JPH07323660A - Photosensitive thermal recording material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive thermal recording material forming a developed color image excellent in light fastness and preservability and reduced in background stainings by providing a recording layer containing a diazo compd., a coupling component and an org. base on a support and using a specific compd. as the coupling component. CONSTITUTION:In a photosensitive thermal recording material obtained by providing a recording layer containing a diazo compd., a coupling component and an org. base on a support, at least one of coupling components represented by formulae I-III is used. In the formulae I-III, R1 and R2 are an alkyl group, an aryl group or the like, R3 is an alkyl group, R4 is an alkyl group, an alkoxy group or the like, R5 is an org. residue forming a nitrogen-containing heterocyclic group along with >N-, R6 is an alkyl group, R7 is an alkyl group, an alkoxy group or the like, R8 is an alkyl group, an aryl group or the like, Q is a non-metal atom group necessary for forming a 3-5-membered heterocyclic ring, R9 is an alkyl group, R10 is an alkyl group, an alkoxy group or the like and n is an integer of 0-4.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording material utilizing the photosensitivity of a diazo compound (diazonium salt). More specifically, it relates to a diazo light and heat sensitive recording material for forming a yellow color image comprising a diazo compound, a coupling component and a base.

[0002]

2. Description of the Related Art As recording materials utilizing the photosensitivity of diazo compounds, three types are known. One is a type known as wet development type, in which a photosensitive layer containing a diazo compound and a coupling component as a main component is provided on a support, and this material is superposed on an original document and exposed to an alkaline solution. It is to develop. The second is a type known as a dry development type, which is different from the wet type in that development is performed with ammonia gas. The third type is known as a heat development type, which contains a type of ammonia gas generating agent such as urea that can generate ammonia gas by heating in the photosensitive layer and trichloroacetic acid in the photosensitive layer. There are a type containing an alkali salt of an acid which loses its properties as an acid by various heating, a type utilizing activation of a diazo compound and a coupling component by heating and melting using a higher fatty acid amide as a color forming aid.

The wet type uses a developing solution, which requires replenishment and disposal of the solution, and a large size of the apparatus. In addition to maintenance problems, the wet type immediately after recording makes it easy to add data. There are some problems such as not being present or the recorded image cannot be stored for a long time. Also, the dry type requires replenishment of the developing solution as well as the wet type, a gas absorption facility is required to prevent the generated ammonia gas from leaking to the outside, and thus the device becomes large, and so on. Immediately after recording, it has problems such as smell of ammonia. On the other hand, unlike the wet type and dry type, the heat development type has an advantage in maintenance because it does not require a developing solution, but all the conventionally known types have a high development temperature of 150 ° C to 200 ° C. However, if the temperature is not controlled to about ± 10 ° C., the development cost may be insufficient or the color tone may change, resulting in an increase in apparatus cost. Further, the diazo compound used for such high temperature development also needs to have high heat resistance, but such a compound is often disadvantageous for forming a high concentration. Low temperature development (90 ° C ~
Many attempts have been made at 130 ° C), but there is a drawback in that the shelf life of the material itself is shortened. As described above, the heat-development type is expected to have a merit in maintenance as compared with the wet type and the dry type, but is not yet the mainstream of the diazo recording system. Now,
In order to obtain the desired color density by heating the material provided with the layer containing the diazo compound and the coupling component on the support, each component instantly melts, diffuses and reacts by heating to form a coloring dye. However, it is preferable to make the system basic during this reaction because it has the effect of promoting the reaction. Therefore, in order to prepare a light and heat sensitive recording material having a recording speed at which heating at low temperature does not cause a serious problem in practical use, it is an essential requirement that the coating material contain a basic substance.

On the other hand, for the light and heat sensitive recording material, it is also an essential requirement to prevent the background portion from being colored and the color density from being lowered during storage before recording.

With such a good shelf life,
In addition, although some of the above-mentioned attempts have been made to prepare a light and heat sensitive recording material having a high recording speed, the present situation is that it has not yet been put to practical use.

When a material is designed so that a sufficient color can be obtained even if the heating temperature is low, precoupling (coloring reaction) may occur during storage before recording. It appears as a phenomenon in which the background, which must be white, is colored.

Various improvements have been made in order to eliminate this coloring (fog). For example, one of the components involved in color development is present in the form of discontinuous particles (solid dispersion), or one of the components involved in color development is separately provided as a separate layer ( JP-A-57-123086). Therefore, it is intended to prevent contact between the components and prevent the progress of precoupling. However, in either case, the storability (so-called raw storability) is satisfactorily improved, but the thermal responsiveness (meltability to heat), which is one of the important performances, tends to decrease.

Further, as a technique for simultaneously improving both the raw preservation property and the thermal responsiveness, a non-polar wax-like substance (JP-A-57-44141 and JP-A-57-142636) or a hydrophobic polymer. Substance (JP-A-57-192
No. 944), it is known to encapsulate one of the color-forming components and separate it from the other components.

In these encapsulation methods, a wax-like substance or a polymer substance is dissolved in an appropriate solvent, and a coloring component or the like is dissolved or dispersed in this solution to form a capsule. It is different from the usual concept of a capsule that is surrounded by a shell. Therefore, when the color-forming component is dissolved to form a capsule,
The color-forming component does not necessarily become the core substance of the capsule and is uniformly mixed with the encapsulating substance, pre-coupling gradually progresses at the wall interface of the capsule and the raw storability cannot be maintained, and the color-forming component is dispersed. In the case of forming a capsule, there is a problem that the color responsiveness does not occur unless the wall of the capsule is melted by heat, resulting in a decrease in thermal responsiveness. Further, there is a manufacturing problem that the solvent used for dissolving the wax-like substance or the polymer substance must be removed after the formation of the capsule, which is not sufficiently satisfactory.

Therefore, as a method for solving these problems, at least one of the components involved in the color development reaction is contained in the core substance, and a wall is formed around this core substance by polymerization to form microcapsules. Method (JP-A-59)
-190886, JP-A-60-6493)
Are also proposed.

By the way, an acylacetanilide type compound is widely used as a coupling component of an azo dye for yellow to orange, but the obtained image does not always have sufficient light fastness. As a method of improving the light fastness of an image, a method of adding an anti-fading agent or an ultraviolet absorber, a method of strongly dyeing a substrate, and a method of insolubilizing in a solvent (forming a pigment) are known.

On the other hand, the aniline portion of the coupling component
It is said that light fastness is improved by combining Cl, OCH _3, etc., and compounds such as Naphthol AS-LG (color index NO.37615) and Naphthol AS-L3G (color index NO.37620) are also known. There is. However, these compounds are not sufficiently oil-soluble, for example, when trying to obtain an emulsion by dissolving in a solvent or a plasticizer, it is difficult to obtain a high-concentration emulsion, or a homogeneous emulsion that precipitates over time is obtained. There were drawbacks such as difficulty in obtaining.

It is also known to use a compound such as 2,5-dimethoxy-4-chloroacetoacetanilide. However, although it is easily dissolved in a solvent, it has a low molecular weight and becomes water-soluble. When this happens, precoupling occurs and the background part is colored.

Further, as a compound having these drawbacks improved, an oil-soluble acylacetanilide compound (Japanese Patent Application Laid-Open No. 4-201283) which forms a color image with improved light fastness is known, but its image light Robustness is still not enough.

[0015]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a diazo light and heat sensitive recording material which has high light fastness of a color image and little background stain and has good storage stability.

[0016]

The above objects of the present invention are as follows.
A light and heat sensitive recording material in which a recording layer containing a diazo compound, a coupling component and an organic base is provided on a support is represented by the following general formula (I), general formula (II) and general formula (III). It was achieved by using at least one of the coupling components.

[0017]

[Chemical 3]

In the general formula (I), R ₁ and R ₂ represent an alkyl group, an aryl group or a heterocyclic group, R ₃ represents an alkyl group, and R ₄ represents an alkyl group, an alkoxy group, an alkylthio group or an arylthio group. Represents an alkylamino group or a halogen atom. n represents an integer of 0 to 4, and when n is 2 or more, R ₄ may be different from each other. R
The total carbon number of ₃ and R ₄ is preferably 6 or more, and 8
The above is more preferable.

When R ₁ and R ₂ represent an alkyl group, a straight chain, branched or cyclic group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms,
It is a saturated, unsaturated, substituted or unsubstituted alkyl group.
Examples of alkyl groups include methyl, ethyl, propyl,
Butyl, cyclopropyl, allyl, t-octyl, i-
Butyl, dodecyl and 2-hexyldecyl can be mentioned.

When R ₁ and R ₂ represent a heterocyclic group, 3 to 12 containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Membered rings, preferably 5 or 6
A membered ring, saturated or unsaturated, substituted or unsubstituted,
It is a monocyclic or condensed-ring heterocyclic group. Examples of the heterocyclic group include 3-pyrrolidinyl, 1,2,4-triazol-3-yl, 2-pyridyl, 4-pyrimidinyl, 3-pyrazolyl, 2-pyrrolyl, 2,4-dioxo-1,3-
Examples include imidazolidin-5-yl or pyranyl.

When R ₁ and R ₂ represent an aryl group, they represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

[0022]

[Chemical 4]

In the general formula (II), R ₅ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-, R ₆ represents an alkyl group, R ₇ represents an alkyl group, an alkoxy group,
It represents an alkylthio group, an arylthio group, an alkylamino group or a halogen atom. n represents an integer of 0 to 4,
When n is 2 or more, R ₇ may be different from each other. The total carbon number of R ₆ and R ₇ is preferably 6 or more, more preferably 8 or more.

The nitrogen-containing heterocyclic group represented by R ₅ <and> N- is a saturated or unsaturated, monocyclic or condensed ring having 1 or more carbon atoms, preferably 1 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms. It may be substituted or unsubstituted. In addition to the nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or the like may or may not be contained in the ring, and one or more of each of these hetero atoms may be contained. The number of ring members is a 3-membered ring or more, preferably a 3- to 12-membered ring, and particularly preferably a 5- or 6-membered ring.

Specific examples of the heterocyclic group represented by R ₅ <and> N- include morpholino, 1-imidazolidinyl, 1
-Pyrazolyl, 1-piperazino, 1-indolinyl,
1,2,3,4-tetrahydroquinoxalin-1-yl, 1-pyrrolinyl, pyrazolidin-1-yl, 2,3
-Dihydro-1-indazolyl, isoindoline-2-
Yl, 1-pyrrolyl, 2-pyrazolin-1-yl, benzothiazin-4-yl, 4-thiazinyl, perhydro-
1,1-dioxo-1,4-thiazin-4-yl, benzodiazin-1-yl, aziridin-1-yl, benzoxazin-4-yl, 2,3,4,5-tetrahydroquinolyl or phenoxazine- 10-yl and the like can be mentioned.

The heterocyclic group formed by R ₅ <and> N- is preferably a nitrogen-containing heterocyclic group containing at least one unsaturated carbon. Examples of such heterocyclic groups include indolinyl, 2,3,4,5-tetrahydroquinolyl, isoindolino or 4-oxopiperidino.

The heterocyclic group formed by R ₅ <and> N- is preferably a nitrogen-containing heterocyclic group containing at least two hetero atoms as ring-constituting atoms. Examples of such heterocyclic groups include morpholino, piperazino, perhydro-1,1-dioxo-1,4-thiazin-4-yl or benzomorpholino.

When R ₁ and R _{2 each} represent a substituted alkyl, aryl or heterocyclic group, and
When the nitrogen-containing heterocyclic group formed by R ₅ together with> N- has a substituent, examples of the substituent include an alkoxy group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonyl group and carbamoyl. Group, sulfamoyl group, sulfonamide group, nitro group, cyano group, alkyl group or aryl group.

[0029]

[Chemical 5]

In the general formula (III), R₈Is alkyl
Group, aryl group, alkoxy group, aryloxy group, ha
Represents a logen atom and a cyano group, and Q is C, together with C3 to
Hydrocarbon ring or less selected from N, S, O, P
And 3- to 5-membered heterocycle having one hetero atom in the ring
Represents a group of non-metal atoms necessary for forming. However, R
₈Does not combine with Q to form a ring. R₉Is al
Represents a kill group, R_TenIs an alkyl group, an alkoxy group,
Kirthio group, arylthio group, alkylamino group or
Represents a halogen atom. n represents an integer of 0 to 4, and n is
R is 2 or more _TenMay be different from each other. R
₉, R_TenThe total carbon number of is preferably 6 or more, and 8
The above is more preferable.

R ₈ is preferably a halogen atom, a cyano group, or a total carbon number 1 to which either of them may be substituted.
30 alkyl groups, alkoxy groups or total carbon number 6 to
Examples of the aryl group and aryloxy group of 30 and their substituents include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group, a sulfonamide group, and an acyl group. R ₈ is particularly preferably a halogen atom or an alkyl group, and most preferably a methyl group or an ethyl group.

Q is preferably a hydrocarbon ring having a total carbon number of 3 to 30 which may be substituted with any of 3 to 5 members together with C or at least one hetero atom selected from N, S, O and P. Represents a group of non-metal atoms necessary to form a heterocycle having 2 to 30 carbon atoms in total. The ring formed by Q together with C may contain an unsaturated bond in the ring.
Examples of the ring formed by Q together with C include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring,
There are cyclobutene ring, cyclopentene ring, oxetane ring, oxolane ring, 1,3-dioxolane ring, thietane ring, thiolane ring and pyrrolidine ring. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aryl group,
There are an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group and an arylthio group. Q is particularly preferably a nonmetallic atom group ring made with C to form a hydrocarbon ring 3-5 _{membered, - [CR 2] 2 -} , - [CR 2] 3 -, - [C
R ₂ ] ₄ − can be mentioned as an example. Where R
Represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of R and CR ₂ may be the same or different. Q is most preferably to form a 3-membered ring with C binding - [CR _{2] 2} - is.

The above R ₃ , R ₄ , R ₆ , R ₇ , R ₉ , R
₁₀ may further have a substituent, and as those,
Examples thereof include an alkyl group, an aryl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a nitro group and a cyano group.

[0034]

[Chemical 6]

In the general formula (IV), R ₁₁ and R ₁₂ represent an alkyl group. R ₁₁ and R ₁₂ may be the same or different. However, the total carbon number of R ₁₁ and R ₁₂ is preferably 6 or more, more preferably 8 or more. Y represents a halogen atom, and specifically, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. X ^- is PF ₆
^-, BF ₄ ^- represents a counter anion such as. R ₁₁ , R ₁₂ , Y,
As a preferable combination of X ^−, a combination in which R ₁₁ and R ₁₂ are n-butyl groups, Y is a chlorine atom, and X ⁻ is PF ₆ ^— can be mentioned.

In the general formula (IV), R ₁₁ and R ₁₂ may further have a substituent, and examples thereof include an aryl group, an alkoxy group, a cyano group, an ester group, an acyloxy group, an acylamino group and carbamoyl. Groups, halogen atoms and the like.

As a result of intensive studies, the inventors of the present invention have obtained a stable light and heat sensitive recording layer in which a high image light fastness is obtained by using the above-mentioned coupling component, and the background coloration by pre-coupling is small. The present invention has been completed and the present invention has been completed. Further, they have found that higher image light fastness can be obtained by using the above-mentioned diazo compound, and have completed the present invention.

General formula (I), general formula (II) and general formula (I
The compound represented by II) can be preferably selected from both an oily substance and a crystalline state. Further, for the purpose of obtaining an emulsion, it is dissolved in an appropriate solvent (eg, tricresyl phosphate, dioctyl phthalate) or supplementarily dissolved in a low boiling point solvent (eg, ethyl acetate). For this reason, it is preferable to have appropriate solubility in these solvents and low water solubility. Specifically, it preferably has a solubility of 5% or more in the solvent and a solubility of 1% or less in water. Further, these coupling components are preferably used in the range of 0.05 to 5 g / m ² in the light and heat sensitive recording layer, but are used in the range of 0.1 to 4 g / m ² from the viewpoint of color density. More preferable. Specific examples of the coupling component according to the present invention are shown below, but the present invention is not limited thereto.

[0039]

[Chemical 7]

[0040]

[Chemical 8]

[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

The coupling components according to the present invention may be used alone or in combination of two or more. The combined use of two or more kinds is more preferable because the precipitation of the coupling component over time can be suppressed and a stable and uniform light and heat sensitive recording layer can be formed.

The diazo compound that can be used in the present invention can be arbitrarily selected from known compounds as long as it produces a color by reacting with the above coupling component in a basic atmosphere. Specific examples thereof include the following compounds.

[0047]

[Chemical 13]

[0048]

[Chemical 14]

Further, the diazo compound preferable in the present invention is the diazo compound represented by the above general formula (IV). Although a specific example of this is shown, the present invention is not limited thereto.

[0050]

[Chemical 15]

Further, the diazo compound of the present invention is preferably used by being encapsulated in microcapsules for the purpose of preventing precoupling, but when forming the microcapsules, it is dissolved in a suitable solvent (eg tricresyl phosphate). Therefore, it is desirable to have appropriate solubility in these solvents for use. Specifically, it is preferable that the solvent has a solubility of 5% or more. Further, the water solubility is preferably 1% or less.

Specific examples of the acid (counter anion) forming the diazo compound (diazonium salt) include polyfluoroalkylcarboxylic acids having 1 to 9 carbon atoms and 1 carbon atom.
To polyfluoroalkylsulfonic acid, tetrafluoroboric acid, tetraphenylboric acid, hexafluorophosphoric acid, aromatic carboxylic acid, and aromatic sulfonic acid, but preferably hexafluorophosphoric acid,
Tetrafluoroboric acid, and more preferably hexafluorophosphoric acid. Further, a complex compound may be formed using zinc chloride, cadmium chloride, tin chloride or the like to stabilize the diazonium salt. These diazo compounds may be used alone or in combination of two or more. Further, these diazo compounds are preferably used in the range of 0.02 to 3 g / m ^{2 in} the light and heat sensitive recording layer, but are more preferably used in the range of 0.1 to ² g / m ² from the viewpoint of color density. preferable.

The diazo compound used in the present invention is preferably encapsulated in microcapsules. The forming method can be carried out using a known method. Below is a brief description. First, the above diazo compound is dissolved or dispersed in an appropriate organic solvent, and then this solution or dispersion (oil liquid) is emulsified and dispersed in an aqueous medium. It is more preferable that the diazo compound of the present invention used for this purpose has an appropriate solubility in an organic solvent. Examples of the organic solvent include phosphoric acid ester, phthalic acid ester, carboxylic acid ester, fatty acid amide, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, carbonic acid ester, diarylethane and the like.

Next, a wall made of a polymer material is formed around the oil droplets that have been emulsified and dispersed. Reactants for forming polymeric substances are added to oily liquids and / or aqueous media. The polymer substance forming the capsule wall is impermeable at room temperature and needs to be permeable at the time of heating, and it is particularly preferably one having a glass transition temperature of 60 to 200 ° C. Examples thereof include polyurethane, polyurea, polyamide, polyester, urea / formaldehyde resin, melamine resin, polystyrene, styrene / methacrylate copolymer, styrene / acrylate copolymer, and mixed systems thereof.

As the method for forming microcapsules, an interfacial polymerization method and an internal polymerization method are suitable. Details of the capsule forming method and specific examples of the reactant are described in US Pat. Nos. 3,726,804 and 3,796,669. For example, when polyurea polyurethane is used as a capsule wall agent, polyisocyanate and a second substance (for example, polyol, polyamine) which reacts with it to form a capsule wall are mixed in an aqueous medium or an oily liquid to be encapsulated, Then, these are emulsified and dispersed, and then heated, whereby a polymer forming reaction occurs at the oil droplet interface to form a microcapsule wall. An auxiliary solvent having a low boiling point and a strong dissolving power may be added to the oily liquid. Polyurea is produced even when the addition of the second substance is omitted.

When forming microcapsules, a water-soluble polymer compound can be used as a protective colloid. Examples of the water-soluble polymer compound include a water-soluble anionic polymer compound, a nonionic polymer compound and an amphoteric polymer compound. These water-soluble polymer compounds are used as 0.01 to 10% by weight aqueous solution.

In the present invention, an organic base is added for the purpose of making the system basic during heat development and promoting the coupling reaction. These organic bases may be used alone or in combination of two or more. Examples of the basic substance include nitrogen-containing compounds such as tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines and morpholines.

[0058] Especially, N, N ^'- bis (3-phenoxy-2-hydroxypropyl) piperazine, N, ^N' - bis [3- (p-methylphenoxy) -2-hydroxypropyl] piperazine, N, N ^'- bis [3- (p-methoxyphenoxy) -2-hydroxypropyl] piperazine, N, ^N' - bis (3-phenylthio-2-hydroxypropyl) piperazine, N, N ^'- bis [3- (beta-
Naphthoxy) -2-hydroxypropyl] piperazine,
N-3- (beta-naphthoxy) -2-hydroxypropyl -N ^'- methylpiperazine, 1,4-bis {[3- (N
-Methylpiperazino) -2-hydroxy] propyloxy} benzene and other piperazines, N- [3- (β-naphthoxy) -2-hydroxy] propylmorpholine,
Morpholines such as 1,4-bis [(3-morpholino-2-hydroxy) propyloxy] benzene and 1,3-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, N- (3-phenoxy) Specifically, piperidines such as 2-hydroxypropyl) piperidine and N-dodecylpiperidine, and guanidines such as triphenylguanidine, tricyclohexylguanidine, and dicyclohexylphenylguanidine are specifically preferable.

In the present invention, it is preferable to use the coupling component in an amount of 0.1 to 30 parts by weight and the basic substance in an amount of 0.1 to 30 parts by weight per 1 part by weight of the diazo compound.

In the present invention, in addition to the organic base, a color forming auxiliary agent can be added for the purpose of promoting the color forming reaction.

Included in the color forming aid of the present invention are:
For example, a phenol derivative, a naphthol derivative, an alkoxy-substituted benzene, an alkoxy-substituted naphthalene, a hydroxy compound, an amide compound, or a sulfonamide compound is added to the light and heat sensitive recording layer so that the thermal development can be performed quickly and completely with low energy. You can It is considered that these compounds lower the melting point of the coupling component or the basic substance or improve the heat permeability of the microcapsule wall, and as a result, high color density can be obtained.

The color-forming aid of the present invention also includes a heat-meltable substance. The heat-fusible substance is a substance having a melting point of 50 ° C. to 150 ° C. that is solid at room temperature and melts by heating, and is a substance that dissolves a diazo compound, a coupling component, or a basic substance. Specific examples of these compounds include fatty acid amides, N-substituted fatty acid amides, ketone compounds, urea compounds, and esters.

The coupling component used in the present invention is
With a basic substance, other coloring aids, etc., it can also be used by solid-dispersing it together with a water-soluble polymer by a sand mill or the like, but after dissolving it in an organic solvent that is sparingly soluble or insoluble in water, it is used as a surfactant and It is preferable to mix it with an aqueous phase having a water-soluble polymer as a protective colloid to prepare an emulsion dispersion. From the viewpoint of facilitating emulsion dispersion, it is preferable to use a surfactant.

The organic solvent used in this case can be appropriately selected from the high boiling point oils described in JP-A-2-141279. Among these, it is preferable to use esters from the viewpoint of emulsion stability of the emulsified dispersion, and tricresyl phosphate is particularly preferable. The above oils can be used together or with other oils.

An auxiliary solvent may be added to the above organic solvent as a dissolution aid having a low boiling point. As such an auxiliary solvent, for example, ethyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like can be mentioned as particularly preferable ones. In some cases, it is possible to use only the low boiling auxiliary solvent without the high boiling oil.

The water-soluble polymer to be contained as a protective colloid in the aqueous phase mixed with the oil phase containing these components is
It can be appropriately selected from known anionic polymers, nonionic polymers, and amphoteric polymers. Examples of preferable water-soluble polymers include polyvinyl alcohol, gelatin, cellulose derivatives and the like.

The surfactant to be contained in the aqueous phase may be appropriately selected from anionic or nonionic surfactants that do not cause precipitation or aggregation by acting on the protective colloid. it can. Preferred surfactants include sodium alkylbenzene sulfonate, sodium alkylsulfate, dioctyl sodium sulfosuccinate, polyalkylene glycol (eg, polyoxyethylene nonylphenyl ether), and the like.

In the recording material of the present invention, a free radical generator (a compound which generates a free radical upon irradiation with light) used in a photopolymerizable composition or the like for the purpose of reducing yellowing of the background after recording.
Can be added. Examples of the free radical generator include aromatic ketones, quinones, benzoin, benzoin ethers, azo compounds, organic disulfides, acyloxime esters and the like. The amount to be added is preferably 0.01 to 5 parts by weight with respect to 1 part by weight of the diazo compound.

Similarly, for the purpose of reducing yellow coloring, a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as vinyl monomer) can be used. A vinyl monomer is a compound having at least one ethylenically unsaturated bond (vinyl group, vinylidene group, etc.) in its chemical structure and has a chemical form of a monomer or a prepolymer. Examples of these include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic polyhydric alcohols, and amides of unsaturated carboxylic acids with aliphatic polyhydric amine compounds. The vinyl monomer is used in a proportion of 0.2 to 20 parts by weight with respect to 1 part by weight of the diazo compound. The free radical generator and the vinyl monomer may be contained in a microcapsule together with the diazo compound and used.

In the present invention, citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid and the like can be added as an acid stabilizer in addition to the above materials.

The recording material of the present invention is prepared by preparing a coating solution containing a microcapsule containing a diazo compound, a coupling component, an organic base and other additives, and coating it on a support such as paper or a synthetic resin film. 2.5 to 30 g / solid content by coating and drying by a coating method such as bar coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating or curtain coating.
An m ² light and heat sensitive recording layer is provided. In the recording material of the present invention, microcapsules, coupling components, bases and the like may be contained in the same layer as described in the above method, or may have a laminated structure in which they are contained in different layers. You can also

The support used in the present invention can be arbitrarily selected from materials known as supports for heat-sensitive recording materials such as high-quality paper, synthetic paper, and synthetic resin films, depending on the purpose. For example, as the paper support, neutral paper of pH 5 to 9 sized with a neutral sizing agent such as alkyl ketene dimer (described in JP-A-55-14281),
Paper satisfying the relationship between Steckigt sizing degree and metric basis weight described in JP-A-57-1166887 and having Beck smoothness of 90 seconds or more, and optical surface roughness described in JP-A-58-136492. Is 8 μ or less and the thickness is 30 to
150 μ paper, paper having a density of 0.9 g / cm ³ or less and an optical contact rate of 15% or more described in JP-A-58-69091, and Canadian standard drainage described in JP-A-58-69097. (JIS P8121) paper made from pulp beaten to 400 cc or more to prevent bleeding of the coating liquid, the glossy surface of the base paper made by the Yankee machine described in JP-A-58-65695 being the coated surface. Improving color density and resolution, JP-A-59-35
It is possible to use, for example, a paper whose coating suitability is improved by subjecting the base paper described in Japanese Patent Publication No. 985 to corona discharge treatment.

Further, the synthetic resin film used as the support in the present invention can be arbitrarily selected from known materials which are not deformed by heating in the developing process and have dimensional stability. Examples of such a film include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate film, polystyrene films, polypropylene films, polyolefin films such as polyethylene, and the like. Can be used. The thickness of the support used is 20 to 200 μm.

When an image is formed on the recording material of the present invention,
The following method can be used. One is a method of exposing a document to form a latent image, and then irradiating light to a portion other than the image forming portion to fix the latent image.
This is a method in which a color image is obtained by heat from a hot pen, a thermal head, etc., and then the area other than the image area is irradiated with light to fix it. Either method can be preferably used.
As a light source for exposure, various fluorescent lamps, xenon lamps,
A mercury lamp or the like is used, and it is preferable that the emission spectrum thereof substantially coincides with the absorption spectrum of the diazo compound used in the recording material, because the portions other than the image forming portion can be efficiently photofixed. In the step of heating and developing the material, a heating pen, a thermal head, an infrared ray, a high frequency, a heat block, a heat roller, or the like can be used as the heating means.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. All "parts" in the examples represent parts by weight.

[0076]

【Example】

Example 1 (Preparation of Diazo Compound Capsule Liquid) As a diazo compound, 3.0 parts of 2,5-di-n-butoxy-4-tolylthiobenzenediazonium hexafluorophosphate was dissolved in 20 parts of ethyl acetate, and then the solution was further increased. 20 parts of alkylnaphthalene was added as a boiling solvent, and heated to uniformly mix. 1/3 of xylylene diisocyanate / trimethylolpropane as a capsule wall agent in the obtained solution.
15 parts of the adduct was added and uniformly mixed to obtain a solution of the diazo compound. The solution of the obtained diazo compound was added to an aqueous solution obtained by mixing 54 parts of a 6% by weight aqueous solution of gelatin and 2 parts of a 2% by weight aqueous solution of sodium dodecylbenzenesulfonate, and then emulsified and dispersed using a homogenizer.
To the obtained emulsified dispersion liquid, 68 parts of water was added, and the homogeneously mixed solution was heated to 40 ° C. with further stirring to carry out an encapsulation reaction for 3 hours so that the average particle size of the capsules became 1.3 μm. To obtain a capsule solution.

(Preparation of Coupling Component Emulsion Dispersion) As a coupling component, (N, N-diethylamino) carbonylacetic acid 2 ′, 4′-di-n-hexyloxyanilide (Compound I-3 of the present invention) 2 Part, 1,2,3-triphenylguanidine 1 part, tricresyl phosphate 0.3 part, dimethyl maleate 0.1 part with ethyl acetate 1
Dissolved in 0 parts. The resulting solution is 6% by weight of gelatin
After 50 parts of the aqueous solution and 2 parts by weight of a 2% by weight sodium dodecylbenzenesulfonate aqueous solution were mixed, the mixture was put into an aqueous solution and then emulsified for 10 minutes using a homogenizer to obtain an emulsion dispersion. (Preparation of coating liquid) Next, the above-mentioned diazo compound capsule liquid /
The emulsified dispersion of the coupling component was mixed at a weight ratio of 2/3 to obtain a coating liquid.

(Coating) A coating solution was coated on one surface of a transparent polyethylene terephthalate film having a thickness of 75 μm and dried to prepare a recording material having a light and heat sensitive recording layer of 7.2 g / m ² .

Example 2 Instead of the coupling component of Example 1, (1-indolinyl) carbonylacetic acid 2 ', 5'-di-n-octyloxyanilide (Compound II-1 of the present invention) in equimolar amount. A recording material was prepared in the same manner as in Example 1 except that the recording material was replaced and added.

Example 3 Instead of the coupling component of Example 1, (1-methylcyclopropyl) carbonylacetic acid 2 ', 5'-di-n-
Butyloxy-4'-chloroanilide (the compound of the present invention
Example 1 except that III-1) was replaced by an equimolar amount and added.
A recording material was prepared in the same manner as in.

Example 4 Instead of the diazo compound of Example 1, 2,5-di-n-
Butoxy-4-morpholinobenzenediazonium hexafluorophosphate was substituted for (1-ethylcyclopropyl) carbonylacetic acid 2 ′, 5′-di-n-heptyloxyanilide (compound of the present invention instead of the coupling component of Example 1). A recording material was prepared in the same manner as in Example 1 except that III-10) was added in an equimolar amount.

Example 5 Instead of the diazo compound of Example 1, 2,5-di-n-
A recording material was prepared in the same manner as in Example 1 except that butoxy-4- (4-chlorophenyl) thiobenzenediazonium hexafluorophosphate (IV-3) was added in an equimolar amount.

Example 6 Instead of the diazo compound of Example 2, 2,5-di-n-
A recording material was prepared in the same manner as in Example 2 except that butoxy-4- (4-chlorophenyl) thiobenzenediazonium hexafluorophosphate (IV-3) was added in an equimolar amount.

Example 7 Instead of the diazo compound of Example 3, 2,5-di-n-
A recording material was prepared in the same manner as in Example 3 except that butoxy-4- (4-chlorophenyl) thiobenzenediazonium hexafluorophosphate (IV-3) was added in an equimolar amount.

Example 8 Instead of the diazo compound of Example 4, 2,5-di-n-
A recording material was prepared in the same manner as in Example 4 except that butoxy-4- (4-chlorophenyl) thiobenzenediazonium hexafluorophosphate (IV-3) was added in an equimolar amount.

Comparative Example 1 In the same manner as in Example 1 except that instead of the coupling component of Example 1, 3-oxobutanoic acid 2 ′, 5′-dimethoxy-4′-chloroanilide was added in an equimolar amount. The recording material was created.

Comparative Example 2 Instead of the coupling component of Example 1, 4,4-dimethyl-3-oxopentanoic acid 2 ', 5'-di-n-hexyloxy-4'-chloroanilide was used in an equimolar amount. A recording material was prepared in the same manner as in Example 1 except that the recording material was replaced and added.

Comparative Example 3 As a coupling component, naphthol AS-LG (Cl
NO. 37615) was used, but it was hardly soluble in ethyl acetate and an emulsion could not be obtained.

(Coloring and Fixing Test) Using the Kyocera thermal head KST type, the applied power and pulse width to the thermal head were determined so that the recording energy per unit area was 46 mJ / mm ^2, and the above recording material was printed. . The recording material has an emission center wavelength of 420 nm and an output of 40
It was fixed with a W ultraviolet lamp. In Examples 1-8 and Comparative Examples 1-2, yellow images were obtained. The densities of the image part and the background part were measured with a Macbeth densitometer.

Next, an image light fastness test was conducted. The comparative test was carried out by irradiating a fluorescent lamp at 32000 lux for 72 hours.
The change in color density was measured with a Macbeth densitometer. Let D _{0 be} the density before irradiation and D be the density after irradiation, and (D / D ₀ ) ×
The light resistance was evaluated with 100 (%) as the residual ratio of the dye.
The results are shown in Table 1.

[0091]

[Table 1]

From these results, it can be seen that by using the coupling component according to the present invention, the obtained light and heat sensitive recording material exhibits high image light fastness, less background coloring, and excellent storage stability. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 1/52 A

Claims (3)

[Claims] 1. A photosensitive and heat-sensitive recording material comprising a support and a recording layer containing a diazo compound, a coupling component and an organic base, wherein the following general formula (I), general formula (II),
A light and heat sensitive recording material comprising at least one coupling component represented by the general formula (III). [Chemical 1] In the general formula (I), R ₁ and R ₂ represent an alkyl group, an aryl group or a heterocyclic group, R ₃ represents an alkyl group, R ₄ represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, an alkylamino group. Represents a group or a halogen atom. n represents an integer of 0 to 4. General formula (II)
In the formula, R ₅ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-, R ₆ represents an alkyl group, R ₇ represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, an alkylamino group or Represents a halogen atom.
n represents an integer of 0 to 4. In the general formula (III), R
₈ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom or a cyano group, and Q represents a 3- to 5-membered hydrocarbon ring together with C or at least one hetero atom selected from N, S, O and P. 3 to have atoms in the ring
It represents a group of non-metal atoms necessary for forming a 5-membered heterocycle. R ₉ represents an alkyl group, and R ₁₀ represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, an alkylamino group or a halogen atom. n represents an integer of 0 to 4. 2. The light and heat sensitive recording material according to claim 1, further comprising a diazo compound represented by the following general formula (IV). [Chemical 2] In formula (IV), R ₁₁ and R ₁₂ represent an alkyl group. Y represents a halogen atom and X ⁻ represents a counter anion. 3. The light and heat sensitive recording material according to claim 1, wherein the diazo compound is contained in the microcapsules.