JPH11249295A - Photosensitive and thermosensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an image which can be recorded by an infrared laser beam, does not require the use of a developer or the like, generates no waste, and has a completely dry white and black or color and clear and high contrast by containing a diazonium salt compound having a specific anion component in a photosensitive and thermosensitive recording layer. SOLUTION: This photosensitive and thermosensitive recording layer has an anion component expressed by a formula I or II, where R<1> and R<2> indicate a phenyl group or other aromatic hydrocarbon group which may contain a hetero-atom, R<2a> indicates a phenylene or an other bivalent aromatic hydrocarbon group which may contain s hetero-atom, R<3> indicates an alkly group substituted with-Si (R<9> )(R<10> )(R<11> ) and having carbon atoms of 1-20 or a phenyl group or the like, R<4> indicates a phenyl group or an other aromatic hydrocarbon group which may contain a hetero-atom, E indicates P(R<14> )(R<15> ), S(R<6> ), N(R<7> )(R<8> ), and R<6> -R<11> and R<14> -R<16> indicate an alkyl group having carbon atoms of 1-12 or the like, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a green laser beam,
The present invention relates to a color or black and white light and heat sensitive recording material using a red laser light or an infrared laser light.

[0002]

2. Description of the Related Art Conventionally, various dry-type image forming methods which do not use a liquid developer or the like and have no problem of waste have been studied, and among them, a method using a composition which is cured by light is used. Attention has been paid. In this method, a composition that is cured by light contained in a recording material by exposure cures to form a latent image, and components related to color development or decoloration move in the recording material according to the latent image by heating. To form a color image. Using such a recording material, the photosensitive recording material is exposed to light through an image document, and photo-cured in an exposed portion to form a latent image.
By heating the recording material, a portion relating to the coloring or decoloring of the uncured portion is moved, and this method of forming a visible image makes it possible to realize a completely dry system with no waste.

There are several types of recording materials to be used in this method, and these are characteristic methods as a black-and-white image recording method, but are particularly useful when used as a color recording material. It is. As a specific recording material, for example, a recording material disclosed in JP-A-52-89915 is known. This is achieved by separating two components of a two-component thermosensitive color recording material, for example, an electron-accepting compound and an electron-donating colorless dye, inside and / or outside or on both sides of a microcapsule containing a photocurable composition. This is the arranged recording material. However, in the case of this recording material, even if the photocurable composition in the microcapsules is sufficiently cured, the color development of the cured portion cannot be sufficiently suppressed, so that the non-image portion is slightly colored, and the contrast tends to be poor. There is.

As a more preferable recording material having no coloring in the non-image area, for example, as disclosed in JP-A-61-123838, a photopolymerization comprising a vinyl monomer having an acidic group and a photopolymerization initiator is disclosed. There is known a recording material in which a layer containing a hydrophilic composition, a separating layer, and a layer composed of an electron-donating colorless dye are laminated. In the case of this recording material, the non-image portion, that is, the thermal curing property of the acidic group in the portion cured by the photopolymerized portion is almost eliminated, so that the non-image portion is not colored, but the coloring density is slightly low. As a method of obtaining a negative image by the same method, for example, there is a method disclosed in JP-A-60-119552. This method uses a photopolymerizable composition comprising a monomer or prepolymer for bleaching a dye and a photopolymerization initiator, and a recording material in which a dye bleached by the monomer or the prepolymer is present in isolation. This recording material also has the same disadvantages as the above-mentioned recording material.

As a preferable recording material capable of overcoming the coloring of the non-image area and the low image density, the present applicant has previously proposed JP-A-3-87827 and JP-A-4-21252. In the former recording material, one of the two components of the one-component type thermosensitive color recording material is encapsulated in a microcapsule, and the other component is used as a curable compound of a photocurable composition, or the other component is used as a photocurable composition. It is a recording material arranged outside the microcapsule together with the material, the latter recording material, an electron-accepting compound, a photocurable composition containing a polymerizable vinyl monomer and a photopolymerization initiator is arranged outside the microcapsule, This is a recording material provided with a layer containing a microcapsule containing an electron-donating colorless dye.

In order to perform color recording with these photosensitive recording materials, basically, a recording material having a plurality of photosensitive layers having mutually different photosensitive wavelengths and coloring hues may be used. Examples of more preferable multicolor recording materials include the recording materials proposed by the present applicant. For example, it has a plurality of photosensitive layers that are sensitive to light of different wavelengths and develop colors of different hues, and as a layer configuration from the exposure light source side to the support side of the recording material, the second photosensitive layer is sensitive to light of the central wavelength λ1. 1, an intermediate layer that absorbs light having a center wavelength λ1, a second photosensitive layer that is sensitive to light having a center wavelength λ2 and develops a color different from that of the first photosensitive layer,. 1, an intermediate layer that absorbs the light of the first wavelength, and the first, second,.
And at least two or more photosensitive layers are laminated on the support in the order of the i-th photosensitive layer that develops a color different from that of the (i-1) -th photosensitive layer, and the center wavelength λ1 <λ2 <
.. <Λi. Here, i is an integer of 2 or more.

Although these recording materials can be applied to various uses, they all use UV light and short-wave visible light, and cannot use a small and inexpensive infrared laser or green-red light. .

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to perform recording by using infrared laser light and green to red laser light, and does not require the use of a developing solution or the like and generates unnecessary waste. An object of the present invention is to provide a high-sensitivity light- and heat-sensitive recording material capable of forming a clear, black-and-white or color clear and high-contrast image without any problem.

[0009]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have found that the above-mentioned object can be achieved by a composition which is cured by irradiation with light which is emulsified and dispersed outside the microcapsule by exposure (hereinafter referred to as photocurable as appropriate). Is cured and fixed, and the electron-accepting compound having mobility moves in the recording material by heating to form a colorless electron-donating dye in the microcapsule to form an image. The present invention has been completed by finding out that this can be achieved by a light and heat sensitive recording material characterized in that a light and heat sensitive recording layer is provided on at least one surface of a support.

That is, the light- and heat-sensitive recording material of the present invention is a light- and heat-sensitive recording material having a light- and heat-sensitive recording layer provided on a support, wherein the light and heat-sensitive recording layer is an electron-donating material encapsulated in heat-responsive microcapsules. A heat-sensitive recording material comprising a recording layer containing an electron-accepting developer, a photopolymerizable monomer, and a photopolymerization initiator, in addition to the colorless dye of the present invention, and the thermoresponsive microcapsules. Has the following general formula (I-
1) or a diazonium salt compound having an anionic component represented by the general formula (I-2).

[0011]

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In the formula, R ¹ and R ² are each independently a phenyl group, another aromatic hydrocarbon group optionally containing a hetero atom, —Si (R ⁹ ) (R ¹⁰ ) (R ¹¹ ) An alkyl group having 1 to 20 carbon atoms substituted with the following formula (II):
Represents a group represented by (IIa) or (IIb). Here, the phenyl group and the aromatic hydrocarbon group have 1 to 20 carbon atoms.
An alkyl group having 2 to 20 carbon atoms including O, S (O) _p , NR ⁵ , OR ⁶ , R ⁶ S (O)
_p , R ⁶ SO ₃ , N (R ⁷ ) (R ⁸ ), R ⁶ OCO, C
ON (R ⁷ ) (R ⁸ ), COR ⁹ , Si (R ⁹ )
(R ¹⁰ ) (R ¹¹ ), Sn (R ⁹ ) (R ¹⁰ ) (R ¹¹ ), B
(R ¹² ) (R ¹³ ), halogen group, (R ⁹ ) (R ¹⁰ ) P
(O) _q and CN may be substituted, and at least one of the phenyl group and the aromatic hydrocarbon group is substituted with these substituents.

R^2aIncludes phenylene and heteroatoms
Represents another divalent aromatic hydrocarbon group which may be
The aromatic hydrocarbon group is an alkyl group having 1 to 20 hydrocarbons,
O, S (O)_p, NR^Five2 to 2 carbon atoms containing
An alkyl group of 0, OR⁶, R ⁶S (O)_p, R⁶S
O_Three, N (R⁷) (R⁸), R⁶OCO, CON
(R⁷) (R⁸), COR⁹, Si (R⁹) (R^Ten)
(R¹¹), Sn (R⁹) (R^Ten) (R¹¹), B (R¹²)
(R¹³), A halogen group, (R⁹) (R^Ten) P (O)_q,
CN or a group represented by the following formula (a)
Is also good.

[0014]

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[0015]

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In the formula (a), R ^a and R ^b are an alkylene group,
Alkyl group having 1 to 12 carbon atoms, 1 to 12 carbon atoms
Represents an alkoxy group, R ⁶ OCO, CN, and a substituted alkylene group substituted with a halogen atom. Here, R ⁶ has the same meaning as described above.

In the above formulas (II), (IIa) and (IIb), the aromatic ring is an alkyl group having 1 to 20 carbon atoms, O, S
(O) p, alkyl group having 2 to 20 carbon atoms which contains ^{NR 5, OR 6, R 6} S (O) p, R 6 SO 3, N
(R ⁷ ) (R ⁸ ), R ⁶ OCO, CON (R ⁷ )
(R ⁸ ), COR ⁹ , Si (R ⁹ ) (R ¹⁰ ) (R ¹¹ ),
Sn (R ⁹ ) (R ¹⁰ ) (R ¹¹ ), B (R ¹² ) (R ¹³ ),
It may be substituted with a halogen group, (R ⁹ ) (R ¹⁰ ) P (O) _q , CN. Y is (CH ₂ ) _n , CH = CH,
CO, NR ⁵ , O, and S (O) _p .

R^ThreeIs -Si (R⁹) (R^Ten) (R¹¹)
An alkyl group having 1 to 20 carbon atoms substituted with
Or another aromatic hydrocarbon optionally containing a heteroatom
A phenyl group or an aromatic hydrocarbon group,
An alkyl group having 1 to 20 hydrogen hydrides, O, S (O)_p, NR
^FiveAn alkyl group having 2 to 20 carbon atoms containing
⁶, R⁶S (O)_p, R⁶SO_Three, N (R⁷)
(R⁸), R⁶OCO, CON (R⁷) (R⁸), CO
R⁹, Si (R⁹) (R^Ten) (R¹¹), Sn (R⁹)
(R^Ten) (R¹¹), B (R¹²) (R¹³), Halogen group,
(R⁹) (R^Ten) P (O) _q, Even if substituted with CN
good.

R ⁴ is a phenyl group, another aromatic hydrocarbon group optionally containing a hetero atom, an alkyl group having 1 to 20 carbon atoms, a carbon atom containing O, S (O) _p , NR ⁵ It represents an alkyl group having 2 to 20 atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and groups represented by the following formulas (a) and (b).

[0020]

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In the formulas (a) and (b), R ^a and R ^b each independently represent an alkylene group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R ⁶ OCO,
CN represents a substituted alkylene group substituted with a halogen atom. Here, R ⁶ has the same meaning as described above.

The above R^FourThe substituent represented by is OR⁶, R
⁶S (O)_p, R⁶SO_Three, N (R ⁷) (R⁸), R⁶
OCO, CON (R⁷) (R⁸), COR⁹, Si (R
⁹) (R^Ten) (R¹¹), Sn (R⁹) (R^Ten)
(R¹¹), B (R¹²) (R¹³), A halogen group, (R⁹)
(R^Ten) P (O)_q, CN.

N is an integer of 0, 1, 2; m is an integer of 2, 3; p is an integer of 0, 1, 2;

R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a group represented by the above formula (a), and the phenyl group or the group represented by the above formula (a) is a carbon atom. It may be substituted by an alkyl group having 1 to 6 atoms, an alkoxy group having 1 to 12 carbon atoms, R ⁶ OCO, CN, or a halogen group. R ⁶ has the same meaning as R ⁵ .

R ⁷ , R ⁸ and R ^8a are an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms,
A phenyl group, a group represented by the formula (a), wherein the phenyl group and the group represented by the formula (a) each have 1 to 6 carbon atoms;
An alkyl group having 1 to 12 carbon atoms, R
^{6 It} may be substituted with OCO, CN or a halogen group. Further, R ⁷ and R ⁸ may form a 5-membered ring or a 6-membered ring which may contain O and S together with the nitrogen atom to which they are bonded.

R ⁹ , R ¹⁰ and R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a group represented by the above formula (a). And the phenyl group and the group represented by the formula (a) may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R ⁶ OCO, CN, or a halogen group. .

R ¹² and R ¹³ have the same meanings as R ^{9 to} R ¹¹ , except that the alkyl group and R ¹² and R ¹³ include O and S together with the boron atom to which they are bonded. May form a good five-membered or six-membered ring.

R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, A group represented by the formula (a), wherein the alkyl group, alkenyl group and cycloalkyl group are represented by R ₆ OC
A phenyl group, a group represented by the formula (a), which may be substituted with O or CN, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R ⁶ OCO,
It may be substituted by CN or a halogen group.

E is P (R ¹⁴ ) (R ¹⁵ ), S (R ⁶ ), N
(R ⁷⁾ shows the (R ^8), wherein, R ⁶ to R ¹⁵ are respectively the same as that described above.

The light- and heat-sensitive recording material according to the second aspect of the present invention comprises, on a support, an electron-donating colorless dye encapsulated in a thermoresponsive microcapsule, and an electron-donating dye outside the thermoresponsive microcapsule. A light and heat sensitive recording material provided with a recording layer containing a receptive developer, a photopolymerizable monomer and a photopolymerization initiator, wherein the light and heat sensitive recording layer comprises an anion component represented by the following general formula (II): Characterized by containing a diazonium salt compound having the formula:

[0031]

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In the general formula (II), R ¹ has 1 to 2 carbon atoms.
0 alkyl group, cycloalkyl group having 3 to 12 carbon atoms, alkenyl group having 2 to 8 carbon atoms, the following formula (a):
It represents a group represented by (b), and the substituent represented by R ¹ may be interrupted by O, S (O) _p and NR ⁵ .

[0033]

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In the formulas (a) and (b), R ^a and R ^b each independently represent an alkylene group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R ⁶ OCO,
CN represents a substituted alkylene group substituted with a halogen atom. Here, R ⁶ has the same meaning as described above.

The substituent represented by R ₁ further includes an alkyl group having 1 to 20 carbon atoms, OR ⁶ , R ⁷ S (O) _p ,
R ⁷ SO ₃ , N (R ⁸ ) (R ⁹ ), Si (R ¹⁰ )
(R ¹¹ ) (R ¹² ), B (R ¹³ ) (R ¹⁴ ), a halogen group,
(R ¹⁵ ) (R ¹⁶ ) P (O) _q may be substituted.

R^Two~ R^FourAre each independently a phenyl group,
Represents a biphenyl group. This R^Two~ R ^FourA substituent represented by
Is an alkyl group having 1 to 20 carbon atoms (this alkyl group
Is OR₆, HR₈R₉Is substituted by a halogen atom
), OR⁶, R ⁷S (O)_p, R⁷S
O_Three, N (R⁸) (R⁹), Si (R^Ten) (R¹¹) (R
¹²), B (R¹³) (R¹⁴), A halogen atom, (R^Fifteen)
(R¹⁶) P (O)_qIs substituted with a substituent represented by the following formula:
It may be.

[0037]

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The sum of Hammett σ values of R ^{2 to} R ⁴ is +0.
36 to +2.58. X represents O, S, and NR ^21.

R ⁵ may be substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituent represented by the above formula (a). An alkyl group having 1 to 6 carbon atoms on the ring, 1 to 12 carbon atoms
May have a substituent of an alkoxy group or a halogen atom.

R ^{6 to} R ⁷ may be substituted with an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom, a phenyl group, or a substituent represented by the above formula (a); The phenyl ring of the phenyl group and the substituent represented by the formula (a) may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom substituent. .

R ^{8 to} R ¹⁶ each independently have 1 carbon atom
And an alkyl group having 3 to 12 carbon atoms may be substituted with a cycloalkyl group, a phenyl group or a substituent represented by the formula (a), and represented by a phenyl group and a formula (a). The substituent may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom substituent on the phenyl ring of the substituent.

R ^{8 to} R ⁹ may form an aliphatic 6-membered ring which may further contain another hetero atom O or S together with the nitrogen atom to which they are bonded.

R ^{17 to} R ^{20 each} represent a hydrogen atom or a group having 1 to 1 carbon atoms.
1 carbon atom which may be substituted with 2 alkoxy groups
To 12 may be substituted with an alkyl group, a phenyl group, or a substituent represented by the formula (a), and the phenyl group and the substituent represented by the formula (a) each have 1 carbon atom on the phenyl ring.
It may have an alkyl group of 1 to 6, an alkoxy group having 1 to 12 carbon atoms, and a substituent of a halogen atom.

R ^{22 to} R ^{24 each} represent a hydrogen atom or a group having 1 to 1 carbon atoms.
2 alkoxy groups, OH, an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 12 carbon atoms, OH, a phenyl group which may be substituted with a halogen atom. Represent.

Q represents an integer of 0 to 1. Further, the light and heat sensitive recording material of the present invention is a light and heat sensitive recording material having a light and heat sensitive recording layer provided on a support, wherein the light and heat sensitive recording layer is an electron-donating colorless dye encapsulated in heat-responsive microcapsules. And a compound having an electron-accepting group and a polymerizable group in the same molecule, and an anion component represented by the general formula (I-1) or (I-2) outside the thermoresponsive microcapsules. It is characterized by containing a diazonium salt compound.

As another embodiment of the light- and heat-sensitive recording material of the present invention, in a light- and heat-sensitive recording material having a light- and heat-sensitive recording layer provided on a support, the light and heat-sensitive recording layer is encapsulated in heat-responsive microcapsules. A compound having an electron-donating colorless dye, a compound having an electron-accepting group and a polymerizable group in the same molecule in addition to the thermoresponsive microcapsules, and a diazonium salt compound having an anion component represented by the general formula (II) Is characterized by containing.

Although the function of the present invention is not clear, a compound having an electron-accepting group and a polymerizable group or a compound having an electron-accepting colorant and a polymerizable monomer in the same molecule, which is a composition which is cured by light irradiation, is used. The photopolymerization initiator reacts with the irradiation light to generate radicals, which polymerizes and cures the polymerizable monomer to form a latent image. Reacts with an electron-donating colorless dye to form an image, but due to the presence of the diazonium salt compound having the specific anion component, the reaction of a photopolymerization initiator is promoted, and high sensitivity and high contrast are obtained. It is estimated that a good image is formed.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

In the present invention, the electron-donating colorless dye (hereinafter, appropriately referred to as an electron-donating compound), a photocurable composition containing a polymerizable monomer, and an electron-accepting developer (hereinafter, appropriately, an electron-accepting compound) ) Can be used in any combination of known compounds as long as the effects of the present invention are not impaired. The polymerizable monomer and the electron accepting compound may be one compound having these functions. Among them, specific examples of the recording material according to the present invention include, for example, (1) JP-A-3-8
No. 7827, which has a photocurable composition containing a compound having an electron-accepting portion and a polymerizable monomer portion in the same molecule and a photopolymerization initiator outside the microcapsule, and Examples of the recording material include a recording layer provided with a recording layer containing an electron-donating colorless dye encapsulated in a capsule. When this recording material is exposed, the exposed portions of the photocurable composition outside the microcapsules are polymerized and cured to form a fixed latent image, and then, when heated, are present in the non-fixed portions. The electron-accepting compound moves in the recording material to form a colorless electron-donating dye in the microcapsules. Therefore, in this case, the fixed latent image portion does not develop color, and only the unfixed portion develops color, thereby forming a positive color image with good contrast.

Further, a negative image can be formed by using the same method according to the recording material of the present invention. As a specific example of this method, for example, (2)
No. 1252, a photocurable composition containing an electron-accepting compound, a polymerizable vinyl monomer, and a photopolymerization initiator is provided outside the microcapsule, and is encapsulated in the microcapsule. Recording materials coated with a recording layer containing an electron-donating colorless dye can be mentioned. This recording material forms a negative image with good contrast without coloring the exposed portions and not coloring the unexposed portions. Although the mechanism is not clear, upon exposure, the vinyl monomer at the exposed portion of the photocurable composition outside the microcapsule is polymerized. In this case, the electron accepting compound (developing agent) in the coexisting exposed portion ) Will not be incorporated into the formed polymer, but rather will be present in a state that has reduced interaction with the vinyl monomer, is mobile and has an improved diffusion rate. On the other hand, the unexposed portion of the electron accepting compound is trapped by the coexisting vinyl monomer.
Therefore, only the electron-accepting compound in the exposed area is preferentially heated, and moves in the recording material to form a colorless electron-donating dye in the microcapsule. It is considered that the dye does not pass through the capsule wall and does not develop a colorless electron-donating dye.

As described above, using various methods,
A latent image is formed on the photocurable composition by exposure, and a component related to color development or decoloration is moved by heating in the recording material according to the latent image to form a color image. A photosensitive and heat-sensitive recording material "can be prepared.
The light- and heat-sensitive recording layer used for these recording materials is not limited to the above-described structure, but can have various structures depending on purposes.

The recording material used in the present invention may be a monochromatic recording material of black and white or a multicolor recording material. In the case of a multicolor recording material, for example, the configuration of a multilayer recording material including in each layer a microcapsule containing an electron-donating colorless dye that develops a different hue and a photocurable composition sensitive to light of a different wavelength. Can be used. For example, a microcapsule containing an electron-donating colorless dye that develops cyan and a layer containing a photocurable composition sensitive to wavelength λ1 are provided on a support, and an electron-donating colorless dye that develops magenta thereon. Is provided with a layer containing a photocurable composition sensitive to wavelength λ2, on which a microcapsule containing an electron-donating colorless dye that develops yellow and a photocurable composition sensitive to wavelength λ3 Structure comprising a layer containing the substance, further comprising an intermediate layer between the layers, further comprising a filter dye for absorbing light in the sensitive wavelength range of the photosensitive layer above the intermediate layer in the intermediate layer And the like can be used.

In the case of a multicolor recording material, it is particularly preferable that the intermediate layer contains a dye filter. As its constitution, for example, a layer containing a microcapsule containing an electron-donating colorless dye that develops cyan and a photocurable composition sensitive to a wavelength λ1 is provided on a support. An intermediate layer containing a compound that absorbs short-wave light is provided, and a layer containing a microcapsule containing an electron-donating colorless dye that develops magenta and a photocurable composition sensitive to a wavelength of λ2 is provided thereon. , On which the wavelength λ2
An intermediate layer containing a compound that absorbs shorter wavelength light is provided, and a layer containing a microcapsule containing an electron-donating colorless dye that develops yellow and a photocurable composition sensitive to wavelength λ3 is provided thereon. And a protective layer is further provided thereon.

The compounds constituting the light and heat sensitive recording material of the present invention will be described below. The recording material of the present invention,
It is characterized by containing a diazonium salt compound having a specific anion component. This diazonium salt compound is a compound represented by the above general formula (I-1), general formula (I-2) or general formula (II). An image with excellent contrast can be formed with high sensitivity.

The anion component of the diazonium salt compound having an anion component represented by formula (I-1) or (I-2) contained in the recording material of the present invention will be described.

The compound having an anionic component represented by the general formula (1-1) can be obtained, for example, by reacting triorganylborane (A) with an organometallic reagent, for example, an alkyllithium compound or a Grignard reagent. it can.

[0057]

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M represents, for example, an alkali metal (for example, Li or Na) or MgX (where X represents a halogen atom, especially Br). Another possibility for preparing compounds of the formula I is, for example, the reaction of alkyldihaloboranes, alkyldialkoxy or alkyldiaryloxyboranes (B) with organometallic compounds, such as Grignard reagents or lithium organoyl compounds. Can be obtained.

[0059]

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X represents a halogen atom, particularly Br, and X ′
Represents a halogen atom, an alkoxy group or an aryloxy group. The definitions of the other groups are the same as described above. G in the general formula (1-1) is a positive group other than lithium or magnesium, and these compounds are obtained by, for example, a cation exchange reaction.

The compound having an anionic component represented by the general formula (I-2) may be, for example, a triorganylborane substituted by a group E having the above-defined meaning according to one of the methods described above. To form a borate.

In the case of operations involving an organometallic reaction, the reaction conditions will be apparent to those skilled in the art. Thus, the reaction is advantageously carried out in an inert organic solvent such as an ether or an aliphatic hydrocarbon, specifically, for example, diethyl ether, tetrahydrofuran or hexane. Examples of suitable organometallic reagents for preparing such borates are the lithium compounds of the corresponding aliphatic and aromatic hydrocarbon groups. The preparation of Grignard reagents is known to those skilled in the art,
It is widely described in textbooks and other publications.
The reaction with the organometallic reagent is preferably carried out under the exclusion of air or under an inert gas, for example a nitrogen atmosphere. Generally, the reaction is carried out by cooling to 0 ° C. or below and then warming to room temperature. It is advantageous to stir the reaction mixture from the viewpoint of reaction efficiency. The product is isolated and purified by known methods, for example, chromatography, recrystallization and the like.

When such a borate salt compound anion component contains a diazonium salt group as a cation as in the present invention, these compounds are subjected to a cation exchange reaction between the corresponding borate salt (borate) and the diazonium salt. Manufactured. Examples of borates suitable for the exchange are lithium, magnesium, sodium, ammonium and tetraalkylammonium salts.

Among the triorganylboranes (A) used in the synthesis of the compounds according to the invention, the production of alkyldiarylboranes is described, for example, in Tetrahedron 1993, 49, 2965.
It is described in. The synthesis of triarylboranes is described in J. Organomet. Chem. 1972, 38, 229, J. Organomet.
t. Chem. 1981, 209, 1, J. Amer. Chem. Soc. 1957, 7
9, 2302 and Chem. Ber. 1955, 88, 962, respectively. Alkyl dihaloboranes (B) are described, for example, in JACS 1977,99, 7097 and US Pat.
It can be produced according to the scheme described in No. 88. In addition, Zh. Obshch. Khim. 1959, 29, 3405 and
Bull. Chim. Soc. France, 1967, 11, 4160 also describes a method for producing the compound (B). The production of phenyldifluoroborane is described in J. Organomet. Chem. 1972, 3
It is described in 5, 9. Tris (trimethylsilylmethyl) furan is described, for example, in J. Amer. Chem. Soc. 1959, 81,
It can be produced by the method described in 1844. The borane required as a starting material of a borate compound useful as a counter anion component of the diazonium salt of the present invention can be obtained, for example, according to one of the methods described in the above documents.

Specific examples of the anion component represented by the general formula (I-1) or (I-2) which can be used in the present invention are described in the following Tables 1 to 3 by describing each functional group. Although shown, the invention is not limited thereto.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

Next, another anionic component of the diazonium salt used in the recording material of the present invention, that is, the above-mentioned general formula (I)
The anion component represented by I) will be described.

The compound containing the anion component represented by the general formula (II) may be, for example, a triorganoboran (A) and an organometallic reagent such as an alkyllithium compound or a Grignard reagent as represented by the following formula: Can be obtained by reacting

[0071]

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(Wherein, M represents, for example, an alkali metal, for example, Li or Na, or MgX, and X represents a halogen atom, especially Br). As another method for producing a compound containing an anion component represented by the general formula (II), for example, an alkyldihaloborane and / or an alkyldi (alkoxy) borane or an alkyldiamine as represented by the following formula: A method of reacting (aryloxy) borane (B) with an organometallic compound, for example, a Grignard reagent or an organotin compound, may be mentioned.

[0073]

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(In the formula, X represents a halogen atom, particularly Br, X ′ represents a halogen atom, an alkoxy group or an aryloxy group, and the definitions of the other groups are as described above.) These organometallic reagents The reaction conditions in the case of using are the same as those described in the method for producing the anion component represented by the general formula (I-1) or (I-2). The method of containing the anion component represented by the general formula (II) as a cation with a group of a diazonium salt is also the same as described above, and the corresponding borate salt (borate) and diazonium salt It is produced by a cation exchange reaction.

The method for producing triorganoborane (A) used for the synthesis of the compound according to the present invention is described, for example, in Che
m.Ber.1955,88,962. Some synthetic routes for alkyl dihaloboranes (B) include, for example,
JACS 1977,99,7097 and U.S. Pat.No. 3,083,288, and Zh.Obshch.Khim.1959,29,3405, and Bull.Chim.Soc.France, 1967,11,4160. The manufacturing method is described. The borane required as a starting material of a borate compound useful as a counter anion component of the diazonium salt of the present invention can be obtained, for example, according to one of the methods described in the above documents.

Specific examples of the anion component represented by the general formula (II) which can be used in the present invention are shown in the following Tables 4 to 6 by describing each functional group, but the present invention is not limited to these. Not something.

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

The boric acid compounds having these anionic components are described in, for example, JP-A-9-188865 and JP-A-9-188686.

[0081] This diazonium salt compound used in the invention is represented by the following general formula Ar-N ₂ ⁺ X ^- is a compound represented by (Ar wherein represents an aromatic moiety), X ^- acid anion represented by The site has a borate component represented by the general formula (I-1), the general formula (I-2) or the general formula (II).

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

In the above formula, Ar represents a substituted or unsubstituted aryl group. As the substituent, an alkyl group,
Alkoxy, alkylthio, aryl, aryloxy, arylthio, acyl, alkoxycarbonyl, carbamoyl, carbamide, sulfonyl, sulfamoyl, sulfonamide, ureido, halogen, amino, heterocycle And the like, and these substituents may be further substituted.

The aryl group is preferably a compound having 6 to 6 carbon atoms.
30 aryl groups are preferred, for example a phenyl group, 2
-Methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- (2-
An ethylhexyloxy) phenyl group, a 2-octyloxyphenyl group, a 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, a 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, 4
-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-methyl Amino) -2-dodecyloxycarbonylphenyl group, and the like, but are not particularly limited thereto.
Further, these groups may be further substituted by an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a halogen atom, a heterocyclic group, or the like.

Hereinafter, specific examples of the cation portion of the diazonium salt compound which can be suitably used for the recording material of the present invention will be shown, but the present invention is not limited thereto.

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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

The diazonium salt compound having a specific anion component used in the present invention may be contained in the recording layer in an amount of from 0.01 to 0.01%.
3 g / m ² is preferable, and 0.02 to
0 g / m ² is more preferred. Effect of the present invention is less than 0.01 to 3 g / m ² can not be sufficiently obtained, since the improvement effect is not observed even if added over 3 g / m ^2, both undesirable. In addition, this diazonium salt compound is preferably contained in the same layer as the photopolymerization initiator in the recording layer from the viewpoint of the effect.

As the electron-accepting compound and the polymerizable vinyl monomer mainly used in the positive recording material used in the present invention, a compound containing an electron-accepting group and a polymerizable group in one molecule may be used. it can.

Examples of such compounds include 3-halo-4-hydroxybenzoic acid described in JP-A-4-226455 and benzoic acid having a hydroxy group described in JP-A-63-173682. Methacryloxyethyl ester, acryloxyethyl ester which can be synthesized by the same synthesis method, JP-A-59-83693, JP-A-59-83693,
Esters of hydroxymethyl-containing benzoic acid and hydroxymethylstyrene described in JP-A-141587 and JP-A-62-99190, hydroxystyrene described in European Patent No. 29323, JP-A-62-167077.
And N-vinylimidazole complexes of zinc halide described in JP-A-62-16708 and JP-A-63-3175.
Various compounds which can be synthesized with reference to the developer monomer described in JP-A-58-58, and the like.

Specific examples of the compound having the electron-accepting group and the polymerizable monomer portion in the same molecule include 3-halo-4-hydroxybenzoic acid represented by the following general formula. .

[0097]

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In this general formula, X represents a halogen atom, and among them, a chlorine atom is preferable. Y represents a monovalent group having a polymerizable ethylene group, and among them, an aralkyl group having a vinyl group, an acryloyloxyalkyl group or a methacryloyloxyalkyl group is preferable, and has 5 to 5 carbon atoms.
11 acryloyloxyalkyl groups or 6-1 carbon atoms
Two methacryloyloxyalkyl groups are particularly preferred.
Z represents a hydrogen atom, an alkyl group or an alkoxyl group.

Specific 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 And 4-hydroxybenzoic acid- (8-methacryloyloxyoctyl) ester.

Specific examples of the compound having the electron accepting group and the polymerizable monomer portion in the same molecule include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, β-methacryloxyethoxysalicylate, β-acrylic acid, and the like. Zinc roxyethoxysalicylate, vinyloxyethyloxybenzoic acid, β-methacryloxyethylorselinate, β-acryloxyethylorselinate, β-methacryloxyethoxyphenol, β-acryloxyethoxyphenol, β-methacryloxyethyl- β-resorcinate, β-acryloxyethyl-β
-Resorcinate, hydroxystyrene sulfonic acid -N
-Ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p
-Hydroxybenzoate, methacryloxymethylphenol, acryloxymethylphenol, methacrylamidopropanesulfonic acid, acrylamidopropanesulfonic acid, β-methacryloxyethoxy-dihydroxybenzene, β-acryloxyethoxy-dihydroxybenzene, γ-styrenesulfonyloxy-β -Methacryloxypropanecarboxylic acid, γ-acryloxypropyl-
α-hydroxyethyloxysalicylic acid, β-hydroxyethynylphenol, β-methacryloxyethyl-
p-hydroxycinnamate, β-acryloxyethyl-p-hydroxycinnamate, 3,5-distyrenesulfonic acid amide phenol, methacryloxyethoxyphthalic acid, acryloxyethoxyphthalic acid, methacrylic acid,
Acrylic acid, methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid, 3
-Β-hydroxyethoxyphenol, β-methacryloxyethyl-p-hydroxybenzoate, β-acryloxyethyl-p-hydroxybenzoate, β′-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoic acid ,
β-acryloxyethyloxycarbonylhydroxybenzoic acid, N, N′-di-β-methacryloxyethylaminosalicylic acid, N, N′-di-β-acryloxyethylaminosalicylic acid, N, N′-di-β- Methacryloxyethylaminosulfonylsalicylic acid, N, N'-di-β
-Acryloxyethylaminosulfonylsalicylic acid, metal salts thereof (eg, zinc salts), and the like are also preferably mentioned.

The photopolymerization initiator suitably used in the recording material of the present invention is a compound capable of initiating the photopolymerization of the above-mentioned polymerizable monomer, and when used in combination with a green, red or infrared absorbing dye. Having the following general formula (III-) which is sensitive to the wavelength region and generates radicals upon irradiation with light.
1) The compound represented by formula (III-2) or (IV), the organic borate salt compound described in JP-A-62-143044, or the organic borate salt of a cationic dye can be exemplified.

In the recording material of the present invention, the recording layer contains a diazonium salt compound containing an organic borate salt-based anion component, and the organic borate salt generates radicals based on the irradiated laser light. This radical initiates polymerization of the polymerizable monomer contained in the composition which is cured by light irradiation, and the formed polymer becomes a latent image.

Next, the organic borate used in the recording material of the present invention will be described. The compound used in the recording material of the present invention is an organic borate salt compound,
Preferably, the following general formula (III-1) and general formula (III-
2) or a compound represented by the general formula (IV).

[0104]

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In the general formulas (III-1) and (III-2), R
¹ , R ² , R ^2a , R ³ and R ⁴ are those represented by the general formula (I-
1) and (I-2).

E is P (R ¹⁴ ) (R ¹⁵ ) (R ¹⁶ ), S (R
⁶ ) (R ^6a ) and N (R ⁷ ) (R ⁸ ) (R ^8a ), wherein R ^{6 to} R ¹⁶ are as defined above.

G represents a group capable of forming a cation.

[0108]

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In the general formula (III), R ¹ , R ² , R ^2a , R
³ and R ⁴ have the same meanings as in the above formula (II).

G represents a group capable of forming a cation. here
Where G is quaternary ammonium, pyridinium, quinoli
, Diazonium, morpholinium, tetrazolium
, Acridinium, phosphonium, sulfonium,
Xosulfonium, sulfur, oxygen, carbon, halogenium,
Cu, Ag, Hg, Pd, Fe, Co, Sn, Mo, C
r, Ni, As, Se, n represents an integer of 1 to 6,
¹, R^Two, R^ThreeAnd R^FourMay be the same or different
A halogen atom, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted aryl group, substituted or unsubstituted aryl group
Alkyl, substituted or unsubstituted alkaryl, substituted or unsubstituted
Or unsubstituted alkenyl group, substituted or unsubstituted alkyl
Nyl group, substituted or unsubstituted alicyclic group, substituted
Or unsubstituted heterocyclic group, substituted or unsubstituted allyl
A group selected from a group and a substituted or unsubstituted silyl group.
R¹, R^Two, R ^ThreeAnd R^FourAre the two or more groups
May combine to form a cyclic structure.

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

Specific examples of the organic borate salts which can be suitably used as a photopolymerization initiator in the present invention are shown below. However, the effects of the present invention are not limited to the following compounds.

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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

In the present invention, if desired, the maximum absorption wavelength used in combination with the organic borate salt is 500 to 1100 n.
Examples of the infrared absorbing dye having a wavelength region of m include cationic dyes, and are dyes selected from cationic methine dyes, polymethine dyes, triarylmethane, indoline, azine, xanthene, oxazine, and acridine dyes. Is preferred.

It is preferable that the cationic dye is a dye selected from cationic cyanine, hemicyanine, rhodamine and azamethine dyes.

As the cationic dye (spectral sensitizing dye) that can be used in the present invention, any organic cationic dye having an absorption peak in a wavelength region of 500 nm or more, preferably 500 to 1100 nm, is preferably used. be able to.

Examples of the organic cationic dyes usable in the present invention include cationic methine dyes, cationic carbonium dyes, cationic quinone imine dyes, cationic indoline dyes and cationic styryl dyes. As the methine dye, preferably a polymethine dye, a cyanine dye, an azomethine dye,
More preferably cyanine, carbocyanine, dicarbocyanine, tricarbocyanine, hemicyanine and the like, as the cationic carbonium dye, preferably a triarylmethane dye, xanthene dye, alicidine dye,
More preferably rhodamine and the like, as the cationic quinone imine dye, preferably a dye selected from azine dyes, oxazine dyes, thiazine dyes, quinoline dyes, thiazole dyes and the like, and these are used alone or in combination of two or more. Can be used.

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

Further, an organic borate salt of a cationic dye, that is, an organic borate salt in which G is a cationic dye may be used.

Examples of the cationic dye represented by G ⁺ include:
It is preferably a dye selected from cationic methine dyes, polymethine dyes, triarylmethane, indoline, azine, xanthene, oxazine and acridine dyes.

Further, it is preferable that the cationic dye is a dye selected from cationic cyanine, hemicyanine, rhodamine and azamethine dyes.

Specific examples of the organic borate of the cationic dye which can be used in the present invention are shown below. However, the effects of the present invention are not limited to the following compounds.

[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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The content of the photopolymerization initiator is preferably from 0.01 to 20% by weight, and more preferably from 0.2 to 15% by weight, based on the total weight of the photocurable composition. The amount is between 1 and 10% by weight. 0.01% by weight
If it is less than 10%, the sensitivity is insufficient. If it exceeds 10% by weight, an increase in sensitivity cannot be expected.

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

[0141]

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In the general formula (3), X represents a halogen atom. Y ¹ is —CX ₃ , —NH ₂ , —NHR, —N
R ₂ represents —OR. Here, R represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Also,
Y ² represents -CX _3, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a substituted alkenyl group. The substituent may be the general formula (3) itself.

[0143]

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

[0145]

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

Examples of the compound represented by the general formula (3) include Written by Wakabayashi et al., Bulletin of Chemical Society Japan (Bull, Chem, Soc, Japan) 42, 292.
Compounds described on page 4 (1969), specifically, for example, 2-phenyl-4,6-bis (trichloromethyl)
-S-triazine, 2- (p-chlorophenyl) -4,
6-bis (trichloromethyl) -S-triazine, 2-
(P-tolyl) -4,6-bis (trichloromethyl)-
S-triazine, 2- (p-methoxyphenyl) -4,
6-bis (trichloromethyl) -S-triazine, 2-
(2 ′, 4′-Dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis ( Trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) 4,6-bis (trichloromethyl)- S-triazine and the like can be mentioned. In addition, British Patent 138849
No. 2, for example, 2-styryl-4,
6-bis (trichloromethyl) -S-triazine, 2-
(P-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxy Styryl) -4-amino-6
-Trichloromethyl-S-triazine, etc.
Compounds described in the specification of 133428, for example, 2-
(4-methoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1- Yl] -4,6-bis-trichloromethyl-S-triazine, 2- (4,7-dimethoxy-
Naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphth-5-yl)-
4,6-bis-trichloromethyl-S-triazine and the like,
Compounds described in German Patent No. 3337024, for example, compounds represented by the following structural formula can be mentioned.

[0148]

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

[0150]

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

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

[0153]

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[0154]

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

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

[0157]

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

[0159]

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

[0161]

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Can be obtained. In the present invention, as the compound represented by the general formula (4) having an active halogen group used as an auxiliary of a spectral sensitizing dye, a compound described in JP-B-51-8330, specifically, Is, for example, carbon tetrachloride, carbon tetrabromide, iodoform, p-nitro-α, α, α-tribromoacetophenone, ω, ω, ω-tribromoquinaldine, tribromomethylphenylsulfone, trichloro Methylphenyl sulfone and the like can be mentioned. In addition, Japanese Patent Publication No. 49-121
No. 80, for example, compounds of the following structure,

[0163]

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[0164]

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

[0166]

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

[0168]

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[0169]

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

The recording material of the present invention is highly sensitive and sensitive to infrared light. Further, as an auxiliary for promoting the formation of a latent image, a reducing agent such as an oxygen removing agent (Oxygens) is used.
cavenger) and an active hydrogen donor chain transfer agent,
Other compounds can be used in combination.

Oxygen scavengers which have been found to be useful in the recording material of the present invention as auxiliaries for accelerating the formation of a latent image are readily available with phosphine, phosphonate, phosphite, stannous salt and oxygen. Other compounds that are oxidized to: Specifically, for example, N-phenylglucin, trimethylbarbituric acid, N, N-dimethyl-
2,6-diisopropylaniline, N, N, N-2,
4,6-pentamethylaniline and the like. Further, the following thiols, thioketones, lofin dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, azides, and the like are also useful as auxiliaries.

As the thiols,

[0174]

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As thioketones,

[0176]

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[0177]

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The loffin dimer compound includes:

[0179]

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The iodonium salts include:

[0181]

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As the sulfonium salts,

[0183]

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As azinium salts,

[0185]

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As the organic peroxides,

[0187]

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As azides,

[0189]

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And the like can be used. Further, in the photocurable composition of the negative recording material used in the present invention, instead of the compound having the electron accepting group and the photopolymerizable monomer part in one molecule, an electron accepting compound and a photopolymerizable monomer are used. Can be used in combination. Further, in the photocurable composition in the positive recording material, if necessary, the electron-accepting compound is added in addition to the compound having the electron-accepting group and the photopolymerizable monomer in one molecule. The coloring density is improved by this addition.

Examples of the electron-accepting compound that can be used in the present invention include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, pentonite, novolak resins, metal-treated novolak resins, and metal complexes. Examples of these are Japanese Patent Publication No. 40-9309 and Japanese Patent Publication No. 4
5-14039, JP-A-52-140483, JP-A-48-51510, JP-A-57-210886,
JP-A-58-87089, JP-A-59-11286
No., JP-A-60-176799, JP-A-61-959
No. 88, etc. To illustrate some of these, as phenolic compounds, 2,2′-bis (4
-Hydroxyphenyl) propane, 4-t-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, 1,1'-bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1'-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1′-bis (3-chloro-4-hydroxyphenyl) -2-ethylbutane, 4,4′-sec-isooctylidenediphenol, 4,4′-sec-butylidenediphenol, 4
-Tert-octylphenol, 4-p-methylphenylphenol, 4,4'-methylcyclohexylidenephenol, 4,4'-isopentylidenephenol,
Benzyl p-hydroxybenzoate and the like. As salicylic acid derivatives, 4-pentadecylsalicylic acid, 3,5-
Di (α-methylbenzyl) salicylic acid, 3,5-di (t
tert-octyl) salicylic acid, 5-octadecylsalicylic acid, 5-α- (p-α-methylbenzylphenyl)
Ethyl salicylic acid, 3-α-methylbenzyl-5-te
rt-octylsalicylic acid, 5-tetradecylsalicylic acid, 4-hexyloxysalicylic acid, 4-cyclohexyloxysalicylic acid, 4-decyloxysalicylic acid,
-Dodecyloxysalicylic acid, 4-pentadecyloxysalicylic acid, 4-octadecyloxysalicylic acid and the like, and zinc, aluminum, calcium, copper and lead salts thereof. When these electron accepting compounds are used in combination, it is preferable to use 5 to 1000% by weight of the electron donating colorless dye.

In the photocurable composition of the negative recording material used in the present invention, a photopolymerizable monomer having at least one vinyl group in a molecule can be used. Specifically, for example, acrylic acid and its salts, acrylic esters, acrylamides; methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride,
Maleic esters; itaconic acid, itaconic esters; styrenes; vinyl ethers; vinyl esters; N-vinyl heterocycles; aryl ethers; Among these, a monomer having a plurality of vinyl groups in the molecule is particularly preferable,
For example, acrylic acid esters and methacrylic acid esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol; acrylic acid esters and methacrylic acid esters of polyhydric phenols such as resorcinol, pyrogallol, and phloroglucinol; And acrylate or methacrylate terminated epoxy resins, acrylate or methacrylate terminated polyesters, and the like. Specific examples of particularly preferable compounds include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol diacrylate. Methacrylate and the like. Regarding the molecular weight of the polyfunctional monomer, about 100 to
Preferably about 5000, more preferably about 300 to about 2000.

In addition to these compounds, a photocrosslinkable composition such as polyvinyl cinnamate, polycinnamylidene vinyl acetate, and a photocurable composition having an α-phenylmaleimide group can be added. Further, these photocrosslinkable compositions may be used as photocurable components.

Further, in addition to these compounds, a heat polymerization inhibitor can be added to the photocurable composition as needed. The thermal polymerization inhibitor is added to prevent the photocurable composition from undergoing ripening polymerization or polymerization with time, and thereby, the chemical stability during the preparation and storage of the photocurable composition. Can be increased. Examples of thermal polymerization inhibitors include p
-Methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t- Butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine and the like. The preferable addition amount of the thermal polymerization inhibitor is 0.1% based on the total weight of the photocurable composition.
001 to 5% by weight, more preferably 0.01 to 5% by weight.
1% by weight. If it is less than 0.001% by weight, the thermal stability is poor, and if it exceeds 5% by weight, the sensitivity decreases.

The photocurable composition of the recording material of the present invention is contained in the photosensitive and heat-sensitive layer by emulsification and dispersion. At this time, a natural oil or a synthetic oil can be used as a solvent for dissolving each material contained in the photocurable composition. Examples of these solvents include cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffins, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes and 1-phenyl-1-.
Diarylethanes such as xylylethane, 1-phenyl-1-p-ethylphenylethane, 1,1′-ditolylethane; Phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, etc.), phosphate ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.) citrate (eg, tributyl acetyl citrate) Benzoic acid esters (e.g., octyl benzoate), alkylamides (e.g., diethyl laurylamide), trimesic acid esters (e.g., tributyl trimesic acid), acetate esters (ethyl acetate, propyl acetate, iso-propyl acetate),
Butyl acetate, tert-butyl acetate, s-butyl acetate, etc.), propionate ester (eg, propionate ester), butyric acid (isobutyrate) ester (eg, methyl butyrate), acrylic acid (methacrylic acid) ester (eg, methyl acrylate) , Alkyl halides (methylene chloride, carbon tetrachloride, etc.), tertiary butyl alcohol, thimer isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone and the like. Of these, aliphatic esters and alkyl halides are preferred, and those having a solubility in water of 10% by volume or less are more preferred. These solvents are preferably used in a proportion of 1 to 500 parts by weight based on the polymerizable electron-accepting compound.

As the water-soluble polymer that can be used for emulsifying and dispersing the photocurable composition in the present invention, a compound that is soluble in water at 25 ° C. in an amount of 5% by weight or more is preferable. Gelatin derivatives, proteins such as albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, sugar derivatives such as sodium alginate, starches (including denatured starch),
Gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymer, synthetic polymer of polystyrene sulfonate sugar No. Among these, gelatin and polyvinyl alcohol are preferred.

The colorless electron-donating dyes relating to the recording material of the present invention include conventionally known triphenylmethanephthalide compounds, fluoran compounds, phenothiazine compounds,
Various compounds such as an indolylphthalide compound, a leuco auramine compound, a rhodamine lactam compound, a triphenylmethane compound, a triazene compound, a spiropyran compound, and a fluorene compound can be used. Specific examples of phthalides are described in U.S. Reissue Patent Specification No. 2
No. 3,024, U.S. Pat. No. 3,491,111
No. 3,491,112, No. 3,491,11
No. 6,509,174 and specific examples of fluorans are described in U.S. Pat. Nos. 3,624,107, 3,627,787, 3,641,011, and No. 3,462,828, No. 3,681,390,
No. 3,920,510, No. 3959,571,
Specific examples of spirodipyrans are described in US Pat.
No. 1,808, pyridine and pyrazine compounds are described in U.S. Pat. Nos. 3,775,424 and 3,853.
Nos. 3,869 and 4,246,318, and specific examples of fluorene compounds are described in Japanese Patent Application No. 61-240989.

If these compounds are partially disclosed, triarylmethane compounds include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3-bis (p-dimethylaminophenyl) phthalide, 3
-(P-dimethylaminophenyl) -3- (1,3-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, etc. And diphenylmethane-based compounds include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine, and the like. Rhodamine-B-anilinolactam, rhodamine-
(P-Nitrino) lactam, 2- (dipendylamino)
Fluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-dibutylaminofluoran, 2-anilino-3-methyl-
6-N-ethyl-N-isoamylaminofluoran, 2
-Anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, 2-anilino-3-
Methyl-6-N-ethyl-N-isobutylaminofluoran, 2-anilino-6-dibutylaminofluoran,
2-anilino-3-methyl-6-N-methyl-N-tetrahydrofurfurylaminofluoran, 2-anilino-
3-methyl-6-biperidinoaminofluoran, 2-
There are (o-chloroanilino) -6-diethylaminofluoran, 2- (3,4-dichloroanilino) -6-diethylaminofluoran, and the like. Examples of the thiazine-based compound include benzoyl leucon methylene blue and p-nitrobenzyl leucomethylene blue. And spiro-based compounds such as 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran 3,3′-dichloro-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, and 3-methyl-naphthopyran; Methoxy-benzo) spiropyran, 3-propyl-spiro-dibenzopyran and the like. In particular, when used for a full-color recording material, U.S. Pat. No. 4,800,149 is used as an electron-donating colorless dye for cyan, magenta and yellow, and U.S. Pat.
No. 63-535 as a cyan coloring type.
No. 42 etc. can be referred to.

For the microencapsulation of the electron-donating colorless dye of the recording material of the present invention, a method known in the art can be used. For example, US Patent Nos. 2,800,457 and 2,800
U.S. Pat. No. 3,287,715, which utilizes coacervation of a hydrophilic wall forming material as found in US Pat.
4, UK Patent No. 990443, JP-B-38-195
No. 74, No. 42-446, No. 42-771, an interfacial polymerization method, a method by precipitation of a polymer described in U.S. Pat. Nos. 3,418,250 and 3,660,304, and an isocyanate described in U.S. Pat. No. 3,796,669. Method using polyol wall material, US Patent 391
No. 4511, a method using an isocyanate wall material, US Pat. Nos. 4,001,140 and 4,087,376.
U.S. Pat. No. 4,089,802 and U.S. Pat. No. 4,089,802 using a urea-formaldehyde-based, urea-formaldehyde-resorcinol-based wall-forming material, and U.S. Pat. JP-B-36-9168 and JP-A-51-9079, in situ method by polymerization of monomer, British Patent No. 9
Nos. 52807 and 965074, the electrolytic dispersion cooling method, US Pat. No. 3,111,407, British Patent No. 930
No. 422, for example. Although not limited thereto, it is preferable to form a polymer film as a microcapsule wall after emulsifying the core substance.

As for the method of forming the microcapsule wall of the recording material of the present invention, the effect is particularly large when a microencapsulation method by polymerization of a reactant from the inside of an oil droplet is used. That is, it is possible to obtain a capsule having a uniform particle size in a short time, and which is preferable as a recording material having excellent raw preservability. For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and, if necessary, a second substance (eg, polyol or polyamine) which reacts with the polyisocyanate to form a capsule wall are mixed in an oily liquid to be encapsulated and emulsified in water. By dispersing and then raising the temperature, a polymer forming reaction occurs at the oil droplet interface to form microcapsule walls. At this time, an auxiliary solvent having a low boiling point and strong dissolving power can be used in the oily liquid. In this case, the polyvalent isocyanate to be used and the polyol and polyamine to be reacted therewith are described in US Pat.
No. 1383, No. 3773695, No. 3793268
No., JP-B-48-40347, JP-B-49-24159
And JP-A-48-80191 and JP-A-48-84086, and they can also be used.

As the polyvalent isocyanate, for example, m
Phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,
4-tolylene diisocyanate, naphthalene-1,4-
Diisocyanate, diphenylmethane-4,4-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-
1,4-diisocyanate, 4,4′-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene
Diisocyanates such as 1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene 1,4-diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, toluene Triisocyanates, such as -2,4,6-triisocyanate, 4,4 '
Tetradimethylisocyanate such as -dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, an adduct of hexamethylene diisocyanate and tremethylolpropane, an adduct of 2,4-tolylenediisocyanate and trimethylolpropane, xylylene There are isocyanate prepolymers such as adducts of diisocyanate and trimethylolpropane, and adducts of tolylene diisocyanate and hexanetriol.

Examples of the polyol include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters, and hydroxypolyalkylene ethers. JP-A-60-
The following polyols described in No. 49991 can also be used. Ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, propylene glycol, 2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2,2-dimethyl -1,3-propanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-1,
5-Bentanediol, 1,4-cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, 2-phenylpropylene glycol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol Pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,4-di (2-hydroxyethoxy) benzene,
Condensation product of aromatic polyhydric alcohol such as resorcinol dihydroxyethyl ether and alkylene oxide, p-xylylene glycol, m-xylylene glycol, α, α′-dihydroxy-p-diisopropylbenzene, 4,4′-dihydroxy -Diphenylmethane,
Examples thereof include 2- (p, p'-dihydroxydiphenylmethyl) benzyl alcohol, an adduct of ethylene oxide with bisphenol A, and an adduct of propylene oxide with bisphenol A. The polyol is preferably used in a ratio of 0.02 to 2 mol of the hydroxyl group to 1 mol of the isocyanate group.

Examples of the polyamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, Examples thereof include 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds. Polyvalent isocyanates can also react with water to form polymeric substances.

When making microcapsules, a water-soluble polymer can be used, and this water-soluble polymer may be any of a water-soluble anionic polymer, a nonionic polymer, and an amphoteric polymer. As the anionic polymer, either a natural polymer or a synthetic polymer can be used.
Those having an O—, —SO ₂ — group or the like can be mentioned. Specific examples of anionic natural polymers include arabic gum, alginic acid, and vectin.Semi-synthetic products include carboxymethyl cellulose, gelatin derivatives such as phthalated gelatin, sulfated starch, sulfated cellulose, and ligninsulfonic acid. is there. In addition, as synthetic products, maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers ,
Carboxy-modified polyvinyl alcohol and the like. Examples of the nonionic polymer include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose. Examples of the amphoteric compound include gelatin. Among them, gelatin, gelatin derivatives and polyvinyl alcohol are preferred. These water-soluble polymers are used as a 0.01 to 10% by weight aqueous solution. The average particle size of the capsule used in the recording material of the present invention is 20 μm or less, and particularly preferably 5 μm or less from the viewpoint of resolution. On the other hand, if the capsule is too small, the surface area for a certain solid content becomes large, and a large amount of a wall material is required. Therefore, the thickness is preferably 0.1 μm or more.

The colorless electron-donating dye according to the recording material of the present invention may be present in a microcapsule in a solution state or in a solid state. When the electron-donating colorless dye is present in a solution state, it may be encapsulated in a state where the electron-donating colorless dye is dissolved in a solvent. At this time, the amount of the solvent is preferably from 1 to 500 parts by weight based on 100 parts by weight of the electron-donating colorless dye. As the solvent used at the time of encapsulation, the same solvents as those used for emulsification of the above-mentioned photocurable composition can be used. Also,
At the time of microencapsulation, a volatile solvent may be used in combination with another solvent as an auxiliary solvent for dissolving the electron-donating colorless dye. Examples of this type of solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like.

In the recording material of the present invention, it is preferable to add a matting agent to the protective layer. Examples of the matting agent include silica, magnesium oxide, barium sulfate, strontium sulfate, inorganic compounds such as silver halide and polymethyl methacrylate, polyacrylonitrile, polymer particles such as polystyrene, carboxy starch, corn starch,
There are starch particles such as carboxynitrophenyl starch, and those having a particle diameter of 1 to 20 μm are preferred. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. Examples of silica particles include F
UJI-DEVICE CHEMICAL LTD.
SYLOD AL-1, 65, 72, 79, 74, 4
04, 620, 308, 978, 161, 162, 24
4, 255, 266, 150, etc. are preferable. The addition amount of the matting agent is preferably 2-500 mg / m ² , particularly preferably 5-100 mg / m ² .

In the recording material of the present invention, it is preferable to use a curing agent in combination with each layer of the recording material of the present invention such as a light and heat sensitive layer, an intermediate layer and a protective layer. In particular, it is preferable to use a curing agent in the protective layer to reduce the tackiness of the protective layer. As the curing agent, for example, a "gelatin curing agent" used in the production of a photographic light-sensitive material is useful, for example, an aldehyde compound such as formaldehyde and glutaraldehyde, and a reactive agent described in US Pat. Compounds having a halogen, compounds having a reactive ethylenically unsaturated bond described in U.S. Pat. No. 3,635,718, and others, aziridine compounds described in U.S. Pat. No. 3,017,280, and US Pat. No. 30,915
Epoxy compounds described in No. 37 and others, halogenocarboxaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, and vinyl sulfones described in US Pat. No. 3,642,486 and US Pat. No. 3,687,707 ,
Vinyl sulfone breakers described in U.S. Patent No. 3,841,872, ketovinyls described in U.S. Patent No. 3,640,720, or chromium alum, zirconium sulfate, boric acid, and the like can be used as an inorganic curing agent. . Among these curing agents, a particularly preferred compound is 1,3,5-triacloyl-hexahydro-
s-Triazine, 1,2-pispinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamide)
Compounds such as ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenino-s-triazine and boric acid. The addition amount is preferably 0.5-5% by weight based on the binder.

In addition, colloidal silica may be added to the protective layer in order to reduce the adhesiveness. As the colloidal silica, for example, Nissan Chemical's Snowtex 20, Snowtex 30, Snowtex C, Snowtex O, Snowtex N, and the like are preferable. The addition amount is preferably 5-80% by weight based on the binder. Further, a fluorescent whitening agent for increasing the whiteness of the recording material used in the present invention or a blue dye as a bluing agent may be added to the protective layer.

In the case of the multicolor recording material of the recording material used in the present invention, for example, a microcapsule containing an electron-donating colorless dye that develops a different hue and a photocurable composition sensitive to light of a different wavelength are applied to each layer. A multi-layered recording material may be used, and an intermediate layer containing a filter dye may be provided between the photosensitive and heat-sensitive layers. The intermediate layer is mainly composed of a binder and a filter dye, and can contain additives such as a curing agent and a polymer latex, if necessary.

The dye for a filter used in the recording material of the present invention can be emulsified and dispersed by an oil-in-water dispersion method or a polymer dispersion method and added to a desired layer, particularly to an intermediate layer. In the oil-in-water dispersion method, after dissolving in a single solution or a mixture of both a high-boiling organic solvent having a boiling point of, for example, 175 ° C. or more and a so-called auxiliary solvent having a boiling point of, for example, 30 ° C. to 160 ° C. The agent is finely dispersed in an aqueous medium such as water, an aqueous gelatin solution or an aqueous polyvinyl alcohol solution in the presence of an agent. Examples of high boiling organic solvents are described in U.S. Pat.
No. 2,027. Further, as specific examples of the high boiling point organic solvent and the auxiliary solvent, the same solvents as those used in the above-mentioned encapsulation can be preferably used. Further, the dispersion may be accompanied by a phase inversion, or the auxiliary solvent may be removed or reduced by distillation, Nudel washing, ultrafiltration or the like as necessary before use for coating.

A specific example of the latex dispersion process, a latex for curing and impregnation is described in US Pat. No. 4,199,38.
3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, JP-A-49-745.
No. 38, No. 51-59943, No. 54-32552
Issue, each gazette and Research Disclosur
e, Vol. 148, August 1976, Item 14
850, etc. Suitable latexes include, for example, acrylates or methacrylates (eg, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate) and acid monomers (eg, acrylic acid, 2-acrylamide). -2-methylpropanesulfonic acid).

In the recording material of the present invention, as a binder for each layer of the recording material such as a protective layer, a light and heat sensitive layer and an intermediate layer, the binder is used for emulsifying and dispersing a photocurable composition and encapsulating an electron donating colorless dye. In addition to water-soluble polymers that can
Polystyrene, polyvinyl formal, polyvinyl butyral, acrylic resin: for example, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and copolymers thereof, phenol resin, styrene-butadiene resin, ethyl cellulose, epoxy resin, urethane resin, Solvent-soluble polymers such as these or latexes of these polymers can also be used. Among these, gelatin and polyvinyl alcohol are preferred.

In each layer of the light- and heat-sensitive recording material of the present invention, various surfactants may be used for various purposes such as a coating aid, an antistatic property, an improvement in slipperiness, an emulsification dispersion, and an adhesion prevention. Examples of the surfactant include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide derivatives such as alkyl ether of polyethylene oxide, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N -Anionic surfactants such as -acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylenalkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, aliphatic or Cationic surfactants such as aromatic quaternary ammonium salts can be used as needed.

Various additives can be added to the recording material of the present invention, if necessary, including the additives described above. For example, typical examples of dyes, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids, curing agents, antistatic agents and slipperiness improvers for preventing irradiation and halation are Research Disclosure,
Vol. 176, December 1978, Item 176
43, and Vol. 187, November 1979, I
tem 18716.

The coating solution for light and heat of the recording material of the present invention and the coating solution for each of the above-mentioned layers may be dissolved in a solvent as necessary, coated on a desired support, and dried to obtain the recording material of the present invention. The material is obtained. Examples of the solvent used in this case include water and alcohol: for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, methyl cellosolve, 1-methoxy-2-propanol; a halogen-based solvent; Chloride, ethylene chloride: ketone: for example, acetone, cyclohexanone, methyl ethyl ketone: ester: For example, a single substance such as methyl acetate cellosolve, ethyl acetate, methyl acetate: toluene, xylene and the like, and a mixture of two or more thereof are exemplified. Of these, water is particularly preferred.

To apply the coating solution for each layer onto the support, a blade coater, a rod coater, a knife coater, a roll doctor coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a curtain coater, an extender A lution coater or the like can be used. As the coating method, Rcscan Disclosurc, V
ol. 200, December 1980, Item 2003
Section 6 XV can be referred to. As the thickness of the recording layer,
0.1 μm to 50 μm is appropriate.

The recording material of the present invention can be used for various uses. For example, copiers, faxes, printers, labels,
The recording material of the present invention can be used for applications such as color proofing and second original drawing.

Examples of a support suitable for the recording material of the present invention include films such as paper, coated paper, laminated paper, synthetic paper, polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, polycarbonate film, and the like. Examples thereof include metal plates made of aluminum, zinc, copper, etc., and those obtained by subjecting the surface of these supports to various treatments such as surface treatment, undercoating, and metal vapor deposition. In addition, Research
Disclosure, Vol. 200, 1980 1
In February, the support of Item 20036 XVII can also be referred to. Further, if necessary, an antihalation layer can be provided on the front surface, and a sublayer, an antistatic layer, an anti-curl layer, a pressure-sensitive adhesive layer, or the like can be provided on the back surface according to the purpose.

The recording material of the present invention can perform recording with light in the near infrared region of 0.7 to 3 μm. Known light sources such as a semiconductor laser light emitting diode and a xenon lamp can be appropriately used as the near infrared light source.
Further, by irradiating two or more kinds of near-infrared dyes from two or more kinds of light sources having different wavelengths, multicolor recording as described above can be performed.

The recording material of the present invention is subjected to a heat development treatment simultaneously with or after the image exposure. Various conventionally known methods can be used as a heating method in the heat development processing. The heating temperature is generally 80 ° C to 200 ° C.
° C, preferably 85 ° C to 130 ° C. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute.
It is preferable that the entire surface of the recording material of the present invention is exposed after the heat development treatment, and the uncured portion is also light-cured. Since the entire surface exposure suppresses the coloring reaction of the background and the decoloring reaction of the coloring portion, the storability of the image is improved.

Further, in the recording material, the sensitivity is further improved by including a process of uniformly preheating the entire surface of the recording material to a predetermined temperature lower than the color development temperature, similarly to the above-described recording methods. It is.

The recording material of the present invention can be applied to not only the above-mentioned recording method but also a known recording method. For example, for the purpose of improving heat sensitivity, contrast, and image quality, irradiation with a laser beam described in a publication of a silver halide light-sensitive and heat-sensitive recording material proposed by 3M in International Application WO95 / 31754 has a predetermined overlap. Can be applied to the recording method of performing

That is, in the laser beam irradiation for forming a latent image, (1) a beam is supplied from a radiation light source which forms a spot at least one of a height and a length of 600 μm or less at a target position; (3) supplying a recording material sensitive to the light source to the target position, and (3) first applying the recording material according to an image distribution by a radiation light source that forms a spot in which at least one of a length or a width has a size of 250 μm or less. Irradiating, (4) a technique of irradiating the recording material according to an image distribution such that at least some spots from the second irradiating beam overlap the first irradiating spot of the recording material, A method of forming a latent image on the material by exposing the material to (1) exposing the material to a radiation light source capable of sensitizing the material, and (2) exposing the material to a size of 600 μm or less in one direction. Irradiating at least 10% of the individual sub-regions of the material with another sub-region in the sense of at least 10% of the total energy of the at least one sub-region, It is the basis.

A recording method proposed by Canon Inc. in JP-A-60-195568 can also be applied. That is, by tilting the angle at which the irradiation laser beam is incident on the recording material surface, the reflection pitch at which the incident beam interfacially reflects the thin layer of the recording material is made larger than the beam spot diameter of the beam, By applying a technique characterized by preventing light interference occurring in the recording material, a higher quality image can be obtained.

[0225]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. Unless otherwise specified in the text, "%" is "% by weight"
And “parts” means “parts by weight”.

[0226] 1. [Preparation of Electron-donating Colorless Dye (1) Capsule] 8.9 g of the electron-donating colorless dye (1) was added to ethyl acetate.
Takenate D-11 as an encapsulating agent
20 g of 0N (manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 g of Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. This solution was added to a mixture of 42 g of 8% phthalated gelatin and 1.4 g of a 10% sodium dodecylbenzenesulfonate solution, and emulsified and dispersed at 20 ° C. to obtain an emulsion. 14 g of water and 72 g of a 2.9% aqueous solution of tetraethylenepentamine are added to the obtained emulsion, and the mixture is heated to 60 ° C. with stirring, and after 2 hours, the electron-donating colorless dye (1)
Was obtained in a core and having an average particle size of 0.5 μm.

[0227] 2. [Preparation of emulsion of photocurable composition (1)] 0.13 g of photopolymerization initiator (1) and spectral sensitizing dye (23)
0.1 g, a diazonium salt cation part (exemplified compound (3) -2) and an exemplified borate anion part (I-35) of the general formula (I-1) or (I-2) shown in Table 3 above.
5 g of a polymerizable electron accepting compound (1) was added to a mixed solution of 0.05 g of a 1: 1 complex compound with a) and 3 g of isopropyl acetate (solubility in water: about 4.3%). This solution was combined with 13 g of a 13% aqueous gelatin solution and 2 g of a 2% surfactant (1) 0.8 g of an aqueous solution of 2% surfactant (1)
It was added to a mixed solution with 0.8 g of an aqueous solution, and emulsified at 10,000 rpm for 5 minutes with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsion of the photocurable composition (1).

Hereinafter, the polymerizable electron-accepting compound (1)
And the chemical structural formulas of the compounds used for preparing the above-mentioned emulsions and the like.

[0229]

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[0230]

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[0231]

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[0232] 3. [Preparation of Coating Solution for Photosensitive and Thermosensitive Recording Layer] Electron-donating colorless dye (1) 4 g of capsule and 12 g of emulsion of photocurable composition (1) and 12 g of 15% aqueous gelatin solution
Were mixed to prepare a coating solution for the photosensitive and heat-sensitive recording layer (1).

[0233] 4. [Preparation of Coating Solution for Protective Layer] 4.5 g of a 10% gelatin aqueous solution, 4.5 g of distilled water and 2%
0.5 g of a surfactant (3) aqueous solution and 0.3 g of a 2% surfactant (4) aqueous solution and 0.5 g of a 2% hardener (1) aqueous solution
g and Syloid 72 (FUJI-DEVICE CH)
EMICALLTD. Was mixed with 1 g of Snowtex N to give a coating amount of 50 mg / m ² to prepare a coating solution for the protective layer (1). The chemical structural formulas of the surfactants (1), (2), (3) and (4) are shown below.

[0234]

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[0235] 5. [Support] 75 μm thick transparent polyester base. (Example 1) A coating solution for a photosensitive and heat-sensitive layer was coated on a support with a coating bar at a dry weight of 10 g / m using a coating bar.
² and dried at 30 ° C. for 10 minutes. A coating solution for the protective layer (1) is applied thereon using a coating bar such that the dry weight of the applied layer is 2 g / m ² ,
The sample of Example 1 was obtained by drying at 30 ° C. for 10 minutes. (Example 2) In the photocurable composition (1) of the coating solution (1) for the photosensitive and heat-sensitive layer used in Example 1, the exemplified borates shown in Table 1 were used instead of the exemplified borate anion part (I-35a). A light- and heat-sensitive recording material was prepared in the same manner as in Example 1, except that a coating solution for a light- and heat-sensitive layer was prepared using the complex compound obtained by the anion portion (I-6a).
evaluated. (Example 3) In the photocurable composition (1) of the coating solution (1) for the photosensitive and heat-sensitive layer used in Example 1, instead of the exemplified borate anion (I-35a), the general formula (Table 4) Except for preparing a coating solution for a photosensitive and heat-sensitive layer using the complex compound obtained by the exemplified borate anion part (II-5) of II), a photosensitive and heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1. . (Example 4) In the photocurable composition (1) of the coating solution (1) for the photosensitive and heat-sensitive layer used in Example 1, instead of the exemplified borate anion part (I-35a), a general formula (Table 4) Except that a coating solution for a photosensitive and heat-sensitive layer was prepared using the complex compound obtained by the exemplified borate anion part (II-16) of II), a photosensitive and heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1. . (Example 5) In the photocurable composition (1) of the coating solution (1) for the photosensitive and heat-sensitive layer used in Example 1, an exemplified compound in place of the diazonium cation part of the diazonium salt (exemplified compound (3) -2) (3) A light- and heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1, except that a coating solution for a light- and heat-sensitive layer was prepared using the complex compound obtained by the diazonium cation portion of -3. (Example 6) In the photocurable composition (1) of the coating solution (1) for the photosensitive and heat-sensitive layer used in Example 1, an exemplified compound in place of the diazonium cation part of the diazonium salt (exemplified compound (3) -2) (4) A light- and heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1, except that a coating solution for a light- and heat-sensitive layer was prepared using the complex compound obtained by the diazonium cation part of -1. (Comparative Example 1) From the photocurable composition (1) of the coating solution (1) for the photosensitive and heat-sensitive layer used in Example 1, a diazonium salt cation part (exemplified compound (3) -2) and an exemplified borate anion part (I- A light- and heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a coating solution for a light- and heat-sensitive layer was prepared except for removing the 1: 1 complex compound with 35a). (Evaluation of the light- and heat-sensitive recording material) For each of the obtained light- and heat-sensitive recording materials, using a semiconductor laser beam having a wavelength of 657 nm from the heat-sensitive layer side, changing the scanning speed and changing the irradiation energy in the form of a step wedge, Up to 50
Irradiation exposure was performed so that the energy became mJ / cm ² .

When the recording material having the latent image formed thereon was heated with a hot plate at 120 ° C. for 5 seconds, a step wedge image was obtained in each material. The sensitivity was evaluated based on the energy at which the background appeared in a wedge image with a constant exposure.
The color density and the background fog were measured with a Macbeth transmission densitometer. The transparency of the recording material was measured using a haze meter (DIG
ITAL HAZE COMPUTER HGM-2D
P Suga Test Machine Co., Ltd.). Table 7 shows the results.

[0237]

[Table 7]

As is clear from Table 7, photosensitive and heat-sensitive recording using the diazonium salt compounds having a borate anion moiety of the general formulas (I-1), (I-2) and (II) of the present invention. All of the materials had good sensitivity, excellent color density, little background fog, and were able to form images with high contrast. Also, the transparency was excellent. On the other hand, the sample of Comparative Example 1 containing no specific diazonium salt compound did not form an image.

[0239]

As described above, the photosensitive and heat-sensitive recording material of the present invention can perform recording using green to red laser light and infrared laser light. An excellent effect is obtained in that a clear, high-contrast image of full dry black and white or color with no objects can be formed.

Claims (5)

[Claims] 1. A thermo-responsive microcapsule on a support
Electron-donating colorless dye encapsulated in
Outside the capsule, an electron-accepting developer, a photopolymerizable monomer
With a photosensitive and heat-sensitive recording layer containing a polymer and a photopolymerization initiator
A light- and heat-sensitive recording material, wherein the light- and heat-sensitive recording layer has the following general formula (I-1) or
Diazoniu having an anionic component represented by (I-2)
Photosensitive and heat-sensitive recording material characterized by containing a salt compound
Fees. Embedded imageWhere R¹, R^TwoAre each independently a phenyl group,
Another aromatic hydrocarbon group which may contain a terrorist atom,-
Si (R⁹) (R^Ten) (R¹¹) Substituted carbon atoms
1 to 20 alkyl groups represented by the following formulas (II), (IIa) and (II)
represents a group represented by b). Here, the phenyl group,
The aromatic hydrocarbon group is an alkyl group having 1 to 20 carbon atoms,
O, S (O)_p, NR^Five2 to 2 carbon atoms containing
An alkyl group of 0, OR⁶, R⁶S (O)_p, R⁶S
O_Three, N (R⁷) (R⁸), R⁶OCO, CON
(R⁷) (R⁸), COR⁹, Si (R⁹) (R^Ten)
(R¹¹), Sn (R⁹) (R^Ten) (R¹¹), B (R¹²)
(R¹³), A halogen group, (R⁹) (R^Ten) P (O)_q,
A phenyl group, an aromatic group,
In the hydrocarbon group, at least one ortho position has these substituents.
Has been replaced by R^2aRepresents a phenylene, heteroatom
Represents another divalent aromatic hydrocarbon group which may be contained,
This aromatic hydrocarbon group is an alkyl having 1 to 20 hydrocarbons.
Group, O, S (O)_p, NR^FiveNumber of carbon atoms containing
2-20 alkyl groups, OR⁶, R ⁶S (O)_p, R⁶
SO_Three, N (R⁷) (R⁸), R⁶OCO, CON (R
⁷) (R⁸), COR⁹, Si (R⁹) (R^Ten)
(R¹¹), Sn (R⁹) (R^Ten) (R¹¹), B (R¹²)
(R¹³), A halogen group, (R⁹) (R^Ten) P (O)_q,
CN or a group represented by the following formula (a)
Is also good. Embedded imageEmbedded imageIn the formula (a), R^aIs an alkylene group, having 1 to 12 carbon atoms.
An alkyl group having 1 to 12 carbon atoms, R
⁶OCO, CN, substituted alkyl substituted with halogen atoms
Represents a len group. Where R⁶Is synonymous with
You. In the formulas (II), (IIa) and (IIb), the aromatic ring is
An alkyl group having 1 to 20 carbon atoms, O, S (O) p, N
R^FiveAn alkyl group having 2 to 20 carbon atoms containing
R⁶, R⁶S (O) p, R⁶SO_Three, N (R⁷)
(R⁸), R⁶OCO, CON (R⁷) (R⁸), CO
R⁹, Si (R⁹) (R^Ten) (R¹¹), Sn (R⁹)
(R^Ten) (R¹¹), B (R¹²) (R¹³), Halogen group,
(R⁹) (R^Ten) P (O)_q, Even if substituted with CN
good. Y is (CH_Two)_n, CH = CH, CO, N
R^Five, O, S (O)_pIt is represented by R^ThreeIs -Si (R
⁹) (R^Ten) (R¹¹1) to 20 carbon atoms substituted with
Containing alkyl, phenyl and heteroatoms
A good alternative aromatic hydrocarbon group;
The aromatic hydrocarbon group is an alkyl group having 1 to 20 hydrocarbons,
O, S (O)_p, NR^Five2 to 2 carbon atoms containing
An alkyl group of 0, OR⁶, R⁶S (O)_p, R⁶S
O_Three, N (R⁷) (R⁸), R⁶OCO, CON
(R⁷) (R⁸), COR⁹, Si (R⁹) (R^Ten)
(R¹¹), Sn (R⁹) (R^Ten) (R¹¹), B (R¹²)
(R¹³), A halogen group, (R⁹) (R^Ten) P (O) _q,
It may be substituted by CN. R^FourIs a phenyl group,
Another aromatic hydrocarbon group which may contain
An alkyl group having 1 to 20 atoms, O, S (O)_p, NR^Five
An alkyl group having 2 to 20 carbon atoms containing
A cycloalkyl group having 3 to 12 carbon atoms and 2 to 8 carbon atoms
An alkenyl group, a group represented by the following formulas (a) and (b):
You. Embedded imageIn the formulas (a) and (b), R^a, R^bAre each independently
Cylene group, alkyl group having 1 to 12 carbon atoms, carbon atom
An alkoxy group of the formulas 1 to 12, R⁶OCO, CN, halogen
And represents a substituted alkylene group substituted with a nitro atom. here,
R⁶Has the same meaning as described above. R described above^FourIndicated by
The substituent is OR⁶, R⁶S (O)_p, R⁶SO_Three, N (R
⁷) (R⁸), R⁶OCO, CON (R⁷) (R⁸),
COR⁹, Si (R⁹) (R^Ten) (R¹¹), Sn
(R⁹) (R^Ten) (R¹¹), B (R¹²) (R¹³),Halo
Gen group, (R⁹) (R^Ten) P (O)_q, Substituted with CN
May be. n is an integer of 0, 1, 2;
An integer, p is an integer of 0, 1, 2; g is an integer of 0, 1
Respectively. R^FiveIs a hydrogen atom, having 1 to 12 carbon atoms
An alkyl group, a phenyl group, a group represented by the formula (a)
And the phenyl group and the group represented by the formula (a) are carbon
An alkyl group having 1 to 6 atoms and an alkyl group having 1 to 12 carbon atoms
Coxy group, R⁶OCO, CN, substituted with a halogen group
Is also good. R⁶Is R^FiveIs synonymous with R⁷, R⁸, R
^8aIs an alkyl group having 1 to 12 carbon atoms, 3 to
A cycloalkyl group or a phenyl group represented by the formula (a):
Represents a group represented by the formula: a phenyl group represented by the formula (a);
Group is an alkyl group having 1 to 6 carbon atoms, 1 carbon atom
~ 12 alkoxy groups, R⁶OCO, CN, halogen group
May be substituted. Also, R⁷, R⁸Are they combined
O and S together with the nitrogen atom
A good 5- or 6-membered ring may be formed. R⁹, R^Ten,
R¹¹Is independently alkyl having 1 to 12 carbon atoms
Group, cycloalkyl group having 3 to 12 carbon atoms, phenyl
A group represented by the formula (a); a phenyl group;
The group represented by the formula (a) is an alkyl having 1 to 6 carbon atoms.
Group, an alkoxy group having 1 to 12 carbon atoms, R⁶OC
It may be substituted with O, CN or a halogen group. R¹², R¹³
Is R⁹~ R¹¹Has the same meaning as above, but an alkyl group, R¹²,
R¹³Together with the boron atoms to which they are attached
Forming a 5- or 6-membered ring which may contain O and S
Is also good. R¹⁴, R^Fifteen, R¹⁶Are independently the number of carbon atoms
An alkyl group having 1 to 12 carbon atoms and an alkenyl having 2 to 12 carbon atoms
Phenyl, cycloalkyl having 3 to 12 carbon atoms, phenyl
A group represented by the formula (a);
Group, alkenyl group and cycloalkyl group are represented by R₆OCO, C
A phenyl group, which may be substituted with N,
Is an alkyl group having 1 to 6 carbon atoms,
An alkoxy group having 1 to 12 atoms, R⁶OCO, CN, C
It may be substituted with a logene group. E is P (R¹⁴)
(R^Fifteen), S (R⁶), N (R⁷) (R⁸)
Where R⁶~ R^FifteenIs the same as defined above. 2. A thermo-responsive microcapsule on a support.
Electron-donating colorless dye encapsulated in a thermoresponsive microphone
Outside the capsule, an electron-accepting developer, a photopolymerizable monomer
And heat-sensitive recording layer containing photopolymerization initiator
A light and heat sensitive recording material, wherein the light and heat sensitive recording layer is an anisotropic material represented by the following general formula (II).
Contains a diazonium salt compound having an ON component
A light and heat sensitive recording material characterized by the following. Embedded imageIn the general formula (II), R¹Is alkyl having 1 to 20 carbon atoms
Group, cycloalkyl group having 3 to 12 carbon atoms, carbon atom
An alkenyl group of Formulas 2 to 8, represented by the following formulas (a) and (b)
Represents a group represented by¹Is O, S
(O)_p, NR^FiveMay be interrupted. Embedded imageIn the formulas (a) and (b), R^a, R^bAre each independently
Cylene group, alkyl group having 1 to 12 carbon atoms, carbon atom
An alkoxy group of the formulas 1 to 12, R⁶OCO, CN, halogen
And represents a substituted alkylene group substituted with a nitro atom. here,
R⁶Has the same meaning as described above. Also, R₁Indicated by
The substituent further includes an alkyl group having 1 to 20 carbon atoms, O
R⁶, R⁷S (O)_p, R⁷SO_Three, N (R⁸)
(R⁹), Si (R^Ten) (R¹¹) (R¹²), B (R¹³)
(R¹⁴), A halogen group, (R^Fifteen) (R¹⁶) P (O)_qso
It may be replaced. R^Two~ R^FourAre independent
Represents a phenyl group or a biphenyl group. This R^Two~ R ^FourIndicated by
Substituent is an alkyl group having 1 to 20 carbon atoms (this
The alkyl group is OR₆, HR₈R₉Depending on the halogen atom
OR)⁶, R ⁷S (O)_p,
R⁷SO_Three, N (R⁸) (R⁹), Si (R^Ten)
(R¹¹) (R¹²), B (R¹³) (R¹⁴), Halogen source
Child, (R^Fifteen) (R¹⁶) P (O)_q, Represented by the following formula
It may be substituted with a substituent. Embedded imageR^Two~ R^FourAre +0.36 to +2.
58 is shown. X is O, S, NR^{twenty one}Represents R^FiveIs hydrogen field
, An alkyl group having 1 to 12 carbon atoms, in the above formula (a)
May be substituted with a substituent represented by the formula (a)
Having 1 to 6 carbon atoms on the phenyl ring of the substituent
Kill group, alkoxy group having 1 to 12 carbon atoms, halogen
It may have an atomic substituent. R⁶~ R⁷Is haloge
Having 1 to 12 carbon atoms which may be substituted with
Alkyl group, phenyl group, substituent represented by the above formula (a)
May be substituted with a phenyl group and a compound represented by the formula (a).
Having 1 to 6 carbon atoms on the phenyl ring of the substituent
Kill group, alkoxy group having 1 to 12 carbon atoms, halogen
It may have an atomic substituent. R⁸~ R¹⁶Each
Independently an alkyl group having 1 to 12 carbon atoms,
3 to 12 are cycloalkyl groups, phenyl groups,
(A) may be substituted with a substituent,
On the phenyl ring of the benzyl group and the substituent represented by the formula (a)
An alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms
It may have an alkoxy group or a halogen atom substituent
No. R⁸~ R⁹Together with the nitrogen atom to which they are attached
Aliphatic 6 which may further contain other hetero atoms O and S
It may form a member ring. R¹⁷~ R²⁰Is hydrogen atom, charcoal
It may be substituted with an alkoxy group having 1 to 12 atoms.
An alkyl group having 1 to 12 carbon atoms, a phenyl group,
May be substituted with a substituent represented by the formula (a),
On the phenyl ring of the phenyl group and the substituent represented by the formula (a)
An alkyl group having 1 to 6 carbon atoms, 1 to 12 carbon atoms
Having an alkoxy group or a halogen atom substituent
Good. R^{twenty two}~ R^{twenty four}Is a hydrogen atom, an atom having 1 to 12 carbon atoms.
May be substituted with a alkoxy group, OH or a halogen atom
Alkyl groups having 1 to 12 carbon atoms, 1 to 1 carbon atoms
2 substituted with an alkoxy group, OH or a halogen atom
Represents a phenyl group which may be substituted. q represents an integer of 0 to 1. 3. An electron-donating colorless dye encapsulated in thermoresponsive microcapsules on a support, and an electron-accepting group and a polymerizable group in the same molecule outside the thermoresponsive microcapsules. A light- and heat-sensitive recording material provided with a light- and heat-sensitive recording layer containing a compound having the compound and a photopolymerization initiator, wherein the light and heat-sensitive recording layer is represented by the general formula (I-1) or the general formula (I-2). A light- and heat-sensitive recording material comprising a diazonium salt compound having an anion component to be used. 4. An electron-donating colorless dye encapsulated in thermoresponsive microcapsules on a support, and an electron-accepting group and a polymerizable group in the same molecule outside the thermoresponsive microcapsules. And a light- and heat-sensitive recording material provided with a light- and heat-sensitive recording layer containing a photopolymerization initiator, wherein the light- and heat-sensitive recording layer comprises a diazonium salt compound having an anion component represented by the general formula (II). A light and heat sensitive recording material characterized by containing. 5. A first photosensitive layer in which the light and heat sensitive recording material is exposed to light having a center wavelength λ1 from an exposure light source side to a support side of the recording material, and an intermediate layer which absorbs light having a center wavelength λ1. , A second photosensitive layer sensitized to light having a center wavelength λ2 and developing a color different from that of the first photosensitive layer,..., A center wavelength λi−
, And the first photosensitive layer that is sensitive to light of the central wavelength λi and develops a different color from the first, second,..., And i−1th photosensitive layers. 5. The photoconductor according to claim 1, wherein at least two or more photosensitive layers have a layer structure laminated on a support, and a center wavelength λ1 <λ2 <... <Λi. The photosensitive and heat-sensitive recording material as described in the above. Here, i represents an integer of 2 or more.