JP2001033956A - Recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording material having high sensitivity, excellent in light resistance and capable of forming a high contrast image having high image quality by using various lasers. SOLUTION: A recording material 10 has, on a substrate 12, a photosensitive and heat sensitive recording layer 14 containing heat responsive microcapsules which house a color developing component A and further containing a phtotopolymerizable composition comprising a substantially colorless compound B having at least a polymerizable group and a moiety which reacts with the color developing component A and develops a color in the same molecule and a photopolymerization initiator at the outside of the microcapsules and contains a UV absorber and/or its precursor in the photosensitive and heat sensitive recording layer 14 and/or in a protective layer 16 situated above the layer 14. The photopolymerization initiator preferably contains a spectral sensitizing compound having the maximum absorption at 300-1,000 nm wavelength and a compound which interacts with the spectral sensitizing compound.

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 capable of utilizing various light sources in the ultraviolet to infrared region, and more particularly, it is excellent in sensitivity, contrast and whiteness of a non-image portion. The present invention also relates to a recording material capable of forming an image having excellent light fastness in an image area and a non-image area.

[0002]

2. Description of the Related Art Various dry-type image recording methods which do not use a liquid developer or the like and which do not generate waste have been studied. Among them, a method using a photocurable composition which is cured by light is used. Attention has been paid to an image forming method. The image forming method of this method is a method of forming an image by applying light and heat or light and pressure to a recording material (hereinafter, the recording material used in the former method is referred to as a "photosensitive heat-sensitive recording material", The recording material used in the latter method is called "photosensitive pressure-sensitive recording material".) For example, in an image forming method using a photosensitive and heat-sensitive recording material, the recording material is irradiated with light, the photocurable composition in the exposed portion is cured to form a latent image, and then heat is applied to the recording material. Thus, an image is formed by developing the color components of the exposed portion or the unexposed portion.

As the light and heat sensitive recording material, for example,
The two-component photosensitive and heat-sensitive color recording material described in JP-A-52-89915 can be used. This light- and heat-sensitive color recording material is, as two components, for example, an electron-accepting compound and an electron-donating colorless dye, and contains a photocurable composition inside or outside a microcapsule, or both, and contains a heat-sensitive color-forming type. This is a positive recording material. However, even when the photocurable composition contained inside or outside the microcapsules is sufficiently cured by exposure to light, the photosensitive thermosensitive recording material can sufficiently suppress color development in the cured portion (non-image portion). However, there is a disadvantage that the cured portion is colored and the contrast of the formed image is reduced.

As a light- and heat-sensitive recording material in which coloring of a non-image portion is reduced, for example, a photopolymerizable composition comprising a vinyl monomer having an acidic group and a photopolymerization initiator described in JP-A-61-123838. Recording material in which a layer containing a substance, a separating layer, and a layer composed of an electron-donating colorless dye are laminated. When an image is formed using the recording material, a non-image portion, that is, a portion cured by a photopolymerization reaction has no heat diffusion property of an acidic group and does not cause coloring, but on the other hand, a coloring density of an image portion However, it has the disadvantage of being slightly lower.

As a negative type photosensitive and heat-sensitive recording material of the same type, there is a recording material described in JP-A-60-119552. This recording material 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 bleached by the monomer or the prepolymer are present separately. This recording material, like the recording material described above, does not cause coloring in the non-image area, but has a disadvantage that the color density of the image area is slightly low.

On the other hand, examples of a photosensitive pressure-sensitive recording material of the same type include recording materials disclosed in US Pat. Nos. 4,399,209 and 4,440,846. This recording material contains a microcapsule containing a coloring precursor as an image forming agent, and a coloring agent outside the microcapsule. After exposing the recording material imagewise, a uniform pressure is applied to the recording material to rupture the microcapsules in the non-photocured area, and the colored precursor released from the capsule and the developer outside the capsule are separated. Allow to react and visualize. U.S. Pat. No. 3,399,91 discloses the use of this photosensitive pressure-sensitive recording material in a method for forming a multicolor image.
7, No. 4,576,891, and the like. However, when an image is formed using this recording material, only a low-contrast, low-quality image with a colored background portion can be obtained. Also,
Since most of the compositions to be photocured have photosensitivity under short wavelengths, none of them can record images with a light source other than UV light and short-wavelength visible light, and use a small and inexpensive infrared laser or blue to red light. The used image recording is not possible.

In view of the above drawbacks, the present applicants have disclosed a recording material capable of reducing coloring in a non-image area and obtaining a high image density as disclosed in JP-A-3-87827 and JP-A-4-87827.
A new recording material has been proposed in JP-A-212252. The former recording material is a two-component type photothermographic recording material, and one of the two components is encapsulated in a microcapsule.
The other as a curable compound of the photocurable composition, or
The other is a recording material contained outside the microcapsules together with the photocurable composition. 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

Further, the present applicants have proposed a plurality of recording layers which are sensitive to light of different wavelengths and develop different colors, as photosensitive and thermosensitive recording materials capable of forming multicolor images of the same type.
That is, a first recording layer that is sensitive to light having a center wavelength λ1 and develops a color, an intermediate layer that absorbs light having a center wavelength λ1, and a center wavelength λ2
And the second recording layer, which is different from the first recording layer.
, A recording layer,..., An intermediate layer that absorbs light having a center wavelength λi−1, is sensitive to light having a center wavelength λi, and has first, second,.
And an i-th recording layer that develops a color different from that of the (i-1) -th recording layer is sequentially stacked from the exposure light source side toward the support at least i ≧ 2, and the center wavelength λ at this time is λ1 <Λ2 <... <Λi, a multicolor recording material is proposed.

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 use a small and inexpensive infrared laser or blue to red light. Use is not possible. Further, in order to enable high-speed and high-definition image formation, when using a small and inexpensive infrared laser or blue to red light as described above,
It is necessary to introduce dyes having absorption in the ultraviolet to infrared region, which is the absorption wavelength of each irradiation light, in the recording layer, and these dyes and the like, among which dyes having absorption in the visible light region, were used. In such a case, the background portion is colored and the contrast of the formed image is reduced, and as a result, the image quality may be reduced. By using a dye or the like that absorbs in the near-infrared region, the coloring of the background can be reduced, but the recordable laser is limited, which is disadvantageous in general versatility.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems. 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, Another object of the present invention is to provide a monochrome or color recording material capable of forming a high-sensitivity, high-contrast, high-quality image. In particular, an object of the present invention is to provide a black-and-white or color recording material having the above-mentioned performance with excellent light resistance.

[0011]

Means for Solving the Problems In order to solve the above problems, the recording material according to the first aspect of the present invention comprises a coloring material A on a support.
And a substantially colorless compound B having, outside the thermoresponsive microcapsules, at least a polymerizable group in at least the same molecule and a site that reacts with the color forming component A to form a color. And a photopolymerizable composition comprising: a photopolymerization initiator; and a photothermographic recording layer containing at least one layer from the outermost layer of the recording material to the photothermographic recording layer. Alternatively, it is characterized by containing an ultraviolet absorber precursor.

[0012] In order to solve the above-mentioned problems, a recording material according to a second aspect of the present invention comprises a thermo-responsive microcapsule containing a color-forming component A on a support, and at least the color-forming microcapsule outside the thermo-responsive microcapsule. A substantially colorless compound C which reacts with the component A to form a color, and 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 photopolymerizable composition comprising: a photopolymerization initiator; and a photothermographic recording layer containing at least one layer from the outermost layer of the recording material to the photothermographic recording layer. Alternatively, it is characterized by containing an ultraviolet absorber precursor.

[0013] In order to solve the above-mentioned problems, a recording material according to a third aspect of the present invention includes, on a support, a photopolymerizable composition containing a coloring component A, a polymerizable compound and a photopolymerization initiator. A microcapsule, and at least a photosensitive and pressure-sensitive recording layer containing a substantially colorless compound E that reacts with the color-forming component A to form a color outside the microcapsule. One of the layers up to the photosensitive pressure-sensitive recording layer contains an ultraviolet absorber and / or an ultraviolet absorber precursor.

The photopolymerization initiator is 300 to 1000 n
It preferably contains a spectral sensitizing compound having a maximum absorption wavelength at m and a compound that interacts with the spectral sensitizing compound.

The recording materials according to the first to third aspects of the present invention can be cured by hardening the photopolymerizable composition contained in the light- and heat-sensitive recording layer or the light- and pressure-sensitive recording layer by imagewise irradiation with light. Is formed. The recording material can form a highly sensitive and sharp image even when irradiated with light using lasers of various wavelengths such as a blue to red laser, and can form a recording layer (a photosensitive heat-sensitive recording layer and a photosensitive photosensitive layer). Pressure-sensitive recording layer, the same applies hereinafter) or a protective layer provided above the recording layer contains an ultraviolet absorber and / or an ultraviolet absorber precursor. Also, when stored by being exposed to light or sunlight, high-contrast images can be maintained without fading of the image portion and coloring of the background portion.

[0016]

FIG. 1 shows an embodiment in which the recording material of the first invention is applied to a recording material for forming a monochromatic image.
The recording material 10 is a positive-type photosensitive and heat-sensitive recording material, and has a support 12, a photosensitive and heat-sensitive recording layer 14 thereon, and a protective layer 16 thereon. The photosensitive and heat-sensitive recording layer 14 has a thermo-responsive microcapsule containing the color-forming component A, and a portion outside the microcapsule, which at least has a polymerizable group in the same molecule and a color that reacts with the color-forming component A. It contains a substantially colorless compound B and a photopolymerizable composition comprising a predetermined photopolymerization initiator. The protective layer 16
It contains at least an ultraviolet absorber and / or a precursor of an ultraviolet absorber.

When the recording material 10 is imagewise exposed from the protective layer 16 side, the compound B in the light and heat sensitive recording layer 14 undergoes a polymerization reaction by radicals and the like generated from the photopolymerization initiator and is cured. Is formed to form a hardened latent image. When the photopolymerization initiator contains a spectral sensitizing compound having a maximum absorption at the exposure wavelength and a compound interacting with the spectral sensitizing compound, the photopolymerization initiator has more excellent sensitivity to light at the exposure wavelength. Thereafter, when the entire surface of the recording material 10 is heated, the compound B present in the non-exposed portion moves into the microcapsule and reacts with the color-forming component A to form the color-forming component A in the non-exposed portion. On the other hand, since the compound B in the exposed portion is cured, it cannot be moved from that position, the exposed portion does not develop color, and a positive image is formed. Thereafter, the entire surface is irradiated with light to inactivate the photopolymerization initiator in the non-exposed area and fix the formed image, and it is possible to decolor the spectral sensitizing compound contained in the photopolymerization initiator. .

FIG. 2 shows an embodiment in which the recording material of the second invention is applied to a recording material for forming a monochromatic image. The recording material 20 is a negative-type photosensitive and heat-sensitive recording material.
2, a light and heat sensitive recording layer 24 thereon, and a protective layer 26 thereon. The light- and heat-sensitive recording layer 24 includes a thermo-responsive microcapsule containing the color-forming component A, and at least the color-forming component A outside the thermo-responsive microcapsule.
And a substantially colorless compound C having a polymerizable group and a site for suppressing the reaction between the coloring component A and the compound C in the same molecule;
A photopolymerizable composition comprising a predetermined photopolymerization initiator. The protective layer 26 includes at least an ultraviolet absorber and / or
Or it contains an ultraviolet absorber precursor.

When the recording material 20 is exposed imagewise from the protective layer 26 side, the compound D contained in the light and heat sensitive recording layer 24 undergoes a polymerization reaction by radicals generated from the photopolymerization initiator and is cured, A latent image in which only the exposed portion is cured is formed. When the photopolymerization initiator contains a spectral sensitizing compound having a maximum absorption at the exposure wavelength and a compound interacting with the spectral sensitizing compound, the composition has higher sensitivity to exposure. Thereafter, when the entire surface of the recording material 20 is heated, the compound C in the exposed portion moves into the microcapsule and reacts with the color forming component A to form the color forming component A in the exposed portion. On the other hand, the compound C
At the same time, the compound D moves into the microcapsules and suppresses the reaction between the color-forming component A and the compound C, so that the color-forming component A in the non-exposed area does not develop color, and a negative image is formed. Thereafter, the entire surface is irradiated with light to inactivate the photopolymerization initiator in the non-exposed area and fix the formed image, and it is possible to decolor the spectral sensitizing compound contained in the photopolymerization initiator. .

FIG. 3 shows an embodiment in which the recording material of the third invention is applied to a recording material for forming a monochromatic image. The recording material 30 is a positive-type photosensitive pressure-sensitive recording material.
2, a light-sensitive and pressure-sensitive recording layer 34 thereon, and a protective layer 36 thereon. The photosensitive pressure-sensitive recording layer 34 includes a microcapsule containing a color-forming component A, a photopolymerizable composition containing a polymerizable compound and a predetermined photopolymerization initiator, and at least the color-forming outside the microcapsule. A substantially colorless compound E which reacts with the component A to form a color. The protective layer 36 contains at least an ultraviolet absorber and / or a precursor of an ultraviolet absorber.

When the recording material 30 is exposed imagewise from the protective layer 36 side, the polymerizable compound encapsulated in the microcapsules of the photosensitive pressure-sensitive recording layer 34 undergoes a polymerization reaction due to radicals generated from the photopolymerization initiator. To form a latent image in which only the exposed portions are cured. When the photopolymerization initiator contains a spectral sensitizing compound having a maximum absorption at the exposure wavelength and a compound interacting with the spectral sensitizing compound, the composition has more excellent sensitivity to exposure. Thereafter, when the entire surface of the recording material 30 is pressurized, the microcapsules in the non-exposed portions are broken, and the compound E and the color forming component A come into contact with each other and react to form the color forming component A in the non-exposed portion. On the other hand, in the exposed portion, the microcapsules whose interior is hardened are not broken, so that the exposed portion does not develop color and a positive image is formed. Thereafter, the entire surface is irradiated with light to inactivate the photopolymerization initiator in the non-exposed area and fix the formed image, and it is possible to decolor the spectral sensitizing compound contained in the photopolymerization initiator. .

In the above embodiment, the protective layer provided on the light- and heat-sensitive recording layer or the light-sensitive and pressure-sensitive recording layer contains an ultraviolet absorber and / or a precursor of the ultraviolet absorber. Even when stored in a fluorescent lamp or under sunlight for a long time, no fading of the image portion and no coloring of the background portion occur, and as a result, a high-contrast, high-quality image can be maintained.

In the above embodiment, the ultraviolet absorbent and / or the ultraviolet absorbent precursor are contained in the protective layer. However, the recording material of the present invention is not limited to this constitution, and may be used from the outermost layer of the recording material to the recording layer. All of the configurations containing an ultraviolet absorber or the like are included in any of the layers described above. For example, when another layer is provided between the light- and heat-sensitive recording layer and the light- and pressure-sensitive recording layer (hereinafter, both layers are collectively referred to as a “recording layer”) and the protective layer, the layer is made of an ultraviolet absorbent. Etc. may be contained. Note that the “outermost layer” here refers to the outermost layer on the side opposite to the side where the support is located when viewed from the center of the recording layer, and when only the recording layer is provided. In the above, the recording layer becomes the outermost layer, and the recording layer contains an ultraviolet absorber or the like. Further, an ultraviolet absorber or the like may be contained in a plurality of layers.

As the above-mentioned ultraviolet absorber, 300 nm to 3
It is preferable to use a compound having a maximum absorption wavelength of 70 nm. The use of an ultraviolet absorber that absorbs wavelengths in the above range is preferable because the light resistance of the recording material can be improved without lowering the sensitivity or the like of the recording material of the present invention formed using the materials described below. . Examples of such an ultraviolet absorber include an ultraviolet absorber represented by the general formula (1) disclosed in JP-A-11-44930, and more preferred ultraviolet absorbers are described in the publication. Compounds represented by the general formulas [1] to [7].

The above-mentioned ultraviolet absorber precursor is a compound which forms an ultraviolet absorber by external stimulus such as light or heat. The ultraviolet absorber formed from the ultraviolet absorber precursor is preferably a compound having a maximum absorption wavelength of 300 nm to 370 nm. The ultraviolet absorber precursor contained in the recording layer or the protective layer is heated at the time of image formation, at the time of light irradiation at the time of image fixing,
Alternatively, when exposed to environmental light such as sunlight or a fluorescent lamp, light or heat is supplied to form an ultraviolet absorber. Examples of such an ultraviolet absorber precursor include compounds represented by formulas (1) to (4) described in JP-A-09-95487, and JP-A-07-276.
No. 808, compounds represented by formulas (1) to (4), JP-A-08-80667, compounds represented by formulas (1) to (3), and JP-A-08-2529.
The compounds of the general formulas (1) to (4) described in JP-A-81 can be mentioned.

In the case of using the above-mentioned ultraviolet absorber precursor, it is preferable to use a reducing agent or a nucleophilic agent together with the precursor, since the light resistance of the recording material is further improved. Examples of the reducing agent include compounds exemplified in columns [0059] to [0060] of JP-A-09-95487 and [0099] of JP-A-07-276808.
Compounds exemplified in columns [41] to [0042] are preferably used. Further, as the nucleophile, JP-A-08-08
The compounds exemplified in columns [0021] to [0026] of 80667 are preferably used.

When an ultraviolet absorber precursor is used, at the time of forming a latent image, the state of the ultraviolet absorber precursor that does not absorb ultraviolet light is maintained, and thereafter, heat or pressure is applied, light irradiation for fixing an image, or ambient light is performed. By generating an ultraviolet absorber from the precursor by irradiation, high sensitivity can be maintained even when a latent image is formed using ultraviolet light. For example, an ultraviolet absorber precursor is encapsulated in a thermoresponsive or pressure-responsive microcapsule, the reducing agent is present outside the microcapsule, and when heat or pressure is applied to the recording material, the precursor inside or outside the microcapsule is applied. And the reducing agent may be contacted to form an ultraviolet absorber.

The content of the ultraviolet absorber and / or the precursor of the ultraviolet absorber is 0.05 g / m ^{2 to 3} g.
Is preferably from / m ^2, and more preferably 0.1-2 g / m ^2.

Hereinafter, the recording material of the present invention will be described.
Various compounds contained in the light and heat sensitive recording layer and the light and pressure sensitive recording layer will be described in detail. In the recording material according to the first to third aspects of the present invention, the recording layer comprises a color-forming component A encapsulated in microcapsules and a substantially colorless compound that reacts with the color-forming component A to form the color-forming component A (the above-described compound). Compound B,
Compound C or compound E; hereinafter, may be referred to as “compound that causes color development”. ) As a color-forming source, and a photopolymerizable composition capable of forming a latent image by light irradiation.

The combination of the two components (color-forming component A and the compound to be colored) as the color-forming source includes the following (A) to (A).
The combination of (T) can be preferably mentioned (in the following examples, the former represents a color-forming component and the latter represents a compound to be colored).

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

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

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

Examples of the combination of the two components as the color-forming source include (A) a combination of an electron-donating dye precursor and an electron-accepting compound, and (A) a diazonium salt compound and a coupling component (hereinafter referred to as a “coupler” as appropriate). Compounds) are preferred. That is, as the color-forming component A, an electron-donating dye precursor and a diazonium salt compound are preferable, and as the compound for forming a color, an electron-accepting compound and a coupler compound are preferable.

As the electron-donating dye precursor, compounds capable of forming a color in combination with an electron-accepting compound can be widely used. Specifically, phthalide compounds,
Fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, pyridine compounds, pyrazine compounds, fluorene compounds And the like.

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

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

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

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 the rhodamine lactam compound include rhodamine-B-anilinolactam and rhodamine- (p-
Nitrino) lactam and the like.

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

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

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

When the recording material of the present invention is applied to a full-color recording material, an electron-donating dye precursor which develops hues of cyan, magenta and yellow is used.
As the electron-donating dye precursor capable of forming a color of each of magenta and yellow, compounds described in U.S. Pat. No. 4,800,149 can be used. Also,
As the electron-donating dye precursor capable of forming a yellow hue, the compounds described in U.S. Patent No. 4,800,148 and the like can also be used. As the electron-donating dye precursor capable of forming a cyan hue, The compounds described in JP-A-63-53542 can also be used.

[0045] The said electron-donating dye precursor is present in the heat sensitive recording layer or photosensitive and pressure sensitive recording layer is preferably be contained 0.01 to 3 g / m ^2, to 0.1 to 1 g / m ² containing Is more preferred. If the amount is less than 0.01 g / m ² , it may not be possible to obtain a sufficient color density, and if it exceeds 3 g / m ² , the coating aptitude may be degraded. When the recording material has a plurality of recording layers,
The content of the electron-donating dye precursor in each recording layer is preferably within the above range.

As the diazonium salt compound, a compound represented by the following formula is preferably used. Ar-N ₂ + X ^- in the formula, Ar represents an aromatic ring group, X ^- represents an acid anion.

The diazonium salt compound represented by the above formula is a compound which undergoes a coupling reaction with a coupler upon heating to form a color and is decomposed by being irradiated with light. The maximum absorption wavelength of these can be adjusted to a preferable range by variously changing 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 λmax of the diazonium salt compound used as the coloring component A is 450 from the viewpoint of the effect.
nm or less, and more preferably 290 to 440 nm. The diazonium salt compound used in the present invention has a carbon number of 12 or more, a solubility in water of 1% or less, and a solubility in ethyl acetate of 5% or less.
% Of the diazonium salt compound is preferred.

The diazonium salt compound which can be suitably used as the color forming component A is described in JP-A-07-276808.
And the compounds exemplified in columns [0044] to [0049] of JP-A No. 2000-209, 1989. However, the coloring component A is not limited to the above compounds. The diazonium salt compound may be used alone as the color forming component A, or two or more diazonium salt compounds may be used according to various purposes such as hue adjustment.

The diazonium salt compound is preferably contained in the light and heat sensitive recording layer or the light and pressure sensitive recording layer in an amount of 0.01 to 3 g / m ² , more preferably 0.02 to 1.0 g / m ^2. More preferred. If the content is less than 0.01 g / m ² , sufficient color developability may not be obtained. If the content is more than 3 g / m ² , the sensitivity may decrease or the fixing time may need to be increased. Sometimes. When the recording material has a plurality of recording layers, the content of the diazonium salt compound in each recording layer is preferably within the above range.

In the recording material according to the first invention, the compound B combined with the color forming component A as a color forming source in the light and heat sensitive recording layer reacts with the polymerizable group and the color forming component A in the same molecule. , A substantially colorless compound having a site where the coloring component A is colored. That is, compound B
Is a substantially colorless compound having a function of reacting with the color forming component A to form the color forming component A and a function of polymerizing and curing by radicals or the like generated from a photopolymerization initiator.

When an electron-donating dye precursor is used as the color-forming component A, an electron-accepting compound having a polymerizable group can be used as the compound B. When a diazonium salt compound is used as the color-forming component A, As the compound B, a coupler compound having a polymerizable group can be used.

An electron-accepting compound having the polymerizable group,
That is, examples of the compound having an electron accepting group and a polymerizable group in the same molecule include 3-halo-4-hydroxybenzoic acid described in JP-A-4-226455, and
3-173682, methacryloxyethyl ester and acryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-3-173682;
Esters of hydroxymethyl-containing benzoic acid and hydroxymethylstyrene described in JP-A-141587 and JP-A-2-99190; hydroxystyrene described in EP 29323; JP-A-62-167077;
N-vinylimidazole complex of zinc halide described in JP-A-2-16708; electron-accepting compound described in JP-A-63-317558; and compounds that can be synthesized with reference to these compounds. Among the compounds having the electron accepting group and the polymerizable group in the same molecule, the compound B is preferably a 3-halo-4-hydroxybenzoic acid represented by the following general formula.

[0058]

Embedded image

In the above 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 has 5 to 5 carbon atoms.
11 acryloyloxyalkyl groups or 6-1 carbon atoms
Two 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-acid
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.

Further, when a compound having an electron-accepting group and a polymerizable group in the same molecule is used as the compound B, preferred examples include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, β-methacryloxy Zinc ethoxysalicylate, β-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) are exemplified.

When an electron-accepting compound having a polymerizable group is used as the compound B, the amount thereof is 0.1 to 1 part by weight of the combined electron-donating dye precursor.
It is preferably from 5 to 20 parts by weight, more preferably from 3 to 10 parts by weight. If the amount used is less than 0.5 part by weight, it may not be possible to obtain a sufficient color density, and if it exceeds 20 parts by weight, sensitivity may be lowered or application suitability may be deteriorated.

The coupler compound having a polymerizable group is a compound having a polymerizable group in a molecule and forming a dye by coupling with a diazonium salt compound in a basic atmosphere and / or a neutral atmosphere. A plurality of types can be used in combination for various purposes such as hue adjustment.

When a coupler compound having a polymerizable group is used as the compound B, the content in the light-sensitive heat-sensitive recording layer or the light-sensitive pressure-sensitive recording layer is from 0.02 to 5 g / m ^2.
Is preferred, and 0.1 to 4 g / m ² is more preferred from the viewpoint of the effect. If the content is less than 0.02 g / m ² , the color developability may be poor, and if it exceeds 5 g / m ² , the coating suitability tends to decrease.

When a coupler compound having a polymerizable group is used as the compound B, the amount of the compound is based on 1 part by weight of the combined diazonium salt compound.
Preferably it is 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight. If the amount is less than 0.5 part by weight, sufficient coloring properties may not be obtained,
When the amount is more than the weight part, the suitability for coating may be deteriorated.

When a diazonium salt compound is used as the color forming component A and a coupler having a polymerizable group is used as the compound B, tertiary amines, piperidines, piperazines, amidines are used for the purpose of accelerating the coupling reaction. , Formamidines, pyridines, guanidines,
It is preferable to use an organic base such as morpholines.

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.

The organic base is described in JP-A-57-12.
No. 3086, JP-A-60-49991, JP-A-60-
No. 94381, JP-A-09-077737, JP-A-09-77737
Compounds described in JP-A-9-077729 and JP-A-09-071048 can also be used.

The amount of the organic base to be used is not particularly limited, but is preferably 1 to 30 mol per 1 mol of the diazonium salt used as the coloring component A.

When a diazonium salt compound is used as the color-forming component A and a coupler having a polymerizable group is used as the compound B, the color-forming reaction is further promoted by
A coloring aid can also be added. Examples of the coloring aid include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, and sulfonamide compounds.

In the recording material according to the second invention, the compound C combined with the color-forming component A in the light- and heat-sensitive recording layer is a substantially colorless compound having a site for coloring the color-forming component A in the molecule. is there. That is, the compound C is a substantially colorless compound having a function of reacting with the color forming component A to form the color forming component A. Note that, unlike the compound B, the compound C does not have a polymerizable group in the same molecule. Therefore, in the recording material according to the second invention, the compound D having a polymerizable group described below is polymerized when irradiated with light. By doing so, a latent image is formed.

When an electron-donating dye precursor is used as the color-forming component A, an electron-accepting compound can be used as the compound C. When a diazonium salt compound is used as the color-forming component A, the compound As C, a coupler compound can be used.

Examples of the electron accepting compound used as the compound C 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. 40-9
No. 309, JP-B-45-14039, JP-A-52-1
No. 40483, JP-A-48-51510, JP-A-57
JP-A-2108686, JP-A-58-87089, JP-A-59-11286, JP-A-60-176799, JP-A-61-95988, and the like.

Of the above, the following compounds can be specifically mentioned. Examples of the phenol derivative include 2,2′-bis (4-hydroxyphenyl) propane, 4-t-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, and 1,1′-bis (3-chloro-4 -Hydroxyphenyl) cyclohexane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1,1'-bis (3-chloro-4-hydroxyphenyl) -2-ethylbutane, 4,4'-sec-
Isooctylidenediphenol, 4,4'-sec-butylidenediphenol, 4-tert-octylphenol, 4-p-methylphenylphenol, 4,4'-
Methylcyclohexylidenephenol, 4,4′-isopentylidenephenol, benzyl p-hydroxybenzoate and the like can be mentioned.

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.

When an electron-accepting compound is used as the compound C, its amount is preferably 5 to 1000% by weight based on the amount of the electron-donating dye precursor to be combined.

The coupler compound to be used as the compound C is one which forms a dye by coupling with a diazonium salt compound in a basic atmosphere and / or a neutral atmosphere. Can be used together. Specific examples 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, which can be appropriately selected and used within a range consistent with the purpose of the present invention. .

The coupler compound used as the compound C includes resorcin, phloroglucin, 2,3-dihydroxynaphthalene, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, -Hydroxy-
Sodium 3-naphthalenesulfonate, 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.

Other coupler compounds usable as compound C include JP-A-4-201483, JP-A-7-223667, JP-A-7-223368 and
JP-A-7-323660, JP-A-5-278608
JP-A-5-297024, JP-A-6-18669
JP-A-6-18670, JP-A-7-316280
JP-A-09-216468, JP-A-09-216
469, JP-A-09-319025, JP-A-10-
35113, JP-A-10-193801, JP-A-1
Compounds described in gazettes such as 0-264532 are exemplified.

When a coupler compound is used as the compound C, the content in the light and heat sensitive recording layer is 0.0
² to 5 g / m ² is preferable, and 0.1 to 4 g from the viewpoint of the effect.
/ M ² is more preferred. If the content is less than 0.02 g / m ² , sufficient color density may not be obtained,
If it exceeds g / m ² , the coating aptitude may deteriorate.

When a diazonium salt compound is used as the coloring component A and a coupler compound is used as the compound C, an organic base can be used for the purpose of accelerating the coupling reaction. Auxiliaries can be used. Specific examples of usable organic bases, and preferable amounts thereof, and specific examples of usable color forming aids are the same as those in the case of using a diazonium salt compound as the color forming component A and using a coupler compound as the compound B. It is.

In the recording material according to the second invention, the light- and heat-sensitive recording layer further has a polymerizable group and a site for suppressing the reaction between the color-forming component A and the compound C in the same molecule. Contains colorless compound D. The compound D is
The compound is a substantially colorless compound having a function of suppressing the reaction between the coloring component A and the compound C and a function of being polymerized and cured by radicals generated from a photopolymerization initiator.

When an electron-donating dye precursor is used as the coloring component A and an electron-accepting compound is used as the compound C, the compound D has a function of suppressing the reaction between the electron-donating dye precursor and the electron-accepting compound. And a photopolymerizable monomer having at least one vinyl group in the molecule (hereinafter, may be referred to as “photopolymerizable monomer D ₁ ”). 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;

The photopolymerizable monomer D ₁ is preferably a compound having a plurality of vinyl groups in the molecule. Specifically, acrylic acid esters and methacrylic acid esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol Preferred are acrylic esters and methacrylic esters of polyhydric phenols such as resorcinol, pyrogallol, and phloroglucinol; 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, diethylene glycol dimethacrylate, and the like are particularly preferable.

The photopolymerizable monomer D ₁ preferably has a molecular weight of about 100 to about 5000, more preferably about 300 to about 2000.

[0093] As the compound D, when using the photopolymerizable monomer D ₁ is the amount used relative to the electron-donating compound, 1 part by weight to be used in combination as the compound C, 0.1 to 10 weight Part, preferably 0.5 part
More preferably, it is 5 parts by weight. If the amount used is less than 0.1 part by weight, a latent image may not be formed in the exposure step, and if the amount used exceeds 10 parts by weight, the color density may decrease.

When a diazonium salt compound is used as the color-forming component A and a coupler compound is used as the compound C, the compound D may include an acidic group for suppressing a coupling reaction between the diazonium salt compound and the coupler compound, A photopolymerizable monomer having a functional group (hereinafter, may be referred to as “photopolymerizable monomer D ₂ ”) is preferable,
It is preferably not a metal salt compound.

[0095] 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.

When the photopolymerizable monomer D ₂ is used as the compound D, the amount of the compound is
Is preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 10 parts by weight, based on 1 part by weight of the coupler compound used in combination.
More preferably, it is 5 to 5 parts by weight. 0.1 used
If the amount is less than 10 parts by weight, a latent image may not be formed in the exposure step. If the amount is more than 10 parts by weight, the color density may decrease.

In the recording material according to the third invention, the compound E combined with the color-forming component A in the photosensitive pressure-sensitive recording layer substantially reacts with the color-forming component A to form the color-forming component A. It is a colorless compound. Compound E
May be a compound having a polymerizable group in the molecule or a compound having no polymerizable group in the molecule. When a compound having a polymerizable group is used as the compound E, its specific examples and preferable amounts thereof are the same as those of the compound B. When a compound having no polymerizable group is used as the compound E, specific examples thereof and preferable amounts thereof are the same as those of the compound C.

The recording materials according to the first to third aspects of the present invention contain a photopolymerizable composition for forming a latent image in the light- and heat-sensitive recording layer or the light- and pressure-sensitive recording layer. In the recording material according to the first invention, the photopolymerizable composition contains the compound B and a predetermined photopolymerization initiator. In the recording material according to the second invention, the photopolymerizable composition contains the compound C,
It contains the compound D and a predetermined photopolymerization initiator.
In the recording material according to the third invention, the photopolymerizable composition contains a polymerizable compound and a predetermined photopolymerization initiator.
In the recording material according to the third invention, the polymerizable compound contained in the photopolymerizable composition is encapsulated in microcapsules, photopolymerizable monomer D ₁ exemplified as the D compounds. The preferred amount is the same.

In the recording materials according to the first to third aspects of the present invention, the photopolymerization initiator contained in the photopolymerizable composition generates radicals and the like when irradiated with light, and is contained in the photopolymerizable composition. It has a function of causing a polymerization reaction to occur in the compound B, the compound D, or the polymerizable compound contained therein and promoting the reaction to form a desired latent image. In the present invention, the photopolymerization initiator is 300 to
It preferably contains a spectral sensitizing compound having a maximum absorption wavelength at 1000 nm and a compound that interacts with the spectral sensitizing compound. When a spectral sensitizing compound and a compound that interacts with the compound are used together as a photopolymerization initiator, the photopolymerization initiator responds to light of various wavelengths with high sensitivity and generates radicals and the like with high efficiency. can do. As a result, it is possible to form a more sharp image while having higher sensitivity to various light sources such as a blue, green, and red light source and an infrared laser.

Further, when the recording material of the present invention is applied to a recording material for forming a multicolor image, two or more monochromatic recording layers emitting different hues are laminated. In such a case, each monochromatic recording layer is laminated. It is preferred that spectral sensitizing dyes having mutually different maximum absorption wavelengths be present in the recording layer. With such a configuration, each recording layer (each color) is further exposed by sequentially exposing each recording layer using a light source adapted to the maximum absorption wavelength of the spectral sensitizing dye contained in each recording layer. Sensitive to high sensitivity, a sharper image can be formed, and when applied to a recording material for forming a multicolor image, higher sensitivity and sharper image can be obtained.

The spectral sensitizing compound is 300 to 1000
having a maximum absorption wavelength in nm, preferably between 350 and 80
A compound having a maximum absorption wavelength at 0 nm. The spectral sensitizing compound is preferably a spectral sensitizing dye. For example, JP-A-62-143044, JP-A-9-1886
No. 85, JP-A-9-188686, JP-A-9-188
No. 710, “Research Disclosure”
gure, Vol. 200, December 1980, Item
m 20036 "and" sensitizer "(p. 160 to p. 163,
Kodansha; Katsumi Tokumaru, Shin Okawara / ed., 1987) can be used.

Specifically, 3-ketocoumarin compounds described in JP-A-58-15603, JP-A-58-40
No. 302, JP-B-59-
No. 28328 and No. 60-53300, naphthothiazole merocyanine compounds, JP-B-61-962.
No. 1, 62-3842, JP-A-59-89303.
And the merocyanine compounds described in JP-A-60-60104.

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, 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 above-mentioned various spectral sensitizing dyes may be used alone or in combination of two or more.

The amount of the spectral sensitizing compound used is preferably from 0.1 to 5% by weight based on the total solid content of the materials contained in the light and heat sensitive recording layer or the light and pressure sensitive recording layer. More preferably, it is 0.5 to 2% by weight.

Compounds that can be contained in the photopolymerization initiator and interact with the spectral sensitizing compound (hereinafter, sometimes referred to as “interacting compounds”) are irradiated by the spectral sensitizing compound present in the vicinity. When absorbing light, interacts with the spectral sensitizing compound to generate radicals and the like with high efficiency,
It has a function of initiating the polymerization of the compound B, the compound D, or the polymerizable compound present in the vicinity. Examples of such compounds include organic borate salt compounds and the following compounds.

Benzophenone, 4,4-bis (dimethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzylanthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine from CIBA Aromatic ketones such as bisacylphosphine oxides such as oxides;

Benzoin 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-butyl diperoxyisophthalate, 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.

Further, the interacting compounds include:
Materials consisting of a combination of two or more compounds can also be used. For example, a combination of 2,4,5-triarylimidazole dimer with mercaptobenzoxazole and the like, 4,4 described in U.S. Pat. No. 3,427,161.
Combination of 4'-bis (dimethylamino) benzophenone, benzophenone and benzoin methyl ether, benzoyl-N described in U.S. Pat. No. 4,239,850.
Combination of -methylnaphthothiazoline and 2,4-bis (trichloromerchi) -6- (4'-methoxyphenyl) -triazole, dialkylaminobenzoic acid ester and dimethylthioxanthone described in JP-A-57-23602. And three combinations of 4,4'-bis (dimethylamino) benzophenone, benzophenone and a polymethyl halide compound described in JP-A-59-78339.

Among them, the interacting compounds include
A combination of 4,4′-bis (diethylamino) benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate,
Alternatively, it is preferable to use a combination of 4,4′-bis (diethylamino) benzophenone and 2,4,5-triarylimidazole dimer.

When an organic borate salt compound, a benzoin ether, an S-triazine derivative having a trihalogen-substituted methyl group, an organic peroxide, or an azinium salt compound is used as the interacting compound, the exposed portion becomes more exposed. It is preferable because it can locally and effectively generate radicals and can increase the sensitivity,
Among them, organic borate salt compounds are preferable. Further, when an organic borate salt compound is used as the interacting compound, when a spectral sensitizing dye is used as the spectral sensitizing compound, the coexisting spectral sensitizing dye is favorably removed by light irradiation at the time of image fixing. It is preferable because the color can be erased.

Examples of the organic borate salt compounds preferably used as the interacting compound include JP-A-62-143044, JP-A-09-188684,
JP-A-09-188865, JP-A-09-18868
No. 6, JP-A-09-188710, JP-A-62-14
No. 3044, Japanese Unexamined Patent Publication No. Sho 62-150242,
-09643 and DE 198501139A1
The compounds described in the specification are also preferably used. However, the interacting compounds are not limited to these compounds.

The organic borate compounds include:
"Chemistry of Functional Dyes" (1981, CMC Publishing Co., p.
393-p. 416) and “colorants” (60 [4] 212-2).
24 (1987)) and the like, and a spectral sensitizing dye-based organic borate compound having a cationic dye as a cation moiety in the structure. The spectral sensitizing dye-based organic borate compound, upon light irradiation, effectively absorbs light energy by the light absorption function of the dye cation part, and promotes the polymerization reaction by the radical release function of the borate anion part, and coexists. It has three functions of decoloring the spectral sensitizing dye. As the spectral sensitizing dye-based organic borate compound, JP-A-62-143044,
JP-A-1-138204, JP-A-6-505287
And compounds described in JP-A-4-261406 and the like.

As the dye constituting the cation portion of the spectral sensitizing dye-based organic borate compound, a cationic dye having a maximum absorption wavelength in a wavelength region of 300 nm or more, preferably in a wavelength region of 400 to 1100 nm is used. Can be. Among them, cationic methine dye, polymethine dye, triarylmethane dye, indoline dye,
Azine dyes, xanthene dyes, cyanine dyes, hemicyanine dyes, rhodamine dyes, azamethine dyes, oxazine dyes or acridine dyes are preferred, and cationic cyanine dyes, hemicyanine dyes, rhodamine dyes or azamethine dyes are more preferred.

The spectral sensitizing dye-based organic borate compound can be synthesized using an organic cationic dye and an organic boron compound anion with reference to the method described in EP 223,587 A1 and the like.

The following are specific examples of the spectral sensitizing dye-based organic borate compound suitably used as the interacting compound. The compound interacting with the spectral sensitizing compound contained in the photopolymerization initiator is as follows. However, the present invention is not limited to these.

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[0128]

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Since the spectral sensitizing dye-based organic borate compound also has a function as a spectral sensitizing compound, a photopolymerization initiator may be used as the spectral sensitizing compound. Further, the spectral sensitizing dye-based organic borate compound may be used as the spectral sensitizing compound and as the interacting compound.

Examples of the photopolymerization initiator include (1) the spectral sensitizing dye as the spectral sensitizing compound, and the organic borate compound (hereinafter, the cation portion is a dye having a cation moiety as the compound interacting with the spectral sensitizing compound). A non-cationic organic borate compound may be referred to as “organic borate compound I” in some cases, and (2) the spectral sensitizing dye-based organic borate compound (hereinafter referred to as “organic borate compound”) as the spectral sensitizing compound. And a photopolymerization initiator containing an organic borate compound I as a compound that interacts with the spectral sensitizing compound.

When the photopolymerization initiator having the constitution (1) is used, the organic borate compound I is contained in the photopolymerization initiator in an equimolar amount or more with respect to the spectral sensitizing dye contained together. Is preferable in that sufficient polymerization reactivity can be obtained. Further, it is preferable that the organic borate compound I is in excess of the spectral sensitizing dye contained together, because the spectral sensitizing dye remaining in the recording layer at the time of image fixing can be sufficiently decolored. From such a viewpoint, in the photopolymerization initiator having the constitution (1), the molar ratio of the spectral sensitizing dye / organic borate compound I is 1/1.
１／1/50, preferably 1 / 1.2〜1 / 30
Is more preferable, and particularly preferably 1 / 1.2 to 1/20. When the molar ratio is within the above range, sufficient polymerization reactivity and decoloring property can be obtained, and application suitability can be maintained.

When the photopolymerization initiator having the constitution (2) is used, the organic borate compound I and the organic borate compound II are mixed so that the molar amount of the borate moiety is at least equimolar to the dye moiety. It is preferable to use them in combination from the viewpoint of obtaining sufficient sensitivity and decoloring performance. From such a viewpoint, in the photopolymerization initiator having the configuration of the above (2),
The molar ratio of the organic borate compound I / organic borate compound II is preferably from 1/1 to 50/1, and is preferably 1.2 / 1.
３０30/1, more preferably 1.2 / 1-20.
/ 1 is particularly preferred. When the molar ratio is in the above range, radicals can be generated with high efficiency, and sufficient polymerization reactivity and decoloring performance can be obtained.

The total content of the spectral sensitizing compound and the interacting compound in the photopolymerization initiator is determined based on the content of the compound B, the compound D, or the compound contained in the photopolymerizable composition. For the content of the polymerizable compound,
It is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and particularly preferably 0.1 to 1% by weight. When the total content of the spectral sensitizing compound and the interacting compound is within the above range, a sufficient effect can be obtained without lowering the storage stability and the coating suitability, so that it is preferable.

Other photopolymerization initiators may be used as the photopolymerization initiator. As such a photopolymerization initiator,
For example, US Pat. No. 4,950,581 (column 20, column 3)
(Line 5 to column 21, line 35). Further, for example, EP-A-1374
52, DE-A-2718254, DE-A-2243
621, U.S. Pat. No. 4,950,581 (column 14, column 60)
Line to column 18, line 44); 2,4-
And triazine compounds such as trihalomethyltriazine such as bis (trichloromethyl) -6- (4-stilphenyl) -s-triazine. Furthermore, you may use together with a cationic photoinitiator. Examples of usable cationic photopolymerization initiators include, for example, benzoyl peroxide, US Pat. No. 4,950,581 (columns 19, 17).
Peroxide compounds such as peroxides described in US Pat. No. 4,950,581 (column 18, sixth column).
Aromatic sulfonium or iodonium salts described in (line 0 to column 19, line 10); cyclopentadienyl-arenes such as (η6-isopropylbenzene)-(η5-cyclopentadienyl) -iron (II) hexafluorophosphate Iron (II) complex salts and the like.

The photopolymerizable composition may be added to the photopolymerizable composition as an auxiliary for the purpose of accelerating the polymerization reaction.
Scavengers, reducing agents such as chain transfer agents for active hydrogen donors, and other compounds that promote polymerization by chain transfer can also be added. As the oxygen removing agent, phosphine, phosphonate, phosphite,
Other examples include silver salts or other compounds that are easily oxidized by oxygen. Specific examples include N-phenylglycine, trimethylparbituric acid, N, N-dimethyl-2,6-diisopropylaniline, and N, N, N-2,4,6-pentamethylanilinic 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.

In the recording material according to the first to third aspects, the recording layer further contains a binder resin for forming a layer. As the binder resin, for example,
Acrylic resins such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polystyrene, polyvinyl formal, polyvinyl butyral, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, copolymers of acrylate and methacrylate monomers, phenolic resins, styrene -Solvent-soluble polymers such as butadiene resin, ethyl cellulose, epoxy resin and urethane resin, and polymer latexes thereof. Among them, gelatin and polyvinyl alcohol are preferable as the binder resin.

Further, in the recording material according to the first to third aspects of the present invention, the recording layer is provided with the ultraviolet absorber, the ultraviolet absorber precursor, the coating aid, the antistatic property, the improvement of slipperiness, the emulsification dispersion, and the prevention of adhesion. For various purposes such as, for example, various surfactants may be contained. Examples of the surfactant include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and alkyl sulfates. Esters, N-acyl-N-alkyltaurines, sulfosuccinates, anionic surfactants such as sulfoalkylpolyoxyethylenalkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, And cationic surfactants such as aliphatic or aromatic quaternary ammonium salts.

If necessary, the recording layer may further contain, for example, a dye, a plasticizer, a fluorescent brightener, a matting agent, a coating aid,
You may contain additives, such as a hardening | curing agent, an antistatic agent, and a slipperiness improving agent. Specific examples of the additive include “Research
h Disclosure, Vol. 176 "(197
December 1981, Item 17643) and "Ibid. Vol.
187 "(November 1979, Item 18716)
It is described in.

In the recording materials according to the first and second aspects of the invention, the color-forming component A is contained in the light- and heat-sensitive recording layer in a state of being encapsulated in the thermo-responsive microcapsules. Component A and the photopolymerizable composition are contained in the photosensitive pressure-sensitive recording layer in a state of being encapsulated in microcapsules.

In the recording materials according to the first and second aspects of the present invention, the microcapsules containing the color-forming component A exhibit heat responsiveness. The term “thermally responsive microcapsule” means that at normal temperature, the microcapsule wall (hereinafter simply referred to as “capsule wall”) has a substance isolating function and prevents contact of substances existing inside and outside the microcapsule, but a certain value or more. Is a microcapsule capable of contacting a substance inside and outside the capsule when heat energy is applied. On the other hand, in the third invention, the microcapsules containing the coloring component A and the photopolymerizable composition do not need to have a property of transferring to an external stimulus such as heat responsiveness. When the capsule wall has a substance isolating function and a certain pressure is applied, when the encapsulating photopolymerizable composition is cured, contact of substances existing inside and outside the microcapsule is prevented (for example, Microcapsules are not broken),
When the encapsulating photopolymerizable composition is not cured, it is a microcapsule in which a substance existing inside and outside the microcapsule can be contacted (for example, the microcapsule is broken). The physical properties of such a microcapsule can be adjusted to a preferable range by appropriately selecting a material for the capsule wall, a capsule core substance (a substance included in the capsule), an additive, and the like.

As a method for enclosing the color forming component A and the like in microcapsules, a conventionally known method can be used. For example, US Patent Nos. 2,800,457 and 2,800
0458, a method utilizing coacervation of a hydrophilic wall forming material, US Pat. No. 3,287,154.
No., British Patent No. 990443, Japanese Patent Publication No. 38-1
No. 9574, No. 42-446, Interfacial polymerization described in No. 42-771, U.S. Pat.
No. 3,660,304, a method using polymer precipitation, a method using a isocyanate polyol wall material described in US Pat. No. 3,796,669, a method using an isocyanate wall material described in US Pat. No. 3,914,511, a US patent No. 4001140, 408
Urea described in US Pat.
Method using formaldehyde-based, urea-formaldehyde-resorcinol-based wall-forming material, U.S. Pat.
No. 455, a method using a wall-forming material such as melamine-formaldehyde resin and hydroxybromo cellulose; Japanese Patent Publication No. 36-9168;
No. 79, in situ by polymerization of monomer
u method, the electrolytic dispersion cooling method described in British Patent Nos. 952807 and 965074, US Pat.
7, the spray drying method described in British Patent No. 930422, Japanese Patent Publication No. 7-73069,
No. 101885 and JP-A-9-263057.

In particular, the oil phase prepared by dissolving or dispersing the color-forming component A and the like in a hydrophobic organic solvent serving as the core of the capsule is:
After mixing with the aqueous phase in which the water-soluble polymer is dissolved and emulsifying and dispersing by means of a homogenizer or the like, the polymer formation reaction occurs at the oil droplet interface by heating, forming the microcapsule wall of the polymer substance. Preferably, microcapsulation is performed by employing an interfacial polymerization method. The interfacial polymerization method is preferable in that 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.

Hereinafter, an example of the microencapsulation process by the interfacial polymerization method will be described. First, an oil phase is prepared by dissolving a material encapsulated in microcapsules such as the coloring component A in a high-boiling organic solvent that is hardly soluble or insoluble in water. As the high boiling organic solvent, generally, phosphoric acid ester, phthalic acid ester, acrylic acid ester, methacrylic acid ester, other carboxylic acid ester, fatty acid amide, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated Naphthalene, diallylethane,
Compounds that are solid at room temperature, oligomer oils, polymer oils, and the like are used. Specifically, JP-A-59-1784
51-59-178455, 59-178457
No. 60-242094, No. 63-85633,
JP-A-6-194825, JP-A-7-13310-JP-A-7
And organic solvents described in JP-A-13311 and JP-A-9-106039 and Japanese Patent Application No. 62-75409. The organic solvent is preferably used in an amount of 1 to 500 parts by weight based on 100 parts by weight of the coloring component A.

When the solubility of the coloring component A or the like contained in the microcapsules in the organic solvent is low, a low-boiling solvent having high solubility can be used as an auxiliary solvent. It is also possible to use only a low-boiling solvent without using a high-boiling organic solvent. Examples of the low boiling point solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like.

Further, a component to be a material for the capsule wall is added to the oil phase. Examples of the material for 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 material of the capsule wall may be a material obtained by mixing two or more kinds of the above-mentioned polymer substances. In the oil phase, monomers, oligomers and the like constituting the above-mentioned polymer substance are added.

For example, when the capsule wall is composed of polyurethane, a polyvalent isocyanate and a second substance (for example, polyol or polyamine) which reacts with the polyisocyanate to form the capsule wall are mixed in an oil phase and emulsified and dispersed in water. After doing
By heating, a polymer-forming reaction occurs at the oil droplet interface to form a microcapsule wall.

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 3,7932.
No. 68, JP-B-48-40347, JP-B-49-2415
9, JP-A-48-80191 and JP-A-48-84086.
The one described in the item can also be used.

Next, the oil phase containing the color-forming component A, the material for the capsule wall, etc., prepared as described above,
An emulsified dispersion is prepared by mixing a surfactant and / or a polymer aqueous solution (aqueous phase) containing a water-soluble polymer as a protective colloid, and emulsifying and dispersing the oil phase with a homogenizer or the like.
The emulsification and dispersion are carried out by using an oil phase containing the above components and an aqueous phase containing a surfactant and / or a protective colloid for fine particle emulsification such as high-speed stirring and ultrasonic dispersion, for example, a homogenizer, a Manton-Gawley, It can be easily performed using a known emulsifying apparatus such as a sonic disperser, a dissolver, and a Keddy mill. In this case, if necessary, a low boiling point solvent can be used as a dissolution aid. The particle size of the emulsified dispersion formed in the aqueous phase by emulsification and dispersion is preferably 1 μm or less. In addition, all the components included in the microcapsules, including the coloring component A, can be separately emulsified and dispersed, and the respective emulsified dispersions can be mixed thereafter. Further, the material of the capsule wall is a coloring component A.
Add oil phase containing water to the aqueous phase, emulsified and dispersed,
After the oil droplets composed of the oil phase are formed, they may be added to the aqueous phase.

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. The water-soluble polymer contained in the aqueous phase has a function as a protective colloid that can make the dispersion of the oil phase uniform and easy, and also functions as a dispersion medium for stabilizing the emulsified aqueous solution. The water-soluble polymer 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, and methyl cellulose. Examples of the amphoteric polymer include gelatin. Among them, it is preferable to use gelatin, a gelatin derivative, and polyvinyl alcohol as the water-soluble polymer. The aqueous phase comprises
An aqueous solution containing the water-soluble polymer in an amount of 0.01 to 10% by weight is preferable.

In order to perform the emulsification and dispersion more uniformly and to obtain a more stable dispersion, a surfactant can be added to at least one of the oil phase and the aqueous phase. As the surfactant, known surfactants for emulsification can be widely used, and may be anionic or nonionic. Specific examples include sodium alkylbenzene sulfonate, sodium alkyl sulfate, dioctyl sulfosuccinate sodium salt, polyalkylene glycol (eg, polyoxyethylene nonyl phenyl ether), and the like. The amount of the surfactant is preferably 0.1% to 5%, more preferably 0.5% to 2%, based on the weight of the oil phase.
Is more preferred.

Next, the obtained emulsified dispersion was subjected to 30 to 70
Heat to ° C. to accelerate the capsule wall formation reaction. Also,
During the reaction, in order to prevent agglomeration of the capsules, it is preferable to add water to lower the probability of collision between the capsules or to perform sufficient stirring. During the reaction, a dispersion for preventing aggregation may be separately added.

At the end point of the microencapsulation reaction, generation of carbon dioxide gas is observed with the progress of the polymerization reaction, and the end of the generation can be regarded as an approximate end point. Usually, microcapsules containing the coloring component A and the like can be obtained by performing the reaction for several hours.

The average particle size of the microcapsules containing the color-forming component A and the like is preferably as small as possible from the viewpoint of obtaining high resolution, and is usually preferably 20 μm or less, more preferably 5 μm or less.
It is more preferable that: On the other hand, if the average particle size of the microcapsules is too small, the surface area with respect to a certain solid content increases, and a large amount of a wall material is required. Therefore, the average particle size is preferably 0.1 μm or more.

The recording material according to the first to third aspects of the present invention is obtained by mixing the microcapsules containing the color forming component A prepared as described above with other components contained in the recording layer, It can be prepared by preparing a coating solution, applying the coating solution on a support, and drying.

In the preparation of the recording material according to the first invention, the compound B, the photopolymerization initiator and, if desired, other components are used, and in the preparation of the recording material according to the second invention, the compound C is used. , The compound D, the photopolymerization initiator, and other components as required, in the production of the recording material according to the third invention, the compound E,
The photopolymerization initiator, and optionally other components,
After emulsifying with a suitable emulsifying aid, a coating solution for a recording layer can be prepared using the emulsified product. Further, the above components can be solid-dispersed together with a water-soluble polymer by a sand mill or the like to prepare a coating solution for a recording layer. Here, as a method of solid dispersion or emulsification of the components,
JP-A-59-190886, JP-A-2-141279
And Japanese Patent Application Laid-Open No. 7-17145.

A dispersion of the microcapsules prepared above,
An emulsified dispersion of a compound to be colored, etc., and a solution containing a binder resin, if necessary, are mixed to prepare a coating solution for a light- and heat-sensitive recording layer or a coating solution for a light- and pressure-sensitive recording layer. The recording material of the present invention can be prepared by applying the coating solution to the coating solution and drying. When the ultraviolet absorbent and / or the precursor of the ultraviolet absorbent are contained in the light and heat sensitive recording layer or the light and pressure sensitive recording layer, they may be contained inside or outside the microcapsule. As the solvent used for preparing the coating solution,
Water; methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,
Alcohols such as methyl cellosolve and 1-methoxy-2-propanol; halogen solvents such as methylene chloride and ethylene chloride; acetone, cyclohexanone,
Ketones such as methyl ethyl ketone; esters such as methyl acetate cellosolve, ethyl acetate and methyl acetate; toluene;
A single substance such as xylene and a mixture of two or more of these substances may be mentioned. Among them, water is particularly preferred.

To apply the coating solution on the support, a blade coater, rod coater, knife coater, roll doctor coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, curtain coater, extrusion coater can be used. Etc. can be used. As the application method,
“Rcsearch Disclosurc, Vol.
200 "(December 1980, Item 20036
XV).

The layer thickness of the light and heat sensitive recording layer and the light and pressure sensitive recording layer is preferably 0.1 to 50 μm, and 5 to 3 μm.
More preferably, it is 5 μm.

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 described in Section XVII) can also be used. The various supports may contain a fluorescent whitening agent, a bluing dye, a pigment and the like.

In the recording material according to the first to third aspects,
A protective layer can be provided on the recording layer. The protective layer may have a single-layer structure or a stacked structure of two or more layers. When the protective layer contains the ultraviolet absorber and / or the precursor of the ultraviolet absorber,
In the case of a laminated structure having more than two layers, the protective layer may be contained in one protective layer or may be contained in two or more protective layers.

The protective layer contains a binder resin for forming the layer and, if desired, contains the ultraviolet absorber and / or the precursor of the ultraviolet absorber. As the binder resin, for example, gelatin, polyvinyl alcohol, carboxy-modified polyvinyl alcohol,
Vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch, methylcellulose,
Carboxymethylcellulose, hydroxymethylcellulose, gelatin, gum arabic, casein, styrene-maleic acid copolymer hydrolyzate, styrene-maleic acid copolymer half ester hydrolyzate, isobutylene-
Water-soluble polymer compounds such as maleic anhydride copolymer hydrolysate, polyacrylamide derivative, polyvinylpyrrolidone, sodium polystyrene sulfonate, sodium alginate, styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene Latexes such as rubber latex and vinyl acetate emulsion are exemplified.

By crosslinking the water-soluble polymer compound used in the protective layer, the storage stability can be further improved. Examples of the crosslinking agent include water-soluble initial condensates such as N-methylol urea, N-methylol melamine, and urea-formalin; dialdehyde compounds such as glyoxal and glutaraldehyde; inorganic crosslinking agents such as boric acid and borax; and polyamide epichlorohydrin. And the like.

Further, it is preferable that the protective layer contains a curing agent to reduce the tackiness of the protective layer. As the curing agent, for example, a "gelatin curing agent" used in the production of a photographic light-sensitive material is useful. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, and the reactivity described in US Pat. No. 3,635,718, etc. A compound having a reactive ethylenically unsaturated group described in U.S. Pat. No. 3,635,718;
Aziridine compounds described in No. 17280, etc., epoxy compounds described in U.S. Pat. No. 3,091,537, halogenocarboxaldehydes such as mucochloric acid, dioxane such as dihydroxydioxane, dichlorodioxane, U.S. Pat. No. 3,642,486 and U.S. Pat. 3687
No. 707, vinyl sulfones, U.S. Pat.
1872 and the ketovinyls described in U.S. Pat. No. 3,640,720. Chromium alum, zirconium sulfate, boric acid, and the like can also be used as the inorganic curing agent.

Among them, 1,3,5-triacroyl-hexahydro-s-triazine, 1,2-pispinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamide) ) Compounds such as ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenino-s-triazine and boric acid are preferred. The addition amount of the curing agent is preferably 0.5 to 5% by weight based on the binder amount. The curing agent is
It can be contained in a recording layer, an intermediate layer or the like.

The protective layer may further contain known pigments, metal soaps, waxes, surfactants, optical brighteners and the like.

The protective layer can be formed by preparing a coating solution containing the binder resin and, if desired, other components such as an ultraviolet absorber, and applying the coating solution on the recording layer. As the application amount of the coating liquid,
Preferably ^{0.2~5g / m 2, 0.5~3g / m} 2 is more preferable.

In the recording materials according to the first to third aspects of the present invention, if necessary, the recording material may be placed between the support and the light- and heat-sensitive recording layer or the light- and pressure-sensitive recording layer, or between the light- and heat-sensitive recording layers of the support. An antihalation layer may be provided on the surface on which the photosensitive pressure-sensitive recording layer is provided, and a slip layer, an antistatic layer, an anti-curl layer, an adhesive layer, etc. may be provided on the back surface. 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 on the side of the support where the light and heat sensitive recording layer or the light and pressure sensitive recording layer is not provided. When the antihalation layer is provided on the surface of the substrate, an antihalation layer that can be bleached by light irradiation or heat can be provided.

When an antihalation layer bleachable by light irradiation is provided, the layer may be, for example, a combination of the above-mentioned spectral sensitizing compound and an organic borate salt compound (the above-mentioned spectral sensitizing dye and organic Combination with borate compound I, and organic borate compound I and organic borate compound
In the case where a layer capable of bleaching by heat is used, for example, a configuration in which a base or a nucleophile is generated by heat and can bleach the coexisting spectral sensitizing dye is used. it can.

A layer containing a polymer having low oxygen permeability, such as gelatin or polyvinyl alcohol (PVA), may be provided between the support and the light and heat sensitive recording layer or the light and pressure sensitive recording layer. By providing this layer, it is possible to effectively prevent fading due to photo-oxidation of the formed image.

In the embodiment in which the first to third recording materials of the present invention are applied to a multicolor recording material, a plurality of single-color photosensitive / thermosensitive recording layers or photosensitive / pressure-sensitive recording layers are laminated on a support. Be composed. Each recording layer contains a microcapsule containing a color-forming component A that develops a different hue, and a photopolymerizable composition containing a spectral sensitizing compound having a different maximum absorption wavelength. When the recording material is irradiated with light,
Due to the difference in the light source wavelength, each recording layer is exposed to light and develops a different hue, so that a multicolor image can be formed as a whole.

For example, in one embodiment in which the recording material according to the first invention is applied to a multicolor recording material, a microcapsule containing a color-forming component for producing yellow, a photopolymerizable material sensitive to a central wavelength λ1 of a light source, A first composition comprising:
Is provided on a support, and a second recording layer containing a microcapsule containing a color-forming component for magenta coloring and a photopolymerizable composition sensitive to a central wavelength λ2 is provided on the recording layer. Further, a third recording layer containing a microcapsule containing a color-forming component for forming cyan and a photopolymerizable composition sensitive to a wavelength of λ3 is provided and laminated on the layer. It is preferable to provide an intermediate layer between the recording layers.

In the case where an image is formed using the multicolor recording material, the image exposure is performed by using a plurality of light sources having different wavelengths suitable for the absorption wavelength of each recording layer in the exposure step. The recording layers having the above absorption wavelengths can selectively form a latent image, and a multicolor image can be formed with high sensitivity and high sharpness. After the exposure of each recording layer is completed, the latent image formed on each recording layer is exposed by heating or pressing. Next, 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 each recording layer can be erased. Can be formed. Furthermore, since the recording material has the protective layer or the like containing the ultraviolet absorber, even when stored after being exposed to a fluorescent lamp or sunlight, the background portion is not colored,
High contrast images can be maintained.

In the multicolor recording material, the ultraviolet absorber and / or the precursor of the ultraviolet absorber may be:
It may be contained in a plurality of recording layers or may be contained in only one recording layer. Also, a protective layer is provided as the outermost layer,
The protective layer may contain the ultraviolet absorber or the like,
It may be contained in an intermediate layer located between recording layers.

In a multicolor recording material, an intermediate layer located between each monocolor recording layer provided as required is mainly composed of a binder, and if necessary, the above-mentioned curing agent, polymer latex, filter dye, mica, etc. It contains.

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 the intermediate layer.

In the oil-in-water dispersion method, the boiling point is 175 ° C.
After dissolving the filter dye in one of the above high-boiling solvents or low-boiling solvents at 30 to 160 ° C., or a mixture thereof, water, an aqueous solution of gelatin or polyvinyl alcohol in the presence of a surfactant Finely dispersed in aqueous solution such as aqueous solution. As the high boiling point solvent, US Pat.
Solvents described in No. 322027 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.
In the polymer dispersion method, latex is used in the curing and impregnation steps. Specific examples of the latex include U.S. Pat. No. 4,199,383 and West German Patent Application (OL).
S) Nos. 2541274, 2541230, JP-A-49-74538, JP-A-51-59943, and 54
No. 32552 and "Research Disclos"
ure Vol. 148 "(August 1976, Item
14850) and the like. Among them, ethyl acrylate, n-butyl acrylate,
acrylic acid esters such as n-butyl methacrylate and 2-acetoacetoxyethyl methacrylate or methacrylic acid esters; acrylic acid; 2-acrylamide-
A copolymer latex of an acid monomer such as 2-methylpropanesulfonic acid is preferred.

The recording material according to the first and second aspects of the present invention comprises, at least, an exposure step in which the photopolymerizable composition forms a latent image by image exposure, and a heating operation in which a coloring component develops a color in accordance with the latent image. An image can be formed by an image recording method including a color forming step of forming, 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. Further, the recording material according to the third invention comprises, at least, an exposure step in which the photopolymerizable composition forms a latent image by image exposure, and a color formation in which a color-forming component develops a color according to the latent image by pressurization to form an image. An image can be formed by an image recording method including a step of irradiating the surface of the recording layer with light to fix a formed image and decolorizing the photopolymerization initiator component.

In the exposure step, a light source having a light source wavelength in the ultraviolet to infrared region can be widely used as a light source for forming an image, and the maximum absorption of the spectral sensitizing compound contained in the recording layer can be used. What is necessary is just to select the preferable light source according to a wavelength range. Maximum absorption wavelength 300-1000
A light source in the range of nm is preferable, and among them, a laser light source of blue, green, red, or the like or an LED is more preferable in that the device can be simplified and reduced in size and cost can be reduced. In the case where an image is formed using the multicolor recording material, in the exposure step, each recording layer is image-exposed using a plurality of light sources having different wavelengths and adapted to the absorption wavelength of each recording layer.

In the recording material according to the first and second aspects, the recording material is heated in the color forming step. The heating can be performed by a known method such as a method using a heat roller or the like. The heating temperature is generally 8
0-200 degreeC is preferable and 85-130 degreeC is more preferable. When the heating temperature is lower than 80 ° C., the color density may be insufficient. When the heating temperature is higher than 200 ° C., the non-image portion (background portion) may be colored or the support may be damaged. is there. The heating time is preferably from 1 second to 5 minutes, more preferably from 3 seconds to 1 minute. At a predetermined temperature below the color development temperature,
By heating the entire surface of the recording material uniformly and then heating it at the color development temperature, the sensitivity of the recording material can be further improved. The heating may be performed simultaneously with the exposure.

In the recording material according to the third invention, the recording material is pressurized in the color forming step. The pressurization can be performed by a conventionally known method such as a pressurized platen roller and a point contact ball. The pressure at the time of pressurization is 10-300k
g / cm ² is preferable, and 130 to 200 kg / cm ² is more preferable. If the pressure at the time of pressurization is less than 10 kg / cm ² , a sufficient color density may not be obtained, and 300
If it exceeds kg / cm ² , the contained photopolymerizable composition may be broken down to hardened microcapsules, and image discrimination may be insufficient. The pressing may be performed simultaneously with the exposure.

In the fixing step, by irradiating the entire surface of the recording layer with light from a specific light source, the image formed in the color forming step is fixed and the photopolymerization initiator component remaining in the recording layer is used. Eliminates coloring. Through the fixing step, the whiteness of the non-image area can be enhanced, and a chemically stable final image can be obtained. Further, when a diazonium salt compound is used as a color forming component, the diazonium salt compound remaining in the recording layer after image formation can be deactivated by light irradiation, so that a formed image without density fluctuation, 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 once may also be employed 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 sufficient time 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.

The light and heat sensitive recording material of the present invention can form an image by using the following recording method. For example,
A thermal recording method using a heating device such as a thermal head can be used. Further, for the purpose of improving the contrast and the image quality, a recording method proposed by 3M Company described in International Application WO95 / 31754 can be used. This recording method is a method of irradiating a recording material with a laser beam such that the beam spots overlap in a predetermined range. Specifically, in the process of irradiating the laser beam in the latent image forming step, (1) a radiation light source capable of forming a beam spot with at least one of height and length of 600 μm or less on the target object And (2) after arranging a recording material sensitive to this light source at a predetermined target position, first, (3) the light source has at least one of a length and a width of 2
The beam spot is adjusted so as to have a beam spot of 50 μm or less, and this beam is used for irradiation in accordance with the image distribution. (4) an image forming technique of irradiating according to an image distribution such that at least some spots of a beam to be subsequently irradiated overlap with the irradiated spot, and

Alternatively, in the method of forming a latent image by exposing a recording material, (1) preparing a light source capable of exposing the recording material, and (2) making one of the height and length of the beam spot of this light source A plurality of small regions of 600 μm or less are irradiated, and at least 10% of energy required for at least one small region, that is, at least 10% of the plurality of small regions overlaps with another small region. Image forming technology for irradiating the laser beam.

Further, 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. Can be used. Using this technique, a higher quality image can be formed.

The recording materials according to the first to third inventions can be used for various purposes. For example, it can be used as a recording material for Copier (registered trademark), fax, and color printers, and can be used for labels, color proofs, second original drawings, and the like.

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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><Preparation of Electron-donating Colorless Dye-Encapsulating Microcapsule Solution> (1-a) Preparation of Electron-donating Colorless Dye-Encapsulating Microcapsule Solution (I) Ethyl acetate In 16.9 g, 8.9 g of the following electron-donating colorless dye (1) of yellow color was dissolved, and a 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) Enclosing 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 following organic borate compound (1) (organic borate compound I), 0.1 g of the following spectral sensitizing dye-based organic borate compound (1) (organic borate compound II), pentamethyl 0.1 g of aniline was dissolved, and capsule wall material (trade name: Takenate D-110N,
20 g of Takeda Pharmaceutical Co., Ltd.) and 2 g of capsule wall material (trade name: Millionate MR200, manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. 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 predetermined photopolymerizable composition as a core, and an average particle diameter of 7 μm.
m of microcapsule liquid (V) was obtained.

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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 (1) (organic borate compound I) and 0.1 g of the spectral sensitizing dye-based organic borate compound (1) (organic borate compound II), 0.1 g of the following auxiliary agent (1) for the purpose of increasing sensitivity, and isopropyl acetate (solubility in water of about 4. 3%) and 3 g of an electron-accepting compound (1) having a polymerizable group shown below.
g was added. 13 g of a 13% aqueous solution of gelatin was mixed with 0.8 g of a 2% aqueous solution of surfactant (1) described below.
And 0.8 g of a 2% aqueous solution of a surfactant (2) shown below, and added to a homogenizer (Nippon Seiki Co., Ltd.).
), And emulsified at 10,000 rpm for 5 minutes to obtain an emulsion (1) of a photopolymerizable composition.

(2-b) Preparation of Photopolymerizable Composition Emulsion (2) In place of the spectral sensitizing dye-based organic borate compound (1) used in the above (2-a), the following spectral sensitizing dye compound (2)
Except for using 0.1 g, a photopolymerizable composition emulsion (2) was obtained in the same manner as in the above (2-a).

(2-c) Preparation of photopolymerizable composition emulsion (3) In place of the spectral sensitizing dye-based organic borate compound (1) used in (2-a), the following spectral sensitizing dye compound (3)
Except for using 0.1 g, a photopolymerizable composition emulsion (3) was obtained in the same manner as in the above (2-a).

(2-d) Preparation of Photopolymerizable Composition Emulsion (4) In the preparation of the photopolymerizable composition emulsion (2), an ultraviolet ray represented by the following structural formula was further added to the mixed solution. A photopolymerizable composition emulsion (4) was prepared in the same manner as in (2-b), except that the absorber (1) and the ultraviolet absorber (2) represented by the following structural formula were mixed. The content of the ultraviolet absorber (1) in the mixed solution is an amount necessary for a dry coating amount to be 0.1 g / m ^2, and the content of the ultraviolet absorber (2) is a dry coating amount. The amount required was 0.4 g / m ² .

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<Emulsion of Electron-Accepting Compound> (2-e) Preparation of Emulsion of Electron-Accepting Compound (α) The polymerizable group is contained in 3 g of isopropyl acetate (solubility in water: about 4.3%). 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 for Photosensitive and Thermosensitive Recording Layer (1) — [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-[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-c) Coating solution for photosensitive and heat-sensitive recording layer (3)
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 gelatin solution 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 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 (4) for a light and heat sensitive recording layer.

(3-e) Coating solution for photosensitive and heat-sensitive recording layer (5)
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 (5) for a photosensitive and heat-sensitive recording layer.

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

<Preparation of Coating Solution for Photosensitive Pressure-Sensitive Recording Layer> (3-g) 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 a 2% aqueous solution of surfactant (4) shown below. (1) was prepared.

<Preparation of Coating Solution for Protective Layer> (4-a) Preparation of Coating Solution for Protective Layer (1) 4.5 g of a 10% gelatin aqueous solution, 4.5 g of distilled water,
0.5 g of the following 2% surfactant (3) aqueous solution and the following 2%
0.3 g of an aqueous solution of a surfactant (4), 0.5 g of a 2% aqueous solution of a vinyl sulfone compound (hardener), and “Syloid 72” (FUJI-DEVICE CHEMICAL)
LTD. ), 1 g of “Snowtex N”, an ultraviolet absorber (1) represented by the structural formula, and an ultraviolet absorber (2) represented by the structural formula, and a protective layer coating solution ( 1) was prepared. The content of “Syloid 72” is an amount necessary for a dry application amount to be 50 mg / m ^2, and the content of the ultraviolet absorber (1) is 0.1 g / dry application amount.
m ^2, and the ultraviolet absorber (2)
Was set to an amount necessary for a dry coating amount to be 0.4 g / m ² .

(4-b) Preparation of Coating Solution (2) for Protective Layer In the preparation of the coating solution (1) for the protective layer, the ultraviolet absorber (1) and the ultraviolet absorber (2) were used in place of the ultraviolet absorber (1).
A protective layer coating solution (2) was prepared in the same manner except that an ultraviolet absorber (3) represented by the following structural formula was used. The content of the ultraviolet absorber (3) is such that the dry coating amount is 0.5 g / m ^2.
And the amount required to obtain

(4-c) Preparation of Coating Solution (3) for Protective Layer In the preparation of the coating solution (1) for the protective layer, in place of the ultraviolet absorber (1) and the ultraviolet absorber (2),
A protective layer coating solution (2) was prepared in the same manner except that an ultraviolet absorber (4) represented by the following structural formula was used. The content of the ultraviolet absorber (4) is such that the dry coating amount is 0.5 g / m ^2.
And the amount required to obtain

(4-d) Preparation of Coating Solution (4) for Protective Layer Ultraviolet absorber precursor (1) represented by the following structural formula
5 parts and 2 parts of a reducing agent (1) represented by the following structural formula were mixed with 6.6 parts of ethyl acetate and 2.9 parts of a phthalate-based solvent (A-1) shown below. 2.0 parts of xylylene diisocyanate / trimethylolpropane adduct (75% ethyl acetate solution Takenate D110N: trade name of Takeda Pharmaceutical Co.) as a capsule wall material was further added to this solution,
The mixture was stirred to be uniform. Separately, 60 parts of a 10% by weight aqueous solution of polyvinyl alcohol (PVA217E: trade name of Kuraray Co., Ltd.) to which 3.2 parts of a 10% by weight aqueous solution of sodium dodecylsulfonate were added were prepared, and the above solution was added, followed by emulsification and dispersion with a homogenizer. The obtained emulsion was heated to 50 ° C. while stirring, and an encapsulation reaction was performed for 3 hours to obtain a target capsule liquid. The average particle size of the capsule is 0.
It was 2 μm. 50 parts of ion-exchanged water was added to 13 parts of the capsule liquid, and the mixture was stirred uniformly to prepare a protective layer coating liquid (4).

(4-e) Preparation of Coating Solution (5) for Protective Layer The preparation of the coating solution (1) for the protective layer was the same except that the ultraviolet absorbers (1) and (2) were not used. Then, a coating solution (5) for a protective layer was prepared.

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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). .

(Example 2): Black color development A photosensitive and heat-sensitive recording material (2) was prepared in the same manner as in Example 1 except that the coating solution for protective layer (2) was used in place of the coating solution for protective layer (1). I got

(Example 3): Black color development A photosensitive and heat-sensitive recording material (3) was prepared in the same manner as in Example 1 except that the coating solution for protective layer (3) was used in place of the coating solution for protective layer (1). I got

(Example 4): Cyan-colored polyester film filled with 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 (4). .

(Example 5): Cyan color development The coating solution (2) for the photosensitive and heat-sensitive recording layer used in Example 4 was replaced with the coating solution (6) for the photosensitive and heat-sensitive recording layer.
A photosensitive and heat-sensitive recording material (5) was obtained in the same manner as in Example 4, except that the protective layer coating liquid (1) was changed to the protective layer coating liquid (5).

(Example 6) Polyester film filled with a multicolored white pigment (Lumirror E
-68L, manufactured by Toray Industries, Inc.) On a support having a thickness of 100 [mu] m, the coating solution (5) (cyan color) for the photosensitive and heat-sensitive layer was dried with a coating bar using a coating bar so that the dry weight of the coating layer was 6 g / m.
² and dried, and the intermediate layer coating solution (1) was applied on this layer using a coating bar so that the dry weight was 1.5 g / m ² , and dried. further,
On the intermediate layer, a coating solution (4) (magenta coloring) for a light and heat sensitive recording layer was applied using a coating bar so that the dry weight of the applied layer was 6 g / m ² , and dried. The dry weight of the coating solution for intermediate layer (1) is 1.5 g / m ^2.
And dried. Further, on this layer, a coating solution (3) (yellow color) for a light and heat sensitive recording layer was applied using a coating bar so that the dry weight of the applied layer was 6 g / m ² , and dried. The protective layer coating solution (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 (6).

(Example 7): Magenta coloring 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 solution (1) for a protective layer 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 (7). Was.

(Example 8): Cyan color development Photosensitive and heat-sensitive recording was performed in the same manner as in Example 4, except that the coating liquid (4) for the protective layer was used in place of the coating liquid (1) for the protective layer. Material (8) was obtained.

(Comparative Example 1): Black color development Photosensitive and heat-sensitive recording was performed in the same manner as in Example 1 except that the coating liquid for protective layer (5) was used in place of the coating liquid for protective layer (1). Material (9) was obtained.

(Comparative Example 2): Cyan color development Photosensitive and heat-sensitive recording was conducted in the same manner as in Example 1 except that the coating liquid for protective layer (5) was used in place of the coating liquid for protective layer (1). Material (10) was obtained.

(Comparative Example 3): Multi-color development In the same manner as in Example 6, except that the protective layer coating liquid (5) was used instead of the protective layer coating liquid (1) in Example 6, A recording material (11) was obtained.

(Comparative Example 4): Magenta Coloring The procedure of Example 7 was repeated except that the protective layer coating liquid (5) was used in place of the protective layer coating liquid (1). A recording material (12) was obtained.

With respect to each of the light and heat sensitive recording materials (1) to (5) and (8) to (10), the irradiation energy was changed from the protective layer side using a semiconductor-excited YLF solid laser beam having a wavelength of 657 nm. The exposure was performed by changing the image shape in the form of a step wedge. Maximum irradiation energy is 15
mJ / cm ² . Next, after heating each recording material on which a latent image was formed by the above-mentioned exposure with a hot plate at 120 ° C. for 5 seconds, each recording material was placed on a 58000 lux high-intensity Shark Sten, and the recording layer surface was heated for 30 seconds. The whole was irradiated with light. As a result, a clear wedge-shaped image was obtained in the image portion, and the background portion had high whiteness.

The light and heat sensitive recording materials (6) and (1)
Regarding 1), first, from the protective layer side, a wavelength of 780 n
m is imagewise exposed using a semiconductor laser light of m, then imagewise exposed using a semiconductor-excited YLF solid-state laser light having a wavelength of 657 nm, and further exposed to YAG having a wavelength of 532 nm.
Imagewise exposure was performed using solid state laser 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, 58000 l of each recording material was heated.
ux, and the recording layer surface was irradiated with light for 30 seconds. Then, the image area is clearly colored,
In addition, a color image having high whiteness in the background was obtained.

The photosensitive and pressure-sensitive recording materials (7) and (1)
Regarding 2), each was exposed to a step wedge-like image shape by changing the irradiation energy using semiconductor-excited YLF solid laser light having a wavelength of 657 nm from the protective layer side. The maximum irradiation energy was 15 mJ / cm ² . Each of the recording materials on which a latent image was formed by the exposure was subjected to a pressure of 150 kg / cm ² by a hydraulic static pressure tester.
After developing with pressure, each recording material is 58000lux
And the entire recording layer surface of the recording material was irradiated with light for 30 seconds. As a result, a clear wedge-shaped image was obtained in the image portion, and the background portion had high whiteness.

<Evaluation of Light Resistance> For each of the recording materials (1) to (12) on which images were formed as described above,
Light irradiation was performed at 0.9 W / m ² for 24 hours using “HEROMETER CI 65” (manufactured by ATLAS ELECTRIC DEVICES CO). With respect to the background, the reflection densities of the yellow component before and after the light irradiation were measured, and the light resistance of the background was evaluated. For the image area, the color density of the image area was measured before and after light irradiation, respectively, and the residual ratio (%) calculated from the following equation:
Was determined, and the light resistance of the image area was evaluated. Residual rate (%) = [(reflection density after light irradiation) / (reflection density before light irradiation)] × 100 The reflection density of the yellow component in the background is determined by a Macbeth reflection densitometer (manufactured by Macbeth Corporation). ) And the color density of the image area is measured using a Macbeth transmission densitometer (Macbeth Co., Ltd.)
Was used for the measurement. The evaluation results are shown in Table 1 below.

[0237]

[Table 1]

From the evaluation results shown in Table 1, since the recording materials (1) to (8) of the examples contain an ultraviolet absorber or a precursor of an ultraviolet absorber in the protective layer or the recording layer, the comparative examples were not used. In comparison with the recording materials (9) to (12), it was demonstrated that the residual ratio of the color density of the image area after light irradiation was higher and the color development of the background after light irradiation was suppressed.

[0239]

The recording material of the present invention is a completely dry processing system which does not use a developing solution or the like and does not generate waste.
Recording can be performed using a blue to red laser or a small and inexpensive infrared laser, and a high-sensitivity, high-contrast, high-quality black-and-white or color image can be formed. In particular, the recording material of the present invention is excellent in light resistance.

[Brief description of the drawings]

FIG. 1 is a schematic view of one embodiment in which a recording material according to the present invention is applied to a monochromatic recording material.

FIG. 2 is a schematic view of an embodiment in which the recording material according to the present invention is applied to a monochromatic recording material.

FIG. 3 is a schematic diagram of an embodiment in which the recording material according to the present invention is applied to a monochromatic recording material.

[Explanation of symbols]

 10, 20 Monochromatic photosensitive / thermosensitive recording material 30 Monochromatic photosensitive / pressure sensitive recording material 12, 22, 32 Support 14, 24 Photosensitive / thermosensitive recording layer 34 Photosensitive / pressure sensitive recording layer 16, 26, 36 Protective layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/028 G03F 7/028 7/11 501 7/11 501 7/26 521 7/26 521 F term ( (Reference) 2H025 AA00 AA01 AB20 AC08 BA01 BC12 BC32 BC42 CA01 CA18 CA28 CA44 CA50 CC02 CC20 DA01 DA10 FA03 FA19 FA26 FA30 2H096 AA00 AA30 BA05 BA20 CA20 EA04 GA52 HA03 4D075 AE03 CA35 DA04 DB18 DC27 EA21 EC17 EC47 EC47

Claims (4)

[Claims] 1. A thermo-responsive microcapsule enclosing a color-forming component A on a support, and a polymerizable group and the color-forming component A reacting at least in the same molecule outside the thermo-responsive microcapsule. A recording material having at least a light- 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, and the outermost layer of the recording material A recording material wherein any one of the layers from to the light- and heat-sensitive recording layer contains an ultraviolet absorber and / or an ultraviolet absorber precursor. 2. A thermo-responsive microcapsule enclosing a color-forming component A 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, a substantially colorless compound D having a polymerizable group and a site for suppressing the reaction between the coloring component A and the compound C in the same molecule, and a photopolymerizable composition comprising a photopolymerization initiator. ,
A recording material having at least a light- and heat-sensitive recording layer containing: wherein any one of the layers from the outermost layer of the recording material to the light- and heat-sensitive recording layer contains an ultraviolet absorber and / or an ultraviolet absorber precursor. 3. A microcapsule enclosing a color-forming component A, a photopolymerizable composition containing a polymerizable compound and a photopolymerization initiator on a support, and at least the microcapsule outside the microcapsule. A recording material having at least a photosensitive pressure-sensitive recording layer containing a substantially colorless compound E which reacts with a color-forming component A to form a color, and wherein the recording material comprises any one of a layer from the outermost layer of the recording material to the photosensitive pressure-sensitive recording layer. The recording material wherein the layer of the above contains an ultraviolet absorber and / or an ultraviolet absorber precursor. 4. The photopolymerization initiator has a wavelength of 300 to 1000 nm.
The recording material according to any one of claims 1 to 3, further comprising a spectral sensitizing compound having a maximum absorption wavelength and a compound that interacts with the spectral sensitizing compound.