JP2000221674A - Photopolymerizable composition, photosensitive and heat sensitive recording material and method for recording image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable composition excellent in sensitivity and shelf stability and a photosensitive and heat sensitive recording material capable of stably forming a high sensitivity and high contrast image in a perfectly dry processing system using infrared, blue to red laser and excellent in shelf stability. SOLUTION: The photopolymerizable composition contains a compound having a polymerizable group and microcapsules housing a photopolymerization initiator. When an image is recorded using the composition, heating is carried out before and after exposure. The photosensitive and heat sensitive recording material has a photosensitive and heat sensitive recording layer containing microcapsules housing a coloring component A and a photopolymerizable composition containing at least a compound B having a polymerizable group and a site which colors together with the coloring component A in the same molecule and microcapsules housing a photopolymerization initiator on the substrate. An image is recorded using the material through an exposure step in which a latent image is formed, a coloring step in which the coloring component is allowed to color by heating and a fixing step in which the formed image is fixed by irradiation with light and the photopolymerization initiator is decolored.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition,
The present invention relates to a single-color or multicolor light- and heat-sensitive recording material and an image recording method capable of using various light sources in the ultraviolet to infrared region, specifically, a photopolymerizable composition having excellent sensitivity and storage stability, sensitivity, contrast and The present invention relates to a light- and heat-sensitive recording material having a high whiteness in a non-image portion and excellent storage stability, and an image recording method using the same.

[0002]

2. Description of the Related Art Conventionally, various dry-type image forming methods which do not use a liquid developer or the like and do not generate waste have been studied, and among them, a method using a composition which is cured by light has attracted attention. I have. In this method, a latent image is formed by curing a composition that is cured by light contained in a recording material by exposing, while a color is formed by heating or contained in an unexposed portion of the recording material. It is characterized in that components acting on the decoloring reaction move in the recording material to form a color image. When using a recording material of such a type, first, light is exposed onto the recording material through an image original, and the exposed portion is cured to form a latent image, and then the recording material is heated to form an uncured portion. (Unexposed part)
Is moved to form a visible image. According to this method, a complete dry system that does not generate waste can be realized.

There are several types of recording materials used in the above-mentioned system, and the system is characterized as a black-and-white image recording system. In particular, a system useful for a color image recording material is used. It is. Above all, for example,
A two-component type light- and heat-sensitive color recording material disclosed in JP-A-89915 is known. This is a thermosensitive recording material containing, as two components, for example, an electron-accepting compound and an electron-donating colorless dye, and containing a photocurable composition inside or outside a microcapsule, or both. However, even if this recording material sufficiently cures the photocurable composition contained in the microcapsules, the color development in the cured portion cannot be sufficiently suppressed, so that the non-image portion is colored, Contrast tends to decrease.

As a recording material having no coloring in the non-image area,
For example, it comprises a layer containing a photopolymerizable composition comprising a vinyl monomer having an acidic group and a photopolymerization initiator, an isolation layer, and an electron-donating colorless dye disclosed in JP-A-61-123838. Recording materials in which layers are stacked are known. In the case of this recording material, the non-image portion, that is, the portion cured by the photopolymerization reaction has no heat diffusion property of the acidic group and the non-image portion is not colored, but on the other hand, the disadvantage that the color density itself is slightly low. is there.

As a method for obtaining a negative image by the same method, there is a recording material disclosed in JP-A-60-119552. This is a recording material in which a photopolymerizable composition comprising a monomer or prepolymer for bleaching a dye and a photopolymerization initiator, and a dye that is bleached by the monomer or the prepolymer are present in isolation. The recording material also has no coloring in the non-image area as in the case of the above-mentioned recording material, but has a drawback that the coloring density itself is slightly low.

In view of the above-mentioned drawbacks, the present applicant has previously disclosed in JP-A-3-87827 and JP-A-4-87827 as a recording material capable of reducing coloring in a non-image portion and obtaining a high image density. A recording material described in Japanese Patent Publication No. 211252 was proposed. As the former recording material, one of the two components in the two-component type heat-sensitive and heat-sensitive coloring recording material is encapsulated in a microcapsule, and the other is a polymerizable compound constituting a photopolymerizable composition having a photopolymerization initiator, Alternatively, the other is a recording material that is contained outside the microcapsules together with the photopolymerizable composition having a photopolymerization initiator, and the latter recording material includes a microcapsule containing an electron-donating colorless dye, This is a photosensitive and heat-sensitive recording material in which a layer having an electron-accepting compound, a polymerizable vinyl monomer and a photocurable composition containing a photopolymerization initiator is provided outside the capsule. A color image can also be recorded by using such a photosensitive and heat-sensitive recording material as a recording material in which a plurality of recording layers having mutually different photosensitive wavelengths and coloring hues are laminated on a support.

However, the photopolymerization initiator may be destabilized due to environmental effects, and the polymerization reaction may progress gradually with time even in an unexposed state, or the sensitivity may fluctuate due to destabilization of the photopolymerization initiator itself. Tends to occur. Therefore, when such a tendency is assumed, a polymerization inhibitor must be used in combination even if it is apparent that the sensitivity is slightly lowered.
Further, there is a restriction that even a photopolymerization initiator useful for increasing the sensitivity cannot be used if it is unstable.

Although the above-mentioned photopolymerizable composition and photosensitive and heat-sensitive recording material can be applied to various uses, none of them can record images with a light source other than UV light or short-wave visible light, and is small and inexpensive. Use with an external laser or blue to red light was not possible.

Further, in order to enable high-speed and high-definition image formation, when a small and inexpensive infrared laser or blue to red light as described above is used, each irradiation light is absorbed in the recording layer. It is necessary to introduce a dye or the like having absorption in the ultraviolet to infrared region which is the wavelength. However, these dyes, etc.
Above all, when a pigment or the like that absorbs in the visible light region is used, the background portion is colored and only a low-quality image with low contrast can be obtained. On the other hand, if a dye or the like that absorbs in the near infrared region is used, the coloring of the background can be reduced, but there is a disadvantage that the corresponding laser is expensive.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a photopolymerizable composition having excellent sensitivity and storage stability. Also,
The present invention uses a blue-red laser or a small and inexpensive infrared laser in a completely dry processing system that does not require the use of a developer or the like and generates no waste, and has high sensitivity and high contrast. An object of the present invention is to provide a monochrome or color photosensitive and heat-sensitive recording material capable of forming a high-quality image and having excellent storage stability, and an image recording method using the same.

[0011]

The present inventors have conducted intensive studies on the composition of a composition which cures by photopolymerization (hereinafter referred to as "photopolymerizable composition"). By using a specific photopolymerization initiator as the photopolymerization initiator contained in the composition and enclosing the photopolymerization initiator in microcapsules, the photopolymerization sensitivity and storage stability of the photopolymerizable composition can be improved. By using this photopolymerizable composition in the recording layer of the light and heat sensitive recording material, it is possible to increase the sensitivity and contrast of the light and heat sensitive recording material, They have found that the storage stability can be improved, and have completed the present invention.
In addition, after exposing to a desired image shape, curing the photopolymerizable composition to form a latent image, and heating, the color forming component is colored to form an image, and the image forming method of the light and heat sensitive recording material for forming an image is eagerly discussed. As a result of the examination, by further irradiating the surface of the recording layer after image formation with light, the formed image can be fixed and the photopolymerization initiator component remaining in the recording layer can be decolorized. By using a photosensitive and heat-sensitive recording material having a photosensitive composition, it is possible to further improve the photo-decoloring property with respect to the remaining photopolymerization initiator component, and to stabilize a high-contrast image having excellent whiteness in a non-image area. Can be obtained. The means for solving the above problems are as follows. That is,

<1> A photopolymerizable composition comprising a thermoresponsive microcapsule containing a photopolymerization initiator and a compound having a polymerizable group outside the microcapsule. <2> The above-mentioned <1>, wherein the photopolymerization initiator is a photopolymerization initiator containing a spectral sensitizing compound having a maximum absorption wavelength at 300 to 1000 nm and a compound interacting with the spectral sensitizing compound. It is a photopolymerizable composition of the description. <3> The above <2>, wherein at least one of the compounds interacting with the spectral sensitizing compound is an organic borate salt compound.
3. The photopolymerizable composition according to item 1. <4> In an image recording method using the photopolymerizable composition, the photopolymerizable composition is the photopolymerizable composition according to any one of <1> to <3>, and is exposed imagewise. After forming, an image is formed by heating and curing the entire exposed portion to form an image, or after heating the photopolymerizable composition, exposing the heated portion imagewise and curing to form an image. It is a recording method.

<5> A substance having a color-forming component A encapsulated in a thermoresponsive microcapsule and at least a polymerizable group in the same molecule and a site that reacts with the color-forming component A to form a color on a support. This is a light- and heat-sensitive recording material having a light- and heat-sensitive recording layer containing a photopolymerizable composition containing a colorless compound B and a photopolymerization initiator encapsulated in thermoresponsive microcapsules.

<6> A color-forming component A encapsulated in a thermoresponsive microcapsule on a support, and at least a substantially colorless compound C which reacts with the color-forming component A to form a color.
And a polymerizable group, the coloring component A and the compound C in the same molecule.
A photosensitive and heat-sensitive recording layer containing a substantially colorless compound D having a site that inhibits the reaction with a compound, a photopolymerization initiator encapsulated in thermoresponsive microcapsules, and a photopolymerizable composition. This is a photosensitive and heat-sensitive recording material.

<7> When the photopolymerization initiator is 300 to 100
The photosensitive and heat-sensitive recording material according to <5> or <6>, which is a photopolymerization initiator containing a spectral sensitizing compound having a maximum absorption wavelength at 0 nm and a compound interacting with the spectral sensitizing compound. is there.

<8> The light- and heat-sensitive recording material according to <7>, wherein at least one of the compounds interacting with the spectral sensitizing compound is an organic borate compound.

<9> The photosensitive / thermosensitive recording material according to any one of the above items <5> to <8>, wherein the photosensitive / thermosensitive recording material is a multicolor multilayer photosensitive / thermosensitive recording material obtained by laminating photosensitive / thermosensitive recording layers which develop colors of different colors. Is a light and heat sensitive recording material.

<10> A multi-color, multi-layer, light- and heat-sensitive recording material is formed on a support by being exposed to light having a central wavelength of λ _{1 from} a light source toward a thickness direction of the light- and heat-sensitive recording layer from an incident surface of irradiation light. A first recording layer, a _second recording layer that is sensitive to light having a center wavelength λ ₂ and develops a color different from that of the first recording layer;
.., sensitive to light having a center wavelength λ _i , wherein the first, second,.
And a multi-layer light- and heat-sensitive recording material having a light- and heat-sensitive recording layer in which at least i ≧ 2 or more i-th recording layers that develop colors different from the (i-1) -th recording layer are sequentially laminated. <9> The light- and heat-sensitive recording material described in <9>.

<11> As the photosensitive / thermosensitive recording material, the photosensitive / thermosensitive recording material described in any of the above <5> to <10> is used, and at least an exposure at which the photopolymerizable composition forms a latent image by image exposure. Step, the color forming component is colored according to the latent image by heating, the color forming step of forming an image, the fixing step of irradiating the surface of the recording layer with light to fix the formed image, and decolorizing the photopolymerization initiator component, An image recording method comprising:

<12> The photosensitive / thermosensitive recording material of the above <9> or <10> is used as the photosensitive / thermosensitive recording material, and at least an exposure step in which the photopolymerizable composition forms a latent image by image exposure; The color forming component forms a color according to the latent image, and a color forming step of forming an image, and a fixing step of irradiating the surface of the recording layer with light to fix the formed image and decolorizing the photopolymerization initiator component, and The exposing step is an image exposing step using a plurality of light sources having different wavelengths, and the color forming step is different in hue depending on each latent image formed on the photosensitive and heat-sensitive recording layer having a different color hue by heating. The image recording method is characterized in that it is a step of forming a multi-color image by developing a color.

<13> Exposure step is 300 to 1000
The image recording method according to <11> or <12>, wherein the image-forming is performed by exposing the image using a laser light source having a wavelength of nm.

<14> In the fixing step, the surface of the recording layer is irradiated with light using a light source having a wavelength in the range of the maximum absorption wavelength of the photopolymerization initiator contained in the light and heat sensitive recording material ± 50 nm to form a formed image. The image recording method according to any one of the above items <11> to <13>, which is a step of fixing and decoloring the photopolymerization initiator component.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable composition of the present invention contains a photopolymerization initiator and a compound having a polymerizable group, and is used by encapsulating the photopolymerization initiator in microcapsules. . In the light- and heat-sensitive recording material of the present invention, the light- and heat-sensitive recording layer is formed by using a photopolymerization initiator encapsulated in microcapsules in a photopolymerizable composition constituting the light- and heat-sensitive recording layer and providing the light- and heat-sensitive recording layer on a support. You. In the image recording method of the present invention, for the photopolymerizable composition of the present invention, after imagewise exposure, by heating and curing the entire exposed portion, or after heating the photopolymerizable composition, By exposing the heating part imagewise and curing it,
Form an image. Further, in the image recording method of the present invention, the photosensitive and heat-sensitive recording material of the present invention comprises, at least, an exposure step in which a photopolymerizable composition forms a latent image by image exposure, and a coloring component is turned into a latent image by heating. Color according to
The method includes a color forming step of forming an image, and a fixing step of irradiating the surface of the recording layer with light to fix the formed image and decolorize the coloring component in the photopolymerizable composition of the present invention. Hereinafter, the photopolymerizable composition of the present invention and the photosensitive and heat-sensitive recording material of the present invention using the same will be described in detail, and the image recording method of the present invention will be clarified.

<Photopolymerizable composition and image recording method> The photopolymerizable composition of the present invention comprises a photopolymerization initiator and a compound having a polymerizable group. Use in capsules. As the photopolymerizable composition, from the viewpoint of improving the photopolymerization sensitivity at the time of light irradiation, it is preferable to use a photopolymerization initiator and a compound having a polymerizable group in the presence of, but the photopolymerization initiator If the stability to acidic groups contained in the compound having a polymerizable group or the like is low, a photopolymerizable composition having sufficient storage stability during raw storage cannot be formed. Therefore, by encapsulating the photopolymerization initiator in microcapsules as described above, coexisting in the same system, having an acid component such as an acidic group, and isolating from the compound having a polymerizable group, the photopolymerizable composition It is possible to improve the storage stability during raw storage of a product.

The photopolymerization initiator encapsulated in the microcapsules generates radicals upon exposure to light, and when heated, reduces the viscosity in the layer and promotes the diffusion of the radicals. As a result of the rapid progress of the polymerization reaction of the compound having the compound, the photopolymerizable composition in that portion is cured to form a latent image having a desired image shape.

When the photopolymerization initiator is encapsulated in microcapsules, the microcapsules formed are not particularly limited, and can be encapsulated by a conventionally known method for producing microcapsules. For example, a method utilizing coacervation of a hydrophilic wall forming material described in U.S. Pat. Nos. 2,800,457 and 2,800,458, U.S. Pat. No. 3,287,154, and British Patent 990443.
No. 38-19574, 42-446, 42-771, U.S. Pat.
Nos. 18250 and 3660304, a method using polymer precipitation, a method using a isocyanate polyol wall material described in U.S. Pat. No. 3,796,669, a method using an isocyanate wall material described in U.S. Pat. No. 3,914,511, U.S. Pat. , 40873
Nos. 76 and 4089802, a method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall-forming material, and a melamine-formaldehyde resin described in U.S. Pat. In situ method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079, UK Patent No. 95
Nos. 2807 and 965074, the electrolytic dispersion cooling method described in US Pat. No. 3,111,407, and British Patent No. 9304.
Spray drying method described in No. 22, JP-B 7-73
No. 069, JP-A-4-101885, JP-A-9-26
No. 3057.

The method for microencapsulation is not limited to these, but in the photopolymerizable composition of the present invention, in particular, the photopolymerization initiator is added to a hydrophobic organic solvent serving as a core of the capsule. The oil phase prepared by dissolution or dispersion is mixed with an aqueous phase in which a water-soluble polymer is dissolved, emulsified and dispersed by a homogenizer or the like, and then heated to cause a polymer formation reaction at the oil droplet interface, It is preferable to employ an interfacial polymerization method for forming a microcapsule wall of a polymer substance. According to the interfacial polymerization method, a capsule having a uniform particle size can be formed in a short time, and a recording material having excellent raw storability can be obtained. As a specific method for producing a microcapsule having a photopolymerization initiator as a core of the capsule, it can be produced by a microencapsulation method described later. That is, the production of the microcapsules containing the photopolymerization initiator used in the photopolymerizable composition of the present invention is used for the light-sensitive and heat-sensitive recording material of the present invention, and a method for preparing microcapsules containing the photopolymerization initiator described below. It can be manufactured by a similar method.

As the microcapsules in the photopolymerizable composition of the present invention, the contact between substances inside and outside of the capsules is caused by the substance sequestering action of the microcapsule wall (hereinafter sometimes simply referred to as “capsule wall”) under normal temperature environment. In such a way that the substance inside and outside the capsule can only be contacted when heat is applied above a certain value. This phenomenon is caused by appropriately selecting the material of the capsule wall, the capsule core substance (the substance contained in the capsule), the additives, etc.
It can be freely controlled as a change in the physical properties of the capsule.

The capsule wall material which can be used in the present invention is added inside and / or outside the oil droplets. As the material of the capsule wall, for example, polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, melamine-formaldehyde resin, gelatin, Examples include inorganic substances such as silica, hydrophobic polymers such as styrene, and nylon. Among them, polyurethane, polyurea, polyamide, polyester, and polycarbonate are preferable, and polyurethane and polyurea are particularly preferable. The above-mentioned polymer substances can be used in combination of two or more kinds.

Examples of the water-soluble polymer include gelatin, polyvinylpyrrolidone, and polyvinyl alcohol.

For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and a second substance (for example, polyol or polyamine) which reacts with the polyisocyanate to form a capsule wall may be mixed with a water-soluble polymer aqueous solution (aqueous phase) or After mixing in an oily medium (oil phase) to be encapsulated, emulsifying and dispersing in water, and then heating, a polymer forming reaction occurs at the oil droplet interface to form microcapsule walls.

Examples of the polyvalent isocyanate and the polyol and polyamine to be reacted therewith are US Pat. Nos. 3,281,383, 3,737,695 and 3,7932.
No. 68, JP-B-48-40347, JP-B-49-2415
9, JP-A-48-80191 and JP-A-48-84086.
The one described in the item can be used.

The average particle size of the microcapsules containing the photopolymerization initiator is preferably 10 μm or less, and is 1.0 μm or less from the viewpoint of increasing the specific surface area so that the generated radicals can efficiently diffuse out of the capsules. Is more preferable. On the other hand, if the average particle size of the microcapsules is too small, the surface area with respect to a certain solid content increases, and a large amount of a wall material is required. Therefore, the average particle size is preferably 0.1 μm or more.

The photopolymerization initiator can be appropriately selected from known ones.
A compound containing a spectral sensitizing compound having a maximum absorption wavelength at 00 nm and a compound interacting with the spectral sensitizing compound is preferable. However, if the compound interacting with the spectral sensitizing compound is a compound (dye / boron compound) having both a structure of a dye portion having a maximum absorption wavelength of 300 to 1000 nm and a structure of a borate portion in the structure thereof, A sensitizing dye may not be used.

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 according to 7 to 25 lines); U.S. Pat. No. 4,950,581 (column 18, aromatic sulfonium or iodonium salts described in the 60th row to the column 19, line 10); (eta ⁶ - A cyclopentadienyl-arene iron (II) complex salt such as isopropylbenzene)-(η ⁵ -cyclopentadienyl) -iron (II) hexafluorophosphate can be preferably used.

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. By selecting any desired dye from the spectral sensitizing dye in the wavelength region, by adjusting the photosensitive wavelength to suit the light source used,
High sensitivity can be obtained, and a blue, green, or red light source, an infrared laser, or the like can be suitably selected as a light source used for image exposure. Therefore, for example, when a multicolor light- and heat-sensitive recording material is formed by laminating single-color light- and heat-sensitive recording layers that develop different hues, and a color image is formed, different single-color layers having different color hues are used. By using a spectral sensitizing dye having an absorption wavelength and using a light source adapted to the absorption wavelength, each layer (each color) can have a high sensitivity and a sharp image even in a multi-color multilayer light- and heat-sensitive recording material. Since it can be formed, high sensitivity and high sharpness can be achieved as a whole of the multicolor photosensitive and heat-sensitive recording material.

Known compounds can be used as the spectral sensitizing dye. Specific examples of the spectral sensitizing dye include a compound that interacts with a spectral sensitizing compound described below.
And the “Research Discl”
ogure, Vol. 200, December 1980, It
em 20036 ”and“ sensitizers ”(p. 160-p. 16)
3, Kodansha; Katsumi Tokumaru, Shin Okawara / ed., 1987).

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, a merocyanine compound.

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. Sex styryl dyes.

Spectral sensitizing dyes include coumarin (including ketocoumarin or sulfonocoumarin) 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, 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 spectral sensitizing dye, the spectral sensitivity of the photopolymerization initiator of the present invention can be obtained in the ultraviolet to infrared region, and the photopolymerization sensitivity can be improved. The various spectral sensitizing dyes may be used alone or in combination of two or more.

The amount of the spectral sensitizing compound to be 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 photopolymerizable composition.

As the compound interacting with the spectral sensitizing compound, one or two of compounds capable of initiating a photopolymerization reaction of a compound having a polymerizable group in the photopolymerizable composition can be used.
More than one compound can be selected for use. By allowing this compound to coexist with the spectral sensitizing compound,
Sensitively sensitive to the irradiation light in the spectral absorption wavelength range, and can generate radicals with high efficiency, achieving higher sensitivity,
The generation of radicals can be controlled using any light source in the ultraviolet to infrared region. Examples of the compound interacting with the spectral sensitizing compound include an organic borate salt compound 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 and benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin phenyl ether; 2- (o-chlorophenyl) -4,5-diphenylimidazole duplex, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole duplex, 2- (o-fluorophenyl) -4,5-diphenylimidazole duplex, 2- (o-methoxyphenyl) -4,5-diphenylimidazole Mers, 2-
2,4,6-triarylimidazole duplex such as (p-methoxyphenyl) -4,5-diphenylimidazole duplex; polyhalogen compound such as carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone; JP-A-59-133428, JP-B-57-133
No. 1819, JP-B-57-6096, U.S. Pat.
A compound described in No. 15455;

2,4,6-tris (trichloromethyl)
-S-triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, 2-amino-4,6
-Bis (trichloromethyl) -S-triazine, 2-
JP-A-58-29803 such as (P-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine
S-triazine derivatives having a trihalogen-substituted methyl group described in (1);

Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, di-tert-butyldiperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) ) Hexane, tert-butylperoxybenzoate, a, a'-bis (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 3,3 ', 4,4'-tetra- (tert-butylperoxycarbonyl) ) Japanese Patent Application Laid-Open No.
Organic peroxides described in No. 9-189340;

Azinium salt compounds described in US Pat. No. 4,743,530; tetramethylammonium salt of triphenylbutyrate borate, tetrabutylammonium salt of triphenylbutyrateborate, tetramethylammonium salt of tri (P-methoxyphenyl) butyrateborate Organic boron compounds described in European Patent No. 0223587; other diaryliodonium salts, iron allene complexes, and the like.

Also, a combination of two or more compounds is known, and these can be used in the photopolymerizable composition of the present invention. Examples of the combination of two or more compounds include a combination of a 2,4,5-triarylimidazole dimer and a mercaptobenzoxazole and the like, and the 4,4′- described in US Pat. No. 3,427,161. Combination of bis (dimethylamino) benzophenone and benzophenone or benzoin methyl ether, benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromerchi) -6- (4'-) described in U.S. Pat. No. 4,239,850. Methoxyphenyl)-
Combinations of triazoles, combinations of dialkylaminobenzoic acid esters and dimethylthioxanthone described in JP-A-57-23602, and 4,4'-bis (dimethylamino) benzophenone and benzophenone described in JP-A-59-78339. And three kinds of combinations of a compound and a polymethyl halide compound.

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

Among the compounds interacting 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 preferable. A system borate salt compound is more preferable.

When a compound interacting with the spectral sensitizing compound is used in combination with the spectral sensitizing compound, a radical can be locally and effectively generated in the exposed portion at the time of exposure, thereby increasing the 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 are shown below, but the present invention is not limited thereto.

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Further, in the photopolymerizable composition of the present invention, the above-mentioned “Functional Dye Chemistry” (1981, CMC Publishing Co., p.
393-p. 416) and “colorants” (60 [4] 212-2).
24 (1987)) and the like, and a spectral dye-based organic borate compound (borate compound II) which can be obtained from the cationic dye described in JP-A No. 24 (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 absorption function of the dye part and polymerizes by the radical release function of the borate part. It has the three functions of accelerating the reaction 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 I obtained from the organic cationic dye can be obtained by using an organic cationic dye and an organic boron compound anion and referring 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, but the present invention is not limited thereto.

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The above borate compound II is, as described above,
Although it is a multifunctional compound, from the viewpoint of obtaining high photopolymerization sensitivity and sufficient storage stability, in the photopolymerizable composition of the present invention, the photopolymerization initiator includes a spectral sensitizing compound and the spectral sensitizing compound. It is preferred that the compound is appropriately combined with a compound that interacts with the sensitizing compound. In this case, as the photopolymerization initiator, the photopolymerization initiator (1) obtained by combining the spectral sensitizing compound and the borate compound I, or the borate compound I
Photoinitiator in which the compound is combined with a borate compound II (2)
Is more preferable.

At this time, the use ratio of the spectral sensitizing dye and the organic borate compound present in the photopolymerization initiator is improved to improve the photopolymerization sensitivity, to increase the sensitivity when used in a light and heat sensitive recording material, and to improve the image formation. This is very important in obtaining sufficient decoloring property by light irradiation when a fixing step described below is provided in the step.
In the case of the photopolymerization initiator (1), in addition to the spectral sensitizing compound / borate compound I ratio (= 1/1: molar ratio) necessary for the photopolymerization reaction, the photopolymerization initiator further contains When the process has a fixing step described below, it is sufficient to add the borate compound I in an amount necessary to sufficiently decolor the remaining spectral sensitizing compound. It is particularly preferable from the viewpoint of obtaining the sensitivity at the time of the above and the decoloring property when the fixing step described later is provided in the image forming step. That is, the ratio of the used amount of the spectral sensitizing dye / the borate compound I is preferably 1/1 to 1/50, and 1 / 1.2 to 1/50.
30 is more preferable, and 1 / 1.2 to 1/20 is most preferable. If the ratio is less than 1/1, sufficient polymerization reactivity and decolorability may not be obtained, and 1/50
If the ratio exceeds the above range, the performance may be saturated due to instability due to crystal precipitation of the borate compound or the like, or the use amount may be excessive, and the suitability for coating may be deteriorated.

In the case of the photopolymerization initiator (2), it is preferable to use the borate compound I and the borate compound II in combination such that the borate portion is at least equimolar to the dye portion. It is particularly preferable from the viewpoints of obtaining sufficient photopolymerization sensitivity and high sensitivity when a photosensitive and heat-sensitive recording material is used, and obtaining sufficient decoloring performance by light irradiation when a fixing step described below is provided in the image forming step. The ratio of the amount of the borate compound I / the amount of the borate compound II is preferably from 1/1 to 50/1, more preferably from 1.2 / 1 to 30/1.
2/1 to 20/1 is most preferred. When the ratio is less than 1/1, the generation of radicals is small, and sufficient polymerization reactivity, sensitivity and decoloring performance when a photosensitive and heat-sensitive recording material is obtained may not be obtained, and the ratio exceeds 50/1. In some cases, sufficient sensitivity may not be obtained.

The total amount of the spectral sensitizing compound and the compound interacting with the spectral sensitizing compound in the photopolymerizable composition is as follows:
0.1 to 20 with respect to the amount of the compound having a polymerizable group used.
% By weight, more preferably 0.1 to 10% by weight, and most preferably 0.1 to 5% by weight. The usage amount is
When the content is less than 0.1% by weight, sufficient photopolymerization sensitivity and high sensitivity of the light- and heat-sensitive recording material are obtained, and sufficient decoloring performance by light irradiation when a fixing step described below is provided in the image forming step is obtained. If the content exceeds 20% by weight, the storage stability of the photopolymerizable composition and the light- and heat-sensitive recording material may be reduced, and the coating suitability for producing the light- and heat-sensitive recording material may be lowered.

The photopolymerizable composition of the present invention may further contain, as an auxiliary agent, a reducing agent such as an oxygen scavenger or a chain transfer agent of an active hydrogen donor or a chain transfer agent for the purpose of accelerating the polymerization reaction. Other compounds that promote the polymerization can also be added. Examples of the oxygen removing agent include phosphine, phosphonate, phosphite, a first silver salt, and other compounds easily oxidized by oxygen. Specifically, N-phenylglycine, trimethylparbituric acid, N, N-dimethyl-
2,6-diisopropylaniline, N, N, N-2,
4,6-pentamethylanilic acid is mentioned. Further, thiols, thioketones, trihalomethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, azides and the like are also useful as polymerization accelerators.

Next, the compound having a polymerizable group contained in the photopolymerizable composition of the present invention will be described. The compound having a polymerizable group is a compound having at least one ethylenically unsaturated bond in a structure, and undergoes a photopolymerization reaction by receiving a radical released from the photopolymerization initiator by light irradiation. And all materials capable of curing the film. Examples of the compound having a polymerizable group include a polymerizable group such as a photopolymerizable monomer and a prepolymer such as a dimer, trimer or other oligomer thereof, a mixture thereof, or a copolymer. And the like.

The photopolymerizable monomer (hereinafter, referred to as “photopolymerizable monomer”) can be appropriately selected from known photopolymerizable monomers, and among them, at least one vinyl monomer in the molecule. Photopolymerizable monomers having a group are preferred. Further, the photopolymerizable monomer, for example,
For example, when used in a light- and heat-sensitive recording material having an electron-donating colorless dye as a color-forming component, it has a function of suppressing the reaction between the electron-donating colorless dye and an electron-accepting compound that forms a color by reacting therewith. Photopolymerizable monomer (hereinafter referred to as
It may be referred to as “photopolymerizable monomer D ¹ ”. Is more preferable, and when used in a light- and heat-sensitive recording material having a diazonium salt compound as a color-forming component, for example, a photopolymerizable monomer having an acidic group having an effect of suppressing a coupling reaction and not being a metal salt compound (hereinafter, referred to as “ Photopolymerizable monomer D ² ”may be used.). However, the photopolymerizable monomers D ¹ and D ² are not limited to the case where they are used in combination with an electron-donating colorless dye or a diazonium salt compound.
Can be used alone.

Examples of the photopolymerizable monomer D ¹ include acrylic acid and salts thereof, acrylic esters with aliphatic polyhydric alcohol compounds, polyhydric phenols such as resorcinol, pyrogallol and phloroglucinol, and bisphenols. And acrylamides with aliphatic polyamines; methacrylic acid and its salts, methacrylic esters with aliphatic polyhydric alcohol compounds, polyphenols such as resorcinol, pyrogallol, and phloroglucinol; Methacrylic esters with bisphenols, methacrylamides with aliphatic polyamines; acrylate or methacrylate terminated epoxy resins; acrylate or methacrylate terminated polyesters;

Maleic anhydrides and maleic esters with aliphatic polyhydric alcohol compounds; itaconic acid and itaconic esters with aliphatic polyhydric alcohol compounds, with aliphatic polyhydric amines; crotonic acid and aliphatic polyhydric amines Crotonic esters with polyhydric alcohol compounds; isocrotonic acid, isocrotonic esters with aliphatic polyhydric alcohol compounds; styrenes; vinyl ethers; vinyl esters; N-vinyl heterocycles; aryl ethers; And the like. Examples of the salt of each of the unsaturated acids include a sodium salt and a potassium salt.

Of the above, it is preferable to use a photopolymerizable monomer having a plurality of vinyl groups in the molecule, and examples thereof include the following compounds. Examples of the acrylate include ethylene glycol diacrylate, triethylene glycol triacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, penta Erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate,
Sorbitol hexaacrylate, polyester acrylate oligomer and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate,
3-butanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis- [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] Dimethylmethane, bis- [p- (acryloxyethoxy) phenyl] dimethylmethane and the like.

Examples of the itaconate include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate,
Examples include tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. As crotonic esters,
For example, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetracrotonate and the like can be mentioned. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of amides with acrylic acid or methacrylic acid include, for example, methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriaminetris Acrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like can be mentioned.

In addition, for example, Japanese Patent Publication No. 48-41708
Described in JP-vinyl urethane compounds having two or more isocyanate groups in one molecule, CH ₂ = C
(R ³¹ ) COOCH ₂ CH (R ³² ) OH wherein R ³¹ and R ³² represent H or CH ₃ . And a vinyl urethane compound having two or more polymerizable vinyl groups in one molecule to which a vinyl monomer having a hydroxyl group is added. Further, a polymer compound having a vinyl group or a vinylidene group, for example, a polymer compound having a hydroxyl group, an amino group, an epoxy group, a halogen atom, a sulfonyloxy group in a side chain and acrylic acid, methacrylic acid, or a derivative thereof And the like. Furthermore, compounds containing a vinyl group in the molecule of a color image forming substance, for example, a dye or a leuco dye, can also be used as the polymerizable compound.

Among them, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate and diethylene glycol dimethacrylate are particularly preferable. .

The molecular weight of the photopolymerizable monomer D ¹ is preferably about 100 to about 5000, and about 300 to about 2
000 is more preferred.

Examples of the photopolymerizable monomer D ² include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, zinc β-methacryloxyethoxysalicylate, zinc β-acryloxyethoxysalicylate, vinyloxyethyloxybenzoic acid, β -Methacryloxyethyl orselinate, β-acryloxyethylorselinate, β-methacryloxyethoxyphenol, β-acryloxyethoxyphenol, β-methacryloxyethyl-β-resorcinate, β-acryloxyethyl-β-resorcinate , Hydroxystyrenesulfonic acid-N-ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p-hydroxybenzoate, methacryloxymethylphenol, acryloyl Shi-methyl phenol,
Methacrylamidopropanesulfonic acid, acrylamidopropanesulfonic acid, β-methacryloxyethoxy-dihydroxybenzene, β-acryloxyethoxy-dihydroxybenzene, γ-styrenesulfonyloxy-β
-Methacryloxypropanecarboxylic acid,

Γ-acryloxypropyl-α-hydroxyethyloxysalicylic acid, β-hydroxyethynylphenol, β-methacryloxyethyl-p-hydroxycinnamate, β-acryloxyethyl-p-hydroxycinnamate, 3,5 Distyrenesulfonic acid amide phenol, methacryloxyethoxyphthalic acid, acryloxyethoxyphthalic acid, methacrylic acid, acrylic acid,
Methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid, 3-β-hydroxyethoxyphenol, β-methacryloxyethyl-
p-hydroxybenzoate, β-acryloxyethyl-p-hydroxybenzoate,

Β′-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoic acid, β-acryloxyethyloxycarbonylhydroxybenzoic acid, N, N′-di-β-methacryloxyethylaminosalicylic acid , N, N'-di-β
-Acryloxyethylaminosalicylic acid, N, N'-di-β-methacryloxyethylaminosulfonylsalicylic acid, N, N'-di-β-acryloxyethylaminosulfonylsalicylic acid and the like are preferred.

Examples of the compound having a polymerizable group include an electron-accepting compound having a polymerizable group and a coupler compound having a polymerizable group. The electron-accepting compound having a polymerizable group, that is, the compound having an electron-accepting group and a polymerizable group in the same molecule, includes a polymerizable group and one of the color-forming components A. Any material can be used as long as it reacts with the donor colorless dye and develops a color, and can cure the film by photopolymerization.

Examples of the electron accepting compound having a polymerizable group include 3-halo-halides described in JP-A-4-226455.
4-hydroxybenzoic acid, methacryloxyethyl ester and acryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-63-173682, JP-A-59-83693, JP-A-60-141587 and JP-A-62.
-99190, an ester of benzoic acid having a hydroxy group with hydroxymethylstyrene, EP 2
No. 9323, hydroxy styrene described in
Nos. 167077 and 62-16708, N-vinylimidazole complexes of zinc halides, 63-31
Compounds that can be synthesized with reference to the electron-accepting compound described in No. 7558, and the like. Among these compounds having an electron-accepting group and a polymerizable group in the same molecule, 3-halo-4-hydroxybenzoic acid represented by the following general formula is preferable.

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[Wherein, X represents a halogen atom, and among them, a chlorine atom is preferable. Y is 1 having a polymerizable ethylene group
An aralkyl group having a vinyl group,
An acryloyloxyalkyl group or a methacryloyloxyalkyl group is preferable, and an acryloyloxyalkyl group having 5 to 11 carbon atoms or a methacryloyloxyalkyl group having 6 to 12 carbon atoms is more preferable. Z is a hydrogen atom,
Represents an alkyl group or an alkoxyl group. ]

Examples of the 3-halo-4-hydroxybenzoic acid include 3-chloro-4-hydroxybenzoic acid ester vinylphenethyl ester and 3-chloro-4-hydroxybenzoic acid ester
Hydroxybenzoic acid vinylphenylpropyl ester,
3-chloro-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-methacryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2 −
Acryloyloxypropyl) ester, 3-chloro-
4-hydroxybenzoic acid- (2-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (3-acryloyloxypropyl) ester,
3-chloro-4-hydroxybenzoic acid- (3-methacryloyloxypropyl) ester,

3-chloro-4-hydroxybenzoic acid
(4-acryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (4-methacryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (5-acryloyloxypentyl) ester, 3-chloro -4-hydroxybenzoic acid- (5-methacryloyloxypentyl) ester, 3-chloro-4
-Hydroxybenzoic acid- (6-acryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid- (6-methacryloyloxyhexyl) ester, 3
-Chloro-4-hydroxybenzoic acid- (8-acryloyloxyoctyl) ester, 3-chloro-4-hydroxybenzoic acid- (8-methacryloyloxyoctyl)
Esters and the like.

Examples of the compound having the electron accepting group and the polymerizable group in the same molecule include, for example, styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, β-methacryloxyethoxysalicylate, β
-Zinc acryloxyethoxysalicylate, vinyloxyethyloxybenzoic acid, β-methacryloxyethylorselinate, β-acryloxyethylorselinate, β
-Methacryloxyethoxyphenol, β-acryloxyethoxyphenol,

Β-methacryloxyethyl-β-resorcinate, β-acryloxyethyl-β-resorcinate, hydroxystyrenesulfonic acid-N-ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p -Hydroxybenzoate, methacryloxymethylphenol, acryloxymethylphenol, methacrylamidopropanesulfonic acid, acrylamidopropanesulfonic acid, β-
Methacryloxyethoxy-dihydroxybenzene, β-
Acryloxyethoxy-dihydroxybenzene, γ-styrenesulfonyloxy-β-methacryloxypropanecarboxylic acid,

Γ-acryloxypropyl-α-hydroxyethyloxysalicylic acid, β-hydroxyethynylphenol, β-methacryloxyethyl-p-hydroxycinnamate, β-acryloxyethyl-p-hydroxycinnamate, 3,5 Distyrenesulfonic acid amide phenol, methacryloxyethoxyphthalic acid, acryloxyethoxyphthalic acid, methacrylic acid, acrylic acid,
Methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid,

3-β-hydroxyethoxyphenol,
β-methacryloxyethyl-p-hydroxybenzoate, β-acryloxyethyl-p-hydroxybenzoate, β′-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoic acid, β-acryloxyethyloxy Carbonylhydroxybenzoic acid, N, N′-di-β-methacryloxyethylaminosalicylic acid, N, N′-di-β-acryloxyethylaminosalicylic acid, N, N′-di-β-
Methacryloxyethylaminosulfonylsalicylic acid,
N, N′-di-β-acryloxyethylaminosulfonylsalicylic acid and metal salts thereof (eg, zinc salt) can also be suitably mentioned.

Further, as the coupler compound having a polymerizable group, the coupler compound having a polymerizable group and one of the color forming components A may be used.
All of them can be mentioned as long as they can react with the diazonium salt compound to form a color and photopolymerize to cure the film. The coupler compound couples with the diazo compound in a basic atmosphere and / or a neutral atmosphere to form a dye, and according to various purposes such as hue adjustment,
A plurality of types can be used in combination. Hereinafter, specific examples of the coupler compound will be shown, but the present invention is not limited thereto.

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The coupler compound may be used by adding a water-soluble polymer together with other components and solid-dispersing it with a sand mill or the like, or may be emulsified with a suitable emulsifying aid and used as an emulsion. Here, the method of solid dispersion or emulsification is not particularly limited, and a conventionally known method can be used. For details of these methods, see JP-A-59-190886.
JP-A-2-141279, JP-A-7-17145
No.

In the present invention, an organic base such as a tertiary amine, piperidine, piperazine, amidine, formamidine, pyridine, guanidine or morpholine is used for the purpose of accelerating the coupling reaction. Is preferred.

As the organic base, for example, N, N '
-Bis (3-phenoxy-2-hydroxypropyl) piperazine, N, N'-bis [3- (p-methylphenoxy) -2-hydroxypropyl] piperazine, N, N '
-Bis [3- (p-methoxyphenoxy) -2-hydroxypropyl] piperazine, N, N'-bis (3-phenylthio-2-hydroxypropyl) piperazine, N,
N′-bis [3- (β-naphthoxy) -2-hydroxypropyl] piperazine, N-3- (β-naphthoxy)-
2-hydroxypropyl-N′-methylpiperazine,

Piperazines such as 1,4-bis {[3- (N-methylpiperazino) -2-hydroxy] propyloxy} benzene; N- [3- (β-naphthoxy) -2;
-Hydroxy] propylmorpholine, 1,4-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, 1,3-bis [(3-morpholino-2-
Morpholines such as (hydroxy) propyloxy] benzene, piperidines such as N- (3-phenoxy-2-hydroxypropyl) piperidine and N-dodecylpiperidine, triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenylguanidine, 4
-Hydroxybenzoic acid 2-N-methyl-N-benzylaminoethyl ester, 4-hydroxybenzoic acid 2-N,
N-di-n-butylaminoethyl ester, 4- (3-
(N, N-dibutylaminopropoxy) benzenesulfonamide, 4- (2-N, N-dibutylaminoethoxycarbonyl) phenoxyacetic acid amide and the like. These organic bases may be used alone or in combination of two or more.

These are disclosed in JP-A-57-123086,
JP-A-60-49991, JP-A-60-94381
JP-A-9-71048, JP-A-9-77729
And JP-A-9-77737.

The amount of the organic base to be used is not particularly limited, but is preferably from 1 to 30 based on 1 mol of the diazonium salt.
It is preferred to use it in the molar range.

Further, a coloring aid may be added for the purpose of accelerating the coloring reaction. Examples of the coloring aid include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, and sulfonamide compounds. These compounds reduce the melting point of the coupler compound or the basic substance, or have the effect of improving the heat permeability of the microcapsule wall,
It is considered that high color density can be obtained.

The photopolymerizable composition of the present invention may contain, if necessary, the same components as those usable for the photopolymerizable composition in the light and heat sensitive recording material of the present invention described below. Can be. The amounts of other components other than the photopolymerization initiator and the compound having a polymerizable group are the same as in the case of the light- and heat-sensitive recording material of the present invention described later.

As a mode of use of the photopolymerizable composition of the present invention, a binder or the like may be added and the photopolymerizable composition itself may be used as it is as a recording material, or the photopolymerizable composition may be prepared into a coating liquid. When coated on a support or the like, it can be used as a photosensitive material such as an alkali development or water development type lithographic printing plate or various color proof materials.
As a support and a coating method for coating on the support, the same materials as in the case of the light- and heat-sensitive recording material of the present invention described later can be used.

In the image recording method of the present invention, the photopolymerizable composition of the present invention is used, the photopolymerizable composition is imagewise exposed, and the entire exposed portion is heated and cured. After heating the photopolymerizable composition, the heated portion is imagewise exposed and cured to form a latent image of a desired image.

When the photopolymerizable composition of the present invention is imagewise exposed and then heated to cure the entire exposed portion to form an image, first, the photopolymerizable composition is present in the capsule in the photopolymerizable composition by exposure. By generating radicals from the photopolymerization initiator and then supplying heat, the permeability of the material membrane of the microcapsules is increased, and the diffusion of the radicals is promoted as the viscosity in the system is reduced, so that the radicals are present outside the capsule. The polymerization reaction of the compound having a polymerizable group is accelerated. That is, when radicals are generated in the microcapsules in the exposure unit, the radicals are released around the capsules by heating, and are cured around the capsules to form an image. Therefore, not only the storage stability is improved by the encapsulation, but also the photopolymerization sensitivity at the time of recording can be improved.

On the other hand, when the photopolymerizable composition of the present invention is heated and then the heated portion is imagewise exposed and cured to form an image, first, the microcapsules containing the photopolymerization initiator by heating are formed. Improves the permeability of the material on the capsule wall and at the same time reduces the viscosity of the system, then releases the radicals generated during the exposure directly to the outside of the capsule by imagewise exposure, and immediately cures around the capsule. And
An image is formed. Therefore, as described above, not only the storage stability is improved by the encapsulation, but also the photopolymerization sensitivity at the time of recording can be improved. In this case, it is not always necessary to heat the entire photopolymerizable composition, but it is sufficient that the imagewise exposure can be performed and only the portion where an image is formed can be heated.

Particularly, in the case of an image recording method in which the recording is performed by exposing after heating, radicals are generated in a state where the permeability of the material of the capsule wall is increased in advance, so that the loss of the generated radicals is minimized. Can be suppressed. Also, when necessary for image formation, only necessary parts are heated,
Highly active photopolymerization initiator and photopolymerizable monomer coexist,
A state where the photopolymerization initiator is in contact with the polymerizable monomer can be realized stably and can be used stably.

As a light source used for image formation in the exposure step, a light-absorbing material such as a spectral sensitizing compound having absorption in a specific region in a light- and heat-sensitive recording layer is used, so that a light source wavelength in an ultraviolet to infrared region is obtained. Can be appropriately selected from known light sources having a maximum absorption wavelength of 300 to
A light source in the range of 1000 nm is preferable, and a laser light source of blue, green, red or the like or an LED is more preferable in that the device can be simplified and reduced in size and cost can be reduced. In this case, from the viewpoint of achieving high sensitivity, it is preferable to appropriately select a light source having a wavelength suitable for the absorption wavelength of a light absorbing material such as a spectral sensitizing compound to be used. On the other hand, in each recording layer, by selectively using a light absorbing material suitable for the light source, a blue to red light source or a small and inexpensive infrared laser can be used, and the use thereof is expanded. In addition, high sensitivity and high sharpness can be achieved.

The heating method for heating can be appropriately selected from conventionally known methods. For example, the treatment can be performed by a heat roller or the like. The heating method is not particularly limited, and even a method of irradiating the entire surface of the recording layer at once, a method of gradually heating the recording surface by roller conveyance or the like, and finally heating a desired portion or the entire surface. However, any method that can heat the recording surface at a substantially uniform temperature may be used. Generally, the heating temperature is preferably from 80 to 200 ° C, and from 85 to 130 ° C.
C is more preferred. The heating time is from 1 second to 5 seconds.
Minutes are preferred, and 3 seconds to 1 minute are more preferred.

The photopolymerizable composition of the present invention can be exposed and heated as described above, and then developed with an alkali developer to form a final image. The developer is not particularly limited as long as it is an alkaline aqueous solution, and can be appropriately selected from known alkaline aqueous solutions and developers.

The method of the development treatment is not particularly limited, and the photopolymerizable composition of the present invention is immersed in a bath containing an alkali developing solution, or sprayed with the alkali developing solution. Or can be processed. The development temperature of the alkaline developer during development is preferably 5 to 40C. It is also effective to provide a fixing step as described below.

<Photosensitive and Thermosensitive Recording Material and Image Recording Method> The photosensitive and thermosensitive recording material used in the image recording method of the photosensitive and thermosensitive recording material of the present invention comprises (a) a thermoresponsive material having a color developing component A embedded on a support. A microcapsule, at least a substantially colorless compound B having a polymerizable group and a site that reacts with the color forming component A to form a color in the same molecule, and a thermoresponsive microcapsule including a photopolymerization initiator. And (b) a heat-responsive microcapsule containing a color-forming component A on a support, and A substantially colorless compound C which forms a color by reacting with the color forming component A
And a polymerizable group, the coloring component A and the compound C in the same molecule.
A photosensitive and heat-sensitive recording layer comprising: a substantially colorless compound D having a site that inhibits the reaction with and a thermoresponsive microcapsule containing a photopolymerization initiator, and a photopolymerizable compound. A light and heat sensitive recording material, wherein the light and heat sensitive recording layer in (a) and (b) is a single layer or 2
It is constituted by coating more than layers.

When the photosensitive and heat-sensitive recording material (a) is exposed to a desired image shape, radicals are generated from the photopolymerization initiator encapsulated in the microcapsules, and the radicals diffuse out of the capsules to form a neighborhood. Initiates the polymerization reaction. Then, by heating, the radical diffusion is further promoted and the viscosity in the recording layer decreases, whereby the curing reaction proceeds rapidly, forming a latent image in a desired image shape and at the same time existing in the unexposed portion. The compound B moves in the recording material by heating, and reacts with the coloring component A in the capsule to form an image. Therefore, it is a positive photosensitive and heat-sensitive recording material in which no color is formed in an exposed portion, and an uncured portion in an unexposed portion forms a color to form an image.

The mechanism that contributes to the polymerization after the generation of radicals from the exposure of the light and heat sensitive recording material is not necessarily clear, but the exposure generates radicals from the photopolymerization initiator encapsulated in the microcapsules, and the radicals Although the photopolymerizable composition outside the microcapsules gradually diffuses out of the capsule and polymerizes near the outside of the microcapsule, the radically hardened by heating promotes the diffusion of radicals. The compound B present in an unexposed portion,
For example, it is considered that the electron-accepting compound moves in the recording material by heating, and reacts with and develops a color-forming component A such as an electron-donating colorless dye in the microcapsules. Therefore,
Only the uncured portions develop color, and a clear, high-contrast positive image can be formed.

When the photosensitive and heat-sensitive recording material (b) is exposed to a desired image shape, radicals are generated from the photopolymerization initiator encapsulated in the microcapsules. The compound D having the polymerizable group starts a polymerization reaction. Then, by heating, the radical diffusion is further promoted and the viscosity in the recording layer is reduced, whereby the polymer is rapidly polymerized and the film is hardened to form a desired image latent image. Simultaneously with the formation of the latent image (cured portion), the compound C moves depending on the film property of the formed latent image and reacts with the color forming component A in the capsule to form an image. Therefore, this is a negative type heat and heat sensitive recording material in which an exposed portion develops a color to form an image.

Although the mechanism is not clear, radicals are generated from the photopolymerization initiator encapsulated in the microcapsules by the exposure, and the radicals gradually diffuse out of the capsules and exist outside the microcapsules in the vicinity. While the compound D, for example, a vinyl monomer is gradually polymerized, the radical polymerization is promoted by heating, and the viscosity of the vinyl monomer is reduced, whereby the polymer is completely polymerized.
The electron-accepting compound coexisting in the exposed portion is not taken into the formed polymer at all, but rather has a reduced interaction with a vinyl monomer or the like, and exists in a movable state with a high diffusion rate. Accordingly, the compound C, for example, the electron accepting compound in the exposed portion is preferentially moved in the recording material simultaneously with the diffusion of the radical by the heating, and the color forming component A such as an electron donating colorless dye in the microcapsule is transferred. Will react.

On the other hand, the electron-accepting compound in the unexposed area is trapped by the coexisting vinyl monomer and exists.
It is considered that even when heated, it does not pass through the capsule wall and does not react with the electron-donating colorless dye, so that it cannot contribute to color development. Therefore, in this photosensitive and heat-sensitive recording material, an exposed portion develops a color and an unexposed portion forms an image without coloring, so that a clear negative image with high contrast can be formed.

Further, a light and heat sensitive recording material having a light and heat sensitive recording layer formed by forming a plurality of recording layers on a support may be used. In this case, a multi-color image can be realized by irradiating light using a light- and heat-sensitive recording material in which a plurality of light- and heat-sensitive recording layers of a single color in which a color-forming component A that develops a different hue is present in a capsule are used. .

The image recording method of the present invention is an image recording method using the above-described light- and heat-sensitive recording material. At least a microcapsule is exposed by exposing the image according to a desired pattern. The exposure step of generating radicals from the photopolymerization initiator in the, the radical diffusion is promoted by heating, the photopolymerizable composition forms a latent image,
An image recording method comprising: a coloring step of simultaneously forming a color component according to a latent image to form an image; and a fixing step of irradiating the surface of the recording layer with light to fix the formed image and decolorizing the photopolymerization initiator component. It is.

In the exposure step, the photopolymerizable composition in the layer is exposed according to a desired image shape pattern to form a latent image. Thereafter, in a color forming step, a color forming component contained in the recording layer by heating the recording layer surface reacts with a compound that forms a color by reacting with the color forming component or a specific group that forms a color in the compound, and is formed in advance. The latent image is colored to form an image.

As the light source used for image formation in the exposure step, the same light sources as those usable for exposure of the photopolymerizable composition of the present invention can be used.

Next, in the color forming step, by heating, the diffusion of the radicals generated in the exposure step out of the capsule is promoted, the viscosity in the layer is reduced, and the vicinity of the photopolymerizable composition is rapidly reduced. At the same time as forming a latent image, the color-forming component contained in the light- and heat-sensitive recording layer and a compound that forms a color by reacting with the color-forming component, or a specific group that forms a color in the compound, react with each other to form a latent image in advance. Color in the shape of the latent image
Form an image.

In the image recording method of the present invention, a fixing step is provided after the color forming step. In the fixing step,
By irradiating the entire surface of the recording layer with light from a specific light source, the image formed in the color forming step is fixed, and the coloring due to the photopolymerization initiator component remaining in the recording layer is eliminated. Through this fixing step, the whiteness of the non-image area can be enhanced, and a chemically stable final image can be obtained. Further, when a diazonium salt compound is used as a color-forming component, the diazonium salt compound remaining in the recording layer after image formation can be deactivated by light irradiation, so that a formed image without density fluctuation or discoloration can be obtained. It is also useful for stabilizing the storage.

As a light source that can be used in the fixing step, a light source having a wavelength in the range of the maximum absorption wavelength ± 50 nm of the photopolymerization initiator contained in the light and heat sensitive recording layer of the light and heat sensitive recording material is used. It is preferable, but it is more preferable to appropriately select and use a light source having a wavelength suitable for the absorption wavelength of the photopolymerization initiator to be used. Specifically, a wide range of light sources such as a mercury lamp, an ultra-high pressure mercury lamp, an electrodeless mercury lamp, a xenon lamp, a tungsten lamp, a metal halide lamp, and a fluorescent lamp can be suitably exemplified.

For the purpose of promoting the photo-decoloring property against coloring of the spectral sensitizing compound or the like in the fixing step, a known photopolymerization initiator generally used for photopolymerization may be used in combination. That is, when the generated radical adds a radical to the resonance structure of the spectral sensitizing compound, the resonance structure is cut off, and the spectral sensitizing dye is decolorized. For example, when spectral sensitization is performed in the visible region, it is useful to use an anionic organic borate compound corresponding to a cationic cyanine dye. In this case, radicals are generated by electron transfer of the anionic organic borate compound, and the photoexcited state of the spectral sensitizing compound is cut off and erased. This is an effective mode. Therefore, it is more preferable that the photopolymerization initiator is used together with the microcapsules containing the photopolymerization initiator.

When the above-mentioned known photopolymerization initiator generally used for photopolymerization is used in combination in a capsule, the total amount of the photopolymerization initiator and the later-described borate compound I or borate compound II is used. Can be used in a range that satisfies the ratio of the spectral sensitizing dye / borate compound I or the ratio of borate compound I / borate compound II (that is, the ratio of the dye portion to the borate portion) described later.

The method of irradiating light in the fixing step is not particularly limited, and a method of irradiating the entire surface of the recording layer at one time may also be adopted by gradually irradiating the recording surface with light by scanning or the like. Irradiation may be used, but any method may be used as long as it can finally irradiate the entire recording surface of the photosensitive and heat-sensitive recording material after image formation using substantially uniform irradiation light. Thus, it is preferable to irradiate the entire recording surface with light from the viewpoint of more effectively achieving the effects of the present invention. As the light irradiation time in the fixing step, the formed image is fixed, it is necessary to irradiate the time required to sufficiently decolor the background, while obtaining sufficient image fixing property and light decoloring property, From the viewpoint that the recording speed is not reduced, several seconds to several tens of minutes are preferable, and several seconds to several minutes are more preferable.

Next, the light and heat sensitive recording material of the present invention used in the image recording method of the present invention will be described. The basic structure of the light and heat sensitive recording material of the present invention includes those corresponding to the light and heat sensitive recording material (a) or (b) described above. The components used in the light and heat sensitive recording material of the present invention are described below.

In the light- and heat-sensitive recording material, as a color-forming source, a color-forming component A encapsulated in microcapsules and a substantially colorless compound which reacts with the color-forming component A to form a color (compound B or compound C; , "Compounds that cause color development").

The combination of the two components (color-forming component A and the compound to be colored) as the color-forming source includes the following (A) to (A).
The combination of (T) can be preferably mentioned (in the following examples, the former represents a color-forming component and the latter represents a compound to be colored). (A) Combination of an electron donating dye precursor and an electron accepting compound. (A) A combination of a diazonium salt compound and a coupling component (hereinafter, appropriately referred to as a “coupler compound”). (C) A combination of a metal salt of an organic acid such as silver behenate and silver stearate with a reducing agent such as protocatechinic acid, spiroindane and hydroquinone. (D) A combination of iron salts of long-chain fatty acids such as ferric stearate and ferric myristate and phenols such as tannic acid, gallic acid and ammonium salicylate. (E) Organic acid heavy metal salts such as nickel, cobalt, lead, copper, iron, mercury, and silver salts such as acetic acid, stearic acid, and palmitic acid; and alkali metals or alkaline earths such as calcium sulfide, strontium sulfide, and potassium sulfide. A combination with a metal-like sulfide or a combination of the organic acid heavy metal salt with an organic chelating agent such as s-diphenylcarbazide and diphenylcarbazone.

(F) Heavy metal sulfates such as sulfates such as silver, lead, mercury, and sodium, and sodium tetrathionate;
Combination with sulfur compounds such as sodium thiosulfate and thiourea. (G) an aliphatic ferric salt such as ferric stearate;
Combination with an aromatic polyhydroxy compound such as 4-hydroxytetraphenylmethane. (H) organic acid metal salts such as silver oxalate and mercury oxalate;
Combination with organic polyhydroxy compounds such as polyhydroxy alcohol, glycerin and glycol. (K) A combination of a ferric fatty acid salt such as ferric pelargonate or ferric laurate with a thiocetyl carbamide or isothiocesyl carbamide derivative. (Co) A combination of a lead salt of an organic acid such as lead caproate, lead pelargonate or lead behenate with a thiourea derivative such as ethylenethiourea or N-dodecylthiourea.

(B) Combination of higher aliphatic heavy metal salts such as ferric stearate and copper stearate with zinc dialkyldithiocarbamate. (B) Those which form an oxazine dye such as a combination of resorcinol and a nitroso compound. (S) A combination of a formazan compound and a reducing agent and / or a metal salt. (C) A combination of a protected dye (or leuco dye) precursor and a deprotecting agent. (So) A combination of an oxidizing color former and an oxidizing agent. (T) Combination of phthalonitriles and diiminoisoindolines. (A combination in which a phthalocyanine is formed.) (H) A combination of an isocyanate and a diiminoisoindoline (a combination in which a colored pigment is formed). (T) A combination of a pigment precursor and an acid or a base (a combination formed by a pigment).

As the color-forming component included in the microcapsules of the recording material of the present invention, of the color-forming component A, a substantially colorless electron-donating dye precursor (hereinafter referred to as “electron-donating colorless dye”). Or a diazonium salt compound is preferable.

As the electron-donating colorless dye, conventionally known colorless dyes can be used, and any dye which reacts with the compound B or C to form a color can be used. Specific examples are shown below, but the electron donating compound that can be used in the present invention is not limited to these. Specifically, phthalide compounds,
Fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, pyridine compounds, pyrazine compounds, fluorene compounds And the like.

Examples of the phthalide compound include, for example, US Pat. No. Re. 23,024 and US Pat. No. 3,491,
No. 111, No. 3,491,112, No. 3,49
1,116 and 3,509,174, specifically, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3,3-bis (p-diethylamino-o-butoxyphenyl) -4-azaphthalide, 3- (p-diethylamino-o-butoxyphenyl) -3- (1-pentyl-2-
Methylindol-3-yl) -4-azaphthalide, 3
-(P-dipropylamino-o-methylphenyl) -3
-(1-octyl-2-methylindol-3-yl)
-5-aza (or -6-aza, or -7-aza) phthalide and the like.

Examples of the fluoran compounds include, for example, US Pat. Nos. 3,624,107 and 3,627,78.
No. 7, No. 3,641,011, No. 3,462,8
No. 28, No. 3,681, 390, No. 3,920,
No. 510 and No. 3959,571, specifically, 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-ethyl-N-tetrahydrofurfurylaminofluoran, 2-anilino-3-methyl-6-piperidinoaminofluoran , 2- (o-chloroanilino) -6-diethylaminofluoran, 2-
(3,4-Dichloroanilino) -6-diethylaminofluoran and the like.

Examples of the thiazine-based compound include benzoyl leucon methylene blue, p-nitrobenzyl leucomethylene blue and the like.

Examples of the leuco auramine compounds include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like. Is mentioned.

Examples of rhodamine lactam compounds include rhodamine-B-anilinolactam and rhodamine- (p-
Nitrino) lactam and the like.

Examples of spiropyran compounds include, for example,
The compounds described in U.S. Pat. No. 3,971,808 are specifically mentioned, and specifically, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3- Benzylspiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxy-benzo) spiropyran, 3-propyl-spiro-dibenzopyran and the like can be mentioned.

Examples of the pyridine and pyrazine compounds include those described in US Pat. Nos. 3,775,424, 3,853,869 and 4,246,318.

Examples of the fluorene-based compound include compounds described in Japanese Patent Application No. 61-240989.

When the light- and heat-sensitive recording material of the present invention is used as a full-color recording material, an electron-donating colorless dye for each of cyan, magenta and yellow coloring dyes is used. As the cyan, magenta and yellow coloring dyes, the respective dyes described in U.S. Pat. No. 4,800,149 can be used. Further, as the electron-donating colorless dye for yellow coloring dyes, dyes described in U.S. Pat. No. 4,800,148 and the like can also be used. The dyes described in JP-A-53542 and the like can also be used.

The amount of the colorless electron-donating dye to be used is preferably 0.01 to 3 g / m ² , more preferably 0.1 to 1 g / m ² in the light and heat sensitive recording layer. If the amount is less than 0.01 g / m ² , it may not be possible to obtain a sufficient color density, and if it exceeds 3 g / m ² , the coating aptitude may be degraded. In the case of a multi-layer recording layer, the recording layer is formed by laminating a plurality of recording layers containing the used amount of the electron donating colorless dye.

Examples of the diazonium salt compound include compounds represented by the following formula. Ar—N ₂ ⁺ X ⁻ [wherein, Ar represents an aromatic ring group, and X ⁻ represents an acid anion. ]

This diazonium salt compound is a compound which undergoes a coupling reaction with a coupler upon heating to form a color or is decomposed by light. These can control the maximum absorption wavelength depending on the position and type of the substituent in the Ar portion.

In the above formula, Ar represents a substituted or unsubstituted aryl group. As the substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxamide group, a sulfonyl group, a sulfamoyl group, a sulfonamide group, a ureido group, Examples thereof include a halogen group, an amino group, a heterocyclic group, a nitro group, and a cyano group, and these substituents may be further substituted.

The aryl group may have 6 carbon atoms.
~ 30 aryl groups are preferable, for example, a phenyl group,
2-methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- (2
-Ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group,
2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2 -Ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group,
3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group,

3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, -Benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2
-Ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3-acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5 −
Butoxyphenyl group, 4- (N-benzyl-N-methylamino) -2-dodecyloxycarbonylphenyl group,
And the like.

These groups further include an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group,
It may be substituted by a substituted amino group, a halogen atom, a heterocyclic group or the like.

Specific examples of the salt-forming diazonium include 4- (p-tolylthio) -2,5-dibutoxybenzenediazonium and 4- (4-chlorophenylthio)-
2,5-dibutoxybenzenediazonium, 4- (N,
N-dimethylamino) benzenediazonium, 4-
(N, N-diethylamino) benzenediazonium, 4
-(N, N-dipropylamino) benzenediazonium, 4- (N-methyl-N-benzylamino) benzenediazonium, 4- (N, N-dibenzylamino) benzenediazonium, 4- (N-ethyl-N -Hydroxyethylamino) benzenediazonium, 4- (N, N-
Diethylamino) -3-methoxybenzenediazonium, 4- (N, N-dimethylamino) -2-methoxybenzenediazonium, 4- (N-benzoylamino)-
2,5-diethoxybenzenediazonium, 4-morpholino-2,5-dibutoxybenzenediazonium,

4-anilinobenzenediazonium, 4-
[N- (4-methoxybenzoyl) amino] -2.5-
Diethoxybenzenediazonium, 4-pyrrolidino-3
-Ethylbenzenediazonium, 4- [N- (1-methyl-2- (4-methoxyphenoxy) ethyl) -N-hexylamino] -2-hexyloxybenzenediazonium, 4- [N- (2- (4-methoxy Phenoxy) ethyl) -N-hexylamino] -2-hexyloxybenzenediazonium, 2- (1-ethylpropyloxy) -4- [di- (di-n-butylaminocarbonylmethyl) amino] benzenediazonium and the like. Can be

The maximum absorption wavelength λ _max of the diazonium salt compound used in the present invention is preferably 450 nm or less from the viewpoint of the effect, and more preferably 290 to 440 nm. Further, the diazonium salt compound used in the present invention preferably has 12 or more carbon atoms, a solubility in water of 1% or less, and a solubility in ethyl acetate of 5% or more.

Hereinafter, specific examples of the diazonium salt compound that can be suitably used for the recording material of the present invention are shown, but the present invention is not limited to these compounds.

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In the present invention, the diazonium salt compound may be used alone, or two or more diazonium salt compounds may be used in combination according to various purposes such as hue adjustment.

The amount of the diazonium salt compound used in the light and heat sensitive recording layer is 0.01 to 3 g / m ^2.
Is preferable, and 0.02 to 1.0 g / m < ² > is more preferable. If the amount is less than 0.01 g / m ² , sufficient color developability may not be obtained, and 3 g / m 2
^If it exceeds ² , the sensitivity may decrease or the fixing time may be prolonged. In the case of a multi-layer recording layer, the recording layer is formed by laminating a plurality of recording layers containing the used amount of the electron donating colorless dye.

The light- and heat-sensitive recording material of the present invention comprises the light- and heat-sensitive recording layer containing at least a photopolymerizable composition in addition to the color-forming component A. As the photopolymerizable composition, the above-described photopolymerizable composition of the present invention is used. Here, among the compounds having a polymerizable group constituting the photopolymerizable composition of the present invention, in particular, substantially having a polymerizable group and a site that reacts with the color-forming component A to form a color in the same molecule. A substantially colorless compound B or a substantially colorless compound D having a polymerizable group and a site for suppressing the reaction between the coloring component A and the compound C in the same molecule.
However, when compound D is used as the compound having a polymerizable group, there is no compound capable of forming a color by reacting with the color forming component A, and image formation is difficult. And a substantially colorless compound C, which reacts with the color forming component A to form a color.

The substantially colorless compound B having a polymerizable group and a site which reacts with the color-forming component A in the same molecule to be used in the light- and heat-sensitive recording layer includes the photopolymerizable compound of the present invention. Usable in the hydrophilic composition, such as an electron-accepting compound having a polymerizable group or a coupler compound having a polymerizable group, reacts with the coloring component A to form a color, and reacts with light to polymerize and cure. Any one having both functions can be mentioned.

In the light- and heat-sensitive recording material of the present invention, when a colorless component contains an electron-donating colorless dye,
By using the electron accepting compound having a polymerizable group in combination, a desired latent image can be formed by light irradiation,
An image can be formed by developing a color according to the latent image. The amount of the electron accepting compound having a polymerizable group in the light and heat sensitive recording layer of the light and heat sensitive recording material is preferably 0.1 to 1 part by weight of the electron donating colorless dye used.
It is preferably 5 to 20 parts by weight, more preferably 3 to 10 parts by weight. If the amount is less than 0.5 parts by weight, it may not be possible to obtain a sufficient color density, and if it exceeds 20 parts by weight, the sensitivity may be lowered or the suitability for coating may be deteriorated.

In the light- and heat-sensitive recording material of the present invention, when a diazonium salt compound is present as a color-forming component, a desired latent image can be formed by irradiation with light by using the coupler compound having a polymerizable group in combination. And an image can be formed by developing a color in accordance with the latent image. In the light and heat sensitive recording layer of the light and heat sensitive recording material,
The amount of the coupler compound having a polymerizable group is 0.5 to 2 parts by weight based on 1 part by weight of the diazonium salt compound.
0 parts by weight is preferable, and 1 to 10 parts by weight is more preferable.
If the amount is less than 0.5 part by weight, it may not be possible to obtain a sufficient color density, and if it exceeds 20 parts by weight, the coating aptitude may deteriorate.

Instead of the compound B having a polymerizable group as described above, a substantially colorless compound C having no polymerizable group and reacting with the color forming component A to form a color can be used. However, since the compound C has no polymerizable group, it is used in combination with a compound D having another polymerizable group for the purpose of imparting a film curing effect by photopolymerization to the recording layer.
Examples of the compound D, depending on the compound C used, adapted compounds D, i.e., used to select the photopolymerizable monomer D ¹ or photopolymerizable monomer D ² mentioned above.

As the compound C, any electron-accepting compound or coupler compound having no polymerizable group can be used. As the electron-accepting compound having no polymerizable group, any compound capable of forming a color by reacting with the electron-donating colorless dye, which is one of the coloring components A, can be used.

Examples of the electron accepting compound having no polymerizable group include phenol derivatives, salicylic acid derivatives,
Metal salts of aromatic carboxylic acids, acid clay, pentonite,
Novolak resins, metal-treated novolak resins, metal complexes, and the like. Specifically, Japanese Patent Publication No. 40-9309,
JP-B-45-14039, JP-A-52-140483
JP-A-48-51510, JP-A-57-2108
No. 86, JP-A-58-87089, JP-A-59-11
No. 286, Japanese Unexamined Patent Publication No.
95988 and the like.

Of the above, the following compounds can be specifically mentioned. Examples of the phenol derivative include 2,2′-bis (4-hydroxyphenyl) propane, 4-t-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, and 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-tert-octylphenol, 4-p-methylphenylphenol, 4,4'-
Methylcyclohexylidenephenol, 4,4′-isopentylidenephenol, benzyl p-hydroxybenzoate and the like can be mentioned.

As the salicylic acid derivative, for example, 4-
Pentadecylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (tert-octyl)
Salicylic acid, 5-octadecylsalicylic acid, 5-α-
(P-α-methylbenzylphenyl) ethylsalicylic acid, 3-α-methylbenzyl-5-tert-octylsalicylic acid, 5-tetradecylsalicylic acid, 4-hexyloxysalicylic acid, 4-cyclohexyloxysalicylic acid, 4-decyloxysalicylic acid, 4-dodecyloxysalicylic acid, 4-pentadecyloxysalicylic acid, 4
-Octadecyloxysalicylic acid and the like, and zinc, aluminum, calcium, copper and lead salts thereof.

The amount of the electron accepting compound having no polymerizable group is preferably 5 to 1,000% by weight based on the amount of the electron donating colorless dye.

In this case, the above photopolymerizable monomer D ¹ is used in combination, and the amount of the photopolymerizable monomer D ¹ used is as follows.
The amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 1 part by weight of the substantially colorless compound C which reacts with the color forming component A to form a color. The usage amount is
If the amount is less than 0.1 part by weight, a latent image may not be formed in the exposure step, and if the amount is more than 10 parts by weight, the color density may decrease.

As the coupler compound having no polymerizable group, any compound can be used as long as it can react with the diazonium salt compound as one of the coloring components A to form a color. The coupler compound having no polymerizable group forms a dye by coupling with a diazonium salt compound in a basic atmosphere and / or a neutral atmosphere, and a plurality of types are used in combination according to various purposes such as hue adjustment. It is possible to

Examples of the coupler compound having no polymerizable group include a so-called active methylene compound having a methylene group next to the carbonyl group, a phenol derivative, a naphthol derivative, and the like. , Can be selected and used.

Examples of the coupler compound having no polymerizable group include resorcin, phloroglucin, 2,3-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene-.
Sodium 6-sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 2-hydroxy-3
-Sodium naphthalene sulfonate, 2-hydroxy-
3-naphthalenesulfonic acid anilide, 2-hydroxy-
3-naphthalenesulfonic acid morpholinopropylamide,
2-hydroxy-3-naphthalenesulfonic acid-2-ethylhexyloxypropylamide, 2-hydroxy-3
-Naphthalenesulfonic acid-2-ethylhexylamide,
5-acetamido-1-naphthol,

Sodium 1-hydroxy-8-acetamidonaphthalene-3,6-disulfonate, 1-hydroxy-8-acetamidonaphthalene-3,6-disulfonic acid dianilide, 1,5-dihydroxynaphthalene, 2-
Hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid octylamide,
2-hydroxy-3-naphthoic acid anilide, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-cyclopentanedione, 5- (2-n-tetradecyloxyphenyl) -1,3-cyclohexanedione , 5-phenyl-4-methoxycarbonyl-1,3-cyclohexanedione, 5- (2,5-di-n-octyloxyphenyl) -1,3-cyclohexanedione, N, N'-dicyclohexylbarbituric acid, N, N′-di-n-dodecyl barbituric acid,

Nn-octyl-N'-n-octadecyl barbituric acid, N-phenyl-N '-(2,5-di-n-octyloxyphenyl) barbituric acid, N,
N'-bis (octadecyloxycarbonylmethyl) barbituric acid, 1-phenyl-3-methyl-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-
Anilino-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-benzamido-5-pyrazolone,
6-hydroxy-4-methyl-3-cyano-1- (2-
Ethylhexyl) -2-pyridone, 2,4-bis- (benzoylacetamide) toluene, 1,3-bis- (pivaloylacetoamidomethyl) benzene, benzoylacetonitrile, thenoylacetonitrile, acetoacetanilide, benzoylacetanilide, pivaloyl Acetanilide, 2-chloro-5- (Nn-butylsulfamoyl) -1-pivaloylacetamidebenzene, 1
-(2-ethylhexyloxypropyl) -3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridin-2-one, 1- (dodecyloxypropyl) -3
-Acetyl-4-methyl-6-hydroxy-1,2-dihydropyridin-2-one, 1- (4-n-octyloxyphenyl) -3-tert-butyl-5-aminopyrazole and the like.

The details of the coupler compound having no polymerizable group are described in JP-A-4-201483 and JP-A-7-22336.
7, JP-A-7-223368, JP-A-7-3236
No. 60, JP-A-5-278608, JP-A-5-297
024, JP-A-6-18669, JP-A-6-186
70, JP-A-7-316280, and the like, and JP-A-9-31902 previously submitted by the present applicant.
5 (Japanese Patent Application No. 8-132394), JP-A-9-2164
No. 68, JP-A-9-216469, JP-A-9-31902
5, JP-A-10-35113, JP-A-10-193
801 and JP-A-10-264532 can also be referred to.

The amount of the coupler compound having no polymerizable group in the light- and heat-sensitive recording layer may be 0.02 to 5 g / m ² , as in the case of the coupler compound having a polymerizable group.
Is preferred, and 0.1 to 4 g / m ² is more preferred from the viewpoint of the effect. If the amount is less than 0.02 g / m ² , it may not be possible to obtain a sufficient color density,
If it exceeds g / m ² , the suitability for coating may deteriorate.

[0199] In this case, a combination of the photopolymerizable monomer D ^2, as the amount of the photopolymerizable monomer D ² is
0.1 to 10 parts by weight is preferable with respect to 1 part by weight of the substantially colorless compound C which forms a color by reacting with the color forming component A,
0.5 to 5 parts by weight is more preferred. When the used amount is 0.
If the amount is less than 1 part by weight, a latent image may not be formed in the exposure step, and if the amount is more than 10 parts by weight, the color density may decrease.

The coupler compound having no polymerizable group can be used by solid dispersion or emulsification in the same manner as in the case of the coupler compound having a polymerizable group.
As the method of solid dispersion or emulsification, the same method as in the case of the coupler compound having a polymerizable group can be used.

For the purpose of accelerating the coupling reaction, the same organic base as in the case of the coupler compound having a polymerizable group can be used, and the amount used is also the same.

As the color-forming auxiliary used for the purpose of accelerating the color-forming reaction, the same ones as in the case of the coupler compound having a polymerizable group can be used.

Next, the photopolymerization initiator contained in the light and heat sensitive recording layer of the light and heat sensitive recording material of the present invention will be described. The photopolymerization initiator is the light- and heat-sensitive recording material (a) of the present invention,
It is used in any of the cases (b) and is used by being encapsulated in microcapsules. Here, the microcapsule to be formed is not particularly limited, and can be formed by the same method as in the case where the coloring component A is included in the microcapsule. The encapsulation can be performed by using a material similar to the material of the capsule wall usable in the photopolymerizable composition of the present invention, and by a method for producing microcapsules described later. That is, as the photopolymerization initiator contained in the microcapsules, the same photopolymerization initiator as used in the above-described photopolymerizable composition of the present invention can be used. The amount of the photopolymerization initiator used is the same as that in the case of the photopolymerizable composition of the present invention.

The photopolymerization initiator encapsulated in the microcapsules generates radicals upon exposure to light, and when heated in the color forming step, the viscosity in the layer is reduced and the diffusion of the radicals is promoted. As the recording layer progresses rapidly, the recording layer film is cured to form a latent image having a desired image shape.

The image recording method of the present invention is preferably an image recording method using a light and heat sensitive recording material having a light and heat sensitive recording layer containing the photopolymerization initiator. As described above, by encapsulating the photopolymerization initiator in the microcapsules, the photopolymerization initiator can be converted into the acidic component in the layer or the compound B having the polymerizable group in the light- and heat-sensitive recording layer, or Since the photopolymerization initiator can be kept isolated from the compound C having a group, the photopolymerization initiator can be stably maintained, and at the same time, the polymerization reaction proceeds with time in an unexposed state, or the photopolymerization initiator itself can be used. Sensitivity fluctuations due to destabilization can be effectively suppressed. In addition, while avoiding the above-mentioned concerns, the spectral sensitizing compound and the compound interacting with the spectral sensitizing compound can be present in the vicinity, which also contributes to increasing the sensitivity of the light and heat sensitive recording material. Can.

The light and heat sensitive recording layer of the light and heat sensitive recording material of the present invention is not limited to the light and heat sensitive recording materials (a) and (b) but can have various structures depending on purposes. The recording material may be a single-color recording material or a multi-color recording material. If necessary, a protective layer can be provided on the outermost layer on the light and heat sensitive recording layer. The protective layer may have a single-layer structure or a stacked structure of two or more layers.

Examples of the material used for the protective layer include gelatin, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch, methylcellulose, carboxymethylcellulose, and the like.
Hydroxymethyl cellulose, gelatins, gum arabic, casein, styrene-maleic acid copolymer hydrolyzate, styrene-maleic acid copolymer half ester hydrolyzate, isobutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivative Water-soluble polymer compounds such as polyvinylpyrrolidone, sodium polystyrenesulfonate and sodium alginate, and styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and latexes such as vinyl acetate emulsion. Can be

By cross-linking the water-soluble polymer compound used for the protective layer, the storage stability can be further improved. As the cross-linking agent used for the cross-linking, a known cross-linking agent can be used, and specifically, a water-soluble initial condensate such as N-methylol urea, N-methylol melamine, urea-formalin, glyoxal, glutaraldehyde, etc. And diorganic cross-linking agents such as boric acid and borax, and polyamide epichlorohydrin.

For the protective layer, known pigments, metal soaps, waxes, surfactants, optical brighteners and the like can also be used.
Known UV absorbers such as hydroxybenzophenone type and hydroxyphenyltriazine type and UV absorber precursors can also be added.

The coating amount of the protective layer is 0.2 to 5
preferably ^{g / m 2, 0.5~3g / m} 2 is more preferable.

In the case of a multicolor light and heat sensitive recording material, microcapsules are formed by laminating a plurality of single color light and heat recording layers on a support, and each of the light and heat recording layers contains a color forming component having a different coloring hue. And a microcapsule containing a photopolymerizable initiator component that is sensitive to light of different wavelengths, and a photopolymerizable composition that contributes to the formation of a latent image. be able to. By using spectral sensitizing compounds having different absorption wavelengths for the photopolymerizable initiator, a photopolymerizable composition sensitive to light of different wavelengths can be obtained. In this case, an intermediate layer may be provided between the light- and heat-sensitive recording layers of each single color.

Sensitivity of the multicolor, multi-layer, light- and heat-sensitive recording material of the present invention
The photothermographic layer can be obtained, for example, as follows.
it can. Micro that contains a coloring component that produces yellow color
Center wavelength λ of capsule and light source ₁Photosensitive to radicals
Microcapsules containing a photopolymerization initiator component,
A first recording layer containing a photopolymerizable composition and
And contains a color forming component that develops magenta on the layer
Microcapsules and center wavelength λ_TwoExposed to radio
Encapsulating a photopolymerization initiator component that emits
And a second recording layer containing a photopolymerizable composition.
In addition, a color developing component that develops cyan is included on that layer.
And the wavelength λ_ThreeExposed to radicals
Microcapsules containing photopolymerization initiator components
And a third recording layer containing a photopolymerizable composition and
And heat-sensitive recording layer A, and
And heat-sensitive recording layer B provided with an intermediate layer between each layer of recording layer A
And the like.

In the case of forming an image using a light- and heat-sensitive recording material having a multicolored multi-layer light- and heat-sensitive recording layer as described above, in the exposure step, a plurality of light- and heat-sensitive recording layers each having a different wavelength suitable for the absorption wavelength of the light and heat-sensitive recording layer are used. By performing image exposure using a light source, a recording layer having an absorption wavelength of the light source selectively forms a latent image, so that a multicolor image can be formed with high sensitivity and high sharpness. By irradiating the entire surface with light, it is possible to eliminate the coloring of the background portion due to the photopolymerization initiator including the spectral sensitizing compound remaining in the layer, thereby forming a high-quality image having high contrast. can do.

In the light- and heat-sensitive recording material of the present invention, an electron-donating colorless dye or a diazonium salt compound (hereinafter, referred to as a compound) is used.
It may be referred to as a “color-forming component”. ) And a photopolymerization initiator are used by encapsulating them in separate microcapsules.
As a method for microencapsulation, a conventionally known method can be used. For example, there may be mentioned various methods known in the art which can be used for microencapsulation of the photopolymerization initiator contained in the photopolymerizable composition of the present invention.

The method for microencapsulation is not limited to these, but in the light- and heat-sensitive recording material of the present invention, in particular, a color-forming component or a photopolymerization initiator is preferably used as a hydrophobic organic material serving as a core of the capsule. The oil phase prepared by dissolving or dispersing in a solvent is mixed with an aqueous phase in which a water-soluble polymer is dissolved, and emulsified and dispersed by means of a homogenizer or the like. It is preferable to employ an interfacial polymerization method that causes the microcapsule wall of the polymer substance to be formed. The interfacial polymerization method,
Capsules having a uniform particle size can be formed in a short time, and a recording material having excellent raw preservability can be obtained.

The microcapsules used in the light- and heat-sensitive recording material of the present invention are microcapsule walls (hereinafter sometimes simply referred to as “capsule walls”) under normal temperature environment.
The contact of the substance inside and outside the capsule is prevented by the substance isolating action of the above, and the substance inside and outside the capsule can be contacted only when heated above a certain value. This phenomenon can be freely controlled as a change in the physical properties of the capsule by appropriately selecting the material of the capsule wall, the capsule core substance (the substance contained in the capsule), the additives, and the like.

The capsule wall material which can be used in the present invention is added inside the oil droplets and / or outside the oil droplets. As the material of the capsule wall and the water-soluble polymer, in the photopolymerizable composition of the present invention, a material similar to the material of the capsule wall and the water-soluble polymer that can be used for encapsulation of a photopolymerization initiator can be used. Can be used.

In the present invention, when preparing microcapsules containing a color-forming component and microcapsules containing a photopolymerization initiator, the color-forming component and the photopolymerization initiator contained therein are each present in a solution state in the capsule. Or may exist in a solid state. When the electron-donating colorless dye or diazonium salt compound or the photopolymerization initiator is encapsulated in a solution state in the capsule, the electron-donating colorless dye or diazonium salt compound or the photopolymerization initiator is dissolved in an organic solvent and the capsule is dissolved. It should just be.
In this case, the amount of the organic solvent used is preferably 1 to 500 parts by weight based on 100 parts by weight of the electron-donating colorless dye or diazonium salt compound or the photopolymerization initiator.

In general, the organic solvent can be appropriately selected from solvents having a high boiling point.
Phthalates, acrylates, methacrylates, other carboxylic esters, fatty acid amides, alkylated biphenyls, alkylated terphenyls,
Chlorinated paraffins, alkylated naphthalenes, diallylethane, compounds which are solid at room temperature, oligomer oils, polymer oils and the like are used. Specifically, Japanese Patent Application Laid-Open No. Sho 59-1
Nos. 78451-59-178455, 59-178
No. 457, No. 60-242094, No. 63-8563
No. 3, JP-A-6-194825, JP-A-7-13310 to JP-A-7-13311, JP-A-9-106039 and the organic solvents described in Japanese Patent Application No. 62-75409. At the time of encapsulation, a so-called oilless capsule may be used without using the above organic solvent.

When the solubility of the electron-donating colorless dye or diazonium salt compound or the photopolymerization initiator to be encapsulated in the organic solvent is low, a low-boiling solvent having high solubility is further used as an auxiliary solvent. Can also be used in combination. Examples of the low boiling point solvent include ethyl acetate, propyl acetate, isopropyl acetate,
Butyl acetate, methylene chloride and the like.

As the aqueous phase in which the oil phase is emulsified and dispersed, an aqueous solution in which a water-soluble polymer is dissolved is used. After the oil phase is charged into the aqueous phase, emulsification and dispersion are performed by a means such as a homogenizer.The water-soluble polymer has a function as a protective colloid capable of making the dispersion uniform and easy, and the emulsified aqueous solution is dispersed. Also acts as a dispersion medium for stabilizing. Here, a surfactant can be added to at least one of the oil phase and the aqueous phase in order to perform the emulsification and dispersion more uniformly and obtain a more stable dispersion.

The water-soluble polymer contained as the protective colloid can be appropriately selected from known anionic polymers, nonionic polymers and amphoteric polymers.

As the anionic polymer, any of natural and synthetic polymers can be used. For example, -COO
-, - it includes those having a linking group such as - SO _2.
Specifically, natural products such as arabic gum, alginic acid, and pectin; semi-synthetic products such as carboxymethylcellulose, phthalated gelatin and other gelatin derivatives, sulfated starch, sulfated cellulose, and ligninsulfonic acid; maleic anhydride (hydrolysis) Products), synthetic products such as acrylic acid (methacrylic acid) polymers and copolymers, vinylbenzenesulfonic acid polymers and copolymers, and carboxy-modified polyvinyl alcohol.

Examples of the nonionic polymer include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. Examples of the amphoteric polymer include gelatin. Among them, gelatin, gelatin derivatives and polyvinyl alcohol are preferred. The water-soluble polymer,
It is used as a 0.01 to 10% by weight aqueous solution.

The surfactant can be appropriately selected from known surfactants for emulsification. For example, anionic or nonionic surfactants act as protective colloids as described above. Those that do not cause precipitation or aggregation can be appropriately selected and used. Specific examples include sodium alkylbenzene sulfonate, sodium alkyl sulfate, dioctyl sulfosuccinate sodium salt, polyalkylene glycol (eg, polyoxyethylene nonyl phenyl ether), and the like. The amount of the surfactant added is preferably 0.1 to 5%, more preferably 0.5 to 2%, based on the weight of the oil phase.

In a photopolymerizable composition, a photopolymerization initiator and a compound having a polymerizable group, or in a light- and heat-sensitive recording material, all components including a color-forming component, Along with the molecule, sensitizer and other color-forming aids, it can be used as a solid dispersion by means of a sand mill or the like. Agent and / or
Alternatively, it is preferably used as an emulsified dispersion obtained by mixing with a polymer aqueous solution (aqueous phase) containing a water-soluble polymer as a protective colloid and emulsifying with a homogenizer or the like. In this case, if necessary, a low boiling point solvent can be used as a dissolution aid. Further, in the photopolymerizable composition, a photopolymerization initiator and a compound having a polymerizable group, or, in a light and heat sensitive recording material, all the components including the color forming component are separately emulsified and dispersed. It can also be dissolved in a high-boiling solvent and / or a low-boiling solvent after mixing in advance,
It is also possible to emulsify and disperse. The particle size of the emulsified particles formed by emulsification is preferably 1 μm or less.

In the emulsification dispersion, the oil phase containing the above-mentioned components and the aqueous phase containing a surfactant and / or a protective colloid are used.
It can be easily carried out using a means used for emulsification of fine particles such as high-speed stirring and ultrasonic dispersion, for example, a known emulsifying apparatus such as a homogenizer, a Manton-Gawley, an ultrasonic disperser, a dissolver, and a Keddy mill.

After the emulsification, the emulsion is heated to 30 to 70 ° C. in order to accelerate the capsule wall forming reaction. In order to prevent aggregation of the capsules during the reaction, it is necessary to reduce the probability of collision between the capsules by adding water or to perform sufficient stirring. On the other hand, during the reaction, a dispersion for preventing aggregation may be separately added. As for the end point of the capsule wall forming reaction, generation of carbon dioxide gas is observed as the polymerization reaction proceeds, and the end of the generation can be regarded as an approximate end point. Usually, a microcapsule containing a coloring component can be obtained by performing the reaction for several hours.

In the light and heat sensitive recording material of the present invention, the average particle size of the microcapsules containing the color forming component is preferably 20 μm or less, and more preferably 5 μm or less from the viewpoint of obtaining high resolution. If the diameter of the formed microcapsules is too small, the surface area with respect to a certain solid content becomes large and a large amount of a wall material is required. Therefore, the average particle diameter is preferably 0.1 μm or more.

The average particle size of the microcapsules containing the photopolymerization initiator is preferably 10 μm or less, as in the case of the photopolymerizable composition of the present invention, and is preferably 1.0 μm or less.
m or less is more preferable.

When the light and heat sensitive recording material of the present invention is used as a multi-color light and heat sensitive recording material, the light and heat sensitive recording layer of the light and heat recording material is formed by laminating a plurality of single-color light and heat recording layers on a support. Each of the light and heat sensitive recording layers has a microcapsule containing a colorless electron-donating dye that develops a different hue, a microcapsule containing a photopolymerization initiator having a different maximum absorption wavelength, and a photopolymerizable composition. When irradiated with light, it is sensitive to the difference in the wavelength of the light source to form a multicolor image.

Further, an intermediate layer may be provided between the single-color photosensitive and heat-sensitive recording layers constituting the photosensitive and heat-sensitive recording layer. The intermediate layer is composed of a binder as a seed, and may contain additives such as a curing agent, a polymer latex, a filter dye, mica, and an ultraviolet absorber as needed.

The filter dye may be selected from the above-mentioned spectral sensitizing compounds, but it is preferable to use a compound having the same light absorption wavelength as the spectral sensitizing compound in the upper layer of each intermediate layer. It is preferable in that an image can be formed. The filter dye 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 the filter dye in a single solution of a high-boiling solvent having a boiling point of 175 ° C. or higher or a low-boiling solvent having a boiling point of 30 to 160 ° C., or in a mixture of both, It is finely dispersed in an aqueous solution such as water, an aqueous solution of gelatin or an aqueous solution of polyvinyl alcohol in the presence of a surfactant. As the high boiling point solvent, US Pat.
Solvents described in No. 2027 and the like. Further, as the high boiling point solvent and the low boiling point solvent, the same solvents as those used in the production of the microcapsules can be used.

Specific examples of the latex for the step of polymer dispersion method, curing and impregnation are described in US Pat. No. 4,199,938.
No. 3, West German Patent Application (OLS) No. 2541274, No. 2541230, JP-A-49-74538 and No. 5
Nos. 1-59943, 54-32552 and "Rese
arch Disclosure Vol. 148 "
(August 1976, Item 14850).

Among them, acrylates or methacrylates such as ethyl acrylate, n-butyl acrylate, n-butyl methacrylate and 2-acetoacetoxyethyl methacrylate; acrylic acid; acids such as 2-acrylamide-2-methylpropanesulfonic acid A copolymer latex of a monomer is preferred.

Further, the dispersion may be accompanied by a phase inversion, and the auxiliary solvent may be removed or reduced by distillation, Nudel washing, ultrafiltration or the like, and then used for coating.

In the light- and heat-sensitive recording material of the present invention, the binder used for each layer such as the protective layer, the light- and heat-sensitive recording layer, and the intermediate layer is the same as the binder used for emulsifying and dispersing the photopolymerizable composition, Acrylic resins such as polystyrene, polyvinyl formal, polyvinyl butyral, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and copolymers thereof, as well as water-soluble polymers used for encapsulating Solvent-soluble polymers such as styrene-butadiene resin, ethylcellulose, epoxy resin, urethane resin and the like, or polymer latexes thereof can also be used. Among them, gelatin and polyvinyl alcohol are preferable.

Each photosensitive and heat-sensitive recording layer constituting the photosensitive and heat-sensitive recording material of the present invention may contain various surfactants for various purposes such as a coating aid, an antistatic property, an improvement in slipperiness, an emulsifying dispersion, and an adhesion preventing property. Can be used. Examples of the surfactant include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and alkyl sulfates. Ester, N-
Anionic surfactants such as acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylenalkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, aliphatic and aromatic Cationic surfactants such as quaternary ammonium salts can be used.

Further, in addition to the additives described above, other additives can be added to the photosensitive and heat-sensitive recording layer as needed. For example, dyes, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, coating aids, curing agents, antistatic agents, slipperiness improvers, and the like can be added. A typical example of each of the additives is “Research Disclosure”.
Sure, Vol. 176 "(December 1978, It
em 17643) and “Id. Vol. 187” (197)
November 19, Item 18716).

In the light and heat sensitive recording material of the present invention, it is preferable to use a curing agent in combination with each of the light and heat sensitive recording layer, the intermediate layer and the protective layer. In particular, it is preferable to use a curing agent together in the protective layer to reduce the tackiness of the protective layer. As the curing agent, for example, a "gelatin curing agent" used in the production of a photographic light-sensitive material is useful. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, and the reactivity described in US Pat. No. 3,635,718, etc. A compound having a reactive ethylenically unsaturated group described in U.S. Pat. No. 3,635,718;
Aziridine compounds described in No. 17280, etc., epoxy compounds described in U.S. Pat. No. 3,091,537, halogenocarboxaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane, dichlorodioxane, U.S. Pat. 3687
No. 707, vinyl sulfones, U.S. Pat.
1872 and the ketovinyls described in U.S. Pat. No. 3,640,720. Chromium alum, zirconium sulfate, boric acid, and the like can also be used as the inorganic curing agent.

Among them, 1,3,5-triacloyl-hexahydro-s-triazine, 1,2-pispinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamide) ) Compounds such as ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenino-s-triazine and boric acid are preferred. The addition amount of the curing agent is preferably 0.5 to 5% by weight based on the binder amount.

The light- and heat-sensitive recording material of the present invention is prepared by preparing a coating solution for the light- and heat-sensitive recording layer and a coating solution for the protective layer, and then coating and drying it on a desired support. Can be obtained. Water as the solvent;
Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, methyl cellosolve and 1-methoxy-2-propanol; halogen solvents such as methylene chloride and ethylene chloride; ketones such as acetone, cyclohexanone and methyl ethyl ketone And the like; methyl cellosolve acetate,
Ester such as ethyl acetate and methyl acetate; toluene; xylene and the like alone; and mixtures of two or more thereof. Among them, water is particularly preferred.

To coat the coating solution for the light and heat sensitive recording layer on the support, a blade coater, rod coater, knife coater, roll doctor coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, curtain coater , An extrusion coater or the like can be used.

As a coating method, “Rcscan
Disclosurc, Vol. 200 "(December 1980, Item 20036 XV). As the layer thickness of the light and heat sensitive recording layer,
0.1 to 50 μm is preferable, and 5 to 35 μm is more preferable.

The light- and heat-sensitive recording material of the present invention obtained as described above can be used for various uses. For example, it is used for copiers, faxes, color printers, labels, color proofs, second original drawings, and the like.

As the support used in the light and heat sensitive recording material of the present invention, synthetic paper such as neutral paper, acidic paper, coated paper, laminated paper; polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, Films such as polycarbonate films; metal plates such as aluminum, zinc, and copper;
Alternatively, there may be mentioned those obtained by subjecting the surface of these supports to various treatments such as surface treatment, undercoating, and metal vapor deposition. In addition, "Research Disclosur
e, Vol. 200 "(December 1980, Item
The support described in section 20036 XVII) can also be used. The various supports include a fluorescent whitening agent, a bluing dye,
A pigment or the like can be contained.

Further, if necessary, an antihalation layer may be provided between the support and the light and heat sensitive recording layer, or on the surface of the support on which the light and heat sensitive recording layer is provided, and on the back surface thereof. A slip layer, an antistatic layer, an anti-curl layer, a pressure-sensitive adhesive layer, and the like can also be provided. Further, an adhesive layer may be provided between the support and the light and heat sensitive recording layer to form a seal in which the used support is used as release paper.

Between the support and the light and heat sensitive recording layer, or
In the case of a transparent support, an antihalation layer which can be bleached by light irradiation or heat can be provided when the antihalation layer is provided on the surface of the support on which the photosensitive and heat-sensitive recording layer is not provided. .

When the layer capable of being bleached by light irradiation is used, for example, a combination of the above-mentioned spectral sensitizing compound and a borate salt compound (a combination of the above-mentioned spectral sensitizing dye and borate compound I or a borate compound) I and borate compounds
In the case of a layer capable of being bleached by heat, for example, a structure in which a base or a nucleophile is generated by heat and capable of bleaching a coexisting spectral sensitizing dye can be used. Is available.

Between the support and the light- and heat-sensitive recording layer,
A layer containing a polymer having low oxygen permeability, such as gelatin or polyvinyl alcohol (PVA), can be provided. By providing this layer, fading due to photo-oxidation of a formed image can be effectively prevented. be able to.

The heating method at the time of heat development can be appropriately selected from conventionally known methods, and is the same as the heating method which can be used at the time of heat-treating the photopolymerizable composition of the present invention. For example, the treatment can be performed with a heat roller or the like. Generally, the heating temperature is preferably from 80 to 200 ° C.,
~ 130 ° C is more preferred. If the heating temperature is lower than 80 ° C., the color density may be insufficient,
If the temperature exceeds 0 ° C., the non-image area (background area) may be colored or the support may be damaged. The heating time is preferably from 1 second to 5 minutes, more preferably from 3 seconds to 1 minute. In the case of performing the heat development process, the sensitivity can be further improved by providing a process of uniformly preheating the entire surface of the recording material at a predetermined temperature lower than the color development temperature.

By providing a fixing step of irradiating the surface of the recording layer with light after the heat development, the formed image is fixed and the whiteness of the background such as the spectral sensitizing compound and the diazonium salt compound remaining in the recording layer is improved. It is preferable to decolor, decompose, or deactivate the components that reduce the odor. By doing so, it is possible to remove the components coloring the background portion remaining in the recording layer including the background portion (non-image portion), and also inactivate the remaining diazonium salt compound. Since the color development reaction can be suppressed, the density fluctuation in the image can be suppressed, and the image storability can be greatly improved.

The light and heat sensitive recording material of the present invention can be used not only in the above-described recording method but also in other known recording methods. For example, in order to improve thermal recording, contrast, and image quality using a heating device such as a thermal head, the method described in International Application WO95 / 31754 describes the method described in WO95 / 31754.
When irradiating a laser beam used for a silver halide light-sensitive and heat-sensitive recording material proposed by Company M, it can also be used in a recording method of forming an image by irradiating so that the beam spots overlap in a predetermined range. That is,
In the process of laser beam irradiation during latent image formation,
(1) A radiation light source capable of forming a beam spot having a height or length of at least 600 μm or less on a target object is prepared. (2) A recording material sensitive to the light source is provided with a predetermined target. After placing it in position,
(3) The light source has a length or width of at least 250.
The beam spot is adjusted to have a beam spot of μm or less, and the beam is used for irradiation in accordance with the image distribution. (4) With respect to the irradiated spot, at least some spots of a beam to be subsequently irradiated are overlapped and irradiated.
Image forming technology that irradiates according to image distribution,

Alternatively, in the method of forming a latent image by exposing a recording material, (1) preparing a light source capable of exposing
(2) A plurality of small areas in which one of the height or the length of the beam spot of the light source is 600 μm or less are irradiated, and at least 10% of the energy required for at least one of the small areas, that is, among the plurality of small areas, At least 10% of
Is based on an image forming technique for irradiating so as to overlap with another small area.

A recording method proposed by Canon Inc. described in JP-A-60-195568 can also be used. That is, by tilting the incident angle of a laser beam applied to the recording material surface, the reflection pitch at which the incident beam is reflected at the photosensitive layer interface of the recording material is made larger than the beam spot diameter, thereby preventing light interference occurring on the recording material. , A higher quality image can be obtained.

[0257]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
Hereinafter, “%” in the examples represents “% by weight”.

<Preparation of Electron-donating Colorless Dye-Containing Microcapsule Solution> (1-a) Preparation of Electron-donating Colorless Dye-Encapsulating Microcapsule Solution (I) The following electron-donating colorless yellow color was added to 16.9 g of ethyl acetate. 8.9 g of Dye (1) was dissolved, and capsule wall material (trade name: Takenate D-110N, Takeda Pharmaceutical Co., Ltd.)
20g) and capsule wall material (trade name: Millionate MR)
200, manufactured by Nippon Polyurethane Industry Co., Ltd.). The resulting solution was added to a mixture of 42 g of 8% phthalated gelatin and 1.4 g of a 10% sodium dodecylbenzenesulfonate solution, and then emulsified and dispersed at a temperature of 20 ° C. to obtain an emulsion. Next, water 1 was added to the obtained emulsion.
4 g and 2.9% tetraethylenepentamine aqueous solution 72 g
After heating for 2 hours, a microcapsule solution (I) having the following electron-donating colorless dye (1) as a core and having an average particle size of 0.5 μm was obtained.

(1-b) Preparation of Electron-donating Colorless Dye-Encapsulated Microcapsule Solution (II) The following electron-donating colorless dye (1) used in (1-a) above
In the same manner as in the above (1-a) except that the following electron-donating colorless dye (2) of magenta color was used instead of A 0.5 μm microcapsule solution (II) was obtained.

(1-c) Preparation of Electron-donating Colorless Dye-Encapsulated Microcapsule Solution (III) The following electron-donating colorless dye (1) used in (1-a) above
In place of, the following electron-donating colorless dye of cyan color (3)
Except that the following electron-donating colorless dye (3) was used as a core in the same manner as in the above (1-a), except that the average particle diameter was 0.1.
A 5 μm microcapsule solution (III) was obtained.

(1-d) Preparation of Electron-donating Colorless Dye-Encapsulated Microcapsule Solution (IV) The following electron-donating colorless dye (1) used in (1-a) above
In place of the above, the following electron-donating colorless dye (4) was used as a core in the same manner as in the above (1-a) except that the following black electron-donating colorless dye (4) was used. 0.5 μm
To obtain a microcapsule liquid (IV).

[0262]

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<Preparation of microcapsules containing photopolymerization initiator> (2-a) Microcapsule solution containing photopolymerization initiator (a)
Preparation of the above organic borate compound (20-i) 0.6 g
And the above-mentioned exemplified spectral sensitizing dye-based borate compound (26)
(Borate compound II) 0.25 g, the following auxiliary agent (1) for the purpose of increasing sensitivity: 0.25 g, tricresyl phosphate as a dissolving oil 6.0 g, and ethyl acetate 14 as a dissolving aid. In a mixed solution of 1.0 g and 11.2 g of capsule wall material (trade name: Takenet D110N, manufactured by Takeda Pharmaceutical Co., Ltd.) and capsule wall material (trade name: bar
1.1 g of Knock D750 (manufactured by Dainippon Ink and Chemicals, Inc.) was added and dissolved at 40 ° C. for 15 minutes to obtain a mixed solution. 52 g of 8% aqueous solution of phthalated gelatin was
18 g of water and the following 10% surfactant (1) aqueous solution 0.4
g of the mixture, and emulsified with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 10,000 rpm for 10 minutes to obtain an emulsion.

To the emulsion obtained above, 54 g of water and 0.62 g of tetraethylenepentamine were added, and the mixture was heated to 65 ° C. with stirring, and after 3 hours, an average containing the photopolymerization initiator in the core was added. A microcapsule solution (a) containing a photopolymerization initiator and having a particle size of 0.3 μm was obtained.

(2-b) Preparation of Microcapsule Solution (b) Enclosing Photopolymerization Initiator The spectral sensitizing dye-based borate compound (26) used in (2-a) is replaced with the spectral sensitizing dye described in the above. A microcapsule solution (b) containing a photopolymerization initiator was obtained in the same manner as in (2-a) except that the dye-based borate compound (28) (borate compound II) was used.

(2-c) Preparation of Microcapsule Solution (c) Enclosing Photopolymerization Initiator The spectral sensitizing dye-based borate compound (26) used in (2-a) is replaced with the spectral sensitizing dye described above. A microcapsule solution (c) containing a photopolymerization initiator was obtained in the same manner as in the above (2-a) except that the dye-based borate compound (30) (borate compound II) was used.

(2-d) Preparation of Microcapsule Solution (d) Enclosing Photopolymerization Initiator The organic borate compound (20) used in (2-a) was used.
-I) in place of the organic borate compound (2)
9) except that (borate compound I) was used,
A microcapsule solution (d) containing a photopolymerization initiator was obtained in the same manner as in (a).

<Preparation of Emulsion of Electron-Accepting Compound> (3) Preparation of Emulsion of Electron-Accepting Compound To 87.5 g of isopropyl acetate, 70 g of the following electron-accepting compound (1) having a polymerizable group was added. 1 under ℃
The mixture was stirred and dissolved for 5 minutes. This solution was mixed with 115 g of a 15% aqueous gelatin solution, 92 g of water and the following 10% surfactant (1)
The solution was added to a mixture of 12 g of the aqueous solution, and the mixture was stirred at 8,000 rpm with a homogenizer (manufactured by Nippon Seiki Co., Ltd.).
After emulsification for one minute, an emulsion of the electron-accepting compound was obtained.

[0269]

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[0270]

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<Preparation of emulsion of photopolymerizable composition> (4-a) Preparation of emulsion of photopolymerizable composition (1) 2.8 g of organic borate compound (20-i) shown above
And the spectral sensitizing dye-based borate compound (2
6) A mixture of 0.7 g of (borate compound II), 0.7 g of the auxiliary (1) for the purpose of increasing sensitivity, and 87.5 g of isopropyl acetate (solubility in water: about 4.3%) In the solution, the electron accepting compound (1) having a polymerizable group (7)
0 g was added, and the mixture was stirred and dissolved at 40 ° C. for 15 minutes. The obtained solution was mixed with 115 g of a 15% aqueous gelatin solution and water 9
11. 2.0 g of the 10% surfactant (1) aqueous solution
0 g, 0.8 g of the 2% surfactant (2) aqueous solution,
And emulsified at 8,000 rpm for 10 minutes using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain a photopolymerizable composition emulsion (1).

(4-b) Preparation of Photopolymerizable Composition Emulsion (2) In place of the spectral sensitizing dye-based borate compound (26) used in (4-a) above, A photopolymerizable composition emulsion (2) was obtained in the same manner as in (4-a) except that the spectral sensitizing dye-based borate compound (28) (borate compound II) was used.

(4-c) Preparation of Photopolymerizable Composition Emulsion (3) In place of the spectral sensitizing dye-based borate compound (26) used in (4-a) above, A photopolymerizable composition emulsion (3) was obtained in the same manner as in (4-a), except that the spectral sensitizing dye-based borate compound (30) (borate compound II) was used.

(4-d) Preparation of emulsion of photopolymerizable composition (4) In place of the above-mentioned organic borate compound (20-i) used in (4-a), the organic borate described above is used. A photopolymerizable composition emulsion (4) was obtained in the same manner as in the above (4-a) except that the compound (29) (borate compound I) was used.

<Preparation of Coating Solution for Intermediate Layer> A mixture of 4.5 g of a 15% aqueous gelatin solution, 4.5 g of distilled water and 0.3 g of the 2% aqueous solution of the surfactant (4) was mixed. ) Was prepared.

<Preparation of Coating Solution (1) for Protective Layer> 98 g of water
1.7 g of polyvinyl alcohol, 1.7 g of hydroxypropylmethylcellulose and 8.7 g of polyvinylpyrrolidone were added thereto and mixed to obtain a coating solution (1) for a protective layer.

<Preparation of Coating Solution (2) for Protective Layer> 4.5 g of a 10% aqueous gelatin solution, 4.5 g of distilled water, and the above 2%
0.5 g of a surfactant (3) aqueous solution, 0.3 g of the 2% surfactant (4) aqueous solution, 0.5 g of a 2% vinyl sulfone compound (hardener) aqueous solution, and 50 mg of a dry coating amount
/ M ² , the amount of thyroid 72 (FUJ
I-DEVICE CHEMICAL LTD. Made)
And Snowtex N1g were mixed to prepare a protective layer coating solution (2).

-Photopolymerizable composition- (Example 1) The following compounds were mixed to prepare a mixed solution. · Pentaerythritol tetraacrylate ··· 1.0 g (PET-4A) · Benzyl methacrylate / methacrylic acid ··· 0.8 g (copolymer of 73/27 (molar ratio)) · Acetone ··· 5 g Methyl ethyl ketone 10 g Propylene glycol monomethyl ether acetate 5 g

To the above mixture, 0.5 g of the microcapsule solution containing the photopolymerization initiator (a) was added, and mixed and dispersed at 10,000 rpm for 10 minutes with a homogenizer to prepare a photopolymerizable composition of the present invention. did.

Next, the obtained photopolymerizable composition was
film thickness of 2 μm on polyethylene terephthalate film
μm, and dried at a temperature of 100 ° C. for 5 minutes to provide a photopolymerizable composition layer. On this layer, the protective layer coating solution (1) was further coated to a thickness of 1 μm. The photosensitive sheet (1) was obtained by drying the coating at a temperature of 100 ° C. for 2 minutes.

<Thermo Treatment> The photosensitive sheet (1) obtained above was left under the following conditions for 3 days to obtain thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ , respectively. Hereinafter, the photosensitive sheets obtained under the respective conditions were used as thermo samples S ⁽ⁱ⁾ and S ⁽ⁱ⁾ , respectively.
⁽ⁱⁱ⁾ . (I) Temperature 40 ° C., relative humidity 90% RH: thermo sample S ⁽ⁱ⁾ (ii) Temperature 60 ° C., relative humidity 30% RH: thermo sample S ⁽ⁱⁱ⁾

Using a vacuum sintering apparatus, each of the untreated sample (Fr) of the photosensitive sheet (1) obtained above and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ of the photosensitive sheet (1) was obtained. A step wedge (trade name: Fuji Step Guide P (density difference of each step: 0.15, number of density steps: 0) from each protective layer surface side by a xenon lamp (manufactured by Ushio Inc.)
After exposing the photosensitive sheet (1) to the photosensitive sheet (1) through a developing solution at 25 ° C. for 15 seconds, a developing process was performed to form an image.

<Developer D> A developer D was prepared by dissolving 10 g of anhydrous sodium carbonate and 5 g of butyl cellosolve in 1 L of water.

<Evaluation of sensitivity of photopolymerizable composition>
As a result of the development processing, the exposed portion is hardened as a result of being cured, and remains undeveloped. In accordance with the difference in density of the step wedge, the photopolymerizable composition is changed into a developer in the order of decreasing amount of light irradiated on the photosensitive sheet (1). In the part which was eluted in and was not irradiated with light at all, the photopolymerizable composition was entirely eluted and the polyethylene terephthalate surface was exposed. After exposure at a fixed exposure amount, the number of steps formed by development was determined, and this number was used as an index indicating the sensitivity of the photopolymerizable composition (photosensitive sheet).
Therefore, the greater the number of steps formed, the higher the sensitivity. The number of steps after development is shown in Table 1 below.

(Example 2) Using the photosensitive sheet (1) obtained in Example 1, in the same manner as in Example 1, the untreated sample (Fr), the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ Are prepared, and the entire surface of each photosensitive sheet on which a latent image is formed by exposing each of the
After heating with a hot plate at 5 ° C. for 5 seconds, development processing was performed in the same manner as in Example 1 to form an image. For each photosensitive sheet, the number of steps formed in the same manner as in Example 1 was determined and used as an index of sensitivity. The number of steps after development is shown in Table 1 below.

Example 3 Using the photosensitive sheet (1) obtained in Example 1, in the same manner as in Example 1, the untreated sample (Fr), the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ Are prepared. First, the entire surface of each photosensitive sheet is subjected to a heat treatment in the same manner as in Example 2, and then the heating unit is exposed imagewise in the same manner as in Example 1, and further developed. To form an image. Also, for each photosensitive sheet,
The number of steps formed by the same method as in Example 1 was obtained and used as an index of sensitivity. The number of steps after development is shown in Table 1 below.

(Comparative Examples 1 to 3) Instead of the photopolymerization initiator-containing microcapsules (a) used in Example 1, the above-mentioned spectral sensitizing dye-based borate compound (26) (borate compound II) was used. Photosensitive sheet (2) was obtained in the same manner as in Example 1, except that 02 g and 0.04 g of organic borate compound (20-i) (borate compound I) described above were used. Using the photosensitive sheet (2), an unprocessed sample (Fr) and thermosamples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared in the same manner as in Example 1. An image was formed in the same manner as in each method of Example 3. For each photosensitive sheet, the number of steps formed in the same manner as in Example 1 was determined and used as an index of sensitivity.
The number of steps after development is shown in Table 1 below.

[0288]

[Table 1]

As is clear from Table 1, in the photosensitive sheet (1) comprising the photopolymerizable composition of the present invention in which the photopolymerization initiator was encapsulated in microcapsules, the sensitivity was not lowered by the thermotreatment, and the photosensitive sheet was stable. An image could be formed.
That is, by encapsulating the photopolymerization initiator in microcapsules, a photopolymerizable composition having excellent storage stability during raw storage could be obtained. Further, in Examples 2 and 3, in which the entire exposed portion was heated or heated after imagewise exposure, and then the heated portion was imagewise exposed to form an image, and heating was not performed before and after exposure in Examples 2 and 3. As compared with Example 1, higher sensitivity could be obtained. On the other hand, in the photosensitive sheet (2) made of the photopolymerizable composition in which the photopolymerization initiator is not encapsulated in the microcapsules, the sensitivity is greatly reduced by the thermotreatment, the polymerization cannot be cured, and the photosensitive image (2) is eluted into the developing solution to obtain a desired image. Could not be formed. That is, when the photopolymerization initiator was not included in the microcapsules, a photopolymerizable composition having excellent storage stability during raw storage could not be obtained.

-Light and heat sensitive recording material-(Example 4)-Black color microcapsule liquid (IV) containing an electron-donating colorless dye
0 g, microcapsule liquid containing photopolymerization initiator (b)
8.0 g, an electron-accepting compound emulsion 10.0 g, 1
2.0 g of a 5% aqueous gelatin solution were mixed to prepare a coating solution (1) for a light and heat sensitive recording layer.

On a polyethylene terephthalate (PET) blue base support having a thickness of 175 μm, the coating solution (1) for the light and heat sensitive recording layer was coated with a coating bar to make the dry weight of the entire coating layer 30 g / m ² . It was applied and dried. On this layer, using a coating bar, the coating liquid (2) for the protective layer was dried to a dry weight of 2%.
g / m ² and dried to obtain a light and heat sensitive recording material (1). In the first embodiment, the thermo sample S ⁽ⁱ⁾
And by a method similar to the method that created the S ^(ii), was created thermo sample S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ of the light and heat sensitive recording material (1).

The unprocessed sample (Fr) of the light and heat sensitive recording material (1) and the thermo samples S ⁽ⁱ⁾ and S ^{(ii) of} the light and heat sensitive recording material (1) were placed at a wavelength of 660 nm from the protective layer side.
Using a semiconductor-excited solid-state laser beam of m, exposure was performed in a step wedge-like image shape such that the maximum irradiation energy was gradually changed at 15 mJ / cm ² .

Each recording material on which a latent image was formed by the above exposure was heated for 5 seconds with a hot plate at 120 ° C., and then this recording material was placed on a 58,000 lux high-brightness Sharksten for 30 seconds.
The entire surface of the recording layer of the recording material was irradiated with light for one second. Then, not only the unprocessed sample Fr but also the thermo sample S
^{Also in (i)} and S ⁽ⁱⁱ⁾ , it was possible to obtain a step-wedge-like image which had a clear color and almost no residual color of the spectral sensitizing dye on the background.

<Evaluation of Sensitivity of Photosensitive Thermosensitive Recording Material> The sensitivity of the photosensitive thermosensitive recording material corresponds to the same exposure amount in the wedge image of each material. Energy difference from the energy required to form the background portion (energy to form the background portion-irradiation energy in the step)
Was measured and calculated, and used as an index of sensitivity. Therefore, the smaller the value of the sensitivity, the higher the sensitivity and the higher the stability. The results of the measurement are shown in Table 2 below.

<Evaluation of Image> An image formed using the unprocessed sample Fr and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ of the light and heat sensitive recording material (1) was evaluated according to the following criteria.
The sensory evaluation was performed visually. The evaluation results are shown in Table 2 below. ：: The sensitivity fluctuation is extremely small, and the image is clear. Δ: Although the sensitivity was slightly lowered or the sensitivity fluctuated, there was no problem in practical use. ×: Sensitivity reduction or sensitivity fluctuation was large, and a clear image was not obtained.

<Measurement of Fog Density> The background fog (Dmin) and the background fog (Dmin ⁽ⁱ⁾ and Dmin ⁽ⁱⁱ⁾ ) of the photosensitive and heat-sensitive recording material (1) were measured using a Macbeth transmission densitometer (Macbeth). Using its transmission Vi
The sual concentration value was measured. The measurement results are shown in Table 2 below together with the results. The reflection densities shown below were measured using a Macbeth reflection densitometer (manufactured by Macbeth Co., Ltd.).
The reflection density values of C and V (Visual) were measured.

(Example 5)-Black color microcapsule liquid (IV) containing an electron-donating colorless dye
0 g, microcapsule liquid containing photopolymerization initiator (d)
8.0 g, an electron-accepting compound emulsion 10.0 g, 1
2.0 g of a 5% gelatin aqueous solution was mixed to prepare a coating solution (2) for a light and heat sensitive recording layer.

The photosensitive and heat-sensitive recording material was prepared in the same manner as in Example 1 except that the coating solution (2) for the light and heat sensitive recording layer was used in place of the coating solution (1) for the light and heat sensitive recording layer used in Example 4. 2)
I got Further, an untreated sample (Fr) and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared in the same manner as in Example 4 using the photosensitive and heat-sensitive recording material (2). An image was formed in the same manner as described above. Then, not only the unprocessed sample Fr but also the thermo samples S ⁽ⁱ⁾ and S
^{Also in (ii)} , it was possible to obtain a step-wedge-like image which had a clear color and almost no residual color of the spectral sensitizing dye in the background.

In the same manner as in Example 4, the sensitivity and the fog density of the untreated sample Fr and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were measured (transmission Visual density value).
And the formed image was evaluated. The results are shown in Table 2 below.

(Example 6)-Yellow color development Microcapsule solution (I) containing an electron-donating colorless dye
0 g, microcapsule liquid containing photopolymerization initiator (a)
8.0 g, an electron-accepting compound emulsion 10.0 g, 1
2.0 g of a 5% gelatin aqueous solution was mixed to prepare a coating solution (3) for a light and heat sensitive recording layer.

Instead of the polyethylene terephthalate (PET) blue base support used in Example 4, a polyester film filled with a white pigment (trade name: Lumirror E)
(-68L, manufactured by Toray Industries, Inc.) A 100 μm support was used, and the coating solution for a light and heat sensitive recording layer (1) 3 used in Example 4 was further used.
In the same manner as in Example 1, except that 6 g / m ² (dry weight of the entire coating layer) was used instead of 0 g / m ² (dry weight of the entire coating layer), the coating solution (3) for the light and heat sensitive recording layer was used instead of 0 g / m ² (dry weight of the entire coating layer). A light and heat sensitive recording material (3) was obtained. Using the photosensitive and heat-sensitive recording material (3), an unprocessed sample (Fr), the thermosamples S ⁽ⁱ⁾ and S ^{(ii) in the same} manner as in Example 4,
Was prepared.

Further, the wavelength 660 nm used in Example 4 was used.
532nm wavelength instead of semiconductor-pumped solid-state laser
An image was formed in the same manner as in Example 4 except that the semiconductor-excited solid-state laser was used. Then, the unprocessed sample Fr
In addition, in each of the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ , it was possible to obtain a sharply formed step wedge-like image with almost no residual color of the spectral sensitizing dye on the background.

In the same manner as in Example 4, the measurement of the sensitivity and fog density (reflection density value of Y ⁾ in the untreated sample Fr and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ , and the An evaluation was performed. The results are shown in Table 2 below.

(Example 7)-Magenta coloring Microcapsule solution (II) containing an electron-donating colorless dye
0 g, microcapsule liquid containing photopolymerization initiator (b)
8.0 g, an electron-accepting compound emulsion 10.0 g, 1
Then, 2.0 g of a 5% gelatin aqueous solution was mixed to prepare a coating solution (4) for a light and heat sensitive recording layer.

The photosensitive / thermosensitive recording material was prepared in the same manner as in Example 6, except that the photosensitive / thermosensitive recording layer coating solution (4) was used in place of the photosensitive / thermosensitive recording layer coating solution (3) used in Example 6. (4) was obtained. An unprocessed sample (Fr) was prepared in the same manner as in Example 4 using the photosensitive and heat-sensitive recording material (4).
The thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared, and an image was formed in the same manner as in Example 4. Then, not only the unprocessed sample Fr but also the thermo samples S ⁽ⁱ⁾ and S
^{Also in (ii)} , it was possible to obtain a step-wedge-like image which had a clear color and had almost no residual color of the spectral sensitizing dye on the background.

In the same manner as in Example 4, the sensitivity and the fog density of the untreated sample Fr and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were measured (the reflection density value of M), and the density of the formed image was measured. An evaluation was performed. The results are shown in Table 2 below.

(Example 8)-Cyan coloration Microcapsule liquid (III) containing an electron-donating colorless dye
0 g, microcapsule liquid containing photopolymerization initiator (c)
8.0 g, an electron-accepting compound emulsion 10.0 g, 1
Then, 2.0 g of a 5% aqueous gelatin solution was mixed to prepare a coating solution (5) for a light and heat sensitive recording layer.

A light- and heat-sensitive recording material was prepared in the same manner as in Example 6, except that the light-and-heat-sensitive recording layer coating solution (5) was used in place of the light-and-heat-sensitive recording layer coating solution (3) used in Example 6. (5) was obtained. An untreated sample (Fr) was prepared in the same manner as in Example 4 using the photosensitive and heat-sensitive recording material (5).
The thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared.

Further, the wavelength 660 nm used in Example 4 was used.
780nm wavelength instead of semiconductor-pumped solid-state laser
An image was formed in the same manner as in Example 4 except that the semiconductor laser was used. Then, not only in the unprocessed sample Fr but also in the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ , it is possible to obtain a sharply developed step wedge-like image having almost no residual color of the spectral sensitizing dye on the background. Was completed.

In the same manner as in Example 4, the sensitivity and the fog density of the untreated sample Fr and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were measured (the reflection density value of C), and the An evaluation was performed. The results are shown in Table 2 below.

(Example 9)-Multicoloring Polyester film filled with white pigment (trade name: Lumirror E-68L, manufactured by Toray Industries, Inc.) A coating film was formed on a support having a thickness of 100 μm using a coating bar. The coating solution for photosensitive and heat-sensitive layer (5) (cyan color development) used in Example 5 was applied so that the dry weight of the coating layer became 6 g / m ² , and dried, and the coating solution for intermediate layer (1 ) Was applied using a coating bar so as to have a dry weight of 1.5 g / m ² and dried. Further, on this intermediate layer, the coating weight of the coating layer (6) (the magenta color) used in Example 7 was dried using a coating bar to a dry weight of 6 g / g.
m ² , and dried, and a coating solution for an intermediate layer was applied on this layer so that the dry weight was 1.5 g / m ² .
Dried. Further, on this layer, the coating solution (3) (yellow color) for the light and heat sensitive recording layer used in Example 6 was applied using a coating bar so that the dry weight of the coating layer was 6 g / m ² , and dried. , A coating liquid for a protective layer on the layer (2)
Was applied so as to have a dry weight of 1.5 g / m ² and dried to obtain a light and heat sensitive recording material (6).

Using the photosensitive and heat-sensitive recording material (6), an untreated sample (Fr) and the thermosamples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were produced in the same manner as in Example 4. The unprocessed sample (Fr) of the light and heat sensitive recording material (6) and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were ^separated from the protective layer side by:
First, imagewise exposure is performed using a semiconductor laser beam having a wavelength of 780 nm, and then imagewise exposed using a solid-state laser beam excited by a semiconductor having a wavelength of 660 nm.
m was exposed imagewise using a solid-state laser beam excited by a semiconductor. The recording material on which the latent image is formed by the exposure is
After heating on a hot plate at 20 ° C. for 5 seconds,
The surface of the recording layer was irradiated with light for 30 seconds on a high-brightness 7000 lux Sharksten. Then, not only in the unprocessed sample Fr, but also in the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ ,
A clear full-color image could be obtained. In the same manner as in Example 4, the measurement of the fog density (reflection density value of Visual) and the evaluation of the formed image were performed on the untreated sample Fr and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ . The results are shown in Table 2 below.

(Comparative Example 4)-Black color microcapsule liquid (IV) containing an electron-donating colorless dye
0 g, 12.0 g of the photopolymerizable composition emulsion (2), and 1
2.0 g of a 5% gelatin aqueous solution was mixed to prepare a coating solution (6) for a light and heat sensitive recording layer.

The photosensitive / thermosensitive recording material was prepared in the same manner as in Example 4, except that the photosensitive / thermosensitive recording layer coating solution (6) was used in place of the photosensitive / thermosensitive recording layer coating solution (1) used in Example 4. (7) was obtained. An unprocessed sample (Fr) was prepared in the same manner as in Example 4 using the photosensitive and heat-sensitive recording material (7).
The thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared, and an image was formed in the same manner as in Example 4. In the unprocessed sample Fr, although a clear step wedge image with almost no residual color of the spectral sensitizing dye in the background was obtained,
In the samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ subjected to the thermotreatment, the sensitivity was reduced, and a clear image could not be obtained. Measurement of the sensitivity and fog density and evaluation of the formed image were performed in the same manner as in Example 4. The results are shown in Table 2 below.

(Comparative Example 5)-Black color microcapsule liquid (IV) containing an electron-donating colorless dye
0 g, 12.0 g of the photopolymerizable composition emulsion (4), and 1
2.0 g of a 5% aqueous gelatin solution were mixed to prepare a coating solution (7) for a light and heat sensitive recording layer.

The photosensitive / thermosensitive recording material was prepared in the same manner as in Example 5, except that the photosensitive / thermosensitive recording layer coating solution (7) was used in place of the photosensitive / thermosensitive recording layer coating solution (2) used in Example 5. (8) was obtained. An unprocessed sample (Fr) was prepared in the same manner as in Example 5 using the photosensitive and heat-sensitive recording material (8).
The thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared, and an image was formed. In the case of the untreated sample Fr, a step wedge image which was clear and had almost no residual color of the spectral sensitizing dye in the background was obtained. However, in the samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ subjected to the thermotreatment, the sensitivity decreased. And a clear image could not be obtained. Measurement of the sensitivity and fog density and evaluation of the formed image were performed in the same manner as in Example 4. The results are shown in Table 2 below.

(Comparative Example 6) -Yellow color development Microcapsule solution (I) containing an electron-donating colorless dye
0 g, 12.0 g of the photopolymerizable composition emulsion (1), and 1
Then, 2.0 g of a 5% aqueous gelatin solution was mixed to prepare a coating solution (8) for a light and heat sensitive recording layer.

The light- and heat-sensitive recording material was prepared in the same manner as in Example 6, except that the light- and heat-sensitive recording layer coating solution (8) was used in place of the light-and-heat-sensitive recording layer coating solution (3) used in Example 6. (9) was obtained. An unprocessed sample (Fr) was prepared in the same manner as in Example 6 using the photosensitive and heat-sensitive recording material (9).
The thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared, and an image was formed. In the case of the untreated sample Fr, a sharp step wedge image with a high whiteness of the background was obtained, but in the samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ subjected to the thermotreatment, the sensitivity was reduced, and the sharpness was observed. No image could be obtained. Measurement of the sensitivity and fog density and evaluation of the formed image were performed in the same manner as in Example 4. The results are shown in Table 2 below.

(Comparative Example 7)-Magenta coloring Microcapsule solution (II) containing an electron-donating colorless dye
0 g, 12.0 g of the photopolymerizable composition emulsion (2), and 1
Then, 2.0 g of a 5% gelatin aqueous solution was mixed to prepare a coating solution (9) for a light and heat sensitive recording layer.

The photosensitive / thermosensitive recording material was prepared in the same manner as in Example 7 except that the photosensitive / thermosensitive recording layer coating solution (9) was used in place of the photosensitive / thermosensitive recording layer coating solution (4) used in Example 7. (10) was obtained. Further, the light and heat sensitive recording material (10)
And untreated sample (Fr) in the same manner as in Example 7.
And the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared to form an image. In the case of the unprocessed sample Fr, although a sharp step wedge image with high whiteness of the background was obtained, the samples S ⁽ⁱ⁾ and S
^{In (ii)} , a decrease in sensitivity was observed, and a clear image could not be obtained. Measurement of the sensitivity and fog density and evaluation of the formed image were performed in the same manner as in Example 4. The results are shown in Table 2 below.

(Comparative Example 8)-Cyan coloration Microcapsule solution (III) containing an electron-donating colorless dye
0 g, 12.0 g of the photopolymerizable composition emulsion (3), and 1
Then, 2.0 g of a 5% gelatin aqueous solution was mixed to prepare a coating solution (10) for a light and heat sensitive recording layer.

In place of the coating solution for photosensitive and heat-sensitive recording layer (5) used in Example 8, the coating solution for photosensitive and heat-sensitive recording layer (10)
In the same manner as in Example 8, except that was used, a light and heat sensitive recording material (11) was obtained. Further, the light and heat sensitive recording material (11)
And untreated sample (Fr) in the same manner as in Example 8.
And the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared to form an image. In the case of the unprocessed sample Fr, although a sharp step wedge image with high whiteness of the background was obtained, the samples S ⁽ⁱ⁾ and S
^{In (ii)} , a decrease in sensitivity was observed, and a clear image could not be obtained. Measurement of the sensitivity and fog density and evaluation of the formed image were performed in the same manner as in Example 4. The results are shown in Table 1 below.

(Comparative Example 9)-Multicoloring In place of the coating solution (3) for the photosensitive / thermosensitive recording layer used in Example 9, the coating solution (8) for the photosensitive / thermosensitive recording layer used in Comparative Example 6 was used. The coating solution for photosensitive and heat sensitive recording layer (9) used in Comparative Example 7 was used in place of the coating solution for photosensitive and heat sensitive recording layer (4), and the coating solution for photosensitive and heat sensitive recording layer (5) was further replaced. Except for using the coating solution (10) for the light and heat sensitive recording layer used in Example 8,
In the same manner as in Example 9, a light and heat sensitive recording material (12) was obtained. Further, an unprocessed sample (Fr) and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared using the photosensitive and heat-sensitive recording material (12) in the same manner as in Example 9 to form an image. . In the unprocessed sample Fr, although a clear full-color image was obtained, the sample S ⁽ⁱ⁾ subjected to the thermoprocessing was used.
In S and ⁽ⁱⁱ⁾ , a decrease in sensitivity was observed, and an unclear image with a disturbed color balance was obtained. The measurement of the fog density and the evaluation of the formed image were performed in the same manner as in Example 4. The results are shown in Table 2 below.

Comparative Examples 10 to 12 Examples 4, 6 and 9
(1), (3) or (6)
, Except that no light irradiation was performed on the recording layer surface for 30 seconds on a 58,000 lux high-intensity Shark Sten.
A step wedge-shaped image or a full-color image was formed in the same manner as in Example 4, 6, or 9. The fog density before and after the thermotreatment was measured by the same method as in Example 4, and the results are shown in Table 2 below.

[0325]

[Table 2]

As is clear from Table 2, in the light- and heat-sensitive recording materials (1) to (6) of the present invention in which the photopolymerization initiator was encapsulated in microcapsules, the sensitivity decrease or the sensitivity fluctuation due to the thermotreatment was extremely low. By providing a small fixing step for irradiating the entire surface of the recording layer with light, it was possible to obtain a clear and high-quality image with almost no residual color of the spectral sensitizing dye in the background. Further, even in a full-color image, a high-quality image with extremely clear colors could be obtained. On the other hand, in the light- and heat-sensitive recording materials (7) to (12) used in which the photopolymerization initiator is not encapsulated in the microcapsules but coexists with a compound having a polymerizable group outside the capsules, the sensitivity decreases or the sensitivity varies due to the thermotreatment. However, a clear and stable image could not be obtained. Furthermore, in a full-color image, the color balance was disturbed, and a clear image could not be formed. Further, even when the light and heat sensitive recording materials of Examples 4, 6 and 9 were used, Comparative Examples 10 to 1 in which the fixing step of irradiating the entire surface of the recording layer with light was not provided.
In No. 2, the density increase in the background portion due to the thermoprocessing was extremely large, and a high-contrast clear image could not be formed.

<Preparation of microcapsule solution containing diazonium salt compound> (5) Preparation of microcapsule solution (V) containing diazonium salt compound In 13.7 g of ethyl acetate, 4.6 g of a diazonium salt compound (compound a shown below) and phthalate were added. Acid diphenyl ester 1
And 0.4 g were added and mixed uniformly. Next, a capsule wall material (trade name: Takenate D110) was added to this mixture.
N, manufactured by Takeda Pharmaceutical Co., Ltd.) and 5.5 g of capsule wall material (trade name: Millionate MR200, manufactured by Nippon Polyurethane Industry Co., Ltd.).

The obtained solution was combined with 62.7 g of an 8% aqueous solution of phthalated gelatin, 14 g of water, and sucrapA part-S
(Manufactured by Nippon Seika Co., Ltd.) was added to a mixed solution of 0.4 g, and the temperature was 40 ° C. and the number of revolutions was 8000 rpm using a homogenizer.
m for 10 minutes. Water 50 was added to the obtained emulsion.
g and 0.26 g of diethylenetriamine, and after homogenization, a microencapsulation reaction was performed at 60 ° C. for 3 hours with stirring to obtain a diazonium salt compound-encapsulated microcapsule liquid (V). The average particle size of the microcapsules was 0.3 to 0.4 μm.

[0329]

Embedded image

<Preparation of microcapsule solution containing photopolymerization initiator> (6) Preparation of microcapsule solution (e) containing photopolymerization initiator 0.6 g of the above-mentioned organic borate compound (20-i)
And the above-mentioned exemplified spectral sensitizing dye-based borate compound (26)
(Borate compound II) 0.25 g, the following auxiliary agent (compound j below) for the purpose of increasing the sensitivity 0.25 g, tricresyl phosphate 6.0 g as a dissolving oil, and acetic acid as a dissolving aid In a mixed solution of 14.0 g of ethyl,
11.2 g of capsule wall material (trade name: Takenet D110N, manufactured by Takeda Pharmaceutical Co., Ltd.) and capsule wall material (trade name: Burnock D750, manufactured by Dainippon Ink Co., Ltd.)
1 g was added and dissolved at 40 ° C. for 15 minutes to obtain a mixed solution. This solution was added to an aqueous 8% phthalated gelatin solution 5
2 g, 18 g of water and 0.4 g of the 10% surfactant (1) aqueous solution were added to a mixed solution, and emulsified with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 10,000 rpm for 10 minutes to obtain an emulsion. Was.

To the emulsion obtained above, 54 g of water and 0.62 g of tetraethylenepentamine were added, and the mixture was heated to 65 ° C. with stirring. A microcapsule solution (e) containing a photopolymerization initiator and having a particle size of 0.3 μm was obtained.

<Preparation of Coupler Compound Emulsion> (7) Preparation of Coupler Compound Emulsion A compound having the following composition was dissolved in 10.5 g of ethyl acetate.
Furthermore, tricresyl phosphate 0.48 which is a high boiling point solvent is used.
g, diethyl maleate 0.24 g and Bionin A4
After adding 1.27 g of 1C (manufactured by Takemoto Yushi Co., Ltd.), the mixture was heated to obtain a uniform mixed solution. -Coupler compound (the following compound d): 3.0 g-Triphenylguanidine-4.0 g-1,1- (p-hydroxyphenyl) -2-ethylhexane ... 4.0 g-4,4 ' -(P-phenylenediisopropylidene) diphenol ··· 8.0 g · 2-ethylhexyl-4-hydroxybenzoate ··· 8.0 g · Antioxidant (the following compound e) ··· 2.0 g · 1, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane 2.0 g

The above mixture was added to 93 g of an aqueous solution of 8% gelatin (# 750 gelatin, manufactured by Nitta Gelatin Co., Ltd.) and emulsified and dispersed with a homogenizer at 10,000 rpm for 5 minutes. The remaining ethyl acetate was evaporated from the obtained emulsion to obtain a coupler compound emulsion.

[0334]

Embedded image

<Preparation of Photopolymerizable Composition Emulsion> (8) Preparation of Photopolymerizable Composition Emulsion (5) A compound having the following composition was dissolved in 10.5 g of ethyl acetate.
Furthermore, tricresyl phosphate 0.48 which is a high boiling point solvent is used.
g, diethyl maleate 0.24 g and Bionin A4
After adding 1.27 g of 1C (manufactured by Takemoto Yushi Co., Ltd.), the mixture was heated to obtain a uniform mixed solution. -The above-mentioned organic borate compound (20-i) ... 0.6 g (borate compound I)-The above-mentioned spectral sensitizing dye-based borate compound (26) ... 0.1 g (borate compound II) Auxiliary for the purpose of increasing sensitivity (compound j) 0.1 g Coupler compound (compound d) 3.0 g Triphenylguanidine 4.0 g 1,1- ( p-Hydroxyphenyl) -2-ethylhexane 4.0 g4,4 '-(p-phenylenediisopropylidene) diphenol ... 8.0 g2-ethylhexyl-4-hydroxybenzoate ... 8 2.0 g Antioxidant (compound e) 2.0 g 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane 2.0 g

The above mixture was added to 93 g of an aqueous solution of 8% gelatin (# 750 gelatin, manufactured by Nitta Gelatin Co., Ltd.) and emulsified and dispersed with a homogenizer at 10,000 rpm for 5 minutes. The remaining ethyl acetate was evaporated from the obtained emulsion to obtain a photopolymerizable composition emulsion (5) of the coupler compound.

(Example 10): Microcapsule liquid (V) 1 containing a yellow colored diazonium salt compound
0 g, microcapsule liquid (e) containing photopolymerization initiator 30
g and 30 g of the coupler compound emulsion were mixed to prepare a coating solution (11) for a photosensitive and heat-sensitive recording layer.

A coating solution (11) for the photosensitive and heat-sensitive recording layer and a coating solution (2) for the protective layer were sequentially applied from a support side using a Meyer bar on a photographic paper support obtained by laminating polyethylene on wood free paper. The resultant was dried to obtain a light and heat sensitive recording material (13). The dry coating amount of the light and heat sensitive recording layer is 3.5.
g / m ^2, dry coating amount of the protective layer was 1.23 g / m ^2. Example 4 using the light and heat sensitive recording material (13)
An untreated sample (Fr) and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared in the same manner as in
An image was formed in the same manner as described above. Then, not only in the unprocessed sample Fr but also in the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ , it is possible to obtain a step wedge-like image which is clearly colored and has almost no residual color of the spectral sensitizing dye on the background. Was completed.

In the same manner as in Example 1, the measurement of the sensitivity and the fog density (reflection density value of Y ⁾ in the untreated sample Fr and the thermo samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ , and the An evaluation was performed. The results are shown in Table 3 below.

(Comparative Example 11): Yellow color development In place of 30 g of the photopolymerization initiator-containing microcapsule solution (e) and 30 g of the coupler compound emulsion used in Example 10, 30 g of a photopolymerizable composition emulsion of a coupler compound. Was prepared in the same manner as in Example 10, except that was mixed, to obtain a light and heat sensitive recording material (14) in the same manner as in Example 10.

Using the photosensitive and heat-sensitive recording material (14), an untreated sample (Fr) and the thermo-samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ were prepared in the same manner as in Example 4. In the same manner as in Example 4, an image was formed. Unprocessed sample F
r, a step wedge image was obtained which was clear and had almost no residual color of the spectral sensitizing dye in the background, but in the samples S ⁽ⁱ⁾ and S ⁽ⁱⁱ⁾ subjected to the thermo-treatment, a decrease in sensitivity was observed. A clear image could not be obtained. Measurement of these sensitivity and fog density (reflection density value of Y);
Evaluation of the formed image was performed in the same manner as in Example 4.
The results are shown in Table 3 below.

[0342]

[Table 3]

As is clear from Table 3, the photosensitive and heat-sensitive recording material (13) of the present invention using the photopolymerization initiator encapsulated in microcapsules did not cause a decrease in sensitivity or a change in sensitivity due to thermoprocessing, and showed extremely high sensitivity. In addition, by providing a fixing step of irradiating the entire surface of the recording layer with light, it is clear,
In addition, a high-quality image with almost no residual color of the spectral sensitizing dye on the background was obtained. On the other hand, a photosensitive and heat-sensitive recording material (1) was used in which a photopolymerization initiator was not encapsulated in a microcapsule, but was used together with a compound having a polymerizable group outside the capsule.
In 4), a sharp and stable image could not be obtained due to a large decrease in sensitivity or a large change in sensitivity due to the thermoprocessing.

[0344]

According to the present invention, a photopolymerizable composition having excellent photopolymerization sensitivity and storage stability, and a light and heat sensitive recording excellent in sensitivity, contrast and whiteness of a non-image area and excellent in storage stability. Material can be provided. According to the light- and heat-sensitive recording material of the present invention, it is possible to stably provide a high-sensitivity, high-contrast, high-contrast, high-contrast image with high sensitivity, which is hardly affected by environmental changes. Can be. According to the image recording method of the present invention, it is possible to provide a clear, high-quality image with almost no residual color of the spectral sensitizing dye in the non-image portion (background portion).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/26 521 B41M 5/18 112 F term (Reference) 2H025 AA00 AA01 AB20 AC08 BC31 BC51 CA00 CA41 CC14 DA10 DA11 FA06 FA12 FA22 FA30 2H026 AA07 AA24 AA32 BB01 BB41 BB46 BB48 DD01 DD43 DD53 FF01 FF05 2H096 AA30 BA05 BA16 BA20 CA20 EA04 EA14 GA52 HA03 KA07

Claims (14)

[Claims] 1. A photopolymerizable composition comprising: a thermoresponsive microcapsule in which a photopolymerization initiator is encapsulated; and a compound having a polymerizable group outside the microcapsule. 2. The photopolymerization initiator has a wavelength of 300 to 1000 nm.
The photopolymerizable composition according to claim 1, which is a photopolymerization initiator containing a spectral sensitizing compound having a maximum absorption wavelength and a compound that interacts with the spectral sensitizing compound. 3. The photopolymerizable composition according to claim 2, wherein at least one of the compounds interacting with the spectral sensitizing compound is an organic borate salt compound. 4. An image recording method using a photopolymerizable composition, wherein the photopolymerizable composition is the photopolymerizable composition according to claim 1, and is exposed imagewise. After, to form an image by heating and curing the entire exposed portion, or, after heating the photopolymerizable composition,
An image recording method, wherein an image is formed by exposing and curing a heating section imagewise. 5. Substantially having, on a support, a color-forming component A encapsulated in a thermoresponsive microcapsule, and at least a polymerizable group and a site that reacts with the color-forming component A to form a color in the same molecule. And a photopolymerizable composition containing a colorless compound B and a photopolymerization initiator encapsulated in thermoresponsive microcapsules. 6. A polymer in the same molecule as a color-forming component A encapsulated in a thermo-responsive microcapsule, and at least a substantially colorless compound C that reacts with the color-forming component A to form a color. A substantially colorless compound D having a reactive group and a site for suppressing the reaction between the coloring component A and the compound C, and a photopolymerization initiator encapsulated in a thermoresponsive microcapsule. A light- and heat-sensitive recording material having a light- and heat-sensitive recording layer comprising: a composition; 7. The photopolymerization initiator has a thickness of 300 to 1000 nm.
7. The light and heat sensitive recording material according to claim 5, which is a photopolymerization initiator containing a spectral sensitizing compound having a maximum absorption wavelength and a compound interacting with the spectral sensitizing compound. 8. The light and heat sensitive recording material according to claim 7, wherein at least one of the compounds interacting with the spectral sensitizing compound is an organic borate salt compound. 9. The light-sensitive heat-sensitive recording material according to claim 5, wherein the light-sensitive heat-sensitive recording material is a multi-color multi-layer light-sensitive heat-sensitive recording material obtained by laminating light-sensitive heat-sensitive recording layers each emitting a different hue. material. 10. A multi-color, multi-layer, light- and heat-sensitive recording material is colored on a support by light having a central wavelength of λ _{1 from} a light source toward a thickness direction of a light- and heat-sensitive recording layer from an incident surface of irradiation light. the first recording layer, and sensitive to the central wavelength lambda ₂ of light, a second recording layer which develops a color different from the first recording layer, and photosensitive ..., in the light of the center wavelength lambda _i, the first A multi-layer photosensitive structure having a light- and heat-sensitive recording layer in which the i-th recording layer which develops a color different from that of the first, second,... The light- and heat-sensitive recording material according to claim 9, which is a heat-sensitive recording material. 11. A photosensitive and thermosensitive recording material according to claim 5, wherein the photopolymerizable composition forms a latent image by image exposure, and a heating step. The color forming component forms a color according to the latent image, thereby forming an image, and a fixing step of irradiating the surface of the recording layer with light to fix the formed image and decolorizing the photopolymerization initiator component. Characteristic image recording method. 12. The light- and heat-sensitive recording material according to claim 9 or 10, wherein at least an exposure step in which the photopolymerizable composition forms a latent image by image exposure, and a heat-development of a color-forming component by heating. A color-forming step of forming a color in accordance with an image to form an image, and a fixing step of irradiating the surface of the recording layer with light to fix the formed image and decolorizing the photopolymerization initiator component. Is a step of image exposure using a plurality of light sources having different wavelengths, wherein the color forming step develops a different hue according to each latent image formed on the photosensitive and heat-sensitive recording layer having a different color hue by heating, An image recording method, which is a step of forming a multicolor image. 13. The exposure step in which the photopolymerizable composition forms a latent image by performing image exposure using a laser light source having a wavelength of 300 to 1000 nm.
13. The image recording method according to 1 or 12. 14. The fixing step comprises fixing the formed image by irradiating the surface of the recording layer with light using a light source having a wavelength in the range of the maximum absorption wavelength of the photopolymerization initiator contained in the light and heat sensitive recording material ± 50 nm. 14. The image recording method according to claim 11, wherein the step of decolorizing the photopolymerization initiator component is performed.