JPH0218083A - Photosensitive thermal recording material - Google Patents

Abstract

PURPOSE:To enable high speed recording to be performed and besides, to improve raw keeping quality, color density, and recording shelf life by a method wherein either one of a diazo compound or a coupler is contained in a microcapsule, the other part is mixed as a form of emulsifying dispersion matter and further, the coupler is used by a specific structure. CONSTITUTION:Either one of diazo compound or coupler is contained in a microcapsule, the other substance is mixed as a form of emulsifying dispersion matter and further, said coupler which is expressed by belowmentioned general formula (1) is used. In the coupler of the formula (1), A expresses alkylene radical which may contain ether or thioether bond among C1 to C20, and B expresses hydrogen, phenyl radical, cyclohexyl radical, and morpholine radical. Though whether either component of diazo compound or coupler is contained in the microcapsule, or is made to be composition of emulsifying dispersion matter is often optional, it is preferable that diazo compound is especially contained in the microcapsule and the coupler is made to be the composition of emulsifying dispersion matter. Organic solvent used in this case can be suitably selected among high boiling point oils.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a heat-sensitive recording material with excellent fixing properties, and particularly to a light- and heat-sensitive recording material that can also be used as a light-sensitive recording material.

(Prior Art) Photosensitive and thermosensitive materials in which a photosensitive and thermosensitive layer containing a diazo compound and a coupler are provided on a support have been known.

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 has excellent recording stability. It has the advantage of being

However, similar to the leuco color-forming heat-sensitive recording material, the above-mentioned recording materials mainly do not have sufficient shelf life, such as fogging during raw storage. is proposed.

Among them, microcapsules are created by using at least one of the components involved in the coloring reaction as a core material and forming a wall by polymerization around the core material, such as containing either a diazo compound or a coupler in a microcapsule. The recording material developed (Japanese Patent Application Laid-Open No. 10-101010, !10μ3 @) has the advantage that it can be improved in raw shelf life without reducing the recording speed or color density.

<Problems to be Solved by the Invention> However, conventional light- and heat-sensitive recording materials, including recording materials using the above-mentioned microcapsules, have poor transparency and cannot fully form a color image consisting of chromatic colors such as red, spine, and yellow. If you do,
There were problems in that the color image was dull and a clear image could not be obtained, and the whiteness of the background part was not sufficient. Therefore, a recorded matter obtained by performing color recording on a light and heat sensitive layer provided on a transparent support is projected onto an overhead projector (
Conventionally, when placed on an OHP (OHP) and projected, the background is projected black and the overall contrast is poor.
In addition, color images such as chromatic colors also have the disadvantage of poor color reflection, and when performing multicolor recording on a light and heat sensitive recording material provided with two or more ridge layers on the light and heat sensitive layer 1 in which different color images are formed. There was also a problem in that the mixed color reproduction of the overlapping parts of each color was poor.

It is true that silver halide color photography solves these problems, but silver halide color photography is expensive and the recording surface is
There was also a problem that the development process in 1 to obtain 1 was complicated and time consuming.

Therefore, the first object of the present invention is to be able to perform high-speed recording to the extent that commercially available diazo copying machines and thermal recording printers can be used, and to have excellent storage stability, color density, and record storage stability, and to improve background and color images. To provide a material from which clear recorded images can be obtained at low cost without dulling.

A second object of the present invention is to provide a light and heat sensitive recording material that has excellent transparency and sufficient color density.

A third object of the present invention is to provide a light and heat sensitive recording material which has excellent mixed color reproducibility in overlapping areas of various colors after one color recording and is therefore suitable for multicolor recording.

Means for Solving Problems> The above-mentioned object of the present invention is to provide a light and heat sensitive recording material in which a light and heat sensitive layer having a diazo compound and a coupler is provided on one side of a support, in which either the diazo compound or the coupler is provided. is encapsulated in microcapsules, the other is mixed in the form of an emulsified dispersion, and the coupler has the following general formula (I).
This was achieved using a transparent light- and heat-sensitive recording material characterized by the use of a material having the following form.

H (wherein A is an alkylene group tmb which may contain an ether or thioether bond between C1 and C2o, and B
represents hydrogen, a phenyl group, a cyclohexyl group, or a morpholino group) The coupler represented by the general formula (I) used in the present invention has a high compatibility with water-insoluble or unusable organic solvents used during emulsification. In addition, since it has a high degree of familiarity with high boiling point oils used in the production of microcapsules, it is possible to increase the concentration and increase the coloring density. Specific examples of couplers used in the present invention are shown below, but these couplers may be used alone or in combination of two or more to obtain any desired color tone.

The diazo compound used in the present invention refers to a photodegradable diazo compound that decomposes and loses color-forming reactivity when the reactant is exposed to light of a specific wavelength, and mainly refers to aromatic diazo compounds and the like. Specifically, it refers to aromatic diazonium salts, diazosulfonate compounds, and diazoamino compounds. below,
The explanation will be given mainly using diazonium salt as an example.

It is generally said that the photodecomposition wavelength of a diazonium salt is its thickest absorption wavelength. Also, the absorption maximum wavelength of diazonium salt varies from about 20nm to 700nm depending on its chemical structure.
It is known that it can change up to m. (“Photolysis and chemical structure of photosensitive diazonium salts” by Takahiro Tsunoda and Ao Yamaoka
Journal of the Photographic Society of Japan Kota (≠) 177~λor members (15'
jj)) That is, when used as a diazonium mt-photodegradable compound, it decomposes under a specific wavelength depending on its chemical structure. Furthermore, by changing the chemical structure of the diazonium salt, the hue of the dye after the reaction can be changed even when the same coupling component is used in the coupling reaction.

A diazonium salt is a compound represented by the general formula ArN2+X- (wherein Ar ld represents a substituted or actively substituted aromatic moiety, N2+ represents a diazonium group, and X- represents an acid anion. ).

Among these, compounds with Kf and decomposition wavelength near lAOOnm include Gudiazo-7-dimethylaminebenzene, Hiro-diazo-7-diethylaminobenzene, ≠-diazo/-dipropylaminobenzene, ≠-diazo-7
-Methylbenzylaminobenzene, μm diazo-! -dibenzylaminobenzene %Hiro-diazo-7=ethylhydroxyethylaminobenzene, p-diazo-7-diethylamino-3-methoxybenzene, ≠-diazo-7-dimethylamino-2-methylbenzene, μm diazo-l-
Penzoylaminoco, j-jethoxybenzene, μm
Diazo-l-morpholinobenzene, φ-diazo7-morpholino2. j-jethoxybenzene, μm diazo-
1-morpholino-2゜j-dibutoxybenzene, μm diazo-/-aniJnobenzene, μm diazo-/-tolylmercapto-λ,! -Jethoxybenzene, Hiro-diazo-/, 4L-methoxybenzoylami-2! -jethoxybenzene and the like. 300~J
As a compound having a photolysis wavelength of 70 nm, l-diazo-! -(N,N-dioctylcarbamoyl)benzene, /-diazocooctadecyloxybenzene, l
-Diazo-≠-(4L-l er t-octylphenoxy)benzene, l-Diazo-≠-(2,j-t
ert-amylphenokidinebenzene, l-diazo-λ
-(Hiro-tert-octylphenoxy)benzene, /
-Diazo-! -chlorokho(≠-tert-octylphenoxy)inoxy, l-diazoco, j-bis-octadecyloxybenzene, l-diazo-22μm2μ
mbis-oftatacyloxybenzenediazo-a-(N
-octylteraroylamino)benzene and the like. The photolysis wavelength of the aromatic diazonium compounds typified by the examples mentioned above can be varied widely by arbitrarily changing the electron group.

Specific examples of acid anions include CnF2n+tCOO-
(n represents 3 to ri), CmF2m+tSQ3-
(m represents 2 to ti), (αF21+L802)2C
H- (l represents /-/Ik), C(C)ia)a is given.

Specific examples of the diazo compound (diazonium salt) include the following examples.

C4H9 C2H5 OC2)1s The diazosulfonate compound that can be used in the present invention is a compound represented by the general formula. In the formula, □ is an alkali metal or ammonium compound, R2, R3, 5 and R6 are hydrogen, halogen, alkyl group, or alkoxy group, and 4 is hydrogen, halogen, alkyl group, amino group, benzoylamido group, It is a morpholino group, a trimercapto group, or a pyrrolidino group.

A large number of such diazosulfonates are known and can be obtained by treating each diazonium salt with a sulfite.

Among these compounds, preferred compounds include λ-methoxy, cophenoxy, comethoxy Hiro-phenoxy, J, 4! -dimethoxy, λ-methyl-dermethoxy, co, ≠-dimethyl, λ, Hiro.

-trimethyl, μm phenyl, ≠-phenoxy, μm
Benzenediazosulfonate having a substituent such as acetamide, or also u-(N-ethyl, N-benzylamino), μm(N
, N-dimethylamine], Hiro-(N, N-diethylamino), "(NtN-diethylamino/) -
J-chlor, g-hylodinino-3-chlor, methoxy-morpholino-comethoxy, <C-(methoxybenzoylamino)-2,! It is a benzenediazosulfonic acid salt having a substituent such as -dibutoxy, ≠-(μ'-trimercapto)-λ, or tadimethoxy. 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. Examples of diazoamino compounds include dicyandiamide, sarcosine, methyltaurine, N-ethylanthranic acid-! - Compounds coupled with sulfonic acid, monoethanolamine, jetanolamine, guanidine, etc.

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, water-releasable or water-insoluble basic substances and substances that generate alkali upon heating are used.

Basic substances include inorganic and organic ammonium salts,
organic amines, amides, urea and thiourea and their derivatives,
Nitrogen-containing compounds such as thiazoles, virols, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidacillines, triazoles, morpholines, piperidines, amidines, formazines, and pyridines are mentioned. , these basic substances are 2
Can be used in combination with more than one building.

The light- and heat-sensitive recording material of the present invention contains a hydroxy compound, a carbamate ester compound, an aromatic methoxy compound, or an organic sulfonamide compound in the photosensitive layer for thermal color sensitization so that heat development can be performed quickly and completely with low energy. It can be added as an agent. It is believed that these compounds lower the melting point of the coupling component or basic substance or improve the thermal permeability of the microcapsule wall, resulting 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, either the diazo compound or the coupler is encapsulated and used.

A preferable microcapsule is one that prevents contact between substances inside and outside the capsule at room temperature due to the substance isolation effect of the microcapsule wall, and whose permeability to substances increases only when heated above a certain temperature.

This phenomenon is a new technology previously discovered by the present inventors, and by appropriately selecting the capsule wall material, capsule core material, and additives, the permeation start temperature can be freely controlled. In this case, the transmission start temperature corresponds to the glass transition m degree of the capsule wall (eg, Japanese Patent Application Laid-open No. 9/90111.
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. . In the present invention, these polymeric substances are 2a! The above can also be used together.

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

The microcapsules used in the present invention are preferably microencapsulated by emulsifying a core material containing a diazo compound or coupler and then forming a wall of a polymer material around the oil droplets. A polymeric material or actant is added to the interior of the oil droplet and/or to the exterior of 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, Japanese Patent Application Laid-Open No. 22271-1A.

Here, the organic solvent for forming all the 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% or more of the ingredient to be microencapsulated.

The coupling component for the diazo compound type 7 part is 0.
/-10 parts by weight, and the basic substance is preferably used in a proportion of 0.1 to 20 parts by weight.

In the present invention, the size of the microcapsules is preferably 1 μm or less, particularly 111 m or less, as measured by the measurement method described in JP-A No. 6 (1-2/μ Tata No. 0). It is preferable that

The preferred microcapsules produced as described above are different from those that are destroyed by heat or pressure as used in conventional recording materials, and the reactive substances contained in the core and outside of the microcapsules are Sometimes it can penetrate through the microcapsule wall and react.

In the present invention, it is also possible to use one color development aid.

The color development aid that can be used in the present invention is one that increases the color development temperature at the time of heating color development, or the minimum color development temperature! ? It is a substance that lowers the melting point of coupling components, basic substances, or diazo compounds, and lowers the softening point of the capsule wall, making it easier for diazo, basic substances, and coupling components to react. It is meant to create a situation.

Coloring aids include phenolic compounds, alcoholic compounds, amide compounds, sulfonamide compounds, etc.
Specific examples include p-1ert-octylphenol,
p-benzyloxyphenol, p-phenyl p-oxybenzoate, benzyl carbanylate, phenethyl carbanylate, hydroquinone dihydroxyethyl ether, xylylene diol, N-hydroxyethyl-methanesulfonic acid amide, N-phenyl-methanesulfonic acid amide, etc. Compounds 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 heat-sensitive layer, the coupler is used when the diazo compound is contained in the microcapsules, and the diazo compound is used as a coupler in the case where the diazo compound is contained in the 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 coupler 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. It is preferable to use it as a component of the dispersion.The organic bath agent used in this case can be appropriately selected from high boiling point oils. In addition to esters, preferred oils include those of the following general formulas (I) to (IV).
Compounds represented by and triallylmethane (e.g., tritolylmethane, tolyldiphenylmethane), terphenyl compounds (e.g., terphenyl), alkyl compounds (e.g., eva, terphenyl), alkylated siphenyl ethers h < e.g. n, propyl diphenyl ether),
Examples include hydrogenated terphenyl (eg, hexahydroterphenyl), diphenyl ether, etc.

In the present invention, it is preferable to use esters among these from the viewpoint of emulsion stability of the emulsified dispersion.

In the formula, R represents hydrogen or an alkyl group having a carbon number of /-/r, and R represents an alkyl group having a carbon number of i or iz. plq is l-
Represents a Buddhist integer, and the total number of alkyl groups must be no greater than three.

The alkyl group in R% is preferably an alkyl group having carbon number/-f.

In the formula, R is a hydrogen atom or an alkyl group having /-/co carbon atoms,
几represents an alkyl group having carbon number / , /co. n represents l or 2.

p and q represent integers from / to μ. When number=7, the total number of alkyl groups is within m, and when 1=J, the total number of alkyl groups is within 6.

(Ill) In the formula, R5 and R6 represent a hydrogen atom or the same or different alkyl groups having 7 to 11 carbon atoms.

m represents an integer of /-/J, e p3 and q3 represent an integer of 1 to 3, and the total number of alkyl groups is 3 or less.

Note that the alkyl groups for H5 and H6 are particularly preferably alkyl groups having -2 l carbon atoms.

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

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

Examples of compounds represented by formula (III) include l-methyl-7-dimethylphenyl-l-phenylmethane, l-ethyl-l-dimethylphenyl-/-phenylmethane,
/-f lobi-i-dimethylphenyl-/-phenylmethane.

Examples of esters include phosphate esters (for example, triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, cresyl diphenyl phosphate), phthalate esters (
Dibutyl phthalate, phthal@-2-ethylhexyl, ethyl phthalate, octyl phthalate, butylbenzyl phthalate) dioctyl tetrahydrophthalate, benzoate ester (ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzoate) benzyl acid], abietate ester (ethyl abietate, benzyl abietate), dioctyl adipate, isodecyl succinate, dioctyl azelate, oxalate ester (dibutyl oxalate, dipentyl oxalate), diethyl malon, maleate ester ( dimethyl maleate, diethyl maleate, dibutyl maleate), tributyl citrate, sorbate esters (methyl sorbate, ethyl sorbate, butyl sorbate), sebacate esters (dibutyl sebacate, dioctyl sepacate), ethylene glycol ester (quinic acid monoesters and diesters, butyric acid monoesters and diesters, lauric acid monoesters and diesters, normitic 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 ester (tributyl borate, butyl borate), and the like. Among these, when tricresyl phosphate is used alone or in combination, the emulsification and dispersion stability of the color developer is particularly good, which 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-density solution aid. Particularly preferred examples of such co-solvents include ethyl acetate, isopropyl acetate, butyl acetate and methylene chloride.

The water bathing polymer to be included as a protective colloid in the aqueous phase 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.

As the surfactant to be contained in the aqueous phase, a surfactant that does not cause precipitation or aggregation by acting with the protective colloid can be appropriately selected from anionic or nonionic surfactants.

Preferred surfactants include sodium alkylbenzene sulfonate, sodium alkyl sulfate, diocternatorum sulfosuccinate, polyalkylene glycol (
For example, polyoxyethylene nonylphenyl ether)
etc. can be mentioned.

The emulsified dispersion in the present invention is prepared 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.

The oil droplet size (diameter) of this emulsified dispersion is determined by the haze reference θ.
In order to obtain a transparent photosensitive thermosensitive material of 14% or less, it is preferably 7μ or less. More preferably, it is within the range of o and i-tμ.

Also, the value of the ratio of the oil phase to the water phase (oil phase weight t/water phase weight)
is 0.0λ~0. A is preferred. More preferably o,
t-o, this is Hiroshi. If it is less than 0.02, the aqueous phase will be too large and it will be diluted, and sufficient color development will not be obtained.

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

As a binder, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylic acid ester, ethylene-vinegar! Various emulsions such as vinyl copolymers can be used. The amount used is 0.5-j in terms of solid content! i'/m
” is.

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

Further, the light-sensitive and heat-sensitive material of the present invention can be viewed as a transmitted ItIl image from one side of the transparent support.

The photosensitive and heat sensitive layer made by Raibusha is J t 7m 2 ~ 20? /
It is preferable that it is between m2, Tomohitin'' and /jf/m2.If it is less than 3t/1rL2, sufficient sensitivity will not be obtained, and if it is applied more than 20 f/m2, no improvement in quality will be seen. Therefore, it is disadvantageous in terms of cost.

The photosensitive and thermosensitive layer in the present invention needs to be substantially transparent. Substantially transparent here means haze (%
) (measured using an integrating sphere HTR meter manufactured by Nippon Seimitsu Kogyo ■) is ≠0% or less, preferably 30% or less, and most preferably 20% or less. However, the transparency of an actual photosensitive/thermosensitive layer test sample is greatly influenced by light scattering due to minute irregularities on the surface of the photosensitive/thermosensitive layer. Therefore, when measuring the inherent transparency of the photosensitive/thermosensitive layer, which is a problem in the present invention, that is, the transparency inside the photosensitive/thermosensitive layer, using a haze meter, a simple method is to attach a transparent adhesive tape on the photosensitive/thermal layer. Evaluation is made using the measured values with almost all surface scattering removed.

In the present invention, the protective layer that may be provided on the photosensitive and thermosensitive layer is preferably made of silicon-modified polyvinyl alcohol and colloidal silica.

The silicon-modified polyvinyl alcohol used in the present invention is
There are no particular limitations as long as the silicon atom is contained in the molecule, but usually the silicon atom contained in the molecule is an alkoxy group, an acyloxyl group, a hydroxyl group obtained by hydrolysis, etc., or an alkali metal salt thereof, etc. It is preferable to use those containing reactive substituents.

Details of the method for producing such modified polyvinyl alcohol containing silicon atoms in the molecule are given in Japanese Patent Application Laid-open No. 31-311.
It is stated in Public Relations No. 9.

The colloidal silica used in the present invention is used as a colloidal solvent in which ultrafine particles of silicic anhydride are dispersed in water using water as a dispersion medium. The particle size of colloidal silica is preferably 10rrLμ to 100mμ, specific gravity /, /-/, J. In this case, the pH value of the colloid m liquid is approximately φ~
A case of about IO is preferably used.

When the above-mentioned protective layer is provided on the surface of the light- and heat-sensitive recording material, the surface scattering phenomenon is suppressed in the same way as when the above-mentioned transparent adhesive tape is applied, and surprisingly, the transparency of the protective layer is extremely good. As a result, the transparency of the entire light- and heat-sensitive recording material can be further and significantly improved. In addition, when this TI layer is provided as the outermost layer of the recording material, the mechanical strength of the surface of the photosensitive and thermosensitive layer is improved, and when it is provided as an intermediate layer between laminated layers, it prevents unnecessary color mixture between layers. A preventive role can additionally be played.

A suitable blending ratio of silicon-modified polyvinyl alcohol and colloidal silica in the invention is 0.1 parts by weight of colloidal silica to 1 part by weight of silicon-modified polyvinyl alcohol.
The amount is 5 to 3 parts by weight, more preferably /-2 parts by weight. If the amount of colloidal silica used is less than 0.3 parts by weight, the effect of improving transparency will be small, and if it is used more than 3 parts by weight, cracks will occur in the protective layer, and the transparency will be reduced.

The protective layer may further contain one or more polymers. Specific examples of polymers that can be used in combination include methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, starches, gelatin, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate, and styrene-maleic anhydride copolymer half ester. Water bath polymers such as hydrolysates, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide conductors, polyvinylpyrrolidone, sodium polystyrene sulfonate, sodium alginate, styrene-butadiene rubber latex, acricenitrile-bradiene rubber latex, Examples include water-insoluble polymers such as methyl acrylate-butadiene rubber latex and polyvinyl acetate emulsion. The amount used in combination is o, oi~o per 1M part of silicon-modified polyvinyl alcohol.
A triple view part is preferred.

The protective layer contains pigments, metallic soap, wax, etc. for the purpose of improving mating properties with a thermal head during heat-sensitive recording or a heating roller during heat fixing after photosensitive recording, and improving the water resistance of the S retaining layer. A crosslinking agent and the like are added.

Pigments include zinc oxide, calcium carbonate, barium sulfate, titanium oxide, lithopone, Merck, Rouseki, kaolin, aluminum hydroxide, amorphous silica, etc., and the amount added is 0°00jt to 0 of the total weight of the polymer. .2 times, particularly preferably o, ot-o.

He is a child of 05 times. If the amount is less than o, oz times, it is ineffective in improving the matching property with the thermal head during thermal recording or the heating roller during heat fixing after thermal recording.
Q: If the amount is more than twice the amount, the transparency and sensitivity of the light and heat sensitive recording material will drop significantly, impairing its commercial value.

Metal soaps include emulsions of higher fatty acid metal salts such as zinc stearate, potassium stearate, and aluminum stearate, and the total weight of the protective layer is 0, j −.
J is added in a proportion of 0% by weight, preferably 1 to IO% by weight. Waxes include emulsions such as norahin wax, microcrystalline wax, carnauba wax, methylroll stearamide, polyethylene wax, and silicone, and the amount is 0.2 to 4 c of the total weight of the protective layer.
It is added in an amount of 1% by weight, preferably 1-20% by weight.

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, di(2-ethylhexyl)sulfocobalic acid, ')-(n-hexyl)sulfosuccinic acid, etc. There are ammonium salts, etc.

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

The solid content of the protective layer is usually O02~j f/m
is preferable, and more preferably 12 to 27 m2.

A transparent support such as a synthetic resin film is used in the light and heat sensitive recording material of the present invention.

The transparent support used in the present invention will be described.

The transparent supports mentioned here include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose fermentation conductor films such as cellulose triacetate films, polystyrene films, polypropylene films, polyolefin films such as polyethylene, etc. They can be used alone or in combination.

The thickness of the transparent support used is KjO or zoopTIL, and preferably KjO to 100 μm.

In the present invention, an undercoat layer can be provided between the transparent support and the photosensitive/thermosensitive layer in order to enhance the adhesion between the two layers.
Gelatin, synthetic polymer latex, nitrocellulose, etc. are used as the material for the undercoat layer. The coating amount of the undercoat layer is preferably in the range of 0.111 m'' to 7 m2, particularly 0.2 f/m'' to 0.2 f/m, Ot/
m'' (D range is preferred.

If it is less than 0.111 m", the adhesion between the support and the photosensitive/thermosensitive layer will not be sufficient, and even if it is increased to more than 0.111 m", the adhesive force between the support and the photosensitive/thermosensitive layer will reach saturation. This is disadvantageous in terms of cost.

The undercoating layer is a hardening layer because when the photosensitive/thermosensitive layer is coated on top of it, the image quality of the photosensitive/thermosensitive layer may deteriorate if the undercoat layer swells due to the water contained in the photosensitive/thermosensitive layer. It is desirable to cure the resin using an agent.

Hardeners that can be used in this invention include the following.

■Divinylsulfone N, N'-ethylenebis(vinylsulfonylacetamide), /, J-bis(peelsulfonyl)-coprobanol, methylenebismaleimide,
! -acetyl-1,3-diacryloyl-hexahyto'
o −s −) riazine, /, J,! -) lyacryloyl-hexahydro-a -) riazine, i, z, z-trivinylsulfonyl-hexahydro-3-triazine,
Activated vinyl thread compounds such as.

■J,! -dichloro-6-hydroxy-3-triazine sodium salt, λ, ≠-dichloro-6-medoxy a
-) riazine, λ, sulfo-dichloro4-(sulfo-sulfoanilino) -g -) lyazine sodium salt, co,
l-dichloro-6-(cosulfoethylamino)-a
-) Active halogen compounds such as riazine and N-N'-bis(2-chloroethylcarbamyl)piperazine.

■Bis(,2,j-epoxypropyl)methylpropylammonium-p-toluenesulfonate, /,4t-
bis(a?,31-epoxypropyloxy)butane,
i, s, s-triglycidyl isocyanurate, /,!
-Epoxy compounds such as diglycidyl-j-(γ-acetoxyβ-oxypropyl)in cyanurate.

■Co, Section, 4-) Liethylene-S-triazine, /, A
Ethyleneimino compounds such as -hexamethylene-N, N'-bisethyleneurea, and bis-β-ethyleneiminoethylthioether.

■／,,,2-cy(methanesulfonoxy)ethane, l
, 4! -di(methanesulfonoxy)butane%'1j-
α-methane sulfonic acid ester compound of di(methanesulfoneoxy)pentane.

■Dicyclohexylcarbodiimide, l-cyclohexyl-3-(3-trimethylaminopropyl)carbodiimide-p-trienesulfone &! , l-ethyl-3-(
3-dimethylaminopropyl) carbodiimide hydrochloride.

(2) Inoxazole compounds such as coethyl-j-dimethylisoxazole perchlorate, coethyl-j-phenylisoxazole-3'-sulfonate, and j,j'-(paraphenylene)bisisoxazole.

■Inorganic compounds such as chromium alum and chromium acetate.

■N-carboethoxycoisoproboxy/, Z-
Dihydroquinoline%N('-morpholinocarboxy)-
Dehydration condensation type peptide reagents such as .mu.m methylpyridinium chloride S.sub.N, active ester compounds such as N'-aziboyldioxydisuccinimide and N,N'terephthaloyldioxydisuccinimide.

Isocyanates such as 0 toluene-2, Hiro-diisocyanate)%'#t-hexamethylene diisocyanate.

The amount of these hardeners added per wrinkle of the undercoat material is as follows:
Appropriate addition can be selected from a range of 0.20TJ@% to 0% by weight according to the coating method and desired oxidized INK.

If the amount added is less than 0.20M1k%, the degree of curing will be insufficient no matter how long it is allowed to last, and the undercoat layer will swell when applying the light and heat sensitive layer. If the amount is too high, the degree of curing will proceed too much, and the adhesion between the undercoat layer and the support will deteriorate, resulting in the disadvantage that the undercoat layer will become film-like and peel off from the support.

Depending on the curing agent used, if necessary, the pH of the solution can be made alkaline by adding caustic soda or the like, or the pH of the solution can be made acidic by adding citric acid or the like.

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. .

Moreover, it is also possible to add an antistatic agent if necessary.

Furthermore, before applying the undercoat layer, it is desirable to activate the surface of the support by a known method.

As a method of activation treatment, etching treatment with acid is used.
, flame treatment using a gas burner, corona treatment, glow discharge treatment, etc. are used, but from the point of view of cost or simplicity, US Patent No. 2.7/! , No. 071, same No.-
1! Hiro 1. ．． No. 727, same No. 3. jtllri, a, o6
No. 3. ! The corona discharge treatment described in No. 90,107 and the like is most preferably used.

The light- and heat-sensitive recording material of the present invention only needs to be provided with the above-mentioned substantially transparent light- and heat-sensitive layer on one side of the support, and the light- and heat-sensitive layers each capable of developing different colors may be provided on the support directly or It is also possible to provide one or more layers through the above-mentioned protective layer or undercoat layer, and furthermore, one layer selected from known photosensitive layers, heat-sensitive layers, and light-sensitive and heat-sensitive layers is provided on the support, and further a layer is formed on this layer. Various embodiments are possible depending on the use and purpose, such as the provision of a substantially transparent light- and heat-sensitive layer as described herein that can develop a color different from that of the material.

The coating liquid according to the present invention can be applied by a generally well-known coating method,
For example, dip coating method, air knife coating method, curtain coating method, roller coating method, doctor coating method,
Coating can be performed by a wire barcode method, a slide coating method, a gravure coating method, or an extrusion coating method using a hopper as described in US Pat. As appropriate, U.S. Pat.
, riμγ issue, same No. 2. 2 by the method described in ``Coating Engineering'' by Yuji Harasaki, page 2j 3 (published by Asakura Shoten in 1973), etc. It is also possible to separate the layers into more than one layer and apply them simultaneously, and an appropriate method can be selected depending on the amount of coating, the speed of production, etc.

Pigment dispersants, thickeners, flow modifiers, antifoaming agents, foam inhibitors, mold release agents, and colorants may be appropriately added to the coating liquid used in the present invention as long as they do not impair the properties. I can't help it.

The light- and heat-sensitive recording material of the present invention performs copying by image exposure using light in the photodecomposition wavelength range of a photodegradable diazo compound, or performs optical recording by point exposure using a light valve such as a liquid crystal light valve. Color development is carried out by uniformly heating the light-sensitive heat-sensitive layer with a heated roller to a temperature higher than the heat bath melting temperature of the heat-sensitive material containing microcapsules, and after thermal recording with a thermal head, it is sufficiently exposed to light in the above wavelength range. By doing so, a recorded image with excellent fixing properties can be obtained in any case. As the light source for photolysis at this time, various light sources that emit light of the desired wavelength can be used, such as various fluorescent lamps, xenon lamps, xenon flash lamps, mercury lamps of various pressures,
A variety of light sources such as photographic flashes and strobes can be used.

Further, in order to make the light irradiation zone durable, the light source section and the original irradiation section may be separated using an optical fiber.

(Effects of the Invention) The light and heat sensitive recording material of the present invention has high light sensitivity during copying and original printing by image exposure, and can be developed and fixed by constant temperature heating. Since it can be fixed in a short time using a light source with relatively low output, it can be suitably used for various types of thermal recording and photosensitive recording.

According to the light and heat sensitive recording material of the present invention, it has excellent transparency and can provide color image transparency after heat and light recording. A variety of uses are possible using transparent color images.

Historically, the heat-sensitive recording material of the present invention provides recorded images with excellent background and color image transparency, resulting in good mixed color reproduction when transparent color images are superimposed, and also suitable for multicolor recording. It can be used suitably.

(Example) The present invention will be further explained with reference to Example 1 below, but the present invention is not limited thereto.

Note that the "part" indicating "Akinakahai" represents "part by weight" r.

[Example 1. ] Preparation of capsule liquid A Diazo compound 3.4 parts tricresyl phosphate 6 parts methylene chloride 72 parts trimethylolpronotone (trimethacrylate) it part Takenate D-110N (71% by weight ethyl acetate was added to the bath solution) ) (manufactured by Takeda Pharmaceutical Co., Ltd. (trade name)) was mixed and added to a water bath solution consisting of 63 parts of polyvinyl alcohol rTLt% aqueous solution and 10 parts of distilled water, and then 20o (:
The mixture was emulsified and dispersed to obtain an emulsion having an average particle size of λμ. Next, the resulting emulsion was stirred for 3 hours at tl-≠O'C.

2 of this liquid )IR-i-2 Product name)) Afterwards After cooling to 0’C, amber light OB (manufactured by Rohm and Haas (commercial) Add OQ and stir for 1 hour. Pusell's liquid A was obtained.

Solution I Polyvinyl alcohol μ% by weight water bath liquid Bath liquid ■ Coupler 170 parts Triphenylguanidine <m group> /, Hirobe Otobe Color development aid mp / 77 ~ / u O'C Tricresyl phosphate 70 parts Ethyl acetate, 20 Add solution (■) to part bath solution (I), mix, and emulsify with Co., Ltd. to obtain an average particle size of 3.
An emulsified dispersion of μm was obtained.

Preparation of Coating Liquid A 4 parts of capsule liquid A, 2 parts of water bath liquid O0, 2 parts of water bath liquid, and 3.7 parts of coupler/base dispersion liquid A were stirred and mixed to prepare coating liquid A.

Preparation of protective layer coating solution Silica-modified polyvinyl alcohol (PVA R2tos, manufactured by Kuraray ■) 1 part (solid content) Colloidal silica (Snowtex J (7) manufactured by Nikki Kagaku ■, 37 parts (solid content) Zinc stearin (Middle East) Hydrin Z-7 manufactured by Yushi ■ 0.02 parts (solid content) Paraffin wax (Hydrin P-7 manufactured by Middle East Yushi ■) 0.0 parts (solid content) 7jμ
A protective layer coating solution was applied and dried on a polyethylene terephthalate transparent film to form a protective layer with a dry weight of 29/m2, and then coating solution A was applied and dried on top of this to form a protective layer with a dry weight of 1 f/m''. A light and heat sensitive recording material of Example 1 was obtained by forming a light and heat sensitive layer.

The haze transmittance of this light- and heat-sensitive recording material was measured using an integral method HT meter manufactured by Nippon Seimitsu Kogyo, and the transparency was also visually confirmed.

The results are shown in Table 1.

My father used this light and heat sensitive recording material as a Hitachi Hifax ψ00.
When I printed it, it turned blue.

Next, original irradiation was performed for 70 seconds using the Ricopy Super Dry IOQ type, and then heating was performed again for 5 seconds using a heat block at 1O0C.No recoloring occurred and a blue image with excellent fixing properties was obtained.

Furthermore, a transparent original was superimposed on the surface of the light and heat sensitive layer of the light and heat sensitive recording material, and the Ricoh Suno Dry I was applied.

After heating for 10 seconds in O type, /JO0 in heat block
When heated at C for 1 second, a clear positive blue image was obtained.

Next, when the art records obtained by the above recording were placed on an overhead projector and projected, clear blue transmitted images were projected, and there was no background stain.

[Example 2] Example 1. Implementation example 1. was used in place of the coupler. A light and heat sensitive recording material similar to that of Example 2 was obtained.

The transparency of this light and heat sensitive recording material was determined in Example 1. It was evaluated in the same way.

The results are also listed in Table 1.

Further, when the same heat-sensitive recording as in Example 1 was carried out using this light- and heat-sensitive recording material, a blue image with excellent fixability was obtained.

In the following, Example 1 was prepared using this light and heat sensitive recording material. When photosensitive recording was carried out in the same manner as above, a clear positive blue image was obtained.

Next, when the one-time recorded material obtained by the above recording was placed on an overhead projector and projected, a clear blue transparent image was obtained, and there was no background stain.

[Comparative example 1. ] Preparation of coupler/base dispersion B Using the composition of coupler/base dispersion fiA with tricresyl phosphate and ethyl acetate removed, the coupler, base, and polyvinyl alcohol were mixed, and Dynomil (Willy A. Pacofen A. (trade name) manufactured by G Co., Ltd.) to obtain a dispersion having an average particle size of 3 μm.

Preparation of coloring aid dispersion fiB The coloring aid, polyvinyl alcohol, mW ``1'' parts by weight of water were mixed and dispersed in a Dynomill to obtain a dispersion having an average particle size of 3 μm.

Preparation of Coating Solution B Coating solution B was obtained in the same manner as Coating Solution A except that 3.7 parts of coupler/base dispersion B and 3.7 parts of color development aid dispersion B were used.

Example 1 except that coating liquid B was used instead of coating liquid A for coating the recording sheet. Comparative example 1. A photosensitive and thermosensitive recording material was obtained.

The transparency of this light and heat sensitive recording material was determined in Example 1. It was evaluated in the same way.

[Comparative Example 2] Example 1. Embodiment 1 except that the coupler was replaced by C in Example 1. A light- and heat-sensitive recording material of Comparative Example 2 similar to the above was obtained.

Example 1. For the light and heat sensitive recording materials from Comparative Example λ to Comparative Example λ, the transmission density was measured after heating at 1.30'c.

The results are shown in Table 1.

It can be seen that the light and heat sensitive recording material of the present invention has excellent transparency and color development.

Table 1 Example 1゜ Comparative example L /2 r j /,! ! Good 1. Good condition −Bad 0.12 Slightly good

Claims (1)

[Scope of Claims] A light and heat sensitive recording material in which a light and heat sensitive layer containing a diazo compound and a coupler is provided on one side of a support, in which either the diazo compound or the coupler is encapsulated in microcapsules, and the other is an emulsified dispersion. A substantially transparent light- and heat-sensitive recording material, characterized in that the coupler is represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, A represents an alkylene group that may contain an ether or thioether bond between C_1 and C_2_0, and B represents hydrogen, a phenyl group, a cyclohexyl group, (represents a morpholino group)