy to handle, (4) the color density is high, (5) the recording device is simple and inexpensive, and (6) it is used during recording. Because it has advantages such as no noise, it has rapidly become popular in the fields of facsimile machines and printers in recent years, and the use of thermal recording is also expanding.

Against this background, in order to adapt to multicolorization or for use in overhead projectors (abbreviated as ○HP), transparent light and heat sensitive recording materials that can be directly recorded with a thermal head have been developed. has been developed (for example, Japanese Patent Laid-Open No. 63-318546), and the requirements for image quality are becoming even higher.

Incidentally, the image quality of a light- and heat-sensitive recording material is significantly affected not only by the light- and heat-sensitive layer but also by the support.

Conventionally, as a support for heat-sensitive recording, for example, TAC, PE, etc.
Transparent plastic films such as T, and reflective materials such as paper, synthetic paper, and plastic films containing white pigments are known. In particular, in order to improve the whiteness of the support, fine powder of a metal oxide or an inorganic compound (for example, titanium oxide, barium sulfate, magnesium oxide, etc.) can be mixed or contained as a pigment on the surface of the support. As described above, increasing the whiteness of the support improves white reproduction and improves image sharpness, but the results are still not satisfactory. As a result of investigation, it was discovered that the image quality could be significantly improved by using a support having a specular reflection or type 2 diffuse reflection metal layer as a support for light and heat sensitive recording materials, and the present invention was achieved.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a light and heat sensitive recording material that can improve the brightness and chroma of an image.

A second object of the present invention is to provide a light- and heat-sensitive recording material that has excellent gradation reproducibility and sharpness in dark areas of an image.

Furthermore, a third object of the present invention is to provide a light and heat sensitive recording material capable of forming images with a three-dimensional effect.

(Means for Solving the Problems) The above-mentioned objects of the present invention are to provide microcapsules containing either a diazo compound or a coupler and the other being dissolved in an organic solvent that is sparingly soluble or insoluble in water, and then emulsified and dispersed. A substantially transparent photosensitive and heat-sensitive layer formed by coating and drying a coating solution containing the emulsified dispersion obtained by This was achieved by using a light and heat sensitive recording material with 01!I! indicating that it has at least one layer.

The diazo compound used in the present invention refers to a photodegradable diazo compound that decomposes and loses coloring reactivity when exposed to light of a specific wavelength before reaction, and mainly refers to aromatic diazo compounds. Specifically, it refers to aromatic diazonium salts, diazosulfonate compounds, cyasia ξ) compounds, and the like. Hereinafter, explanation will be given mainly using diazonium salt as an example.

It is generally said that the photodecomposition wavelength of a diazonium salt is at its maximum absorption wavelength. Also, the maximum absorption wavelength of diazonium salts varies from about 200 nm to 700 nm, depending on their chemical structure.
It is known that the change occurs down to about nanometers (“Photodecomposition and chemical structure of photosensitive diazonium salts” by Takahiro Tsunoda and Ao Yamaoka, Journal of the Photographic Society of Japan 29 (4), pp. 197-205 (
1965)).

That is, when a diazonium salt is used as a photodegradable compound, it is decomposed by light of a specific wavelength depending on its chemical structure. Furthermore, by changing the chemical structure of the diazonium salt, it is possible to change the hue of the dye after the reaction even when the diazonium salt undergoes a coupling reaction with the same coupling component.

A diazonium salt is a compound represented by the formula ArN,'X- (wherein Ar represents a substituted or unsubstituted aromatic moiety, N2' represents a diazonium group, and X- represents an acid anion. Hail,). Of these, 400
Examples of compounds having a photolysis wavelength near nm include 4-diazo-1-dimethylaminohenzene, 4-diazo-1-
Diethylaminobenzene, 4-diazo-1-dipropylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-diazo-1-dibenzylaminobenzene, 4-diazo-1-ethylhydroxyethylagonobenzene, 4 -Diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4-diazo-l-benzoylamino-2
, 5-jethoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-jethoxybenzene, 4-diazo-1-morpholino-2,
5-dibutoxybenzene, 4-diazo-1-anilinobenzene, 4-thia 7'-1-tolylmercapto-2,
Examples include 5-jethoxybenzene, 4-diazo-1,4-methoxybenzoylamino-2,5-jethoxybenzene, and the like. As a compound having a photolysis wavelength of 300 to 370 nm, 1-diazo-4-(N,N
-dioctylcarbamoyl)benzene, 1-diazo-2
-octadecyloxybenzene, 1-diazo4 (4
tert-octylphenoxy)benzene, 1-diazo-4-(2,4-di-tert-amylphenoxy)benzene, l-diazo-2(4-tert-octylphenoxy)benzene, 1-diazo-5-chloro-2 (4-
tert-octylphenoxy)benzene, l-diazo-2,5-bis-octadecyloxybenzene, ■-diazo2,4-bis-octadecyloxybenzene, 1
-Diazo-4-(N-octylteraroyl))benzene and the like.

The photolysis wavelength of the aromatic diazonium compounds typified by the examples listed above can be varied widely by arbitrarily changing the substituents.

Specific examples of acid anions and diazo compounds that can be used in the present invention include, for example, JP-A-63-3
No. 18546.

Preferred compounds among these compounds include 2-methoxy, 2-phenoxy, 2-methoxy-4-phenoxy, 2,4-dimethoxy, 2-methyl-4-methoxy,
Benzenediazosulfonate having a substituent such as 2,4-dimethyl, 2,4゜6-trimethyl, 4-phenyl, 4-phenoxy, 4-acetamide, etc., or 4-(N-ethyl, N-hensylua) Eup)), 4-(N,
N-dimethylamino), 4-(N,N-diethylamino), 4-(N,N-diethylamino/)-3-10l, 4
-Pyrodanino 3-'Furol, 4-morpholino-2-methoxy, 4-(4''-methoxybenzoylamino)-
2,5-dibutoxy, 4-(4”-trimercapto)-
It is a benzenediazosulfonate having a substituent such as 2,5-dimethoxy. When using these diazosulfonate compounds, it is desirable to irradiate the diazosulfonate with light to activate the diazosulfonate before printing.

Further, other diazo compounds that can be used in the present invention include diazoamino compounds. Diazoamino compounds include compounds in which a diazo group is coupled with dicyandiamide, sarcosine, methyltaurine, N-ethylanthranic acid-5-sulfonic acid, monoethanolamine, jetanolamine, guanidine, etc.

The coupler used in the present invention is one that forms a dye by coupling with a diazo compound (diazonium salt), and specific examples include resorcin, phloroglucin, 2,
Sodium 3-hydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 15-dihydroxynaphthalene, 2.3-dihydroxynaphthalene, 2.3-dihydroxy-6-sulfanylnaphthalene, 2-hydroxy- 3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid-2'-methylamide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid octylamide Acid-N-dodecyl-oxy-probylamide, 2-hydroxy-3-naphthoic acid tetradodecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, 1-phenyl-3-methyl-5-virazolone, 2.
4-bis(benzoylacetamino)toluene, 1.3
-bis(pivaloylacetaminomethyl)benzene, 1
-(2°, 4″6′ -) IJ chlorophenyl)-3-bensuaξdo-5-pyrazolone, 1-(2″
,4',6'trichlorophenyl)-3-anilino-
Examples thereof include 5-pyrazolone, l-phenyl-3-phenylacedodando-5-pyrazolone, and the like. Furthermore, by using two or more of these coupling components in combination, an image of any color tone can be obtained.

It is preferable to add a basic substance to the recording layer of the photosensitive and thermosensitive recording material of the present invention, if necessary, for the purpose of making the system basic and promoting the coupling reaction.

As these basic substances, used are sparingly water-soluble or water-insoluble basic substances, and substances that generate alkali upon heating.

Basic substances include inorganic and organic ammonium salts,
organic amines, amides, urea and thiourea and their derivatives,
Examples include nitrogen-containing compounds such as thiazoles, virols, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidacillines, triazoles, morpholines, piperidines, amidines, formazines, and pyridines. . These basic substances are
Two or more types can be used in combination.

In the light and heat sensitive recording material of the present invention, a hydroxy compound, a carbamate ester compound, an aromatic methoxy compound, or an organic sulfonamide compound is added in the light and heat sensitive layer for thermal color development so that heat development can be performed quickly and completely with low energy. Can be added as a sensitizer. These compounds are thought to lower the melting point of the coupling component or basic substance or to improve the thermal permeability of the microcapsule wall, and are thought to result in a higher practical concentration.

Materials that produce the above color-forming reaction are selected from the viewpoint of improving the transparency of the photosensitive and heat-sensitive layer, from the viewpoint of shelf life (preventing fogging) by preventing contact between the diazo compound and the coupler at room temperature, and from the viewpoint of color development with the desired impression and heating energy. From the viewpoint of controlling color development sensitivity, at least one of the diazo compound and the coupler is encapsulated and used.

Preferred microcapsules are those in which the IFJi isolation effect of the microcapsule wall prevents contact between substances inside and outside the capsule at room temperature, and the permeability of substances increases only when heated above a certain temperature; By appropriately selecting the @IJ quality, additives, etc., the permeation start temperature can be freely controlled. The transmission start temperature in this case corresponds to the glass transition temperature of the capsule wall.

In order to control the glass transition point specific to the capsule wall, it is necessary to change the type of capsule wall forming agent. Examples of the wall material of the microcapsule include polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, etc. . Two or more of these polymeric substances can also be used in combination.

In the present invention, among the above-mentioned polymeric substances, polyurethane, polyurea, polyamide, polyester, polycarbonate, etc. are preferable, and polyurethane and polyurea are particularly preferable.

When the preferred microcapsules produced as described above are used, during thermal printing, the reactive substances contained in the core and outside of the microcapsules permeate through the microcapsule walls and react.

In the present invention, the wall material of the microcapsule is selected,
If necessary, a glass transition point adjusting agent (for example,
277490) to prepare microcapsules consisting of walls with different glass transition points, and by selecting combinations of diazo compounds and couplers with different hues, multicolored intermediate colors can be realized. I can do it. Therefore, the present invention is not limited to monochromatic light and heat sensitive recording materials, but can also be applied to two color or multicolor light and heat sensitive recording materials and light and heat sensitive recording materials suitable for recording images with gradation. can.

Further, if necessary, photofading inhibitors described in, for example, JP-A-61-283589, JP-A-61-283590, and JP-A-61283591 can be appropriately added.

The above-mentioned microcapsules are preferably microencapsulated by emulsifying a core material containing a diazo compound or a coupler, and then forming a wall of a polymer material around the oil droplets. In this case, a polymer material is formed. A reactant is added inside the oil droplet and/or outside the oil droplet. Details of microcapsules that can be preferably used in the present invention, such as a preferred method for producing microcapsules, are described in, for example, JP-A-59-222716.

Here, the organic solvent for forming oil droplets can generally be appropriately selected from high boiling point oils.

When making microcapsules, they can be made from an emulsion containing 0.2% by weight or more of the component to be microencapsulated.

The amount of coupling component is 0.0% per 1 part by weight of the diazo compound.
It is preferable to use 1 to 10 parts by weight, and the basic substance to be used in a proportion of 0.1 to 20 parts by weight.

In the present invention, it is also possible to use a color development aid. The above-mentioned color development aid is a substance that increases the color density during heat color development or lowers the minimum color development temperature, and lowers the melting point of coupling components, basic substances, diazo compounds, etc. This is to create a situation in which diazo, basic substances, coupling components, etc. are more likely to react by lowering the softening point.

Such color development aids include phenolic compounds, alcoholic compounds, amide compounds, sulfonamide compounds, etc. Specific examples include p-tert-octylphenol, p-benzyloxyphenol, phenyl p-oxybenzoate, Hensyl carbanylate, phenethyl carbanylate, hydroquinone dihydroxyethyl ether, xylylene diol, N-hydroxyethyl-
Compounds such as methanesulfonic acid adduct and N-phenyl-methanesulfonic acid adduct can be mentioned. These may be contained in the core material or may be added outside the microcapsules as an emulsified dispersion.

In the present invention, in order to obtain a substantially transparent photosensitive and thermosensitive layer, a coupler is used when a diazo compound is contained in microcapsules, and a coupler is used when a diazo compound is contained in microcapsules; This is mixed with an aqueous phase containing a surfactant and having a water-soluble polymer as a protective colloid, and used in the form of an emulsified dispersion. In this case, it is often arbitrary whether the diazo compound or the puller is contained in the microcapsules or as a component of the emulsified dispersion, but in particular, the diazo compound is contained in the microcapsules and the coupler is emulsified and dispersed. It is preferable to use it as a component of something.

The organic solvent used in this case can be appropriately selected from high boiling point oils. In addition to esters, preferable oils include the following formulas (1) to (I[I
) and triallylmethane (e.g.
Trittle methane, tolyldiphenylmethane), terphenyl compounds (e.g. terphenyl), alkyl compounds'! Examples include Fl (eg, terphenyl), alkylated diphenyl ether (eg, Eva, propyl diphenyl ether), hydrogenated terphenyl (eg, hexahydroterphenyl), diphenyl ether, and the like.

(I) In the formula, R1 is hydrogen or alkyl 114 having 1 to 18 carbon atoms,
R2 represents an alkyl group having 1 to 18 carbon atoms. p +
, q l represents an integer of 1 to 4, and the number of alkyl groups is 4 or less.

Incidentally, the alkyl groups for R' and R'' are preferably alkyl groups having 1 to 8 carbon atoms.

(n) (II[) In the formula, R3 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R4 represents an alkyl group having 1 to 12 carbon atoms. n is l
Or represents 2.

pZqZ represents an integer from 1 to 4. When n=1, the total number of alkyl groups is 4 or less, and n=2
When , the total number of alkyl groups is 6 or less.

In the formula, R5 and R6 represent a hydrogen atom or the same or different alkyl groups having 1 to 18 carbon atoms.

m represents an integer from 1 to 13. p3, q3 is 1~
represents an integer of 3, and the total number of alkyl groups is 3 or less.

In addition, the alkyl group of R5 and R6 is particularly preferably an alkyl group having 2 to 4 carbon atoms.

Examples of the compound represented by formula (I) include dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene, and the like.

Examples of the compound represented by formula (II) include dimethylbiphenyl, diethylbiphenyl, diisopropylbiphenyl, and diisobutylbiphenyl.

Examples of compounds represented by formula (III) include 1-methyl-1-dimethylphenyl-1-phenylmethane, 1-ethyl-1-dimethylphenyl-1-phenylmethane,
-propyl=1-dimethylphenyl-1-phenylmethane.

Among these, it is particularly preferable to use esters from the viewpoint of emulsion stability of the emulsified dispersion.

Examples of esters include phosphate esters (e.g., triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, talesyl diphenyl phosphate), phthalate esters (
Dibutyl phthalate, 2-ethylhexyl phthalate, ethyl phthalate, octyl phthalate, butylbenzyl phthalate) dioctyl tetrahydrophthalate, benzoic acid ester (ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzoic acid) hensyl abietate), abietate ester (ethyl abietate, hensyl abietate), dioctyl adipate, isodecyl succinate, dioctyl azelate, oxalate ester (dibutyl oxalate, dipentyl oxalate), diethyl malonate, maleate ester ( dimethyl maleate, diethyl maleate, dibutyl maleate), tributyl citrate, sorbate esters (methyl sorbate, ethyl sorbate, butyl sorbate), sebacate esters (dibutyl sebacate, dioctyl sebacate), ethylene glycol ester (formic acid monoesters and diesters, butyric acid monoesters and diesters, lauric acid monoesters and diesters, palmitic acid monoesters and diesters, stearic acid monoesters and diesters, oleic acid monoesters and diesters),
Examples include triacetin, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, boric acid esters (tributyl borate, tripentyl borate), and the like. Among these, when tricresyl phosphate is used alone or in combination, the emulsion dispersion stability of the color developer is particularly good, and therefore it is preferable.

It is also possible to use the above oils together or with other oils.

In the present invention, an auxiliary solvent may be added to the above-mentioned organic solvent as a low boiling point dissolution aid. Particularly preferred examples of such co-solvents include ethyl acetate, isopropyl acetate, butyl acetate and methylene chloride.

The water-soluble polymer to be included as a protective colloid in the aqueous phase to be mixed with the oil phase containing these components can be appropriately selected from known anionic polymers, nonionic polymers, and amphoteric polymers. Yes, but polyvinyl alcohol,
Gelatin, cellulose derivatives, etc. are preferred.

The surfactant to be contained in the aqueous phase can be appropriately selected from anionic or nonionic surfactants that do not interact with the protective colloid to cause precipitation or aggregation. Preferred surfactants include sodium alkylbenzene sulfonate, sodium alkyl sulfate, dioctyl sodium sulfosuccinate, polyalkylene glycol (eg, polyoxyethylene nonylphenyl ether), and the like.

The emulsified dispersion in the present invention is produced by mixing an oil phase containing the above components and an aqueous phase containing a protective colloid and a surfactant using means commonly used for fine particle emulsification, such as high-speed stirring and ultrasonic dispersion. It can be easily dispersed and obtained.

Also, the ratio of oil phase to water phase is 4M (oil phase type I/water phase weight I
) is preferably 0.02 to 0.6, particularly 0.1 to 0.
It is preferable that it is 4. If it is less than 0.02, the aqueous phase will be too large and diluted, making it impossible to obtain sufficient color development, while if it is more than 0.6, the viscosity of the liquid will increase, resulting in inconvenience in handling and a decrease in stability of the coating liquid.

The light and heat sensitive recording material of the present invention can be coated using a suitable binder.

Binders include polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylic acid ester, ethylene-vinyl acetate, etc. Various emulsions such as polymers can be used. The amount used is 0.5 to 5 g/rrr in terms of solid content.
It is.

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 acid stabilizers.

The light and heat sensitive layer provided as described above surprisingly has extremely good transparency.

The light and heat sensitive recording material of the present invention is produced by preparing a coating solution containing microcapsules encapsulating either a diazo compound or a coupler, a dispersion in which the other is emulsified, and other additives such as a binder. Manufactured by coating and drying on a reflective or type 2 diffuse reflective support by a coating method such as bar coating to form at least one heat-sensitive layer with a solid content of 2.5 to 25 g/n. be done.

The support of the present invention will be explained below.

In general, the reflection characteristics of the surface of an object can be roughly divided into specular reflection and diffuse reflection, and diffuse reflection can be further divided into type 1 diffuse reflection and type 2 diffuse reflection. Type 2 diffuse reflectance generally refers to reflection on a rough surface with a small slope boundary such as ground glass or a polished metal surface, and in the present invention, it particularly refers to the case where the reflectance R is 0.5 or more. The details are described in JP-A-63-118154.

Metals that provide a type 2 diffusely reflective surface include F. Benford et al. J. Opt.
Soc.

Amar, Vol. 32, pp. 174-184 (1942), such as silver, aluminum, gold, copper,
Chrome nickel, platinum, alloys thereof such as aluminum/magnesium alloy, aluminum/li4, aluminum/antimony, sinchu, etc. are used.

In addition, the surface of the metal thin film layer that provides type 2 diffuse reflection can be formed by patterning the surface of a metal plate having specular reflection during rolling, mechanically, for example by using a brush with appropriate strength, or by polishing with an abrasive such as pumice. It can be obtained by graining, in which fine particles are sprayed with a jet stream, or by electrolytic etching. Metal V having reflective properties according to the present invention
The s-film layer can be laminated or stacked on a substrate to serve as a support. Furthermore, vacuum evaporation, sputtering, ion brazing, electrodeposition, electroless plating, and other methods are known as methods for forming metal thin film layers. A metal thin film layer may also be provided.

The degree of surface unevenness in the case of a type 2 diffuse reflection surface can be determined by embedding and fixing the sample in resin, cutting an ultrathin section, and observing the cross section using an electron microscope. In addition, it can be directly measured with sub-clockwise accuracy using a cross-sectional shape measuring device using electron beam irradiation. The number of cylinders of unevenness can be measured as the frequency of surface roughness, and in the present invention, the average frequency is preferably 0.1 to 2.000 ke/W, particularly 1 to 1,000 ke/m. is preferred.

By using the support of the present invention, the brightness of image highlights, the saturation of images, and the reproducibility of gradations in dark areas are significantly improved. Also, surprisingly, the sharpness of the image was dramatically improved.

As the substrate of the support according to the present invention, those conventionally used in the field of heat-sensitive recording materials can be used as they are without any problem. For example, synthetic resin film, paper, RC paper, synthetic paper, etc. are used. Among these, paper, RC paper and synthetic resin film are particularly preferred. R
It is also possible to use low-density polyethylene in combination with the polyethylene layer of C paper and laminate an aluminum vapor-deposited film or aluminum foil to form a base.

The synthetic resin film used as a substrate in the present invention has excellent abrasion resistance, water resistance, and chemical resistance, and has a thickness and/or rigidity to the extent that curling does not occur when a heat-sensitive layer is applied. Any material can be selected from among known materials that do not deform and have dimensional stability.

Examples of such films include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate films, polystyrene films, polypropylene films, and polyolefin films such as polyethylene. It can be used as

The thickness of the substrate is preferably 20-200μ, particularly preferably 50-100μ.

In the present invention, an undercoat layer can be provided between the support and the photosensitive/thermosensitive layer in order to enhance the adhesion between the two layers.

Materials for the undercoat layer include gelatin, synthetic polymer latex, nitrocellulose, thermoplastic resins such as polyethylene and polypropylene, and ionomer resins containing epoxy adhesives. The coating amount of the undercoat layer is O
, 1 g/mZ to 2.0 g/m", particularly preferably 0.2 g/m" to 10 g/m2. O, if it is less than 1g/m2, the adhesion between the film and the photosensitive and heat-sensitive layer will not be sufficient, and if it is less than 2°0g/m2
Even if the amount is increased above, the adhesive force between the film and the photosensitive/thermosensitive layer reaches saturation, which is disadvantageous in terms of cost.

The undercoat layer may swell due to the water contained in the light and heat sensitive layer when the light and heat sensitive layer is applied thereon, so in that case it must be cured using a hardening agent. is desirable.

As the hardening agent, glutaraldehyde, dialdehydes such as 2,3 dihydroxy-1,4-dioxane, and boric acid are preferred.

The amount of these hardeners added is based on the weight of the base coat material.
An appropriate addition amount can be selected in the range of 0.20% by weight to 3.0% by weight depending on the coating method and desired degree of curing.

It is also possible to add an antifoaming agent to eliminate foam generated during coating, or to add an activator to improve liquid leveling and prevent coating streaks.

It is also possible to add an antistatic agent if necessary.

A protective layer can also be provided as appropriate on the photosensitive and thermosensitive layer.

Specific examples of polymers used in the protective layer include methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, starches, gelatin, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate,
Water-soluble polymers such as styrene-maleic anhydride copolymer half ester hydrolyzate, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, polyacrylic acid derivatives, polyvinylpyrrolidone, sodium polystyrene sulfonate, sodium alginate, etc. and styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex,
Examples include water-insoluble polymers such as methyl acrylate-butadiene rubber latex and polyvinyl acetate emulsion.

Pigments, metal soaps, wax, cross-linking agents, etc. can be added to the protective layer for the purpose of improving matching with the thermal head during heat-sensitive recording, preventing sticking, and improving the water resistance of the protective layer. .

Pigments include zinc oxide, calcium carbonate, barium sulfate,
Titanium oxide, lithopone, talc, gravel, kaolin, aluminum hydroxide, amorphous silica, colloidal silica, etc. are added, and the amount added is 0.00 of the total weight of the polymer.
The amount is 5 to 3 times, particularly preferably 0.01 to 1.5 times.

Metal soaps include emulsions of higher fatty acid metal salts such as zinc stearate, calcium stearate, and aluminum stearate, and the amount thereof is 0.5 to 30% by weight, preferably 1 to 10% by weight of the total weight of the protective layer. It is added in

The wax preferably has a melting point of 40 to 80°C, and examples of such waxes include paraffin wax, polyethylene wax, and microcrystalline wax. The amount of wax used is 0.5 to 40% by weight, preferably 1 to 20% by weight, based on the total weight of the protective layer.

In addition, in order to uniformly form a protective layer on the photosensitive and thermosensitive layer,
A surfactant is added to the coating solution for forming the protective layer. Surfactants include sulfosuccinic acid-based alkali metal salts, fluorine-containing surfactants, etc. Specifically, sodium salts of di(2-ethylhexyl)sulfosuccinic acid, di(n-hexyl)sulfosuccinic acid, etc. Or ammonium salt etc.

Furthermore, a surfactant, a polymer electrolyte, etc. may be added to the protective layer to prevent the photosensitive and thermosensitive recording material from being charged.

The solid coating amount of the protective layer is 0.2 to 5 g/m2, more preferably 1 to 3 g/m''.

Coating for producing the photosensitive and thermosensitive recording material of the present invention can be carried out using generally well-known coating methods, such as dip coating,
Air knife coating method, curtain coating method, roller coating method, doctor coating method, wire barcode method,
Coating can be performed by a slide coating method, a gravure coating method, or an extrusion coating method using a hopper as described in US Pat. No. 2,681.294. As appropriate, U.S. Patent No. 2,761°79
No. 1, No. 3,508,947, No. 2941.89
No. 8, and the specification of No. 3,526.528, Yuji Harasaki, "Coating Engineering", page 253 (published by Asakura Shoten, 1973), etc., by the method described, etc., to separate into two or more layers and apply at the same time. is also possible, and an appropriate method can be selected depending on the coating amount, coating speed, etc.

In the present invention, a back layer may be provided on the back surface of the support for the purpose of curl correction, antistatic properties, improved slipperiness, and the like. As the constituent components of the hack layer, it is preferable to use the same components as those of the protective layer.

(Effects of the Invention) The light and heat sensitive recording material of the present invention has a substantially transparent light and heat sensitive recording layer provided on a support having a specular reflective or type 2 diffuse reflective metal layer. , it is possible to obtain an image with excellent sharpness, and it is possible to obtain a novel image that is different from conventional light- and heat-sensitive recorded images.

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

Example 1 Preparation of 5-Support A 25 μm polyethylene terephthalate film filled with 2% silica with an average particle size of 3 μm was placed in a vacuum deposition apparatus, and vacuum deposition was performed at a vacuum level of 10-'torr to form a substrate. An aluminum evaporated film having a thickness of 600 mm was formed on the surface.

An undercoat having the following composition diluted with ethyl acetate was applied to the surface of this vapor-deposited film so that the film thickness after drying was 4 g/rrf, and dried at 80''C for 2 minutes.

Copolymer of vinylidene chloride/vinyl chloride/vinyl acetate/maleic anhydride 50 parts (weight ratio 10/65/2015) 50 parts adduct of tolylene diisocyanate and trimethylolpropane Next,
A wood valve consisting of 20 parts of LBSP and 80 parts of LBKP is processed to Canadian Freeness 3 using a disc refiner.
Beating to 00cc, 1 part of sodium stearate, 0.5 part of anionic polyacrylamide, 1.5 parts of aluminum g acid, 0 part of polyamide polyamine epichlorohydrin
．． 5 parts of alkyl ketene dimer and 0.5 parts of alkyl ketene dimer were added in the absolute dry weight ratio to the wood pulp, and a paper having a basis weight of 160 g/rrf was made by fourdrinier paper making. The density was set to 1.0 g/cd using a machine calender. After corona discharge treatment on the wire side of this base paper, high-density polyethylene (M, I, = 8 g/10 minutes, density 0.950 g/c
c) was melt extrusion coated to form a 30 μm thick polyethylene resin layer.

Next, a two-component polyurethane adhesive having the following composition was applied to the back side of the aluminum vapor-deposited film (the side opposite to the vapor-deposited surface) so that the film thickness after drying was 3 g/bottom. It was dried at C for 2 minutes.

Polybond AY-651A (trade name manufactured by Sanyo Kakai Industries ■) 100 parts Polybond AY-651C (trade name manufactured by Sanyo Kakai Industries ■) 15 parts Align this coated side with the base paper side of the single-sided laminated paper mentioned above and tilt it at an 80° angle. Heat compression bonding is performed at a C1 pressure of 20 kg/am.
A seed diffusely reflective support was obtained.

f1+ of capsule A Compounds below diazo compound O.C., H.

After adding it into an aqueous solution consisting of 100 parts of distilled water, 20″
The mixture was emulsified and dispersed with C to obtain an emulsion with an average particle size of 2 μm. next,
The resulting emulsion was stirred at 40°C for 3 hours.

After cooling this liquid to 20°C, Amberlite+R-
120B (manufactured by Rohm and Haas (product name))
0 cc was added, stirred for 1 hour, and then filtered to obtain capsule liquid A.

3.4 parts tricresyl phosphate 6 parts methylene chloride 12 parts trimethylolpropane trimethacrylate 18 parts Takenate D-11ON (75% by weight ethyl acetate solution) (manufactured by Narita Pharmaceutical Co., Ltd. (trade name)) 24 parts were mixed. , 63 parts of an 8% by weight aqueous solution of polydonyl alcohol and vaporized 4% by weight aqueous solution of polyvinyl alcohol Gold layer 1 170 parts of coupler ＼ CH3 Triphenylguanidine (base) Color aid 4 parts 6 parts 3 parts Tricresyl phosphate 10 parts Acetic acid ethyl
Solution (2) was added to 20 parts of solution (I), mixed, and emulsified at 20"C to obtain an emulsified dispersion having an average particle size of 3 μm.

Ma3'' Note: Capsule liquid A 4.9 parts Hydroquinone 5% by weight water-soluble i! 0.2 parts coupler/base dispersion A 3.7 parts were combined with stirring;
Coating liquid A was used.

-゛U Silica-modified polydonyl alcohol (PVA manufactured by Kuraray@)
R2105) 1 part (solid content) Colloidal silica (Nissan Chemical Co., Ltd. Snow Tenx 30)
1.5 parts (solid content) Zinc stearate (Hydrin Z-7 manufactured by Middle East Yushi ■)
0.02 part (solid content) Paraffin wax (Hydrin P-7 manufactured by Chukyo Hozo ■) 0.02 part (solid content) The above coating solution A was applied onto the specular reflective support prepared above in Sensitivity 12. was coated to form a photosensitive and heat sensitive layer with a dry weight of 12 g/m'', and then the above protective layer coating solution was applied and dried to have a dry weight of 2 g/m''.
m2's maintenance! A light and heat sensitive recording material was obtained by forming layers.

The obtained light and heat sensitive recording material was processed using Hitachi Hifax 400.
When I printed it, it turned yellow.

Next, the image was irradiated with light for 10 seconds using a Rifby Super Dry Model 100, and then heated again at 120° C. for 5 seconds using a heat block. There was no recoloring, and a yellow image with excellent fixability was obtained.

The resulting image had extremely good sharpness and was full of three-dimensional effect.

Example 2゜Metal aluminum was roughly rolled, and further, two sheets of metal aluminum with annealed skin were overlapped and rolled on the center rolling roller by reading the top and bottom between the upper and lower two adjoining rolling rollers. An aluminum whistle with a thickness of about 10 μm was obtained. This adjoining surface had second type diffuse reflection. Next, metal aluminum was deposited on the RC paper while extrusion coating low density polyethylene to obtain a support having a second N diffusely reflective aluminum layer.

A thin layer of ionomer resin was formed on the aluminum surface of the obtained support, a transparent light-sensitive and heat-sensitive layer was formed using coating solution A prepared in Example 1, and a protective layer was further formed in the same manner as in Example 1. . When the obtained photosensitive photothermal recording material was used, very high quality images with good sharpness were obtained.

Example 3 The same procedure was carried out except that the following were used in place of the diazo compound and coupler used in Example 1: diazo compound: C6H and \ coupler: C3Hz(t) / H2C-C-HN C0 11 0=CN \ / Coated MB prepared as in Example 1
A light and heat sensitive recording material was obtained in exactly the same manner as in Example 1, and an image was formed to obtain a magenta image with a three-dimensional effect.

Example 4゜The dry coating amount was 6 g/m'' on the support prepared in the example process.
After coating the coating liquid A in the following manner, a 3% aqueous solution of sodium alginate (manufactured by Snow Algin SH Fuji Chemical Co., Ltd.) was coated as an intermediate layer so that the dry coating amount was 0.5 g/mz.

Next, Coating Solution B was applied to give a dry coating amount of 6 g/ml, and then Protective Solution N was applied to a dry coating amount of 2 g/ml to obtain a recording sheet.The coating was carried out using a wire bar. After use, it was dried in an oven at 50°C.

The obtained recording sheet was printed with low energy (thermal head voltage 14 V, printing time 1.0 to 2.0 m5ec), then irradiated with light with a wavelength of 420 nm for 15 seconds, and then the printing energy was After thermal printing with energy (thermal head voltage 16V, printing time 2.0~3
．． The entire surface was irradiated with light having a wavelength of 365 nm for 20 seconds.

The resulting image is a clear two-color print in which the low-energy print area is yellow and the high-energy print area is magenta, and the sharpness of each image is good, which is different from images of conventional heat-sensitive recording materials. The result is a two-color image with a three-dimensional effect.

Claims (1)

[Claims] Applying and drying a coating solution containing microcapsules containing either a diazo compound or a coupler and an emulsified dispersion obtained by dissolving the other in an organic solvent that is poorly soluble or insoluble in water and then emulsifying and dispersing the microcapsules. 1. A light and heat sensitive recording material, comprising at least one substantially transparent light and heat sensitive layer formed by the method of the present invention, provided on a support having a specular reflective or second type diffuse reflective metal layer.