JPH11249294A - Photosensitive-thermosensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide photosensitive-thermosensitive recording material that can easily form a black-and-white or color complete dry image with high coloring density by short-time exposure using a laser, dispensing with the use of a developer or the like. SOLUTION: Photosensitive-thermosensitive recording material is provided with a recording layer, containing a microcapsule including electron donative achromatic dye, an electron acceptable compound, a photopolymerized monomer, a photopolymerization initiator, and an oxide of an element selected from the 4-7 groups of a periodic table or this oxide salt, on a carrier. The recording layer containing the microcapsule including electron donative achromatic dye, the photopolymerized monomer having an electron acceptable group in a molecule, the photopolymerization initiator, and the oxide of an element selected from the 4-7 groups or this oxide salt, is provided on the carrier.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light and heat sensitive recording material, and more particularly to a light and heat sensitive recording material capable of forming black and white and color images by laser scanning exposure.

[0002]

2. Description of the Related Art In recent years, research on an image forming technique using a photopolymerizable composition has been actively conducted. For example, an image forming system using a photosensitive microcapsule in which a photopolymerizable composition is encapsulated in a microcapsule has been proposed.
Also, spectrally sensitize the photopolymerizable composition to the visible light region,
Attempts to form a digital image using a laser as a light source (Journal of the Photographic Society of Japan, Vol. 49, No. 5, p. 210 (1986), etc.) and application to a full-color photosensitive material have been studied (JP-A-59-189340, etc.). ). Further, a novel photopolymerizable composition using an organic boron anion salt of an organic cationic dye has also been proposed (European Patent No. 223,5).
87A1, etc.).

[0003] However, these photopolymerizable compositions are sensitive to ultraviolet light but not visible to infrared light, or have insufficient sensitivity even if exposed. Therefore, even if these photopolymerizable compositions are used for a light and heat sensitive recording material, it is not possible to form an image with high sensitivity,
There are problems such as. On the other hand, when forming an image, it is advantageous if not only UV light and short-wave visible light but also inexpensive infrared lasers and green to red light can be used. In addition, as a color proof method using a light and heat sensitive recording material, an overlay method, a surprint method, a color paper method, and the like are known. In these methods, waste is generated. Is difficult, and a developing system using a developing solution is necessary.
A completely dry system is desired.

[0004]

In order to solve the above-mentioned problems, the present inventors have developed a microcapsule containing an electron-donating colorless dye, an electron-accepting compound, a photopolymerizable monomer, and a photopolymerizable monomer. A photosensitive and heat-sensitive recording material having a recording layer containing an initiator was studied. As a result, ultraviolet light ~
A photosensitive and heat-sensitive recording material having high sensitivity to exposure in a wide range up to infrared light has been developed, and the present invention has been filed before.

However, when recording is performed by laser scanning exposure, it is necessary to form an image having a high color density with a short exposure, and there is room for improvement in the light- and heat-sensitive recording material. If the sensitivity of the recording material is improved, the color density can be improved. However, if the sensitivity is improved, there is a problem in storage stability and the like.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and does not require the use of a developing solution or the like. It is an object of the present invention to provide a light- and heat-sensitive recording material capable of easily forming the image of (1).

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to increase the color density of an image while maintaining the sensitivity of the light and heat sensitive recording material. By adding an oxide of a metal element, they found that an image having an extremely high color density can be formed,
Based on this finding, the present invention has been completed.

That is, the above-mentioned problem is solved by the following items 1) to 3). 1) A microcapsule enclosing an electron-donating colorless dye on a support, an electron-accepting compound, a photopolymerizable monomer, a photopolymerizable initiator, and an element selected from Groups 4 to 7 of the periodic table. And heat-sensitive recording material provided with a recording layer containing an oxide of the above or a salt of the oxide. 2) A microcapsule enclosing an electron-donating colorless dye on a support, a photopolymerizable monomer having an electron-accepting group in the molecule, a photopolymerizable initiator, and an element selected from Group 4 to Group 7 And heat-sensitive recording material provided with a recording layer containing an oxide of the above or a salt of the oxide. 3) The oxide of an element selected from Group 4 to Group 7 or a salt of the oxide is a polyacid of an element selected from Group 4 to Group 7 or a salt of the polyacid. Or the light and heat sensitive recording material according to claim 2.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to embodiments.

First, group 4 to 4 of the periodic table used in the present invention are described.
An oxide of an element selected from Group 7 or a salt of the oxide will be described.

The oxide or the salt of the oxide used in the present invention is an element belonging to Groups 4 to 7 of the periodic table, specifically, Ti, Z
r, Hf, V, Nb, Ta, Cr, Mo, W, Mn, T
An oxide of any element selected from c and Re, or a salt of the oxide. Any conventionally known structural formula can be used. The details are described in corresponding sections such as the Dictionary of Chemistry (Kyoritsu Shuppan) and the Dictionary of Physical and Chemical Research (Iwanami Shoten). For example, any of an acidic oxide formed of a covalent bond molecule, a basic oxide formed of an ionic crystal, and an oxide having intermediate properties thereof can be used. In addition, not only an oxide having a mononuclear structure but also a polyacid having a polynuclear structure or a salt thereof can be used. As the polyacid, both isopolyacid and heteropolyacid can be used. Further, an oxide or a salt of the oxide in which one or more water molecules are hydrated can also be used. Among them, it is preferable to use an oxide of Cr, Mo, W belonging to Group 6 or a salt thereof, since an image having an extremely high color density can be formed. In addition, the periodic table followed IUPAC inorganic chemical nomenclature revised edition (1989).

When the oxide forms an oxide salt together with a counter ion, the counter ion includes an ammonium ion (NH ₄ ⁺ ) and an alkali metal ion (Na ⁺ ,
K ⁺ , Li ⁺ , Cs ⁺ ), alkaline earth metal ions (M
g ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ ), silver ion (A
g ⁺ ).

Among the oxides having various structural formulas or salts of the oxides, it is preferable to use a polyacid or a polyacid salt because an image having a high color density can be formed. The polyacid generally has a structure represented by the following formula. During M _x O _y ^n- formula, M represents an element selected from 4-7 of the periodic table.
x and y each represent an integer of 1 or more, and are values specific to the metal element M. n represents an integer of 0 or more, and is a value unique to the metal M. When n is -1 or less, a heteropolyacid salt is formed together with a counter ion. In this case, examples of the counter ion include the same as described above.

Heteropoly acids comprising two or more oxo acids can also be used. The heteropolyacid is generally represented by the following formula, wherein a metal other than M (or its equivalent such as PO ₄ ) Z is a central atom, to which a polyacid group of the metal M represented by the above formula is arranged. In many cases, it has a structure that is positioned at the top. The ^{_{[Z m + · M x O y}} n- ] ^(mn) central atom Z, H, Cu, Be, B, Al, C,
Si, Ge, Sn, Ti, Zr, Ce, Th, N, P,
As, Sb, V, Nb, Ta, Cr, Mo, W, U,
S, Se, Te, Mn, I, Fe, Co, Ni, Rh,
Os, Ir, Pt and the like can be mentioned. Here, m represents an integer of 0 or more, and is a value unique to Z. When (mn) is -1 or less, a heteropolyacid salt is formed together with a counter ion. In this case, examples of the counter ion include the same as described above.

Hereinafter, specific examples of the oxide or a salt of the oxide suitably used in the present invention will be shown, but the present invention is not limited thereto. Cr (VI) (NH ₄ ) ₂ CrO ₄ , K ₂ CrO ₄ , Na ₂ CrO ₄
・ 4H ₂ O, Cs ₂ CrO ₄ , BaCrO ₄ , MgCr
_{O 4 · 5H 2 O, K} 2 Mg (CrO 4) 2 · 2H 2 O,
_{(NH 4) 2 Mg (CrO} 4) 2 · 6H 2 O, Mo (VI) MoO 3 H 2 O, (NH 4) 6 Mo 7 O 24 · 4H 2 O K 2 MoO 4, Na 2 MoO 4 · 2H ₂ O, CaMoO
_4, (NH _{4) 3} [PMo ₁₂ O _40] 3H ₂ O, Na ₃
[PMo ₁₂ O _{40] · 10H 2 O, Li 2 MoO} 4 W (VI) WO 3 · H 2 O, K 2 WO 4, Na 2 WO 4 · 2H 2
O, CaWO ₄ , MgWO ₄ , Na ₃ [PW ₁₂ O ₄₀ ]
_{15H 2 O, (NH 4)} 10 WO 12 O 21 · 5H 2 O

The metal oxide or a salt thereof may be added to a microcapsule containing an electron-donating colorless dye, or may be added to a recording layer outside the microcapsule.
The amount is preferably from 0.1mg / m ² ~2000mg / m ² in different but each element in terms of the class of compounds used, 1
mg / m ² ~1000mg / m ² is more preferred. A water-soluble compound is particularly preferable because a large effect can be obtained with a small amount of use.

The compound of the present invention is a water-soluble compound as an aqueous solution, and a compound which is poorly soluble in water is disclosed in JP-A-59-174830.
And a fine particle dispersion prepared by the method described in JP-A-53-102733 and the like. The additive (liquid) is preferably neutralized with an acid such as sulfuric acid or phosphoric acid from the viewpoint of storage stability of the light and heat sensitive recording material.

Next, the photopolymerization initiator used in the light and heat sensitive recording material of the present invention will be described. The photopolymerization initiator suitably used in the light and heat sensitive recording material of the present invention is a compound capable of initiating photopolymerization of a photopolymerizable monomer,
When used in combination with green, red or infrared absorbing dyes, it has sensitivity in this wavelength range and is supposed to generate radicals upon irradiation with light (JP-A-62-143044). And organic borate salts of When an organic borate compound is contained as a photopolymerization initiator in the recording layer, radicals are generated based on the laser light irradiated with the organic borate, and the radicals initiate polymerization of the photopolymerizable monomer, and the formed polymer is formed. Is the latent image.

The organic borate compound used as an initiator in the light and heat sensitive recording material of the present invention is preferably an organic borate salt represented by the following general formula (1). This compound is preferably used in combination with a spectral sensitizing dye.

[0020]

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Here, M is an alkali metal atom, quaternary ammonium, pyridinium, quinolinium, diazonium, morpholinium, tetrazolium, acridinium, phosphonium, sulfonium, oxosulfonium, sulfur, oxygen, carbon, halogenium, Cu, Ag, H
g, Pd, Fe, Co, Sn, Mo, Cr, Ni, A
s and Se, n represents an integer of 1 to 6, and R ¹ , R ² , R
³ and R ⁴ may be the same or different and include a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, Or an unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted allyl group, a substituted or unsubstituted silyl group R ¹ , R ² ,
R ³ and R ⁴ may be combined with each other to form a cyclic structure.

Preferred examples of the borate anion include, for example, tetramethyl borate, tetraethyl borate,
Tetrabutyl borate, triisobutyl methyl borate, di-n-butyl-di-t-butyl borate, tetra-n-butyl borate, tetraphenyl borate, tetra-p-chlorophenyl borate, tetra-m-chlorophenyl borate, tri-m -Chlorophenyl-n-hexyl borate, triphenylmethyl borate, triphenylethyl borate, triphenylpropyl borate, triphenyl-n-butyl borate, trimesityl butyl borate, tolyl isopropyl borate, triphenyl benzyl borate, tetraphenyl borate, Tetrabenzyl borate, triphenylphenethyl borate, triphenyl-p-chlorobenzyl borate, triphenylethenylbutyl borate, di (α-naphthyl) -dipropyl borate DOO, triphenylsilyl triphenyl borate, preparative Little yl silyl triphenyl borate, tri -n- butyl (dimethylphenylsilyl) borate, and the like.

Specific examples of the organic borate salt represented by the general formula (1) are shown below. However, the effects of the present invention are not limited to the following compounds.

[0024]

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[0025]

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[0026]

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[0027]

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It is preferable that the organic borate salt is used in combination with a green to red region or infrared absorbing dye from the viewpoint of increasing the laser absorption efficiency.

The infrared absorbing dye having a maximum absorption wavelength in the wavelength region of 500 to 1100 nm, which is used in combination with the organic borate salt, if desired, includes cationic dyes, such as cationic methine dyes, polymethine dyes, and triaryl dyes. It is preferably a dye selected from methane, indoline, azine, xanthene, oxazine and acridine dyes. Further, the cationic dye is preferably a dye selected from cationic cyanine, hemicyanine, rhodamine and azamethine dyes.

As the cationic dye (spectral sensitizing dye), a wavelength region of 500 nm or more, preferably 500 to 1
Any organic cationic dye having an absorption peak in a wavelength region of 100 nm can be preferably used. For example, cationic methine dye, cationic carbonium dye, cationic quinone imine dye, cationic indoline dye, cationic styryl dye, and further,
As cationic methine dyes, preferably polymethine dyes, cyanine dyes, azomethine dyes, more preferably cyanine, carbocyanine, dicarbocyanine, tricarbocyanine, hemicyanine, etc., as the cationic carbonium dye, preferably tria Reel methane dye, xanthene dye, aricin dye, more preferably rhodamine, etc., as the cationic quinonimine dye, preferably a dye selected from azine dye, oxazine dye, thiazine dye, quinoline dye, thiazole dye, etc. These can be used alone or in combination of two or more.

Many organic cationic dye compounds having an absorption peak in the wavelength region of 500 nm or more are known. For example, "Functional dye chemistry"
1981, CMC Publishing Co., pp. 393-416, and "Coloring Materials", 60 [4] 212-224 (1987).

Next, an organic borate salt of a cationic dye, which is another preferred embodiment of the photopolymerizable initiator used in the light and heat sensitive recording material of the present invention, will be described. The organic borate salt of the cationic dye according to the present invention is preferably
It is a compound represented by the following general formula (2).

[0033]

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Here, D ⁺ represents a cationic dye, and R ^+
1 , R ² , R ³ and R ⁴ may be the same or different and are each a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. Alkaryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted allyl group, substituted or It is a group selected from unsubstituted silyl groups, and two or more of R ¹ , R ² , R ³ and R ⁴ may combine to form a cyclic structure.

As the cationic dye represented by D ⁺ ,
It is preferably a dye selected from cationic methine dyes, polymethine dyes, triarylmethane, indoline, azine, xanthene, oxazine and acridine dyes. Further, the cationic dye is preferably a dye selected from cationic cyanine, hemicyanine, rhodamine and azamethine dyes.

The organic borate salt of the organic cationic dye represented by the general formula (2) uses an organic cationic dye and an organic boron compound anion, and is disclosed in European Patent No. 223,58.
It can be obtained by referring to the method described in No. 7A1.

The cationic dye (spectral sensitizing dye) represented by D ⁺ in the general formula (2) is an organic cationic dye having an absorption peak in a wavelength region of 500 nm or more, preferably 550 to 1100 nm. Any dye can be preferably used. For example, a cationic methine dye, a cationic carbonium dye, a cationic quinone imine dye, a cationic indoline dye, a cationic styryl dye, and further, as the cationic methine dye, preferably a polymethine dye, a cyanine dye,
Azomethine dyes, more preferably cyanine, carbocyanine, dicarbocyanine, tricarbocyanine, hemicyanine, etc., as cationic carbonium dyes,
Preferably triarylmethane dye, xanthene dye,
Alicudin dyes, more preferably rhodamine and the like, as cationic quinone imine dyes, preferably azine dyes, oxazine dyes, thiazine dyes, quinoline dyes,
Dyes selected from thiazole dyes and the like can be mentioned, and these can be used alone or in combination of two or more.

Many of these organic cationic dye compounds having an absorption peak in the wavelength region of 500 nm or more are known. For example, "Functional dye chemistry"
1981, CMC Publishing Co., pp. 393-416, and "Coloring Materials", 60 [4] 212-224 (1987).

Specific examples of the organic boron compound anion salt (organic borate salt) of the organic cationic dye compound represented by the general formula (2) are shown below. However, the effects of the present invention are not limited to the following compounds.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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The content of the photopolymerizable initiator varies depending on the type of the photopolymerizable initiator used, but is preferably 0.01 to 20% by weight based on the total amount of the photocurable composition. Preferably, it is 0.2 to 15% by weight, and the most preferred content is 1 to 10% by weight. If the content is less than 0.01% by weight, the sensitivity may be insufficient. If the content exceeds 10% by weight, a corresponding increase in sensitivity cannot be expected.

Further, in the present invention, together with the spectral sensitizing dye and the organic borate salt, the following general formula (3):
An auxiliary such as a compound having an active halogen group in a molecule represented by the general formula (4) can be used in combination as appropriate.

[0048]

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In the general formula (3), X represents a halogen atom. Y ¹ is —CX ₃ , —NH ₂ , —NHR, —NR ₂ ,
Represents -OR. Here, R represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Y ² represents —CX ₃ , an alkyl group, a substituted alkyl group, an aryl group,
Represents a substituted aryl group or a substituted alkenyl group. The substituent is
The formula (3) itself may be used.

[0050]

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In the general formula (4), X represents a halogen atom. Y ³ and Y ⁴ may be the same or different and represent a hydrogen atom or a halogen atom. Z represents a group represented by the following formula.

[0052]

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Here, R ′ is a hydrogen atom, a halogen atom,
Represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a substituted alkenyl group, a heterocyclic group, or a substituted heterocyclic group.

The compound represented by the general formula (3) includes
Wakabayashi et al., Bulletin of Chemical Society
Japan (Bull, Chem, Soc, Japan) 42, 2924
Page (1969), specifically, for example,
2-phenyl-4,6-bis (trichloromethyl) -S
-Triazine, 2- (p-chlorophenyl) -4,6-
Bis (trichloromethyl) -S-triazine, 2- (p
-Tolyl) -4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-methoxyphenyl) -4,6-
Bis (trichloromethyl) -S-triazine, 2-
(2 ′, 4′-Dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis ( Trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) 4,6-bis (trichloromethyl)- S-triazine and the like can be mentioned. In addition, British Patent 138849
No. 2, for example, 2-styryl-4,
6-bis (trichloromethyl) -S-triazine, 2-
(P-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxy Styryl) -4-amino-6
-Trichloromethyl-S-triazine, etc.
Compounds described in the specification of 133428, for example, 2-
(4-methoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1- Yl] -4,6-bis-trichloromethyl-S-triazine, 2- (4,7-dimethoxy-
Naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphth-5-yl)-
4,6-bis-trichloromethyl-S-triazine and the like,
Compounds described in German Patent No. 3337024, for example, compounds represented by the following structural formula can be mentioned.

[0055]

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As other compounds, compounds represented by the following structural formulas can also be used as auxiliaries.

[0057]

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Further, F.S. C. Journal of Organic Chemistry by Schaefer et al. (J.O.
rg. Chem. 29, 1527 (1964)
The compounds described, for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6
-Tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like. .

Further, there may be mentioned the compounds described in Japanese Patent Application No. 60-198868, for example, compounds represented by the following structural formulas.

[0060]

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[0061]

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When the compound represented by the general formula (3) is used as an auxiliary in the recording material of the present invention, Y ¹ is -CX ₃
It is particularly preferred to use a compound of the formula

The compound of the general formula (3) used in the present invention can be synthesized by a method known to those skilled in the art. Specifically, Bulletin of Chemical Society Japan (Bull, Chem, Soc, Jpn) Vol. 42, p. 2924 (196)
9 years), for example, a compound having the following structure can be obtained.

[0064]

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With reference to the description of DE 2718259 (application number), for example, a compound having the following structure can be obtained.

[0066]

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Further, referring to US Pat. No. 4,619,998, for example, a compound having the following structure can be obtained.

[0068]

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In the present invention, the compound represented by the general formula (4) having an active halogen group, which is used as an auxiliary of a spectral sensitizing dye, is disclosed in JP-B-51-833.
No. 0, specifically, for example, carbon tetrachloride, carbon tetrabromide, iodoform, p-nitro-α,
α, α-tribromoacetophenone, ω, ω, ω-tribromoquinaldine, tribromomethylphenylsulfone, trichloromethylphenylsulfone, and the like. Further, compounds described in JP-B-49-12180, for example, compounds having the following structure can be mentioned.

[0070]

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[0071]

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Further, there may be mentioned the compounds described in JP-A-60-138439, for example, compounds having the following structures.

[0073]

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The following are examples of compounds having an active halogen group which can be preferably used in the present invention. It goes without saying that the invention is not limited to these compounds.

[0075]

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[0076]

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The compound represented by formula (3) or (4) is used in an amount of 0.01 to 20 per mole of the spectral sensitizing dye.
Mol, preferably 0.1 to 10 mol.

Next, the photopolymerizable monomer used in the present invention will be described. The photopolymerizable monomer used in the present invention starts a polymerization reaction by a radical generated from the photopolymerizable initiator and cures. As the photopolymerizable monomer having such a function, a polymerizable compound having at least one ethylenically unsaturated double bond in a molecule is preferably used. For example, acrylic acid esters, acrylic acid and salts thereof such as acrylamides, methacrylic acid esters, methacrylic acid and salts thereof such as methacrylamides, maleic anhydride, maleic esters, itaconic acid, itaconic esters, Styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles,
Conventionally known monomers such as allyl ethers and allyl esters can be widely used.

The photopolymerizable monomer is preferably a compound having a plurality of ethylenically unsaturated double bonds in the molecule from the viewpoint of advantageous polymerization efficiency (curing speed). For example, trimethylolpropane and pentaerythritol Acrylic or methacrylic esters of polyhydric alcohols, acrylate or methacrylate terminated epoxy resins, acrylate or methacrylate terminated polyesters,
And the like. Particularly preferred specific examples among these are, for example, ethylene glycol diacrylate,
Examples include ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol dimethacrylate.

In the present invention, a photopolymerizable monomer having an electron-accepting group in the molecule may be used. It is preferable to use a photopolymerizable monomer having such a structure since an image having a higher contrast can be formed.
Examples of the photopolymerizable monomer having such a structure include 3-halo-4-hydroxybenzoic acid described in JP-A-4-226455 and JP-A-63-173682.
Methacryloxyethyl ester of a benzoic acid having a hydroxy group described in JP-A No. 62-99190, JP-A-59-83693, JP-A-60-141587 and JP-A-62-99190.
Of benzoic acid having hydroxy group and hydroxymethyl styrene described in JP-A No. 29323/1990
Hydroxystyrene described in JP-A-62-1980
Nos. 67077 and 62-16708, N-vinylimidazole complexes of zinc halides, 63
And various compounds that can be synthesized with reference to the developer monomer described in JP-A-317558.

For example, an ester composed of 3-halo-4-hydroxybenzoic acid and a compound having an ethylenically unsaturated double bond is preferably used. Specific examples of 3-halo-4-hydroxybenzoic acid esters include 3-chloro-4-hydroxybenzoic acid ester vinylphenethyl ester, 3-chloro-4-hydroxybenzoic acid vinylphenylpropyl ester, and 3-chloro-4-hydroxy acid. Benzoic 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- (2-acryloyloxyethyl) 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) ester, and the like.

Other specific examples include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, β
-Zinc methacryloxyethoxy salicylate, zinc β-acryloxyethoxy salicylate, vinyloxyethyloxybenzoic acid, β-methacryloxyethylorselinate, β-acryloxyethylorselinate, β-methacryloxyethoxyphenol, β-acrylic Roxyethoxyphenol, 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-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, metal salts thereof (eg, zinc salt) and the like are preferably mentioned.

When the photopolymerizable monomer used in the present invention has a molecular weight of 1.0 × 10 ^{2 to} 5.0 × 10 ^3, it is preferable in that it hardly diffuses into the capsule, and more preferably 2 0.010 ² or more.

Next, a microcapsule containing an electron-donating colorless dye will be described. As the electron-donating colorless dye used in the present invention, conventionally known triphenylmethanephthalide compounds, phthalide compounds such as indolylphthalide compounds, fluoran compounds, phenothiazine compounds, leuco-lamin compounds, Rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, pyridine compounds,
Various compounds such as a pyrazine-based compound and a fluorene-based compound are exemplified.

Specific examples of the phthalide compound include US Pat. No. Re. 23,024 and US Pat.
Nos. 91,111, 3,491,112, 3,491,116 and 3,50
9,174 and the like. Specific examples of the fluoran compounds are described in U.S. Pat. Nos. 3,624,107 and 3,627,787.
No. 3,641,011 and No. 3,641,011
Nos. 462,828, 3,681,390, 3,920,510, and 3,953.
9,571 and the like. Specific examples of the spiropyran-based compound include compounds described in U.S. Pat. No. 3,971,808 and the like. Specific examples of the pyridine-based and pyrazine-based compounds include U.S. Pat. Nos. 3,775,424 and 3,853,869 and 4,246,31.
No. 8 and the like. Specific examples of the fluorene-based compound include Japanese Patent Application No. 61-2409.
No. 89 and the like.

Some of these are exemplified below. Examples of the triarylmethane-based compound include, for example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethyl Aminophenyl)-
3- (1,3-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-
Methylindol-3-yl) phthalide and the like.

Examples of the diphenylmethane-based compound include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like. Can be

Examples of xanthene compounds include rhodamine-B-anilinolactam and rhodamine- (p-
Nitrino) lactam, 2- (dibenzylamino) fluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-dibutylaminofluoran, 2-anilino-3-methyl- 6-N
-Ethyl-N-isoamylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluoran, 2-anilino-3-chloro-6-
Diethylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-isobutylaminofluoran,
2-anilino-6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-tetrahydrofurfurylaminofluoran, 2-anilino-3-methyl-6-piperidinoaminofluoran , 2- (o-chloroanilino) -6-diethylaminofluoran, 2-
(3,4-Dichloroanilino) -6-diethylaminofluoran and the like.

Examples of the thiazine compound include benzoyl leucon methylene blue, p-nitrobenzyl leucomethylene blue and the like. Examples of the spiro-based compound include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran 3,3′-dichloro-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, and 3-methyl-naphtho-pyran. Methoxy-benzo) -spiropyran, 3-propyl-spiro-
Dibenzopyran and the like.

Among the electron-donating colorless dyes, particularly, in the case of a full-color (multicolor) light- and heat-sensitive recording material, cyan,
For magenta and yellow, see, for example, US Pat.
No. 00,149, etc., are described as yellow coloring types, for example, those described in U.S. Pat. No. 4,800,148, etc., and cyan coloring types are described, for example, in JP-A-63-53542. References in publications and the like can be referred to.

The method of microencapsulation of the electron-donating colorless dye is not particularly limited, and any method conventionally used as a technique of microencapsulation can be used. For example, a method utilizing coacervation of a hydrophilic wall-forming material as described in U.S. Pat. Nos. 2,800,457 and 2,800,458; U.S. Pat. No. 3,287,154;
43, JP-B-38-19574, 42
Interfacial polymerization method as disclosed in JP-A-446 and JP-A-42-771, U.S. Pat.
A method by precipitation of a polymer as in 660304, a method using isocyanate polyol wall material as in US Pat. No. 3,796,669,
Method using isocyanate wall material as in U.S. Pat. No. 3,914,511, U.S. Pat.
No. 40, No. 4087376, No. 4089
802, a method using a urea-formaldehyde-based, urea-formaldehyde-resorcinol-based wall-forming material, and a method using a melamine-formaldehyde resin, a hydroxypropylcellulose, or the like as described in U.S. Pat. No. 4,025,455. ,
JP-B-36-9168 and JP-A-51-9079 disclose an in-situ method by polymerization of monomers, and an electrolytic dispersion cooling method disclosed in British Patent Nos. 952807 and 965074. ,
U.S. Pat. No. 3,111,407; British Patent No. 9304
No. 22, the spray drying method, and the like.

The present invention is not limited to the above methods, but among these methods, a method of emulsifying a core substance and then forming a polymer film as a microcapsule wall is preferable. As a method of microencapsulation, microencapsulation by polymerization of a reactant from the inside of an oil droplet is particularly preferable. In this case, it is advantageous in that a microcapsule having a uniform particle size, excellent raw storability, and suitable for a light and heat sensitive recording material can be formed in a short time.

For example, when polyurethane is used as a capsule wall material of a microcapsule, a polyvalent isocyanate and, if necessary, a second substance (for example, polyol or polyamine) which reacts with the polyisocyanate to form a capsule wall are mixed with an oily liquid to be encapsulated. Mixed in, emulsified and dispersed in water,
Then, by raising the temperature, a polymer forming reaction occurs at the oil droplet interface to form a capsule wall, and microcapsules can be obtained. At this time, an auxiliary solvent having a low boiling point and strong dissolving power can be used in the oily liquid. Regarding polyvalent isocyanates and their counterpart polyols and polyamines, for example, US Pat.
Nos. 281383, 3773695, 3793268, JP-B-48-40347, JP-A-49-24159, and JP-A-48-8019.
Nos. 1 and 48-84086 can also be used.

Specifically, as a polyvalent isocyanate,
For example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,
4'-diisocyanate, 3,3'-dimethoxy-4,
4′-biphenyl-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate,
Xylylene-1,4-diisocyanate, 4,4′-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2
Diisocyanates such as diisocyanate, cyclohexylene-1,2-diisocyanate and cyclohexylene-1,4-diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, toluene-2,
Triisocyanates such as 4,6-triisocyanate,
4,4'-dimethyldiphenylmethane-2,2 ', 5
Tetraisocyanates such as 5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-tolylenediisocyanate and trimethylolpropane, adducts of xylylenediisocyanate and trimethylolpropane, tolylenediisocyanate And an isocyanate prepolymer such as an adduct of hexanetriol and the like.
Incidentally, the polyvalent isocyanate can also react with water to form a polymer substance.

Examples of the polyol include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters, and hydroxypolyalkylene ethers. Further, as the polyol, a polyol described in JP-A-60-49991, that is, ethylene glycol,
3-propanediol, 1,4-butanediol, 1,
5-pentanediol, 1,6-hexanediol,
1,7-heptanediol, 1,8-octanediol, propylene glycol, 2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2,2-dimethyl-1,3-propanediol , 2,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4
-Cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, 2-phenylpropylene glycol,
1,1,1-trimethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,4-di (2-hydroxyethoxy) benzene, resorcinol dihydroxyethyl ether and the like Condensation product of aromatic polyhydric alcohol and alkylene oxide, p-xylylene glycol, m-
Xylylene glycol, α, α'-dihydroxy-p-
Diisopropylbenzene, 4,4′-dihydroxy-diphenylmethane, 2- (p, p′-dihydroxydiphenylmethyl) benzyl alcohol, an ethylene oxide adduct to bisphenol A, a propylene oxide adduct to bisphenol A, and the like can also be used. it can.
In addition, it is preferable that the ratio of the hydroxyl group in a polyol is 0.02-2 mol with respect to 1 mol of isocyanate groups in a polyvalent isocyanate.

Examples of the polyamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, and 2,5-dimethyl. Piperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine,
Examples include triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds.

In the present invention, a water-soluble polymer can be used for microencapsulation. The water-soluble polymer may be any of a water-soluble anionic polymer, a nonionic polymer, and an amphoteric polymer. As the anionic polymer, for example, a natural or synthetic polymer can be used. For example, a -COO ^- group, -SO ₂
^- group, may be mentioned those having a like. Examples of the anionic polymer include, as natural products, arabic gum, alginic acid, pectin, etc., and semi-synthetic products such as carboxymethyl cellulose, gelatin derivatives such as phthalated gelatin, sulfated starch, sulfated cellulose, lignin sulfonic acid, etc. Synthetic products include maleic anhydride (including hydrolyzed) copolymers, acrylic acid (including 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 and the like. Among these water-soluble polymers, gelatin, gelatin derivatives and polyvinyl alcohol are preferred. The water-soluble polymer is used as a 0.01 to 10% by weight aqueous solution.

The average particle size of the microcapsules is 0.1 μm.
m or more and 20 μm or less, more preferably 0.
It is 1 μm or more and 5 μm or less. If the average particle size of the microcapsules is too small, the surface area for a certain solid content becomes large, and a large amount of capsule wall material of the microcapsules is required. On the other hand, if the average particle size of the microcapsules is too large, the resolution of the image tends to be poor.

The colorless electron-donating dye contained in the microcapsules may exist in a solution state or a solid state.

When the electron-donating colorless dye is present in a solution state in the microcapsules, the microencapsulation may be performed with the electron-donating colorless dye dissolved in a solvent. At this time, the amount of the solvent is 10
1 to 500 parts by weight to 0 parts by weight is preferred. As the solvent to be used, various organic solvents and water-soluble polymers can be used.

As the organic solvent, for example, natural oil or synthetic oil can be used, and specific examples thereof include cottonseed oil, kerosene, aliphatic ketone, aliphatic ester, paraffin, naphthenic oil, alkylated biphenyl, and alkylated oil. Terphenyl, chlorinated paraffin, alkylated naphthalene, diarylethane such as 1-phenyl-1-xylylethane, 1-phenyl-1-p-ethylphenylethane, 1,1′-ditolylethane, alkyl phthalate (dibutyl phthalate, Dioctyl phthalate, dicyclohexyl phthalate, etc.), phosphates (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), citrates (eg, tributyl acetyl citrate), benzoate esters (Eg, octyl benzoate), alkyl amide (eg, diethyl lauryl amide), trimesate (eg, tributyl trimesate), acetate (ethyl acetate, propyl acetate,
Iso-propyl acetate, butyl acetate, tert-butyl acetate, s-butyl acetate, etc.), propionate ester (for example, ethyl propionate), butyric acid (isobutyrate) ester (for example, methyl butyrate), acrylic acid (methacrylic acid) ester ( Examples thereof include methyl acrylate), alkyl halides (methylene chloride, carbon tetrachloride, etc.), tertiary butyl alcohol, thimer isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone and the like. Among these, fatty acid esters and alkyl halides are preferable, and those having a solubility in water of 10% by volume or less are more preferable.

As the water-soluble polymer, for example, a compound which is soluble in water at 25 ° C. in an amount of 5% by weight or more is preferable. Specific examples include proteins such as gelatin, gelatin derivatives, albumin and casein, methylcellulose and carboxymethylcellulose. , Cellulose derivatives such as sodium alginate, sugar derivatives such as starches (including modified starch),
Synthetic polymers such as gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymer, and polystyrene sulfonate are preferred. It is listed. Among these, gelatin and polyvinyl alcohol are preferred.

At the time of microencapsulation, a volatile solvent may be used in combination as an auxiliary solvent for dissolving the electron-donating colorless dye. Examples of the volatile solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like.

The microcapsules used in the present invention are heat-responsive, and heat-induced electron-accepting compounds described below (when the photopolymerizable monomer has an electron-accepting group,
Photopolymerizable monomer) thermally diffuses into the microcapsules,
It reacts with an electron-donating colorless dye to form a color.

Next, the electron accepting compound used in the present invention will be described. Examples of the electron accepting compound used in the present invention include a phenol derivative, a salicylic acid derivative, a metal salt of an aromatic carboxylic acid, acid clay, bentonite, a novolak resin, a metal-treated novolak resin, and a metal complex.

For example, JP-B-40-9309, JP-B-45-14039, and JP-A-52-14048
No. 3, JP-A-48-51510, JP-A-57
JP-A-2108686, JP-A-58-87089, JP-A-59-11286, and JP-A-60-17
Electron-accepting compounds described in JP-A-6795 and JP-A-61-95988 can be suitably used.

Some specific examples of the electron accepting compound are shown below. Examples of phenol derivatives 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.

Examples of salicylic acid derivatives include 4-pentadecylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (tert-octyl) salicylic acid, 5-octadecylsalicylic acid, and 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, the amount of the electron-accepting compound is 5 to 1000% by weight based on the total weight of the electron-donating colorless dye encapsulated in the microcapsules.
Is preferred.

Next, the recording layer will be described. The recording layer contains at least a microcapsule containing an electron-donating colorless dye, an electron-donating compound, a photopolymerizable initiator, and a photopolymerizable monomer, or at least contains an electron-donating colorless dye. Containing microcapsules, a photopolymerizable monomer having an electron donating group, and a photopolymerizable initiator, but according to the purpose within a range that does not impair the effects of the present invention, other components, for example, spectral Sensitizing dye,
It may contain an oxygen scavenger, a polymerization accelerator and the like.

It is preferable to add a spectral sensitizing dye because the photosensitive wavelength of the recording layer can be adjusted. The spectral sensitizing dye to be used is not particularly limited, and various compounds known in the art can be used. Examples of the above-described patent specification relating to the photopolymerization initiator, and Research Disclosur
e, Vol. 200, December 1980, Item 2
0036 or “Sensitizers” (Katsumi Tokumaru, Shin Okawara / ed. Kodansha 1987), pages 160 to 163, etc. can be referred to.

Specific examples of the spectral sensitizing dye are described in
3-Ketocoumarin compounds described in JP-A-8-15503, thiopyrylium salts described in JP-A-58-40302, JP-B-59-28328 and JP-A-60-53.
No. 300, naphthothiazole merocyanine compound, JP-B-61-9621, JP-A-62-3842.
JP, JP-A-59-89303, JP-A-60-60
No. 104, the merocyanine compounds described in each of the publications, and the like. By adding these spectral sensitizing dyes, the photopolymerization initiator becomes sensitive to visible light.

Furthermore, keto dyes such as coumarin (including keto coumarin or sulfono coumarin) dyes, merostyril dyes, oxonol dyes and hemioxonol dyes, non-keto dyes non-ketopolymethine dyes, anthracene dyes, rhodamine dyes, acridine dyes , Aniline dyes and azo dyes, and cyanine, hemicyanine and styryl dyes as non-ketopolymethine dyes can also be used as spectral sensitizing dyes.

It is preferable to add a reducing agent, for example, an oxygen scavenger and a chain transfer agent of an active hydrogen donor to the recording layer, because the polymerization of the photopolymerizable monomer can be promoted. As the oxygen remover, conventionally known ones can be widely used,
Among them, in the present invention, phosphine, phosphonate,
Useful are phosphites, stannous salts and other compounds that are easily oxidized by oxygen, and include, for example,
N-phenylglycine, trimethylbarbituric acid,
N, N-dimethyl-2,6-diisopropylaniline,
N, N, N-2,4,6-pentamethylaniline and the like are preferred. As the polymerization accelerator, thiols, thioketones, trihalomethyl compounds, lophine dimer compounds,
Preferred are iodonium salts, sulfonium salts, azinium salts, organic peroxides and the like.

Further, in the present invention, in addition to the above compounds, a thermal polymerization inhibitor can be added to the recording layer as needed. The thermal polymerization inhibitor has a function of preventing the thermal polymerization of the photopolymerizable monomer and the polymerization with the passage of time. This is preferable in that the chemical stability of the adjustment liquid containing the hydrophilic monomer can be enhanced. Examples of thermal polymerization inhibitors include, for example, p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β- Naphthol, 2,6-di-t
-Butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine and the like.

The addition amount of the thermal polymerization inhibitor in the recording layer is preferably from 0.001 to 5% by weight, and more preferably from 0.01 to 5% by weight based on the total weight of the photopolymerizable monomer and the photopolymerizable initiator.
1% by weight is more preferred. 0.001% by weight
If it is less than 5%, the thermal stability may be poor, and if it exceeds 5% by weight, the sensitivity may decrease.

The recording layer comprises a metal oxide or an oxide salt thereof,
A solution containing the photopolymerizable monomer, photopolymerizable initiator, electron-accepting compound, and, if desired, the above-mentioned various additives is emulsified and dispersed, and a capsule containing an electron-donating colorless dye is added thereto, followed by coating. It is formed by preparing a liquid, applying the coating liquid on a support, and then drying.

As a method of application, a coating bar,
Blade coater, rod coater, knife coater,
A method using a roll doctor coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a curtain coater, an extrusion coater, or the like can be employed.
In addition, as an application method, for example, Research
Disclosure, Vol. 200, 1980 1
February, Item 20036, section XV.

As the solvent used for preparing the emulsified dispersion, an organic solvent, a water-soluble polymer or the like can be used.
These mixed solutions can also be used.

As the organic solvent, for example, natural oil or synthetic oil can be used, and specific examples thereof include cottonseed oil, kerosene, aliphatic ketone, aliphatic ester, paraffin, naphthenic oil, alkylated biphenyl, and alkylated oil. Terphenyl, chlorinated paraffin, alkylated naphthalene, diarylethane such as 1-phenyl-1-xylylethane, 1-phenyl-1-p-ethylphenylethane, 1,1′-ditolylethane, alkyl phthalate (dibutyl phthalate, Dioctyl phthalate, dicyclohexyl phthalate, etc.), phosphates (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), citrates (eg, tributyl acetyl citrate), benzoate esters (Eg, octyl benzoate), alkyl amide (eg, diethyl lauryl amide), trimesate (eg, tributyl trimesate), acetate (ethyl acetate, propyl acetate,
Iso-propyl acetate, butyl acetate, tert-butyl acetate, s-butyl acetate, etc.), propionate ester (eg, ethyl propionate), butyric acid (isobutyrate) ester (eg, methyl butyrate), acrylic acid (methacrylic acid) ester ( Examples thereof include methyl acrylate), alkyl halides (methylene chloride, carbon tetrachloride, etc.), tertiary butyl alcohol, thimer isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, and the like. Among these, fatty acid esters and alkyl halides are preferable, and those having a solubility in water of 10% by volume or less are more preferable. These solvents are preferably used in a proportion of 1 to 500 parts by weight based on the electron accepting compound.

As the water-soluble polymer, for example, a compound which is soluble in water at 25 ° C. in an amount of 5% by weight or more is preferable. Specific examples include proteins such as gelatin, gelatin derivatives, albumin and casein, methylcellulose and carboxymethylcellulose. , Cellulose derivatives such as sodium alginate, sugar derivatives such as starches (including modified starch),
Synthetic polymers such as gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymer, and polystyrene sulfonate are preferred. It is listed. Among these, gelatin and polyvinyl alcohol are preferred.

In the present invention, the recording layer may have a single-layer structure or a multilayer structure. Further, the recording layer may be a recording layer for recording monochromatic so-called black and white (B / W) images, or may be a recording layer for recording multicolor images.

Examples of the recording layer for recording a multicolor image include a microcapsule containing an electron-donating colorless dye that emits light of different colors and a recording layer composed of a plurality of layers that are sensitive to light of different wavelengths. And the like. As a specific example of the light- and heat-sensitive recording material having such a recording layer, a microcapsule containing an electron-donating colorless dye that develops cyan and a recording layer that is sensitive to a wavelength λ1 are provided on a support. A microcapsule enclosing an electron-donating colorless dye that develops magenta, a recording layer sensitive to a wavelength λ2, a microcapsule enclosing an electron-donating colorless dye that develops yellow, and a wavelength λ.
3, an embodiment in which a recording layer sensitive to light is provided, an embodiment in which an intermediate layer having a barrier function is provided between the recording layers, an embodiment in which the intermediate layer contains an ultraviolet absorber, and a light absorption layer in which an ultraviolet absorber is contained. There may be mentioned a mode in which a light absorbing layer is further provided in addition to the intermediate layer having a barrier function.

Among these embodiments, an embodiment in which an intermediate layer and / or a light absorbing layer is provided between the recording layers is particularly preferable. When the light absorbing layer is provided between the recording layers, the light reaching the lower layer of the light absorbing layer is restricted, and the overlapping of the photosensitive wavelength ranges of the recording layers can be eliminated, so that high sensitivity can be achieved. Is preferred. Specific examples of the embodiment in which the light absorbing layer is provided between the recording layers include a microcapsule containing an electron-donating colorless dye that develops cyan, a wavelength λ.
1. A recording layer sensitive to 1 is provided on a support, on which a light absorbing layer containing an ultraviolet absorber that absorbs light having a wavelength shorter than λ1 is provided, and an electron-donating colorless magenta color is formed thereon. A microcapsule containing a dye and a recording layer sensitive to wavelength λ2 are provided, and a light absorbing layer containing an ultraviolet absorber that absorbs light having a shorter wavelength than wavelength λ2 is provided thereon.
A mode in which a microcapsule containing an electron-donating colorless dye that develops yellow and a recording layer sensitive to a wavelength of λ3 is provided thereon, and a protective layer is further provided thereon. The wavelength of the recording layer to which the photosensitive layer is exposed depends on the properties of the photopolymerizable initiator and / or the photopolymerizable monomer contained in the recording layer.

The light- and heat-sensitive recording material of the present invention comprises at least a recording layer on a support, and further comprises an intermediate layer, a light-absorbing layer, an undercoating layer, a protective layer and the like appropriately selected according to the purpose. May be provided.

The support used in the present invention can be produced by using a known material conventionally used for a support. For example, polyester and the like can be mentioned.

The light and heat sensitive recording material of the present invention comprises an undercoat layer,
When having another layer such as an intermediate layer, a light absorbing layer, a protective layer, and a back coat layer, each layer preferably contains a curing agent, and particularly, when the protective layer contains a curing agent, This is preferable because the tackiness of the protective layer can be reduced.

As a curing agent to be used, 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, US Pat. No. 3,635,718 and others A compound having a reactive ethylenically unsaturated bond described in U.S. Pat. No. 3,635,718 and others;
No. 017280 and others, aziridine compounds described in US Pat. No. 3,091,537 and others, halogenocarboxaldehydes such as mucochloric acid, dioxane such as dihydroxydioxane, dichlorodioxane, US Pat. No. 3,642,486
, US Pat. No. 3,687,707, vinyl sulfone precursors described in US Pat. No. 3,841,872, US Pat.
Ketovinyls described in 640720 and chromium alum, zirconium sulfate, boric acid and the like can be used as an inorganic curing agent.

Among these curing agents, 1,3,5-triacroyl-hexahydro-s-triazine, 1,2
-Bisvinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamido) ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt,
2,4,6-triethylenimino-s-triazine, boric acid and the like are preferred. The amount of the curing agent added is preferably 0.5 to 5% by weight based on the binder contained in the layer to which the curing agent is added.

Further, in the present invention, layers such as an undercoat layer, an intermediate layer, a light absorbing layer, a protective layer, and a back coat layer may be coated with coating aids, antistatic, improved slipperiness, emulsification and dispersion, and adhesion prevention. It can be formed using various surfactants for various purposes.

As the surfactant, for example, saponin,
Nonionic surfactants such as polyethylene oxide, polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyltaurines Surfactants, sulfosuccinates, anionic surfactants such as sulfoalkylpolyoxyethylenalkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, and aliphatic or aromatic quaternary ammonium salts And cationic surfactants.

Further, in the present invention, other layers such as an undercoat layer, an intermediate layer, a light absorbing layer, a protective layer, and a back coat layer may contain other additives as necessary. Other additives include, for example, dyes for preventing irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids, curing agents, antistatic agents, slip improvers, and the like. And representative examples of these are:
Research Disclosure, Vol. 1
76, December 1978, Item 17643, and Vol. 187, November 1979, Item 18
716 etc.

The protective layer may contain, in addition to the curing agent, colloidal silica to reduce the tackiness of the protective layer. Suitable examples of the colloidal silica include Snowtex 20, Snowtex 30, Snowtex C, Snowtex O, and Snowtex N manufactured by Nissan Chemical. As the amount of colloidal silica added,
The content is preferably 5 to 80% by weight based on the binder contained in the protective layer.

Furthermore, it is preferable that the protective layer contains a matting agent. As a matting agent, for example, silica, magnesium oxide, barium sulfate, strontium sulfate,
Examples include inorganic compounds such as silver halide, and polymer particles such as polymethyl methacrylate, polyacrylonitrile, and polystyrene, and starch particles such as carboxy starch, corn starch, and carboxynitrophenyl starch. These may be used alone or in combination of two or more. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. As the silica particles, for example, FUJI-DEVION C
HEMICAL LTD. AL-1 and SILOID 6
5, 72, 79, 74, 404, 620, 308, 97
8, 161, 162, 244, 255, 266, 150
And the like. As the average particle size of the matting agent,
1-20 μm is preferred. The content of the matting agent in the protective layer is preferably from ² to 500 mg / m ² ,
100 mg / m ² is more preferred.

Further, the protective layer may contain a fluorescent whitening agent for increasing the whiteness of the light and heat sensitive recording material, a blue dye as a bluing agent, and the like.

The intermediate layer is a layer having a barrier function against oxygen permeation, and usually contains mainly a binder, and may further contain a curing agent or an additive such as a polymer latex, if necessary. In the present invention, a light absorbing agent such as an ultraviolet absorbing agent described below may be added to the intermediate layer, so that the intermediate layer has a function as a light absorbing layer.

The light absorbing layer is a layer having a function of absorbing light such as ultraviolet rays, and usually contains mainly a binder and a light absorbing agent such as an ultraviolet absorber, and further includes a curing agent, if necessary.
An additive such as a polymer latex may be contained.
As the light absorber, an ultraviolet absorber is generally used. Examples of the ultraviolet absorber include known benzotriazole compounds, cinnamic acid ester compounds, aminoarylidenemalon nitrile compounds, and benzophenone compounds. Compounds can be used. The UV absorber is preferably added to the intermediate layer by an oil-in-water dispersion method or a latex dispersion method, but may be added to a desired layer after emulsification and dispersion.

In the oil-in-water dispersion method, the boiling point is, for example, 175.
High boiling point organic solvent having a boiling point of 30 to 160 ° C or higher.
After dissolving in either one of the so-called co-solvents or a mixed solution of both, the solution is finely dispersed in water or an aqueous medium such as an aqueous gelatin solution or aqueous polyvinyl alcohol solution in the presence of a surfactant. Specific examples of the high boiling organic solvent are described in U.S. Pat. No. 2,322,027. As high-boiling organic solvents and auxiliary solvents,
The same solvent as that used in the above-mentioned microencapsulation can be preferably used. Further, the fine dispersion may be accompanied by a phase inversion. After the fine dispersion, if necessary, the auxiliary solvent may be removed or reduced by distillation, Nudel washing, ultrafiltration, or the like, and then used for coating.

Details of the latex dispersion method and specific examples of latex are described in, for example, US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541. , 230, JP-A-49
-74538, 51-59943, 5
No. 4-32552 and Research Disc
loss, Vol. 148, August 1976, It
em 14850 and the like. Suitable examples of latex include acrylates or methacrylates (e.g., ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, etc.) and acid monomers (e.g., acrylic acid, -Acrylamide-2-methylpropanesulfonic acid, etc.).

As the above-mentioned ultraviolet absorber, a particularly preferable example is an ultraviolet absorber having a structure hardly diffused into the adjacent layer, for example, an ultraviolet absorber copolymerized with a polymer or a latex. Examples of such ultraviolet absorbers include, for example, EP 127,819, JP-A-59-68731, JP-A-59-26733, JP-A-59-23344, and British Patent 2,118,
No. 315, JP-A-58-111942, U.S. Pat. No. 4,307,184 and 4,202,83.
No. 6, No. 4,202,834, No. 4,2
Reference can be made to the descriptions in JP-A-07-253, JP-A-4,178,303 and JP-A-47-560. These are usually added to the light absorbing layer, but if necessary, to the intermediate layer, the protective layer, the recording layer, the antihalation layer and the like.

As the binder contained in the undercoat layer, the intermediate layer, the light absorbing layer, the back coat layer, the protective layer, etc., in addition to those described above, the emulsification dispersion of the photocurable composition and the aforementioned electron donating colorless Water-soluble polymers exemplified for microencapsulation of dyes, other, for example, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, acrylic resins such as copolymers thereof, polystyrene, polyvinyl formal,
Solvent-soluble polymers such as polyvinyl butyral, phenolic resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, urethane resins, and the like, or polymer latexes thereof can also be used. Among these,
Gelatin and polyvinyl alcohol are preferred.

The undercoat layer, the intermediate layer, the light absorbing layer, the back coat layer, and the protective layer are formed on the support by using the above-described method for forming the recording layer. That is, the coating solution for the undercoat layer, the coating solution for the intermediate layer, the coating solution for the light absorbing layer, the coating solution for the protective layer, the coating solution for the back coat layer, or the like, or after dissolved in a solvent as needed It can be obtained by coating on an appropriately selected support and drying.

The solvent used in this case includes, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,
Alcohols such as methyl cellosolve, 1-methoxy-2-propanol, methylene chloride, halogenated solvents such as ethylene chloride, acetone, cyclohexanone,
Ketones such as methyl ethyl ketone, methyl cellosolve acetate, ethyl acetate, esters such as methyl acetate, toluene,
Xylene, water and the like can be mentioned. These may be used alone or in combination of two or more. Among these, water is particularly preferred.

As a method of applying the coating solution for each layer on the support, a method similar to the method of applying the recording layer on the support can be used. As described above, the thickness of each layer formed on the support, particularly the thickness of the recording layer is 0.1
５０50 μm is appropriate.

In the light and heat sensitive recording material of the present invention, an image is formed as follows. First, when the photosensitive and heat-sensitive recording material is exposed, radicals are generated in the recording layer. The radical initiates the polymerization of the photopolymerizable monomer in the exposed area, cures the recording layer in the exposed area, and forms a fixed latent image on the recording layer. Thereafter, when the entire surface of the recording layer is heated, the electron-accepting compound present in the unfixed portion of the non-exposed portion (if the photopolymerizable monomer has an electron-accepting group in the molecule, the photopolymerizable monomer ) Moves in the light- and heat-sensitive recording material, reacts with the electron-donating colorless dye encapsulated in the microcapsules, and develops color. As a result, a positive image having good contrast is formed in the recording layer.

The photosensitive and heat-sensitive recording material of the present invention can perform high-sensitivity recording using light in a wide range from ultraviolet light to visible light. Various light sources such as mercury lamps, ultra-high pressure mercury lamps, electrodeless mercury lamps, xenon lamps, tungsten lamps, metal halide lamps, argon lasers, helium neon lasers, and semiconductor lasers,
Light sources capable of producing a wide range of wavelengths, such as EDs and fluorescent lamps, can be used.

When recording an image using the light- and heat-sensitive recording material of the present invention, various methods such as contact exposure of an original such as a lithographic film, enlargement exposure of a slide or a liquid crystal image, and reflection exposure using reflected light of the original are used. An exposure method can be used. When multicolor image recording is performed using the light and heat sensitive recording material of the present invention, exposure is performed once or more using light of different wavelengths. However, by changing the light source or changing the optical filter, the wavelength is changed. Exposure can be performed many times with different light.

The light and heat sensitive recording material of the present invention is subjected to a heat development treatment simultaneously with or after the imagewise exposure. As a heating method in the heat development treatment, various conventionally known methods can be used, and the heating temperature is usually from 80 to
The heating temperature is 200 ° C., preferably 100 to 160 ° C., and the heating time is usually 1 second to 5 minutes, preferably 3 seconds to 1 minute.

It is preferable that the photosensitive and heat-sensitive recording material of the present invention is subjected to an overall exposure after the heat development processing, and the non-cured portions are also light-cured. Performing the whole-surface exposure in this way is advantageous in that the color development reaction of the background portion and the color erasure reaction of the color development portion are suppressed, and the storability of the image is improved.

The light- and heat-sensitive recording material of the present invention can be suitably used for various uses, for example, copiers, faxes, printers, labels, color proofs, second original drawings, and the like.

[0152]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “%” is used unless otherwise specified.
Means "% by weight", and "parts" means "parts by weight".

Embodiment 1 1. [Preparation of Electron-donating Colorless Dye Capsule] 8.9 g of the electron-donating colorless dye (1) was added to ethyl acetate.
Takenate D-11 as an encapsulating agent
20 g of 0N (manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 g of Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. This solution was added to a mixture of 42 g of 8% phthalated gelatin and 1.4 g of a 10% sodium dodecylbenzenesulfonate solution, and emulsified and dispersed at 20 ° C. to obtain an emulsion. 14 g of water and 72 g of a 2.9% aqueous solution of tetraethylenepentamine are added to the obtained emulsion, and the mixture is heated to 60 ° C. with stirring, and after 2 hours, the electron-donating colorless dye (1)
Was encapsulated in a core to obtain a capsule liquid having an average particle size of 0.5 μm.

[0154]

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[0155] 2. [Preparation of emulsion of photopolymerizable composition (composition comprising photopolymerizable monomer and photopolymerizable initiator)] 0.1 g of organic borate salt (1) of an organic cationic dye having the following structural formula 5 g of a photopolymerizable monomer (1) having the following electron-accepting group was added to a mixed solution of isopropyl acetate and 3 g of isopropyl acetate (solubility in water: about 4.3%). This solution was added to a mixed solution of 13 g of a 13% aqueous gelatin solution, 0.8 g of a 2% aqueous solution of a surfactant (1), and 0.8 g of a 2% aqueous solution of a surfactant (2), and a homogenizer (Nippon Seiki) (Manufactured by Co., Ltd.) at 10,000 rpm for 5 minutes to obtain an emulsion of the photopolymerizable composition (1).

[0156]

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[0157]

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[0158]

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[0159] 3. [Preparation of coating solution for recording layer] 4 g of the prepared electron-donating colorless dye (1) capsule, 12 g of the prepared emulsion of the photopolymerizable composition (1), and (NH
_{4) 6 Mo 7 O 24 ·} 4H 2 O 15% aqueous solution of 0.96g
(5% by weight based on the photopolymerizable monomer (1)) and 15
Then, 12 g of a 1% aqueous solution of gelatin was mixed to prepare a recording layer coating solution (1).

4. [Preparation of Coating Solution for Protective Layer] 4.5 g of a 10% gelatin aqueous solution, 4.5 g of distilled water,
0.5 g of a 2% surfactant (3) aqueous solution, 0.3 g of a 2% surfactant (4) aqueous solution, 0.5 g of a 2% hardener (1) aqueous solution, and Syloid 72 (FUJI-DEVISO)
N CHEMICAL LTD. 50mg)
The amount of only the / m ^2, mixing the Snowtex N1G, to prepare a protective layer (1) coating liquid.

[0161]

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5. [Support] A transparent polyester base having a thickness of 75 μm was used.

The coating solution for recording layer (1) was coated on the support by using a coating bar and the dry weight of the coating layer was 10 g / g.
m ² and dried at 30 ° C. for 10 minutes.
The coating solution for the protective layer (1) was applied thereon using a coating bar so that the dry weight of the applied layer was 2 g / m ² , and dried at 30 ° C. for 10 minutes to obtain a light and heat sensitive recording material. This was designated as Example 1.

[0164] The _{(NH 4) 6 Mo 7 O} 24 · 4H 2 O was used in the preparation of the recording layer coating solution of Example 2 Example _{1 (1), (NH 4} ) 3
A light- and heat-sensitive recording material was prepared in the same manner as in Example 1 except that [PMo ₁₂ O ₄₀ ] · 3H ₂ O was used.

[0165] The _{(NH 4) 6 Mo 7 O} 24 · 4H 2 O was used in the preparation of the recording layer coating solution of Example 3 Example 1 (1), Na ₂ MoO
_A light- and heat-sensitive recording material was prepared in the same manner as in Example 1 except that 4.2H ₂ O was used.

[0166] The _{(NH 4) 6 Mo 7 O} 24 · 4H 2 O was used in the preparation of the recording layer coating solution of Comparative Example 1 Example 1 (1), except for not adding to Example 1 Similarly, prepare a light and heat sensitive recording material,
This was designated as Comparative Example 1.

Each of the light- and heat-sensitive recording materials of Examples 1 to 3 and Comparative Example 1 was applied with a wavelength of 657 nm from the recording layer side.
Using a semiconductor laser beam, the irradiation energy was changed in the form of a step wedge while changing the scanning speed, and the recording layer surface was irradiated and exposed to an energy of 50 mJ / cm ² at the maximum. When the light and heat sensitive recording material on which the latent image was formed was heated with a hot plate at 120 ° C. for 5 seconds, a step wedge image was obtained in each light and heat sensitive recording material. The sensitivity was evaluated based on the energy at which the background appeared in a wedge image with a constant exposure. The color development density and background fogging were measured with a Macbeth transmission densitometer. The transparency of the light and heat sensitive recording material is
Haze meter (DIGITAL HAZE COMP)
UTER HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.). The evaluation results are summarized in the following table.

[0168]

[Table 1]

From the results shown in Table 1, it can be seen that the light- and heat-sensitive recording materials of Examples 1 to 3 have remarkably improved color density of the obtained images while maintaining the same sensitivity as Comparative Example 1. all right.

[0170]

The light and heat sensitive recording material of the present invention does not require the use of a developing solution, and can easily form an image having a high color density with a short exposure.

Claims (3)

[Claims] 1. A microcapsule enclosing an electron-donating colorless dye on a support, an electron-accepting compound, a photopolymerizable monomer, a photopolymerizable initiator, and a group consisting of groups 4 to 7 of the periodic table. A light- and heat-sensitive recording material provided with a recording layer containing an oxide of a selected element or a salt of the oxide. 2. A microcapsule enclosing an electron-donating colorless dye on a support, a photopolymerizable monomer having an electron-accepting group in a molecule, a photopolymerizable initiator, A light- and heat-sensitive recording material provided with a recording layer containing an oxide of a selected element or a salt of the oxide. 3. An oxide of an element selected from Group 4 to Group 7 or a salt of the oxide is a polyacid or a salt of the polyacid of an element selected from Group 4 to Group 7. 3. The light and heat sensitive recording material according to claim 1 or 2.