JP2000199952A - Recording material and image recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an image of high picture quality with high sensitivity and high contrast which can be recorded in a complete dry processing system, without requiring the use of a developer or the like and without producing waste by using a blue to red laser or small-sized inexpensive IR laser by using a specified photopolymn. initiator in a recording layer. SOLUTION: This recording material has a photosensitive thermosensitive recording layer containing a color developing component (A) encapsulated in heat-responding microcapsules and a photopolymerizable compsn. outside of the heat-responding microcapsules. The photopolymerizable compsn. consists of a photopolymn. initiator and a compd. (B), which is substantially colorless and has polymerizable groups and a portion to react with the color developing molecules (A) to develop a color in one molecule. In the image recording method using this recording material, the photopolymerizable compsn. forms a latent image by exposure for an image in the exposure process. In the color developing process, the color developing component develops a color according to the latent image by heating to form an image. In the fixing process, the surface of the recording layer is irradiated with a light to fix the formed image and to decolorize the photopolymn. initiator component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monochromatic or multicolor recording material and an image recording method capable of utilizing various light sources in the ultraviolet to infrared region, and more particularly, to sensitivity, contrast, and whiteness of a non-image portion. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material capable of forming an image having excellent properties and an image recording method thereof.

[0002]

2. Description of the Related Art Conventionally, various dry-type image recording methods which do not use a liquid developer or the like and do not generate waste have been studied. Among them, a method using a composition which is cured by light has attracted attention. ing. 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 method, first, light is exposed on the recording material through an image original, the exposed portion is cured to form a latent image, and then the recording material is heated to be uncured. A component that acts on the color development or decoloration reaction contained in the portion (unexposed portion) 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 to be used in the above-mentioned system, and the system is characterized as a black-and-white image recording system, but is particularly useful for recording a color image. As a specific recording material, for example, a two-component photosensitive and thermosensitive color recording material disclosed in JP-A-52-89915 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 applicant of the present invention has previously disclosed in JP-A-3-87827 and JP-A-4-21252 as recording materials capable of reducing coloring in a non-image area and obtaining a high image density. Was proposed. The former recording material is the two-component type photosensitive and thermosensitive color recording material.
A recording material in which one of the components is encapsulated in a microcapsule and the other is contained as a curable compound of the photocurable composition, or the other is contained together with the photocurable composition outside the microcapsule. Further, the latter recording material, a microcapsule containing an electron-donating colorless dye, a photocurable composition containing an electron-accepting compound, a polymerizable vinyl monomer and a photopolymerization initiator outside the microcapsule, Is a light and heat sensitive recording material provided with a layer having

[0007] Using such a light and heat sensitive recording material,
-To record an image, the photosensitive wavelength and the color
Uses a recording material in which multiple different recording layers are laminated on a support.
That can be achieved. Multicolor photosensitive heat
Examples of the recording material include, for example, the photosensitive sensitivity proposed by the present applicant.
Thermal recording materials can be mentioned, specifically, different waves
Multiple records sensitive to long light and developing different hues
Layer, ie, center wavelength λ₁The first note that develops color when exposed to light
Recording layer, center wavelength λ₁Intermediate layer that absorbs light of center wavelength λ
_TwoThe first recording layer is sensitive to
2 recording layers,..., Center wavelength λ_i-1Absorbing the light of
Interlayer, center wavelength λ_i, The first, second, ...
. And the i-th recording layer having a color different from that of the (i-1) th recording layer.
The i-th recording layer, in order from the exposure light source side toward the support,
Laminated at least i ≧ 2, and the center wavelength at this time
λ is λ₁<Λ _Two<... <λ_iIs characterized by
Multicolor recording materials can be mentioned.

However, although these recording materials can be applied to various uses, none of them can record an image with a light source other than UV light and short-wave visible light, and a small and inexpensive infrared laser or blue to red light is used. Use was not possible.

Furthermore, when a small and inexpensive infrared laser or blue to red light as described above is used in order to enable high-speed and high-definition image formation, the recording layer has an absorption wavelength of each irradiation light. It is necessary to introduce a dye or the like having absorption in a certain ultraviolet to infrared region. However, when these dyes and the like, particularly dyes and the like that absorb in the visible light region, are used, the background is colored, and only low-quality images 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.

On the other hand, as a pressure-sensitive coloring type recording material, for example, US Pat. No. 4,399,209 and US Pat.
No. 846, and the like. This is to use a recording material in which a colored precursor as an image forming agent is encapsulated in microcapsules, and after imagewise exposing, uniformly apply pressure and the like to microcapsules in a region that has not been photocured. The colored precursor released from the inside of the capsule is made to react with the developer outside the capsule to visualize. Examples of the multicolor recording material include U.S. Pat. Nos. 339,917 and 45,768.
No. 91 and the like.

However, also in this recording material, most of the compositions to be photocured have photosensitivity at short wavelengths. Therefore, similarly to the above-mentioned photothermographic recording material, all of the light sources other than UV light and short-wave visible light are used. Cannot record an image, and it is impossible to use a small and inexpensive infrared laser or blue to red light. Furthermore, in order to enable high-speed and high-definition image formation, the background portion is colored and only low-quality images with low contrast can be obtained.

[0012]

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, the present invention is a completely dry processing system that does not require the use of a developer or the like and generates no waste, and can be recorded using a blue to red laser or a small and inexpensive infrared laser, It is another object of the present invention to provide a black-and-white or color recording material capable of forming a high-sensitivity, high-contrast, high-quality image, and an image recording method thereof.

[0013]

Means for Solving the Problems The inventors of the present invention have disclosed a recording material in which a recording layer is provided on a support, a component constituting the recording layer, and exposing the recording material to a desired image shape. A composition which is present outside the microcapsules and which is cured by photopolymerization (hereinafter referred to as “photopolymerizable composition”).
After curing to form a latent image, the color forming component is colored by heating or pressing, and as for the image recording method of the recording material for forming the image, as a result of intensive studies, a specific photopolymerization initiator in the recording layer To fix the formed image by further irradiating the surface of the recording layer after image formation with light,
Further, the inventors have found that by erasing the remaining photopolymerization initiator component, it is possible to obtain a high-quality image excellent in not only sensitivity but also in contrast and image quality, thereby completing the present invention. The means for solving the above problems are as follows. That is,

<1> A color-forming component A encapsulated in a thermo-responsive microcapsule on a support, and a polymerizable group and the color-forming component A are reacted outside the thermo-responsive microcapsule at least within the same molecule. An image recording method using a recording material having a photosensitive and heat-sensitive recording layer containing a substantially colorless compound B having a site to be colored by photopolymerization, and a photopolymerizable composition comprising a photopolymerization initiator. In addition, at least, an exposure step in which the photopolymerizable composition forms a latent image by image exposure, a color forming component develops a color according to the latent image by heating, a color forming step in which an image is formed, and irradiating the surface of the recording layer with light. A fixing step of fixing the formed image and decoloring the photopolymerization initiator component.

<2> A color-forming component A encapsulated in a thermo-responsive microcapsule on a support, and a substantially colorless color-forming component outside the thermo-responsive microcapsule that reacts with at least the color-forming component A to form a color. A photopolymerizable composition comprising: a compound C; a substantially colorless compound D having a polymerizable group and a site for suppressing the reaction between the color forming component A and the compound C in the same molecule; and a photopolymerization initiator. An image recording method using a recording material having a light- and heat-sensitive recording layer containing a photosensitive material, wherein at least an exposure step in which the photopolymerizable composition forms a latent image by image exposure, and a coloring component is latent by heating. An image recording method comprising: a color forming step of forming a color according to 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 decolorize the photopolymerization initiator component. Is the way.

<3> When the photopolymerization initiator is 300 to 100
The image recording method according to <1> or <2>, 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.

<4> A microcapsule containing at least a color-forming component A, a photopolymerizable composition containing a polymerizable compound and a photopolymerization initiator on a support, and a microcapsule outside the microcapsule. , At least the coloring component A
An image recording method using a recording material having a photosensitive pressure-sensitive recording layer containing a substantially colorless compound E that reacts with and develops a color, wherein at least the photopolymerizable composition is exposed to the latent image by image exposure. An exposure process for forming a color, a color forming component develops a color according to the latent image by applying pressure, and a color forming process for forming an image; and irradiating the surface of the recording layer with light to fix the formed image and decolorize the photopolymerization initiator component. And an image fixing method.

<5> When the photopolymerization initiator is 300 to 100
The image recording method according to <4>, 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.

<6> The color-forming component A encapsulated in the thermo-responsive microcapsule on the support, and the polymerizable group and the color-forming component A react outside the thermo-responsive microcapsule at least within the same molecule. A substantially colorless compound B having a site to be colored by photopolymerization, and a photopolymerizable composition comprising: a photopolymerizable composition comprising: The agent is 300 to 1000
A recording material comprising: a spectral sensitizing compound having a maximum absorption wavelength in nm; and a compound interacting with the spectral sensitizing compound.

<7> A color-forming component A encapsulated in a heat-responsive microcapsule on a support, and a substantially colorless component that reacts with at least the color-forming component A to form a color outside the thermoresponsive microcapsule. A photopolymerizable composition comprising: a compound C; a substantially colorless compound D having a polymerizable group and a site for suppressing the reaction between the color forming component A and the compound C in the same molecule; and a photopolymerization initiator. And a recording material having a light- and heat-sensitive recording layer, wherein the photopolymerization initiator has a spectral sensitizing compound having a maximum absorption wavelength at 300 to 1000 nm, and a compound that interacts with the spectral sensitizing compound. And a recording material containing:

<8> A microcapsule containing at least a color-forming component A, a photopolymerizable composition containing a polymerizable compound and a photopolymerization initiator on a support, and a microcapsule outside the microcapsule. , At least the coloring component A
A substantially pressure-sensitive recording layer containing a substantially colorless compound E, which reacts with and develops a color, wherein the photopolymerization initiator has a maximum absorption wavelength of 300 to 1000 nm. A recording material comprising a compound and a compound that interacts with the spectral sensitizing compound.

<9> The recording material according to any one of <6> to <8>, wherein at least one of the compounds interacting with the spectral sensitizing compound is an organic borate salt compound.

<10> The recording material according to any one of the items <6> to <9>, wherein the recording material is a multicolor multilayer recording material in which recording layers each emitting a different hue are laminated.

<11> First, a multi-colored multi-layered recording material is formed on a support from the incident surface of irradiation light toward the thickness direction of the multi-layered recording material in response to light having a central wavelength λ ₁ of a light source.
The second recording layer, which is sensitive to light having a center wavelength λ ₂ and develops a color different from that of the first recording layer,..., Is sensitive to light having a center wavelength λ _i , And a multi-color multilayer recording material in which the i-th recording layer that develops a color different from that of the second,..., I-1st recording layers is sequentially stacked at least i ≧ 2 or more. A recording material according to <10>.

<12> The recording material according to <10> or <11>, wherein the multicolor multilayer recording material is a multilayer recording material having an intermediate layer between recording layers having different coloring hues.

<13> The above-mentioned <10>, wherein the multicolor multilayer recording material has a protective layer on the outermost layer on the incident surface side of the irradiation light.
<12> The recording material according to any one of <1> to <12>.

<14> The recording material may be any of the above <10> to <10
13> The recording material according to any one of the above, wherein the exposing step is a step in which the photopolymerizable composition forms a latent image by exposing the image using a plurality of light sources having different wavelengths, <1> to <4>, wherein the multicolor image is formed by applying a different hue according to each latent image formed on the light and heat sensitive recording layer having a different color hue by pressing.
3> The image recording method according to any one of the above.

<15> The recording material may be any of the above <10> to <
13> The recording material according to any one of the above, wherein the exposing step is a step in which the photopolymerizable composition forms a latent image by exposing the image using a plurality of light sources having different wavelengths, The process according to <4> or <5>, wherein the heating is performed to form a multicolor image by forming a different hue according to each latent image formed on the photosensitive pressure-sensitive recording layer having a different color hue. This is an image recording method.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the recording material and the image recording method of the present invention will be described in detail. The recording material used in the image recording method of the present invention is a light and heat sensitive recording material in which a light and heat sensitive recording layer is provided on a support or a light and pressure sensitive recording material in which a light and pressure sensitive recording layer is provided on a support. , A recording material having any one of the following constitutions (a) to (c). Further, the recording material is constituted by coating a single layer or two or more layers of a light and heat sensitive recording layer or a light and pressure sensitive recording layer on a support. That is,

(A) A thermoresponsive microcapsule enclosing a color-forming component A on a support, and a color is formed outside the microcapsule by reacting at least the polymerizable group in the same molecule with the color-forming component A. (B) a light- and heat-sensitive recording material having a light- and heat-sensitive recording layer containing a substantially colorless compound B having a moiety and a photopolymerizable composition comprising a photopolymerization initiator; A thermo-responsive microcapsule containing the color-forming component A, a substantially colorless compound C that reacts with the color-forming component A to form a color, and a polymerizable group and the color-forming group in the same molecule, outside the microcapsule Photosensitive and heat-sensitive recording layer having a photosensitive and heat-sensitive recording layer containing a substantially colorless compound D having a site for inhibiting the reaction between component A and compound C, and a photopolymerization initiator Recording material, also , (C) on a support, at least,
A microcapsule enclosing a color-forming component A, a photopolymerizable composition containing a polymerizable compound and a photopolymerization initiator, and at least outside the microcapsules, react with the color-forming component A to form a color. Substantially colorless compound E
And a photosensitive and pressure-sensitive recording material having a photosensitive and pressure-sensitive recording layer.

The photosensitive and heat-sensitive recording material (a) is cured by exposing it to a desired image shape to cause a photopolymerizable composition outside the microcapsules to undergo a polymerization reaction by radicals generated from a photopolymerization initiator. Then, a latent image having a desired image shape is formed. Next, by heating, the compound B present in the unexposed portion moves in the recording material and reacts with the color forming component A in the capsule to form a color. 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 photosensitive and heat-sensitive recording material (b) is exposed to a desired image shape, whereby the compound D having a polymerizable group is polymerized by radicals generated from a photopolymerization initiator reacted by the exposure to form a film. Cures to form a latent image having a desired image shape. Depending on the film properties of the latent image (cured portion), the compound C moves 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.

By exposing the photosensitive pressure-sensitive recording material (c) to a desired image shape, the polymerizable compound contained in the microcapsules coexists in the capsule.
The capsule is cured by radicals generated from the photopolymerization initiator reacted by the exposure, and the inside of the capsule is cured to form a latent image having a desired image shape. That is, in the exposed portion, the color-forming reaction with the compound C present outside the capsule is suppressed, and the compound C present in the unexposed portion moves within the recording material by applying pressure, and the color-forming component A in the capsule and It reacts and develops color. Therefore, it is a positive photosensitive pressure-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.

Further, a light and heat sensitive recording material or a light and pressure sensitive recording material having a light and heat sensitive recording layer or a light and pressure sensitive recording layer formed by forming a plurality of recording layers on a support may be used. In this case, it is possible to realize a multicolor image by laminating a plurality of monochromatic recording layers in which a coloring component A that develops a different hue is present in a capsule, and irradiating with a plurality of light sources having different wavelengths. it can.

Specific examples of the recording material include the following (1) to (3). (1) A photocurable composition and a microcapsule containing a compound having an electron-accepting group and a polymerizable group in the same molecule, a photopolymerization initiator, and a microcapsule described in JP-A-3-87827. A positive-type light- and heat-sensitive recording material provided with a light- and heat-sensitive recording layer containing an encapsulated electron-donating colorless dye. This light and heat sensitive recording material, the photocurable composition outside the microcapsule is polymerized and cured by exposure,
A latent image is formed. Thereafter, by heating, the compound having the electron accepting group and the polymerizable group present in the unexposed portion in the same molecule moves in the recording material, reacts with the colorless electron donating dye in the microcapsules, and develops a color. Therefore, the cured latent image portion of the exposed portion does not develop color, and only the uncured portion develops color, so that a clear positive image with high contrast can be formed.

(2) A photosensitive composition described in JP-A-4-21252, which contains an electron-accepting compound, a polymerizable vinyl monomer, a photopolymerization initiator, and an electron-donating colorless dye encapsulated in the microcapsules outside the microcapsules. Negative-type photosensitive and heat-sensitive recording material provided with a heat-sensitive recording layer. Although the mechanism is not clear, the vinyl monomer present outside the microcapsule is polymerized by the exposure, while the electron-accepting compound coexisting in the exposed portion is not incorporated into the formed polymer at all, but rather is formed with the vinyl monomer. Is reduced, and exists in a movable state with a high diffusion rate. On the other hand, the electron-accepting compound in the unexposed area is trapped by the coexisting vinyl monomer, so that when heated, the electron-accepting compound in the exposed area moves preferentially in the recording material, and the microcapsules This is presumably because, although it reacts with the electron-donating colorless dye, the electron-accepting compound in the unexposed portion cannot pass through the capsule wall even when heated, does not react with the electron-donating colorless dye, and 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.

(3) A photosensitive pressure-sensitive recording layer containing a microcapsule containing a developer, a photocurable composition, and a colored precursor is coated on the outside of the microcapsule described in US Pat. No. 4,399,209 or the like. Positive photosensitive pressure-sensitive recording material installed. In this photosensitive pressure-sensitive recording material, the photocurable composition inside the microcapsules is cured by exposure, and a latent image is formed. Thereafter, the developer existing in the unexposed portion moves in the recording material due to the pressurization, reacts with the colored precursor in the microcapsule, and develops a color. Therefore, the cured latent image portion of the exposed portion does not develop color, and only the uncured portion develops color, so that a clear positive image with high contrast can be formed.

The image recording method of the present invention is an image recording method using the above-mentioned light- and heat-sensitive recording material or light- and pressure-sensitive recording material. First, at least the photopolymerizable composition forms a latent image by image exposure. Exposure step, the color forming component develops a color according to the latent image by heating, and the color forming step of forming an image, and the fixing step of irradiating the surface of the recording layer with light to fix the formed image and decolorize the photopolymerization initiator component Second, an image recording method having
At least, an exposure step in which the photopolymerizable composition forms a latent image by image exposure, a coloring component in which a color-forming component develops a color according to the latent image by applying pressure, and a color-forming step in which an image is formed, and the recording layer surface is formed by light irradiation. Fixing the image and decoloring the photopolymerization initiator component.

In the first image forming method, the light and heat sensitive recording material (a) or (b) is suitably used.
In the second image forming method, the photosensitive and pressure-sensitive recording material (c) is used.
Is preferably used.

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 the color forming step, the color forming component contained in the recording layer by heating or pressurizing the recording layer surface reacts with the compound that forms a color by reacting with the color forming component or a specific group in the compound that forms a color. A color is formed in the shape of the formed latent image to form an image.

In the exposure step, a light-absorbing material such as a spectral sensitizing compound having absorption in a specific region in the recording layer is used as a light source for forming an image, so that the light source wavelength is in the ultraviolet to infrared region. Can be appropriately selected from known light sources. Specifically, a light source having a maximum absorption wavelength in the range of 300 to 1000 nm is preferable. Among them, a laser light source or an LED such as blue, green, or red is preferred in that the device can be simplified and reduced in size and cost can be reduced. More preferred. In this case, it is preferable to appropriately select a light source having a wavelength compatible with 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, a small and inexpensive infrared laser, or the like can be used, and not only can its use be expanded, but also the sensitivity and sharpness of the recording material itself can be improved.

In the image recording method of the present invention, a fixing step is provided after the color forming step. In the fixing step, the image formed in the color forming step is fixed by irradiating the entire surface of the recording layer with light from a specific light source, and the coloring by the photopolymerization initiator component remaining in the recording layer is eliminated. To color. By going through the fixing step,
The whiteness of the non-image area can be improved, 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, discoloration, etc. It is also useful for stabilizing the storage.

Light sources usable in the fixing step include:
Mercury lamp, ultra high pressure mercury lamp, electrodeless mercury lamp, xenon lamp, tungsten lamp, metal halide lamp,
A wide range of light sources such as fluorescent lamps can be suitably mentioned. Above all, it is preferable to appropriately select and use a light source having a wavelength suitable for the absorption wavelength of the photopolymerization initiator used in the photosensitive heat-sensitive recording layer or the photosensitive pressure-sensitive recording layer of the recording material.

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 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.

The light irradiation time in the fixing step may be such that the formed image is fixed and the non-image area (background area) is irradiated for a time sufficient to erase the color. From the viewpoint of not lowering the recording speed while obtaining, it is preferably several seconds to several tens of minutes, more preferably several seconds to several minutes.

Next, the recording material of the present invention used in the image recording method of the present invention will be described. Examples of the basic structure of the recording material of the present invention include those corresponding to the recording materials (a) to (c), and each component thereof will be described in detail below. In the recording material, a coloring component A encapsulated in a microcapsule and the coloring component A
And a substantially colorless compound capable of forming a color by reacting with the compound (compound B, compound C or compound E; hereinafter, it may be referred to as “compound that causes color development”). As the combination of the two components (color-forming component A and the compound to be colored) as the color-forming source, the following combinations (A) to (T) can be preferably mentioned (in the following examples, the former is a color-forming component and the latter is a latter). Represents a compound that develops color.).

(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) A combination of a higher aliphatic heavy metal salt 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).

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

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

Examples of the phthalide compound include, for example, US Pat. No. Re. 23,024 and US Pat.
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 compound include benzoyl leucon methylene blue, p-nitrobenzyl leucomethylene blue and the like.

The leuco auramine compounds include, for example, 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.

As the spiropyran-based compound, 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 the compounds described in US Pat. Nos. 3,775,424, 3,853,869 and 4,246,318.

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

When the recording material of the present invention is used as a full-color recording material, electron-donating colorless dyes for cyan, magenta and yellow coloring dyes are used. As cyan, magenta and yellow coloring dyes, U.S. Pat.
Each dye described in JP-A No. 0,149 or the like 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 electron-donating colorless dye used may be 0.01 to 0.01 in the light and heat sensitive recording layer or the light and pressure sensitive recording layer.
To 3 g / m ² is preferred, and 0.1 to 1 g / m ² is more preferred. If the amount is less than 0.01 g / m ² , a sufficient color density may not be obtained,
If it exceeds 3 g / m ² , the coating aptitude may deteriorate. 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. ]

The 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 has 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, 4-cyanophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-butoxyphenyl, 4- (2-ethylhexyloxy) phenyl, -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.

The maximum absorption wavelength λ _max of the diazonium salt compound used in the present invention is preferably 450 nm or less, more preferably 290 to 440 nm, from the viewpoint of the effect. The diazonium salt compound used in the present invention is preferably a diazonium salt compound having 12 or more carbon atoms, having 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 will be shown, but the present invention is not limited thereto.

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The diazonium salt compounds may be used alone or in combination of two or more according to various purposes such as hue adjustment.

The amount of the diazonium salt compound used is 0.01 to 0.01 in the light and heat sensitive recording layer or the light and pressure sensitive recording layer.
Preferably ^{3g / m 2, 0.02~1.0g / m} 2 is more preferable. When the amount is less than 0.01 g / m ² , sufficient coloring may not be obtained,
If it exceeds 3 g / m ² , the sensitivity may decrease or the fixing time may need to be increased. 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 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 an electron having a polymerizable group. Any one having both functions of reacting with the color-forming component A, such as a receptor compound or a coupler compound having a polymerizable group, to form a color and reacting with light to polymerize and cure, can be used. . Further, in the photosensitive pressure-sensitive recording material of the present invention, the compound B can be used as a substantially colorless compound E which is present outside the microcapsules and reacts with the color forming component A to form a color.

An electron-accepting compound having the polymerizable group,
That is, as the compound having an electron-accepting group and a polymerizable group in the same molecule, the compound having a polymerizable group and the coloring component A
Any one can be used as long as it reacts with an electron-donating colorless dye, which is one of the above, and develops a color, and can cure the film by photopolymerization. Examples of the electron accepting compound include 3-halo-4-hydroxybenzoic acid described in JP-A-4-226455, methacryloxyethyl ester of a benzoic acid having a hydroxy group described in JP-A-63-173682, Acryloxyethyl ester, 59-8369
Nos. 3, 60-141587 and 62-99190, esters of hydroxymethyl benzoic acid and hydroxymethylstyrene, hydroxystyrenes described in EP 29323, JP-A-62-167077.
No. 62-16708.
-Vinyl imidazole complex, and compounds that can be synthesized with reference to the electron-accepting compound described in JP-A-63-317558, 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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[In the formula, X represents a halogen atom, and among them, a chlorine atom is preferable. Y represents a monovalent group having a polymerizable ethylene group, and among them, 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 carbon number 6-12 methacryloyloxyalkyl groups are more preferred. Z represents a hydrogen atom, 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.

The electron accepting compound having a polymerizable group is used in combination with the electron donating colorless dye.
In this case, the amount of the electron accepting compound used is 0.5 to 20 parts by weight based on 1 part by weight of the electron donating colorless dye used.
A weight part is preferable and 3 to 10 weight parts is more preferable.
If the amount is less than 0.5 part by weight, a sufficient color density may not be obtained, and if the amount is more than 20 parts by weight, sensitivity may be lowered and coating suitability may be deteriorated.

As the coupler compound having a polymerizable group, the film is formed by reacting with a diazonium salt compound having a polymerizable group and being one of the color forming components A, and photopolymerizing to form a film. Any material that can be cured can be used. 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 is a diazonium chloride
Use in combination with the compound. Light and heat sensitive recording layer or light and pressure sensitivity
In the recording layer, as the amount of the coupler compound used
Is 0.02 to 5 g / m^TwoIs preferable, and from the point of effect,
0.1-4 g / m ^TwoIs more preferred. The addition amount is,
0.02 g / m^TwoIf it is less than the above, the coloring property may be poor.
5g / m^TwoIf it exceeds, the suitability for application may deteriorate
is there.

The amount of the coupler compound used is as follows:
The amount is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 1 part by weight of the diazonium salt compound. If the amount is less than 0.5 part by weight, sufficient coloring properties may not be obtained. If the amount is more than 20 parts by weight, coating suitability may be deteriorated.

The coupler compound can be used by adding a water-soluble polymer together with other components and solid-dispersing it with a sand mill or the like, but can also 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 can be appropriately selected from known methods. For details of the method, see JP-A-59-190886.
JP-A-2-141279, JP-A-7-17145
No.

For the purpose of accelerating the coupling reaction, it is preferable to use an organic base such as tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines, morpholines and the like. .

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. The 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
No., Japanese Patent Application No. 7-228731, Japanese Patent Application No. 7-23515
No. 7, Japanese Patent Application No. 7-235158, and the like.

The amount of the organic base to be used is not particularly limited, but is preferably 1 mol of the diazonium salt.
1 to 30 mol is preferred.

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

In the present invention, instead of the compound B having a polymerizable group as described above, the compound which reacts with the color forming component A and reacts with the color forming component A having no polymerizable group is used. A substantially colorless compound C that develops color can also 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. As the compound D, a suitable compound D, that is, a specific photopolymerizable monomer (D ¹ , D ² ) is selected and used according to the compound C to be used. Also, in the photosensitive pressure-sensitive recording material of the present invention, the compound C can be used as a substantially colorless compound E which is present outside the microcapsules and reacts with the color forming component A to form a color.

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.

Among 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.

Examples of the salicylic acid derivative include, 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 use amount of the electron accepting compound having no polymerizable group is preferably 5 to 1000% by weight based on the use amount of the electron donating colorless dye.

When an electron-accepting compound having no polymerizable group is used, compound D, that is, a specific photopolymerizable monomer D
^{Use 1} together. Further, in the photosensitive pressure-sensitive recording material of the present invention,
Said photopolymerizable monomer D ^1, used as a polymerizable compound to be contained in microcapsules. The photopolymerization monomer D ^1, has a reaction suppressing function of the electron-donating colorless dye and an electron accepting compound is preferably a photopolymerizable monomer having at least one vinyl group in the molecule. Specifically, acrylic acid and its salts, acrylic esters, acrylamides; methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride, maleic esters; itaconic acid, itaconic esters Styrenes; vinyl ethers; vinyl esters; N-vinyl heterocycles; aryl ethers;

Of the above, it is preferable to use a photopolymerizable monomer having a plurality of vinyl groups in the molecule, for example, an acrylate or methacrylate of a polyhydric alcohol such as trimethylolpropane or pentaerythritol; Examples include acrylic acid esters and methacrylic acid esters of polyhydric phenols such as resorcinol, pyrogallol, and phloroglucinol, and bisphenols; acrylate or methacrylate-terminated epoxy resins; and acrylate or methacrylate-terminated polyester.

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. .

[0115] The molecular weight of the photopolymerizable monomers D ^1, preferably from about 100 to about 5000, from about 300 to about 2
000 is more preferred.

[0116] The amount of the photopolymerizable monomer D ^1, to substantially colorless compound C1 parts by weight of color by reacting with the color forming component A, preferably 0.1 to 10 parts by weight, 0. 5 to 5 parts by weight are more preferred. 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 form a color by reacting with the diazonium salt compound which is one of the color forming components A. 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 a 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.

Details of coupler compounds 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
No. 70, JP-A-7-316280 and the like. The present applicant has previously filed Japanese Patent Application No. Hei 8-02270.
No. 95, Japanese Patent Application No. 8-027096, Japanese Patent Application No. 8-030
No. 799, Japanese Patent Application No. 8-12610, Japanese Patent Application No. 8-132
394, Japanese Patent Application No. 8-358755, Japanese Patent Application 8-35
No. 8756, Japanese Patent Application No. 9-069990 and the like 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.
² is preferred, and from the viewpoint of the effect, 0.1 to 4 g / m ² is more preferred. If the amount is less than 0.02 g / m ² , a sufficient color density may not be obtained, and 5 g / m ²
If it exceeds m ² , the coating aptitude may deteriorate.

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.

[0127] When using a coupler compound free the polymerizable group, compound D, ie, used together specific photopolymerizable monomer D ^2, as the photopolymerizable monomer D ^2, the coupling reaction It is preferably a photopolymerizable monomer having an acidic group having a suppressing effect and not being a metal salt compound.

[0128] As the photopolymerizable monomer D ^2, for example, styrene sulfonylamino acid, vinyl benzyloxy phthalate, beta-methacryloxy ethoxy salicylic acid zinc, beta-acryloxy ethoxy salicylic acid zinc, vinyloxy ethyl oxybenzoate, beta -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.

[0131] The amount of the photopolymerizable monomer D ^2, to substantially colorless compound C1 parts by weight of color by reacting with the color forming component A, preferably 0.1 to 10 parts by weight, 0. 5 to 5 parts by weight are more preferred. 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 exceeds 10 parts by weight, the color density may decrease.

As the substantially colorless compound E which reacts with the color-forming component A and forms a color, the compound E having a polymerizable group may be used in the photosensitive pressure-sensitive recording layer of the photosensitive pressure-sensitive recording material of the present invention.
Any of those which do not have the coloring component A
Any substance capable of forming a color by reacting with the above can be used. For example, as described above, the same electron accepting compounds and coupler compounds as those described in Compound B having a polymerizable group and Compound C not having a polymerizable group can be used.

Next, the photopolymerization initiator used in the light and heat sensitive recording layer or the light and pressure sensitive recording layer of the recording material of the present invention will be described. The photopolymerization initiator comprises the recording materials (a) to
It can be used in any of the cases (c), and can generate radicals by light exposure to cause a polymerization reaction in the layer and promote the reaction. The recording layer film is cured by this polymerization reaction, and a latent image having a desired image shape can be formed.

The photopolymerization initiator can be appropriately selected from known ones.
It preferably contains a spectral sensitizing compound having a maximum absorption wavelength at m and a compound that interacts with the spectral sensitizing compound. However, if the compound interacting with the spectral sensitizing compound is a compound having both the structure of the dye portion and the borate portion having the maximum absorption wavelength at 300 to 1000 nm in the structure, the spectral sensitizing dye is used. It is not necessary. The recording material of the present invention is a light and heat sensitive recording material or a light and pressure sensitive recording material having a light and heat sensitive recording layer or a light and pressure sensitive recording layer containing a photopolymerization initiator containing these. Further, the image recording method of the recording material of the present invention is preferably an image recording method using these recording materials.

Known photopolymerization initiators include, 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.

Further, 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.

The spectral sensitizing compound having a maximum absorption wavelength in the range of 300 to 1000 nm is preferably a spectral sensitizing dye having a maximum absorption wavelength in this wavelength region. Select 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 as the light source used for image exposure, a light source such as blue, green, red, or an infrared laser can be selected. . Therefore, for example, when a color image is formed by using a multicolor recording material in which monochromatic recording layers that develop different hues are stacked, spectral enhancement having different absorption wavelengths in each monochromatic layer having a different color hue is used. By using a light source suitable for the absorption wavelength of the dye in the presence of a dye, multi-color recording can be performed because each layer (each color) forms a highly sensitive and sharp image even in a multi-layered recording material. High sensitivity and sharpness can be achieved for the entire material.

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

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

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

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

The spectral sensitivity of the photopolymerization initiator used in the recording material of the present invention can be obtained in the ultraviolet to infrared region by appropriately using the spectral sensitizing dye. In addition, the above-mentioned 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 set to 0.1 to the total weight of the light and heat sensitive recording layer or the light and pressure sensitive recording layer.
It is preferably from 1 to 5% by weight, more preferably from 0.5 to 2% by weight.

As the compound interacting with the spectral sensitizing compound, the photopolymerizable group in the compound B or the compound D
From the known compounds capable of initiating a photopolymerization reaction with the (photopolymerizable monomer), one or more compounds can be appropriately selected and used. By allowing this compound to coexist with the above-mentioned spectral sensitizing compound, it can sensitively respond to irradiation light in the spectral absorption wavelength region and can generate radicals with high efficiency. The generation of radicals can be controlled using an arbitrary light source in the outer region. Examples of the compound that interacts 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 triphenylbutyrate borate, tetramethylammonium salt of tri (P-methoxyphenyl) butyrate borate 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 for the recording material of the present invention. Examples of the combination of two or more compounds include, for example, a combination of a 2,4,5-triarylimidazole dimer and a mercaptobenzoxazole, and the 4,4′- described in US Pat. No. 3,427,161. A combination of bis (dimethylamino) benzophenone, benzophenone and benzoin methyl ether,
Combination of benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromerchi) -6- (4'-methoxyphenyl) -triazole described in U.S. Pat. No. 4,239,850, JP-A-57-23602. Combinations of dialkylaminobenzoic acid esters and dimethylthioxanthone described in the specification, and triads of 4,4'-bis (dimethylamino) benzophenone, benzophenone, and polyhalogenated methyl compounds described in JP-A-59-78339. And the like.

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

Of the "compounds that interact with the spectral sensitizing compound", organic borate salt compounds, benzoin ethers, S-triazine derivatives having a trihalogen-substituted methyl group, organic peroxides and azinium salt compounds are preferred. And organic borate salt compounds are more preferred. By using this “compound that interacts with the spectral sensitizing compound” in combination with the spectral sensitizing compound, it is possible to locally and effectively generate radicals in the exposed portions exposed to light, thereby increasing the sensitivity. Can be achieved.

Examples of the organic borate salt compounds include those described in 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.

[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0162]

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[0163]

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Further, in the recording material of the present invention, the above-mentioned “Functional Dye Chemistry” (1981, CMC Publishing Co., p. 393)
Pp. 416) and “colorants” (60 [4] 212-224)
(1987)) and the like, and spectral sensitizing dye-based organic borate compounds (borate compounds II) obtainable from the cationic dyes described in (1987)). This borate compound
II is a compound that has both a dye part and a borate part in its structure.It absorbs light source energy effectively by the light absorption function of the dye part during exposure and promotes the polymerization reaction by the radical release function of the borate part. At the same time, it has the three functions of decoloring the coexisting spectral sensitizing compound.

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

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

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

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The borate compound II is a multifunctional compound as described above. However, from the viewpoint of obtaining high sensitivity and sufficient decoloration, the photopolymerization initiator is used in the recording material of the present invention. It is preferable that a sensitizing compound and a compound that interacts with the spectral sensitizing compound are appropriately combined. In this case, as the photopolymerization initiator, a photopolymerization initiator (1) obtained by combining the spectral sensitizing compound and the borate compound I, or the borate compound I and the borate compound II
More preferably, the photopolymerization initiator (2) is a combination of

At this time, the use ratio of the spectral sensitizing dye and the organic borate compound present in the photopolymerization initiator is very important from the viewpoint of increasing the sensitivity and obtaining sufficient decolorability by light irradiation in the fixing step. Becomes In the case of the photopolymerization initiator (1), in addition to the spectral sensitizing compound / borate compound I ratio (= 1/1: molar ratio) necessary for the photopolymerization reaction, It is particularly preferable to add an amount of the borate compound I necessary for sufficiently decoloring the remaining spectral sensitizing compound from the viewpoint of obtaining sufficiently high sensitivity and decoloring performance. That is, the ratio of spectral sensitizing dye / borate compound I is 1/1 to 1/5.
It is preferable to use in the range of 0;
More preferably, it is used in the range of 1 / 1.30.
Most preferably, it is used in the range of 2 to 1/20. If the above ratio is less than 1/1, sufficient polymerization reactivity and decoloring property cannot be obtained, and if it exceeds 1/50, coating suitability is deteriorated, which is not preferable.

In the case of the photopolymerization initiator (2), the borate compound I and the borate compound II may be used in combination such that the borate site is at least equimolar to the dye site. It is particularly preferable from the viewpoint of obtaining sufficiently high sensitivity and decoloring performance. The ratio of borate compound I / borate compound II is preferably used in the range of 1/1 to 50/1, more preferably in the range of 1.2 / 1 to 30/1, but is preferably 1.2 to 30/1. Most preferably, it is used in the range of / 1 to 20/1. When the ratio is less than 1/1, the generation of radicals is small, and sufficient polymerization reactivity and decoloring performance cannot be obtained. When the ratio is more than 50/1, sufficient sensitivity cannot be obtained, which is not preferable.

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

The photopolymerizable composition of the recording material 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 for the purpose of accelerating the polymerization reaction. Alternatively, other compounds that promote polymerization by chain transfer can be added.
As the oxygen removing agent, phosphine, phosphonate,
Examples include phosphites, primary silver salts or other compounds that are easily oxidized by oxygen. Specifically, N-phenylglycine, trimethylparbituric acid, N, N-dimethyl-2,6-diisopropylaniline, N, N, N
-2,4,6-pentamethylanilic acid.
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.

The recording material of the present invention is not limited to the recording materials (a) to (c) described above, but can have various structures depending on the purpose, and is a monochromatic recording material. Alternatively, a multicolor recording material may be used. If necessary, a protective layer can be provided on the outermost layer on the light and heat sensitive recording layer or the light and pressure 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 crosslinking the water-soluble polymer compound used in 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 from 0.2 to 5
preferably ^{g / m 2, 0.5~3g / m} 2 is more preferable.

In the case of a multicolor recording material, a plurality of single-color recording layers are laminated on a support, microcapsules each containing a coloring component having a different coloring hue, and microcapsules each having a different wavelength. And a photopolymerizable composition that is sensitive to the above-mentioned light to obtain a multicolored multilayer recording material. The photopolymerizable composition can be a photopolymerizable composition that is sensitive to light of different wavelengths by using spectral sensitizing compounds having different absorption wavelengths. In this case, an intermediate layer may be provided between the recording layers of each single color.

Photothermographic recording of the multicolor multilayer recording material of the present invention
The recording layer or the photosensitive pressure-sensitive recording layer, for example, as follows
Obtainable. Contains a coloring component that produces yellow color
Microcapsule and light source center wavelength λ ₁Exposed to
A first recording layer containing a photopolymerizable composition and
And contains a magenta color-forming component on the layer
Microcapsules and center wavelength λ_TwoSensitized to light
A second recording layer containing
On that layer, a microphone containing a coloring component that develops cyan
Capsule and wavelength λ_ThreeA photopolymerizable composition that is sensitive to
Heat-sensitive recording laminated by providing a third recording layer containing
Layer A or photosensitive pressure-sensitive recording layer A ', if necessary,
A light- and heat-sensitive recording layer B having an intermediate layer between each layer of A or A '
Or a photosensitive pressure-sensitive recording layer B 'or the like.
You.

When an image is formed using a recording material having a multicolor recording layer as described above, image exposure is performed using a plurality of light sources having different wavelengths suitable for the absorption wavelength of each recording layer in the exposure step. Accordingly, the recording layers having the absorption wavelength of the light source can selectively form a latent image, and a multicolor image can be formed with high sensitivity and high sharpness. Furthermore, by irradiating the surface of the recording layer with light, the coloring of the background portion due to the photopolymerization initiator such as the spectral sensitizing compound remaining in the layer can be erased, so that a high-contrast, high-quality image can be formed. Can be.

In the recording material of the present invention, the electron-donating colorless dye or diazonium salt compound to be used (hereinafter sometimes referred to as “color-forming component”) is used by being encapsulated in microcapsules. As a method for microencapsulation, a conventionally known method can be used. For example, a method using 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, British Patent No. 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 of microencapsulation is not limited to these, but in the recording material of the present invention, in particular, the coloring component is prepared by dissolving or dispersing it in a hydrophobic organic solvent serving as the core of the capsule. The oil phase thus obtained 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 for forming a capsule wall. 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.

In the preferred microcapsules of the present invention, at room temperature, contact of substances inside and outside the capsule is prevented by the substance-isolating action of the microcapsule wall (hereinafter, simply referred to as “capsule wall”), and heat and / or heat exceeds a certain value. Or it is such that the substance inside and outside the capsule can be contacted only when pressure is applied. This phenomenon is caused by the material of the capsule wall, the capsule core substance (the substance contained in the capsule),
By appropriately selecting additives and the like, changes in the physical properties of the capsule can be freely controlled.

The capsule wall material which can be used in the present invention is added inside the oil droplets and / or outside the oil droplets. Examples of the material of the capsule wall include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer and the like. Among them, polyurethane, polyurea, polyamide, polyester, and polycarbonate are preferable, and polyurethane and polyurea are more preferable. The polymer substances can be used in combination of two or more kinds.

Examples of the water-soluble polymer include gelatin, polyvinyl pyrrolidone, 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 include US Pat. Nos. 3,281,383, 3,737,695 and 3,792.
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 also be used.

In the present invention, when forming a microcapsule containing a color-forming component, the color-forming component contained therein may be present in a solution state or a solid state in the capsule. When the color-forming component is encapsulated in a solution state in a capsule, the color-forming component may be encapsulated in a state where the electron-donating colorless dye or the diazonium salt compound is dissolved in an organic solvent.

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. In the case of encapsulation, a so-called oil-less capsule may be used without using the above-mentioned organic solvent. The amount of the organic solvent used is preferably from 1 to 500 parts by weight based on 100 parts by weight of the electron-donating colorless dye.

When the solubility of the electron donating colorless dye or diazonium salt compound to be encapsulated in the organic solvent is low, a low-boiling solvent having high solubility may be used as an auxiliary solvent. it can.
On the other hand, the low boiling point solvent can be used without using the organic solvent. As the low boiling point solvent, for example,
Examples 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 to be 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 can be used as described above to interact with the protective colloid. However, those which do not cause precipitation or aggregation can be appropriately selected and used. Specifically, sodium alkylbenzene sulfonate, sodium alkyl sulfate, dioctyl sulfosuccinate sodium salt,
Polyalkylene glycol (for example, polyoxyethylene nonylphenyl ether) and the like can be mentioned. The amount of the surfactant to be added is from 0.1% to the weight of the oil phase.
5% is preferable, and 0.5% to 2% is more preferable.

All the components including the color-forming component can be used as a solid dispersion with a water-soluble polymer, a sensitizer and other color-forming auxiliaries by means of a sand mill or the like. After being dissolved in a high-boiling organic solvent that is hardly soluble or insoluble in water, this was mixed with a polymer aqueous solution (aqueous phase) containing a surfactant and / or a water-soluble polymer as a protective colloid, and emulsified with a homogenizer or the like. It is preferably used as an emulsified dispersion. In this case, if necessary, a low boiling point solvent can be used as a dissolution aid. Furthermore, all of the components including the color-forming component can be separately emulsified and dispersed, or can be mixed in advance and then dissolved in a high-boiling solvent and / or a low-boiling solvent to be emulsified and dispersed. The particle size of the emulsified particles formed by emulsification is preferably 1 μm or less.

In the emulsification and 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. for the purpose of promoting the capsule wall forming reaction. During the reaction, in order to prevent aggregation of the capsules, 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 present invention, the average particle size of the microcapsules 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.

When the recording material of the present invention is used as a multicolor recording material, the light- and heat-sensitive recording layer or the light- and pressure-sensitive recording layer of the recording material is constituted by laminating a plurality of single-color recording layers on a support. In each of the recording layers, a microcapsule containing an electron-donating colorless dye or a diazonium salt compound that develops a different hue, and a photopolymerizable composition containing a spectral sensitizing compound having a different maximum absorption wavelength, respectively. When contained, when irradiated with light, each recording layer is exposed to light due to the difference in the wavelength of the light source, so that a multi-color image is constituted as a whole of the photosensitive heat-sensitive recording layer or the photosensitive pressure-sensitive recording layer.

Further, an intermediate layer may be provided between the monochromatic recording layers constituting the light and heat sensitive recording layer or the light and pressure sensitive recording layer. The intermediate layer is mainly composed of a binder, and may contain additives such as a curing agent, a polymer latex, a filter dye, mica, and an ultraviolet absorber, if necessary.

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 mixed solution thereof, 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).

Above all, 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.

In the recording material of the present invention, the binder used for each layer such as the protective layer, the light and heat sensitive recording layer or the light and pressure sensitive recording layer, and the intermediate layer may be the same as the binder used for emulsifying and dispersing the photopolymerizable composition. In addition to water-soluble polymers used for encapsulating color-forming components, polystyrene,
Solvents such as acrylic resins such as polyvinyl formal, polyvinyl butyral, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and copolymers thereof, phenol resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, urethane resins, etc. Soluble polymers or latexes of these polymers can also be used. Among them,
Gelatin and polyvinyl alcohol are preferred.

In each of the recording layers constituting the recording material of the present invention, various surfactants can be used for various purposes such as a coating aid, antistatic, improvement of slipperiness, emulsification dispersion, and prevention of adhesion. . As the surfactant, for example, a nonionic surfactant saponin, polyethylene oxide,
Polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxy Examples include anionic surfactants such as ethylenalkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, and cationic surfactants such as aliphatic or aromatic quaternary ammonium salts.

Further, if necessary, for example, dyes, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids,
Additives such as a curing agent, an antistatic agent and a slipperiness improver can also be used. Specific examples of the additive include “Resea
rch Disclosure, Vol. 176 "(1
Item 17643), December 978)
l. 187 "(November 1979, Item 1871)
6).

In the recording material of the present invention, it is preferable to use a curing agent in combination with each layer such as a light and heat sensitive recording layer or a light and pressure sensitive recording layer, an intermediate layer and a 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. Halogen compounds, compounds having a reactive ethylenically unsaturated group described in U.S. Pat. No. 3,635,718, aziridine compounds described in U.S. Pat. No. 30,017,280, and epoxy compounds described in U.S. Pat. No. 3,091,537. , Halogenocarboxaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, vinyl sulfones described in US Pat. No. 3,642,486 and US Pat. No. 3,687,707, and vinyl sulfone breakers described in US Pat. No. 3,841,872. Kind, US special It includes Ketobiniru acids according to 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.

After dissolving each component in a solvent as needed, a coating solution for a photosensitive and heat-sensitive recording layer, a coating solution for a photosensitive and pressure-sensitive recording layer, a coating solution for a protective layer, and the like are prepared. By applying and drying, the recording material of the present invention can be obtained. As the solvent, water; methanol, ethanol,
Alcohols such as n-propanol, isopropanol, n-butanol, sec-butanol, methyl cellosolve, 1-methoxy-2-propanol; halogen solvents such as methylene chloride and ethylene chloride; ketones such as acetone, cyclohexanone and methyl ethyl ketone; methyl acetate Esters such as cellosolve, 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 or the coating solution for the light and pressure sensitive recording layer on the support, a blade coater, a rod coater, a knife coater, a roll doctor coater, a reverse roll coater, a transfer roll coater, A gravure coater, kiss roll coater, curtain coater, extrusion coater and the like can be used.

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

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

As the support used for the 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, polycarbonate film And a metal plate of aluminum, zinc, copper or the like; or a substrate obtained by subjecting the surface of such a support to various treatments such as surface treatment, undercoating, and metal vapor deposition. Also,
"Research Disclosure, Vol.
200 "(December 1980, Item 20036
The support of section XVII) can also be used. The various supports may contain a fluorescent whitening agent, a bluing dye, a pigment and the like.

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

Between the support and the light and heat sensitive recording layer or the light and pressure sensitive recording layer, or in the case of a transparent support, the surface of the support on which the light and heat sensitive recording layer or the light and pressure sensitive recording layer is not provided When the antihalation layer is provided,
An antihalation layer that can be bleached by light irradiation or heat can also be provided.

In the case of forming a layer which can be bleached by light irradiation, 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 or the light and pressure sensitive recording layer, a layer containing a polymer such as gelatin or polyvinyl alcohol (PVA) having a low oxygen permeability can be provided. By providing this layer, it is possible to effectively prevent fading due to photo-oxidation of the formed image.

The recording material of the present invention can form an image by performing a heat or pressure development treatment simultaneously with or after exposure for forming a latent image. When the recording material of the present invention is a light- and heat-sensitive recording material, a visible image can be formed by a heat development treatment, and when the recording material is a light- and pressure-sensitive recording material, a visible image can be formed by a pressure development treatment.

The heating method at the time of the heat development treatment can be appropriately selected from conventionally known methods. For example, the treatment can be carried out with a heat roller or the like. Generally, the heating temperature is preferably from 80 to 200 ° C, more preferably from 85 to 130 ° C. The heating temperature is
If the temperature is lower than 80 ° C., the color density may be insufficient. If the temperature is higher than 200 ° C., the non-image portion (background portion) 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.

The light and heat sensitive recording material of the present invention can be used not only in the above-mentioned 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 No. WO95 / 31754 can be used.
When irradiating a laser beam used for a silver halide light- and heat-sensitive recording material proposed by 3M Company, it can also be used in a recording method of forming an image by irradiating the laser beam so that the beam spots overlap in a predetermined range. That is, in the process of irradiating a laser beam at the time of forming a latent image, (1) a radiation light source capable of forming a beam spot whose height or length is at least 600 μm on a target object is prepared. (2) After arranging the recording material sensitive to this light source at a predetermined target 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.

The pressurizing method at the time of the pressurizing development can be appropriately selected from conventionally known methods.
Generally, the treatment can be performed using a pressurized platen roller, a point contact ball, or the like. The pressure at the time of pressurization is preferably 10 to 300 kg / cm ² , and 130 to ² kg / cm ^2.
00 kg / cm ² is more preferable. The pressure is 10k
If it is less than g / cm ² , a sufficient color density may not be obtained, and if it exceeds 300 kg / cm ² , even hardened microcapsules may be destroyed and image discrimination may be insufficient. .

After the heat-development treatment, the surface of the light- and heat-sensitive recording layer is irradiated with light to fix the formed image and to reduce the whiteness of the background of the spectral sensitizing compound, diazonium salt compound, etc. remaining in the recording layer. Decolor, decompose or deactivate the components to be made. Therefore, it is possible to remove a component coloring the background portion remaining in the recording layer including the background portion (non-image portion), and when the diazonium salt compound is used,
Since the remaining diazonium salt compound is also deactivated and the color development reaction can be suppressed, the density fluctuation of the formed image can be suppressed, and the image storability can be greatly improved.

[0234]

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

<Preparation of Electron-donating Colorless Dye-Encapsulated 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 the same manner as in the above (1-a) except that the following electron-donating colorless dye (4) of black color was used in place of 0.5μ
m of microcapsule liquid (IV) was obtained.

(1-e) Preparation of Microcapsule Solution (V) Encapsulating Electron-donating Colorless Dye In 10 g of ethyl acetate, 8.9 g of the following magenta-colored electron-donating colorless dye (2), 3 g of trimethylolpropane triacrylate, 1 g of dipentadierythritol hydroxypentaacrylate, 0.6 g of the organic borate compound (29) (borate compound I) shown above, and 0.1 g of the spectral sensitizing dye-based borate compound (26) (borate compound II) shown above And 0.1 g of pentamethylaniline are dissolved in a capsule wall material (trade name: Takenate D-110)
N, manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 g of capsule wall material (trade name: Millionate MR200, 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. Then
14 g of water and 72 g of a 2.9% aqueous solution of tetraethylenepentamine were added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring, and after 2 hours, the following electron-donating colorless dye (2)
And a microcapsule liquid (V) having an average particle size of 7 μm was obtained.

[0240]

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<Preparation of Photopolymerizable Composition Emulsion> (2-a) Preparation of Photopolymerizable Composition Emulsion (1) 0.6 g of the organic borate compound (29) (borate compound I) shown above was prepared. 0.1 g of the above-mentioned spectral sensitizing dye-based borate compound (26) (borate compound II),
The following electron accepting compound having a polymerizable group in a mixed solution of 0.1 g of the following auxiliary agent (1) for the purpose of increasing the sensitivity and 3 g of isopropyl acetate (solubility in water: about 4.3%) (1) 5 g was added. 13 g of a 13% aqueous solution of gelatin, 0.8 g of a 2% aqueous solution of surfactant (1) described below, and 0.8 g of an aqueous solution of 2% surfactant (2) described below
And emulsified at 10,000 rpm for 5 minutes using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsion (1) of a photopolymerizable composition.

[0242]

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[0243]

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(2-b) Preparation of emulsion of photopolymerizable composition (2) In place of the spectral sensitizing dye-based borate compound (26) used in (2-a), the spectral sensitization described above was used. A photopolymerizable composition emulsion (2) was obtained in the same manner as in (2-a), except that 0.1 g of the dye-based borate compound (28) (borate compound II) was used.

(2-c) Preparation of Photopolymerizable Composition Emulsion (3) In place of the spectral sensitizing dye-based borate compound (26) used in (2-a), the spectral sensitization described above was used. A photopolymerizable composition emulsion (3) was obtained in the same manner as in (2-a) except that 0.1 g of the dye-based borate compound (30) (borate compound II) was used.

<Emulsion of Electron-Accepting Compound> (2-d) Preparation of Emulsion of Electron-Accepting Compound (α) 3 g of isopropyl acetate (solubility in water: about 4.3%) having a polymerizable group 5 g of electron-accepting compound (1)
Was added. The obtained solution was added to a 13% aqueous gelatin solution 1
3 g, and 0.8 g of the 2% aqueous solution of the surfactant (1),
The mixture was added to a mixed solution of 0.8 g of the 2% aqueous solution of the surfactant (2) and emulsified at 10,000 rpm for 5 minutes using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to emulsify the electron-accepting compound. A liquid (α) was obtained.

<Preparation of Coating Solution for Photosensitive and Thermosensitive Recording Layer> (3-a) Preparation of Coating Solution (1) for Photosensitive and Thermosensitive Recording Layer— [Black] Microcapsule solution (IV) containing an electron-donating colorless dye 4 g
And 12 g of a photopolymerizable composition emulsion (2) and 12 g of a 15% aqueous gelatin solution to prepare a coating solution (1) for a photosensitive and heat-sensitive recording layer.

(3-b) Coating solution for photosensitive and heat-sensitive recording layer (2)
Preparation of [Yellow] Electron-donating colorless dye-containing microcapsule liquid (I) 4 g
And 12 g of a photopolymerizable composition emulsion (2) and 12 g of a 15% aqueous solution of gelatin to prepare a coating solution (2) for a photosensitive and heat-sensitive recording layer.

(3-c) Coating solution for photosensitive and heat-sensitive recording layer (3)
Preparation of [Magenta] Electron-donating colorless dye-containing microcapsule liquid (II) 4 g
And 12 g of a photopolymerizable composition emulsion (2) and 12 g of a 15% aqueous solution of gelatin to prepare a coating solution (3) for a photosensitive and heat-sensitive recording layer.

(3-d) Coating solution for photosensitive and heat-sensitive recording layer (4)
Preparation-[cyan] 4 g of microcapsule liquid (III) containing an electron-donating colorless dye
And 12 g of a photopolymerizable composition emulsion (2) and 12 g of a 15% aqueous solution of gelatin to prepare a coating solution (4) for a light and heat sensitive recording layer.

(3-e) Coating solution for photosensitive and heat-sensitive recording layer (5)
Preparation of [Yellow] Electron-donating colorless dye-containing microcapsule liquid (I) 4 g
And 12 g of a photopolymerizable composition emulsion (1) and 12 g of a 15% aqueous solution of gelatin to prepare a coating solution (5) for a photosensitive and heat-sensitive recording layer.

(3-f) Coating solution for photosensitive and heat-sensitive recording layer (6)
Preparation of [Magenta] Electron-donating colorless dye-containing microcapsule liquid (II) 4 g
And 12 g of a photopolymerizable composition emulsion (2) and 12 g of a 15% aqueous gelatin solution to prepare a coating solution (6) for a photosensitive and heat-sensitive recording layer.

(3-g) Coating solution for photosensitive and heat-sensitive recording layer (7)
Preparation-[cyan] 4 g of microcapsule liquid (III) containing an electron-donating colorless dye
And 12 g of a photopolymerizable composition emulsion (3) and 12 g of a 15% aqueous solution of gelatin to prepare a coating solution (7) for a photosensitive and heat-sensitive recording layer.

<Preparation of Coating Solution for Photosensitive Pressure-Sensitive Recording Layer> (3-h) Preparation of Coating Solution (i) for Photosensitive Pressure-Sensitive Recording Layer- [Magenta] 4 g of electron-donating colorless dye-containing microcapsule solution (V)
And 12 g of an electron-accepting compound emulsion (α) and 12 g of a 15% aqueous gelatin solution to prepare a coating solution (i) for a photosensitive pressure-sensitive recording layer.

<Preparation of Coating Solution for Intermediate Layer> A coating solution for an intermediate layer was prepared by mixing 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). (1) was prepared.

<Preparation of Coating Solution for Protective Layer> 4.5 g of a 10% gelatin aqueous solution, 4.5 g of distilled water, 0.5 g of the 2% surfactant (3) aqueous solution, and 2 g of the 2% surfactant ( 4) 0.3 g of an aqueous solution, 0.5 g of a 2% aqueous solution of a vinyl sulfone compound (hardening agent), and a dry coating amount of 50 mg /
The amount of Syloid 72 (FUJI required when the m ²
-DEVICE CHEMICAL DTD. Made)
Was mixed with 1 g of Snowtex N to prepare the coating solution (1) for the protective layer.

Example 1 Black Color Polyethylene terephthalate (PE having a thickness of 175 μm)
T) The coating solution (1) for a light and heat sensitive recording layer was applied on a blue base support using a coating bar so that the dry weight of the entire coating layer was 30 g / m ² , and dried. On this layer, a coating liquid for protective layer (1) was applied using a coating bar so that the dry weight of the coated layer became 2 g / m ² , and dried to obtain a light and heat sensitive recording material (1). .

The photosensitive and heat-sensitive recording material (1) was irradiated from the protective layer side with a semiconductor-excited YLF solid laser beam having a wavelength of 657 nm at a maximum irradiation energy of 15 mJ / cm ² .
Exposure was performed in an image shape in the form of a step wedge so that the irradiation energy gradually changed. After heating the recording material on which the latent image was formed by the exposure with a hot plate at 120 ° C. for 5 seconds,
This recording material was irradiated with light on the entire surface of the recording layer of the recording material for 30 seconds on a 58000 lux high-intensity Sharksten. As a result, a clear wedge-shaped image was obtained in which the color developed vividly and the background had high whiteness.

<Evaluation of Sensitivity> Sensitivity corresponds to the irradiation energy in this step and the energy required to form the background portion of each material in one step, which corresponds to the same exposure amount in the wedge image of each material. (Energy until formation of the background portion-irradiation energy in the step) was measured and calculated, and used as an index of sensitivity.
Therefore, the smaller the sensitivity, the higher the sensitivity. The measured results are shown in Table 1 below.

<Thermo treatment> The light and heat sensitive recording material (1) obtained as described above was allowed to stand for 1 day in an environment of a temperature of 50 ° C. and a relative humidity of 30% RH.

<Measurement of Density> The color density (Dmax), the background fog (Dmin) and the background fog after thermo-processing (Dmin-S) were measured using a Macbeth transmission densitometer or a Macbeth reflection densitometer (Macbeth Co., Ltd.). Was used for the measurement. These measurement results are shown in Table 1 below together with the results.
Shown in

(Example 2): Yellow-colored polyester film filled with a white pigment (Lumirror E
-68 L, manufactured by Toray Industries Co., Ltd.) On a support having a thickness of 100 μm, apply the coating solution (2) for the photosensitive and heat-sensitive layer using a coating bar so that the dry weight of the entire coating layer becomes 6 g / m ^2. And dried. On this layer, a coating liquid for protective layer (1) was applied using a coating bar so that the dry weight of the applied layer was 2 g / m ² , and dried to obtain a light and heat sensitive recording material (2). . A step wedge-shaped image was formed on the photosensitive and heat-sensitive recording material (2) in the same manner as in Example 1. As a result, a clear wedge-shaped image was obtained in which the color developed vividly and the background had high whiteness. The sensitivity, color density, and fog density before and after the thermoprocessing of the light and heat sensitive recording material (2) were measured by the same method as in Example 1, and the results are shown in Table 1 below.

(Example 3): Magenta-colored polyester film filled with a white pigment (Lumirror E
-68L, manufactured by Toray Industries Co., Ltd.) On a support having a thickness of 100 μm, the coating solution (3) for the photosensitive and heat-sensitive layer was coated with a coating bar so that the dry weight of the entire coating layer was 6 g / m ^2. And dried. On this layer, a coating liquid for protective layer (1) was applied using a coating bar so that the dry weight of the applied layer was 2 g / m ² , and dried to obtain a light and heat sensitive recording material (3). . A step wedge-shaped image was formed on the photosensitive and heat-sensitive recording material (3) in the same manner as in Example 1. As a result, a clear wedge-shaped image was obtained in which the color developed vividly and the background had high whiteness. The sensitivity, color density, and fog density before and after the thermoprocessing of the light and heat sensitive recording material (3) were measured by the same method as in Example 1, and the results are shown in Table 1 below.

(Example 4): Cyan-colored polyester film filled with white pigment (Lumirror E
-68L, manufactured by Toray Industries, Inc.) On a support having a thickness of 100 μm, apply the coating solution (4) for the photosensitive and heat-sensitive layer using a coating bar so that the dry weight of the entire coating layer becomes 6 g / m ^2. And dried. On this layer, a coating liquid for protective layer (1) was applied using a coating bar so that the dry weight of the applied layer was 2 g / m ² , and dried to obtain a light and heat sensitive recording material (4). . A step wedge-shaped image was formed on the photosensitive and heat-sensitive recording material (4) in the same manner as in Example 1. As a result, a clear wedge-shaped image was obtained in which the color developed vividly and the background had high whiteness. The sensitivity, color density, and fog density before and after the thermoprocessing of the light and heat sensitive recording material (4) were measured by the same method as in Example 1 and the results are shown in Table 1 below.

(Example 5): Multicolored polyester film filled with white pigment (Lumirror E
-68L, manufactured by Toray Industries Co., Ltd.) On a support having a thickness of 100 μm, the coating solution (7) (cyan color) for the photosensitive and heat-sensitive layer was dried using a coating bar to a dry weight of 6 g / m 2.
^The coating liquid for intermediate layer (1) was applied on this layer using a coating bar to a dry weight of 1.5 g / m ² and dried. Further, on this intermediate layer, a coating solution (6) for a light and heat sensitive recording layer
(Magenta coloring) was applied using a coating bar so that the dry weight of the coating layer was 6 g / m ² , and dried, and a coating liquid for an intermediate layer was dried on this layer at a dry weight of 1.5 g / m ^2.
And dried. Further, a coating solution (5) (yellow color) for a light and heat sensitive recording layer was applied on this layer using a coating bar so that the dry weight of the coating layer was 6 g / m ² , and dried. The coating liquid for protective layer (1) 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 (5).

The light and heat sensitive recording material (5) obtained above
Is exposed imagewise using a semiconductor laser beam having a wavelength of 780 nm from the protective layer side, then imagewise exposed using a semiconductor-excited YLF solid laser beam having a wavelength of 657 nm, and further exposed to a YAG solid laser having a wavelength of 532 nm. It was imagewise exposed using light. After heating the recording material on which the latent image was formed by the exposure with a hot plate at 120 ° C. for 5 seconds,
This recording material was irradiated with light on the surface of the recording layer for 30 seconds on a 58000 lux high-brightness caster. As a result, a color image with clear color development and high whiteness in the background was obtained. The sensitivity, color density, and fog density before and after the thermoprocessing of the light and heat sensitive recording material (5) were measured by the same method as in Example 1, and the results are shown in Table 1 below.

(Comparative Examples 1 to 5) Using the light and heat sensitive recording materials (1) to (5) obtained in the above Examples 1 to 5, 5800
A step wedge-shaped image was obtained in the same manner as in Example 1 except that the recording layer surface was not irradiated with light for 30 seconds on a 0 lux high-intensity shark caster. The sensitivity, color density, and fog density before and after thermoprocessing were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 6 The procedure of Example 1 was repeated except that the spectral sensitizing dye-based borate compound (28) used in the photopolymerizable composition emulsion (2) of Example 1 was not used. Thus, a light and heat sensitive recording material (6) was obtained. Using the photosensitive and heat-sensitive recording material (6), a step wedge-shaped image was formed in the same manner as in Example 1. Further, in the same manner as in Example 1, the sensitivity, color density, and fog density before and after the thermoprocessing of the light and heat sensitive recording material (6) were measured. The results are shown in Table 1 below.

Comparative Example 7 Photosensitive and heat-sensitive recording was carried out in the same manner as in Example 4 except that the organic borate compound (29) used in the photopolymerizable composition emulsion (2) of Example 4 was not used. Material (7) was obtained. Using the photosensitive and heat-sensitive recording material (7), a step wedge-shaped image was formed in the same manner as in Example 1. In the same manner as in Example 1, the sensitivity, color density, and fog density before and after the thermoprocessing of the light and heat sensitive recording material (7) were measured. The results are shown in Table 1 below.

(Example 6): Magenta color development Polyester film filled with white pigment having a thickness of 175 μm (trade name: Lumirror E-68L, manufactured by Toray Industries, Inc.)
Using the coating bar, the coating solution (i) for the photosensitive pressure-sensitive recording layer was dried to a total dry weight of 6 g / m ^2.
And dried. On this layer, a coating liquid for protective layer (1) was applied using a coating bar so that the dry weight of the applied layer was 2 g / m ² , and dried to obtain a photosensitive pressure-sensitive recording material (8). Was.

The photosensitive pressure-sensitive recording material (8) was irradiated from the protective layer side with a semiconductor-excited YLF solid-state laser beam having a wavelength of 657 nm at a maximum irradiation energy of 15 mJ / cm ² .
Exposure was performed in an image shape in the form of a step wedge so that the irradiation energy gradually changed. The recording material on which the latent image has been formed by the exposure is subjected to a pressure of 150 by a hydraulic static pressure tester.
After pressure development at kg / cm ² , the recording material was 580
The entire surface of the recording layer of the recording material was irradiated with light on a 00lux high-brightness shark caster for 30 seconds. As a result, a clear wedge-shaped image was obtained in which the color developed vividly and the background had high whiteness. In the same manner as in Example 1, the sensitivity, color density, and fog density before and after the thermoprocessing of the photosensitive pressure-sensitive recording material (8) were measured. The results are shown in Table 1 below.

Comparative Example 8 The organic borate compound (29) in the electron-donating colorless dye-encapsulated microcapsule solution (V) contained in the photosensitive pressure-sensitive recording layer coating solution (i) used in Example 6 was used. A photosensitive pressure-sensitive recording material (9) was obtained in the same manner as in Example 6, except that the recording material was not used. A step wedge-shaped image was formed in the same manner as in Example 6 using the photosensitive pressure-sensitive recording material (9). Further, in the same manner as in Example 1, the sensitivity, color density, and fog density before and after the thermoprocessing of the photosensitive pressure-sensitive recording material (9) were measured. The results are shown in Table 1 below.

[0273]

[Table 1]

As is clear from Table 1, the photosensitive and heat-sensitive recording materials (1) to (5) and the photosensitive and pressure-sensitive recording material (8) of the present invention were exposed imagewise and heated or pressed. The image formed by the image recording method of the present invention through the fixing step of irradiating the surface of the recording layer with light showed high sensitivity, and almost no increase in the density of the background due to the thermotreatment was observed. In the obtained image, the coloring by the spectral sensitizing compound is sufficiently erased by light irradiation on the recording layer surface, and at the same time, the formed image is fixed, and the whiteness of the background is excellent, and the contrast is high. Thus, an image having good storage stability could be formed.

On the other hand, the light- and heat-sensitive recording materials (1) to (5) of the present invention were used as in Comparative Examples 1 to 5, but they did not go through a fixing step of irradiating the recording layer surface with light after exposure and heating. In the image formed in (1), the density increase of the background portion due to the thermoprocessing was extremely large, and a clear image with high contrast could not be obtained. In the light-sensitive and heat-sensitive recording materials (7) and (9) of Comparative Examples 7 and 8 in which the photopolymerization initiator having the constitution specified in the present invention was not used, sufficient sensitivity was not obtained. In addition, not only could the spectral sensitizing compound not be sufficiently decolorized, but also the storage stability was poor.

<Preparation of microcapsule solution containing diazonium salt compound> (4-a) Preparation of microcapsule solution (VI) containing diazonium salt compound In 13.7 parts of ethyl acetate, 4.6 parts of a diazonium salt compound (compound a below) were added. Part and diphenyl phthalate 1
And 0.4 part 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 parts of capsule wall material (trade name: Millionate MR200, manufactured by Nippon Polyurethane Industry Co., Ltd.).

The obtained solution was added to a mixed solution of 62.7 parts of an 8% aqueous solution of phthalated gelatin, 17.4 parts of water, and 0.4 parts of SucrapA part-S (manufactured by Nippon Seika Co., Ltd.)
Using a homogenizer, at a temperature of 40 ° C. and a rotation speed of 8000
The mixture was emulsified and dispersed at 10 rpm for 10 minutes. To the obtained emulsion, 50 parts of water and 0.26 parts of diethylenetriamine were added,
After homogenization, a microencapsulation reaction was carried out at 60 ° C. for 3 hours with stirring to obtain a diazonium salt compound-encapsulated microcapsule solution (VI). The average particle size of the microcapsules was 0.3 to 0.4 μm.

(4-b) Preparation of microcapsule solution (VII) encapsulating diazonium salt compound In 19.0 parts of ethyl acetate, 2.8 parts of butyl sulfate were replaced with the following compound a used in (4-a). 365 nm
And 2.8 parts of a diazonium salt compound having the maximum absorption wavelength of photolysis (compound b below). In this solution, isopropylphenyl, which is a higher boiling solvent, is added.
9 parts and 2.5 parts of tricresyl phosphate were added, and the mixture was heated and uniformly mixed. A capsule wall material (trade name: Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd.) is added to the obtained solution.
7.6 parts were further added to obtain a uniformly stirred solution.

6% gelatin (trade name: MG) to which 2.0 parts of a 10% aqueous sodium dodecyl sulfonate solution was added.
P-9066, manufactured by Nippi Gelatin Industry Co., Ltd.) Aqueous solution 6
4 parts were prepared, and the above solution of the diazonium salt was added thereto, and the mixture was emulsified and dispersed with a homogenizer. After 20 parts of water was added to the obtained emulsion to homogenize it, 40 parts of the emulsion were stirred.
C., and the encapsulation reaction was performed for 3 hours. Thereafter, the temperature was lowered to 35 ° C., and an ion-exchange resin (trade name: Amberlite IRA68, manufactured by Organo Corporation) was 6.5.
Part, ion exchange resin (trade name: Amberlite IRC5)
(0, manufactured by Organo Co., Ltd.) and stirred for 1 hour. Thereafter, the ion-exchange resin was filtered to obtain a diazonium salt compound-encapsulated microcapsule solution (VII). The average particle size of the microcapsules was 0.64 μm.

(4-c) Preparation of Microcapsule Solution (VIII) Encapsulating a Diazonium Salt Compound To 19 parts of ethyl acetate, 2.8 parts of a diazonium salt compound (the following compound c) and 10 parts of tricresyl phosphate were added, followed by homogenization. Was mixed. Next, 7.6 parts of a capsule wall material (Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd.) was added to the mixed solution and mixed. The obtained solution was combined with 46 parts of an 8% aqueous solution of phthalated gelatin and 17.5 parts of water.
And a mixture of 2 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate using a homogenizer.
The emulsion was emulsified and dispersed at 10,000 rpm for 10 minutes.
After adding 20 parts of water to the obtained emulsion and homogenizing it, an encapsulation reaction was performed at 40 ° C. for 3 hours with stirring.
Microcapsule liquid containing diazonium salt compound (VIII)
I got The average particle size of the microcapsules is 0.7 to
It was 0.8 μm.

[0281]

Embedded image

<Preparation of Photopolymerizable Composition Emulsion> (5-a) Preparation of Photopolymerizable Composition Emulsion (4) A compound having the following composition was dissolved in 10.5 parts of ethyl acetate.
Furthermore, tricresyl phosphate 0.48 which is a high boiling point solvent is used.
Parts, 0.24 parts of diethyl maleate and Bionin A4
After adding 1.27 parts of 1C (manufactured by Takemoto Yushi Co., Ltd.), the mixture was heated to obtain a uniform mixed solution. -Organic borate compound (29) shown above: 0.6 part (borate compound I)-Spectral sensitizing dye-based borate compound (26) ... 0.1 part (borate compound II)-high Auxiliary agent for increasing sensitivity (compound j shown below) 0.1 part Coupler compound (compound d shown below) 3.0 parts Triphenylguanidine 4.0 parts 1.1 -(P-hydroxyphenyl) -2-ethylhexane 4.0 parts4,4 '-(p-phenylenediisopropylidene) diphenol 8.0 parts2-ethylhexyl-4-hydroxybenzoate ··· 8.0 parts · Antioxidant (compound e below) ··· 2.0 parts · 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane・ 2.0 copies

The above mixture was added to 93 parts 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 (4) of the coupler compound.

(5-b) Preparation of Photopolymerizable Composition Emulsion (5) A compound having the following composition was dissolved in 10.5 parts of ethyl acetate.
Furthermore, tricresyl phosphate 0.48 which is a high boiling point solvent is used.
Parts, 0.24 parts of diethyl maleate and Bionin A4
After adding 1.27 parts of 1C (manufactured by Takemoto Yushi Co., Ltd.), the mixture was heated to obtain a uniform mixed solution. -Organic borate compound (29) shown above: 0.6 part (borate compound I)-Spectral sensitizing dye-based borate compound (27) ... 0.1 part (borate compound II)-high Auxiliary agent for increasing sensitivity (compound j below) 0.1 part Coupler compound (compound f below) 3.0 parts triphenylguanidine 3.6 parts 4,4 '-(P-phenylenediisopropylidene) diphenol 6.6 parts

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

(5-c) Preparation of Photopolymerizable Composition Emulsion (6) A compound having the following composition was dissolved in 10.5 parts of ethyl acetate.
A homogeneous mixture was obtained. -Organic borate compound (29) shown above: 0.6 part (borate compound I)-Spectral sensitizing dye-based borate compound (28) ... 0.1 part (borate compound II)-High Auxiliary compound for the purpose of increasing sensitivity (compound j below) 0.1 part Coupler compound (compound g below) 3.0 parts triphenylguanidine 3.0 parts tricresyl Phosphate 0.5 parts Diethyl maleate 0.24 parts

The mixture was mixed with 49 parts of a 15% aqueous solution of lime-processed gelatin and 10 parts of sodium dodecylbenzenesulfonate.
% Aqueous solution and 9.5 parts of water were uniformly mixed at 40 ° C., and the mixture was added at 40 ° C. with a homogenizer at 10 rpm.
Dispersed at 000 rpm for 10 minutes. The remaining ethyl acetate was evaporated from this emulsion to obtain a photopolymerizable composition emulsion (6) of the coupler compound.

[0288]

Embedded image

<Preparation of Coating Solution for Photosensitive and Heat Sensitive Recording Layer> (6-a) Preparation of Coating Solution (8) for Photosensitive and Heat Sensitive Recording Layer— [Yellow] Microcapsule solution (VI) containing diazonium salt compound (compound a) 10 Parts and 30 parts of a photopolymerizable composition emulsion (4) of a coupler compound were mixed to prepare a coating solution (8) for a light and heat sensitive recording layer.

(6-b) Coating solution for photosensitive and heat-sensitive recording layer (9)
Preparation of [Cyan] Diazonium Salt Compound (Compound b) Encapsulated Microcapsule Solution (VII), Photopolymerizable Composition Emulsion of Coupler Compound (5), and Styrene-Butadiene Rubber (SBR: SN3
07, manufactured by Sumitomo Nogatta Co., Ltd.) with a ratio of diazonium salt compound (compound B) / coupler of 1/2.
L-ascorbic acid (vitamin C, manufactured by Takeda Pharmaceutical Co., Ltd.) was further added thereto such that the ratio of L-ascorbic acid / diazonium salt compound (compound b) was 1/40. The mixture was mixed to prepare a coating solution (9) for a light and heat sensitive recording layer.

(6-c) Coating solution for photosensitive and heat-sensitive recording layer (1
Preparation of 0)-[Magenta] 3.6 parts of microcapsule liquid (VIII) containing 3.3 parts of water, 3.3 parts of water and 9.5 parts of a photopolymerizable composition emulsion (6) of a coupler compound containing a diazonium salt compound (compound c) Was mixed to prepare a coating solution (10) for a light and heat sensitive recording layer.

<Preparation of Coating Solution (2) for Intermediate Layer> A 90% aqueous solution of 14% gelatin (# 750 gelatin, manufactured by Nitta Gelatin Co., Ltd.) was mixed with 8.2 parts of a 4% boric acid aqueous solution and (4-nonylphenoxy) 1.2 parts of a 2% aqueous solution of sodium trioxyethylene) butylsulfonate, (CH ₂ ＣＨCHSO ₂ C)
_{H 2 CONHCH 2) - (CH} 2 NHCOCH 2 SO 2
CH = CH ₂ ) and CH ₂ — (CH ₂ NHCOCH ₂ SO
₂ CH = CH _{2) 2} of 3: 1 mixture (by adding 2% aqueous solution 7.5 parts by weight ratio) to give uniformly stirring the intermediate layer coating solution (2).

<Preparation of Coating Solution (3) for Intermediate Layer> 0.4 parts of a 2% aqueous solution of sodium (4-nonylphenoxytrioxyethylene) butylsulfonate was added to 57 parts of a 13% aqueous solution of gelatin, and (CH ₂ = CHSO ₂ CH ₂ CONHCH
_{2) - (CH 2 NHCOCH 2} SO 2 CH = CH 2) and _{CH 2 - (CH 2 NHCOCH 2} SO 2 CH = CH 2)
₂ of 3: 1 2% by weight aqueous solution of a mixture (weight ratio) 8.3
Part, PVP-k15 (GAF Gokyo Sangyo Co., Ltd.) 2.4
Was added, and the mixture was stirred uniformly to obtain a target coating liquid (3) for an intermediate layer.

<Preparation of Coating Solution (2) for Protective Layer> 5.0%
Itaconic acid-modified polyvinyl alcohol (trade name: KL-
318, manufactured by Kuraray Co., Ltd.) 20.5%
Zinc stearate dispersion (trade name: Hydrine F11)
5, Chukyo Yushi Co., Ltd.) and add C ₁₂ H ₂₅ O
8.4 parts of a 2% aqueous solution of (CH ₂ CH ₂ O) H, a fluorine release agent (trade name: ME-313, manufactured by Daikin Co., Ltd.)
8.0 parts and 0.5 part of flour starch (trade name: KF-4, manufactured by Kagoshima Starch Co., Ltd.) were added and uniformly stirred. Hereinafter, this is referred to as “mother liquor”.

Further, 12.5 parts of an ion-exchanged 20% aqueous chao gloss (manufactured by Shiraishi Industry Co., Ltd.) aqueous solution,
A (manufactured by Kao Corporation) 0.06 parts, Hydrin Z-7 (manufactured by Chukyo Yushi Co., Ltd.) 1.87 parts, 10% polyvinyl alcohol (trade name: PVA105, manufactured by Kuraray Co., Ltd.) 1.2
5 parts and 2% aqueous solution of sodium dodecyl sulfonate
39 parts were mixed and finely dispersed by a dyno mill. Hereinafter, this liquid is referred to as a “pigment liquid”. In 80 parts of the mother liquor,
4.4 parts of the pigment liquid was added and stirred for 30 minutes or more. Then, Wetmaster500 (manufactured by Toho Chemical Co., Ltd.)
2.8 parts were added, and the mixture was further stirred for 30 minutes or more to prepare a coating solution (2) for a protective layer.

(Example 7): Yellow coloring On a photographic paper support obtained by laminating polyethylene on high-quality paper, using a Mayer bar, a coating solution (8) for a light and heat sensitive recording layer and a coating solution (2) for a protective layer were used. Was applied in this order from the support side and dried to obtain a light and heat sensitive recording material (10). 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. A step wedge-shaped image was formed on the photosensitive and heat-sensitive recording material (10) in the same manner as in Example 1. As a result, a clear wedge-shaped image was obtained in which the color developed vividly and the background had high whiteness. The sensitivity, color density, and fog density before and after thermoprocessing of the light and heat sensitive recording material (10) were measured in the same manner as in Example 1 and the results are shown in Table 2 below.

(Example 8): Cyan coloration On a photographic paper support obtained by laminating polyethylene on high-quality paper, using a Meyer bar, a coating solution (9) for a photosensitive and heat-sensitive recording layer and a coating solution (2) for a protective layer were used. ) Was sequentially applied from the support side and dried to obtain a light and heat sensitive recording material (11). The dry coated amount of the light and heat sensitive recording layer was 8.33 g / m ² ,
The dry coating amount of the protective layer was 1.23 g / m ² . A step wedge-shaped image was formed on the photosensitive and heat-sensitive recording material (11) in the same manner as in Example 1. As a result, a clear wedge-shaped image was obtained in which the color developed vividly and the background had high whiteness. The sensitivity, color density, and fog density before and after thermoprocessing of the light and heat sensitive recording material (11) were measured in the same manner as in Example 1 and the results are shown in Table 2 below.

(Example 9): Magenta coloring A coating solution for a photosensitive and heat-sensitive layer (10) and a coating solution for a protective layer (2) were coated on a photographic paper support obtained by laminating polyethylene on a high-quality paper using a Meyer bar. Was sequentially applied from the support side and dried to obtain a light and heat sensitive recording material (12). The dry coated amount of the light and heat sensitive recording layer was 8.06 g / m ² ,
The dry coating amount of the protective layer was 1.23 g / m ² . A step wedge-shaped image was formed on the photosensitive and heat-sensitive recording material (12) in the same manner as in Example 1. As a result, a clear wedge-shaped image was obtained in which the color developed vividly and the background had high whiteness. The sensitivity, color density, and fog density before and after the thermoprocessing of the light and heat sensitive recording material (12) were measured by the same method as in Example 1, and the results are shown in Table 2 below.

(Example 10): Multicolor coloring On a photographic paper support obtained by laminating polyethylene on high-quality paper, using a Meyer bar, a coating solution (8) for a light and heat sensitive recording layer and a coating solution for an intermediate layer ( 2), a coating solution for photosensitive and heat-sensitive recording layer (9), a coating solution for intermediate layer (3), a coating solution for photosensitive and heat-sensitive recording layer (10), and a coating solution for protective layer (2) are laminated in this order from the support side. The resultant was coated and dried to obtain a light and heat sensitive recording material (13) having three multicolor light and heat sensitive recording layers. The light and heat sensitive recording material (13) was exposed to light in the same manner as in Example 5 to form an image. As a result, a color image with clear color development and high whiteness in the background was obtained. The sensitivity, color density, and fog density before and after the thermoprocessing of the light and heat sensitive recording material (13) were measured by the same method as in Example 1 and the results are shown in Table 2 below.

(Comparative Examples 9 to 12) Using the light and heat sensitive recording materials (10) to (13) obtained in Examples 7 to 10,
A step wedge-shaped image was obtained in the same manner as in Example 7 except that the recording layer surface was not irradiated with light on a 58000 lux high-intensity shark caster for 30 seconds. The sensitivity, color density, and fog density before and after thermoprocessing of the light and heat sensitive recording materials (10) to (13) were measured by the same method as in Example 1 and the results are shown in Table 2 below.

(Comparative Example 13) Except that the spectral sensitizing dye-based borate compound (26) used in the photopolymerizable composition emulsion (4) of Example 7 was not used, the same procedure as in Example 7 was performed. A light and heat sensitive recording material (14) was obtained. A step wedge-shaped image was formed on the photosensitive and heat-sensitive recording material (14) in the same manner as in Example 7. Light and heat sensitive recording material (1
The sensitivity, color density, and fog density before and after the thermo-processing of 4) were measured by the same method as in Example 1 and the results are shown in Table 2 below.

[0302]

[Table 2]

As is apparent from Table 2, the fixing step of using the light- and heat-sensitive recording materials (10) to (13) of the present invention, imagewise exposing and heating, and then irradiating the surface of the recording layer with light is performed. The image formed by the image recording method according to the present invention obtained high sensitivity, and almost no increase in the density of the background portion due to the thermo-processing was observed. In the obtained image, the coloring by the spectral sensitizing compound is sufficiently decolored by light irradiation on the recording layer surface, the diazonium salt compound remaining in the layer is also deactivated and decomposed, and the formed image is fixed at the same time. Therefore, it was possible to form an image having excellent whiteness of the background portion, high contrast, and good storage stability.

On the other hand, the photosensitive and heat-sensitive recording materials (10) to (13) of the present invention were used as in Comparative Examples 9 to 12, but they did not undergo a fixing step of irradiating the recording layer surface with light after exposure and heating. In the image formed in (1), the density increase of the background portion due to the thermoprocessing was extremely large, and a clear image with high contrast could not be obtained. In the case of the light- and heat-sensitive recording material (14) of Comparative Example 13 in which the photopolymerization initiator having the constitution specified in the present invention was not used, sufficient sensitivity was not obtained, and an image could not be formed.

[0305]

According to the image recording method of the present invention, the formed image is fixed and remains in the recording layer after image formation.
A component that reduces the whiteness of the background can be erased, and a black-and-white or color image having excellent whiteness of the background, high contrast, and good storage stability can be provided. Further, according to the recording material of the present invention, it is possible to provide a high-sensitivity, sharp, high-quality black-and-white or color image while having excellent whiteness of the background portion.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Shintaro Washinasu, Fuji Photo Film Co., Ltd. 200 Fujinaka Film, Fujinomiya City, Shizuoka Prefecture (72) Inventor Masanobu Takashima 200 Onakazato Fujinaka City, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd. Terms (reference) 2H025 AA01 AB20 AC08 AD01 BC83 BJ00 CA00 CC14 DA01 DA10 DA11 DA14 FA19 FA22 FA30 2H026 AA07 AA11 AA13 AA24 AA32 BB01 BB24 DD01 DD03 DD43 DD53 FF01 FF05 FF07

Claims (15)

[Claims] 1. A color-forming component A encapsulated in a thermo-responsive microcapsule on a support, and a polymerizable group and the color-forming component A are reacted outside the thermo-responsive microcapsule at least within the same molecule. An image recording method using a recording material having a photosensitive and heat-sensitive recording layer containing a substantially colorless compound B having a site to be colored and a photopolymerizable composition comprising a photopolymerization initiator, , At least, an exposure step in which the photopolymerizable composition forms a latent image by image exposure, a coloring step in which the coloring component is colored according to the latent image by heating to form an image, and a recording layer surface formed by irradiating the surface with light. A fixing step of fixing an image and decoloring a photopolymerization initiator component. 2. A color-forming component A encapsulated in a thermo-responsive microcapsule on a support, and a substantially colorless compound that reacts with at least the color-forming component A to form a color outside the thermo-responsive microcapsule. C
And a polymerizable group, the coloring component A and the compound C in the same molecule.
A substantially colorless compound D having a site that inhibits the reaction with, a photopolymerization initiator, and a photopolymerizable composition,
An image recording method using a recording material having a light- and heat-sensitive recording layer containing, at least, an exposure step in which a photopolymerizable composition forms a latent image by image exposure, and a coloring component according to the latent image by heating. An image recording method, comprising: a color forming step of forming a color and 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 photopolymerization initiator component. 3. The photopolymerization initiator has a wavelength of 300 to 1000 nm.
The image recording method according to claim 1 or 2, wherein the photopolymerization initiator contains a spectral sensitizing compound having a maximum absorption wavelength and a compound that interacts with the spectral sensitizing compound. 4. A microcapsule enclosing at least a color-forming component A, a photopolymerizable composition containing a polymerizable compound and a photopolymerization initiator on a support, and An image recording method using a recording material having a photosensitive pressure-sensitive recording layer containing at least a substantially colorless compound E that reacts with the color forming component A to form a color, wherein at least photopolymerization is performed by image exposure. Exposure step of forming a latent image by the hydrophilic composition, Color formation component by pressurization to form a color in accordance with the latent image, forming a color image, and irradiating the surface of the recording layer with light to fix the formed image and photopolymerize A fixing step of decolorizing the initiator component. 5. The photopolymerization initiator has a wavelength of 300 to 1000 nm.
5. The image recording method according to claim 4, wherein the photopolymerization initiator contains a spectral sensitizing compound having a maximum absorption wavelength and a compound that interacts with the spectral sensitizing compound. 6. A color-forming component A encapsulated in a thermo-responsive microcapsule on a support, and reacting with a polymerizable group and the color-forming component A at least in the same molecule outside the thermo-responsive microcapsule. A photopolymerizable composition comprising a substantially colorless compound B having a site to be colored, and a photopolymerization initiator; and a recording material having a light- and heat-sensitive recording layer containing the photopolymerization initiator. A spectral sensitizing compound having a maximum absorption wavelength at 300 to 1000 nm, and a compound that interacts with the spectral sensitizing compound. 7. A color-forming component A encapsulated in a thermo-responsive microcapsule on a support, and a substantially colorless compound that reacts with at least the color-forming component A to form a color outside the thermo-responsive microcapsule. C
And a polymerizable group, the coloring component A and the compound C in the same molecule.
A photopolymerizable composition comprising a substantially colorless compound D having a site that inhibits the reaction with and a photopolymerization initiator, and a recording material having a light- and heat-sensitive recording layer containing: A recording material, wherein the photopolymerization initiator contains a spectral sensitizing compound having a maximum absorption wavelength at 300 to 1000 nm, and a compound that interacts with the spectral sensitizing compound. 8. A microcapsule containing at least a color-forming component A, a photopolymerizable composition containing a polymerizable compound and a photopolymerization initiator on a support, and At least a substantially colorless compound E which reacts with the color-forming component A to form a color, and a recording material having a photosensitive pressure-sensitive recording layer, wherein the photopolymerization initiator has a maximum absorption at 300 to 1000 nm. A recording material comprising: a spectral sensitizing compound having a wavelength; and a compound interacting with the spectral sensitizing compound. 9. The recording material according to claim 6, wherein at least one of the compounds interacting with the spectral sensitizing compound is an organic borate salt compound. 10. The recording material according to claim 6, wherein the recording material is a multi-colored multi-layered recording material in which recording layers each emitting a different hue are laminated. 11. A multi-color, multi-layer recording material, comprising:
From the incident surface of the irradiation light toward the thickness direction of the multi-layer recording material, a first recording layer that is sensitive to the central wavelength lambda ₁ of the light source color, and sensitive to the central wavelength lambda ₂ of the light, the first recording The second recording layer that develops a color different from that of the layer,..., Center wavelength λ
_i , and the first, second,.
The recording material according to claim 10, wherein the recording material is a multicolor multilayer recording material in which an i-th recording layer that develops a color different from that of the first recording layer is sequentially stacked at least i≥2. 12. The recording material according to claim 10, wherein the multicolor multilayer recording material is a multilayer recording material having an intermediate layer between recording layers having different coloring hues. 13. A multi-layered multi-layer recording material having a protective layer on the outermost layer on the incident surface side of irradiation light.
The recording material according to any one of the above. 14. The recording material according to claim 10, wherein said recording material further comprises:
A step in which the photopolymerizable composition forms a latent image by exposing the image using a plurality of light sources having different wavelengths,
The image according to any one of claims 1 to 3, wherein the image is formed into a different hue according to each latent image formed on the photosensitive and heat-sensitive recording layer having a different color hue by heating to form a multicolor image. Recording method. 15. The recording material according to claim 10, wherein the exposure step further comprises:
A step in which the photopolymerizable composition forms a latent image by exposing the image using a plurality of light sources having different wavelengths,
The image recording according to claim 4 or 5, wherein a color is formed in a different hue according to each latent image formed in the photosensitive pressure-sensitive recording layer having a different color hue by pressurization to form a multicolor image. Method.