JP2002189295A - Photopolymerizable composition and recording material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition having high sensitivity to not only ultraviolet light but also visible light to infrared light and a recording material containing the photopolymerizable composition, excellent in sensitivity and the decolorability of the ground part and capable of forming a clear high contrast image. SOLUTION: The photopolymerizable composition contains a polymerizable compound and at least one compound of formula (1) [where L1-L2 are each methine; Q is a dye forming group; (m) is 0-1; X is a group capable of simultaneously forming a 5- or 6-membered heterocycle containing two S (sulfur atoms) and a Yn-containing heterocycle; Y is an oxygen atom, a sulfur atom or a nitrogen atom; and (n) is 1-4]. Preferably the photopolymerizable composition further contains a compound capable of generating a radical or a cation by interaction with the compound of the formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ink, a hologram, a proof, a sealant, an adhesive, a lithographic printing plate, a resin letterpress,
Regarding photopolymerizable compositions and recording materials that can be suitably used in a wide range of fields including photoresists, etc.
A novel photopolymerizable composition that can be sensitive to not only ultraviolet light but also visible light to infrared light, and a completely dry processing system that does not require the use of a developer or the like and generates no waste The present invention relates to a recording material capable of forming a black-and-white or color image.

[0002]

2. Description of the Related Art A photopolymerizable composition is basically a photopolymerization initiator and an addition-polymerizable compound containing two or more ethylenically unsaturated bonds in a molecule (hereinafter referred to as "polyfunctional monomer"). ), The composition cures when irradiated with light, changes its tackiness, and becomes insoluble in a solvent. Utilizing these properties, it is widely used in photography, printing, metal surface processing, ink and the like. The functions and application examples of the photopolymerizable composition are described in many books. For example, J. "Lig by Kosar
ht Sensitive Systems "(J.W.
iley & Sons, New York, 1965
Year, pp. 158-193) and K. et al. I. Jacobso
n, R. E. FIG. "Imaging S" by Jacobson
systems (J. Wiley & Sons, Ne.
w York, 1976, pp. 181-222).

In recent years, as an image forming method using a photopolymerizable composition, an image forming system using photosensitive microcapsules in which the photopolymerizable composition is encapsulated in microcapsules has been proposed. For example, Japanese Patent Application Laid-Open No. 57-12434
No. 3, JP-A-57-179636, JP-A-57-19
No. 7538 discloses a dye formed by applying a pressure to the color-forming sheet coated with a photopolymerizable composition comprising a vinyl compound and a photopolymerization initiator and a microcapsule containing the dye and an image-receiving sheet after exposure. An image forming method is disclosed.

Further, JP-A-3-87827 and JP-A-4-21252 describe a light- and heat-sensitive color recording material containing two components, wherein one of the two components is encapsulated in a microcapsule and the other is encapsulated. Is disclosed as a curable compound of the photocurable composition, or the other is contained outside the microcapsules together with the photocurable composition. Further, in the latter recording material, a microcapsule containing an electron-donating colorless dye, and a photocurable composition containing an electron-accepting compound, a polymerizable vinyl monomer and a photopolymerization initiator outside the microcapsule. A light- and heat-sensitive recording material provided with a layer containing

As described above, a recording material using a photopolymerizable composition can record an image in a completely dry system without using a developing solution or the like, and is environmentally friendly in that no waste is generated. Very preferred. When an image is recorded on a photosensitive recording material, it is advantageous if an inexpensive infrared laser or green to red light can be used in addition to UV light and short-wave visible light. However, in a recording material using a photopolymerizable composition, although it is sensitive to ultraviolet light, it is not sensitive to visible light to infrared light, or its sensitivity is not sufficient even when exposed, and as a result, The formed image may be unclear or the contrast between the image portion and the non-image portion may be low. Therefore, further improvement in sensitivity is desired.

On the other hand, spectral sensitizing dyes are generally used in these recording materials for the purpose of increasing the sensitivity to light used for image recording (writing). Therefore, it is known that after obtaining a recorded image, the dye can be decomposed by irradiating light that can be absorbed by the dye again to decolor the hue of the dye present on the recording material. . However, there is a case where the decoloring property is not sufficiently obtained, and there are problems such as a decrease in hue clarity and contrast due to a partial residual color, a long time for decoloring, and the like. Is desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention is not limited to ultraviolet light, visible light ~
An object of the present invention is to provide a photopolymerizable composition that can be sensitive to infrared light with high sensitivity. Further, the present invention does not require the use of a developer or the like, and in a completely dry processing system that does not generate waste, high-sensitivity image recording using not only ultraviolet light but also visible light to infrared light is possible. Another object of the present invention is to provide a recording material which is excellent in the decoloring property of a non-image portion (background portion) and can form a clear, high-contrast black and white or color image.

[0008]

Means for solving the above problems are as follows. <1> A photopolymerizable composition comprising a polymerizable compound and at least one compound represented by the following general formula (1).

[0009]

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[In the general formula (1), Q represents a group capable of forming a dye. L ¹ and L ² each independently represent a methine group which may have a substituent, L ^1, if L ² represents a methine group having a substituent, the substituent is bonded to unsaturated fats An aromatic ring or an unsaturated heterocyclic ring may be formed. m is 0 or 1
Represents X represents a group capable of simultaneously forming a saturated or unsaturated heterocyclic ring containing two sulfur atoms and a saturated or unsaturated, optionally substituted heterocyclic ring containing Yn. Y
Represents an oxygen atom, a sulfur atom, or a nitrogen atom, and n represents 1
Represents an integer of 1 to 4. ]

<2> A compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4) And the at least one compound selected from the compounds represented by the following general formula (5).

[0012]

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[In the general formula (2), Z ² represents an atomic group forming a 5- or 6-membered heterocyclic ring, and the heterocyclic ring may be condensed with an aromatic ring or a heterocyclic ring; The 5- or 6-membered heterocyclic ring and the aromatic or heterocyclic ring condensed to the heterocyclic ring may have a substituent. L ¹ and L ² are
When L ¹ and L ² each independently represent a methine group which may have a substituent, and L ¹ and L ² each represent a methine group having a substituent, the substituents are bonded to each other to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring; May be formed. m represents 0 or 1. X is two S
A saturated or unsaturated heterocyclic ring containing (sulfur atom);
And a group capable of simultaneously forming a saturated or unsaturated, optionally substituted heterocyclic ring. Y represents an oxygen atom, a sulfur atom, or a nitrogen atom, and n represents an integer of 1 to 4. ]

[0014]

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[In the general formula (3), Z ³ represents an atomic group forming a 5- or 6-membered heterocyclic ring, and the heterocyclic ring may be condensed with an aromatic ring or a heterocyclic ring; The 5- or 6-membered heterocyclic ring and the aromatic or heterocyclic ring condensed to the heterocyclic ring may have a substituent. L ¹ and L ² are
When L ¹ and L ² each independently represent a methine group which may have a substituent, and L ¹ and L ² each represent a methine group having a substituent, the substituents are bonded to each other to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring; May be formed. m represents 0 or 1. X is two S
A saturated or unsaturated heterocyclic ring containing (sulfur atom);
And a group capable of simultaneously forming a saturated or unsaturated, optionally substituted heterocyclic ring. Y represents an oxygen atom, a sulfur atom, or a nitrogen atom, and n represents an integer of 1 to 4. ]

[0016]

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[0017] In [Formula (4), Z ⁴ represents an atomic group necessary for forming a 5-membered or 6-membered heterocyclic ring, the heterocyclic ring may also be combined aromatic ring or a heterocyclic ring condensed, The 5- or 6-membered heterocyclic ring and the aromatic or heterocyclic ring condensed to the heterocyclic ring may have a substituent. L ¹ and L ² each independently represent a methine group which may have a substituent, L ^1, if L ² represents a methine group having a substituent, the substituent is bonded to unsaturated fats An aromatic ring or an unsaturated heterocyclic ring may be formed. m represents 0 or 1. X is two S
A saturated or unsaturated heterocyclic ring containing (sulfur atom);
And a group capable of simultaneously forming a saturated or unsaturated, optionally substituted heterocyclic ring. Y represents an oxygen atom, a sulfur atom, or a nitrogen atom, and n represents an integer of 1 to 4. ]

[0018]

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[In the general formula (5), A and B are each independently
Represents an atomic group capable of forming a dye. L¹And L^TwoIs
A methine group which may have a substituent
Then L ¹, L^TwoRepresents a methine group having a substituent,
The substituents combine to form an unsaturated aliphatic ring or unsaturated heterocyclic ring.
May be implemented. m represents 0 or 1. X is two S
A saturated or unsaturated heterocyclic ring containing (sulfur atom);
Or a saturated or unsaturated optionally substituted heterocyclic ring containing
Represents a group which can be formed simultaneously. Y is an oxygen atom, sulfur
Represents an atom or a nitrogen atom, and n represents an integer of 1 to 4.
You. ]

<3> Polymerizable compound, general formula (1)
And the photopolymerizable composition according to the above <1> or <2>, which contains a compound capable of generating a radical or a cation by interacting with the compound represented by the general formula (1). is there. The compound capable of generating a radical or a cation is a compound capable of generating at least one of a radical and a cation.

<4> Compounds capable of generating radicals or cations include organic boron compounds, iodonium salts, sulfonium salts, iron allene complexes, S-triazine derivatives, organic peroxides, titanocene, triarylimidazole dimers, and azinium. The photopolymerizable composition according to <3>, which is at least one selected from salts.

<5> The photopolymerizable composition according to <3>, wherein the polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond, and the compound capable of generating a radical or a cation is an organic boron compound. Things.

<6> The photopolymerizable composition according to <4> or <5>, wherein the organoboron compound is a compound represented by the following general formula (A).

[0024]

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[0025] [In the general formula ^{_{(A), R a 1,}} R a 2, R a 3, and R _a ⁴ each independently an aliphatic group, an aromatic group, a heterocyclic group, or Si (R _a ⁵ ) (R _a ⁶⁾ represents a _{^{-R a 7, R a 5,}} R a 6,
And R _a ⁷ are each independently an aliphatic group, an aromatic group. G ⁺ represents a group capable of forming a cation. ]

<7> having a recording layer on a support,
The recording layer comprises: a coloring component A; a coloring component B having a portion that reacts with the coloring component A to form a color;
And a photopolymerizable composition according to any one of (1) to (3).

<8> The recording material according to <7>, wherein at least one of the polymerizable compounds is a coloring component B. <9> The recording material according to <7>, wherein the polymerizable compound is a color-suppressing compound having a site for suppressing the reaction between the color-forming components A and B in the same molecule. <10> The recording material according to any one of <7> to <9>, wherein the color-forming component A is included in a microcapsule.

<11> a first recording layer that is sensitive to light having a central wavelength λ ₁ , a second recording layer that is sensitive to light having a central wavelength λ ₂ and develops a color different from that of the first recording layer,... , Center wavelength λ
_The above <7> to << 7, which have a multilayer structure in which the first, second,..., and i-th recording layers that are sensitized to the _i-th light and develop a different color from the i-th recording layer are stacked in this order. 10>.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable composition of the present invention is characterized by containing a polymerizable compound and a compound represented by the following general formula (1) as a spectral sensitizing dye. And The recording material of the present invention is characterized in that the recording layer on the support contains the photopolymerizable composition of the present invention together with a coloring component and the like. Hereinafter, the photopolymerizable composition and the recording material of the present invention will be described in detail.

<Photopolymerizable composition> The photopolymerizable composition of the present invention contains at least a polymerizable compound and a compound represented by the following general formula (1). Contains components.

(Polymerizable Compound) The polymerizable compound is not particularly limited, and may be any of low molecular weight (monomer) to high molecular weight (oligomer) having a polymerizable site in the structure. It can be appropriately selected according to the purpose. Specifically, for example, compounds having at least one ethylenically unsaturated double bond in the molecule, epoxy compounds, cyclic ether compounds, oxetane compounds, cyclic thioether compounds, spiroorthoester compounds, spiroorthocarbonate compounds, etc. Can be

Among them, compounds having at least one ethylenically unsaturated double bond in the molecule are preferable, for example, acrylic acid such as acrylates and acrylamides and salts thereof, methacrylates, methacrylamides and the like. Methacrylic acid and salts thereof, maleic anhydride, maleic esters, itaconic acid, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, aryl ethers, allyl esters, maleimide And the like.

Examples of the monomer having a double bond include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
Examples thereof include an alkyl or hydroxyalkyl acrylate or methacrylate such as hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate or ethyl methacrylate. Also advantageous are silicone acrylates. Besides, acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl ester such as vinyl acetate, vinyl ether such as isobutyl vinyl ether, styrene, alkyl- and halostyrene, N
-Vinylpyrrolidone, vinyl chloride or vinylidene chloride and the like.

Examples of the monomer containing two or more double bonds include diacrylates such as ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol and bisphenol A, and 4,4'-bis ( 2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2- (Acryloylethyl) isocyanurate and the like.

Examples of polyunsaturated compounds having a relatively high molecular weight (oligomeric) include epoxy resins having a (meth) acrylic group, polyesters having a (meth) acrylic group, polyesters containing vinyl ether or epoxy group, polyurethanes, And polyethers. In addition, examples of unsaturated oligomers are unsaturated polyester resins, typically made from maleic acid, phthalic acid and one or more diols, from about 500 to 3000
Having a molecular weight of In addition, it is also possible to use vinyl ether monomers and oligomers, and maleate terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxy backbones. Particularly suitable are combinations of oligomers having vinyl ether groups with the polymers described in WO 90/01512. Also suitable are copolymers of vinyl ether and maleic acid functionalized monomers. Such unsaturated oligomers can also belong as prepolymers.

Examples of particularly suitable are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the main or side chains, such as unsaturated polyesters, polyamides, polyurethanes and the like. , Alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth) acrylic groups in the side chain, and mixtures of one or more such polymers.

The ethylenically unsaturated carboxylic acids include, for example, acrylic acid, methacrylic acid, crotonic acid,
Examples include itaconic acid, cinnamic acid, and unsaturated fatty acids such as linoleic acid or oleic acid. Among them, acrylic acid and methacrylic acid are preferred.

As said polyols, aromatic and, in particular, aliphatic and cycloaliphatic polyols are preferred. Other suitable polyols include polymers and copolymers containing hydroxyl groups in the polymer chains or side chains (eg, polyvinyl alcohol and copolymers thereof or polyhydroxyalkyl methacrylates or copolymers thereof), oligoesters having hydroxyl end groups, and the like. No. As the polyepoxide, for example, the above polyols, especially aromatic polyols,
And those based on epichlorohydrin.

As the aromatic polyol, for example,
Hydroquinone, 4,4'-dihydroxydiphenyl,
2,2-di (4-hydroxyphenyl) propane, novolak and resorcin.

Examples of the aliphatic and cycloaliphatic polyols include alkylene diols having preferably 2 to 12 carbon atoms (eg, ethylene glycol, 1, 1
2- or 1,3-propanediol, 1,2-, 1,3
-Or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, etc., more preferably polyethylene glycol having a molecular weight of 200 to 1500; Cyclopentanediol, 1,2-, 1,3- or 1,4-
Examples thereof include cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.

The polyols can be partially or completely esterified with one carboxylic acid or with different unsaturated carboxylic acids, and in the partial esters the free hydroxyl groups can be modified, eg Can be etherified or esterified with a carboxylic acid.

Examples of the ester include the following. That is, trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate , Pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate,

Tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-
Butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate,
Sorbitol tetraacrylate, pentaerythritol-modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylate and methacrylate, glycerol diacrylate and triacrylate, 1,4-cyclohexanediacrylate, and a molecular weight of 200 to 1500 Bisacrylates and bismethacrylates of polyethylene glycol, or mixtures thereof.

Also suitable as the polymerizable compound are the same or different unsaturated carboxylic acids and aromatic or cycloaliphatic aliphatic compounds having preferably 2 to 6, especially 2 to 4, amino groups. And amides with aliphatic polyamines. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,
2-, 1,3- or 1,4-butylenediamine, 1,5
-Pentylenediamine, 1,6-hexylenediamine,
Octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di (β-aminoethoxy)-or Di (β
-Aminopropoxy) ethane. In addition, polymers and copolymers preferably having an additional amino group in the side chain, and oligoamides having an amino terminal group are suitable. Examples of such unsaturated amides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis (methacrylamidopropoxy) ethane, β-
Methacrylamidoethyl methacrylate and N-[(β
-Hydroxyethoxy) ethyl] acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and from diols or diamines. Some of the maleic acid can be replaced by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, for example styrene. Polyesters and polyamides can be derived from dicarboxylic acids, from ethylenically unsaturated diols or diamines, especially from those having a relatively long chain, for example, from 6 to 20 carbon atoms. Examples of polyurethanes include those composed of saturated or unsaturated diisocyanates and unsaturated or, respectively, saturated diols.

Polybutadienes and polyisoprenes and their copolymers are known. Examples of suitable comonomers are olefins such as ethylene, propene, butene and hexene, (meth) acrylates, acrylonitrile, styrene or vinyl chloride. Polymers having (meth) acrylate groups in the side chains are likewise known. For example, it can be obtained as a reaction product of a novolak-based epoxy resin with (meth) acrylic acid, or a homo- or copolymer of vinyl alcohol or (meth) acrylic acid with its hydroxyalkyl derivative esterified with Or a homo- or copolymer of (meth) acrylate esterified with hydroxyalkyl (meth) acrylate.

The polymerizable compound may be a compound having a site exhibiting another function in its structure depending on the use of the photopolymerizable composition. In the case of using the color image forming apparatus, a portion that promotes a coloring reaction of a coloring component constituting the image portion or a portion that suppresses coloring may be provided. These will be described later.

The content of the compound having an ethylenically unsaturated bond is usually in the total mass of the photopolymerizable composition.
It is 10 to 99% by mass, preferably 30 to 95% by mass.

(Compound Represented by Formula (1)) The photopolymerizable composition of the present invention comprises a compound represented by the following formula (1) as a spectral sensitizing dye. The dye has a function of spectrally sensitizing a compound (radical or cation generator) capable of generating a radical or a cation. Therefore, when visible to infrared light corresponding to the absorption of the dye is irradiated, even when a radical or cation generator having no absorption is contained in this region, generation of radicals or cations from the generator is suppressed. Can be promoted. In addition, since the dye exhibits high decolorability when irradiated with light, when used in a recording material using a photopolymerizable composition as described below, the fog density of the background portion is suppressed, and the contrast is reduced. This is useful in that a high clear image can be formed.

[0050]

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In the general formula (1), Q is a group capable of forming a dye, and represents a 5- or 6-membered heterocyclic ring or an acyclic group. The heterocyclic ring may be condensed, and the 5- or 6-membered heterocyclic ring and the aromatic or heterocyclic ring condensed to the heterocyclic ring may have a substituent. As the 5- or 6-membered heterocyclic ring, an acidic nucleus containing a carbon atom and at least one selected from a chalcogen atom (typically, oxygen, sulfur, selenium, tellurium) and a nitrogen atom; Basic nuclei are mentioned, and among them, the following (1-a) to (1-c)
A heterocyclic ring represented by any of the above is preferable. Further, as the acyclic group, a group represented by (1-d) is preferably used.

[0052]

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Z ² and Z ³ in the above (1-a) and (1-b) each independently represent an atomic group forming a 5- or 6-membered heterocyclic ring. The ring or heterocyclic ring may be condensed, and the 5- or 6-membered heterocyclic ring and the aromatic or heterocyclic ring condensed to the heterocyclic ring may have a substituent. Further, Z ⁴ in the above (1-c)
Represents an atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and the nitrogen-containing heterocyclic ring may be condensed with an aromatic ring or a heterocyclic ring. The aromatic ring or the heterocyclic ring may have a substituent.

As the 5- or 6-membered heterocyclic ring, for example,
Thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 1,3-dithiol nucleus, indolenine nucleus (for example, 3,3-dimethylindia Renin), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, pyrroline nucleus, selenazole nucleus, benzselnazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3 -Isoquinoline nucleus, imidazo [4,5-b] quinoxalin nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus,

A pyrimidine nucleus, a pyrazolotriazole nucleus,
Pyrrolotriazole nucleus, imidazotriazole nucleus, pyrazolotriazole nucleus, pyrazolopyrimidineone nucleus, pyrazolopyrimidinedione nucleus, pyrrolopyrimidineone nucleus, imidazopyrimidineone nucleus, pyrrolopyrimidinedione nucleus,
Imidazopyrimidinedione nucleus, pyrrolotriazinedione nucleus, pyrrolotriazinedione nucleus, 2-pyrazolin-5-
On nucleus, pyrazolidine-3,5-dione nucleus, imidazolin-5-one nucleus, hydantoin nucleus, 2- or 4-thiohydantoin nucleus, 2-iminooxazolidin-4-one nucleus, 2-oxazolin-5-one nucleus, 2-thiooxazoline-2,4-dione, isoxazolin-5-one nucleus, 2-thiazolin-4-one nucleus, thiazolidine-4-
On nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiazolidine-2,4-dithione nucleus,

An isorhodanine nucleus, an indane-1,3-dione nucleus, a thiophen-3-one nucleus, a thiophen-3-one-1,1-dioxide nucleus, an indoline-2-one nucleus,
Indoline-3-one nucleus, 2-oxoindazolinium nucleus, 3-oxoindazolinium nucleus, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine nucleus, cyclohexane-1, 3-dione nucleus, 3,4-dihydroisoquinolin-4-one nucleus, 1,3-dioxane-
4,6-dione nucleus, barbituric acid nucleus, 2-thiobarbituric acid nucleus, chroman-2,4-dione nucleus, indazolin-2-one nucleus, pyrido [1,2-a] pyrimidine-
1,3-dione nucleus, pyrazolo [1,5-b] quinazolone nucleus, pyrazolo [1,5-a] benzimidazole nucleus, pyrazolopyridone nucleus, 1,2,3,4-tetrahydroquinoline-2,4-dione nucleus A 3-oxo-2,3-dihydrobenzo [d] thiophen-1,1-dioxide nucleus,
3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-1,1-dioxide nucleus and the like.

Among them, barbituric acid nucleus, thiobarbituric acid nucleus, indolenine nucleus, 1,3-dithiol nucleus, pyrrolotriazole nucleus, imidazotriazole nucleus, pyrazolotriazole nucleus, pyrazolopyrimidine on nucleus, pyrazolopyrimidinedione Nuclei, pyrrolopyrimidine on nuclei, imidazopyrimidine on nuclei, pyrrolopyrimidine dione nuclei, imidazopyrimidine dione nuclei are preferred, and thiobarbituric acid nuclei are particularly preferred.

The 5- or 6-membered heterocyclic ring may be an aromatic ring (benzene ring, naphthalene ring) or a condensed ring obtained by condensing a heterocyclic ring. The aromatic ring or heterocyclic ring fused to the heterocyclic ring may further have a substituent. Examples of the heterocyclic ring fused to the 5- or 6-membered heterocyclic ring include the specific examples described above for the 5- or 6-membered heterocyclic ring.

Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, , A methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group), an alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylaminosulfonyl group having 30 or less carbon atoms, An alkoxy group having 30 or less carbon atoms (for example, a methoxy group, an ethoxy group, a benzyloxy group, a phenoxyethoxy group, a phenethyloxy group, etc.), an alkylthio group having 30 or less carbon atoms (for example, a methylthio group, an ethylthio group,
A methylthioethylthioethyl group or the like), an aryloxy group having 30 or less carbon atoms (for example, a phenoxy group, a p-tolyloxy group, a 1-naphthoxy group, a 2-naphthoxy group or the like);
Nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group, aryloxycarbonyloxy group,

An acyloxy group having 30 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, etc.), a carbamoyl group (eg, carbamoyl group) Group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group,
An N, N-dimethylsulfamoyl group, a morpholinosulfonyl group, a piperidinosulfonyl group, etc., an aryl group having 30 or less carbon atoms (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) And the like, a substituted amino group (for example, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an acylamino group, etc.), a substituted ureido group, a substituted phosphono group, a heterocyclic group and the like. Here, the carboxyl group, sulfo group, hydroxy group, and phosphono group may be in a salt state. At that time, examples of the cation forming a salt include G ⁺ described below.

In the group (1-d), A and B each independently represent a monovalent group which is an atomic group capable of forming a dye. When constituting the group shown in the above (1-d), A and B may be the same or different. A and B can be selected from any monovalent group, but a group having an electron-withdrawing property with respect to the carbon atom to which A and B are bonded is preferably used.

Examples of A and B include an acyl group, a benzoyl group, an aromatic ring group, a heterocyclic group, a sulfonyl group, a cyano group, a nitro group, and the like. These may further have a substituent. Often, a saturated or unsaturated fused ring may be formed.

In the general formula (1), Y represents an oxygen atom, a sulfur atom, or a nitrogen atom, and n represents an integer of 1 to 4. When n is plural, that is, when Y is plural, all of the plural Y may be the same atom or different atoms.

In the general formula (1), X is a saturated or unsaturated heterocyclic ring containing two S (sulfur atoms), Y is
represents a group capable of simultaneously forming a saturated or unsaturated, optionally substituted heterocyclic ring containing n.
Or groups of three or more are preferred.

More specifically, X represents a 5- or 6-membered heterocyclic ring having a structural portion containing two sulfur atoms and a 5- or 6-membered heterocyclic ring having a structural portion containing Yn at the same time. Represents a group that can be formed, but forms a heterocycle having a structural portion containing two sulfur atoms as 5 members and a heterocycle having a structural portion containing Yn as 5 or 6 members and simultaneously forms the heterocycles. It is preferable to use a group that can be used.

The cyclic partial structure containing two S (sulfur atoms), X and Yn in the general formula (1) is preferably a structure represented by the following general formula (6) or (7).

[0067]

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[0068]

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Y and n in the general formulas (6) and (7) have the same meanings as Y and n in the general formula (1). In the general formulas (6) and (7), when the ring is an unsaturated ring, the position of the unsaturated bond is determined by the type and position of Y and n.

The following examples can be given as examples of the heterocyclic structure containing Yn. That is, furan nucleus, thiophene nucleus, pyrrole nucleus, pyrazole nucleus, imidazole nucleus, thiazole nucleus, oxazole nucleus, isoxazole nucleus, oxadiazole nucleus, thiadiazole nucleus, succinimide nucleus, fumaric imide nucleus, sulfosuccinimide nucleus, Sulfofumaric imide nucleus, pyrroline nucleus, thiazoline nucleus, pyrrolidine nucleus, tetrahydrofuran nucleus, tetrahydrothiophene nucleus, imidazoline nucleus, quinoxaline nucleus, acridine nucleus, indole nucleus, pyridine nucleus, pyrimidine nucleus, pyrazine nucleus, piperidine nucleus, piperazine nucleus, morpholine nucleus , Pyridazine nucleus, quinoline nucleus, isoquinoline nucleus, coumarin nucleus, chromone nucleus, chroman nucleus and the like.

The cyclic partial structure containing Yn in the general formulas (6) and (7) may further have a substituent. Examples of the substituent include the specific examples described for the substituent of the 5- or 6-membered heterocyclic ring in Q in the general formula (1). Among such substituents, an alkoxycarbonyl group, a carbamoyl group,
An electron-withdrawing group such as a sulfo group, a cyano group, a halogen atom, and an alkylsulfonyl group is preferable.

In the general formula (1), L ¹ and L ² each independently represent a methine group which may have a substituent. An unsubstituted methine group is preferably used. When L ¹ and L ² represent a methine group having a substituent, examples of the substituent include:
Substituted amino group (for example, amino group, alkylamino group,
Dialkylamino group, arylamino group, diarylamino group, acylamino group, etc., substituted oxy group (for example, hydroxy group, alkoxy group, acyloxy group, aryloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, etc.), substitution Examples include a mercapto group (eg, an alkylmercapto group, an arylmercapto group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, and a bromine atom), a cyano group, an alkyl group, and an aromatic group. The substituents may combine to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. Among them, a 5- or 6-membered unsaturated aliphatic ring is preferable.

In the general formula (1), m represents 0 or 1, and 0 is particularly preferable for improving the sensitivity.

Hereinafter, specific examples of the compound represented by Formula (1) (Exemplary Compounds Nos. 1 to 82) are shown, but the present invention is not limited thereto.

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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The content of the compound represented by formula (1) in the photopolymerizable composition is preferably 0.01 to 5 parts by mass with respect to 1 part by mass of a radical generator described below. 0.05 to 2 parts by mass is more preferred. If the content is less than 0.01 part by mass, the photopolymerization sensitivity may decrease, and if it exceeds 5 parts by mass, it may take time to decolor the dye component. The compound represented by the general formula (1) may be used alone or in combination of two or more.

As long as the effects of the present invention are not impaired,
For the purpose of adjusting the photosensitive wavelength, a spectral sensitizing dye other than the compound represented by the general formula (1) may be contained. As the other spectral sensitizing dye, for example, methine dye, polymethine dye, triarylmethine dye, indoline dye, azine dye, xanthene dye, cyanine dye, hemicyanine dye, rhodamine dye, azomethine dye, azo dye, oxonol dye, Merocyanine dyes,
Known dyes such as an oxazine dye, an acridine dye, and a coumarin dye are exemplified.

As described above, by containing the compound represented by the general formula (1), the photopolymerization sensitivity of the photopolymerizable composition can be improved, and not only ultraviolet light but also visible light to red light can be improved. High sensitivity to external light can be achieved. Moreover, the compound represented by the general formula (1) itself has high decomposability by light and is excellent in decoloring property, and can sufficiently decolor without requiring a long time. Therefore, as described later, even when used for a recording material of a completely dry processing system that does not use a developer or the like, coloring of a non-image portion (background portion) of a formed image is reduced, and a clear and high-contrast image is obtained. Can be formed.

(Compound capable of generating a radical or a cation) In the photopolymerizable composition of the present invention, a radical is generated by interacting with the compound (spectral sensitizing dye) represented by the general formula (1). The resulting compound (hereinafter sometimes referred to as "radical generator") and the compound capable of generating a cation by interacting with the compound represented by formula (1) (hereinafter sometimes referred to as "cation generator"). .) (Hereinafter sometimes referred to as "radical or cation generator" including both of them). The radical or cation generator includes one that generates at least one of a radical and a cation and generates both. The radical or cation generator interacts with the generator when a spectral sensitizing dye (such as a compound represented by the general formula (1)) present in the vicinity thereof absorbs light, and efficiently reacts with the radical or cation generator. It has a function of generating a cation and initiating a polymerization reaction of a nearby polymerizable compound.
Therefore, by coexisting the generator with a spectral sensitizing dye, it is possible to achieve high sensitivity by sensitively irradiating light in the spectral absorption wavelength region, and to use any light source in the visible light to infrared light region. To control the generation of radicals or cations.

Of the above, a radical generator is preferred from the viewpoint of polymerization sensitivity. As the radical generator, one or more kinds can be selected and used from radical generators capable of initiating polymerization of a polymerizable compound contained in the photopolymerizable composition. For example, the following compounds are included.

Benzophenone, camphorquinone, 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 Bisacylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, acylphosphine oxides such as Lucirin TPO, α-hydroxy or α-aminoacetophenones, α-hydroxycycloalkylphenylketone , Aromatic ketones such as dialkoxyacetophenones;

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 dimer, 2- (o-chlorophenyl) ) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- Diphenylimidazole dimer, 2-
2,4,6-triarylimidazole dimers such as (p-methoxyphenyl) -4,5-diphenylimidazole dimer, and other U.S. Patent Nos. 3,784,557 and 42.
Nos. 52887, 4311783, 4459349
Nos. 4,410,621 and 4,622,286;

Polyhalogen compounds such as carbon tetrabromide, phenyltribromomethylsulfone and phenyltrichloromethylketone; JP-A-59-133428, JP-B-57
No.-1819, JP-B-57-6096, U.S. Pat.
A compound described in 615455;

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

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

Azinium salts described in US Pat. No. 4,743,530; organoboron compounds; phenylglyoxalic esters such as phenylglyoxalic acid methyl ester; bis (η ⁵ -2-4-cyclopentadien-1-yl) ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like; η ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluoro Iron allene complexes such as phosphate (1-); iodonium salts such as diaryliodonium salts such as diphenyliodonium salts; and sulfonium salts such as triarylsulfonium salts such as triphenylsulfonium salts.

For more detailed examples of the above radical generators and examples of other types of radical generators, see paragraph [0067] of JP-A-10-45816.
To [0132]. Further, among the above radical generators, sulfonium salts, iodonium salts, iron allene complexes, and the like are known to be compounds that generate radicals and also generate cations.

As the radical generator, a material composed of a combination of two or more compounds can 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 (trichloromethyl) -6- (4'-methoxyphenyl) -triazole, dialkylaminobenzoate 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.

In the case of a radical generator obtained by combining two or more kinds, 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.

Of the above radical generators,
In terms of being able to generate radicals effectively by interacting with the dye and increasing the sensitivity, an organic boron compound, an iodonium salt, a sulfonium salt, an iron allene complex, an S-triazine derivative having a trihalogen-substituted methyl group, Organic peroxides, titanocene, 2,4,5-triarylimidazole dimer, or azinium salts are preferred, and organic boron compounds are particularly preferred. The organoboron compound is
Even when a spectral sensitizing dye is used as the spectral sensitizing compound, it is preferable in that the coexisting spectral sensitizing dye can be satisfactorily decolored when the image is fixed by light irradiation. The organic boron compound may be used in combination with the above-mentioned radical generator.

Examples of the organoboron compound include a compound represented by the following general formula (A) and “Functional dye chemistry”.
(1981, CMC Publishing Co., pp. 393 to 416), and a spectral sensitizer having a cationic dye described in “Coloring Material” (60 [4] 212-224 (1987)) as a cation moiety in the structure. Dye-sensitive organic boron compounds are also included. As the above-mentioned spectral sensitizing dye-based organic boron compound,
Compounds described in JP-A-2-143044, JP-A-1-138204, JP-A-6-505287, JP-A-4-261406 and the like can be mentioned.

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

Among the organoboron compounds, compounds represented by the following general formula (A) are particularly preferred.

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[0105] In the general formula ^{_{(A), R a 1,}} R a 2, R a 3 , and R
_a ⁴ is each independently an aliphatic group, an aromatic group, a heterocyclic group,
Or an ^{_{Si (R a 5) (R}} a 6) -R a 7. If R _a ¹ ~R _a ⁴ represents an aliphatic group, as the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, substituted alkynyl group, an aralkyl group,
Or a substituted aralkyl group, among which an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable,
Alkyl groups and substituted alkyl groups are particularly preferred. Further, the aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

Examples of the alkyl group include linear, branched and cyclic alkyl groups. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkyl portion of the substituted alkyl group is the same as in the case of the alkyl group. The alkyl group may be a substituted alkyl group or an unsubstituted alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, neopentyl, isopropyl, isobutyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, A dodecyl group, an octadecyl group and the like.

Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, , A methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group), an alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylaminosulfonyl group having 30 or less carbon atoms, An alkoxy group having 30 or less carbon atoms (eg, a methoxy group, an ethoxy group, a benzyloxy group, a phenethyloxy group, etc.) and an alkylthio group having 30 or less carbon atoms (eg,
A methylthio group, an ethylthio group, a methylthioethylthioethyl group, etc., an aryloxy group having 30 or less carbon atoms (eg, a phenoxy group, a p-tolyloxy group, a 1-naphthoxy group, a 2-naphthoxy group, etc.), a nitro group, a carbon number 30 or less alkyl groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups,

Acyloxy groups having 30 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), acyl groups having 30 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl groups (eg, carbamoyl group) Group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group,
An N, N-dimethylsulfamoyl group, a morpholinosulfonyl group, a piperidinosulfonyl group, etc., an aryl group having 30 or less carbon atoms (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) And the like, a substituted amino group (for example, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an acylamino group, etc.), a substituted ureido group, a substituted phosphono group, a heterocyclic group and the like. Here, the carboxyl group, sulfo group, hydroxy group, and phosphono group may be in a salt state. At that time, examples of the cation forming a salt include G ⁺ described below.

Examples of the alkenyl group include linear, branched and cyclic alkenyl groups, and the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkenyl portion of the substituted alkenyl group is the same as in the case of the alkenyl group. The alkenyl group may be a substituted alkenyl group or an unsubstituted alkenyl group. Examples of the substituent of the substituted alkenyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the alkynyl group include linear, branched and cyclic alkynyl groups. The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms. The preferred range of the number of carbon atoms in the alkynyl portion of the substituted alkynyl group is the same as in the case of the alkynyl group. Further, the alkynyl group may be either an alkynyl group having a substituent or an unsubstituted alkynyl group. Examples of the substituent of the substituted alkynyl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

Examples of the aralkyl group include linear, branched and cyclic aralkyl groups. The aralkyl group preferably has 7 to 35 carbon atoms, more preferably 7 to 25 carbon atoms. The preferred range of the number of carbon atoms in the aralkyl portion of the substituted aralkyl group is the same as in the case of the aralkyl group. Further, the aralkyl group may be any of an aralkyl group having a substituent and an unsubstituted aralkyl group. Examples of the substituent of the substituted aralkyl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

[0112] The case where R _a ¹ ~R _a ⁴ represents an aromatic group an alkyl group, as the aromatic group, for example, an aryl group, and a substituted aryl group. The number of carbon atoms in the aryl group is preferably from 6 to 30, and more preferably from 6 to 20. The preferred range of the number of carbon atoms in the aryl portion of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, and a β-naphthyl group. Examples of the substituent of the substituted aryl group include the same substituents as in the case of the above-mentioned substituted alkyl group.

[0113] If R _a ¹ ~R _a ⁴ represents a heterocyclic group, the heterocyclic group, a heterocyclic group having a substituent, an unsubstituted heterocyclic group. Examples of the substituent of the heterocyclic group having a substituent group, include the same substituents as substituents exemplified in the case where R _a ¹ ~R _a ⁴ represents an aryl group having a substituent. Among them, as the heterocyclic group represented by R _a ¹ ~R _a ^4, a furan ring,
A heterocyclic group containing a nitrogen atom, a sulfur atom, or an oxygen atom such as a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyridine ring is preferable.

[0114] If R _a ¹ ~R _a ⁴ represents ^{_{-Si (R a 5) (R}} a 6) -R a 7, R a 5, R a 6 and R _a ^7, is an aliphatic independently Represents an aromatic group. The aliphatic group and the aromatic group are represented by R
_a ¹ to R _a ⁴ each represents an aliphatic group are each synonymous with aromatic group,
Preferred examples are also the same.

[0115] In the general formula ^{_{(A), R a 1,}} R a 2, R a 3,
And 2 or more of R _a ⁴ is connected directly or via a substituent, may form a ring. When forming a ring,
As the ring, any ring selected from the following rings (C1) to (C3) is preferable, and among them, the ring (C2) is preferable.

[0116]

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In the ring in the above (C1), R
_b represents a divalent group shown below.

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[0118] Among the above general formula (A) an organic boron compound represented by the terms of the R _a ¹ to R preferably has at least one of alkyl groups of _a ^4, improvement in sensitivity and preservability And a triarylalkyl-type organoboron compound in which one is an alkyl group and the other three are aryl groups are more preferred. In particular, a triarylalkyl-type organoboron compound in which an aryl group is substituted with an electron-withdrawing group is preferable. In particular, the sum of Hammet (σ) values of the substituents (electron-withdrawing groups) on three aryl groups is +0. 36
~ +2.58 is more preferable. As the electron-withdrawing group, a halogen atom and a trifluoromethyl group are preferable, and a fluorine atom and a chlorine atom are more preferable.

The aryl group substituted by the electron-withdrawing group includes 3-fluorophenyl group, 4-fluorophenyl group, 2-fluorophenyl group, 3-chlorophenyl group,
4-chlorophenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-difluorophenyl group, 4-bromophenyl group, 3,4-
Examples include a difluorophenyl group, a 5-fluoro-2-methylphenyl group, a 5-fluoro-4-methylphenyl group, a 5-chloro-2-methylphenyl group, and a 5-chloro-4-methylphenyl group.

The anion part of the general formula (A) includes
For example, tetramethyl borate, tetraethyl borate, tetrabutyl borate, triisobutyl methyl borate, di-n-butyl-di-t-butyl borate, tri-m-chlorophenyl-n-hexyl borate, triphenyl methyl borate, triphenyl ethyl Borate,
Triphenylpropyl borate, triphenyl-n-butyl borate, trimesityl butyl borate, tolyl isopropyl borate, triphenyl benzyl borate, tetra-m-fluorobenzyl borate, triphenyl phenethyl borate, triphenyl-p-chlorobenzyl borate, Triphenylethenylbutyl borate, di (α-naphthyl) -dipropyl borate, triphenylsilyltriphenylborate, tritolylsilyltriphenylborate, tri-n-butyl (dimethylphenylsilyl) borate, diphenyldihexylborate, tri- m-fluorophenylhexyl borate,
Tri (5-chloro-4-methylphenyl) hexyl borate, tri-m-fluorophenylcyclohexyl borate, tri- (5-fluoro-2-methylphenyl) hexyl borate and the like can be mentioned.

[0121] represents a radical in the general formula (A), G ⁺ is capable of forming a cation. Among them, an organic cationic compound, a transition metal coordination complex cation (such as the compound described in Japanese Patent No. 2991143), or a metal cation (for example, Na ⁺ ,
K ⁺ , Li ⁺ , Ag ⁺ , Fe ²⁺ , Fe ³⁺ , Cu ⁺ , Cu ²⁺ ,
Zn ²⁺ , Al ³⁺ , 1 / 2Ca ²⁺ ) are preferable. Examples of the organic cationic compound include a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, an iodonium cation, a sulfonium cation, and a dye cation.

The quaternary ammonium cations include
Examples include a tetraalkylammonium cation (for example, tetramethylammonium cation, tetrabutylammonium cation) and a tetraarylammonium cation (for example, tetraphenylammonium cation). As the quaternary pyridinium cation,
N-alkylpyridinium cations (eg, N-methylpyridinium cations), N-arylpyridinium cations (eg, N-phenylpyridinium cations), N-alkoxypyridinium cations (eg,
4-phenyl-N-methoxy-pyridinium cation), N-benzoylpyridinium cation and the like. Examples of the quaternary quinolinium cation include an N-alkyl quinolinium cation (for example, N-methyl quinolinium cation) and an N-aryl quinolinium cation (for example, N-phenyl quinolinium cation). Can be Examples of the phosphonium cation include a tetraarylphosphonium cation (eg, a tetraphenylphosphonium cation). Examples of the iodonium cation include a diaryliodonium cation (for example, a diphenyliodonium cation). Examples of the sulfonium cation include a triarylsulfonium cation (for example, a triphenylsulfonium cation).

Further, as specific examples of the above G ⁺ , paragraphs [0020] to [00] of JP-A-9-188686.
38].

In each cationic compound (exemplary compound) exemplified above, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group,
An ethyl group, a propyl group, an isopropyl group, a butyl group, or an unsubstituted alkyl group such as hexyl group, the substituted alkyl group represented by R _a ¹ ~R _a ⁴ are preferred. Among them, particularly, having 1 to 1 carbon atoms
Twelve alkyl groups are preferred. In each of the cationic compounds exemplified above, the aryl group is
For example, a phenyl group, a phenyl group substituted with a halogen atom (eg, a chlorine atom), a phenyl group substituted with an alkyl (eg, a methyl group), and a phenyl group substituted with an alkoxy (eg, a methoxy group) are preferable.

Specific examples of the organoboron compound represented by the general formula (A) include US Pat. No. 3,567,453.
No. 4,343,891, JP-A-62
JP-A-143044, JP-A-62-150242, JP-A-9-188684, JP-A-9-188
No. 685, JP-A-9-188686, JP-A-9-188710, JP-B8-9643,
The compounds described in JP-A-11-269210 and the compounds exemplified below are exemplified. The organic boron compound may be used in combination with a radical generator described below.
However, the organic boron compound used in the present invention is not limited to this.

[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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The content of the radical or cation generator in the photopolymerizable composition is preferably 0.01 to 20% by mass based on the content of the polymerizable compound.
0.1-10 mass% is more preferable. However, the preferred range varies depending on the type of the “polymerizable compound having an ethylenically unsaturated bond” used in combination, and is not limited thereto.

(Other components) The photopolymerizable composition of the present invention may contain known additives appropriately selected as other components according to the purpose, as long as the effects are not impaired. Examples of the other components include, for example, a photopolymerization initiator, an oxygen scavenger, a thermal polymerization inhibitor, an ultraviolet absorber, a fluorescent brightener, a chain transfer agent, an antioxidant, and the like, and precursors thereof. These are preferably added in an amount of 0.01 to 20% by mass, more preferably 0.2 to 15% by mass, based on the total weight of the photopolymerizable composition,
It is particularly preferable to add 0.5 to 10% by mass.

Specific examples of the additives such as the chain transfer agent and the antioxidant include paragraphs [0135] to [0141] of JP-A-10-45816 and JP-A-9-188686.
Paragraphs [0087] to [0096] of Japanese Patent Application Laid-Open No.
182621, paragraphs [0079] to [011]
8], paragraph [0080] of JP-A-9-95487
To [0089], and JP-A-1-1314.
No. 0, No. 1-1141, No. 1-1143, No. 1
No. -13144, No. 1-107048, No. 1-2290
No. 03, No. 1-298348, No. 10-138338
And compounds described in JP-A-11-269210, JP-A-2-187762, and the like.

The photopolymerizable composition of the present invention may contain a binder. In particular, it is convenient when the photopolymerizable composition is a liquid or a viscous substance. The content of the binder is preferably from 5 to 95% by mass, more preferably from 10 to 90% by mass, and more preferably from 15 to 90% by mass, based on the total solid content.
~ 85% by weight is most preferred. The choice of the binder is
This is done depending on the field of application and the properties required for that field, such as developing ability in aqueous or organic solvent systems, adhesion to substrates and sensitivity to oxygen.

As the binder, about 5000 to 20
Polymers having a molecular weight of 00000, preferably 10,000 to 1,000,000 are desirable. For example, acrylate and methacrylate homo or copolymers (eg, methyl methacrylate / ethyl acrylate / methacrylic acid copolymers, poly (alkyl methacrylate), poly (alkyl acrylate), etc.), cellulose esters or cellulose ethers (eg, cellulose acetate, cellulose) Acetobutyrate, methylcellulose, ethylcellulose, etc.), polyvinyl butyral,
Polyvinyl formal, cyclized rubber, polyether (for example, polyethylene oxide, polypropylene oxide,
Polytetrahydrofuran), polystyrene, polycarbonate, polyurethane, chlorinated polyolefin, polyvinyl chloride, vinyl chloride / vinylidene copolymer, copolymer of vinylidene chloride and acrylonitrile, methyl methacrylate, vinyl acetate, polyvinyl acetate, copoly (ethylene / vinyl acetate), poly Examples include caprolactam, poly (hexamethylene adipamide), polyester (for example, poly (ethylene glycol terephthalate), poly (hexamethylene glycol succinate), etc.), polyamide, and polyurea.

Further, water-soluble polymers such as gelatins, (modified) polyvinyl alcohol, polyvinylpyrrolidone, styrene-maleic acid copolymer hydrolysate, sodium polystyrene sulfonate, sodium alginate and the like can also be mentioned.
Further, latexes such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, and methyl acrylate-butadiene rubber latex may be used.

Unsaturated compounds can also be used as a mixture with non-photopolymerizable film-forming components, for example, physically dried polymers or polymer solutions in organic solvents, such as nitrocellulose or cellulose acetate. Butyrate. But they are chemically
And / or a thermosetting (thermosetting) resin, for example,
Polyisocyanate, polyepoxide, melamine resin,
In addition, it may be a polyimide precursor. The simultaneous use of thermosetting resins is important for use in systems known as hybrid systems which are photopolymerized in a first step and crosslinked by a thermal post-treatment in a second step. Also, a binder having a polymerizable group can be used.

Other examples of the additives include those described in
-269210.

The light source that can be used for imagewise exposure can be appropriately selected from known light sources having a light source wavelength in the visible to infrared region, and among them, a light source having a maximum absorption wavelength of 300 to 1000 nm. A light source is preferable, and a (semiconductor) laser light source of blue, green, red, or the like or an LED is more preferable from the viewpoint of simple and compact device and low cost. In order to obtain higher sensitivity, it is preferable to appropriately select a light source having a wavelength suitable for the absorption wavelength of a light absorbing material such as a spectral sensitizing dye. On the other hand, as the light source that can be used for decoloring the photopolymerizable composition and the recording material described below, it is more preferable to appropriately select a light source having a wavelength suitable for the absorption wavelength of the photopolymerizable composition. . Specifically, mercury lamps, ultra-high pressure mercury lamps, electrodeless discharge mercury lamps, xenon lamps, tungsten lamps, metal halide lamps, (semiconductors)
A wide range of light sources, such as a laser light source, an LED, and a fluorescent lamp, are preferably mentioned.

As described above, by using the compound represented by the general formula (1) as the spectral sensitizing dye, an image can be formed with high sensitivity not only when using ultraviolet light but also when using visible light to infrared light. Since the compound itself can be formed and the compound itself has excellent color erasing properties, an image without residual color due to the dye component can be obtained.

<Recording Material> The recording material of the present invention comprises a recording layer on a support, and the recording layer comprises a color-forming component A
And at least a color-forming component B having a site to be colored by reacting with the color-forming component A, and the above-described photopolymerizable composition of the present invention. It may have another layer such as a layer, a light absorbing layer, a protective layer, and a back coat layer.

The basic configuration of the recording material of the present invention is not particularly limited, and the recording material can be appropriately configured according to the purpose. As a basic embodiment, for example, image formation in the case where the recording material of the present invention is applied to a positive-type photosensitive and heat-sensitive recording material in which a color-forming component A is encapsulated in a thermoresponsive microcapsule is shown as an example. That is, in the positive-type photosensitive and heat-sensitive recording material of the present embodiment, when light is irradiated imagewise, radicals are generated from a radical generator contained in the photopolymerizable composition in the light-irradiated portion, and polymerization of the polymerizable compound is performed. The reaction is initiated and cured, fixing the photopolymerizable composition in place and forming a latent image. The microcapsules are impermeable to substances at normal temperature, and do not come into contact with the color-forming component A contained in the microcapsules and the color-forming component B having a site in the molecule that reacts with the color-forming component A to form a color. It is in a colored state.

Thereafter, when heat is applied to the entire surface of the light- and heat-sensitive recording material, the microcapsules shift to a material-permeable state, and the color-forming component B in the non-light-irradiated portion penetrates into the microcapsules (and / or the color-forming component). A is released outside the microcapsule), and the color forming components A and B react with each other to form a color only in the non-light-irradiated portion. On the other hand, in the light irradiating section, the photopolymerizable composition is in a cured and fixed state by a polymerization reaction, so that the coloring components A and B are both immobilized and cannot contact,
No color develops in the light-irradiated part. Thereafter, by exposing the photosensitive and heat-sensitive recording material over the entire surface, the unpolymerized region is also polymerized (fixed), and the dye component contained in the photopolymerizable composition can be decolorized.

The recording material of the present invention may be a recording material of the following modes (first and second modes).
The image forming method can be appropriately selected according to each mode. That is, the recording material of the first embodiment is an embodiment in which at least one of the polymerizable compounds contained in the photopolymerizable composition is the color forming component B itself, and the recording layer is formed of the color forming component A.
And at least a photopolymerizable composition of the present invention containing a coloring component B for coloring the coloring component A. Here, when the positive-type photosensitive and heat-sensitive recording material of the above-described basic mode is applied to the example, as described above, the color forming component B has a site for forming the color forming component A and also has an ethylenically unsaturated bond. When light is irradiated imagewise, the color-forming component B starts a polymerization reaction and cures, and the color-forming component B is fixed in place to form a latent image. Therefore, in the light irradiation part, the coloring component B is immobilized and cannot contact with the coloring component A, and the light irradiation part does not develop color.

The recording material according to the second aspect of the present invention is characterized in that the recording layer comprises a coloring component A, a coloring component B which reacts with the coloring component A to form a color, and the photopolymerizable composition of the present invention. And the polymerizable compound having an ethylenically unsaturated bond (polymerizable compound) contained in the photopolymerizable composition contains the color-forming component A and the color-forming component B in the same molecule.
This is an embodiment in which the compound is a color-suppressing compound having a site that inhibits a reaction with a compound (reaction inhibiting site).

The image formation in the case where the recording material of the second embodiment is applied to a negative-type photosensitive and heat-sensitive recording material in which the color-forming component A is encapsulated in thermoresponsive microcapsules will be described below as an example. In the negative-type photosensitive and heat-sensitive recording material of this embodiment, as in the first embodiment, the microcapsules are impermeable to substances at room temperature, do not come into contact with the color forming components A and B, and are in a non-colored state. . When the light and heat sensitive recording material is irradiated with light in an image-like manner, a polymerization reaction of the polymerizable compound in the light irradiated portion starts and cures, and the polymerizable compound is fixed in place and a latent image is formed. . Thereafter, when heat is applied to the entire surface of the light- and heat-sensitive recording material, the microcapsules are transferred to a material-permeable state, and the coloring component B penetrates into the microcapsules (and / or the coloring component A is released outside the microcapsules). However, at the same time, in the non-light-irradiated portion, the polymerizable compound also permeates into the microcapsules as a color-suppressing compound, and the color-forming reaction between color-forming components A and B is suppressed. Therefore, the non-light irradiation part is maintained in a non-colored state. On the other hand, a polymerizable compound (a color-suppressing compound) in the light irradiation part
Is fixed in place by the polymerization reaction, so that the color development reaction proceeds irrespective of the reaction between the color forming components A and B, and the color is formed only in the light irradiation part. Thereafter, the dye contained in the photopolymerizable composition can be decolorized by exposing the entire photosensitive and heat-sensitive recording material to light.

As the light source used for image formation with the recording material of the present invention, the same light sources as those usable for exposure of the photopolymerizable composition of the present invention can be used. Hereinafter, constituent components used in the recording material of the present invention will be described.

(Photopolymerizable composition) The photopolymerizable composition contains at least 1) a polymerizable compound and 2) a compound represented by the general formula (1) (a decolorizable spectral sensitizing dye). If necessary, 3) a compound capable of generating a radical or a cation by interacting with the dye of the above 2) (radical or cation generator), and 4) other components. Specifically, the recording material of the present invention preferably includes the photopolymerizable composition of the present invention described above, and preferably includes the above-described item 3). When the photopolymerizable composition is irradiated with light, the spectral sensitizing dye absorbs light and interacts with the radical generator, and the radical generator generates a radical. The radicals cause the polymerizable compound to undergo radical polymerization and cure to form an image.

For details of the polymerizable compound,
As described above, a plurality of types can be contained in the photopolymerizable composition. Like the recording material of the first aspect,
At least one of them may be a coloring component B having a site for coloring the coloring component A. In this case, a coloring component having an ethylenically unsaturated bond (polymerizable group) in the same molecule is used as described later. . On the other hand, as in the recording material of the second embodiment, the polymerizable compound may also serve as a color-suppressing compound, and the color-forming component A and the color-forming component A are contained in the same molecule. Coloring component B to be colored
A polymerizable compound having a site that suppresses the reaction with is used. These polymerizable compounds will be described later together with the coloring components (A and B) contained in the recording layer.

The content of the photopolymerizable composition in the recording layer is preferably from 0.1 to 50 g / m ² ,
-30 g / m < ² > is more preferable.

(Coloring Component) In the recording material of the present invention, the recording layer contains the coloring component A and the coloring component B as a coloring source together with the photopolymerizable composition. In the case of the recording material of the first embodiment, the coloring component A is contained together with the photopolymerizable composition, and the coloring component B contained as a polymerizable compound on the photopolymerizable composition side is the same as the coloring component A. Reacts and develops color. Coloring component A as a color source constituting image part
And the color-forming component B are as follows:
(T) combinations. In addition, the following combination
The coloring component A and the coloring component B are shown in this order.

(A) Combination of an electron donating dye precursor and an electron accepting compound. (A) A combination of a diazo 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) Combination of pigment precursor and acid or base (combination formed by pigment). (T) Combination of an oxidized precursor of a paraphenylenediamine derivative or a paraaminophenol derivative with a coupling component (coupler compound).

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 diazo compound and a coupling component (hereinafter, appropriately referred to as a “coupler compound”). ).
(C) Combination of a protected dye (or leuco dye) precursor and a deprotecting agent, and (T) Combination of an oxidized precursor of a paraphenylenediamine derivative or a paraaminophenol derivative with a coupling component (coupler compound) Is preferred. That is, the color-forming component A is preferably an electron-donating dye precursor, a diazo compound, a dye precursor or an oxidant precursor, and the color-forming component B is preferably an electron-accepting compound, a coupler compound or a deprotecting agent.

When an electron-donating colorless dye precursor is used as the color-forming component A, the electron-donating colorless dye precursor includes:
Known phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, known in heat-sensitive papers and pressure-sensitive papers, Various compounds such as spiropyran compounds, pyridine compounds, pyrazine compounds, and fluorene compounds can be given.

Examples of the phthalide-based 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-diethylaminophenyl) phthalide, 3,3-bis (2-methyl-1-octylindol-3-yl) phthalide, 3- (4-dipropylamino-2-acetylaminophenyl)- 3- (2-methyl-
1-octylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-octylindole-3
-Yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-
Diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,3-bis (4-diethylamino-2-butyloxyphenyl) -4-azaphthalide, 3- (4-diethylamino-2-butyloxyphenyl) -3- (2
-Methyl-1-pentylindol-3-yl) -4-
Azaphthalide 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 3959, 571, specifically, 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
-Methyl-6-N-ethyl-N-isobutylaminofluoran, 2-anilino-6-dibutylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-
Tetrahydrofurfurylaminofluoran and the like.

Examples of the thiazine-based compound include benzoyl leucon methylene blue, p-nitrobenzyl leucomethylene blue and the like. Examples of leuco auramine compounds include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like. . Examples of rhodamine lactam compounds include rhodamine-B-anilinolactam and rhodamine- (p-nitrino) lactam.

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

Examples of the pyridine and pyrazine compounds include those described in US Pat. Nos. 3,775,424, 3,853,869, and 4,246,318. Examples of the fluorene-based compound include compounds described in Japanese Patent Application No. 61-240989.

As the dye precursors for developing cyan, magenta and yellow, the dye precursors described in US Pat. No. 4,800,149 can be used. Further, as an electron donating dye precursor for a yellow coloring dye, US Pat. Nos. 4,800,148 and 51,623.
No. 3, JP-B-7-88105 and the like. Dye precursors described in JP-A-63-53542 can be used as electron-donating dye precursors for cyan coloring dyes. Can also be used.

When the above-mentioned electron-donating dye precursor is used,
An electron-accepting compound is used as a coloring component B for coloring the electron-donating dye precursor. Examples of the electron-accepting compound include phenol derivatives, which are known from heat-sensitive paper and pressure-sensitive paper.
Examples thereof include salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolak resins, metal-treated novolak resins, and electron accepting compounds such as metal complexes.
Specifically, Japanese Patent Publication No. 40-9309, Japanese Patent Publication No. 45-1
No. 4039, JP-A-52-140483, JP-A-48
JP-A-51510, JP-A-57-210886, JP-A-58-87089, JP-A-59-11286, JP-A-60-176775, and JP-A-61-95988.

Of the above, for example, phenol derivatives include 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (3-chloro-4-hydroxyphenyl) cyclohexane, and 4-hydroxyphenyl-4 '
-Isopropyloxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, α, α'-
Bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, benzyl p-hydroxybenzoate and the like can be mentioned.

Examples of the salicylic acid derivatives include 4-pentadecyl salicylic 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, etc., and zinc and aluminum thereof , Calcium, copper salts and the like.

In the recording material of the first embodiment, the color-forming component B also functions as a polymerizable compound having an ethylenically unsaturated bond. Therefore, at least one of the polymerizable compounds of the recording material of the first embodiment is an electron-accepting compound, and in the molecule, an electron-accepting group and an ethylenically unsaturated bond (hereinafter, referred to as “polymerizable group”) .). As the coloring component B in this case, for example,
3-halo-4-hydroxybenzoic acid described in JP-A-226455, methacryloxyethyl ester, acryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-63-173682, and 59-83693.
Nos. 60-141587 and 62-99190, esters of hydroxymethyl-containing benzoic acid and hydroxymethylstyrene, hydroxystyrenes described in EP 29323, JP-A-62-167077,
Compounds which can be synthesized with reference to the N-vinylimidazole complex of zinc halide described in JP-A-62-16708 and the electron-accepting compound described in JP-A-63-317558.

Of these compounds having an electron-accepting group and a polymerizable group in the same molecule, the compounds represented by the following general formula
-Halo-4-hydroxybenzoic acid is preferred.

[0168]

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 an acryloyloxyalkyl group having 5 to 11 carbon atoms or 6 to 6 carbon atoms is preferable. Twelve methacryloyloxyalkyl groups are more preferred. Z represents a hydrogen atom, an alkyl group or an alkoxy group.

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

3-chloro-4-hydroxybenzoic acid
(4-acryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (4-methacryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (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.

Further, for example, styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, β-
Zinc methacryloxyethoxysalicylate, zinc 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) can also be suitably mentioned.

In the case where an electron-donating dye precursor is used as the color-forming component A and an electron-accepting compound is used as the color-forming component B, the content of the electron-donating dye precursor in the recording layer is from 0.05 to 0.05%. 5 g / m ² is preferred,
1-3 g / m < ² > is more preferable. The amount of the electron accepting compound used is preferably 0.5 to 20 parts by mass, and more preferably 3 to 20 parts by mass, based on 1 part by mass of the electron donating colorless dye used.
-10 parts by mass is more preferred. If the amount is less than 0.5 part by mass, it may not be possible to obtain a sufficient color density, and if it exceeds 20 parts by mass, the sensitivity may be lowered or the suitability for coating may be deteriorated.

On the other hand, when a diazo compound is used as the coloring component A, it is preferable to use a compound represented by the following formula. Ar—N ₂ ⁺ · Y ⁻ [wherein, Ar represents an aromatic ring group, and Y ⁻ represents an acid anion. ]

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

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

Examples of the diazo compound that can be suitably used as the coloring component A include the diazo compounds exemplified in paragraphs 44 to 49 of JP-A-7-276808. However, the present invention is not limited to these compounds.

The maximum absorption wavelength λ _max of the diazo compound is preferably 450 nm or less from the viewpoint of the effect, and more preferably 290 to 440 nm. Further, the diazo compound has 12 or more carbon atoms,
It is desirable that the solubility in water is 1% or less and the solubility in ethyl acetate is 5% or more. The diazo compound as the coloring component A may be used alone or in combination of two or more depending on various purposes such as hue adjustment.

When the diazo compound is used, a coupler compound (having no polymerizable group) may be used as the coloring component B.
Alternatively, a coupler compound having a polymerizable group is used. The two coupler compounds couple with a diazo compound in a basic atmosphere and / or a neutral atmosphere to form a dye, and a plurality of types can be used in combination according to various purposes such as hue adjustment. . Specific examples of the coupler compound having a polymerizable group include a so-called active methylene compound having a methylene group next to a carbonyl group, a phenol derivative, a naphthol derivative, an azole derivative, and a heterocyclic fused azole derivative. These are appropriately selected and used within a range that meets the purpose of the present invention.

Examples of the coupler skeleton compound (coupler) in the coupler compound having a polymerizable group include a so-called active methylene compound having a methylene group next to a carbonyl group, a phenol derivative, a naphthol derivative, an azole derivative, and a hetero-fused azole derivative. It is preferable to use a coupler of Specifically, resorcin, phloroglucin, 2,3-dihydroxynaphthalene, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1
-Hydroxy-2-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthalenesulfonic acid sodium salt, 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-disulfonic acid, 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- (pivaloylacetamidemethyl) benzene, benzoylacetonitrile, thenoylacetonitrile, acetoacetanilide, benzoylacetanilide, pivaloyl Acetanilide, 2-chloro-5- (Nn-butylsulfamoyl) -1-pivaloylacetamidebenzene, 1
-(2-ethylhexyloxypropyl) -3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridin-2-one, 1- (dodecyloxypropyl) -3
-Acetyl-4-methyl-6-hydroxy-1,2-dihydropyridin-2-one, 1- (4-n-octyloxyphenyl) -3-tert-butyl-5-aminopyrazole and the like.

The details of the coupler compound are described in JP-A No. 4-20.
No. 1483, Japanese Unexamined Patent Publication No. 7-223267, Japanese Unexamined Patent Publication No. 7-2
23368, JP-A-7-323660, JP-A5-
278608, JP-A-5-297024, JP-A-6-297
-18669, JP-A-6-18670, JP-A-7-
No. 316280, JP-A-9-216468, JP-A-9-216468
JP-216469, JP-A-9-319025, JP-A-10-03513, JP-A-10-193801,
Reference can also be made to those described in JP-A-10-264532.

The coupler compound forms a dye by coupling with a diazo compound in a basic atmosphere and / or a neutral atmosphere, and may be used for various purposes such as hue adjustment.
A plurality of types can be used in combination.

Hereinafter, specific examples of the coupler having a polymerizable group will be shown, but the present invention is not limited thereto.

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[0192]

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[0193]

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[0194]

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[0195]

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[0196]

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[0197]

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Examples of the coupler compound having no polymerizable group include the compounds listed as the coupler skeleton compound in the coupler compound having a polymerizable group.

When a diazo compound is used as the color-forming component A and a coupler is used as the color-forming component B, the content of the diazo compound in the recording layer is preferably 0.02 to 5.0.
preferably ^{g / m 2, 0.05~3.0g / m} 2 is more preferable. If the content is less than 0.02 g / m ² , a sufficient color density may not be obtained,
If it exceeds 5.0 g / m ² , the applicability of the coating solution may be deteriorated.

The amount of the coupler compound used is 0.5 to 20 parts by mass based on 1 part by mass of the diazo compound.
A mass part is preferable and 1-10 mass parts is more preferable. If the amount is less than 0.5 part by mass, sufficient coloring properties may not be obtained, and if the amount is more than 20 parts by mass, coating suitability may be deteriorated.

The coupler compound used as the color-forming component B can be used by adding a water-soluble polymer together with other components and solid-dispersing it with a sand mill or the like. It can also be used. Here, the method of solid dispersion or emulsification is not particularly limited, and a conventionally known method can be used. For more information on these methods,
JP-A-59-190886, JP-A-2-141279
And JP-A-7-17145.

In order to promote the coupling reaction between the diazo compound and the coupler, tertiary amines, piperidines, piperazines, amidines, formamidines,
It is preferable to use an organic base such as pyridines, guanidines, and morpholines. Examples of the organic base include N, N'-bis (3-phenoxy-2-hydroxypropyl) piperazine, N, N'-bis [3- (p-methylphenoxy) -2-hydroxypropyl] piperazine, N , N'-bis [3- (p-methoxyphenoxy)
-2-hydroxypropyl] piperazine, N, N'-bis (3-phenylthio-2-hydroxypropyl) piperazine, N, N'-bis [3- (β-naphthoxy) -2
-Hydroxypropyl] piperazine, N-3- (β-naphthoxy) -2-hydroxypropyl-N′-methylpiperazine,

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

These are disclosed in JP-A-57-123086,
JP-A-60-49991, JP-A-60-94381
No., Japanese Patent Application No. 7-228731, Japanese Patent Application No. 7-23515
No. 7, Japanese Patent Application No. 7-235158, and the like.

When the above-mentioned organic base is used, an organic base having a polymerizable group may be used as the organic base. When an organic base having a polymerizable group is used for the recording material of the first embodiment, both a diazo compound and a coupler are contained in the microcapsules as the color-forming component A, and the organic base having a polymerizable group is used as the organic base. It can also function as the coloring component B. When the diazo compound and the coupler are encapsulated in the microcapsules as the color forming component A, the diazo compound and the coupler are used in a combination that does not cause a color reaction unless a base is present. Further, in the recording material of the first aspect, a diazo compound may be used as the color-forming component A, and a coupler having a polymerizable group and an organic base having a polymerizable group may be used in combination as the color-forming component B. It is.

The amount of the organic base to be used is not particularly limited, but is based on 1 mol of the diazo compound.
It is preferable to use it in the range of 1 to 30 mol.

Further, a coloring aid may be added for the purpose of accelerating the coloring reaction. Examples of the coloring aid include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, and sulfonamide compounds.

Next, the polymerizable compound used in the recording material of the second embodiment will be described. In the recording material of the second aspect, the recording layer has, as a polymerizable compound, a site for suppressing the reaction between the color-forming component A and the color-forming component B which reacts with the color-forming component A to form a color. A color-suppressing compound having a saturated bond in the same molecule (hereinafter sometimes referred to as a “polymerizable color-suppressing compound”). When an electron-donating dye precursor is used as the color-forming component A, and an electron-accepting compound having no polymerizable group is used as the color-forming component B, the polymerizable color-suppressing compound includes an electron-donating dye precursor and an electron-donating dye. It is preferable to use a photopolymerizable monomer having a site that suppresses the reaction with the acceptor compound and at least one vinyl group in the molecule (hereinafter, may be referred to as “photopolymerizable monomer D ₁ ”).

Specific examples of the photopolymerizable monomer D ₁ include acrylic acid and salts thereof, acrylic esters and acrylamides; methacrylic acid and salts thereof, methacrylic esters and methacrylamides; and maleic anhydride. Maleic esters; itaconic acid, itaconic esters; styrenes; vinyl ethers; vinyl esters; N-vinyl heterocycles;
Allyl esters and the like can be mentioned.

Of these, compounds having a plurality of vinyl groups in the molecule are preferable, and specifically, acrylates and methacrylates of polyhydric alcohols such as trimethylolpropane and pentaerythritol; resorcinol, pyrogallol, phlorogol Acrylic esters and methacrylic esters of polyhydric phenols such as lucinol and bisphenols; acrylate or methacrylate terminated epoxy resins; acrylate or methacrylate terminated polyesters are preferred. Among them, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol dimethacrylate are particularly preferable.

[0211] As the photopolymerizable monomer D ₁ is preferably one a molecular weight of from about 100 to about 5000, about 3
More preferably, the number is from about 2000 to about 2000.

[0212] As the polymerizable coloring inhibiting compound, the case of using the photopolymerizable monomer D _1, as the amount thereof, the electron-donating compound 1 mass to be employed in combination with a coupler compound free of polymerizable group Parts
It is preferably from 10 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass. If the amount is less than 0.1 parts by mass, a latent image may not be formed in the exposure step,
If the amount exceeds the parts by mass, the color density may decrease.

When a diazo compound is used as the color-forming component A and a coupler compound having no polymerizable group is used as the color-forming component B, the polymerizable color-suppressing compound may be a coupling reaction between the diazo compound and the coupler compound. It is preferable to use a photopolymerizable monomer having an acidic group to be suppressed and at least one vinyl group in the molecule (hereinafter, may be referred to as “photopolymerizable monomer D ₂ ”).

Examples of the photopolymerizable monomer D ₂ include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, zinc β-methacryloxyethoxysalicylate, zinc 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, 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.

[0217] As the polymerizable coloring inhibiting compounds, when using the photopolymerizable monomer D _2, as the amount thereof, the coupler compound 1 part by weight for use in combination with the coupler compound free of polymerizable group On the other hand, 0.1
It is preferably from 10 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass. If the amount is less than 0.1 part by mass, a latent image may not be formed in the exposure step, and if it exceeds 10 parts by mass, the color density may decrease.

(Microcapsules) In the recording material of the present invention, it is preferable that the recording layer contains the coloring component A in a state of being encapsulated in microcapsules. As a method for microencapsulation, a conventionally known method can be used. For example, U.S. Pat. No. 2,800,457.
U.S. Pat. No. 3,328,458, a method utilizing coacervation of a hydrophilic wall forming material described in U.S. Pat.
No. 7154, British Patent No. 990443, Japanese Patent Publication No. 38-
Nos. 19574, 42-446 and 42-771, the interfacial polymerization method described in U.S. Pat. Nos. 3,418,250 and 3,660,304, and the isocyanate polyol wall described in U.S. Pat. No. 3,796,669. US Patent No. 3,914,511 using a material
No. 4,001,140, U.S. Pat. No. 4,087,376, U.S. Pat.
No. 9802, a method using a urea-formaldehyde-based, urea-formaldehyde-resorcinol-based wall-forming material, and a melamine-described in US Pat. No. 4,025,455.
A method using a wall-forming material such as formaldehyde resin and hydroxybromocellulose, JP-B-36-9168.
JP-A-51-9079, the in-situ method by polymerization of monomers, the electrolytic dispersion cooling method described in British Patent Nos. 952807 and 965074, and U.S. Pat.
No. 111407 and British Patent No. 930422.

The method for microencapsulation is not limited to these. In particular, the oil phase prepared by dissolving or dispersing the color-forming component A in a hydrophobic organic solvent serving as the core of the capsule is mixed with a water-soluble polymer. Is mixed with a dissolved aqueous phase, emulsified and dispersed by means such as a homogenizer, and then heated to cause a polymer formation reaction at the oil droplet interface, thereby forming a microcapsule wall of the polymer substance. It is preferable to employ it. According to this method, a capsule having a uniform particle size can be formed in a short time, and a recording material having excellent raw preservability can be obtained.

The reactant forming the polymer is added inside the oil droplet and / or outside the oil droplet. Specific examples of the polymer substance include polyurethane, polyurea, polyamide,
Examples include 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 preferred, and polyurethane and polyurea are particularly preferred. The above polymer substances can be used in combination of two or more kinds.

Examples of the water-soluble polymer include gelatin, polyvinylpyrrolidone, and polyvinyl alcohol. For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and a second substance (eg, polyol, polyamine) which reacts with the polyisocyanate to form a capsule wall should be encapsulated in a water-soluble polymer aqueous solution (aqueous phase) or encapsulated. After mixing in an oily medium (oil phase), emulsifying and dispersing these, and then heating, a polymer formation reaction occurs at the oil droplet interface, and microcapsule walls can be formed.

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 3,793.
No. 68, JP-B-48-40347, JP-B-49-2415
9, JP-A-48-80191 and JP-A-48-84086.
The one described in the item can be used.

When preparing microcapsules containing the coloring component A, the coloring component A contained in the microcapsules is used.
May be present in a solution state or a solid state in the capsule. When the coloring component A is encapsulated in a microcapsule in a solution state, the coloring component A may be encapsulated in a state dissolved in a hydrophobic organic solvent. The amount of the organic solvent used is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the coloring component A.

As the hydrophobic organic solvent, generally,
Phosphate, phthalate, acrylate, methacrylate, other carboxylate, fatty acid amide, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, diallylethane, solid compound at room temperature , Oligomer oil, polymer oil and the like. In particular,
JP-A-59-178451 to JP-A-59-178455,
JP-A-59-178457, JP-A-60-242094, JP-A-63-85633, JP-A-6-194825 and JP-A-6-194825
No. -13310 to No. 7-13311, No. 9-1060
Organic solvents described in JP-A No. 39 and Japanese Patent Application No. 62-75409 are exemplified.

Also, the coloring component A to be encapsulated
When the solvent has poor solubility in the organic solvent, a low-boiling solvent having high solubility can be used in combination. Examples of the low boiling point solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like.

On the other hand, an aqueous solution in which a water-soluble polymer is dissolved is used for the aqueous phase, and the oil phase is added thereto, and then emulsified and dispersed by means of a homogenizer or the like. It acts uniformly and easily and acts as a dispersion medium for stabilizing the emulsified aqueous solution. Here, in order to more uniformly emulsify and disperse and stabilize, a surfactant may be added to at least one of the oil phase and the aqueous phase. As the surfactant, a known emulsifying surfactant can be used. When a surfactant is added, the amount of the surfactant is 0.1% to 5% based on the mass of the oil phase.
%, Particularly preferably 0.5% to 2%.

When the color forming component A is microencapsulated, the average particle size of the microcapsules is preferably 20 μm or less, and more preferably 5 μm or less from the viewpoint of obtaining high resolution. If the formed microcapsules are too small, the surface area with respect to a certain solid content becomes large, and a large amount of a wall material is required.

The photopolymerizable composition of the present invention may further comprise, in addition to the above-mentioned recording material of the present invention, inks, color filters, holograms, proofs, sealants, adhesives, lithographic printing, resin relief printing plates,
It can be used in a wide range of fields such as photoresist,
Other components may be added according to each application.
Further, when it is used for other than the recording material of the present invention, 3)
The polymerizable compound does not need to function as the color forming component B and the color formation suppressing compound as described above, and a polymerizable compound having an ethylenically unsaturated bond can be widely used.

In the case of a multicolor recording material, a plurality of monochromatic recording layers are laminated on a support, and each recording layer has a coloring component A having a different coloring hue (may be included in microcapsules). And a color-forming component B (which may have a polymerizable group) having in its molecule a site that reacts with each of the color-forming components A to form a color, and photopolymerization that forms a latent image by being exposed to light of different wavelengths. , A multicolor recording material can be obtained. That is, by using spectral sensitizing dyes having different absorption wavelengths for the photopolymerizable composition, a photopolymerizable composition sensitive to light of different wavelengths can be obtained. In this case, an intermediate layer may be provided between the recording layers of each single color.

The recording layer of the multicolor multilayer recording material of the present invention comprises:
For example, it can be formed as follows. And microcapsules encapsulating the color forming component A ^Y of yellow color, the containing and color forming component B ^Y to develop the color forming component A ^Y, a photopolymerizable composition which is sensitive to a latent image formed on the light source center wavelength lambda ₁ 1 Is provided on a support, and on the layer, a microcapsule containing a coloring component A ^M for magenta coloring, a coloring component B ^M for coloring the coloring component ^AM, and a light source center wavelength λ ₂ are exposed. a second recording layer containing a photopolymerizable composition a latent image formed is provided, more that layer on the microcapsules encapsulating the color forming component a ^C of cyan color, the color developing component to develop the color forming component a ^C B ^C and light source center wavelength λ
_{And a third} recording layer containing a photopolymerizable composition for forming a latent image upon exposure to a third recording layer. The multi-layer recording layer α has a laminated structure, and if necessary, has an intermediate layer between the respective layers of the multi-layer recording layer α. It is composed of a recording layer β provided with a layer.

In the case of forming an image using the recording material having the multi-colored multi-layer recording layer, in the process of imagewise exposing, the image is formed by using a plurality of light sources having different wavelengths suitable for the absorption wavelength of each recording layer. By exposing, the recording layer having the absorption wavelength of the light source selectively forms a latent image, so that a multicolor image can be formed with high sensitivity and sharpness, and the entire surface of the recording layer is irradiated with light. By doing so, it is possible to eliminate the coloring of the background portion by the photopolymerizable composition including the spectral sensitizing dye remaining in the layer, and to form a high-contrast high-quality multicolor image. .

(Support) As the support, any paper support used for ordinary pressure-sensitive paper, thermal paper, dry or wet diazo copy paper, and the like, acid paper, neutral paper, and the like can be used. Paper, coated paper, plastic film laminated paper, synthetic paper, plastic film and the like can be used.

The recording material of the present invention is suitably used for applications such as lithographic printing, a resin convex plate, a resist or photomask for producing a printed board, a monochrome or color transfer coloring sheet or a coloring sheet. For example, when the recording material of the present invention is applied to a light- and heat-sensitive coloring sheet, each component is individually or in combination of several types, and dissolved or dispersed in an appropriate solvent to prepare a solution or dispersion. The mixture can be prepared by mixing and applying the mixture as a coating liquid on a support such as paper or a plastic film and drying. For example, when microencapsulating a predetermined component, a microcapsule dispersion in which any component is encapsulated is prepared, and a liquid in which other components are dispersed or dissolved in a solvent is separately prepared. They can be mixed to form a coating liquid. In preparing the coating solution, each component can be brought into a preferable dispersed state using a homogenizer or the like. The coating and drying can be performed by a conventionally known method.

The recording material of the present invention can form an image by performing a heat development treatment simultaneously with or after the exposure for forming a latent image. As a heating method at the time of the heat development processing, a conventionally known method can be used. Generally, the heating temperature is 80 to 20.
0 ° C is preferable, and 85 to 130 ° C is more preferable. The heating time is preferably from 1 second to 5 minutes, more preferably from 3 seconds to 1 minute.

After the heating and developing treatment, the entire surface of the recording layer is irradiated with light to polymerize the unpolymerized region and fix the formed image, and to remove the white color of the background portion such as the spectral sensitizing dye remaining in the recording layer. It is preferable to decolor, decompose or deactivate the component that lowers the properties. The recording material of the present invention can prevent the residual color of the background portion and the like, and can further improve the whiteness of the background portion by a shorter image fixing process than the conventional recording material.

When an image is formed by the above method, the sensitivity can be further improved by providing a process of uniformly preheating the entire surface of the material at a predetermined temperature lower than the coloring temperature during the image formation. Also, not only the recording method,
It can be used for other known recording methods.

As described above, in a completely dry processing system that does not require the use of a developer or the like and generates no waste, high-sensitivity image recording using not only ultraviolet light but also visible light to infrared light can be performed. It is possible to form a clear and high-contrast black and white or color image with excellent decoloring property of a non-image portion (background portion).

[0238]

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 mass”.

(Examples 1 to 19) As shown in Table 1 below, a photopolymerizable composition having the following composition was prepared by using the above exemplified spectral sensitizing dye (compound represented by the general formula (1)) and an organic boron compound. Was prepared. [Composition of photopolymerizable composition]-Pentaerythritol tetraacrylate-1.41 g-Benzyl methacrylate / methacrylic acid-1.29 g (molar ratio 73 / 27 copolymer)-Methyl ethyl ketone-12 g-Propylene glycol monomethyl ether acetate-8.62 g-Spectral sensitizing dye (the above-mentioned compound; the following table) 1) 1 × 10 ^-4 mol ・ Organic boron compound shown below (see Table 1 below) ・ ・ ・ ・ ・ ・ ・ 6 × 10 ^-4 mol ・ Methanol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・... 6 g The structures of borates (1) to (3) (organic boron compounds) in the following Tables 1 to 3 are shown below.

[0240]

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Each of the prepared photopolymerizable compositions was
2 μm on polyethylene terephthalate film
And dried at 100 ° C. for 5 minutes. The following coating solution (1) for a protective layer was further applied thereon in a thickness of 1 μm, and dried at 100 ° C. for 2 minutes to prepare photosensitive materials (1) to (19) of the present invention.

[Composition of Coating Solution (1) for Protective Layer]-Water-98 g-Polyvinyl alcohol- 1.7g Hydroxypropyl methylcellulose 1.7g Polyvinylpyrrolidone・ ・ ・ ・ 8.7g

(Comparative Examples 1 to 3) The spectral sensitizing dye (exemplary compound No. 1) used in Example 1 was replaced with any one of the following spectral sensitizing dyes d-1 to d-3 as shown in Table 1 below. Except that the photosensitive materials (20) to (2) were changed in the same manner as in Example 1.
2) was produced.

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<Image formation and evaluation> The light-sensitive materials (1) to (19) of the present invention and the light-sensitive material (20) of the comparative example were prepared.
To (22) were respectively exposed using a vacuum frame apparatus. Exposure to the photosensitive material is performed using a step wedge (density step 0.15, density step number 1 to 15 steps, "Fuji Step Guide P" (manufactured by Fuji Photo Film Co., Ltd.) and "SC38 filter" (cuts light of 380 nm or less) Through a sharp cut filter; manufactured by Fuji Photo Film Co., Ltd.).
The irradiation was performed for 2 seconds. After the exposure, each of the photosensitive materials was developed using a developer having the following composition.

[Composition of Developer]-Anhydrous sodium carbonate ... 10 g-Butyl cellosolve ...・ ・ ・ ・ ・ 5g ・ Water ・ ・ ・ ・ ・ ・ ・ 1l

As a result of the above development, the amount of exposure to the region corresponding to the high step number of the step wedge was small, so that the photopolymerizable composition in the region was eluted into the developer and the polyethylene terephthalate (PET) surface was exposed. For the photosensitive material of each example, the photopolymerizable composition was completely eluted and PET
The area where the surface was exposed was examined, and the step number (clear step number) of the step wedge corresponding to the area having the highest exposure was obtained. The higher the determined number of steps, the higher the sensitivity of the photosensitive material. The results are shown in Table 1 below. In addition, when the photopolymerizable composition was eluted into the developer over all the exposed areas due to low sensitivity, "flow" was indicated in the table. still,
The number (No.) in the column of the spectral sensitizing dye in Table 1 below is the number (N) of the exemplified compound represented by the aforementioned general formula (1).
o.). Hereinafter, the same applies to Table 2.

[0248]

[Table 1]

From the results shown in Table 1, the photosensitive materials (1) to (19) of the present invention using the compound represented by the general formula (1) as a spectral sensitizing dye can form images with high sensitivity. did it. On the other hand, the photosensitive materials (20) to (22) of Comparative Examples, which did not use the spectral sensitizing dye specified in the present invention.
Then, sufficient sensitivity could not be obtained.

Example 20 Preparation of Microcapsule Solution Containing Electron-donating Colorless Dye (1)-8.9 g of the following electron-donating colorless dye (1) was dissolved in 16.9 g of ethyl acetate, and further encapsulated. As an agent,
"Takenate D-110N" (manufactured by Takeda Pharmaceutical Co., Ltd.)
20 g 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.
It was emulsified and dispersed at ℃ to obtain an emulsion. Water 14 was added to the obtained emulsion.
g and 72 g of 2.9% tetraethylenepentamine aqueous solution
The mixture was heated to 60 ° C. with stirring, and after 2 hours, the electron-donating colorless dye (1) was encapsulated in the core.
A μm microcapsule solution was obtained.

[0251]

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-Preparation of emulsion of photopolymerizable composition- 0.05 g of the above-mentioned spectral sensitizing dye (Exemplary Compound No. 2; see Table 2 below) and 0 of the borate (1) (organic boron compound) 0.3 g, the following polymerization aid (1) 0.05 g,
To 4.2 g of the following polymerizable electron-accepting compound (1), 5.3 g of isopropyl acetate was added and dissolved by stirring.

[0253]

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This solution was added to 13 g of an 8% aqueous gelatin solution.
0.8 g of a 2% aqueous solution of the following surfactant (1):
% Of the following surfactant (2) aqueous solution (0.8 g), and emulsified with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 10,000 rpm for 5 minutes to obtain an emulsion of the photopolymerizable composition. Obtained.

[0255]

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-Preparation of Coating Solution for Recording Layer- 4 g of the above-mentioned electron-donating colorless dye (1) capsule solution, 12 g of an emulsion of the photopolymerizable composition, and a 15% aqueous solution of gelatin 1
2 g were mixed to prepare a coating solution for a recording layer.

-Preparation of Coating Solution (2) for Protective Layer- 4.5 g of a 10% aqueous gelatin solution, 4.5 g of distilled water,
0.5 g of a 2% aqueous solution of the following surfactant (3), 0.3 g of a 2% aqueous solution of the following surfactant (4), 0.5 g of a 2% aqueous solution of the following hardener (1), and “Syloid 72 ”(F
UJI-DEVICE CHEMICAL LTD.
Was mixed with 1 g of “Snowtex N” to give a coating amount of 50 mg / m ² to prepare a coating solution (2) for a protective layer.

[0258]

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-Preparation of photosensitive and heat-sensitive recording material- A white polyester film filled with a white pigment and having a thickness of 100 µm ("Lumirror E68L", manufactured by Toray Industries, Inc.) was prepared as a support. The coating solution for a recording layer was applied onto the support using a coating bar so that the dry weight of the coating layer was 6 g / m ^2, and dried at 30 ° C. for 10 minutes. The protective layer coating solution (2) was applied thereon using a coating bar so that the dry weight of the coating layer was 2 g / m ² , and dried at 30 ° C. for 10 minutes. A recording material (a) was obtained.

(Examples 21 to 27) The spectral sensitizing dye (exemplified compound No. 2) and the organic boron compound (borate (1)) used in Example 20 were each analyzed by the spectral analysis described in Table 2 below. Example 2 except that the sensitizing dye (the compound represented by the general formula (1)) and the organoboron compound were used instead.
0, the light and heat sensitive recording materials (b) to
(H) was obtained.

Comparative Example 4 As shown in Table 2 below, the spectral sensitizing dye (Exemplary Compound No. 2) used in Example 20 was changed to the spectral sensitizing dye d-2, as shown in Table 2 below. In the same manner as in the above, a light and heat sensitive recording material (i) was obtained.

<Image Formation and Evaluation> The prepared photosensitive and heat-sensitive recording materials (a) to (h) of the present invention and the photosensitive and heat-sensitive recording material (i) of the comparative example were each subjected to a step wedge and 500W through SC38 filter
Irradiation was performed for 30 seconds with a xenon lamp to form a latent image. Thereafter, each photosensitive and heat-sensitive recording material was heated on a hot plate at 125 ° C. for 15 seconds. When the electron-donating colorless dye (1) reacted with the polymerizable electron-accepting compound (1) in the unexposed area Magenta color was generated, and the color density did not decrease or no color formation occurred in the exposed portion. Inspect areas where color development has not occurred, and determine the number of step wedges (clear steps) corresponding to the area with the least exposure.
I asked. The higher the determined number of steps, the higher the sensitivity of the light and heat sensitive recording material. The results are shown in Table 2 below. still,
In the case where the sensitivity was low and color development occurred in all stages, "solid" is shown in Table 2.

Further, after exposing for 10 minutes under a fluorescent lamp (30000 lux), yellow and yellow were measured with a transmission Macbeth densitometer.
The density of the magenta and cyan background portions was measured. The better the decoloring property of the contained spectral sensitizing dye by the exposure, the lower the fog density in the background. The results are shown in Table 2 below.

[0264]

[Table 2]

From the results shown in Table 2 above, in the light and heat sensitive recording materials (a) to (h) of the present invention using the compound represented by the general formula (1) as the spectral sensitizing dye, high sensitivity was obtained. Moreover, it was excellent in decoloring property, and a clear and high-contrast image could be formed. On the other hand, in the photosensitive and heat-sensitive recording material (i) of Comparative Example, which did not use the spectral sensitizing dye specified in the present invention, high sensitivity was not obtained and the decoloring property was poor.

(Examples 28 to 33) The spectral sensitizing dye (exemplified compound No. 2) and the organic boron compound (borate (1)) used in Example 21 were subjected to the above-mentioned spectral analysis as shown in Table 3 below. Sensitizing dye (Exemplary compound No. 3; compound represented by general formula (1)) and the following radical generator (Generators 1 to 3)
In place of 5), 0.05 g of polymerization aid (1)
Was replaced with 0.19 g of the following polymerization aid (2),
In the same manner as in Example 21, photosensitive and heat-sensitive recording materials (k) to (p) of the present invention were obtained.

[0267]

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Comparative Examples 5 to 10 In the same manner as in Examples 28 to 33 except that no spectral sensitizing dye was added to each of Examples 28 to 33, the light and heat sensitive recording material (q ) To (v).

<Image formation and evaluation> The light- and heat-sensitive recording materials (k) to (p) of the present invention and the light- and heat-sensitive recording materials (q) to (v) of the comparative examples were each prepared by using a vacuum printing apparatus. , A step wedge, and a bandpass filter (MIF-W type, manufactured by Nippon Vacuum Optical Co., Ltd.) having a maximum transmission wavelength of 438 nm.
Irradiation was performed for 0 seconds to form a latent image. Thereafter, each of the light- and heat-sensitive recording materials was heated on a hot plate at 120 ° C. for 15 seconds. Magenta color was generated, and the color density was not reduced or no color was generated in the exposed portion. The area where color development did not occur was examined, and the step number (clear step number) of the step wedge corresponding to the area with the least exposure amount was determined. The higher the determined number of steps, the higher the sensitivity of the light and heat sensitive recording material. The results are shown in Table 3 below. In addition, in the case where the sensitivity was low and color development occurred in all stages, "solid" was displayed in Table 3.

Further, 436 of each light and heat sensitive recording material before and after exposure to light under a fluorescent lamp (30000 lux) for 10 minutes.
The reflection density in nm is measured using a spectrophotometer (UV3100
S, manufactured by Shimadzu Corporation). The better the decoloring property of the contained spectral sensitizing dye by the exposure, the better
The concentration will be lower. The results are shown in Table 3 below.

[0271]

[Table 3]

From the results shown in Table 3 above, in the light- and heat-sensitive recording materials (k) to (p) of the present invention using the compound represented by the general formula (1) as the spectral sensitizing dye, the light- and heat-sensitive recording of Comparative Example Compared to the materials (q) to (v), spectral sensitization in a wavelength region having no or little absorption of a radical generator is possible,
In addition, the sensitivity was high, and the decolorizability of the spectral sensitizing dye in post-exposure was also good.

[0273]

According to the present invention, it is possible to provide a photopolymerizable composition which is sensitive to not only ultraviolet light but also visible light to infrared light. In addition, a completely dry processing system that does not require the use of a developer or the like and generates no waste, enables high-sensitivity image recording using not only ultraviolet light but also visible light to infrared light, and has a non-image portion. It is possible to provide a recording material which is excellent in the decoloring property of the (background portion) and can form a clear and high-contrast black and white or color image.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/45 C08K 5/45 9/10 9/10 C08L 101/00 C08L 101/00 G03F 7/004 514 G03F 7/004 514 7/027 7/027 7/029 7/029 (72) Inventor Masanobu Takashima 200 No. Onakazato, Fujinomiya-shi, Shizuoka Fuji Photo Film Co., Ltd. F-term (reference) 2H025 AB20 AC01 AC08 AD01 AD03 BC31 BE07 CA32. QA06 QA08 QA09 QA12 QA13 QA19 QA22 QA26 QB04 QB12 QB14 QB17 QB19 QB24 SA01 SA21 SA31 SA61 SA62 SA63 SA64 SA65 SA76 SA82 SA85 UA 01 UA06 UA08 VA01 WA01 XA02 4J027 AA03 AB01 AB02 AB03 AB06 AB07 AD01 AD02 AE01 AG01 BA01 CA21 CA25 CA26 CA34 CB10 CC04 CD10

Claims (10)

[Claims] 1. A polymerizable compound having the following general formula (1)
A photopolymerizable composition comprising at least one compound represented by the formula: Embedded image [In the general formula (1), Q represents a group capable of forming a dye. L
¹ and L ² each independently represent a methine group which may have a substituent. When L ¹ and L ² represent a methine group having a substituent, the substituents are bonded to each other to form an unsaturated fatty acid. An aromatic ring or an unsaturated heterocyclic ring may be formed. m represents 0 or 1. X represents a group capable of simultaneously forming a saturated or unsaturated heterocyclic ring containing two S (sulfur atoms) and a saturated or unsaturated, optionally substituted heterocyclic ring containing Yn. Y
Represents an oxygen atom, a sulfur atom, or a nitrogen atom, and n represents 1
Represents an integer of 1 to 4. ] 2. A polymerizable compound, a compound represented by the general formula (1), and a compound capable of generating a radical or a cation by interacting with the compound represented by the general formula (1). 2. The photopolymerizable composition according to 1. 3. The compound capable of generating a radical or a cation is an organic boron compound, an iodonium salt, a sulfonium salt, an iron allene complex, an S-triazine derivative, an organic peroxide, a titanocene, a triarylimidazole dimer, and an azinium salt. The photopolymerizable composition according to claim 2, which is at least one selected from the group consisting of: 4. The photopolymerizable composition according to claim 2, wherein the polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond, and the compound capable of generating a radical or a cation is an organic boron compound. 5. An organic boron compound represented by the following general formula (A)
The photopolymerizable composition according to claim 3, which is a compound represented by the formula: Embedded image [In the general formula (A), Ra ¹ , Ra ² , Ra ³ , and Ra ⁴ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, or Si.
(Ra ⁵ ) (Ra ⁶ ) -Ra ⁷ , wherein Ra ⁵ , Ra ⁶ and Ra ⁷ are
Each independently represents an aliphatic group or an aromatic group. G ⁺ represents a group capable of forming a cation. ] 6. A recording layer having a recording layer on a support, wherein the recording layer has a coloring component A, and a coloring component B having a site that reacts with the coloring component A to form a color, and And a photopolymerizable composition according to any one of the above. 7. The recording material according to claim 6, wherein at least one of the polymerizable compounds is a coloring component B. 8. The recording material according to claim 6, wherein the polymerizable compound is a color-suppressing compound having a site for suppressing the reaction between the color-forming components A and B in the same molecule. 9. The recording material according to claim 6, wherein the coloring component A is encapsulated in a microcapsule. 10. A first recording layer sensitized to light having a center wavelength λ ₁ , a second recording layer sensitized to light having a center wavelength λ ₂ and developing a color different from the first recording layer,... 7. A multi-layer structure in which the first, second,..., And i-th recording layers, which are sensitive to light having a center wavelength λ _i and develop a color different from the i-th recording layer, are stacked in this order. 10. The recording material according to any one of items 1 to 9.