JP2001042517A - Negative photo-thermosensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide negative photothermosensitive recording material superior in heat resistance. SOLUTION: The negative phototermosensitive recording material is provided on a support including a biaxially stretched polymer sheet with a photothermosensitive recording layer containing an electron donative colorless dye enclosed in thermoresponsive microcapsules and a photosetting composition comprising a polymerizable compound having an ethylenical unsaturated bond and a polymerization initiator and an electron receptive color forming agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a single-color or multicolor negative-type light- and heat-sensitive recording material which can use various light sources in the ultraviolet to infrared region.

[0002]

2. Description of the Related Art Conventionally, various dry-type image recording methods which do not use a liquid developer or the like and do not generate waste have been studied. Among them, a method using a composition which is cured by light has attracted attention. ing.

[0003] In this method, a latent image is formed by curing a composition which is cured by light contained in a recording material by exposing to light, while a heating method is used to form a latent image in an unexposed portion of the recording material. Accordingly, a component that acts on the color development or decoloration reaction moves in the recording material to form a color image. When using such a recording material,
First, light is exposed on a recording material through an image document, and the exposed portion is cured to form a latent image. Then, by heating the recording material, the coloring or uncolored portion contained in the uncured portion (unexposed portion) is formed. The components acting on the decoloring reaction are moved to form a visible image.

[0004] According to this method, a completely dry system free of waste can be realized.

[0005] However, this method has a drawback that the moisture in the support swells due to heating, and blisters called blisters, which are unacceptable for practical use, are formed.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a negative-type photosensitive and heat-sensitive recording material having excellent heat resistance.

[0007]

The above objects can be attained by providing the following negative type light and heat sensitive recording material. (1) An electron-donating colorless dye encapsulated in thermoresponsive microcapsules and a polymerizable compound having an ethylenically unsaturated bond on a support containing a biaxially stretched polymer sheet,
A negative photosensitive thermosensitive recording material having a photosensitive thermosensitive recording layer containing a photopolymerization initiator and a photocurable composition containing an electron-accepting developer. (2) The biaxially stretched polymer sheet is provided with a stretched polymer core layer having microvoids, and a stretched polymer provided on at least one surface of the polymer core layer and having no microvoids colored with TiO ₂ The negative-type photosensitive and heat-sensitive recording material according to the above (1), which is a composite sheet having a surface layer. (3) The negative according to (1) or (2), wherein the support is a composite support including a base sheet and the biaxially stretched polymer sheet provided on at least one surface of the base sheet. Type heat and heat sensitive recording material. (4) The negative photosensitive and thermosensitive recording material according to (3), wherein the support is formed by laminating the biaxially stretched polymer sheet on at least one surface of the base sheet by extrusion. (5) The negative photosensitive and thermosensitive recording material according to any one of (1) to (4), wherein the biaxially stretched polymer sheet is formed of polypropylene.

The negative photosensitive and heat-sensitive recording material of the present invention is characterized by using a support containing a biaxially stretched polymer sheet, whereby a heat-developable recording material having excellent heat resistance can be provided.

When the biaxially stretched polymer sheet described in (2) is used, scattering of light at the time of light irradiation due to minute voids can be suppressed, and an advantage that sharpness of an image can be enhanced can be obtained.

When a composite support having a biaxially stretched polymer sheet on both sides of a base sheet is used, the effect of suppressing curling after development can be obtained.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the recording material of the present invention will be described in detail.

The recording material of the present invention comprises, on a support containing a biaxially oriented polymer sheet, an electron-donating colorless dye encapsulated in thermoresponsive microcapsules, a polymerizable compound having an ethylenically unsaturated bond, This is a negative-type photosensitive and heat-sensitive recording material having a photosensitive and heat-sensitive recording layer containing a photopolymerization initiator and a photocurable composition containing an electron-accepting color developer.

The thermoplastic polymers suitable for the biaxially oriented polymer sheet used in the present invention include polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polycarbonates, cellulose esters, polystyrene, polyvinyl resins, and polysulfonamides. Polyethers, polyimides, polyvinylidene fluoride, polyurethanes, polyphenylene sulfides, polytetrafluoroethylene, polyacetals, polysulfonates, polyester ionomers, and polyolefin ionomers and mixtures of these polymers can be mentioned. it can. Among them, it is preferable to use polypropylene having good strength and surface characteristics at low cost.

The biaxially stretched polymer sheet used in the present invention is preferably a biaxially stretched polymer sheet having fine voids, and a stretched polymer core layer having fine voids,
It is more preferable that the composite sheet includes a stretched polymer surface layer having no microvoids provided on at least one surface of the polymer core layer, and a composite sheet having the polymer surface layer provided on both surfaces of the polymer core layer. More preferably, it is a sheet. Such a composite sheet is opaque, has high gloss, and has good sharpness. In such a composite sheet, a void is formed around the fine particles contained in the polymer core layer by simultaneously extruding the polymer core layer containing the fine particles and the polymer surface layer and then biaxially stretching the same in a conventional manner. Can be produced.
The production of such a composite sheet is described in detail in US Pat. Nos. 4,377,616, 4,758,462, and 4,632,869. Can be.

[0015] The polymer core layer of the preferred composite sheet is
15 to 95%, preferably 30%, of the total thickness of the composite sheet
~ 85%. The density (specific gravity) of this composite sheet is 4
It is good to be 5% to 100%, preferably 67% to 100%. This density refers to the percentage of the density of the composite sheet relative to the polymer density. When the density is less than 45%, the composite sheet becomes difficult to manufacture due to a decrease in tensile strength and becomes more susceptible to physical damage.

The total thickness of the composite sheet is 12 to 100 μm.
m, preferably 20 to 70 μm. When it is less than 12 μm, the non-planarity of the base sheet such as paper cannot be covered, and when it exceeds 100 μm, further improvement in surface smoothness and mechanical properties is hardly observed.

The composite sheet will be described in more detail. As the resin material for forming the polymer surface layer and the polymer core layer, polyolefins are preferably used. Specifically, polypropylene, polyethylene,
Examples include polymethylpentene, polystyrene, polybutylene and mixtures thereof. Propylene and hexene,
Copolymers such as butene and octene are also useful. Among them, polypropylene having low cost and good strength is preferably used. The materials for the polymer surface layer and the polymer core layer may be the same or different.

As the fine particles contained in the polymer core layer, fine particles made of a polymer material, metal fine particles, glass fine particles, ceramic fine particles, inorganic fine particles such as clay, talc, barium sulfate, calcium carbonate and the like are used. Japanese Patent Application Laid-Open No.
The fine particles described in [0020] to [0023] of JP-B-78 can be used. In the present invention, it is preferable to use fine particles made of a polymer material. The fine particles used preferably have a diameter of 0.1 to 10 μm and are spherical.

A white pigment, for example, titanium oxide, barium sulfate, clay, calcium carbonate, etc., can be added to the polymer surface layer to improve whiteness. The addition amount is suitably from 1 to 40% by weight.

In the present invention, a composite support comprising a substrate and a biaxially stretched polymer sheet on at least one side of the substrate can be used. In this case, the above-mentioned composite sheet can be preferably used as the biaxially stretched polymer sheet particularly on the light- and heat-sensitive recording layer side.

As the substrate, either a transparent substrate or an opaque substrate can be used. Examples of the material that can be used for the transparent substrate include polyesters such as polyethylene terephthalate, cellulose esters such as nitrocellulose, cellulose acetate, cellulose acetate butyrate, polysulfone, polyphenylene oxide, polyimide, polycarbonate, and polyamide.
Among them, polyethylene terephthalate is preferred.

Examples of opaque substrates include high quality paper, medium paper, art paper, coated paper, cast coated paper, base paper used for silver halide photographic supports, baryta paper used for silver halide photographic supports, and the like. High gloss paper; such as polyolefins such as polyethylene, polyesters such as polyethylene terephthalate (PET), cellulose esters such as nitrocellulose, cellulose acetate and cellulose acetate butyrate, polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide and the like. Film made opaque by containing a white pigment or the like in a plastic film, or plastic containing a white pigment or the like in paper (plastics such as the above-mentioned transparent plastics)
And a void-containing film and the like provided with the above-mentioned coating layer.

The substrate preferably has a thickness of 50 to 200 μm because it is easy to handle.

The biaxially stretched polymer sheet on the photosensitive and heat-sensitive recording layer side of the composite support and on the side opposite to the photosensitive support is 690 MPa-
It preferably has a Young's modulus in the longitudinal direction of 5520 MPa, and a Young's modulus in the transverse direction is 690 MPa to 5 MPa.
It is preferably 520 MPa. Also, the substrate preferably has a longitudinal Young's modulus of 1300 MPa to 2760 MPa and a transverse Young's modulus of 6900 MPa to 1380 MPa. The Young's modulus of the biaxially stretched polymer sheet can be achieved by, for example, determining a stretching ratio in which the substrate is stretched in the vertical or horizontal direction so as to oppose a force that tends to curl when the substrate is dried. Thus, by appropriately selecting the Young's modulus of the biaxially stretched polymer sheet, the composite support can be prevented from curling due to environmental changes.

When the support is a composite support having a biaxially stretched polymer sheet on both sides of the substrate, the side opposite to the side on which the light and heat sensitive recording layer is provided (hereinafter referred to as the anti-light and heat sensitive recording layer side) The biaxially stretched polymer sheet may or may not have voids. As a material having a void, a composite sheet as described above can be similarly used. The preferred biaxially oriented polymer sheet is a biaxially oriented polyolefin sheet composed of one layer, for example, a biaxially oriented sheet composed of polyethylene or polypropylene. The thickness of the biaxially stretched sheet is 10 to 150
μm is preferred. If it is less than 10 μm, the non-planarity of the substrate such as paper cannot be covered, and if it exceeds 150 μm, further improvement in surface smoothness and mechanical properties is hardly observed.

A biaxially stretched polymer sheet on the side of the anti-photosensitive recording layer can also be prepared according to a conventional method.

Further, information such as images or indications such as decorations can be carried by printing on the surface of the biaxially stretched polymer sheet on the side of the anti-photosensitive thermosensitive recording layer which is in contact with the base material. Further, by embossing the biaxially stretched polymer sheet, information such as an image or a display such as decoration can be carried.

In the present invention, the composite support may be, for example, a biaxially stretched polymer sheet on the light- and heat-sensitive recording layer side as described above,
It can be produced by laminating a base material and a biaxially stretched polymer sheet on the side of the anti-photosensitive thermosensitive recording layer, preferably by laminating an adhesive between these materials, and crimping between two rolls. it can. As a preferable adhesive, a polyethylene resin is used. In addition, as the composite support used in the present invention, the items described in [0009] to [0050] of JP-A-10-333278 can be used.

If necessary, an antihalation layer may be provided on the surface of the support, and a layer suitable for the purpose, such as a slip layer, an antistatic layer, an anti-curl layer, and an adhesive layer, may be provided on the back surface.

The image according to the present invention is obtained by subjecting a photocurable composition containing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator and an electron-accepting developer to image exposure and curing, and thereafter, By uniformly heating, the electron-accepting color developer is selectively moved in the cured portion, and is obtained by a method of forming a color by contacting the electron-donating colorless dye in the coexisting microcapsules. In the cured part, the interaction between the polymerizable compound having an ethylenically unsaturated bond and the electron-accepting developer is reduced by polymerization, so that the developer diffuses faster and the electron-donating colorless in the capsule. Color develops on contact with dye. On the other hand, in the uncured portion, the electron-accepting developer is trapped in a polymerizable compound having an ethylenically unsaturated bond, and cannot be brought into contact with the electron-donating colorless dye in the capsule even when heated, so that it is visible. No image is formed.

The light- and heat-sensitive layer of the present invention can be formed in various structures depending on the purpose. One preferred configuration is a polymerizable compound having an ethylenically unsaturated bond,
The support is provided with a layer composed of fine droplets of a photocurable composition containing a photopolymerization initiator and an electron accepting developer and microcapsules containing a colorless electron-donating dye. In this case, the fine droplets may be in the form of an emulsion or the core material of a microcapsule. There may be a binder in this layer. Another preferred configuration contains an electron-donating colorless dye in the continuous phase of a photocurable composition containing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and an electron-accepting developer. This is a configuration in which a layer in which microcapsules are present is provided on a support. This continuous phase may be a mixture of the photocurable composition and a binder.

The recording material of the present invention may be a monochromatic so-called B / W recording material or a multicolor recording material by using the above photosensitive and heat-sensitive layer. In this case, for example, it is possible to use a configuration of a multilayer recording material including, in each layer, a microcapsule containing an electron-donating colorless dye that develops a different hue and a photocurable composition sensitive to light of a different wavelength. Specifically, a microcapsule containing an electron-donating colorless dye that develops cyan and a layer containing a photocurable composition sensitive to a wavelength λ1 are provided on a support, and an electron donor that develops magenta thereon. A microcapsule containing a neutral colorless dye and a layer containing a photocurable composition sensitive to wavelength λ2 are provided, and a microcapsule containing an electron-donating colorless dye developing yellow and light sensitive to wavelength λ3 are provided thereon. A configuration in which a layer containing a curable composition is provided, a configuration in which an intermediate layer is provided between layers, a configuration in which an ultraviolet absorber is contained in the intermediate layer, and the like can be used. When using an intermediate layer,
For example, a layer containing a microcapsule containing an electron-donating colorless dye that develops cyan and a photocurable composition sensitive to wavelength λ1 is provided on a support, on which light having a shorter wavelength than wavelength λ1 is absorbed. An intermediate layer is provided, on which a layer containing microcapsules containing an electron-donating colorless dye that develops magenta and a photocurable composition sensitive to wavelength λ2 is provided, and light having a shorter wavelength than wavelength λ2 is provided thereon. Is provided thereon, a layer containing microcapsules containing a colorless electron-donating dye that develops yellow and a photocurable composition sensitive to wavelength λ3 is provided thereon, and a protective layer is further provided thereon. And the like provided as a specific example.

When a conventionally known photopolymerization initiator or a combination of a photopolymerization initiator / spectral sensitizer is used, the photosensitive wavelength ranges of the respective layers are overlapped. By providing an intermediate layer containing an ultraviolet absorber between them to limit the light reaching the lower layer, it is possible to eliminate this overlap region. As a method for introducing the ultraviolet absorbent into the intermediate layer, various conventionally known methods can be used. One is a so-called emulsification and dispersion method in which an ultraviolet absorber is dissolved in a water-insoluble organic solvent, and the solution is emulsified and dispersed in an aqueous dispersion medium containing a surfactant to form fine droplets and introduced into an intermediate layer. There is a method called.
In this method, an organic solvent or a surfactant may act on the adjacent light- and heat-sensitive layer to cause some adverse effects such as a reduction in color density. Another method is to introduce a polymer latex carrying an ultraviolet absorber into the intermediate layer. The polymer latex supporting the ultraviolet absorbent can be obtained by using a method known in the art. For example, an ultraviolet absorber is dissolved in a water-insoluble volatile organic solvent, and the solution is emulsified and dispersed in an aqueous dispersion medium containing a surfactant to form fine droplets, and then mixed with a polymer latex. I just need. Even in this method, adverse effects may occur depending on the amount and type of the surfactant used. As still another method, there is a method of introducing a polymer latex containing an ultraviolet absorber monomer as a polymerization component into an intermediate layer. In this case, the amount of the surfactant to be used is the smallest, and the adverse effect of the surfactant is less likely to occur.

The polymerizable compound having an ethylenically unsaturated bond which can be used in the photocurable composition of the present invention is a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule. . For example, acrylic acid and its salts, acrylic esters, acrylamides;
Methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride, maleic esters; itaconic acid, itaconic esters; styrenes; vinyl ethers; vinyl esters; Ethers; aryl esters and the like can be used. Of these, at least one
A polymerizable compound containing a hetero atom having one lone electron pair is preferable. The term “hetero atom having a lone electron pair” as used herein refers to each atom such as oxygen, nitrogen, sulfur, phosphorus, and halogen. Specifically, those having a group such as an ester bond, an amide bond, a carbonyl bond, a thiocarbonyl bond, an ether bond, a thioether bond, an amine, an alcohol, a thioalcohol, a phosphine, and a halogen are included. Among these, polymerizable with an ethylenically unsaturated bond having at least one ester bond, amide bond, amine, carbonyl bond and / or ether bond in the molecule which has strong interaction with an electron accepting developer. Compounds are preferred, and compounds having ester bonds and amide bonds having high polymerizability are particularly preferred. Also, polymerization efficiency (curing speed)
In order to increase the molecular weight, a polymerizable compound having a plurality of ethylenically unsaturated double bonds in the molecule is preferable, for example, an acrylate or methacrylate of a polyhydric alcohol such as trimethylolpropane or pentaerythritol; There are acrylate or methacrylate terminated epoxy resin, acrylate or methacrylate unterminated polyester, and the like. Specific examples of particularly preferred compounds include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol. Dimethacrylate and the like. The molecular weight of these polymerizable compounds is about 1
It is preferably from about 00 to about 5000, more preferably a compound which does not easily diffuse into the electron-donating colorless dye-containing microcapsules, and a compound having a molecular weight of 200 or more is particularly useful.

Next, the photopolymerization initiator used in the light and heat sensitive recording layer of the recording material of the present invention will be described.

The photopolymerization initiator can generate radicals by light exposure to cause a polymerization reaction in the layer and promote the reaction. The recording layer film is cured by this polymerization reaction, and a latent image having a desired image shape can be formed.

The photopolymerization initiator can be appropriately selected from known ones.
It preferably contains a spectral sensitizing compound having a maximum absorption wavelength at m and a compound that interacts with the spectral sensitizing compound.

However, if the compound interacting with the spectral sensitizing compound is a compound having both the structure of a dye portion having a maximum absorption wavelength at 300 to 1000 nm and the structure of a borate portion in the structure, the spectral sensitizing compound may be used. It is not necessary to use a dye.

As a known photopolymerization initiator, for example, US Pat. No. 4,950,581 (column 20, line 35 to line 21)
Column, line 35). Further, for example, EP-A-137452, DE-A-27
18254, DE-A-2243621, U.S. Pat.
950581 (column 14, line 60 to column 18, 44)
Row); triazine compounds such as trihalomethyltriazines such as 2,4-bis (trichloromethyl) -6- (4-stilphenyl) -s-triazine.

When the photopolymerization initiator is used in a hybrid system, a cationic photopolymerization initiator may be used in addition to the free radical curing agent. Examples of the cationic photopolymerization initiator include benzoyl peroxide and US Pat. No. 4,950,581 (column 19, column 1).
Peroxide compounds such as peroxides described in US Pat. No. 4,950,581 (column 18, line 60 to column 19, line 10); aromatic sulfonium or iodonium salts described in US Pat. No. 4,950,581 (column 18, line 60 to column 19, line 10); Benzene)-(η5-cyclopentadienyl) -iron (II)
Cyclopentadienyl-arene iron (II) complex salts such as hexafluorophosphate are preferred.

Examples of the dye / boron compound are described in JP-A-62-143044 and JP-A-1-138.
No. 204, JP-A-6-505287, JP-A-4-26
Preferred examples include those described in No. 1406 and the like.

As the spectral sensitizing compound having a maximum absorption wavelength in the range of 300 to 1000 nm, a spectral sensitizing dye having a maximum absorption wavelength in this wavelength region is preferable.

High sensitivity can be obtained by selecting any desired dye from the spectral sensitizing dyes in the above wavelength range and adjusting the photosensitive wavelength so as to be compatible with the light source used.
In addition, as a light source used for image exposure, a light source of blue, green, red, or the like, an infrared laser, or the like can be selected.

Therefore, for example, when a color image is formed by using a multicolor recording material in which monochromatic recording layers emitting different hues are stacked, different absorption wavelengths are set in each monochromatic layer having a different hue. Having a spectral sensitizing dye having
By using a light source adapted to the absorption wavelength, even in a recording material in which a plurality of layers are laminated, each layer (each color) forms a high-sensitivity and high-sharp image. And sharpening can be achieved.

The spectral sensitizing dye can be appropriately selected from known compounds, for example, a patent publication relating to “a compound interacting with a spectral sensitizing compound” described later, and “Research Disclosure, Vo”.
l. 200, December 1980, Item 2003
6 "and" Sensitizers "(pp. 160 to 163, Kodansha; Katsumi Tokumaru, Makoto Okawara / ed., 1987) and the like.

Specifically, 3-ketocoumarin compounds described in JP-A-58-15603, JP-A-58-4030
No. 2 thiopyrylium salt, JP-B-59-2832
No. 8, No. 60-53300, and naphthothiazole merocyanine compounds described in JP-B-61-9621, 62
-3842, JP-A-59-89303, JP-A-60-6
No. 0104, and the like.

Further, "Chemistry of functional dyes" (1981)
Year, CMC Publishing Co., p.393-p.416) and "Colorants"
(60 [4] 212-224 (1987)). Specific examples include cationic methine dyes, cationic carbonium dyes, cationic quinone imine dyes, cationic indoline dyes, and cationic dyes. And the like.

The spectral sensitizing dyes include coumarin (including ketocoumarin or sulfoncoumarin) dyes, merostyril dyes, oxonol dyes, hemioxonol dyes, and other keto dyes; non-ketopolymethine dyes, triarylmethane dyes, xanthene dyes Non-keto dyes such as, anthracene dyes, rhodamine dyes, acridine dyes, aniline dyes, and azo dyes; non-ketopolymethines such as azomethine dyes, cyanine dyes, carbocyanine dyes, dicarbocyanine dyes, tricarbocyanine dyes, hemicyanine dyes, and styryl dyes Dyes include azine dyes, oxazine dyes, thiazine dyes, quinoline dyes, quinone imine dyes such as thiazole dyes, and the like.

By appropriately using the above-mentioned spectral sensitizing dye, it becomes possible to obtain the spectral sensitivity of the photopolymerization initiator used in the recording material of the present invention in the ultraviolet to infrared region.

The various spectral sensitizing dyes may be used alone or in combination of two or more.

The amount of the spectral sensitizing compound used is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 2% by weight, based on the total weight of the light and heat sensitive recording layer.

As the compound that interacts with the spectral sensitizing compound, one or more compounds selected from known compounds capable of initiating a photopolymerization reaction with the photopolymerizable group in the compound B can be used. Can be selected and used.

By coexisting this compound with the above-mentioned spectral sensitizing compound, the compound can be sensitively sensitive to irradiation light in the spectral absorption wavelength region and can generate radicals with high efficiency, so that high sensitivity can be achieved, and The generation of radicals can be controlled using any light source in the ultraviolet to infrared region.

Examples of the compound that interacts with the spectral sensitizing compound include organic borate salt compounds and the following compounds.

Benzophenone, 4,4-bis (dimethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzylanthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine from CIBA Aromatic ketones such as bisacylphosphine oxides such as oxides; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoinfe Benzoin and benzoin ethers such as ether; 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer, 2-
(O-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole duplex, 2- (o-fluorophenyl) -4,5-diphenylimidazole duplex, 2-
(O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5
2,4,6-triarylimidazole dimer such as -diphenylimidazole dimer; polyhalogen compound such as carbon tetrabromide, phenyltribromomethylsulfone and phenyltrichloromethylketone; JP-A-59-13342
No. 8, JP-B-57-1819, JP-B-57-6096
No. 3,615,455, compounds described in US Pat.
4,6-tris (trichloromethyl) -S-triazine, 2-methoxy-4,6-bis (trichloromethyl)
Japanese Unexamined Patent Publications Nos. (Kokai) No. S-triazine, 2-amino-4,6-bis (trichloromethyl) -S-triazine, 2- (P-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine 58-29803, an S-triazine derivative having a trihalogen-substituted methyl group; methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, ditert-butyl diperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxybenzoate, a,
a'-bis (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 3,3 ',
JP-A-59-18934 such as 4,4'-tetra- (tert-butylperoxycarbonyl) benzophenone
Organic peroxide described in No. 0; Azinium salt compound described in U.S. Pat. No. 4,743,530; Tetramethylammonium salt of triphenylbutyroborate, tetrabutylammonium salt of triphenylbutylborate, tri (P-methoxyphenyl) EP 0223, such as the tetramethylammonium salt of butyl borate
No. 587; an organic boron compound; other diaryliodonium salts, iron allene complexes, and the like.

Also, a combination of two or more compounds is known, and these can also be used for the recording material of the present invention.

The combination of two or more compounds includes, for example, a combination of a 2,4,5-triarylimidazole dimer and a mercaptobenzoxazole, and a compound described in US Pat. No. 3,427,161. Combination of 4'-bis (dimethylamino) benzophenone, benzophenone and benzoin methyl ether, U.S. Pat.
Benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromerchi) described in 239850
A combination with -6- (4'-methoxyphenyl) -triazole, a combination of a dialkylaminobenzoic acid ester and dimethylthioxanthone described in JP-A-57-23602, and a combination of JP-A-59-78339. 4,
And three combinations of 4'-bis (dimethylamino) benzophenone, benzophenone, and a polymethyl halide compound.

Among them, a combination of 4,4′-bis (diethylamino) benzophenone and benzophenone,
Preferred is a combination of 4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, or a combination of 4,4'-bis (diethylamino) benzophenone and 2,4,5-triarylimidazole dimer.

Of the above "compounds which interact with the spectral sensitizing compound", organic borate salt compounds, benzoin ethers, S-triazine derivatives having a trihalogen-substituted methyl group, organic peroxides and azinium salt compounds are preferred. And organic borate salt compounds are more preferred.

By using this “compound that interacts with the spectral sensitizing compound” in combination with the spectral sensitizing compound, radicals can be locally and effectively generated in the exposed portions exposed to light, High sensitivity can be achieved.

Examples of the organic borate salt compounds include JP-A-62-143044 and JP-A-9-188686.
JP-A-9-188686, JP-A-9-18871
No. 0 or the like (hereinafter sometimes referred to as “borate compound I”), or a spectral sensitizing dye-based borate compound obtained from a cationic dye (hereinafter, referred to as “borate compound I”).
It may be referred to as “borate compound II”. ) And the like.

Specific examples of the borate compound I will be given below, but the present invention is not limited thereto.

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Further, in the recording material of the present invention, the above-mentioned "Functional Dye Chemistry" (1981, CMC Publishing Co., p. 393)
Pp. 416) and “colorants” (60 [4] 212-224)
(1987)) and the like, and spectral sensitizing dye-based organic borate compounds (borate compounds II) obtainable from the cationic dyes described in (1987)).

This borate compound II is a compound having both a dye part and a borate part in its structure, and at the time of exposure, absorbs light source energy effectively by the light absorbing function of the dye part and releases radicals of the borate part. It has three functions of accelerating the polymerization reaction by the function and decoloring the coexisting spectral sensitizing compound.

Specifically, a wavelength region of 300 nm or more,
Preferably, any cationic dye having a maximum absorption wavelength in the wavelength region of 400 to 1100 nm can be suitably used. Among them, cationic methine dye, polymethine dye, triarylmethane dye, indoline dye, azine dye, xanthene dye, cyanine dye, hemicyanine dye, rhodamine dye, azamethine dye, oxazine dye or acridine dye are preferable,
Cationic cyanine dyes, hemicyanine dyes, rhodamine dyes or azamethine dyes are more preferred.

The borate compound II obtained from the organic cationic dye can be obtained by using an organic cationic dye and an organic boron compound anion with reference to the method described in EP 223,587 A1.

Hereinafter, specific examples of the borate compound II obtained from the cationic dye will be described.
It is not limited to these.

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As described above, the borate compound II is a multifunctional compound. However, from the viewpoint of obtaining high sensitivity and sufficient decoloring properties, the recording material of the present invention contains, It is preferable that a sensitizing compound and a compound that interacts with the spectral sensitizing compound are appropriately combined.

In this case, as the photopolymerization initiator, a photopolymerization initiator (1) combining the above-mentioned spectral sensitizing compound and borate compound I, or a photopolymerization initiator combining the above borate compound I and borate compound II. More preferably, it is the polymerization initiator (2).

At this time, the use ratio of the spectral sensitizing dye and the organic borate compound present in the photopolymerization initiator is very important from the viewpoint of increasing the sensitivity and obtaining sufficient decolorability by light irradiation in the fixing step. Becomes

In the case of the photopolymerization initiator (1), in addition to the ratio (= 1/1: molar ratio) of the spectral sensitizing compound / borate compound I required for the photopolymerization reaction, Further, it is particularly preferable to add an amount of the borate compound I necessary for sufficiently decoloring the spectral sensitizing compound remaining in the layer from the viewpoint of obtaining sufficiently high sensitivity and decoloring performance.

That is, the ratio of spectral sensitizing dye / borate compound I is preferably used in the range of 1/1 to 1/50, more preferably in the range of 1 / 1.2 to 1/30. Preferably, it is most preferably used in the range of 1 / 1.2 to 1/20. If the above ratio is less than 1/1, sufficient polymerization reactivity and decoloring property cannot be obtained, and if it exceeds 1/50, coating suitability is deteriorated, which is not preferable.

In the case of the photopolymerization initiator (2), the borate compound I and the borate compound II may be used in combination such that the borate moiety is at least equimolar to the dye moiety. It is particularly preferable from the viewpoint of obtaining sufficiently high sensitivity and decoloring performance.

The ratio of borate compound I / borate compound II is preferably used in the range of 1/1 to 50/1, more preferably in the range of 1.2 / 1 to 30/1. Most preferably, it is used in the range of 1.2 / 1 to 20/1. When the ratio is less than 1/1, the generation of radicals is small, and sufficient polymerization reactivity and decoloring performance cannot be obtained. When the ratio is more than 50/1, sufficient sensitivity cannot be obtained, which is not preferable.

The total amount of the spectral sensitizing dye and the organic borate compound in the photopolymerization initiator is preferably from 0.1 to 10% by weight based on the amount of the compound having a polymerizable group. It is more preferably used in the range of 0.1 to 5 wt%, but most preferably used in the range of 0.1 to 1 wt%. If the use amount is less than 0.1 wt%, the effects of the present invention cannot be obtained. If the use amount exceeds 10 wt%, storage stability decreases and coating suitability decreases, which is not preferable.

Examples of the electron-accepting developer used in the present invention include phenol derivatives, sulfur-containing phenol derivatives, organic carboxylic acid derivatives (eg, salicylic acid, stearic acid, resorcinic acid, etc.), and metal salts thereof. Examples include sulfonic acid derivatives, urea or thiourea derivatives, acidic clay, bentonite, novolak resins, metal-treated novolak resins, metal complexes, and the like. Examples of these are described in the Paper and Pulp Technology Times (1985) pp. 49-54 and 65.
Pp. 70 to 70, and JP-B-40-9309 and 45-
14039, JP-A-52-140483, JP-A-48-51
510, 57-210886, 58-87089,
59-11286, 60-177675, 61-
95988 and the like. Examples of some of these compounds include 2,2′-bis (4-hydroxyphenyl) propane, 4-t-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, 1,1 '-Bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1,1'
-Bis (3-chloro-4-hydroxyphenyl) -2-
Ethylbutane, 4,4'-sec-isooctylidenediphenol, 4,4'-sec-butylidenediphenol, 4-t-octylphenol, 4-p-methylphenylphenol, 4,4'-methylcyclohexylidene Phenol, 4,4′-isopentylidenephenol,
Benzyl p-hydroxybenzoate and the like. Salicylic acid derivatives include 4-pentadecylsalicylic acid, 3,5
-Di (α-methylbenzyl) salicylic acid, 3,5-di (t-octyl) salicylic acid, 5-octadecylsalicylic acid, 5-α- (p-α-methylbenzylphenyl) ethylsalicylic acid, 3-α-methylbenzyl- 5-t-octylsalicylic acid, 5-tetradecylsalicylic acid, 4-
Hexyloxysalicylic acid, 4-cyclohexyloxysalicylic acid, 4-decyloxysalicylic acid, 4-dodecyloxysalicylic acid, 4-pentadecyloxysalicylic acid, 4-octadecyloxysalicylic acid, etc., and zinc, aluminum, calcium, copper and lead salts thereof. .
These electron accepting compounds may be used alone or in combination of two or more. The use amount of the electron-accepting compound is preferably in the range of 10 to 4000% by weight of the electron-donating colorless dye, and particularly preferably 100 to 2000% by weight.

The photocurable composition may further contain a reducing agent such as an oxygen scavenger (oxygen) as an auxiliary for accelerating the polymerization.
Gen scavengers and chain transfer agents for active hydrogen donors, as well as other compounds that promote polymerization by chain transfer, can also be included. Oxygen scavengers that have been found to be useful are phosphines, phosphonates, phosphites, stannous salts and other compounds that are easily oxidized by oxygen. For example, N-phenylglycine, trimethylbarbituric acid, N, N-dimethyl-2,6-diisopropylaniline, N, N, N-2,
4,6-pentamethylaniline and the like. Further, thiols, thioketones, trihalomethyl compounds, lofin dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, and the like are also useful as polymerization accelerators.

Further, in addition to these compounds, a heat polymerization inhibitor can be added to the photocurable composition as required. The thermal polymerization inhibitor is added to prevent the thermal polymerization of the photocurable composition and the polymerization with time, so that the chemical stability during preparation and storage of the photocurable composition can be improved. Can be increased. Examples of thermal polymerization inhibitors include:
p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone,
Cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-
Cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine and the like can be mentioned. The preferable addition amount of the thermal polymerization inhibitor is 0.001 to 5% by weight based on the total weight of the photocurable composition, and more preferably 0.01 to 5% by weight.
1 to 1% by weight. If it is less than 0.001% by weight, the thermal stability is poor, and if it exceeds 5% by weight, the sensitivity decreases.

The photocurable composition of the present invention may be used by encapsulating it in microcapsules, if necessary. For example, they can be encapsulated in microcapsules with reference to European Patent No. 0223587 and the above patent.

In the present invention, the photocurable composition is preferably dispersed in a water-soluble polymer, and the water-soluble polymer that can be preferably used in the present invention is 25 ° C.
A compound that is soluble in water at 5% by weight or more is preferable,
Specifically, gelatin, gelatin derivatives, albumin,
Proteins such as casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose sugar derivatives such as sodium alginate and starches (including modified starches);
Gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, vinyl acetate-acrylic acid copolymer oxide, and synthetic polymers such as polystyrene sulfonate. . Among these, gelatin and polyvinyl alcohol are preferred.

As the electron-donating colorless dye used in the present invention, conventionally known triphenylmethanephthalide compounds, fluoran compounds, phenothiazine compounds,
Various compounds such as an indolylphthalide compound, a leuco auramine compound, a rhodamine lactam compound, a triphenylmethane compound, a triazene compound, a spiropyran compound, and a fluorene compound can be used. Specific examples of phthalides are described in U.S. Reissue Patent Specification No. 2
3,024, U.S. Pat. Nos. 3,491,111, 3,491,112, 3,491,116 and 3,509,174, and specific examples of fluorans are described in U.S. Pat. Nos. 3,624,107 and 3,627,7
No. 87, No. 3,641,011, No. 3,462
No. 828, No. 3,681,390, No. 3,92
Nos. 0,510 and 3,959,571, specific examples of spirodipyrans are disclosed in U.S. Pat. No. 3,971,808, and pyridine and pyrazine compounds are disclosed in U.S. Pat.
No. 75,424 No. 3,853,869, No. 4,
No. 246,318 and specific examples of the fluorene compound are described in Japanese Patent Application No. 61-240989. If some of these compounds are disclosed, 3,3-bis (p-dimethylaminophenyl) -6 is used as a triarylmethane compound.
-Dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,3-dimethylindole-3
-Yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, and the like.
4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-
2,4,5-trichlorophenylleuco auramine and the like, and as the xanthene compound, rhodamine-β-
Anilinolactam, rhodamine- (p-nitrino) lactam, 2- (dibenzylamino) fluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2
-Anilino-3-methyl-6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-
Isoamylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, 2-anilino-3-methyl- 6-N-ethyl-N-isobutylaminofluoran, 2-anilino-
6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-tetrahydrofurfurylaminofluoran, 2-anilino-3-methyl-6-piperidinoaminofluoran, 2- ( o-chloroanilino)
-6-diethylaminofluoran, 2- (3,4-dichloroanilino) -6-diethylaminofluoran and the like; thiazine compounds such as benzoylleucomethylene blue and p-nitrobenzylleucomethylene blue; and spiro compounds. Is 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3′-dichloro-spiro-dinaphthopyran,
3-benzylsilo-dinaphthopyran, 3-methyl-naphtho- (3-methoxy-benzo) -spiropyran, 3-
Propyl-spiro-dibenzopyran and the like. Particularly, as electron-donating colorless dyes for cyan, magenta and yellow used in full-color recording materials, US Pat.
0,149 and the like, U.S. Pat. No. 4,800,148 and the like for the yellow coloring type, and JP-A-63-53542 and the like for the cyan coloring type.

As a method for microencapsulating an electron-donating colorless dye, a method known in the art can be used. For example, a method utilizing coacervation of a hydrophilic wall forming material as disclosed in U.S. Pat. Nos. 2,800,457 and 2,800,458; U.S. Pat. No. 3,287,154; No. 990,443,
JP-B-38-19574, 42-446 42
Interfacial polymerization method as disclosed in US Pat. No. 3,418,250 and US Pat. No. 3,795.
No. 6,669, US Pat. No. 3,914,511, US Pat. Nos. 4,001,140, 4,087, 376 and 4,089,802, a method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall-forming material, a melamine-formaldehyde resin disclosed in U.S. Pat. No. 4,025,455, hydroxypropyl A method using a wall-forming material such as cellulose, in situ by polymerization of a monomer as disclosed in JP-B-36-9168 and JP-A-51-9079.
itu) method, British Patent Nos. 952,807 and 965
No. 074, the electrolytic dispersion cooling method disclosed in US Pat.
No. 11,407 and British Patent No. 930,422. Although not limited thereto, it is preferable to form a polymer film as a microcapsule wall after emulsifying the core substance.

As a method of forming the microcapsule wall, particularly when a microencapsulation method by polymerization of a reactant from the inside of an oil droplet is used, the effect is large. That is, it is possible to obtain a preferable capsule having a uniform particle size and excellent raw preservability within a short time. For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and, if necessary, a second substance (eg, polyol, polyamine) which reacts with the polyisocyanate to form a capsule wall are mixed into an oily liquid to be encapsulated. By emulsifying and dispersing the mixture in water and then raising the temperature of the emulsion, a polymer forming reaction occurs at the oil droplet interface to form microcapsule walls. At this time, an auxiliary solvent having a low boiling point and strong dissolving power can be used in the oily liquid. The polyvalent isocyanate used in this case and the polyol and polyamine to be reacted therewith are described in US Pat. No. 3,281,3.
No. 83, No. 3,773,695, No. 3,793,26
No. 8, JP-B-48-40347 and JP-B-49-24159
And JP-A-48-80191 and JP-A-48-84086, and they can also be used.

As the polyvalent isocyanate, for example, m
-Phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,
4-tolylene diisocyanate, naphthalene-1,4-
Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3,3'-cymethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate 4,4′-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene
Diisocyanates such as 1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate, and 4,4 ′, 4 ″ -triphenylmethane triisocyanate Triisocyanates such as toluene-2,4,6-triisocyanate, 4,4 ′
Tetradimethylisocyanate such as -dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, an adduct of hexamethylenediisocyanate with trimethylolpropane, an adduct of 2,4-tolylenediisocyanate and trimethylolpropane, xylylenediisocyanate And isocyanate prepolymers such as adducts of trimethylolpropane and adducts of tolylene diisocyanate and hexanetriol.

Examples of the polyol include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters and hydroxypolyalkylene ethers. JP 60
Ethylene glycol described in US Pat.
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, propylene glycol, 2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxy Butane, 2,2-dimethyl-1,3-propanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,
4-cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, 2-phenylpropylene glycol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct Glycerin ethylene oxide adduct, glycerin, condensation products of aromatic polyhydric alcohols such as 1,4-di (2-hydroxyethoxy) benzene, resorcinol dihydroxyethyl ether and alkylene oxide, p-xylylene glycol,
m-xylylene glycol, α, α'-dihydroxy-
p-Diisopropylbenzene, 4,4′-dihydroxy-diphenylmethane, 2- (p, p′-dihydroxydiphenylmethyl) benzyl alcohol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, and the like can also be used. The polyol is preferably used in a ratio of 0.02 to 2 mol of the hydroxyl group to 1 mol of the isocyanate group.

As the polyamine, ethylesidiamine,
Trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, Examples include triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds. Polyvalent isocyanates can also react with water to form polymeric substances.

A water-soluble polymer can be used when preparing microcapsules, and the water-soluble polymer may be any of a water-soluble anionic polymer, a nonionic polymer, and an amphoteric polymer. As the anionic polymer, either a natural polymer or a synthetic polymer can be used.
O ^-, -SO ₂ ^- include those having a group. Specific examples of anionic natural polymers include gum arabic, alginic acid, and pectin. Semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, and lignin sulfonic acid. Examples of synthetic products include maleic anhydride (including hydrolyzed) copolymers, acrylic acid (including methacrylic acid) polymers and copolymers, vinylbenzenesulfonic acid polymers and copolymers. Coalescence, carboxy-modified polyvinyl alcohol and the like.

Examples of the nonionic polymer include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. Examples of the amphoteric compound include gelatin.

These water-soluble polymers are used as an aqueous solution of 0.01 to 10% by weight. The particle size of the microcapsules is adjusted to 20 μm or less. The size of the capsule used in the present invention is 80 μm or less, and particularly preferably 20 μm or less from the viewpoint of storage stability and handleability. On the other hand, if the capsule is too small, the surface area for a certain solid content becomes large, and a large amount of a wall material is required. Therefore, the thickness is preferably 0.1 μm or more.

The electron-donating colorless dye used in the present invention may be present in a solution state in microcapsules.
It may exist in a solid state. When a solvent is used, the amount of the solvent used in the capsule is 10% of the electron-donating colorless dye.
A ratio of 1 to 500 parts by weight to 0 parts by weight is preferable.

At this time, a natural oil or a synthetic oil can be used as the solvent. Specifically, for example, cottonseed oil,
Kerosene, aliphatic ketone, aliphatic ester, paraffin, naphthenic oil, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene and 1
-Phenyl-1-xylylethane, 1-phenyl-1-
diarylethanes such as p-ethylphenylethane and 1,1′-ditolylethane, alkyl phthalates (dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, etc.), phosphates (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, Dioctyl butyl phosphate), citrate (eg, tributyl acetyl citrate), benzoate (octyl benzoate),
Alkyl amides (eg, diethyl lauryl amide),
Fatty acid esters (eg, dibutoxyethyl succinate, dioctyl acetate), trimesic esters (eg, tributyl trimesate), ethyl acetate,
There are lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone and the like. At the time of microencapsulation, a volatile solvent may be used in combination with these solvents as an auxiliary solvent for dissolving the electron-donating colorless dye. Examples of the auxiliary solvent include ethyl acetate, butyl acetate, methylene chloride and the like.

In the case of a multicolor recording material, for example, the constitution of a multi-layer recording material comprising in each layer a microcapsule containing an electron-donating colorless dye that develops a different hue and a photocurable composition sensitive to light of different wavelengths And an intermediate layer containing an ultraviolet absorber is preferably provided between the photosensitive and heat-sensitive layers. The intermediate layer mainly consists of a binder and an ultraviolet absorber, and may contain additives such as a curing agent and a polymer latex as needed. As the ultraviolet absorber, benzotriazole compounds, cinnamate compounds,
Compounds known in the art such as aminoallylidenemalon nitrile compounds and benzophenone compounds can be used.

The ultraviolet absorbent used in the present invention can be emulsified and dispersed by an oil-in-water dispersion method or a polymer dispersion method and added to a desired layer, particularly, an intermediate layer. In the oil-in-water dispersion method, after dissolving in a single solution or a mixture of both a high-boiling organic solvent having a boiling point of, for example, 175 ° C. or more and a so-called auxiliary solvent having a boiling point of, for example, 30 ° C. to 160 ° C. The agent is finely dispersed in an aqueous medium such as water, an aqueous gelatin solution or an aqueous polyvinyl alcohol solution in the presence of an agent. Examples of high boiling organic solvents are described in U.S. Pat. No. 2,322,027. Further, as specific examples of the high boiling point organic solvent and the auxiliary solvent, the same soot as the solvent at the time of the above-mentioned encapsulation can be preferably used. The dispersion may be accompanied by a phase inversion, and if necessary, the coating solution may be applied after the auxiliary solvent is removed or reduced by distillation, Nudel washing, ultrafiltration, or the like. Specific examples of the latex dispersion process, effects, and latex for coagulation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OL
S) Nos. 2,541,274 and 2,541,274
No. 30, JP-A-49-74538 and JP-A-51-5994.
Nos. 3 and 54-32552 and Research
Disclosure, Vol. 148, August 1976, Item 14850, and the like. Suitable latexes include, for example, acrylates or methacrylates (eg, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, etc.)
And a copolymer latex of an acid monomer (for example, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc.).

As the ultraviolet absorber most preferably used in the present invention, there is an ultraviolet absorber having a structure hardly diffused into the adjacent layer, for example, a polymer or latex copolymerized with the ultraviolet absorber. Examples of such an ultraviolet absorber include, for example, European Patent No. 127,819, JP-A-59-68731, JP-A-59-26733, and JP-A-59-26733.
23344, British Patent 2,118,315, JP-A-58-111942, U.S. Pat. No. 4,307,184.
Nos. 4,202,836 and 4,202,834
No. 4,207,253 No. 4,178,303
And JP-A-47-560 can be referred to. These ultraviolet absorbers are added to the intermediate layer, but may be added to the protective layer, the light and heat sensitive layer, the antihalation layer, and the like, if necessary.

In the present invention, a protective layer is preferably provided, and a matting agent is preferably added to the protective layer.
As the matting agent, for example, silica, magnesium oxide, barium sulfate, strontium sulfate, inorganic compounds such as silver halide and polymethyl methacrylate, polyacrylonitrile, polymer particles such as polystyrene, carboxy starch, corn starch, carboxynitrophenyl starch And starch particles having a particle size of 1-2.
Those having a thickness of 0 μm are preferred. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. As the silica particles, for example, FUJI DEV
ISION CHEMICAL LTD. AL-1, 65, 72, 79, 74, 404, 62
0, 308, 978, 161, 162, 244, 25
5, 266, 150 and the like are preferable. The addition amount of the matting agent is preferably from ² to 500 mg / m ² , particularly preferably from 5 to 100 mg / m ² .

In the present invention, it is preferable to use a curing agent in each of the layers such as the light and heat sensitive layer, the intermediate layer and the protective layer. In particular, it is preferable to use a curing agent in the protective layer to reduce the tackiness of the protective layer. As the hardener, for example, a "gelatin hardener" used in the production of a photographic light-sensitive material is useful. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, and US Pat. No. 3,635,718 and others are described. Compounds having a reactive halogen, the compounds having a reactive ethylenically unsaturated bond described in U.S. Pat. No. 3,635,718 and others, and the compounds described in U.S. Pat. No. 3,017,280 and others. Compounds, epoxy compounds described in U.S. Pat. No. 3,091,537 and others, halogenocarboxaldehydes such as mucochloric acid, dioxane such as dihydroxydioxane and dichlorodioxane, or U.S. Pat. No. 3,642 No. 486 and U.S. Pat.
687,707, vinyl sulfones,
Vinyl sulfone precursors described in U.S. Pat. No. 3,841,872, U.S. Pat. No. 3,640,7
Ketovinyls described in No. 20 or chromium alum, zirconium sulfate, boric acid or the like can be used as an inorganic curing agent. Particularly preferred compounds among these curing agents are 1,3,5-triacroyl-hexahydro-s-triazine, 1,2-bisvinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (Α-vinylsulfonylacetamido) ethane, 2,4-dichloro-6-hydroxy-s
-Triazine sodium salt, 2,4,6-triethyleneimino-s-triazine, boric acid and the like. The addition amount is preferably 0.5 to 5% by weight based on the binder. In addition, colloidal silica may be added to the protective layer in order to reduce its adhesiveness. As the colloidal silica, for example, Nissan Chemical's Snowtex 20, Snowtex 30, Snowtex C, Snowtex O, Snowtex N, and the like are preferable. The addition amount is preferably from 5 to 80% by weight based on the binder.
Further, a fluorescent whitening agent for increasing the whiteness of the recording material of the present invention or a blue dye as a bluing agent may be added to the protective layer.

In the present invention, as a binder for each layer of the recording material such as a protective layer, a light and heat sensitive layer, an intermediate layer, the above water-soluble polymer and polystyrene, polyvinyl formal,
Solvent solubility of polyvinyl butyral, acrylic resin (for example, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and their copolymers), phenol resin, styrene-butadiene resin, ethyl cellulose, epoxy resin, urethane resin, etc. A polymer or a polymer latex thereof can be used. Among these, gelatin and polyvinyl alcohol are preferred.

In each layer of the light- and heat-sensitive recording material produced by using the present invention, various surfactants may be used for various purposes such as a coating aid, antistatic, improvement of slipperiness, emulsification dispersion, and prevention of adhesion. . Examples of the surfactant include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide derivatives such as alkyl ether of polyethylene oxide, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and alkyl sulfates. , N-acyl-N-alkyltaurines, sulfosuccinates, anionic surfactants such as sulfoalkylpolyoxyethylene alkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, aliphatics Alternatively, a cationic surfactant such as an aromatic quaternary ammonium salt can be used if necessary.

Various additives can be added to the recording material of the present invention, if necessary, including the additives described above. For example, typical examples of a dye, an ultraviolet absorber, a plasticizer, a fluorescent brightener, a matting agent, a coating aid, a curing agent, an antistatic agent and a slipperiness improver for preventing irradiation and halation are Research Disclosur.
e, Vol. 176, December 1978, Item17
643, and Vol. 187, November 1979,
Item 18716.

The recording material of the present invention is obtained by applying a coating solution for a photosensitive and heat-sensitive layer in which an additive or the like is dissolved in a solvent as necessary or the above-mentioned coating solution for each layer on a support, and drying. Can be Examples of the solvent used in this case include water; alcohols (eg, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec.
-Butanol, methyl cellosolve, 1-methoxy-2-
Propanol); halogen-based solvents (eg, methylene chloride, ethylene chloride); ketones (eg,
Acetone, cyclohexanone, methyl ethyl ketone);
Esters (for example, methyl cellosolve acetate, ethyl acetate, methyl acetate); single substances such as toluene and xylene, and mixtures of two or more thereof. Of these, water is particularly preferred.

To apply the coating solution for each layer onto the support, a blade coater, rod coater, knife coater, roll doctor coater, comma coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, curtain coater , An extrusion coater or the like can be used. The application method is Research Discl
osure, Vol. 200, December 1980, It
em20036 XV section can be referred to. The appropriate thickness of the recording layer is 0.1 μm to 50 μm.

The recording material of the present invention can be used for various uses. For example, the recording material of the present invention can be used for applications such as Copier (registered trademark), fax, printer, label, color proof, overhead projector, and 2nd original drawing.

The recording material of the present invention can record at high sensitivity with light in a wide range from ultraviolet light to visible light. Mercury lamps, xenon lamps, tungsten lamps,
Various lasers such as metal halide lamps, argon lasers, helium neon lasers, and semiconductor lasers, LE
D, a wide range of light sources such as fluorescent lamps can be used. As the image recording method, various exposure methods such as contact exposure of an original such as a lith film, enlargement exposure of a slide or a liquid crystal image, and reflection exposure using reflected light of the original can be used. When performing multi-color recording, image recording may be performed multiple times using light of different wavelengths. Light having different wavelengths can be obtained by changing the light source or the optical filter.

The recording material of the present invention is subjected to a heat development treatment simultaneously with or after the above-mentioned imagewise exposure. Various conventionally known methods can be used as a heating method in the heat development processing. The heating temperature is generally 80 ° C to 200 ° C.
° C, preferably 100 ° C to 160 ° C. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute.

[0122]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. [Synthesis of ultraviolet absorbent latex] Synthesis Example 1: Synthesis of ultraviolet absorbent latex (1) 200 ml of distilled water and 0.5 g of a surfactant (sodium dodenrubencene sulfonate) were placed in a flask and placed in a nitrogen stream. Stirred at 80 ° C. 0.5 g of potassium persulfate and 0.25 g of sodium bisulfite were added thereto. Further, a mixture of 16 g of the polymerizable ultraviolet absorber (1), 33 g of butyl acrylate and 1 g of acrylic acid was added thereto little by little, and after adding the whole amount, 0.5 g of potassium persulfate and 0.25 g of sodium hydrogen sulfite were further added. And stirred for 1 hour. The obtained liquid was p-pulped with 1N sodium hydroxide solution.
It was adjusted to H6 and filtered using filter paper to obtain the desired latex. Synthesis Example 2: Synthesis of UV absorber latex (2) 16 g of polymerizable UV absorber (1), 33 g of butyl acrylate, and 1 g of acrylic acid of Synthesis Example 1 were mixed with 5 g of polymerizable UV absorber (2), 44 g of butyl acrylate, and acrylic. An ultraviolet absorbent latex (2) was obtained in the same manner as in Synthesis Example 1 except that the acid was changed to 1 g. [Preparation of coating liquid] Preparation of electron-donating colorless dye capsule (1-a) Preparation of electron-donating colorless dye (1) Capsule 12.4 g of electron-donating colorless dye (1) was added to ethyl acetate 1
0.4 g, and dicyclohexyl phthalate 124
g, Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) and 27 g of Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. This solution was added to a mixture of 4.6 g of polyvinyl alcohol and 74 g of water, and emulsified and dispersed at 20 ° C. to obtain an emulsion having an average particle size of 1.5 μm. 100 g of water was added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring. After 2 hours, a capsule liquid containing the electron-donating colorless dye (1) in the core was obtained. (1-b) Preparation of colorless electron-donating dye (2) Capsule (1-a) except that the colorless electron-donating dye (1) in (1-a) was changed to the colorless electron-donating dye (2). An electron-donating colorless dye (2) capsule was obtained in the same manner. (1-c) Preparation of Electron-donating Colorless Dye (3) Capsule (1-a) except that the electron-donating colorless dye (1) in (1-a) was changed to the electron-donating colorless dye (3). An electron-donating colorless dye (3) capsule was obtained in the same manner. 2. Preparation of emulsion of photocurable composition (2-a) Preparation of emulsion of photocurable composition (1) 0.2 g of photopolymerization initiator (1) and spectral sensitizing dye (1) 0.1.
10 g of an electron-accepting compound (1) in a solution of 2 g of N-phenylglycine ethyl ester in 4 g of ethyl acetate as an auxiliary for promoting polymerization with 2 g of trimethylolpropane triacrylate monomer (trifunctional acrylate, molecular weight about 296) 8 g were added. This solution is added to 15% P
A homogenizer (Nippon Seiki Co., Ltd.) was added to a mixed solution of 19.2 g of VA aqueous solution, 4.8 g of water and 0.8 g of 2% surfactant (1) aqueous solution and 0.8 g of 2% surfactant (2) aqueous solution. Emulsification at 10,000 rpm for 5 minutes,
An emulsion of the photocurable composition (1) was obtained. (2-b) Preparation of emulsion of photocurable composition (2) 0.2 g of photopolymerization initiator (1) and 0.2 g of spectral sensitizing dye (1) of (2-a) are photopolymerization initiators (2) An emulsion of the photocurable composition (2) was obtained in the same manner as in (2-a) except that the amount was changed to 0.2 g. (2-c) Preparation of an emulsion of the photocurable composition (3) 0.2 g of the photopolymerization initiator (1) of (2-a) and 0.2 g of the spectral sensitizing dye (1) are photopolymerization initiators. (3) An emulsion of the photocurable composition (3) was obtained in the same manner as in (2-a) except that the amount was changed to 0.2 g. 3. Preparation of Coating Solution for Photosensitive Layer (3-a) Preparation of Coating Solution for Photosensitive Layer (1) 1 g of an electron-donating colorless dye (1) capsule and 10 g of an emulsion of the photocurable composition (1) are mixed. And heat-sensitive layer (1)
A coating solution was prepared. (3-b) Preparation of Coating Solution for Photosensitive Layer (2) 1 g of an electron-donating colorless dye (2) capsule and 10 g of an emulsion of the photocurable composition (2) were mixed to form a photosensitive layer (2).
A coating solution was prepared. (3-c) Preparation of Coating Solution for Photosensitive Layer (3) 1 g of an electron-donating colorless dye (3) capsule and 10 g of an emulsion of the photocurable composition (3) are mixed to form a photosensitive layer (3).
A coating solution was prepared. 4. Preparation of Coating Solution for Intermediate Layer (4-a) Preparation of Coating Solution for Intermediate Layer (1) 4 g of 15% PVA aqueous solution, 3 g of distilled water, 0.5 g of 2% surfactant (3) aqueous solution, and ultraviolet absorbent latex ( 1)
And 3 g, to prepare a coating solution for the intermediate layer (1). (4-b) Preparation of coating solution for intermediate layer (2) 4 g of 15% aqueous PVA solution, 3 g of distilled water, 0.5 g of 2% surfactant (3) aqueous solution, and ultraviolet absorbent latex (2)
And 4 g of the mixture to prepare a coating solution for the intermediate layer (2). 5. Preparation of Coating Solution for Protective Layer (5-a) Preparation of Coating Solution for Protective Layer (1) 4.5 g of 10% gelatin aqueous solution and 1.5 g of distilled water and 2%
Surfactant (3) aqueous solution (0.5 g), 1% 2,4-dichloro-6-hydroxy-s-triazine sodium salt aqueous solution (1.5 g) and Syloid 72 (FUJI-DEVI)
SON CHEMICAL LTD. Co., Ltd.) and Snowtex N1g in such an amount that the application amount becomes 50 mg / m ^2.
Were mixed to prepare a coating solution for the protective layer (1). The chemical structural formula of the compound used in the present invention is shown below.

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[0126]

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[Adjustment and Evaluation of Photosensitive / Heat-Sensitive Recording Material] Example 1 A support was prepared by extrusion laminating the following sheets on both sides of a paper base material.

Light- and heat-sensitive recording layer side sheet Solid stretched polypropylene core (about 73% of total sheet thickness)
And a composite sheet (38 μm) having, on both sides thereof, a stretched polypropylene layer (titanium dioxide content: 30% by weight) without fine voids and colored with titanium dioxide.
m Thickness) BICOR 70 MLT (Mobil Chemical)
al Co. A coating solution for a photosensitive and heat-sensitive layer (1)
Using a coating bar, the dry weight of the coating layer was 3 g /
m ² and dried at 30 ° C. for 10 minutes.
On this layer, the intermediate layer (1) was coated and dried so that the dry weight was 5 g / m ² , and then the coating solution for the photosensitive and heat-sensitive layer (2)
Is applied and dried so that the dry weight becomes 8 g / m ² , and then the intermediate layer (2) is applied and dried so that the dry weight becomes 5 g / m ² , and the coating solution (3) for the light and heat sensitive layer is applied. 8 dry weight
g / m ² and dried, and then a coating solution for the protective layer (1) is applied thereon using a coating bar so that the dry weight of the coated layer is 5 g / m ² , and then at 30 ° C. 10
After drying for a minute, the sample of Example 1 was obtained. (Example 2) Example 1 except that the support was changed to the following:
A light and heat sensitive recording material was prepared in the same manner as described above.

The following sheet was extrusion-laminated on both sides of a paper substrate to form a composite support.

The light- and heat-sensitive recording layer side sheet OPAlyte 350 TW (Mobil Che
medical Co. ) Having a microvoided, stretched polypropylene core (about 73% of the total sheet thickness) and a titanium dioxide-colored, non-voided, stretched polypropylene layer on either side thereof 3-layer composite sheet (38 μm thickness)
(D = 0.62 g / cc), and the void inducing material is polybutylene terephthalate.

BICOR 70 MLT (Mobil Chemical)
al Co. ) A matte finish polypropylene sheet (18 μm thick) consisting of a solid stretched polypropylene core
(D = 0.9 g / cc). Comparative Example 1 A light and heat sensitive recording material was prepared in the same manner as in Example 1 except that the support was changed to the following polyethylene-coated paper. Production output of polyethylene coated paper 17k
3m width, average weight 169g treated by W corona discharge
/ M ² on a back surface of a paper substrate, using a cooling roll having a surface mat roughness of 10 μm, and using polyethylene (density 0.967 g).
/ Cm ³ HDPE 60wt%, density 0.923g / c
melting LDPE40wt%) resin of m ³ discharge film temperature of 33
Multilayer extrusion lamination was performed at 3 ° C. and a line speed of 250 m / min to provide a 27 μm thick polyethylene resin layer.

Next, using a cooling roll having a surface mat roughness of 0.7 μm on the surface of the paper substrate on which the coating solution is to be applied, LDPE (density 0.921 g / m ³ ratio 85) and titanium dioxide (ratio Line speed 2 of the composition of 15)
Extrusion lamination was performed at 50 m / min, and a water-resistant resin layer having a thickness of 28 μm was provided.
A 2 kW corona discharge treatment was performed to produce a support. <Evaluation> (1) Sharpness A resolving power test chart was printed on the prepared photosensitive and heat-sensitive recording material by blue exposure, green exposure, and red exposure, and thermally developed.
After fixing the image, the density of the yellow image, the magenta image, and the cyan image are measured with a microphone foreometer,
The value represented by the following equation was defined as the sharpness. Sharpness (%) = 100 × ((highest density−lowest density) of 10 lines / mm fine line print image) / ((highest density−lowest density) in large area portion) The larger this value is, the better the sharpness is To indicate that (2) Heat resistance Whether or not blisters were formed on the support after thermal development was visually inspected. × indicates impractical, ○ indicates excellent.

Table 1 shows the results.

[0134]

[Table 1]

It can be seen that the light and heat sensitive recording material of this example has excellent heat resistance. In addition, it can be seen that the sharpness of Example 2 using the composite sheet having minute voids on the light- and heat-sensitive recording layer side is extremely excellent.

[0136]

According to the recording material of the present invention, heat resistance is excellent.

Claims (5)

[Claims] An electron-donating colorless dye encapsulated in a thermoresponsive microcapsule, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, A negative photosensitive heat-sensitive recording material having a light-sensitive heat-sensitive recording layer containing a photocurable composition containing an electron-accepting color developer. 2. The stretched biaxially stretched polymer sheet is provided with a stretched polymer core layer having microvoids and at least one surface of the polymer core layer and having no microvoids colored with TiO _2. 2. A negative-type light- and heat-sensitive recording material according to claim 1, which is a composite sheet provided with a polymer surface layer. 3. The negative type according to claim 1, wherein the support is a composite support including a base sheet and the biaxially stretched polymer sheet provided on at least one surface of the base sheet. Light and heat sensitive recording material. 4. The negative-type light and heat sensitive recording material according to claim 3, wherein the support is formed by laminating the biaxially stretched polymer sheet on at least one surface of the base sheet by extrusion. 5. The negative photosensitive and thermosensitive recording material according to claim 1, wherein the biaxially stretched polymer sheet is formed of polypropylene.