JP2000075476A - Photosensitive and heatsensitive recording material and image recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color or black and white photosensitive and heatsensitive recording material which exhibits high sensitivity and high contrast and can be recorded by using green to red lasers, an infrared laser or the like in a complete dry treating process without causing any waste. SOLUTION: This photosensitive and heatsensitive recording material is provided with a photosensitive and heatsensitive recording layer containing a heat responsive micro-capsule including an electron-donating colorless dye, and electron-accepting compound, a photo-polymerizable monomer, a spectral sensitizing dyestuff and a photopolymerization initiator and/or an organic boron compound on a substrate. In the material, the photosensitive and heatsensitive recording layer contains the spectral sensitizing dyestuff in such a concentration distribution that the content of the dyestuff increases in the thickness direction from the surface of incidence of irradiation light. It is possible to use a compound containing an electron accepting group and a polymerizable group in one molecule in place of the electron accepting compound and the polymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color or black-and-white light- and heat-sensitive recording material for image recording using a green laser light, a red laser light or an infrared laser light as a light source.

[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 do not generate waste have been studied, and among them, a method using a composition which is cured by light has attracted attention. I have. In this method, a latent image is formed by curing a composition that is cured by light contained in a recording material by exposing, while a color is formed by heating or contained in an unexposed portion of the recording material. It is characterized in that components acting on the decoloring reaction move in the recording material to form a color image. When using a recording material of such a method, first, light is exposed on the recording material through an image original, the exposed portion is cured to form a latent image, and then the recording material is heated to be uncured. A component that acts on the color development or decoloration reaction contained in the portion (unexposed portion) is moved to form a visible image. According to this method, a complete dry system that does not generate waste can be realized.

There are several types of recording materials for use in the above-mentioned method, and these are characteristic methods as a black-and-white image recording method. Particularly, a method useful for a color image recording material is used. It is. Specific recording materials include:
For example, a two-component type light- and heat-sensitive color recording material disclosed in JP-A-52-89915 is known. This is, for example, a thermosensitive coloring type recording material containing an electron-accepting compound and an electron-donating colorless dye as two components, inside or outside a microcapsule containing a photocurable composition, or both. is there. However, even if this recording material sufficiently cures the photocurable composition contained in the microcapsules, the color development in the cured portion cannot be sufficiently suppressed, so that the non-image portion is colored, Contrast tends to decrease.

As a recording material having no coloring in the non-image area,
For example, it comprises a layer containing a photopolymerizable composition comprising a vinyl monomer having an acidic group and a photopolymerization initiator, a separating layer, and an electron-donating colorless dye disclosed in JP-A-61-123838. Recording materials in which layers are stacked are known. In the case of this recording material, the non-image portion, that is, the portion cured by the photopolymerization reaction has no thermal diffusion property of the acidic group,
Although there is no coloring in the non-image area, on the other hand, there is a disadvantage that the color density itself is slightly low.

As a method for obtaining a negative image by the same method, there is a recording material disclosed in Japanese Patent Application Laid-Open No. 60-119552. This is a recording material in which a photopolymerizable composition comprising a monomer or prepolymer for bleaching a dye and a photopolymerization initiator, and a dye which is bleached by the monomer or the prepolymer are present in isolation. The recording material also has no coloring in the non-image area as in the case of the above-mentioned recording material, but has a drawback that the coloring density itself is slightly low.

In view of the above-mentioned drawbacks, the applicant of the present invention has previously disclosed in JP-A-3-87827 and JP-A-4-21252 as recording materials capable of reducing coloring in a non-image area and obtaining a high image density. The recording material described in No. was proposed. The former recording material encloses one of the two components in the two-component type light- and heat-sensitive color recording material in a microcapsule,
The other as a curable compound of the photocurable composition, or
A recording material containing the other together with the photocurable composition outside the microcapsule, and the latter recording material includes a microcapsule containing an electron-donating colorless dye, an electron-accepting compound outside the microcapsule, A photocurable composition containing a polymerizable vinyl monomer and a photopolymerization initiator,
Is a light and heat sensitive recording material provided with a layer having

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

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

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a completely dry processing system which does not require the use of a developing solution or the like and which does not generate waste. Another object of the present invention is to provide a high-sensitivity, high-contrast, color or black-and-white light- and heat-sensitive recording material which can be recorded by using such a method.

[0010]

Means for Solving the Problems The present inventors cure a photocurable composition (hereinafter, referred to as a "photocurable composition") provided outside a microcapsule by exposure to light to form a latent image. After formation, by further heating, the electron-accepting compound present outside the microcapsules in the unexposed areas causes a color-forming reaction with the electron-donating colorless dye in the microcapsules to form an image by forming a photosensitive heat-sensitive recording layer. In the heat-sensitive recording material, as a result of intensive studies on the components contained in the light- and heat-sensitive recording layer, and the layer configuration, the spectral sensitizing dye was contained in a plurality of layers constituting the light- and heat-sensitive recording layer of the light and heat-sensitive recording material. Then, a plurality of layers having different contents of the spectral sensitizing dye are laminated so that each recording layer has a high / low distribution in the contents, that is, the above contents increase in order from the exposure light source side. Ri, sensitive, and found that it is possible to obtain a high clear image contrast,
The present invention has been completed.

That is, the above object is achieved by the following light and heat sensitive recording materials [A] to [H] and an image recording method. The light- and heat-sensitive recording material of the present invention comprises, on a support, an electron-donating colorless dye encapsulated in a thermoresponsive microcapsule, and an electron-accepting compound, a photopolymerizable monomer, and a spectral sensitizer outside the thermoresponsive microcapsule. In a light and heat sensitive recording material provided with a light and heat sensitive recording layer containing a dye, and a photopolymerization initiator and / or an organic boron compound, the light and heat sensitive recording layer has a spectral sensitizing dye content distribution of irradiation light. A heat and heat sensitive recording material [A], characterized in that the heat and heat sensitive recording material is a light and heat sensitive recording layer which becomes higher in the thickness direction of the light and heat sensitive recording layer from the incident surface of the photosensitive material.

The light and heat sensitive recording layer of the light and heat sensitive recording material [A] has two recording layers having different contents of the spectral sensitizing dye.
A light- and heat-sensitive recording material [B], which is a light- and heat-sensitive recording layer constituted by laminating at least two layers.

Further, the light- and heat-sensitive recording material of the present invention comprises, on a support, an electron-donating colorless dye encapsulated in a thermo-responsive microcapsule, and an electron-accepting dye outside the thermo-responsive microcapsule within the same molecule. A light- and heat-sensitive recording material provided with a light- and heat-sensitive recording layer containing a compound having a group and a photopolymerizable group, a spectral sensitizing dye, and a photopolymerization initiator and / or an organic boron compound. Wherein the content distribution of the spectral sensitizing dye is a light- and heat-sensitive recording layer whose thickness distribution increases from the incident surface of the irradiation light in the thickness direction of the light- and heat-sensitive recording layer [C].

The light and heat sensitive recording layer of the light and heat sensitive recording material [C] has two recording layers having different contents of the spectral sensitizing dye.
A light- and heat-sensitive recording material [D], which is a light- and heat-sensitive recording layer constituted by laminating at least two layers.

The sensitivity of the light and heat sensitive recording materials [A] to [D]
The light and heat sensitive recording layer is
In the thickness direction, the center wavelength λ of the light source₁Exposed to the light
First recording layer for coloring, center wavelength λ₁Absorbing the light of
Interlayer, center wavelength λ_TwoTo the first recording layer and
Second recording layer that develops a different color, center wavelength λ_TwoThe light of
Absorbing intermediate layer,..., Center wavelength λ_i-1Absorb the light of
Intermediate layer, center wavelength λ _iThe first and the second
2, ..., and a color different from the i-1st recording layer
The i-th recording layer to be colored is sequentially arranged at least i ≧ 2 or more.
The light and heat sensitive recording layer laminated by
Center wavelength λ is λ₁<Λ_Two<... <λ_iSpecially
Light and heat sensitive recording materials [E] to [H].

The image recording is performed by irradiating the light and heat sensitive recording layer of any of the light and heat sensitive recording materials [A] to [H] from the surface of the recording layer having a low content of the spectral sensitizing dye. Image recording method.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the light and heat sensitive recording material and the image recording method of the present invention will be described in detail. The light- and heat-sensitive recording material of the present invention comprises, on a support, (a) a thermoresponsive microcapsule containing an electron-donating colorless dye, an electron-accepting compound, a photopolymerizable monomer, a spectral sensitizing dye, and photopolymerization initiation. Thermosensitive recording material comprising a photosensitive and thermosensitive recording layer containing an agent and / or an organic boron compound, or (b) a thermoresponsive microcapsule containing an electron-donating colorless dye, an electron acceptor in the same molecule A light- and heat-sensitive recording material comprising a compound having a functional group and a photopolymerizable group, a spectral sensitizing dye, and a light and heat-sensitive recording layer containing a photopolymerization initiator and / or an organic boron compound, The light and heat sensitive recording layer in (a) and (b) is constituted by coating a single layer or two or more layers.

When the photosensitive and heat-sensitive recording layer is a single layer, the content distribution of the spectral sensitizing dye in the layer increases from the incident surface of the irradiation light toward the thickness direction of the recording material. In this case, the light and heat sensitive recording layer is preferably a layer in which a plurality of thin layers having different contents of spectral sensitizing dyes are laminated so as to have the above content distribution. In the case where the light and heat sensitive recording layer is a multilayer multicolor light and heat recording layer formed by laminating two or more monochromatic light and heat recording layers having different coloring hues, each light and heat recording layer is a single layer as described above. In the same manner as in the above case, a plurality of thin layers are laminated so as to have the distribution described above, and each light- and heat-sensitive recording layer contains an electron-donating colorless dye that develops a different hue. Accordingly, clear color development can be expected in each of the light- and heat-sensitive recording layers, and a clear multicolor image (color image) with high contrast can be obtained.

More specifically, when a single light and heat sensitive recording layer is formed by laminating a plurality of thin layers, a layer L having the lowest content of the spectral sensitizing dye is provided on the outermost layer which is the incident surface of the irradiation light. ¹
There is coated, the innermost layer, i.e., composed of the support surface to the first recording layer, the highest layer H ¹ of the content of the spectral sensitizing dye is coated. A plurality of thin layers can be further provided between these layers L ¹ H ^{1. In} this case, any layer structure can be adopted regardless of the content of the spectral sensitizing dye in each layer. but it is more preferable to provide the hard coat layer as the content of the spectral sensitizing dye toward the layer L ¹ side layer H ¹ is increased continuously. In the case of forming a multi-layer multi-color photosensitive heat-sensitive recording layer by laminating a plurality of photosensitive heat-sensitive recording layers, a single-color photosensitive heat-sensitive recording layer having a different coloring hue is formed in the same manner as in the case of the single layer. May be arbitrarily laminated to form a multicolor light- and heat-sensitive recording layer, or according to the total content contained in the single-color light- and heat-sensitive recording layer, that is, on the incident surface of the irradiation light. and the least coated with a light and heat sensitive recording layer L ² of monochromatic total content of a spectral sensitizing dye in the outermost layer, the most common of the total amount of spectral sensitizing dyes to the first light and heat sensitive recording layer from the support surface the light and heat sensitive recording layer of H ² monochrome constructed by coating, or may have a multilayer heat sensitive recording layer. In the latter case, a light and heat sensitive recording layer can be further provided between the layers L ^{2 and} H ^{2. In} this case, an arbitrary layer constitution can be adopted regardless of the total content of the spectral sensitizing dye. Is the layer L ²
And more preferably coated so that the total amount of spectral sensitizing dye toward the side in the layer H ² is continuously increased.

As described above, when a single light- and heat-sensitive recording layer is formed by laminating a plurality of thin layers, the spectral sensitizing dye is added to the thin layer L ¹ and the thin layer H ¹ in an amount of 0.002. ~ 0.0
05g / m ^2, is preferably used in a range of 0.005~0.03g / m ^2, respectively from 0.0025 to 0.
003g / m ^2, it is more preferably in the range of 0.01~0.02g / m ^2. The amount (total content) of the entire photosensitive and heat-sensitive recording layer is 0.02 to 0.07 g.
Ranges preferably / m ^2, 0.03~0.06g / m ²
Is more preferable. Furthermore, the spectral sensitizing dye contained in the thin layer that can be coated between the layers L ^{1 and} H ¹ is arbitrarily used within a range from the lower limit of the L ¹ layer to the upper limit of the H ¹ layer. be able to. In the case of forming a multi-layered multi-color photosensitive / thermosensitive recording layer, the range usable as the whole single photosensitive / thermosensitive recording layer in each monochromatic photosensitive / thermosensitive recording layer (the range of the total content in a single layer) It is preferable that the layers are laminated so as to have the above distribution according to the total content within the range.

In the above-mentioned light and heat sensitive recording material, a polymerizable monomer as a curing agent or a compound having an electron-accepting group and a polymerizable group in the same molecule by photoirradiation is used to initiate photopolymerization in response to irradiation light. The polymer is cured by radicals generated from the agent and / or the organic boron compound, whereby the film is cured to form a latent image. The electron-accepting compound moves depending on the film properties of the latent image (cured portion) and reacts with the electron-donating colorless dye in the capsule to form an image. Therefore,
The cured latent image portion of the exposed portion does not develop color, only the uncured portion develops color, and further, when an organic boron compound coexists in addition to the photopolymerization initiator, radicals from the photopolymerization initiator Is promoted, high sensitivity,
An image with high contrast can be formed.

As described above, the light and heat sensitive recording layer of the light and heat sensitive recording material of the present invention has a high and low distribution in the content of the spectral sensitizing dye in the layer, that is, the above content in order from the exposure light source side. Is particularly useful for forming a clear image with high sensitivity and high contrast. In other words, in a recording material in which the spectral sensitizing dye is uniformly distributed in the layer, as the incident light from the light source enters the layer in the thickness direction, the amount of the light gradually decreases, and the irradiation light contributes to image formation. In contrast to the decrease in the rate, in a recording material containing a spectral sensitizing dye so as to have a high and low distribution in the layer as in the light and heat sensitive recording layer of the present invention, irradiation light enters in the thickness direction in the layer. In this case, the attenuation rate of the light amount is small, and the irradiation light can be used more effectively.

Therefore, when the light and heat sensitive recording material of the present invention containing the spectral sensitizing dye is irradiated with light as described above, the characteristics of the light and heat sensitive recording material can be effectively exhibited, and high sensitivity and high sensitivity can be obtained.
From the viewpoint of obtaining a clear image with high contrast, light is irradiated from the side of the recording layer having a low content of the spectral sensitizing dye.
With this method, the effects of the present invention can be sufficiently achieved.

Further, in the light- and heat-sensitive recording material of the present invention, when the light- and heat-sensitive recording layer formed on the support comprises a plurality of light- and heat-sensitive recording layers, an electron-donating colorless dye which develops a different hue is present. By laminating each of the photosensitive and heat-sensitive recording layers thus formed so as to have a distribution in the content of the spectral sensitizing dye as described above, and by irradiating light, a multicolor, high-sensitivity and high-contrast image is realized. be able to. In this case, an intermediate layer can be provided between the respective light- and heat-sensitive recording layers. In each of the intermediate layers, a spectral sensitizing dye that absorbs the sensitive wavelength of the light- and heat-sensitive recording layer on each intermediate layer is contained, and the light-incident surface By absorbing light having a specific wavelength for each layer passing through the device, a sharper image with higher contrast can be formed.

As described above, by using a desired spectral sensitizing dye depending on the purpose, a high-quality image can be easily obtained with a small and inexpensive infrared laser or a light source of green to red light. be able to.

In the present invention, an electron-donating colorless dye, a photocurable composition containing a polymerizable monomer, and an electron-accepting compound may be used in any combination with other known compounds as long as the effects of the present invention are not impaired. It can also be used. The polymerizable monomer and the electron-accepting compound may be one compound having these functions in one molecule.

Specific embodiments of the light and heat sensitive recording material of the present invention include the following (1) and (2). (1) A photocurable composition containing a compound having an electron-accepting group and a polymerizable group in the same molecule, a photopolymerization initiator, and a microcapsule described in JP-A-3-87827. A positive-type light- and heat-sensitive recording material provided with a light- and heat-sensitive recording layer containing an electron-donating colorless dye encapsulated in a capsule. In this photosensitive and heat-sensitive recording material, the photocurable composition outside the microcapsules is polymerized and cured by exposure to form a latent image. Thereafter, the electron-accepting compound present in the unexposed portion due to heating moves in the recording material and reacts with the electron-donating colorless dye in the microcapsule,
Color develops. Therefore, the cured latent image portion of the exposed portion does not develop color, and only the uncured portion develops color, so that a clear positive image with high contrast can be formed.

(2) A photosensitive composition described in JP-A-4-21252, which contains an electron-accepting compound, a polymerizable vinyl monomer, a photopolymerization initiator, and an electron-donating colorless dye encapsulated in the microcapsules outside the microcapsules. Negative-type photosensitive and heat-sensitive recording material provided with a heat-sensitive recording layer. Although the mechanism is not clear, the vinyl monomer present outside the microcapsule is polymerized by the exposure, while the electron-accepting compound coexisting in the exposed portion is not incorporated into the formed polymer at all, but rather is formed with the vinyl monomer. Is reduced, and exists in a movable state with a high diffusion rate.

On the other hand, the electron-accepting compound in the unexposed portion is trapped by the coexisting vinyl monomer and exists.
When heated, the electron-accepting compound in the exposed area preferentially moves in the recording material and reacts with the electron-donating colorless dye in the microcapsule, but the electron-accepting compound in the unexposed area is heated even if heated. This is presumably because they cannot pass through the capsule wall, do not react with the electron-donating colorless dye, and cannot contribute to color development. Therefore, in this photosensitive and heat-sensitive recording material, an exposed portion develops a color and an unexposed portion forms an image without coloring,
A clear negative image with high contrast can be formed.

The light- and heat-sensitive recording layer used in these light- and heat-sensitive recording materials is not limited to the above-mentioned structure, but may have various structures depending on purposes. The light and heat sensitive recording material used in the present invention may be a monochromatic or black and white recording material or a multicolor recording material. In the case of a multicolor light- and heat-sensitive recording material, microcapsules are formed by laminating a plurality of single-color light- and heat-sensitive recording layers on a support, and each light- and heat-sensitive recording layer contains an electron-donating colorless dye having a different coloring hue. And a photo-curable composition that is sensitive to light of different wavelengths, whereby a multicolor photosensitive and heat-sensitive recording material can be obtained.

Specifically, the light and heat sensitive recording material of the present invention can be obtained as follows. Microcapsules containing an electron donating colorless dye to the cyan color, the photocurable composition which is sensitive to the central wavelength lambda ₁ of the light source, a first recording layer containing on a support, on the layer and microcapsules containing an electron donating colorless dye to magenta color, a second recording layer provided containing a photocurable composition which is sensitive to the central wavelength lambda _2, and further the layer on to yellow color Layer configuration A in which a _third capsule layer containing a microcapsule containing an electron-donating colorless dye and a photocurable composition sensitive to wavelength λ ₃ is provided and laminated, A layer structure B having a layer and a layer structure C in which an intermediate layer containing a filter dye for absorbing light in a photosensitive wavelength range of the recording layer on the intermediate layer is provided in the intermediate layer.
And the like.

The above filter dye may be selected from spectral sensitizing dyes described below, which can be used in the light and heat sensitive recording layer of the light and heat sensitive recording material of the present invention.

In the case of a multicolor light- and heat-sensitive recording material, the above-mentioned layer structure C in which an intermediate layer containing a filter dye is provided in the intermediate layer is particularly preferable. As the layer structure C, for example, as a first layer, a layer containing a microcapsule containing an electron-donating colorless dye that develops cyan and a photocurable composition sensitive to a wavelength λ ₁ is used as a support. formed in the upper, in order over the layer, as a second layer, the intermediate layer containing a filter dye that absorbs light of a wavelength shorter than lambda _1, the third layer, the electron-donating colorless dye to magenta color and microcapsules containing a layer containing the photocurable composition, a sensitive to the wavelength lambda _2, as a fourth layer, the intermediate layer containing a filter dye that absorbs light of a wavelength shorter than lambda _2, the As a fifth layer, a layer containing a microcapsule containing an electron-donating colorless dye that emits yellow and a photocurable composition sensitive to a wavelength of λ ₃ , and as a sixth layer, a protective layer was laminated. Recording materials with a layer structure include That.

The components constituting the light and heat sensitive recording material of the present invention will be described below in detail. The light- and heat-sensitive recording material of the present invention preferably contains a specific organic boron compound (hereinafter sometimes referred to as “organic borate compound”) in the light- and heat-sensitive recording layer. The organic borate compound is preferably a compound represented by the following formulas (I-1) to (I-3), and is preferably used in combination with a photopolymerization initiator. By containing these, the photocuring reaction is promoted, and high sensitivity can be achieved.

[0035]

Embedded image

[Wherein R ¹ and R ² each independently represent a phenyl group or an aromatic hydrocarbon group other than a phenyl group, which may have a hetero atom, Si (R ⁹ ) (R ¹⁰ )
(R ¹¹ ) represents an alkyl group having 1 to 20 carbon atoms and substituted by a group represented by the following structural formulas (II), (IIa) and (IIb).

Here, the phenyl group and the aromatic hydrocarbon group are an alkyl group having 1 to 20 carbon atoms, O, S (O) _p ,
An alkyl group having 2 to 20 carbon atoms having NR ⁵ , OR ⁶ ,
R ⁶ S (O) _p , R ⁶ SO, N (R ⁷ ) (R ⁸ ), R ⁶ O
CO, 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 ), a halogen atom, (R ⁹ ) (R ¹⁰ ) P (O) _q or CN in which at least one of the ortho positions is substituted.

In the formula, R ^2a represents a phenylene group or a divalent aromatic hydrocarbon group other than a phenylene group which may have a hetero atom, wherein the aromatic hydrocarbon group has 1 carbon atom.
An alkyl group having from 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms having O, S (O) _p , and NR ⁵ , OR ⁶ , R ⁶ S
(O) _p , R ⁶ SO ₃ , N (R ⁷ ) (R ⁸ ), R ⁶ OC
O, 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 ), a halogen atom, (R ⁹ ) (R ¹⁰ ) P (O) _q , CN
Alternatively, it may be substituted with a group represented by the following structural formula (a).

[0039]

Embedded image

[0040]

Embedded image

In the above structural formula (a), ^Ra is 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, a substituted alkylene substituted by a halogen atom. Represents a group. R ⁶ represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom, or a phenyl group.

The structural formulas (II), (IIa) and (IIb)
In the formula, the aromatic hydrocarbon ring is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms having O, S (O) _p and 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), halogen atom,
(R ⁹ ) (R ¹⁰ ) may be substituted with P (O) _q or CN. Y is (CH ₂ ) _n , CH = CH, CO, NR
⁵ , O, S (O) _p or the following formula.

[0043]

Embedded image

In the general formulas (I-1) and (I-2),
R^ThreeIs -Si (R⁹) (R^Ten) (R¹¹) Substituted carbon number
1-20 alkyl, phenyl, or heteroatoms
An aromatic hydrocarbon other than a phenyl group which may have
A phenyl group and an aromatic hydrocarbon group,
An alkyl group having 1 to 20 carbon atoms, O, S (O)_p, NR ^Five
Having 2 to 20 carbon atoms, OR⁶, R⁶S
(O)_p, R⁶SO_Three, N (R⁷) (R⁸), R⁶OC
O, CON (R⁷) (R⁸), COR⁹, Si (R ⁹) (R
^Ten) (R¹¹), Sn (R⁹) (R^Ten) (R¹¹), B (R¹²) (R
¹³), A halogen atom, (R⁹) (R^Ten) P (O)_qOr
It may be substituted by CN.

In the formula, R ⁴ is a phenyl group or an aromatic hydrocarbon group other than a phenyl group which may have a hetero atom, an alkyl group having 1 to 20 carbon atoms, O, S (O) _p , N
An alkyl group having 2 to 20 carbon atoms having R ⁵ ,
It represents 12 cycloalkyl groups, alkenyl groups having 2 to 8 carbon atoms, or groups represented by the following structural formulas (a) and (b).

[0046]

Embedded image

In the above structural formulas (a) and (b), R ^a and R ^b
Is independently an alkylene group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R ⁶ OC
Represents a substituted alkylene group substituted by O, CN or a halogen atom. R ⁶ has the same meaning as described above.

Further, R ⁴ is OR ⁶ , R ⁶ S
(O) _p , R ⁶ SO ₃ , N (R ⁷ ) (R ⁸ ), R ⁶ OC
O, 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 ), a halogen atom, (R ⁹ ) (R ¹⁰ ) P (O) _q or CN.

The above n is an integer of 0 to 2, m is an integer of 1 to 2, p is an integer of 0 to 2, and q is an integer of 0 to 1, respectively.

R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or the structural formula (a), and the phenyl group and the structural formula (a) each have 1 carbon atom.
To 6 alkyl groups, an alkoxy group having 1 to 12 carbon atoms, R
^It may be substituted by ⁶ OCO-, -CN or a halogen atom. R ⁶ has the same meaning as described above.

The above R⁷, R⁸Is an alkyl having 1 to 12 carbons
Kill group, cycloalkyl group having 3 to 12 carbon atoms, phenyl
Or a phenyl group and
And structural formula (a) is an alkyl group having 1 to 6 carbon atoms,
1 to 12 alkoxy groups, R ⁶OCO, CN or halo
It may be substituted with a gen atom. Also, R⁷And R
⁸Is 5 or 6 members with the nitrogen atom to which they are attached
May be formed into a cyclic structure.
It may have an elemental atom or a sulfur atom.

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 structural formula (a) Wherein the phenyl group and the structural formula (a) are
It may be substituted by 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 atom.

R ¹² and R ¹³ have the same meanings as R ^{9 to} R ¹¹ , but R ¹² and R ¹³ together with the boron atom to which they are attached form a 5- or 6-membered cyclic structure. And the cyclic structure may have an oxygen atom or a sulfur atom.

Where E is P (R¹⁴) (R^Fifteen) (R¹⁶), S
(R⁶) (R^6a) Or N (R⁷) (R ⁸) (R^8a).
R⁶~ R⁸Is the same as defined above. R
^6aIs the R⁶Is synonymous with

R ^8a represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group or the structural formula (a), and the phenyl group and the structural formula (a) C1-C6 alkyl group, C1-C1
It may be substituted with 2 alkoxy groups, R ⁶ OCO, CN or a halogen atom.

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, Represents the structural formula (a), wherein the above alkyl group,
The alkenyl group and the cycloalkyl group may be substituted with R ₆ OCO and CN. The phenyl group, the structural formula (a) is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R ^{6 It} may be substituted by OCO, CN or a halogen atom. In the formula, G represents a group capable of forming a cation. ]

[0057]

Embedded image

Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and 2 to 8 carbon atoms.
Or an group represented by the following structural formulas (a) and (b), wherein R ¹ further contains O, S (O) _p , N
R ⁵ may combine to form a terminal group.

[0059]

Embedded image

In the above structural formulas (a) and (b), R ^a and R ^b
Is independently an alkylene group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, R ⁶ OC
Represents a substituted alkylene group substituted by O, CN or a halogen atom.

In the formula, R ₁ is 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 ), halogen atom or (R ¹⁵ ) (R ¹⁶ ) P
(O) It may be substituted by _q .

Where R^Two~ R^FourAre independent
Represents a phenyl group or a biphenyl group. The R ^Two~ R^FourIs the carbon number
1 to 20 alkyl groups (this alkyl group is₆, H
R₈R₉Or may be substituted with a halogen atom
No. ), OR⁶, R⁷S (O)_p, R⁷SO_Three, N (R
⁸) (R⁹), Si (R^Ten) (R¹¹) (R¹²), B (R¹³) (R
¹⁴), A halogen atom, (R^Fifteen) (R¹⁶) P (O)_qOr
It may be substituted with a substituent represented by the following structural formula.
Also, R^Two~ R^FourSum of Hammett σ value of + 0.36 ~
+2.58.

[0063]

Embedded image

In the above structural formula, X represents O, S, NR ²¹ . R ⁵ may be a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and may be substituted with the structural formula (a), and the benzene ring of the structural formula (a) may be substituted with an alkyl group having 1 to 6 carbon atoms. May be substituted with an alkoxy group having 1 to 12 carbon atoms or a halogen atom.

R ^{6 to} R ⁷ represent an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom, a phenyl group or the above-mentioned structural formula (a). May be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

R ^{8 to} R ¹⁶ each independently represent an alkyl group having 1 to 12 carbon atoms, and 3 to 12 carbon atoms represent a cycloalkyl group, a phenyl group or the above-mentioned structural formula (a). The benzene ring of the formula (a) has 1 carbon atom
Or an alkyl group having 6 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. In addition, the above R
⁸ and R ⁹ may form an aliphatic 6-membered ring together with the nitrogen atom to which they are bonded, and may further contain an oxygen atom and a sulfur atom.

In the formula, R ^{17 to} R ²⁰ are a hydrogen atom, a carbon atom of 1
1 carbon atoms which may be substituted with an alkoxy group
Represents a C12 to C12 alkyl group, a phenyl group or the above formula (a), wherein the phenyl group and the benzene ring of the formula (a) are an alkyl group having 1 to 6 carbon atoms,
It may be substituted with 2 alkoxy groups or halogen atoms.

In the formula, R ²¹ is a hydrogen atom or a group having 1 to 1 carbon atoms.
2 represents an alkyl group, and r represents an integer of 0 to 5.

[0069] In the formula, R ²² to R ²⁴ and R ²² _a is a hydrogen atom, an alkoxy group having 1 to 12 carbon atoms, OH or halogen atoms optionally substituted by an alkyl group having 1 to 12 carbon atoms, carbon Represents an alkoxy group represented by Formulas 1 to 12, a phenyl group which may be substituted by OH or a halogen atom. P represents an integer of 0 to 2, and q represents an integer of 0 to 1. Where:
G represents a group capable of forming a cation. ]

The following formulas (I-1) to (I-
The organic borate compound represented by 3) will be described.
First, the compounds represented by formulas (I-1) and (I-2) will be described in detail. The compound represented by the general formula (I-1) reacts triorganylborane (A) with an organometallic compound such as an alkyllithium compound or an alkylmagnesium halide (Grignard reagent) as shown in the following reaction formula. Can be obtained.

[0071]

Embedded image

[M is an alkali metal (for example, Li or Na) or MgX (X represents a halogen atom;
r is preferred. ). R ^{1 to} R ⁴ are as defined above. ]

Further, as shown in the following reaction formula, alkyldihaloborane, alkyldialkoxy or alkyldiaryloxyborane (B) is reacted with an organometallic compound such as a lithium organoyl compound or an alkylmagnesium halide (Grignard reagent). Can also be obtained.

[0074]

Embedded image

[X represents a halogen atom, and Br is particularly preferred. X ′ represents a halogen atom, an alkoxy group or an aryloxy group. R ¹ and R ⁴ have the same meaning as described above. ]

G ⁺ in the general formula (I-1) is a cation other than Li or Mg and can be obtained by a cation exchange reaction. G ⁺ is preferably an ammonium ion or a tetraalkylammonium ion. The tetraalkylammonium ion is preferably a tetramethylammonium ion or a tetrabutylammonium ion, and a trisalkylammonium ion such as a trimethylammonium ion is also preferable.

Also, a cation of a phosphonium salt or an ammonium salt represented by the following formula can be suitably used. ⁺ P (Rw) (Rx) (Ry) (Rz) or ⁺ N (Rw) (Rx) (Ry) (Rz)

[In the formula, Rw, Rx, Ry and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, a cycloalkyl group, an alkenyl group, a phenyl group or an arylalkyl group. ]

The above alkyl group, cycloalkyl group, alkenyl group, phenyl group and arylalkyl group may be unsubstituted or have a substituent. Examples of the substituent include a halogen atom; a hydroxyl group; a heterocycloalkyl group such as an epoxy group, an aziridyl group, an oxetanyl group, a furanyl group, a pyrrolidinyl group, a pyrrolyl group, a thiophenyl group, and a tetrahydrofuranyl group; a dialkylamino group; Carboxyl group; alkylcarbonyl group; arylcarbonyl group; aryloxycarbonyl group; alkoxycarbonyl group.

N ⁺ in the above formula may form a part of a 5- or 6-membered cyclic group, and this cyclic group may be condensed with another cyclic group. Other cyclic groups include S,
A hetero atom such as N or O may be contained. Further, N ⁺ may be a part of a polycyclic group such as azoniapropellan, and the polycyclic group may also contain a hetero atom such as S, N, or O.

G ⁺ in the above formula can also suitably include cations of a polyammonium salt or a polyphosphonium salt. Among them, bis salts are particularly preferred. Similar to the above, it can have the following substituents. As a substituent, a halogen atom; a hydroxyl group; an epoxy group;
Heterocycloalkyl groups such as aziridyl group, oxetanyl group, furanyl group, pyrrolidinyl group, pyrrolyl group, thiophenyl group and tetrahydrofuranyl group; dialkylamino group; amino group; carboxyl group; alkylcarbonyl group; arylcarbonyl group; An alkoxycarbonyl group.

When G ⁺ is a cation of an ammonium salt or a phosphonium salt, it may be substituted by a neutral dye such as thioxanthene, thioxanthone, coumarin, or ketocoumarin. The cation can be obtained by reacting an ammonium ion or a phosphonium ion substituted with a reactive group such as an epoxy group, an amino group or a hydroxyl group with a suitable derivative of a neutral dye. This is described, for example, in EP 2249.
No. 67 [Qantacure]
QTX]. Similarly, the ammonium ion and the phosphonium ion may be substituted by a colorless electron accepting compound (for example, benzophenone or the like) as in the following structural formula.

[0083]

Embedded image

These electron accepting compounds are available from International Bio-Synthetics (International Bio-s
Synthetics).

Further, as a quaternary ammonium compound,
For example, a trimethylcetylammonium or cetylpyridium compound can be mentioned.

The following structural formula can also be suitably used as G ⁺ .

[0087]

Embedded image

[0088] wherein, Z is P, S or N, R ³
Represents an alkyl group or an aryl group. ]

[0089]

Embedded image

This is described in J. Polym. Sci. Part A: Polymer
Chem. 1992, 30, 1987 and Polymer 1993, 34 (6), 113
0 is described.

[0091]

Embedded image

[Wherein, R ′ represents an unsubstituted or substituted benzyl group or a phenicyl group. ]

The above compounds are described in JP-A-7-70221. The benzyl group, phenicyl group, and pyridinium ring represented by R ′ in the above structural formula may be substituted with a substituent. Examples of the substituent include a halogen atom; a hydroxyl group; a heterocycloalkyl group such as an epoxy group, an aziridyl group, an oxetanyl group, a furanyl group, a pyrrolidinyl group, a pyrrolyl group, a thiophenyl group, and a tetrahydrofuranyl group; a dialkylamino group;
Carboxyl group; alkylcarbonyl group; arylcarbonyl group; aryloxycarbonyl group; alkoxycarbonyl group.

Further, the following cations of a tetraalkylammonium salt can also be suitably used. N (alkyl group having 1 to 4 carbon atoms) ₄ ⁺ [The alkyl group having 1 to 4 carbon atoms may be unsubstituted or may have a substituent. ]

As the above substituent, the same substituents as in the case of R ′ can be used. Examples of the cation of the ammonium salt represented by the above formula include a tetramethylammonium salt, a tetraethylammonium salt, a tetrapropylammonium salt or a tetrabutylammonium salt, and a benzyl-tri (alkyl group having 1 to 4 carbon atoms) ammonium salt. And, among them, tetramethylammonium salt or tetrabutylammonium salt, benzyl-
Cations such as ammonium tri (alkyl groups having 1 to 4 carbon atoms) ammonium salts are preferred.

Cation C ₆ H ₄ —CH ₂ —N (alkyl group having 1 to 4 carbon atoms) _{3 of} ammonium salt of the following benzyl-tri (alkyl group having 1 to 4 carbon atoms) ₃
⁺ Includes, for example, benzyltrimethylammonium ion, benzyltriethylammonium ion, benzyltripropylammonium ion and benzyltributylammonium ion, among which benzyltrimethylammonium ion and benzyltributylammonium ion are preferable.

Examples of G ⁺ include cations of onium salts such as iodonium salts and sulfonium salts, and compounds represented by the following formulas described in European Patent Nos. 555058 and 69,074.

[0098]

Embedded image

[0099]

Embedded image

Further, there may be mentioned those represented by the following structural formulas.

[0101]

Embedded image

[Wherein, Rg represents an alkyl group, and among them, an ethyl group or a benzyl group is particularly preferable. The aromatic ring may be substituted with the same substituent as in the case of R ′. ]

In addition, cations of halonium salts described in European Patent Nos. 334,056 and 5,628,972, among them, cations of diaryliodonium salts, among others, can be mentioned. The cation of a ferrocenium salt represented by the following formula described in (1) can also be preferably exemplified.

[0104]

Embedded image

Further, the cations of onium salts described in JP-A-6-266102 include cations of ammonium salts, phosphonium salts, sulfonium salts, iodonium salts, cellonium salts, arsonium salts, teronium salts and bismuthnium salts. it can.

In addition to the above, cation transition metal complex compounds are also preferred. As the cation transition metal complex compound, a compound described in US Pat. No. 4,954,414 is preferable. Specifically, bis (2,2′-bipyridine) (4,4′-dimethyl-2,2′-bipyridine) ruthenium, tris (4,4′-dimethyl-2,2′-bipyridine) ruthenium, tris (4,4'-dimethyl-
2,2′-bipyridine) iron, tris (2,2 ′, 2 ″-)
Terpyridine) ruthenium, tris (2,2'-bipyridine) ruthenium and bis (2,2'-bipyridine)
(5-Chloro-1,10-phenanthroline) ruthenium is particularly preferred.

The compound represented by the general formula (I-2) can be obtained by reacting a triorganylborane substituted by an E group with an organometallic compound by any of the methods described in the general formula (I-1). Let me get it. Examples of the organic metal compound used in this case include an aliphatic lithium compound or an aromatic lithium compound, and an alkyl magnesium halide (RMgX: Grignard reagent).

When a compound represented by the general formula (I-1) or (I-2) is obtained, an organometallic compound is used for the reaction. In this case, the reaction is carried out with an inert organic compound such as an ether or an aliphatic hydrocarbon. Performed in a solvent. Examples of the inert organic solvent include diethyl ether, tetrahydrofuran and hexane.

The above-mentioned reaction with the organometallic compound is preferably carried out by degassing or under an atmosphere of an inert gas such as nitrogen gas. Generally, the reaction is cooled to 0 ° C. or below and then allowed to warm to room temperature with stirring. After the reaction product is isolated, it is purified by a known method such as chromatography, recrystallization and the like. When the organic borate compound is used as an anionic component and contains a dye cation, it is produced by a cation exchange reaction between the organic borate compound and the dye. Examples of the borate used in the exchange reaction include lithium borate, magnesium borate, sodium borate, ammonium borate, and tetraalkylammonium salts.

When the organic borate compound contains a transition metal complex as a cation, US Pat. No. 4,954,14
It can be obtained by a method similar to that described in No. 1, page 7, paragraph 2. When the triorganyl borane (A) described in the above reaction formula is an alkyldiaryl borane, this can be produced, for example, by the production method described in “Tetrahedron 1993, 49, 2965”.
When (A) is a triarylborane,
This production is based on "J. Organomet. Chem. 1972,38,229",
"J. Organomet. Chem. 1981, 209, 1", "J. Amer. C
hem. Soc. 1957, 79, 2302 "and" Chem. Ber. 1955,
88, 962 ".

The alkyl dihaloborane (B) described in the above reaction formula is, for example, “JACS1977, 99, 7097”,
U.S. Pat. No. 3,083,288, Zh. Obshch. Khi
m. 1959, 29, 3405 "and" Bull. Chim. Soc. Franc
e, 1967, 11, 4160 ". When the above (B) is phenyldifluoroborane, this production method is described in "J. Organomet. Chem. 19
72, 35, 9 ", and in the case of tris (trimethylsilylmethyl) furan,
It can be produced by the production method described in "J. Amer. Chem. Soc. 1959, 81, 1844". Borane used as a starting material of the organic borate compound useful in the present invention can be obtained by any of the methods described in the above-mentioned documents.

Specific examples of the compound represented by formula (I-1) or (I-2) used in the present invention are shown in Tables 1 to 5 below.
3, each functional group is described.
The present invention is not limited to these.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

[Table 3]

Next, the organic borate compound represented by the formula (I-3) will be described in detail. The general formula (I-
The organic borate compound represented by the formula (3) is represented by the following formula:
With an organometallic compound such as an alkyllithium compound or a Grignard reagent (RMgX).

[0117]

Embedded image

[Wherein M is an alkali metal (eg, Li
Or Na) or MgX. X represents a halogen atom, and Br is particularly preferable. ]

The method for producing the triorganoborane (A) used in the synthesis is described, for example, in "Chem. Ber. 19".
55, 88, 962 ".

As another method for producing the organic borate compound represented by the general formula (I-3), an alkyl dihalo borane and / or an alkyl di (alkoxy) borane as represented by the following reaction formula: Or an alkyldi (aryloxy) borane (B) by reacting it with an organometallic compound such as a Grignard reagent or an organotin compound.

[0121]

Embedded image

[Wherein, X represents a halogen atom;
r is preferred. X ′ represents a halogen atom, an alkoxy group or an aryloxy group. R ¹ and R ⁴ are as defined above. ]

The reaction conditions for the above reaction are the same as those described in the above general formula (I-
This is the same as in the method for producing the compounds represented by 1) to (I-3). G ^{+ in} the compound of the general formula (I-3)
Has the same meaning as in the above formula (I-1).

The method for producing the alkyl dihaloborane (B) is described in JACS 1977, 99, 7097, US Pat. No. 3,083,288, Zh. Obshch. Khi
m. 1959, 29, 3405, Bull. Chi
m. Soc. France, 1967, 11, 4160
Can be produced. Also,
Borane used as a starting material of an organic borate compound is
It can be obtained by any of the methods in the above-mentioned documents.

Specific examples of the organic borate compound represented by the above general formula (I-3) are shown by listing their functional groups in the following Tables 4 to 6, but the present invention is not limited to these. Not something.

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Table 6]

The above organic borate compound is disclosed in
No. 88685 and No. 9-188686. In the light and heat sensitive recording material of the present invention, the organic borate compound is preferably contained in the recording layer in an amount of 0.01 to 3 g / m ² , more preferably 0.02 to 1.0 g / m ^2. . Is less than 0.01 to 3 g / m ^2, the effect is not sufficiently obtained in the present invention, also, 3 g / m ²
However, any effect is not expected even if it is added in excess of the above. In addition, this organic borate compound is preferably contained in the same layer as the photopolymerization initiator in the recording layer from the viewpoint of the effect.

The electron accepting compound and the polymerizable vinyl monomer mainly used for the positive recording material can be used in place of the compound containing an electron accepting group and a polymerizable group in the same molecule. Examples of such compounds include 3-halo-4-hydroxybenzoic acid described in JP-A-4-226455, methacryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-63-173682, and acrylic acid. Roxyethyl ester, 59-83
No. 693, No. 60-141587, No. 62-9919
No. 0, esters of benzoic acid having a hydroxy group with hydroxymethylstyrene, hydroxystyrene described in EP 29323, JP-A-62-16707.
And N-vinylimidazole complexes of zinc halide described in JP-A Nos. 7 and 62-16708 and compounds that can be synthesized with reference to the electron-accepting compounds described in 63-317558 and the like. Preferred examples of the compound having the electron accepting group and the polymerizable group in the same molecule include 3-halo-4-hydroxybenzoic acid represented by the following general formula.

[0131]

Embedded image

[In the formula, X represents a halogen atom, and among them, a chlorine atom is preferable. Y is 1 having a polymerizable ethylene group
An aralkyl group having a vinyl group,
An acryloyloxyalkyl group or a methacryloyloxyalkyl group is preferable, and an acryloyloxyalkyl group having 5 to 11 carbon atoms or a methacryloyloxyalkyl group having 6 to 12 carbon atoms is more preferable. Z represents a hydrogen atom, an alkyl group or an alkoxyl group. ]

The above-mentioned 3-halo-4-hydroxybenzoic acid includes, for example, 3-chloro-4-hydroxybenzoic acid ester vinylphenethyl ester, 3-chloro-4-hydroxybenzoic acid ester
Hydroxybenzoic acid vinylphenylpropyl ester,
3-chloro-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-methacryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2 −
Acryloyloxypropyl) ester, 3-chloro-
4-hydroxybenzoic acid- (2-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (3-acryloyloxypropyl) ester,
3-chloro-4-hydroxybenzoic acid- (3-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (4-acryloyloxybutyl)
Ester, 3-chloro-4-hydroxybenzoic acid- (4
-Methacryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (5-acryloyloxypentyl) ester, 3
-Chloro-4-hydroxybenzoic acid- (5-methacryloyloxypentyl) ester, 3-chloro-4-hydroxybenzoic acid- (6-acryloyloxyhexyl)
Ester, 3-chloro-4-hydroxybenzoic acid- (6
-Methacryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid- (8-acryloyloxyoctyl) ester, 3-chloro-4-hydroxybenzoic acid- (8-methacryloyloxyoctyl) ester, and the like.

Examples of the compound having an electron-accepting group and a polymerizable group in the same molecule include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, β-methacryloxyethoxysalicylate,
-Zinc acryloxyethoxysalicylate, vinyloxyethyloxybenzoic acid, β-methacryloxyethylorselinate, β-acryloxyethylorselinate, β
-Methacryloxyethoxyphenol, β-acryloxyethoxyphenol, β-methacryloxyethyl-β
-Resorcinate, β-acryloxyethyl-β-resorcinate, hydroxystyrenesulfonic acid-N-ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p-hydroxybenzoate, methacryloxymethylphenol, acrylic acid Roxymethylphenol, 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 Preferable examples include-[beta] -acryloxyethylaminosulfonylsalicylic acid and metal salts thereof (e.g., zinc salts).

The photopolymerization initiator suitably used in the recording material of the present invention is a compound for initiating the photopolymerization of the above-mentioned polymerizable monomer. Organic borate compounds and borate salts of cationic dyes described in JP-A-62-143044, which generate radicals in response to light in the spectral absorption wavelength region, may be mentioned. In addition, the general formulas (I-1) to (I-1)
Among the organic boron compounds represented by (I-3), those having the above functions can also be mentioned.

When these photopolymerization initiators are present in the recording layer, radicals are generated by irradiation with laser light, and the radicals initiate the polymerization reaction of the polymerizable monomer contained in the photocurable composition. As a result, a polymer is formed on the exposed portion to form a latent image. Therefore, it is preferable to use in combination with a spectral sensitizing dye from the viewpoint of effectively generating radicals and increasing the sensitivity.

Among the organic borate compounds represented by formulas (I-1) to (I-3), the organic borate compound which functions as a photopolymerization initiator will be described. When the organic borate compound functions as a photopolymerization initiator, the photopolymerization reaction is promoted without using the photopolymerization initiator specified in the present invention, and a latent image can be formed. At this time,
This organic borate compound has a photopolymerization initiation effect as well as a photopolymerization reaction promoting effect. Further, the organic borate compound functioning as a photopolymerization initiator and the photopolymerization initiator defined in the present invention can be used in combination. Hereinafter, specific examples of the organic borate compound that functions as a photopolymerization initiator will be described, but the present invention is not limited to the following compounds.

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

The organic borate compound of the present invention is preferably used in combination with a spectral sensitizing dye having a maximum absorption wavelength in the wavelength region of 300 to 1100 nm from the viewpoint of increasing the laser absorption efficiency.

The spectral sensitizing dye preferably has a maximum absorption wavelength in the wavelength region of 300 to 1100 nm. As the spectral sensitizing dye, a cationic dye is preferable. Specifically, methine dye, polymethine dye, triarylmethane dye, indoline dye, azine dye,
Xanthene dyes, oxazine dyes, acridine dyes and the like are preferable, and cationic cyanine dyes, hemicyanine dyes, rhodamine dyes and azamethine dyes are more preferable.

Further, among the above cationic dyes, 30
Any organic cationic dye having a maximum absorption wavelength in the wavelength range of 0 to 1100 nm can be suitably used. Many organic cationic dyes having a maximum absorption wavelength in the above wavelength region are known,
For example, “Chemistry of functional dyes” (1981, CMC Publishing Co., pp. 393 to 416) and “coloring materials” (60 [4] 2
12-224 (1987)) and the like. Among them, examples of the organic cationic dye used in the present invention include a cationic methine dye, a cationic carbonium dye, a cationic quinone imine dye, a cationic indoline dye, and a cationic styryl dye.

The cationic methine dye is preferably a polymethine dye, a cyanine dye, or an azomethine dye, and more preferably a cyanine dye, a carbocyanine dye, a dicarbocyanine dye, a tricarbocyanine dye, a hemicyanine dye, or the like. As the cationic carbonium dye, a triarylmethane dye, a xanthene dye, and an aridudine dye are preferable, and a rhodamine dye is more preferable. As the cationic quinone imine dye, an azine dye, an oxazine dye, a thiazine dye, a quinoline dye, a thiazole dye and the like are preferable. The above various organic cationic dyes may be used alone or in a combination of two or more.

Further, as other organic borates suitably used as a photopolymerization initiator, an organic borate salt obtained from this organic cationic dye can also be mentioned.

Among the above organic cationic dyes, the organic cationic dyes capable of forming a counter ion include:
Many substances are known, for example, "Chemistry of functional dyes" (1981, CMC Publishing Co., pp. 393-41).
6) and “color materials” (60 [4] 212-224 (198
7)) and the like can be used with reference to the dyes. Among them, a wavelength region of 500 nm or more, preferably 5
Any organic cationic dye having a maximum absorption wavelength in the wavelength region of 50 to 1100 nm can be suitably used. Among them, cationic methine dyes, polymethine dyes, triarylmethane dyes, indoline dyes, azine dyes, xanthene dyes, oxazine dyes and acridine dyes are preferable, and cationic cyanine dyes, hemicyanine dyes, rhodamine dyes and azamethine dyes are more preferable. preferable.

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

The following are specific examples of organic borate salts obtained from organic cationic dyes, but are not limited thereto.

[0157]

Embedded image

[0158]

Embedded image

[0159]

Embedded image

[0160]

Embedded image

[0161]

Embedded image

[0162]

Embedded image

The photopolymerization initiator is preferably used in the range of 0.01 to 20% by weight, more preferably 0.2 to 15% by weight, based on the total amount of the photocurable composition. It is preferable, but it is particularly preferable to use it in the range of 1 to 10% by weight. If the amount is less than 0.01% by weight, sufficient sensitivity cannot be obtained, and if it exceeds 10% by weight, it is difficult to increase the sensitivity, which is not preferable. .

Further, in the present invention, a compound having an active halogen group in a molecule represented by the following general formula (3) or (4) is required as an auxiliary agent together with the spectral sensitizing dye and the organic borate compound. They can be used in combination depending on the situation.

[0165]

Embedded image

[In the formula, X represents a halogen atom, and Y ¹ represents —CX ₃ , —NH ₂ , —NHR, —NR _2, or —OR.
Represents Here, R represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and Y ² represents —C
X _{3 represents} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a substituted alkenyl group. The substituent of the group having a substituent may be the general formula (3) itself. ]

[0167]

Embedded image

[In the formula, X represents a halogen atom. Y ³ ,
Y ⁴ represents a hydrogen atom or a halogen atom, which may be the same or different. Z represents a group shown below. ]

[0169]

Embedded image

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

Examples of the compound represented by the general formula (3) include “Bulittin of Chemical Society Japan (Bull, Chem, Soc, Japan)” (Vol. 42, Wakabayashi et al.,
p. 2924 (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.

In addition to the above compounds, compounds described in British Patent No. 1388492, 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-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine and the like.

Compounds described in JP-A-53-133428, 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,

Compounds described in German Patent No. 3337024, for example, compounds represented by the following structural formulas can be mentioned.

[0175]

Embedded image

In addition, compounds represented by the following structural formulas can also be mentioned as auxiliaries.

[0177]

Embedded image

Further, “Journal of Organic Chemistry (J. Org. Chem.)” (29)
Vol., P. 1527, F. C. By Schafer et al. (19
64)), 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,

The compounds described in Japanese Patent Application No. 60-198868, for example, compounds represented by the following structural formulas can also be mentioned.

[0180]

Embedded image

[0181]

Embedded image

As the auxiliary used in the light- and heat-sensitive recording material of the present invention, a compound represented by the above general formula (3) is preferable, and among them, a compound in which Y ¹ is —CX ₃ is particularly preferable.

The compound represented by formula (3) can be synthesized by a known method. For example, "Britin of Chemical Society Japan (Bull,
Chem, Soc, Jpn) "(Vol. 42, p. 2924 (1969)
)), The following compound can be obtained.

[0184]

Embedded image

Further, for example, the following compounds can be obtained by referring to the method described in DE 2718259 (application number).

[0186]

Embedded image

Further, by referring to the method described in US Pat. No. 4,619,998, the following compound can be obtained.

[0188]

Embedded image

Examples of the compound represented by the general formula (4) include compounds described in JP-B-51-8330, for example,
Carbon tetrachloride, carbon tetrabromide, iodoform, p-nitro-
α, α, α-tribromoacetophenone, ω, ω, ω-
Tribromoquinaldine, tribromomethylphenylsulfone, trichloromethylphenylsulfone, etc.

Compounds described in JP-B-49-12180, for example, the following compounds:

[0191]

Embedded image

[0192]

Embedded image

The compounds described in JP-A-60-138538, for example, the following compounds can be mentioned.

[0194]

Embedded image

Specific examples of the compound having an active halogen group represented by formula (3) or (4) are shown below, but the present invention is not limited to these compounds.

[0196]

Embedded image

[0197]

Embedded image

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

Although the light- and heat-sensitive recording material of the present invention has high sensitivity, in order to further promote the formation of a latent image, an oxygen scavenger, a chain transfer agent of an active hydrogen donor, and other easily oxidized materials are used. A reducing agent such as a monkey compound may be used in combination.

Among the oxygen scavengers useful as latent image formation accelerating aids, mention may be made of phosphines, phosphonates, phosphites, stannous salts or other compounds which are easily oxidized by oxygen.

Specifically, for example, N-phenylglucin, trimethylbarbituric acid, N, N-dimethyl-
2,6-diisopropylaniline, N, N, N-2,
4,6-pentamethylaniline and the like, and particularly, thiols, thioketones, lofphin dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, azides and the like such as the following compounds are useful. is there. As the thiols, the following compounds are preferable.

[0202]

Embedded image

As the thioketones, the following compounds are preferred.

[0204]

Embedded image

[0205]

Embedded image

As the lophine dimer compound, the following compounds are preferred.

[0207]

Embedded image

As the iodonium salts, the following compounds are preferred.

[0209]

Embedded image

As the sulfonium salts, the following compounds are preferred.

[0211]

Embedded image

As the azinium salts, the following compounds are preferred.

[0213]

Embedded image

As the organic peroxide, the following compounds are preferred.

[0215]

Embedded image

As the azides, the following compounds are preferred.

[0219]

Embedded image

When the light- and heat-sensitive recording material of the present invention is a negative-type light and heat-sensitive recording material, the photo-curable composition contains, in place of a compound having an electron-accepting group and a photo-polymerizable group in one molecule,
An electron accepting compound and a photopolymerizable monomer can be used in combination. Further, when the light- and heat-sensitive recording material of the present invention is a positive-type light and heat-sensitive recording material, the photocurable composition may optionally contain a compound having an electron accepting group and a photopolymerizable group in one molecule. In addition to the above, an electron accepting compound can be added. By adding this, the coloring density can be improved.

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, metal complexes, and the like. Specifically, Japanese Patent Publication No. 40-9309,
JP-B-45-14039, JP-A-52-140483
JP-A-48-51510, JP-A-57-2108
No. 86, JP-A-58-87089, JP-A-59-11
No. 286, Japanese Unexamined Patent Publication No.
95988 and the like.

Of the above, for example, phenol derivatives include 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-
Butylidene diphenol, 4-tert-octylphenol, 4-p-methylphenylphenol, 4,4 ′
-Methylcyclohexylidenephenol, 4,4'-isopentylidenephenol, benzyl p-hydroxybenzoate and the like.

Examples of the salicylic acid derivatives include 4-pentadecylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (tert-octyl) salicylic acid, 5-octadecylsalicylic acid, and 5-α- (p -Α-
Methylbenzylphenyl) ethylsalicylic acid, 3-α-
Methylbenzyl-5-tert-octylsalicylic acid,
5-tetradecylsalicylic acid, 4-hexyloxysalicylic acid, 4-cyclohexyloxysalicylic acid, 4-decyloxysalicylic acid, 4-dodecyloxysalicylic acid, 4-pentadecyloxysalicylic acid, 4-octadecyloxysalicylic acid and the like, and zinc and aluminum thereof , Calcium, copper, lead salts and the like.

When the above-mentioned electron accepting compound is used,
5 to 100 based on the amount of the electron donating colorless dye used
It is preferable to use it in the range of 0% by weight.

When the light- and heat-sensitive recording material of the present invention is a negative type, a photopolymerizable monomer having at least one vinyl group in a molecule can be used in the photocurable composition. Specifically, acrylic acid and its salts, acrylic esters, acrylamides; methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride, maleic esters; itaconic acid, itaconic esters Styrenes; vinyl ethers;
Vinyl esters; N-vinyl heterocycles; aryl ethers; allyl esters.

Of these, it is particularly preferable to use a photopolymerizable monomer having a plurality of vinyl groups in the molecule. Examples thereof include acrylic acid esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol, and methacrylic acid. Esters; resorcinol, pyrogallol,
Acrylic and methacrylic esters of polyhydric phenols such as phloroglucinol and bisphenols;
And acrylate or methacrylate terminated epoxy resin, acrylate or methacrylate terminated polyester, and the like.

Among them, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate and diethylene glycol dimethacrylate are particularly preferred. .

As the molecular weight of the photopolymerizable monomer,
About 100 to about 5000 are preferred, and about 300 to about 200
0 is more preferred.

In the light- and heat-sensitive recording material of the present invention, a photocurable composition may be used for curing the film in the exposed area, and a photocrosslinkable composition may be used. Examples of the photocrosslinkable composition include polyvinyl cinnamate, polycinnamylidene vinyl acetate, and a photocurable composition having an α-phenylmaleimide group. Further, the photocrosslinkable composition can be used as a photocurable component.

Furthermore, a thermal polymerization inhibitor can be added to the photocurable composition, if necessary. The thermal polymerization inhibitor is added for the purpose of preventing thermal polymerization or temporal polymerization of the photocurable composition, and this addition improves the chemical stability during preparation and storage of the photocurable composition. Can be.

Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone,
-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 thermal polymerization inhibitor is preferably added in the range of 0.001 to 5% by weight, and more preferably in the range of 0.01 to 1% by weight, based on the total amount of the photocurable composition. More preferred. If the amount is less than 0.001% by weight, the thermal stability is poor.

When a photocurable composition is used in the light and heat sensitive recording material of the present invention, it is emulsified and dispersed and contained in the light and heat sensitive recording layer. At this time, a natural oil or a synthetic oil can be used as a solvent for dissolving each component contained in the photocurable composition. Examples of the solvent include cottonseed oil, kerosene, aliphatic ketone, aliphatic ester, paraffin, naphthenic oil, alkylated biphenyl, alkylated terphenyl,
Diarylethanes such as chlorinated paraffins, alkylated naphthalenes, 1-phenyl-1-xylylethane, 1-phenyl-1-p-ethylphenylethane and 1,1′-ditolylethane; phthalates such as dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate Acid alkyl esters; phosphate esters such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate; citrate esters such as acetyl tributyl citrate; benzoic esters such as octyl benzoate; alkyls such as diethyl lauryl amide Amide; trimesic acid ester such as tributyl trimesate; ethyl acetate, propyl acetate, iso-propyl acetate, butyl acetate, tert-butyl acetate, s-acetic acid
Acetate such as butyl; propionate such as methyl propionate; butyrate such as methyl butyrate (isobutyrate); acrylate (methacrylic acid) such as methyl acrylate; alkyl halide such as methylene chloride and carbon tetrachloride Tertiary butyl alcohol; thimer isobutyl ketone; β-ethoxyethyl acetate;
Methyl cellosolve acetate; cyclohexanone and the like.

Of these, aliphatic esters and alkyl halides are preferable, and among them, those having a solubility in water of 10
Those having a volume percent or less are more preferred.

These solvents are preferably used in an amount of 1 to 500 parts by weight based on the amount of the polymerizable electron-accepting compound.

When the photocurable composition used in the light and heat sensitive recording material of the present invention is emulsified and dispersed, a water-soluble polymer can be used. As the water-soluble polymer, a compound which dissolves in water at 25 ° C. in an amount of 5% by weight or more is preferable. For example, gelatin, gelatin derivatives, proteins such as albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, sodium alginate, Saponification of sugar derivatives such as starches (including modified starch), gum arabic and polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolysate, carboxy-modified polyvinyl alcohol, polyacrylamide, vinyl acetate-polyacrylic acid copolymer And synthetic polymers of polystyrene sulfonate sugars. Among them, gelatin or polyvinyl alcohol is particularly preferred.

As the electron-donating colorless dye used in the light- and heat-sensitive recording material of the present invention, conventionally known colorless dyes can be used. Examples thereof include phthalide compounds, fluoran compounds, phenothiazine compounds, and indolylphthalide. And various compounds such as leuco-auramine-based compounds, rhodamine-lactam-based compounds, triphenylmethane-based compounds, triazene-based compounds, spiropyran-based compounds, pyridine-based, pyrazine-based compounds, and fluorene-based compounds.

In particular, the following compounds can be mentioned. Examples of the phthalide compound include, for example, U.S. Pat. No. Re. 23,024 and U.S. Pat. No. 3,491,11.
No. 1, 3,491, 112, 3,491, 1
No. 16, No. 3,509,174, specifically, 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 and the like No.

As the fluoran compounds, for example, US Pat. Nos. 3,624,107 and 3,627,78
No. 7, No. 3,641,011, No. 3,462,8
No. 28, No. 3,681, 390, No. 3,920,
No. 510 and No. 3959,571, specifically, 2- (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- (o-chloroanilino) -6-diethylaminofluoran, 2-
(3,4-Dichloroanilino) -6-diethylaminofluoran and the like.

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

The leuco auramine compounds include, for example, 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like. Is mentioned.

Examples of rhodamine lactam compounds include rhodamine-B-anilinolactam and rhodamine- (p-
Nitrino) lactam and the like.

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

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

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

When the light- and heat-sensitive recording material of the present invention is used for a full-color recording material, electron-donating colorless dyes for cyan, magenta and yellow coloring dyes are used. cyan,
Magenta and yellow coloring dyes include U.S. Pat.
Each of the dyes described in JP-A No. 800,149 or the like can be used. Further, as the electron-donating colorless dye for yellow coloring dyes, dyes described in U.S. Pat. No. 4,800,148 and the like can be used. The dyes described in JP-A-53542 can be used.

In the light- and heat-sensitive recording material of the present invention, the electron-donating colorless dye to be used is used by being encapsulated in microcapsules. As a method for microencapsulation, a conventionally known method can be used. For example, U.S. Pat.
Nos. 0457 and 2800458, the method utilizing coacervation of a hydrophilic wall forming material, U.S. Pat. No. 3,287,154, British Patent No. 990443, JP-B-38-19574, JP-B-42-446, and JP-A-42-446. -7
No. 71, etc., US Pat.
No. 3,660,304, a method using polymer precipitation, a method using an isocyanate polyol wall material described in U.S. Pat. No. 3,796,669, U.S. Pat.
No. 4511, a method using an isocyanate wall material, U.S. Pat. Nos. 4,001,140 and 4,087,376.
No. 4,089,802, a method using a urea-formaldehyde-based, urea formaldehyde-resorcinol-based wall-forming material, and a method using a melamine-formaldehyde resin described in U.S. Pat. , Tokuho Sho36
No. 9168, JP-A-51-9079, in-situ method by polymerization of monomers, British Patent No. 9528.
No. 07,9655074, and the spray drying method described in US Pat. No. 3,111,407 and British Patent No. 930422.

The method of microencapsulation is not limited to these, but in the light- and heat-sensitive recording material of the present invention, in particular, the electron-donating colorless dye is dissolved or dissolved in a hydrophobic organic solvent serving as a core of the capsule. The dispersed and prepared oil phase is mixed with an aqueous phase in which a water-soluble polymer is dissolved, emulsified and dispersed by means of a homogenizer or the like, and then heated to cause a polymer formation reaction at the oil droplet interface. It is preferable to employ an interfacial polymerization method for forming microcapsule walls of the substance. That is, a capsule having a uniform particle size can be formed in a short time, and a recording material having excellent raw preservability can be obtained.

The reactant forming the polymer is added inside the oil droplet and / or outside the oil droplet. Specific examples of the polymer substance include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer and the like. Among them, polyurethane, polyurea, polyamide, polyester, and polycarbonate are preferable, and polyurethane and polyurea are particularly preferable. The above polymer substances can be used in combination of two or more kinds.

Examples of the water-soluble polymer include gelatin, polyvinyl pyrrolidone, and polyvinyl alcohol.

For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and a second substance (for example, polyol or polyamine) which reacts with the polyisocyanate to form a capsule wall are converted to a water-soluble polymer aqueous solution (aqueous phase) or After mixing in an oily medium (oil phase) to be encapsulated, emulsifying and dispersing these, and then heating, a polymer forming reaction occurs at the oil droplet interface to form microcapsule walls.

Examples of the polyvalent isocyanate and the polyol and polyamine to be reacted therewith include US Pat. Nos. 3,281,383, 3,737,695 and 3,793.
No. 268, JP-B-48-40347, and JP-B-49-241
No. 59, JP-A-48-80191 and JP-A-48-8408.
No. 6 can be used.

Examples of the polyvalent isocyanate include, 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, and cyclohexylene 1,4-diisocyanate;

Triisocyanates such as 4,4 ′, 4 ″ -triphenylmethane triisocyanate and toluene-2,4,6-triisocyanate; 4,4′-dimethyldiphenylmethane-2,2 ′, 5,5 ′ A tetraisocyanate such as tetraisocyanate;

Adducts of hexamethylene diisocyanate and tremethylolpropane, adducts of 2,4-tolylenediisocyanate and trimethylolpropane, adducts of xylylenediisocyanate and trimethylolpropane, adducts of tolylenediisocyanate and hexanetriol, etc. Isocyanate prepolymers.

Examples of the polyol include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters, and hydroxypolyalkylene ethers. JP-A-60-49
No. 991 described below may 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-pentanediol, 1,4-cyclohexanedimethanol,
Dihydroxycyclohexane, diethylene glycol,
1,2,6-trihydroxyhexane, 2-phenylpropylene glycol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,4 −
Condensation products of aromatic polyhydric alcohols such as di (2-hydroxyethoxy) benzene, resorcinol dihydroxyethyl ether and alkylene oxide, p-xylylene glycol, m-xylylene glycol, α, α ′
-Dihydroxy-p-diisopropylbenzene, 4,
4'-dihydroxy-diphenylmethane, 2- (p,
p'-dihydroxydiphenylmethyl) benzyl alcohol, an adduct of bisphenol A with ethylene oxide, an adduct of bisphenol A with propylene oxide, and the like.

The above-mentioned polyol is preferably used in the range of 0.02 to 2 mol of hydroxyl group to 1 mol of isocyanate group.

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

In the present invention, when preparing microcapsules containing an electron-donating colorless dye, the encapsulated electron-donating colorless dye may be present in a solution state or a solid state in the capsule. You may. As the solvent, the same solvents as those used when the above-mentioned photocurable composition is emulsified and dispersed can be used. When the electron-donating colorless dye is encapsulated in a capsule in a solution state, the electron-donating colorless dye may be encapsulated in a state in which the electron-donating colorless dye is dissolved in a solvent.
It is preferable to use 1 to 500 parts by weight with respect to parts by weight.

When the solubility of the colorless electron-donating dye to be encapsulated in the solvent is poor, a low-boiling solvent having high solubility may be used in combination. Examples of the low boiling point solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like.

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

As the surfactant to be contained in the aqueous phase, one which does not cause precipitation or aggregation by acting on the protective colloid described above is suitably used from anionic or nonionic surfactants. be able to. Preferred surfactants include, for example, sodium alkylbenzenesulfonate, sodium alkylsulfate, dioctyl sodium sulfosuccinate, polyalkylene glycol (eg, polyoxyethylene nonyl phenyl ether) and the like.

As described above, the water-soluble polymer to be contained as a protective colloid in the aqueous phase in which the oil phase is mixed can be appropriately selected from known anionic polymers, nonionic polymers, and amphoteric polymers. it can. Examples of the anionic polymer, natural, can also be used any of those synthesized, for example, -COO -, - SO ₂ - include those having a group. Specifically, natural products such as arabic gum, alginic acid, and pectin; semi-synthetic products such as carboxymethylcellulose, phthalated gelatin and other gelatin derivatives, sulfated starch, sulfated cellulose, and ligninsulfonic acid; maleic anhydride (hydrolysis) Acrylate-based (methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, and synthetic products such as carboxy-modified polyvinyl alcohol.

Examples of the nonionic polymer include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. Examples of the amphoteric polymer include gelatin. Of these, gelatin, gelatin derivatives, and polyvinyl alcohol are preferred. The water-soluble polymer is used as a 0.01 to 10% by weight aqueous solution.

An electron-accepting compound, a photopolymerizable monomer, a spectral sensitizing dye, and a photopolymerization initiator to be contained in the light- and heat-sensitive recording layer and / or the above-mentioned formulas (I-1) to (I-
The compound represented by any of 3) can be used as a solid dispersion with a water-soluble polymer, a sensitizer and other color-forming auxiliaries by means of a sand mill or the like. An emulsified dispersion obtained by dissolving in a soluble or insoluble high-boiling organic solvent, mixing the resultant with a surfactant and / or a polymer aqueous solution (aqueous phase) containing a water-soluble polymer as a protective colloid, and emulsifying with a homogenizer or the like. It is more preferable to use them. In this case, if necessary,
A low boiling solvent can be used as a dissolution aid. Further, an electron-accepting compound, a photopolymerizable monomer, a spectral sensitizing dye, the above-described sensitizer, and a photopolymerization initiator and / or any of the above formulas (I-1) to (I-3). Can be separately emulsified and dispersed, or can be mixed in advance and then dissolved in a high-boiling solvent and emulsified and dispersed. The preferred emulsified dispersion particle size is 1 μm or less.

The electronic receiver for use in the light and heat sensitive recording material of the present invention.
Soluble compounds have sufficient color development for dyes during heating printing
The amount required to obtain is usually used, but usually 7 to 15 g
/ M ^TwoIt is preferable to use in the range.

The electron-accepting compound used in the heat-sensitive recording material of the present invention is used in an amount of 1 to 5 with respect to 1 part by weight of the electron-donating colorless dye.
It is preferably used in the range of parts by weight, more preferably in the range of 2 to 3 parts by weight.

The photopolymerizable monomer used in the heat-sensitive recording material of the present invention is used in an amount of 0.5 to 0.5 parts by weight based on 1 part by weight of the electron accepting compound.
It is preferably used in a range of 3 parts by weight, more preferably in a range of 1 to 2 parts by weight.

The photopolymerization initiator used in the heat-sensitive recording material of the present invention is used in an amount of 0.01 to 1 part by weight of the photopolymerizable monomer.
It is preferably used in the range of 0.05 part by weight,
More preferably, it is used in the range of from 0.01 to 0.02 parts by weight.

The compound represented by any one of formulas (I-1) to (I-3) used in the heat-sensitive recording material of the present invention is used in an amount of 0.01 to 0 with respect to 1 part by weight of the photopolymerizable monomer. .
It is preferably used in the range of 0.05 parts by weight,
More preferably, it is used in the range of 0.02 parts by weight.

In the emulsification, the oil phase containing the above-mentioned components and the aqueous phase containing the protective colloid and the surfactant are mixed with a means used in ordinary fine particle emulsification such as high-speed stirring and ultrasonic dispersion, for example, a homogenizer, a Manton-Gorry. It can be easily performed using a known emulsifying apparatus such as an ultrasonic disperser, a dissolver, and a Keddy mill. After the emulsification, the emulsified product is heated at 30 to 70 ° C. in order to promote a capsule wall forming reaction.
Warm up. In order to prevent aggregation of the capsules during the reaction, it is necessary to reduce the probability of collision between the capsules by adding water or to perform sufficient stirring.

Further, a dispersion for preventing aggregation may be added again during the reaction. Generation of carbon dioxide gas is observed with the progress of the polymerization reaction, and the end of the generation can be regarded as an approximate end point of the capsule wall forming reaction. Usually, microcapsules containing the target dye can be obtained by reacting for several hours.

The average particle size of the microcapsules used for the light and heat sensitive recording material of the present invention is preferably 20 μm or less.
From the viewpoint of obtaining high resolution, the thickness is more preferably 5 μm or less. If the formed microcapsules are too small, the surface area with respect to a certain solid content becomes large and a large amount of a wall material is required. Therefore, the average particle diameter is preferably 0.1 μm or more.

When the light and heat sensitive recording material of the present invention is used as a multicolor light and heat sensitive recording material, the light and heat sensitive recording layer of the light and heat recording material is constituted by laminating a plurality of single-color light and heat recording layers on a support. In each of the light and heat sensitive recording layers, a microcapsule containing an electron-donating colorless dye that develops a different hue, and a photocurable composition containing a spectral sensitizing dye having a different maximum absorption wavelength. Contained, when exposed to light, it is sensitive due to the difference in its light source wavelength,
Construct a multicolor image.

An intermediate layer containing a filter dye is provided between the single-color light- and heat-sensitive recording layers constituting the light- and heat-sensitive recording layer. 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 filter dye can be selected from the above-mentioned spectral sensitizing dyes, but it is preferable to use the same compound as the spectral sensitizing dye in the upper layer of each intermediate layer in that a clear image can be formed.

The filter dye can be emulsified and dispersed by an oil-in-water dispersion method or a polymer dispersion method and added to a desired layer, particularly, an intermediate layer. In the oil-in-water dispersion method, a high-boiling solvent having a boiling point of 175 ° C. or more or 30 to 1
A single liquid of one of the low-boiling solvents at 60 ° C., or
After dissolving in a mixture of both, in the presence of a surfactant, water,
Finely dispersed in a water-soluble solvent such as an aqueous gelatin solution or aqueous polyvinyl alcohol solution.

As the high boiling point solvent, US Pat.
Solvents described in 2,027 and the like. As the high boiling point solvent and the auxiliary solvent, the same solvents as those used for producing the above-mentioned microcapsules can be used.

The dispersion may be accompanied by a phase inversion, and the auxiliary solvent may be removed or reduced by distillation, Nudel washing, ultrafiltration or the like, and then used for coating.

Specific examples of the latex for the steps of the polymer dispersion method, curing and impregnation are described in US Pat. No. 4,1919.
No. 9,383, West German Patent Application (OLS) No. 2,541,
No. 274, No. 2,541,230, JP-A-49-7
No. 4538, No. 51-59943, No. 54-3255
No. 2 or "Research Disclosure, V
ol148 "(August 1976, Item 1485)
0).

Examples of the latex include acrylates or methacrylates such as ethyl acrylate, n-butyl acrylate, n-butyl methacrylate and 2-acetoacetoxyethyl methacrylate; acrylic acid, 2-acrylamido-2-methylpropane sulfone A copolymer latex of an acid monomer such as an acid is preferred.

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

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

Further, in addition to the above-described additives, other additives can be added to the light and heat sensitive recording layer as needed. For example, dyes, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, coating aids, curing agents, antistatic agents, slipperiness improvers, and the like can be added. Representative examples of each of the above additives are “Research Disclosure”.
Sure, Vol. 176 "(December 1978, It
em 17643) and “Id. Vol. 187” (19)
November 1979, Item 18716).

In the light and heat sensitive recording material of the present invention, it is preferable to use a curing agent in each of the light and heat sensitive recording layer, the intermediate layer, the protective layer and the like. 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, formaldehyde,
Aldehyde compounds such as glutaraldehyde, reactive halogen compounds described in U.S. Pat. No. 3,635,718, compounds having a reactive ethylenically unsaturated group described in U.S. Pat. No. 3,635,718, U.S. Pat.
No. 280, etc., US Pat.
No. 091537 etc., epoxy compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane such as dihydroxydioxane, dichlorodioxane,
U.S. Pat. No. 3,642,486 and U.S. Pat.
No. 7, vinyl sulfones described in US Pat.
No. 72, vinyl ketones described in U.S. Pat. No. 3,640,720, and chromium alum, zirconium sulfate, boric acid and the like can also be used as an inorganic curing agent.

Among them, 1,3,5-triacloyl-hexahydro-s-triazine, 1,2-pispinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamide) ) Compounds such as ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenino-s-triazine and boric acid are preferred. The curing agent, based on the amount of binder used,
It is preferable to add in the range of 0.5 to 5% by weight.

The light- and heat-sensitive recording material of the present invention can be prepared by dissolving the coating solution for the light- and heat-sensitive recording layer and the coating solution for the protective layer in a solvent, if necessary, and then coating and drying on a desired support. Obtainable. Solvents that can be used in that case include water; methanol, ethanol, n-propanol,
Alcohols such as isopropanol, n-butanol, sec-butanol, methyl cellosolve, 1-methoxy-2-propanol; halogen solvents such as methylene chloride and ethylene chloride; ketones such as acetone, cyclohexanone and methyl ethyl ketone; methyl cellosolve acetate and ethyl acetate , Methyl acetate and the like; toluene; xylene and the like alone, and a mixture of two or more thereof. Among them, water is particularly preferred.

To coat the coating solution for the light and heat sensitive recording layer on the support, a blade coater, rod coater, knife coater, roll doctor coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, curtain coater , An extrusion coater or the like can be used.

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

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

As the support used in the light- and heat-sensitive recording material of the present invention, synthetic paper such as paper, coated paper and laminated paper; polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, polycarbonate film, etc. A metal plate of aluminum, zinc, copper, or the like; or a substrate obtained by subjecting the surface of a support to various treatments such as surface treatment, undercoating, or metal deposition. further,
"Research Disclosure, Vol.
200 "(December 1980, Item 20036
(XVII)). Further, if necessary, an antihalation layer can be provided on the front surface of the support to be used, and a slip layer, an antistatic layer, an anti-curl layer, an adhesive layer, and the like can be provided on the back surface.

The light and heat sensitive recording material of the present invention has an optical diameter of 0.7
Recording can be performed with light in the wavelength range of 300 to 1100 nm of ３3 μm. As the light source, a known light source such as a semiconductor laser light emitting diode and a xenon lamp can be appropriately used. When the multicolor light and heat sensitive recording material is used, two or more dyes are used,
By irradiating light sources having different wavelengths of more than one kind, a multicolor image can be formed.

The light and heat sensitive recording material of the present invention can form an image by performing a heat development treatment simultaneously with or after the exposure for forming a latent image. As a heating method at the time of the heat development treatment, a conventionally known method can be used, and generally, the heating temperature is 80 to 200 ° C.
And more preferably 85 to 130 ° C. The heating time is preferably in the range of 1 second to 5 minutes, and more preferably in the range of 3 seconds to 1 minute.

After the heat development, the uncured portion is preferably cured by exposing the entire surface. By doing so, the coloring reaction due to the coloring component remaining in the background portion (non-image portion) is sufficiently suppressed, and the density reduction in the coloring portion can be suppressed, so that the image storability is greatly improved.

When an image is formed by the above method using the light- and heat-sensitive recording material of the present invention, the sensitivity is further improved by providing a step of uniformly preheating the entire surface of the material at a predetermined temperature lower than the coloring temperature during the image formation. can do. The light and heat sensitive recording material of the present invention can be used not only for the above-mentioned recording method but also for other known recording methods. For example, in order to improve thermal recording, contrast, and image quality using a heating device such as a thermal head, international application W
In the recording method of forming an image by irradiating a laser beam used for a silver halide photosensitive and heat-sensitive recording material proposed by 3M Company described in O95 / 31754 so that the beam spots overlap in a predetermined range. Can also be used. That is, in the laser beam irradiation process at the time of forming a latent image, (1) on the target object,
A radiation light source capable of forming a beam spot having at least one of a height and a length of 600 μm or less is prepared. (2) After a recording material sensitive to this light source is arranged at a predetermined target position, first, ( 3) The light source is adjusted so that at least one of the length and the width becomes a beam spot of 250 μm or less, and the beam is radiated using the beam according to the image distribution. (4) an image forming technique of irradiating according to an image distribution such that at least some spots of a beam to be subsequently irradiated overlap with the irradiated spot, and

Alternatively, in the method of forming a latent image by exposing a recording material, (1) preparing a light source capable of exposing
(2) A plurality of small areas each having a height or a length of 600 μm or less are illuminated.
At least 10% of the energy required for at least one sub-region, ie at least 10% of the plurality of sub-regions
% Is based on an image forming technique for irradiating so as to overlap with another small area.

A recording method proposed by Canon Inc. described in JP-A-60-195568 can also be used. That is, by tilting the incident angle of a laser beam applied to the recording material surface, the reflection pitch at which the incident beam is reflected at the photosensitive layer interface of the recording material is made larger than the beam spot diameter, thereby preventing light interference occurring on the recording material. , A higher quality image can be obtained.

[0295]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
Hereinafter, “parts” and “%” in the examples represent “parts by weight” and “% by weight”, respectively. <Preparation of electron-donating colorless dye-containing microcapsules> (1-a) Preparation of electron-donating colorless dye (1) -containing microcapsules 8.9 g of the following electron-donating colorless dye (1) was added to ethyl acetate 1
6.9 g, and 20 g of capsule wall material (trade name: Takenate D-110N, manufactured by Takeda Pharmaceutical Co., Ltd.) and Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.)
2 g were added.

[0296]

Embedded image

This solution was treated with 42 g of 8% phthalated gelatin and 10% sodium dodecylbenzenesulfonate solution.
The mixture was added to 4 g of the mixture, and emulsified and dispersed at 20 ° C. to obtain an emulsion. 14 g of water and 72 g of a 2.9% tetraethylenepentamine aqueous solution were added to the obtained emulsion, and the mixture was stirred at 60 ° C.
After 2 hours, microcapsules containing an electron-donating colorless dye (1) as a capsule core and having an average particle size of 0.5 μm were obtained.

<Preparation of Photocurable Composition Emulsion> (2-1) Photocurable Composition (1) Preparation of Emulsion 0.1 g of the following photopolymerization initiator (29), the following spectral sensitizing dye ( 23) 0.1 g, 0.5 g of the exemplary compound (II-16) of the general formula (I-3) in Table 4 above, and the following auxiliary agent (1) as an auxiliary agent for improving photosensitivity. Compound 0.1
g and isopropyl acetate (solubility in water: about 4.3%)
5 g of the following polymerizable electron-accepting compound (1) was added to the mixed solution obtained by mixing 3 g.

[0299]

Embedded image

[0300]

Embedded image

[0301]

Embedded image

[0302]

Embedded image

This solution was combined with 13 g of a 13% aqueous gelatin solution,
0.8 g of the following 2% surfactant (1) aqueous solution and 2
% Surfactant (2) in a mixed solution with 0.8 g of an aqueous solution, and rotated at 10,000 rpm with a homogenizer (manufactured by Nippon Seiki Co., Ltd.). p. m. For 5 minutes to obtain an emulsion of the photocurable composition (1).

[0304]

Embedded image

(2-2) Photocurable Composition (2) Preparation of Emulsion In the preparation of the emulsion of the photocurable composition (1), 0.07 g of the spectral sensitizing dye (23) was added in the same manner as in the above table. 0.25 g of the exemplary compound (II-16) of the general formula (I-3) in No. 4 and 0.07 g of the compound represented by the above-mentioned auxiliary (1) as an auxiliary for improving photosensitivity. Except that, an emulsion of the photocurable composition (2) was obtained in the same manner as in the above (2-1).

(2-3) Preparation of Emulsion of Photocurable Composition (3) In the preparation of the emulsion of the photocurable composition (1), 0.05 g of the spectral sensitizing dye (23) was added. 0.2 g of the exemplary compound (II-16) of the general formula (I-3) in Table 4 and 0.05 g of the compound represented by the auxiliary (1) as an auxiliary for improving photosensitivity. An emulsion of the photocurable composition (3) was obtained in the same manner as in the above (2-1), except that the above was used.

(2-4) Preparation of Emulsion of Photocurable Composition (4) In the preparation of the emulsion of photocurable composition (1), 0.03 g of the spectral sensitizing dye (23) was added. The exemplified compound (II-16) of the general formula (I-3) in Table 4 was converted to 0.08.
g, and 0.03 g of the compound represented by the tablet (1) as an auxiliary agent for improving photosensitivity,
An emulsion of the photocurable composition (4) was obtained in the same manner as in (2-1).

(2-5) Preparation of emulsion of photocurable composition (5) In the preparation of emulsion of photocurable composition (1), 0.01 g of the spectral sensitizing dye (23) was added. 0.01 g of Exemplified Compound (II-16) of General Formula (I-3) in Table 4 above
And a photocurable composition (5) in the same manner as in (2-1), except that the compound represented by the auxiliary (1) was used in an amount of 0.01 g as an auxiliary for improving photosensitivity. An emulsion was obtained.

<Preparation of Coating Solution for Photosensitive and Thermosensitive Recording Layer> (3-1) Preparation of Coating Solution for Photosensitive and Thermosensitive Recording Layer (1) The electron-donating colorless dye (1) 4 g of microcapsules was prepared.
12 g of an emulsion of the photocurable composition (1) and 15%
A photosensitive and heat-sensitive recording layer (1) was prepared by mixing 12 g of an aqueous gelatin solution.
A coating solution was prepared.

(3-2) Preparation of Coating Solution for Photosensitive and Heat-Sensitive Recording Layer (2) The electron-donating colorless dye (1) 4 g of microcapsules
12 g of an emulsion of the photocurable composition (2) and 15%
12 g of an aqueous gelatin solution is mixed, and the light and heat sensitive recording layer (2)
A coating solution was prepared.

(3-3) Preparation of Coating Solution for Light- and Heat-Sensitive Recording Layer (3) The electron-donating colorless dye (1) 4 g of microcapsules was prepared.
12 g and 15% of an emulsion of the photocurable composition (3)
12 g of an aqueous gelatin solution is mixed, and the light and heat sensitive recording layer (3)
A coating solution was prepared.

(3-4) Preparation of Coating Solution for Photosensitive and Thermosensitive Recording Layer (4) The electron-donating colorless dye (1) 4 g of microcapsules
12 g and 15% of an emulsion of the photocurable composition (4)
12 g of an aqueous gelatin solution is mixed, and the light and heat sensitive recording layer (4)
A coating solution was prepared.

(3-5) Preparation of Coating Solution for Photosensitive and Heat-Sensitive Recording Layer (5) The electron-donating colorless dye (1) 4 g of microcapsules
12 g of an emulsion of the photocurable composition (5) and 15%
An aqueous gelatin solution was mixed to prepare a coating solution for the light and heat sensitive recording layer (5).

<Preparation of Coating Solution for Protective Layer> 4.5 g of a 10% aqueous gelatin solution, 4.5 g of distilled water, 0.5 g of the 2% aqueous solution of the surfactant (3), and 2% of the aqueous solution of the 2% surfactant (4) 0.3 g, 2 g of an aqueous solution of 2% vinyl sulfone compound (hardener) and 0.5 g of Syloid 72 (FUJI-DEV)
ISION CHEMICAL LTD. Was mixed in an amount to give a dry coating amount of 50 mg / m ^2, and 1 g of Snowtex N was further mixed to prepare a coating solution for the protective layer (1).

<Support> Blue base of polyethylene terephthalate having a thickness of 175 μm.

(Example 1) The coating liquids (1) to (5) for the photosensitive and heat-sensitive recording layer were placed on the support in this order from the coating liquid (1) using a coating bar, and the dry weight of each coating layer was measured. Was applied so that the dry weight was 6 g / m ² , and the total coating weight of the five layers coated in a multilayer manner was 30 g / m ² . The coating liquid for the protective layer (1) is coated on this with a coating bar.
The coating layer was applied so that the dry weight of the coating layer became 2 g / m ² and dried to obtain a light and heat sensitive recording material of the present invention.

(Example 2) The coating solutions (1), (3) and (5) for the photosensitive and heat-sensitive recording layer were applied in this order from the coating solution (1) by using a coating bar on the support. Coating so that the dry weight of the layers is 10 g / m ² and the dry weight of the total applied amount of the five layers coated in a multilayer manner is 30 g / m ² ;
Dried. A coating solution for the protective layer (1) was applied on this layer using a coating bar so that the dry weight of the applied layer was 2 g / m ² , and dried to obtain a light and heat sensitive recording material of the present invention.

(Example 3) The general formula (I-3) in Table 4 used for each photocurable composition in the coating solutions (1) to (5) for the light and heat sensitive recording layer of Example 1 Compound (II-)
16) with the exemplified compound (II) of the general formula (I-3) in Table 4
Instead of -5), coating solutions (6) to (1)
A light and heat sensitive recording material of the present invention was obtained in the same manner as in Example 1 except that 0) was prepared.

(Comparative Example 1) In Example 1, the coating solution (4) for the photosensitive and heat-sensitive recording layer was replaced with the multilayer coating using the five coating solutions (1) to (5). ) Alone using a coating bar and the dry weight of the coating layer is 30
g / m ² , and a photosensitive and heat-sensitive recording material was obtained in the same manner as in Example 1, except that the coating was performed and dried.

(Comparative Example 2) In Example 1, instead of the multilayer coating using the five coating solutions (1) to (5) for the photosensitive and heat-sensitive recording layer, the coating solution (9 ) Was measured using a coating bar and the dry weight of the coating layer was 28%.
Example 1 except that the composition was applied and dried so as to obtain g / m ^2.
In the same manner as in the above, a light and heat sensitive recording material was obtained.

Each of the five types of photosensitive and heat-sensitive recording materials obtained as described above was subjected to a wavelength of 65 from the protective layer side.
The exposure was performed in the form of a step wedge using a 7 nm semiconductor laser beam while changing the irradiation energy by changing the scanning speed. The light-sensitive and heat-sensitive recording materials of Examples 1 and 2 and Comparative Example 1 were exposed to light so that the irradiation energy on the surface of the heat-sensitive recording layer at the maximum irradiation was 15 mJ / cm ² . In the light and heat sensitive recording materials of Example 3 and Comparative Example 2,
Irradiation exposure was performed so that the irradiation energy on the surface of the thermosensitive recording layer at the time of maximum irradiation was 40 mJ / cm ² .

When the recording material on which the step wedge-shaped latent image was formed was heated with a hot plate at 120 ° C. for 5 seconds, a step wedge image was obtained in each material.

<Evaluation of Sensitivity> Sensitivity corresponds to the same exposure amount in the wedge image of each material, and in one step, the irradiation energy of this step and the energy required to form a background portion of each material. (Energy until formation of the background portion-irradiation energy in the above step) was measured and calculated, and used as an index of sensitivity.
Therefore, the smaller the sensitivity, the higher the sensitivity. Was evaluated.

<Measurement of Density> The color density (Dmax) and the background fog (Dmin) were measured with a Macbeth transmission densitometer (manufactured by Macbeth Corporation). <Evaluation of Transparency> The transparency of the recording material was measured using a haze meter (DIGITAL HAZE COMPUTER HG).
M-2DP (manufactured by Suga Test Instruments Co., Ltd.), and the value was used as an index for evaluating transparency. Table 7 shows the results of the above.

[0325]

[Table 7]

As is clear from Table 7, the books of Examples 1 to 3 were formed by laminating five thin layers having different contents of the spectral sensitizing dye from the protective layer side so as to increase the content. The photosensitive and heat-sensitive recording material of the present invention has a low spectral sensitizing dye content by irradiating a laser beam from the side of the photosensitive and heat-sensitive recording layer having a low content of the spectral sensitizing dye to perform recording, so that there is no distribution in the content of the spectral sensitizing dye in the layer. Compared to the light and heat sensitive recording materials of Comparative Examples 1 and 2 which were only uniformly dispersed, high sensitivity was obtained, and the color density was high.
A high-contrast image could be formed. Also, the transparency was excellent.

[0327]

According to the light- and heat-sensitive recording material of the present invention, a layer structure having a distribution such that the content of the spectral sensitizing dye is higher than the incidence surface of the laser beam is provided, thereby providing high sensitivity and high contrast. And a clear image with high image quality can be formed. Further, by using the photosensitive and heat-sensitive recording material of the present invention as a multicolor recording material provided with a plurality of different color-forming layers, a clear and clear color image can be formed. Furthermore, according to the image recording method of the present invention, when the irradiation light enters the recording layer in the thickness direction from the incident surface, the attenuation of the light can be suppressed, so that the sensitivity is high, the contrast is high, and In the case of color, a clear image of color development can be obtained. Therefore, according to the present invention, the use of a developer or the like is unnecessary, and a recommended dry processing system that does not generate waste, using a small and inexpensive infrared laser or a green to red light source, A color or black-and-white image having excellent effects as described above can be obtained.

Continued on front page F-term (reference) 2H025 AA00 AA01 AA04 AB09 AB11 AB20 AC01 AC08 AD01 BC12 BC31 BC51 BC81 CA00 CA39 CA41 CC14 CC20 DA09 DA10 DA11 DA13 DA14 FA03 FA06 FA22 2H026 AA07 AA15 AA24 AA25 BB02 DD45 DD45 DD31 DD DD53 FF01 FF03 FF05 FF07 FF13

Claims (6)

[Claims] 1. An electron-donating colorless dye encapsulated in a thermo-responsive microcapsule on a support, and an electron-accepting compound and a photopolymerizable monomer outside the thermo-responsive microcapsule.
In a light and heat sensitive recording material provided with a light and heat sensitive recording layer containing a spectral sensitizing dye, and a photopolymerization initiator and / or an organic boron compound, the photosensitive and heat sensitive recording layer has a content distribution of the spectral sensitizing dye. Is a light- and heat-sensitive recording layer whose height increases from the incident surface of the irradiation light in the thickness direction of the light- and heat-sensitive recording layer. 2. The light and heat sensitive recording layer according to claim 1, wherein the light and heat sensitive recording layer is a light and heat sensitive recording layer formed by laminating two or more recording layers having different contents of the spectral sensitizing dye. Light and heat sensitive recording material. 3. An electron donating colorless dye encapsulated in a thermoresponsive microcapsule on a support, and an electron accepting group and a photopolymerizable group in the same molecule outside the thermoresponsive microcapsule. In a light and heat sensitive recording material provided with a light and heat sensitive recording layer containing a compound, a spectral sensitizing dye, and a photopolymerization initiator and / or an organic boron compound, the light and heat sensitive recording layer contains the spectral sensitizing dye. A light and heat sensitive recording material, wherein the rate distribution increases from the incident surface of the irradiation light toward the thickness direction of the light and heat sensitive recording layer. 4. The light and heat sensitive recording layer according to claim 3, wherein the light and heat sensitive recording layer is formed by laminating two or more recording layers having different contents of the spectral sensitizing dye. Light and heat sensitive recording material. 5. A on a support, toward the incident surface of the irradiation light in the thickness direction of the light and heat sensitive recording layer, a first recording layer that is sensitive to the central wavelength lambda ₁ of the light source color, the central wavelength lambda ₁ the intermediate layer which absorbs light, and sensitive to the central wavelength lambda ₂ of the light, the first
The second recording layer which develops in the recording layer with a different color, the intermediate layer for absorbing light having a center wavelength lambda _2, · · ·, intermediate layer for absorbing light having a central wavelength lambda _i-1, the center wavelength lambda _i The i-th recording layer, which is exposed to light and develops a color different from the first, second,...
5. A light- and heat-sensitive recording layer laminated with ≧ 2 or more, wherein the center wavelength λ of the light source at this time is λ ₁ <λ ₂ <... <Λ _i. The light and heat sensitive recording material according to any one of the above. 6. An image obtained by irradiating a light and heat sensitive recording layer of the light and heat sensitive recording material obtained according to any one of claims 1 to 5 from the surface side of the recording layer having a low content of a spectral sensitizing dye. Image recording method to record.