JPH09301959A - Benzotriazole compound and recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new benzotriazole compound, capable of improving the light resistance of a recording material, especially effectively preventing the coloring of a nonimage part and suitable for use in a protecting layer, etc., in the recording material such as a heat-sensitive recording or a photosensitive material. SOLUTION: This benzotriazole compound is represented by formula I Z is H, a halogen, an alkyl or an alkoxy; X, Y and W are each Z, an alkenyl or an aryl; (m) is 1 or 2; A is a group, etc., represented by formula II [R<1> and R<2> are each H, an alkyl, etc.,; R<3> is H, an alkyl, etc.; R<4> is H, an alkyl, etc.; R<5> is X when (m) is 1] and a group, etc., represented by formula III (R is an alkylene, an arylene, etc.) when (m) is 2}, etc., e.g. 4-t-butyl-6-sec-butyl-2-(2H- benzotriazol-2-yl)phenyl 4-diethylamino-2-hydroxycinnamate. The compound represented by formula I is obtained by reacting a compound represented by formula IV with a compound represented by formula V [X is a halogen, OH, etc.; R<11> is H or a group, etc., represented by the formula COR<12> (R<12> is an alkyl, etc.)] and, as necessary, further hydrolyzing the resultant compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a benzotriazole compound and a recording material, and more specifically, a benzotriazole compound useful as a polymer material, a photographic material, an additive for a recording material, and a recording material having excellent light resistance. Regarding materials.

[0002]

2. Description of the Related Art Various benzotriazole compounds have been known as additives for polymer materials and heat-sensitive recording materials, and have been put into practical use. These are disclosed, for example, in US Pat. Nos. 4,480,052 and 4,436,920.
And JP-A-62-144989.
On the other hand, thermal recording has recently been developed because its recording device is simple, highly reliable and requires no maintenance.
As the heat-sensitive recording material, conventionally, those utilizing the reaction between an electron-donating colorless dye and an electron-accepting compound and those utilizing the reaction between a diazonium salt compound and a coupler have been widely known. In recent years as a thermal recording material (1)
The color density and the color sensitivity (2) have been earnestly studied to improve the characteristics such as the fastness of the color body.

However, in the conventional thermal recording material, when the material is exposed to sunlight for a long time or is posted in an office for a long time, the background portion is colored by light,
It has a defect that the image portion is discolored or discolored. Various methods have been proposed in order to improve the coloring of the background portion and the discoloration or fading of the image portion, but sufficient effects have not always been obtained.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a novel benzotriazole compound which is less colored by light and is useful as an additive for recording materials and the like, and a recording material having excellent light resistance. With the goal.

[0005]

The above-mentioned object is represented by the general formula (I) by a benzotriazole compound represented by the general formula (I) and in a recording material having a recording layer and a protective layer provided on a support. Achieved with recording materials containing the represented benzotriazole compounds.

[0006]

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In the formula, m represents 1 or 2. X is general
Formulas (I)-(1), (I)-(3) and (I)-(4)
In, a hydrogen atom, an alkyl group, an alkenyl group,
Rucoxy group, aryl group or halogen atom is represented by the general formula
In (I)-(2), an alkylene group, -OR^4aO
-Or-OCOR^4aCO_TwoRepresents-. W is a general formula
(I)-(1), (I)-(2) and (I)-(4)
In, hydrogen atom, alkyl group, alkenyl group,
A coroxy group, an aryl group or a halogen atom can be represented by the general formula
In (I)-(3), -OR^4aO- or -OCO
R^4aCO_TwoRepresents-. Y is the general formula (I)-(1),
In (I)-(2) and (I)-(3), the hydrogen source
Child, alkyl group, alkenyl group, alkoxy group, aryl
Group or halogen atom in the general formula (I)-(4)
For -OR^4aO-, -OCOR^4aCO _Two-, -CH_TwoC
H_TwoCO_TwoR^4aOCOCH_TwoCH_Two-, -CH_TwoCH_TwoOCO
R^4aCO_TwoCH_TwoCH_Two-Or -CH_TwoCH_TwoCON
(R^5a) R^4aN (R^5a) COCH_TwoCH_TwoRepresents-. R^4a
Represents an alkylene group or an arylene group. R^5aIs the water
Represents an element atom or an alkyl group. Z is a hydrogen atom or halogen
Represents a hydrogen atom, an alkyl group or an alkoxy group.

A represents a substituent represented by Chemical Formula 5 when m = 1 in the general formula (I)-(1) and in the general formulas (I)-(2) to (4).

[0009]

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In the formula, R ¹ and R ² are a hydrogen atom, an alkyl group, an alkenyl group, --CO ₂ R ⁶ , --CONR ⁷ R ⁸ , --C.
Represents N or an aryl group. R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.
R ³ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a -COR ⁹ or -SO ₂ R ^10. R ⁹ and R ¹⁰
Represents an alkyl group or an aryl group. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an alkenyl group.
R ³ and R ⁴ may be a 4 to 7 membered alkylene group which may be linked to each other and contain a hetero atom. R ⁵ is a hydrogen atom,
It represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom.

In the general formula (I)-(1), m =
When 2, A represents a divalent substituent in which amino groups in the two substituents shown in Chemical formula 6 are linked.

[0012]

[Chemical 6]

In the formula, R ¹ , R ² , R ³ and R ⁵ have the same meanings as in formula 5. R is an alkylene group, an arylene group, -COR ^4a CO- or -SO ₂ R ^4a SO ₂ - represents a.
R ^4a has the same ^meaning as in Chemical ^formula 1.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Among the substituents described later in the benzotriazole compound represented by the general formula (I), the alkyl group may be linear or branched, and may have an unsaturated bond. . Further, these alkyl groups may be substituted with an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group or the like. Further, the alkenyl group and the aryl group may be further substituted with an alkyl group, an alkoxy group or a halogen atom.

X, Y and W are each a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon atom having 6 to 18 carbon atoms. Aryl groups, fluorine atoms, chlorine atoms, and bromine atoms are preferable, and among these, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Groups, phenyl groups or chlorine atoms are particularly preferred.

Specific examples of monovalent ones among X, Y and W include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and s.
ec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, 2
-Butenyl group, benzyl group, α-dimethylbenzyl group,
Methoxy group, ethoxy group, propyloxy group, butyloxy group, octyloxy group, dodecyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxycarbonylethyl group, ethoxycarbonylethyl group, propyloxycarbonylethyl group, butyloxycarbonylethyl group , Octyloxycarbonylethyl group, phenoxycarbonylethyl group, phenyl group, tolyl group, chlorine atom, fluorine atom, bromine atom and the like, and specific examples of the divalent group include the following.

[0017]

[Chemical 7]

A so-called bis compound having two benzotriazole rings in one molecule [m of the general formula (I)-(1)]
= 2 and the case of general formulas (I)-(2) to (I)-(4)], R ^4a represents an alkylene group having 1 to 12 carbon atoms or an arylene having 6 to 12 carbon atoms. A group is preferred, and R ^5a is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Z is hydrogen atom, chlorine atom, fluorine atom, alkyl group having 1 to 12 carbon atoms, or 1 carbon atom.
To 12 alkoxy groups are preferable, and among these, a hydrogen atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are particularly preferable. Specific examples of Z include a hydrogen atom, chlorine atom, methyl group, ethyl group, propyl group, hexyl group, methoxy group, ethoxy group, propyloxy group and octyloxy group.

R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, —CO ₂ R ⁶ having 2 to 12 carbon atoms, and the number of carbon atoms. 2 to 18 —CONR ⁷ R ⁸ , —CN, and 6 to 6 carbon atoms
An aryl group having 18 carbon atoms is preferable, and among these, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 3 to 8 carbon atoms.
The alkenyl group and the aryl group having 6 to 12 carbon atoms are particularly preferable.

Specific examples of R ¹ and R ² include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and hexyl group. Group, octyl group, decyl group, dodecyl group, allyl group, phenyl group, benzyl group,
Methoxyphenyl group, tolyl group, methoxycarbonyl group, ethoxycarbonyl group, butyloxycarbonyl group, carbamoyl group, N-ethylcarbamoyl group, N-
Examples thereof include an octylcarbamoyl group, an N, N-dibutylcarbamoyl group and a cyano group.

As R ³ , a hydrogen atom and a carbon atom number of 1 to
18 alkyl group, alkenyl group having 3 to 12 carbon atoms, aryl group having 6 to 18 carbon atoms, and R ⁹ has 1 carbon atom
-COR ⁹ is a to 18 alkyl or aryl group having 6 to 18 carbon atoms, R ¹⁰ is an alkyl group or an aryl group having 6 to 18 carbon atoms having 1 to 18 carbon atoms -S
O ₂ R ¹⁰ is preferable, and among these, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 16 carbon atoms, and R ⁹ having 1 carbon atom. -COR ⁹ is an 12 alkyl or aryl group having a carbon number 6 to 16, R ¹⁰ is 1 to 12 carbon atoms
Particularly preferred is —SO ₂ R ¹⁰ which is an alkyl group or an aryl group having 6 to 16 carbon atoms.

R ⁴ is a hydrogen atom or a carbon atom number of 1 to
Preferred are an alkyl group having 18 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 18 carbon atoms. Among these, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
An alkenyl group having 3 to 8 carbon atoms and an aryl group having 6 to 16 carbon atoms are particularly preferable. When R ³ and R ⁴ are linked, a 4- to 7-membered alkylene group which may contain —O— or —S— is preferable, and particularly —O— or —S— may be contained. 5- to 6-membered alkylene groups are preferred.

The substitution position of -NR ³ R ⁴ is preferably the meta position with respect to the -OH group. Specific examples of —NR ³ R ⁴ include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dioctylamino group, N
-Methyl-N-cyclohexylamino group, diphenylamino group, N-ethyl-N-tolylamino group, acetylamino group, propionylamino group, isobutyrylamino group, pivaloylamino group, myristoylamino group, stearoylamino group, acryloylamino group , Benzoylamino group, cinnamoylamino group, morpholino group, piperidino group, pyrrolidino group, methanesulfonylamino group,
Examples thereof include a benzenesulfonylamino group, a di (butyloxycarbonylmethyl) amino group, a di (dibutylaminocarbonylmethyl) amino group and a dicyanoethylamino group.

R ⁵ is preferably a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and among these, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or chlorine. Atoms are preferred.

Specific examples of the benzotriazole compound represented by the general formula (I) are shown below, but the invention is not limited thereto.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

The benzotriazole compound represented by the general formula (I) of the present invention includes, for example, a benzotriazole compound represented by the following general formula (II) and a cinnamic acid represented by the following general formula (III). It is easily obtained by reacting the derivative with a base, an acid or a condensing agent.

[0032]

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In the general formula (II), X, W, Y and Z
Is synonymous with the above.

[0034]

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In the general formula (III), R ¹ , R ² , R ³ and R
⁴ and R ⁵ are as defined above. R ¹¹ represents a hydrogen atom, -COR ¹² or -SO ₂ R ^12. X represents a halogen atom, -OH, -OCOR ¹² or -OSO ₂ R ¹² . R ¹² represents an alkyl group or an aryl group.

When R ¹¹ is other than a hydrogen atom, a benzotriazole compound represented by the general formula (II) and a general formula
After reaction with the cinnamic acid derivative represented by (III), hydrolysis (deprotection) gives R ¹¹ = H.

Examples of the base include triethylamine, pyridine, potassium carbonate, sodium hydrogen carbonate,
Examples thereof include sodium carbonate, sodium hydroxide, sodium methoxide, sodium hydride and the like. Examples of the acid or condensing agent include sulfuric acid, p-toluenesulfonic acid, polyphosphoric acid, zinc chloride, dicyclohexylcarbodiimide, and the like. A solvent is preferably added during the reaction. Examples of the solvent include acetone, acetonitrile, tetrahydrofuran, dimethylformamide, dimethylacetamide, water and the like. The reaction temperature is preferably 0 to 100 ° C, particularly preferably 0 to 50 ° C.

The cinnamic acid derivative represented by the general formula (III) is obtained by reacting a compound represented by the following general formula (IV) with a compound represented by the following general formula (V) or (VI). It can be easily obtained.

[0039]

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[0040]

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[0041]

[Chemical 12]

In the general formulas (IV), (V) and (VI),
R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above. R ¹³ represents a hydrogen atom, an alkyl group or an aryl group. In addition, the reaction was carried out at R ¹¹ = H, and then XCO
Reacting with R ¹² , XSO ₂ R ¹² , (R ¹² CO) ₂ O, etc.,
R ¹¹ = COR ¹² and SO ₂ R ¹² may be obtained. Here, X and R ¹² have the same meanings as described above.

A compound represented by the general formula (IV)
The reaction with the compound represented by (V) is preferably carried out in the presence of a base. Examples of the base include pyridine,
Pyrrolidine, piperidine, sodium hydroxide and the like can be mentioned. The reaction temperature is preferably 30 to 200 ° C, particularly preferably 50 to 100 ° C.

The compound represented by the general formula (IV) and the compound represented by the general formula (V
The reaction with the compound represented by I) is preferably carried out in the presence of a solvent. Examples of the solvent include toluene, ethyl acetate, acetonitrile, dimethylacetamide, sulfolane, ethanol and the like. The reaction temperature is preferably 0 to 150 ° C, more preferably 20 to 100 ° C.

The benzotriazole compound represented by the general formula (I) can be used as an additive for polymer materials, photographic materials, recording materials and the like. The benzotriazole compound represented by the general formula (I) has a characteristic that it produces a benzotriazole-based ultraviolet absorber and a coumarin-based fluorescent brightening agent when irradiated with light, and thus it can be used in heat-sensitive recording materials, photosensitive materials and the like. It can be preferably used as a recording material.

The recording material of the present invention has a recording layer and a protective layer, and may further have other layers such as an undercoat layer and an intermediate layer, if necessary. As the recording layer,
It may be a heat-sensitive recording layer, a pressure-sensitive recording layer, a photosensitive recording layer, or the like, and can be appropriately selected according to the purpose. Depending on the type of the recording layer, a heat-sensitive recording material, a pressure-sensitive recording material,
Various recording materials such as photosensitive materials can be obtained. For example, the light-sensitive recording layer in the light-sensitive material contains a photosensitive silver halide capable of forming a latent image upon exposure and rapidly developing. The silver halide may be selected from known silver halides such as silver chloride, silver bromide, silver chlorobromide, silver iodide, silver iodobromide, and silver chloroiodobromide according to the purpose. It can be appropriately selected. The thermal recording layer will be described later.

The recording material of the present invention contains the benzotriazole compound represented by the general formula (I) of the present invention. In the recording material of the present invention, the layer containing the benzotriazole compound represented by the general formula (I) is not particularly limited and may be any of a recording layer, a protective layer, and the other layers described above. Of these, the protective layer is preferable. When the protective layer contains the benzotriazole compound represented by the general formula (I) of the present invention, this protective layer is preferably provided on the recording layer. The content of the benzotriazole compound represented by the general formula (I) in the recording material of the present invention is 0.05 to 3.0 g / m ^2.
Is preferred, and 0.1 to 2.0 g / m ² is more preferred.

As a method of incorporating the benzotriazole compound represented by the general formula (I) into the recording material, for example, (1) a solid dispersion method of the benzotriazole compound represented by the general formula (I), ( 2) a method of emulsifying and dispersing, (3) a method of dispersing a polymer, (4) a method of dispersing a latex, (5) a method of encapsulating microcapsules, and the like. Among these, the method of microencapsulating is particularly preferable.

The details of the emulsifying and dispersing method are as follows. That is, first, the benzotriazole compound represented by the general formula (I) is dissolved in oil. The oil may be solid or liquid at room temperature, and may be a polymer, for example, a low boiling auxiliary solvent such as acetic acid ester, methylene chloride, cyclohexanone and / or phosphoric acid ester, phthalic acid ester, acrylic acid ester, methacrylic acid ester. , Other carboxylic acid ethesul, fatty acid amide, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, diarylethane, chlorinated paraffin, alcohol-based, phenol-based, ether-based, monoolefin-based, epoxy-based oils, etc. To be Specific examples of the oil include tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate,
Tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilaurate phthalate, dicyclohexyl phthalate, butyl olefinate, diethylene glycol benzoate, dioctyl sebacate, dibutyl sebacate, dioctyl adipate, trioctyl trimellitate, acetyltriethyl citrate, Octyl maleate, dibutyl maleate, isoamyl biphenyl, chlorinated paraffin, diisopropyl naphthalene, 1,1 '
Examples thereof include high boiling point oils such as -ditolylethane, 2,4-di-t-amylphenol, N, N-dibutyl-2-butoxy-5-t-octylaniline, hydroxybenzoic acid 2-ethylhexyl ester and polyethylene glycol. Among these, alcohol type, phosphoric acid ester type, carboxylic acid type ester type, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene,
Diarylethane is particularly preferred.

In the present invention, a carbonization inhibitor such as hindered phenol or hindered amine may be added to the high boiling point oil. Also, as oil,
Those having an unsaturated fatty acid are particularly desirable, and specific examples thereof include α-methylstyrene dimer. As the α-methylstyrene dimer, for example, MSD100
(Product name, manufactured by Mitsui Toatsu Chemicals).

Next, the oil solution containing the benzotriazole compound represented by the general formula (I) is added to the aqueous solution of the water-soluble polymer, and the emulsion is dispersed by a colloid mill, a homogenizer or ultrasonic waves.

As the water-soluble polymer used at that time,
A water-soluble polymer such as polyvinyl alcohol is used, but an emulsion or latex of a hydrophobic polymer can be used together. At this time, a conventionally known surfactant or the like may be added, if necessary, for the purpose of improving the emulsion stability. As the water-soluble polymer, for example,
Polyvinyl alcohol, silanol modified polyvinyl alcohol, carboxy modified polyvinyl alcohol, amino modified polyvinyl alcohol, itaconic acid modified polyvinyl alcohol, styrene-maleic anhydride copolymer, butadiene maleic anhydride copolymer, ethylene maleic anhydride copolymer, isobutylene anhydride Examples thereof include maleic acid copolymer, polyacrylamide, polystyrene sulfonic acid, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, gelatin and the like. Among these, carboxy-modified polyvinyl alcohol is particularly preferable.

Examples of the hydrophobic polymer emulsion or latex include styrene-butadiene copolymers, carboxy-modified styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and the like.

As a method for encapsulating the microcapsules, a conventionally known microencapsulation method can be used. That is, the benzotriazole compound of the general formula (I) and the microcapsule wall precursor are dissolved in a water-insoluble or insoluble organic solvent, added to an aqueous solution of a water-soluble polymer, and emulsified and dispersed using a homogenizer or the like. Then, the temperature is raised and the polymer substance that becomes the microcapsule wall can be prepared by forming a wall film at the oil / water interface.

Specific examples of the polymeric substance that forms the wall film of the microcapsule include, for example, polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, and styrene-acrylate copolymer. Examples thereof include polymer resins, styrene-methacrylate copolymer resins, gelatin, polyvinyl alcohol and the like, and mixtures thereof. Among these, microcapsules having a wall film made of polyurethane / polyurea resin are particularly preferable.

A microcapsule having a wall film made of a polyurethane / polyurea resin is prepared by mixing a microcapsule wall precursor such as polyisocyanate into a core substance to be encapsulated and emulsifying it in an aqueous solution of a water-soluble polymer such as polyvinyl alcohol. It is manufactured by dispersing and raising the liquid temperature to cause a polymer formation reaction at the oil drop interface.

Some specific examples of the polyvalent isocyanate compound as the microcapsule wall precursor are shown below. 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'-diphenylmethane-4,4'-diisocyanate, xylene-1,4
-Diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1, Diisocyanates such as 4-diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, triisocyanates such as toluene-2,4,6-triisocyanate, 4,4′-dimethyldiphenylmethane-2,2 ′ , 5,5'-Tetraisocyanate and other tetraisocyanates, addition product of hexamethylene diisocyanate and trimethylolpropane, addition of 2,4-tolylene diisocyanate and trimethylolpropane And isocyanate prepolymers such as an adduct of xylylene diisocyanate and trimethylolpropane, an adduct of tolylene diisocyanate and hexanetriol, etc. These may be used alone or in combination of two or more. Among these, those having two or more isocyanate groups in the molecule are particularly preferable.

In the method of encapsulating microcapsules,
As the organic solvent in which the benzotriazole compound represented by the general formula (I) is dissolved, the oil exemplified in the method of emulsifying and dispersing can be used. The same applies to water-soluble polymers.

The particle size of the microcapsules is 0.1
˜1.0 μm is preferable, and 0.2 to 0.7 μm is more preferable.

In the present invention, a compound known as a reducing agent can be used together with the benzotriazole compound represented by the general formula (I) in order to further reduce the coloration upon photobleaching. This reducing agent may be inside or outside the microcapsules when the microcapsules are used. When the reducing agent is outside the microcapsules, the reducing agent enters into the microcapsules when printed by heating.

Examples of these reducing agents include hydroquinone compounds, hydrazide compounds, hydroxy compounds, phenidone compounds, catechol compounds, resorcinol compounds, hydroxyhydroquinone compounds, pyrrologricinol compounds, phenol compounds, phenylhydrazide compounds. Examples thereof include compounds, gallic acid compounds, ascorbic acid compounds, ethylene glycol compounds and the like.

Regarding these, JP-A-3-191341
JP, JP-A-3-25434, JP, 1-25
2953, JP-A-2-302753, JP-A-1-129247, JP-A-1-227145, JP-A-1-243048, and JP-A-2-26.
It is described in Japanese Patent No. 2649. Specifically, N-
In addition to phenylacetohydrazide, N-phenylbutyrylhydrazide, p-t-butylphenol, and 2-azidobenzoxazole, the following compounds may be mentioned.

[0063]

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The heat-sensitive recording layer is not particularly limited as long as it is a heat-sensitive recording layer containing a known coloring component and the like, but in the present invention, a reaction between a diazonium salt compound and a coupler is utilized. That is, a thermosensitive recording layer containing a diazonium salt compound and a coupler that reacts with the diazonium salt compound to develop a color, and / or one utilizing the reaction between an electron-donating colorless dye and an electron-accepting compound, that is, an electron-donating compound. A heat-sensitive recording layer containing a water-soluble colorless dye and an electron-accepting compound is preferred. Examples of the compound used in the heat-sensitive recording layer containing a diazonium salt compound and a coupler that reacts with the diazonium salt compound to produce a color when used include a diazonium salt compound and a coupler capable of reacting with the diazonium salt compound to form a dye. In addition to the above, basic substances and the like that accelerate the reaction between the diazonium salt compound and the coupler are included.

The diazonium salt compound is a compound represented by the following formula, and in these formulas, the maximum absorption wavelength can be controlled by the position and type of the substituent of the Ar moiety.

[0066]

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In the formula, Ar represents an aryl group. X
^- represents an acid anion.

Specific examples of the diazonium salt compound include 4- (N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium, 4-dioctylaminobenzenediazonium, 4
-(N- (2-ethylhexanoyl) piperazino) benzenediazonium, 4-dihexylamino-2-hexyloxybenzenediazonium, 4-N-ethyl-N-
Hexadecylamino-2-ethoxybenzodiazonium, 3-chloro-4-dioctylamino-2-octyloxyobenzenediazonium, 2,5-dibutoxy-
4-morpholinobenzenediazonium, 2,5-octoxy-4-morpholinobenzenediazonium, 2,5-
Dibutoxy-4- (N- (2-ethylhexanoyl) piperazino) benzenediazonium, 2,5-diethoxy-4- (N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzene Diazonium, 2,5-dibutoxy-4-tolylthiobenzenediazonium, 3- (2-octyloxyethoxy) -4-
Examples thereof include acid anion salts such as morpholinobenzenediazonium and the following diazonium salt compounds D-1 to D-5. Among these, hexafluorophosphate salt, tetrafluoroborate salt, and 1,5-naphthalene sulfonate salt are particularly preferable.

[0069]

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Among these diazonium salt compounds,
Photolyzed by light with wavelength of 300-400 nm 4-
(N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium, 4
-Dioctylaminobenzenediazonium, 4- (N-
(2-Ethylhexanoyl) piperazino) benzenediazonium, 4-dihexylamino-2-hexyloxybenzenediazonium, 4-N-ethyl-N-hexadecylamino-2-ethoxybenzodiazonium, 2,5
-Dibutoxy-4- (N- (2-ethylhexanoyl))
Piperazino) benzenediazonium, 2,5-diethoxy-4- (N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium and compounds shown in the above specific examples D-3 to D-5. Is particularly preferable. The maximum absorption wavelength is 0.1 for each compound.
The coating film of g / m ² to 1.0 g / m ² was measured with a spectrophotometer (MPS-2000 manufactured by Shimadzu Corp.).

Specific examples of the coupler which reacts with the above-mentioned diazonium salt to produce a color when heated are resorcin, flurglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, and 1-hydroxy-2-naphthoic acid morpholinopropylamide. 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy -3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid-N-dodecyloxypurupyramide, 2-hydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, 2-chloro-5 -O Chill acetoacetanilide,
1-phenyl-3-methyl-5-pyrazolone, 1-
(2′-octylphenyl) -3-methyl-5-pyrazolone, 1- (2 ′, 4 ′, 6′-trichlorophenyl)
-3-benzamide-5-pyrazolone, 1- (2 ',
4 ', 6'-trichlorophenyl) -3-anilino-5
-Pyralone, 1-phenyl-3-phenylacetamido-5-pyrazolone, and the compounds of C-1 to 6 shown below may be mentioned. Two or more of these couplers may be used in combination to obtain a desired color hue.

[0072]

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The basic substance includes not only inorganic or organic basic compounds but also compounds capable of decomposing upon heating and releasing an alkaline substance. Typical examples include organic ammonium salts, organic amines, amides, urea and thiourea, and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines,
Examples thereof include nitrogen-containing compounds such as triazoles, morpholines, piperidines, amidines, formazines and pyridines.

Specific examples thereof include tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allylurea, thiourea,
Methylthiourea, allylthiourea, ethylenethiourea,
2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methylimidazole, 2-undecylimidazoline, 2,4,5-trifuryl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-
2-imidazoline, 2-phenyl-2-imidazoline,
1,2,3-triphenylguanidine, 1,2-dicyclohexylguanidine, 1,2,3-tricyclohexylguanidine, guanidine trichloroacetate, N, N ′
-Dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-aminobenzothiazole, 2-benzoylhydrazinobenzothiazole and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the electron-donating dye precursor used in the present invention include triarylmethane compounds, diphenylmethane compounds, thiazine compounds, xanthene compounds, spiropyran compounds, and triarylmethane compounds, among others. Xanthene compounds are useful because of their high color density. To illustrate some of these,
3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone), 3,3-bis (p-dimethylamino) phthalide,
3- (p-dimethylaminophenyl) -3- (1,3-
Dimethylindol-3-yl) phthalide, 3- (p-
Dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (o-methyl-p-diethylaminophenyl) -3- (2-methylindole-
3-yl) phthalide, 4,4'-bis (dimethylamino) benzhydrin benzyl ether, N-halophenylleucouramine, N-2,4,5-trichlorophenylleucouramine, rhodamine-B-anilino Lactam, rhodamine (p-nitroanilino) lactam, rhodamine-B- (p-chloroanilino) lactam, 2-
Benzylamino-6-diethylaminofluorane, 2-
Anilino-6-diethylaminofluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-
Anilino-3-methyl-6-cyclohexylmethylaminofluoran, 2-anilino-3-methyl-6-isoamylethylaminofluoran, 2- (o-chloroanilino) -6-diethylaminofluoran, 2-octylamino-6 -Diethylaminofluoran, 2-ethoxyethylamino-3-chloro-2-diethylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, benzoylleucomethylene blue, p-nitrobenzylleucomethylene blue, 3-methyl- Spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3
-Benzylspirodinaphthopyran, 3-propyl-spiro-dibenzopyran and the like can be mentioned.

Examples of the electron accepting compound include phenol derivatives, salicylic acid derivatives, hydroxybenzoic acid esters and the like. Particularly, bisphenols and hydroxybenzoic acid esters are preferable. Examples of some of these include 2,2-bis (p-hydroxyphenyl) propane (ie, bisphenol A), 4,4 ′-(p-
Phenylenediisopropylidene) diphenol (ie,
Bisphenol P), 2,2-bis (p-hydroxyphenyl) pentane, 2,2-bis (p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis (4 '-Hydroxy-3',
5'-dichlorophenyl) propane, 1,1- (p-hydroxyphenyl) cyclohexane, 1,1- (p-hydroxyphenyl) propane, 1,1- (p-hydroxyphenyl) pentane, 1,1- (p- Hydroxyphenyl) -2-ethylhexane, 3,5-di (α-methylbenzyl) salicylic acid and its polyvalent metal salt, 3,5-di (tert-butyl) salicylic acid and its polyvalent metal salt,
3-α, α-dimethylbenzyl salicylic acid and its polyvalent metal salts, butyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, 2-ethylhexyl p-hydroxybenzoate, p-phenylphenol, p-cumylphenol Etc.

The sensitizer is preferably a low-melting organic compound having an aromatic group and a polar group in the molecule, such as benzyl p-benzyloxybenzoate, α-naphthylbenzyl ether and β-benzyloxybenzoate. Naphthyl benzyl ether,
β-naphthoic acid phenyl ester, α-hydroxy-β
-Naphthoic acid phenyl ester, β-naphthol- (p
-Chlorobenzyl) ether, 1,4-butanediol phenyl ether, 1,4-butanediol-p-methylphenyl ether, 1,4-butanediol-p-ethylphenyl ether, 1,4-butanediol-m-
Methyl phenyl ether, 1-phenoxy-2- (p-
Tolyloxy) ethane, 1-phenoxy-2- (p-ethylphenoxy) ethane, 1-phenoxy-2- (p-
Examples include chlorophenoxy) ethane and p-benzylbiphenyl.

In the recording material of the present invention, the diazonium salt compound, the coupler which reacts with the diazonium salt compound to produce a color when heated, the basic substance, the electron-donating colorless dye, the electron-accepting compound, and the sensitizing compound. As the method of incorporating the agent, for example, as in the case of the compound of the general formula (I), (1) a solid dispersion method, (2) an emulsion dispersion method, (3) a polymer dispersion method, (4) ) A method of dispersing latex, (5) a method of encapsulating microcapsules, and the like. Among these, from the viewpoint of storage stability, the method of microencapsulation is particularly preferable, and in the color-forming system utilizing the reaction of the diazonium salt compound and the coupler, it is preferable to microencapsulate the diazonium salt compound, and an electron-donating colorless dye. In a color-developing system utilizing the reaction of a compound with an electron-accepting compound, it is preferable that the electron-donating colorless dye be microencapsulated.

The recording layer in the recording material of the present invention is not particularly limited and can be appropriately selected according to the purpose. For example, in the case of a heat-sensitive recording layer in a heat-sensitive recording material, (1) a heat-sensitive recording layer containing, on a support, a diazonium salt compound having a maximum absorption wavelength of 360 ± 20 nm and a coupler that reacts with the diazonium salt compound to develop a color. And a thermosensitive recording layer comprising a diazonium salt compound having a maximum absorption wavelength of 400 ± 20 nm and a coupler which reacts with the diazonium salt compound to develop a color,
(2) A thermosensitive recording layer containing, on a support, a diazonium salt compound having a maximum absorption wavelength of 400 ± 20 nm and a coupler that reacts with the diazonium salt compound to develop a color, and a diazonium salt having a maximum absorption wavelength of 360 ± 20 nm. A heat-sensitive recording material comprising a compound and a coupler which reacts with the diazonium salt compound to produce a color,
(3) A thermosensitive recording layer containing a diazonium salt compound having a maximum absorption wavelength of less than 340 nm and a coupler that reacts with the diazonium salt compound to develop a color, and a maximum absorption wavelength of 420 n.
Examples thereof include a heat-sensitive recording layer containing a diazonium salt compound exceeding m and a coupler which reacts with the diazonium salt compound to develop a color.

In the recording material of the present invention, the recording layer may have a laminated structure. In this case, a multicolor recording material can be obtained by changing the hue of each recording layer. In the case of the above-mentioned heat-sensitive recording material, the layer constitution is not particularly limited, but in particular, two kinds of diazonium salt compounds having different photosensitizing wavelengths and a coupler which reacts with each diazonium salt compound under heat to develop different hues. A multicolor heat-sensitive recording material in which two heat-sensitive recording layers in which the above are combined and a heat-sensitive recording layer in which an electron-donating colorless dye and an electron-accepting compound are combined are laminated are preferable. That is, a first heat-sensitive recording layer containing an electron-donating colorless dye and an electron-accepting compound on a support, a diazonium salt compound having a maximum absorption wavelength of 360 ± 20 nm, and a reaction by heat with the diazonium salt compound. A second thermosensitive recording layer containing a color coupler, having a maximum absorption wavelength of 4
The third heat-sensitive recording layer contains a diazonium salt compound having a wavelength of 00 ± 20 nm and a coupler that reacts with the diazonium salt compound to produce a color when heated. In this example, full-color image recording is possible by selecting the hues of the heat-sensitive recording layers to be the three primary colors in subtractive color mixing, yellow, magenta, and cyan.

In the recording method of this multicolor heat-sensitive recording material, first, the third heat-sensitive recording layer is heated, and the diazonium salt compound and the coupler contained in the heat-sensitive recording layer are colored. Then 40
After irradiating light of 0 ± 20 nm to decompose the unreacted diazonium salt compound contained in the third thermosensitive recording layer, sufficient heat is applied so that the second thermosensitive recording layer develops color. The coupler and the diazonium salt compound contained in the thermosensitive recording layer are colored. At this time, the third thermosensitive recording layer is also strongly heated at the same time, but the diazonium salt compound has already been decomposed and the coloring ability is lost, so that no color is produced. Further, light of 360 ± 20 nm is irradiated to decompose the diazonium salt compound contained in the second recording layer, and finally to the first
The heat-sensitive recording layer is colored by applying sufficient heat.
At this time, the third and second heat-sensitive recording layers are also heated strongly at the same time, but do not develop color because the diazonium salt compound has already been decomposed and the color-forming ability has been lost.

In this case, the color-developing mechanism of the thermosensitive recording layer laminated directly on the support surface (the lowermost layer of the recording layer) is not limited to the combination of the electron-donating dye and the electron-accepting dye. And a coupler that reacts with the diazonium salt to develop a color, a diazo color system, a base color system that develops a color by contact with a basic compound, a chelate color system, a color system that develops a color by reacting with a nucleophile to cause an elimination reaction, etc. Any of these may be used, and a multicolor heat-sensitive recording material is provided by providing two heat-sensitive recording layers each containing a diazonium salt compound having a different maximum absorption wavelength and a coupler that reacts with the diazonium salt compound to develop a color. Can be configured.

In the recording material of the present invention, in order to further improve the light resistance, the following known antioxidants can be used. For example, European Patent Publication No. 310 can be used.
551, German Published Patent No. 3435443, European Published Patent No. 310552, Japanese Patent Laid-Open No. 3-121449, European Published Patent No. 459.
416, JP-A-2-262654, JP-A-2-71262, JP-A-63-163351, US Pat. No. 4,814,262, JP-A-54-4.
8535, JP-A-5-61166, JP-A-5-119449, and U.S. Pat. No. 4,980,27.
5, JP-A-63-113536, JP-A-62-
262047, European Published Patent No. 22373
9 publication, European Patent Publication No. 309402 publication,
Examples thereof include those disclosed in European Patent Publication No. 309401. Specific examples include the following compounds.

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[0085]

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[0086]

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Further, it is also effective to use various additives already known as heat-sensitive recording materials and pressure-sensitive recording materials.
If some of these antioxidants are shown, they are disclosed in JP-A-60-
No. 125470, JP-A-60-125471, JP-A-60-125472, and JP-A-60-2.
87485, JP-A-60-287486,
JP-A-60-287487, JP-A-62-146
680, JP-A-60-287488, JP-A-62-282885, JP-A-63-89877.
JP-A-63-88380, JP-A-63-88380
088831, JP 01-239282, JP 04-291685, JP 04-2
No. 91684, Japanese Patent Laid-Open No. 05-188867,
JP 05-188686 A, JP 05-110 A
490, JP 05-1108437 A, JP 05-170361 A, JP 63-2033 A.
72, JP-A-63-224989, JP-A-63-267594, and JP-A-63-182484.
JP, JP-A-60-107384, JP, JP-A-60
-107383, JP 61-160287, JP 61-185483, JP 61-2
11079, JP-A-63-251282,
JP-A-63-051174, JP-B-48-043
The compounds described in Japanese Patent Publication No. 294, Japanese Patent Publication No. 48-033212 and the like can be mentioned.

Specific examples include 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline and 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2. -Dihydroquinoline, 6-ethoxy-1-
Phenyl-2,2,4-trimethyl-1,2,3,4-
Tetrahydroquinoline, 6-ethoxy-1-octyl-
2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, nickel cyclohexanoate, 2,2-bis-4-hydroxyphenylpropane, 1,1-bis-4
-Hydroxyphenyl-2-ethylhexane, 2-methyl-4-methoxy-diphenylamine, 1-methyl-2
-Phenylindole and the compounds shown below.

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[0090]

[Chemical 21]

[0091]

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[0092]

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These antioxidants are used in the recording layer or intermediate layer,
It can be added to the benzotriazole compound-containing protective layer or the protective layer represented by the general formula (I). When using a combination of these antioxidants, etc., specific examples (Q-
7), (Q-45), (Q-46) or compound (Q-1)
0) and the compound (Q-13) in combination.

As the binder in the present invention, conventionally known binders can be used, and examples thereof include water-soluble polymers such as polyvinyl alcohol and gelatin, and polymer latex.

Examples of the support in the recording material of the present invention include plastic film, paper, plastic resin laminated paper and synthetic paper.

In the recording material of the present invention, when color forming layers having different hues are laminated, an intermediate layer can be provided to prevent color mixture and the like. A water-soluble polymer compound is used for the intermediate layer. Examples thereof include polyvinyl alcohol, modified polyvinyl alcohol, methyl cellulose, sodium polystyrene sulfonate, styrene-maleic acid copolymer, gelatin and the like. To the protective layer in the recording material of the present invention, in addition to the same water-soluble polymer compound as in the intermediate layer, various pigments, release agents and the like can be added.

Since the recording material of the present invention contains the benzotriazole compound of the present invention, it is extremely excellent in light resistance.

[0098]

EXAMPLES The production examples of the benzotriazole compound of the present invention are shown below, but the present invention is not limited to these synthetic examples.

<Synthesis Example 1: Synthesis of Benzotriazole Compound Represented by Specific Example (3)> 19.3 g of 4-diethylaminosalicylaldehyde, 38.3 g of carbetoxymethylenetriphenylphosphorane, and 100 m of toluene.
1 and 3 were placed in a three-necked flask and stirred at 40 ° C. for 3 hours, and then the solvent was concentrated. 50m ethanol to this concentrate
1, 50 ml of water and 16.8 g of potassium hydroxide were added, and the mixture was stirred at 80 ° C. for 1 hour. After cooling the reaction to room temperature, the reaction was charged with 100 ml of water and 5 ml of ethyl acetate.
0 ml was added, and after liquid separation, the aqueous layer was separated and concentrated hydrochloric acid was added until the pH reached 6-7. Then, the precipitated crystals were filtered to obtain 19 g of 4-diethylamino-2-hydroxycinnamic acid.

18.9 g of the obtained 4-diethylamino-2-hydroxycinnamic acid and 18 g of acetic anhydride were placed in a three-necked flask. Into this three-necked flask, 14 g of pyridine was added dropwise under ice cooling. After stirring at room temperature for 5 hours,
100 ml of water was added. Then, the precipitated crystals were filtered to obtain 17.2 g of 4-diethylamino-2-acetyloxycinnamic acid. Obtained 4-diethylamino-2
-Acetyloxycinnamic acid 17g and acetonitrile 30
ml and dimethylformamide 0.5 ml into a three-necked flask, and at room temperature, 8 g of thionyl chloride was added dropwise to 85 ° C.
After stirring for 1 hour at room temperature, it was cooled to room temperature. This reaction liquid was designated as "reaction liquid A".

4-t-butyl-6-sec-butyl-2
-(2H-benzotriazol-2-yl) phenol 17.8 g, triethylamine 12.5 g and acetone 5
0 ml was placed in another 3-neck flask, the reaction solution A was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour, then water 200 m
1 was added. Then, the precipitated crystals were filtered to obtain 21.7 g of a compound represented by the following formula (VII).

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21.5 g of the compound represented by the formula (VII), 100 ml of tetrahydrofuran and 20 ml of water were placed in a three-necked flask, and 10.3 g of 48% sodium hydroxide aqueous solution was added dropwise under ice-cooling at room temperature. Stir for 5 hours. 200 g of ice water was added to this reaction solution, and the precipitated crystals were filtered,
After washing with water and then with NaOH, the benzotriazole compound represented by the specific example (3) (melting point 204 to 205
C.) 15.8 g was obtained. The structure of the benzotriazole compound was confirmed by ¹ H-NMR.

The peak data obtained by ¹ H-NMR is shown below. The chemical shift δ value of the following peak indicates the δ value from TMS which is a reference substance, and the number of protons in the peak and the peak shape of singlet, doublet and the like are shown in parentheses. ¹ H-NMR (DMSO) δ (TMS, ppm) 0.80 (3H, t), 1.10 (6H, t), 1.24 (3H, d), 1.39 (9H, s), 1 .64 to 1.66 (2H, m), 2.83 to 2.90 (1H, m), 3.3 (4H, q), 6.13 (1H, d), 6.19 (1H, dd) ), 6.35 (1H, d), 7.39 (1H, d), 7.44 to 7.48 (2H, m), 7.57 (1H, d), 7.75 (1H, d) , 7.78 (1H, d), 7.93 to 7.97 (2H, m)

<Synthesis Example 2: Synthesis of Benzotriazole Compound Represented by Specific Example (6)> In Synthesis Example 1, 4-
A benzotriazole compound represented by Specific Example (6) (melting point) in the same manner as in Synthesis Example 1 except that diethylamino-2-acetyloxycinnamic acid was replaced with 4-diethylamino-2-acetyloxy-α-methylcinnamic acid. 145-148
° C).

<Synthesis Example 3: Synthesis of Benzotriazole Compound Represented by Specific Example (8)> In Synthesis Example 1, 4-
A benzotriazole compound represented by Specific Example (8) in the same manner as in Synthesis Example 1 except that diethylamino-2-acetyloxycinnamic acid was replaced with 4-acetylamino-2-acetyloxy-α-methylcinnamic acid ( Melting point 220-223
° C).

All "parts" in the following examples indicate parts by weight. The reflection density is measured by Macbeth's reflection densitometer R
It was measured using D918. The light resistance is evaluated by the Weather Ometer (WEATHEROMETER CI 65: product name, ATLAS EL
48 at 0.9 W / m ² by ECTRIC DEVICES CO)
This was done with samples that had been irradiated for hours. The evaluation was performed by the reflection density (yellow component) in the non-printed part. The lower the reflection density, the better the light resistance.

In the image area, the residual rate (%) of the image area = [(reflection density after irradiation of fluorescent lamp)
/ (Reflection density before irradiation of fluorescent lamp)] × 100, the residual rate of the dye in the image area was determined and evaluated. The higher the residual ratio of the dye, the better the light resistance.

[Example-1] [Preparation of benzotriazole compound-containing protective layer coating liquid of general formula (I)] 5.3 parts of the benzotriazole compound represented by Specific Example (6) was replaced with ethyl acetate 6.6. Part and the following formula A-
It was mixed with the phthalate ester solvent shown in 1 and sufficiently dissolved. As a capsule wall agent, 2.0 parts of xylylene diisocyanate / trimethylolpropane (75% ethyl acetate solution: Takenate D110N: trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) was added to this solution and stirred to be uniform. Separately, prepare 60 parts of a 10% by weight carboxy-modified polyvinyl alcohol (PVA217E: trade name, manufactured by Kuraray Co., Ltd.) aqueous solution containing 10% by weight of sodium dodecylsulfonate aqueous solution of 3.2 parts, and add the above solution, It was emulsified and dispersed with a homogenizer. The resulting emulsion was heated to 50 ° C. with stirring and the encapsulation reaction was carried out for 3 hours to obtain a target capsule liquid. The average particle size of the capsule was 0.2 μm. To 13 parts of this capsule liquid, 50 parts of ion-exchanged water was added and uniformly stirred to prepare a target coating liquid.

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[Preparation of Thermosensitive Recording Layer Liquid] (Preparation of Diazonium Salt Compound Capsule Liquid) 2.8 parts of a compound represented by the following formula a-1 as a diazonium salt compound:
Dibutyl sulfate 2.8 parts, 2,2-dimethoxy-1,2-
0.56 parts of diphenylethan-1-one (Irgacure 651: trade name, manufactured by Ciba Geigy) was dissolved in 19.0 parts of ethyl acetate. Furthermore, 5.9 parts of isopropyl biphenyl, which is a high boiling point solvent, and 2.5 parts of tricresyl phosphate were added to the above liquid, and heated to uniformly mix.
As a capsule wall agent, xylylene diisocyanate / trimethylolpropane adduct (75% ethyl acetate solution)
7.6 parts of Takenate D110N (manufactured by Takeda Pharmaceutical Co., Ltd.) was further added to this solution and stirred uniformly. Separately, 64 parts of a 6% by weight gelatin (MGP-9066: trade name, manufactured by Nippi Gelatin Industry Co., Ltd.) aqueous solution containing 2.0 parts of 10% by weight sodium dodecylsulfonate aqueous solution was prepared, and the diazonium salt compound solution was added. Then, it was emulsified and dispersed by a homogenizer. After 20 parts of water was added to the obtained emulsion to homogenize it, the temperature was raised to 40 ° C. with stirring, and an encapsulation reaction was performed for 3 hours. After that, the liquid temperature was lowered to 35 ° C., and ion exchange resin Amberlite IRA68 (manufactured by Organo)
6.5 parts, Amberlite IRC50 (manufactured by Organo)
Add 13 parts and stir for an additional hour. Thereafter, the ion exchange resin was filtered to obtain a desired capsule liquid. The average particle size of the capsule was 0.64 μm.

[0112]

[Chemical formula 26]

(Preparation of Coupler Emulsion Dispersion) As a coupler, 3.0 parts of compound b-1 shown below, 4.0 parts of triphenylguanidine and 1,1- (p-hydroxyphenyl) -2-ethylhexane were used. 4.0 parts, 4,4 '-(p
-Phenylene diisopropylidene) diphenol
0 part, 2-ethylhexyl-4-hydroxybenzoate 8.0 parts, b-2 as an antioxidant 2.0 parts,
1,1,3-tris (2-methyl-4-hydroxy-5)
2.0 parts of -t-butylphenyl) butane was dissolved in 10.5 parts of ethyl acetate, and 0.48 parts of tricresyl phosphate as a high-boiling solvent and 0.24 parts of diethyl maleate.
Part, and 1.27 parts of PIONIN A41C (manufactured by Takemoto Yushi Co., Ltd.) were added, and then heated and mixed uniformly. Separately, it was added to 93 parts of an aqueous solution of 8% by weight gelatin (# 750 gelatin: manufactured by Nitta Gelatin Co., Ltd.) and emulsified and dispersed by a homogenizer. The remaining ethyl acetate was evaporated from this emulsion to obtain the target emulsion dispersion.

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(Preparation of coating liquid) The diazonium salt compound capsule liquid, the coupler emulsion dispersion, and the styrene-butadiene rubber (SBR: SN307: trade name, manufactured by Sumitomo Nogatak Co., Ltd.) were each used in the ratio of diazonium salt compound / coupler. Is 1/2, and the ratio of diazonium salt compound / styrene-butadiene rubber is 1/6.
4 was mixed to prepare the target coating liquid.

[Preparation of Protective Layer] 20.5 wt% zinc stearate dispersion liquid (Hydrin F115: trade name) in 61 parts of 5.0 wt% carboxy-modified polyvinyl alcohol (KL-318: manufactured by Kuraray Co., Ltd.) aqueous solution. , Manufactured by Chukyo Yushi Co., Ltd.), 8.4 parts of a 2% by weight aqueous solution of a compound represented by the following formula c-1 and ME which is a fluorine-based releasing agent.
-313 (manufactured by Daikin) and 8.0 parts of wheat starch KF-4 (manufactured by Kagoshima Starch) were added and stirred uniformly. This is called mother liquor. Separately, ion-exchanged 20% by weight aqueous solution of chaogros (Shiraishi Industry Co., Ltd.) 1
2.5 parts, Poise 532A (manufactured by Kao) 0.06 part, Hydrin Z-7 (manufactured by Chukyo Yushi Co., Ltd.) 1.87 parts, 10% by weight polyvinyl alcohol (PVA105: manufactured by Kuraray Co., Ltd.)
1.25 parts and 0.39 part of a 2 wt% sodium dodecyl sulfonate aqueous solution were mixed and finely dispersed with a dyno mill. This liquid is called a pigment liquid. Mother liquor 80
4.4 parts of the pigment liquid is added to the above parts and stirred for 30 minutes or more. After that, Wetmaster 500 (manufactured by Toho Chemical Co., Ltd.) 2.
8 parts was added, and the mixture was stirred for 30 minutes or more to obtain the target coating liquid.

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[Preparation of Thermosensitive Recording Material] A thermosensitive recording layer, a protective layer containing a benzotriazole compound of the general formula (I), and a protective layer were sequentially formed with a Meyer bar on a photographic paper support obtained by laminating polyethylene on high-quality paper. Application and drying were carried out to obtain the desired heat-sensitive recording material. The coating amount as solid content is 1
^They were respectively 8.33 g, 2.50 g and 1.23 g per m ² .

(Thermal recording) Kyocera thermal head KST
Using a mold, (1) the recording energy per unit area is 6
The power applied to the thermal head and the pulse width were determined so as to be ² mJ / mm ^2, and when the thermal recording material was printed, it developed a magenta color.

Example-2 A benzotriazole compound represented by the specific example (9) was used in place of the benzotriazole compound represented by the specific example (6), and carboxy-modified polyvinyl alcohol (KL-318: Kuraray) was used. For the protective layer containing the benzotriazole compound of the general formula (I) in the same manner as in Example 1 except that 0.3 part of the surfactant Skraph AG-8 (manufactured by Nippon Seika Co., Ltd.) was added to the aqueous solution. To obtain a coating solution. The average particle size of the capsule is 0.25
μm. Preparation of the heat-sensitive recording layer, the benzotriazole compound-containing protective layer and the protective layer of the general formula (I) is the same as in Example 1 except that the coating liquid components of the benzotriazole compound-containing protective layer of the general formula (I) are different. Is.

Example 3 A thermal recording material was prepared and evaluated in the same manner as in Example 1 except that the protective layer containing the benzotriazole compound of the general formula (I) was replaced with the following. .

[Preparation of Emulsion Dispersion for Protective Layer Containing Benzotriazole Compound of General Formula (I)] 5.3 parts of the benzotriazole compound represented by Specific Example (9) was added to 6.6 parts of ethyl acetate and A-1. Phthalate ester solvent shown in 2.
Mixed with 9 parts. Xylylene diisocyanate / trimethylolpropane adduct as capsule wall material (75% ethyl acetate solution Takenate D110N: Takeda Yakuhin)
2.0 parts was further added to this solution and stirred so as to be uniform. A 10% by weight polyvinyl alcohol (PVA217E: Kuraray Co., Ltd.) aqueous solution 60 to which 3.2 parts of a 10% by weight sodium dodecyl sulfonate aqueous solution was added separately
A part was prepared, the above solution was added, and the mixture was emulsified and dispersed by a homogenizer. The obtained emulsion was heated to 50 ° C. with stirring and the encapsulation reaction was carried out for 3 hours to obtain a target capsule liquid. The average particle size of the capsule was 0.2 μm. To 13 parts of this capsule solution, 50 parts of ion-exchanged water was added and uniformly stirred to prepare a target coating solution. The thermosensitive recording material layer and the protective layer were prepared and evaluated in the same manner as in Example 1.

Example-4 In Example 1, the diazo heat-sensitive recording layer was replaced with the following leuco-type heat-sensitive recording layer, and the specific example (17) was used instead of the benzotriazole compound represented by the specific example (6). A thermal recording material was prepared and evaluated in the same manner as in Example 1 except that the benzotriazole compound represented by

[Preparation of Liquid B for Thermosensitive Recording Layer] (Preparation of Electron Donor Dye Precursor Capsule Liquid) 3- (o-methyl-p-diethylaminophenyl) -3- (1- 0.39 parts of ethyl-2-methylindol-3-yl) -4-azaphthalide, 2-
Hydroxy-4-methoxybenzophenone 0.19 parts,
2,5-tert-octylhydroquinone 0.29
Parts, 0.27 parts of the compound of b-2 were dissolved in 0.93 parts of ethyl acetate, 0.54 parts of phenethylcumene as a high boiling point solvent was further added, and the mixture was heated and uniformly mixed. As a capsule wall agent, 1.0 part of a xylylene diisocyanate / trimethylolpropane adduct (75% by weight ethyl acetate solution: Takenate D110N: manufactured by Takeda Pharmaceutical Co., Ltd.) was further added to this solution and stirred uniformly.

Separately, 6% by weight of gelatin (MG was added with 0.07 part of 10% sodium dodecylsulfonate aqueous solution).
P-9066: manufactured by Nippi Gelatin Industry Co., Ltd.) aqueous solution 36.
4 parts were prepared, the above-mentioned electron-donating dye precursor solution was added, and the mixture was emulsified and dispersed by a homogenizer. The emulsion dispersion thus obtained will be referred to as a primary emulsion dispersion. Separately 3- (o-methyl-p-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-
Yl) -4-azaphthalide (6.0 parts), 2-hydroxy-4-methoxybenzophenone (3.0 parts), 2,5-te
4.4 parts of rt-octylhydroquinone was dissolved in 14.4 parts of ethyl acetate, 8.4 parts of phenethylcumene as a high-boiling solvent was further added, and the solution was stirred uniformly to prepare a solution of Takenate D110N used previously. 0.8 parts and 5.9 parts of methylene diisocyanate (Millionate MR200: trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) were added and uniformly stirred. The solution thus obtained and 1.2 parts of a 10% sodium dodecyl sulfonate aqueous solution were added to the above-described primary emulsified dispersion, and the mixture was emulsified and dispersed by a homogenizer. The liquid thus obtained will be referred to as a "secondary emulsion dispersion liquid". 60.0 parts of water and 0.4 parts of diethylenetriamine were added to this secondary emulsion dispersion and homogenized, and then the temperature was raised to 65 ° C. with stirring and the encapsulation reaction was carried out for 3.5 hours to obtain the target capsule solution. Obtained. The average particle size of the capsule was 1.9 μm.

(Preparation of Electron-Accepting Compound Dispersion) 30 parts of bisphenol P as an electron-accepting compound was gelatin (MGP-9066: manufactured by Nippi Gelatin Industry Co., Ltd.) 2.0.
It was added to 82.5 parts by weight of an aqueous solution, 7.5 parts of a 2% by weight aqueous solution of 2-ethylhexyl sodium sulfosuccinate was added, and the mixture was dispersed by a ball mill for 24 hours to prepare a dispersion liquid. To this dispersion was added 36.0 parts of a 15% by weight gelatin (# 750 gelatin: manufactured by Nitta Gelatin Co., Ltd.) aqueous solution, and the mixture was stirred uniformly to obtain a target dispersion. The average particle size of the electron-accepting compound in the dispersion was 0.5 μm.

(Preparation of coating liquid) Next, the above-mentioned electron-donating dye precursor capsule liquid, electron-accepting compound dispersion liquid, 15% by weight gelatin (# 750 gelatin: Nitta Gelatin Co., Ltd.) aqueous solution, stilbene-based fluorescence enhancement Whitening agent (Whitex-BB:
Sumitomo Chemical Co., Ltd.), the ratio of electron donating dye precursor / electron accepting compound is 1/14, electron donating dye precursor / # 750 gelatin = 1.1 / 1, electron donating dye precursor / The mixture was mixed so that the optical brightening agent was 5.3 / 1 to prepare a desired coating liquid.

[Coating] On a photographic paper support obtained by laminating polyethylene on a high-quality paper, the above-mentioned heat-sensitive recording layer, a benzotriazole compound-containing protective layer of the general formula (I) and a protective layer are sequentially coated and dried with a Meyer bar. The desired thermosensitive recording material was obtained. The coating amount as a solid content was 7.2 g, 2.50 g and 1.23 g per 1 m ^2, respectively.

[Thermal recording] Kyocera thermal head KST
Recording energy per unit area is 86mJ using a mold
The electric power applied to the thermal head and the pulse width were determined so as to be / mm ^2, and the thermal recording material was printed. The obtained recorded image was an image colored in blue.

[Comparative Example] General formula (I) in Example 1
A coating liquid was prepared in the same manner as in Example 1 except that the benzotriazole compound-containing protective layer was not provided, and a thermal recording material was prepared and evaluated.

The evaluation results of Examples 1 to 4 and Comparative Example are shown in Table 5 below.

[0132]

[Table 5]

As can be seen from Table 5, in each of Examples 1 to 4, the density of the non-printed portion was low and the light resistance of the non-imaged portion was excellent. Further, it can be seen that the residual ratio of the dye in the image area is high and the light resistance of the image area is excellent.

The benzotriazole compound represented by the general formula (I) is allowed to coexist with an active ester such as an acid anhydride or is separated, for example, inside and outside the capsule and heated to give a general compound. It can also be inactivated against light by reacting —OH in the formula (I) with an active ester. Where heat is not applied, it is active with respect to light and can form a fluorescent whitening agent, so that it can be applied to a recording material using the presence or absence of fluorescence.

[0135]

INDUSTRIAL APPLICABILITY As described above, the benzotriazole compound of the present invention is useful as a polymer material, a photographic material, an additive for a recording material, and the like, and particularly a protective layer in a recording material such as a heat-sensitive recording material and a photosensitive material. It is suitable for use as a protective layer or the like, and can impart light resistance to a recording material when used for the protective layer or the like. Further, the recording material of the present invention contains the benzotriazole compound of the present invention, whereby the light resistance of the recording material can be improved and, particularly, the coloring of the non-image area can be effectively prevented.

Claims (4)

[Claims] 1. A compound represented by the general formula (I):
Benzotriazole compound. [Chemical 1]In the formula, m represents 1 or 2. X is the general formula (I)-
In (1), (I)-(3) and (I)-(4)
Is a hydrogen atom, alkyl group, alkenyl group, alkoxy
A group, an aryl group or a halogen atom represented by the general formula (I)-
In (2), an alkylene group, -OR^4aO-or-
OCOR^4aCO_TwoRepresents-. W is the general formula (I)-
In (1), (I)-(2) and (I)-(4)
Is a hydrogen atom, alkyl group, alkenyl group, alkoxy
A group, an aryl group or a halogen atom represented by the general formula (I)-
In (3), -OR^4aO- or -OCOR^4aCO
_TwoRepresents-. Y is represented by the general formula (I)-(1), (I)-
In (2) and (I)-(3), a hydrogen atom,
Kill group, alkenyl group, alkoxy group, aryl group or
In the general formulas (I)-(4), a halogen atom is
OR^4aO-, -OCOR^4aCO _Two-, -CH_TwoCH_TwoCO_Two
R^4aOCOCH_TwoCH_Two-, -CH_TwoCH_TwoOCOR^4aCO
_TwoCH_TwoCH_Two-Or -CH_TwoCH_TwoCON (R^5a) R^4aN
(R^5a) COCH_TwoCH_TwoRepresents-. R^4aIs an alkylene
Represents a group or an arylene group. R^5aIs a hydrogen atom or
Represents a kill group. Z is a hydrogen atom, a halogen atom, an alkyl
Represents an alkyl group or an alkoxy group. A is the general formula (I)-
When m = 1 in (1) and the general formula (I)-(2)-
In (4), the substituent shown in Chemical formula 2 is represented. Embedded imageWhere R¹And R^TwoIs a hydrogen atom, alkyl group, alkene
Group, -CO_TwoR⁶, -CONR⁷R⁸, -CN or Ally
Represents a hydroxyl group. R⁶, R⁷And R⁸Is a hydrogen atom, alkyl
Represents a group, an alkenyl group or an aryl group. R^ThreeIs hydrogen
Atom, alkyl group, aryl group, alkenyl group, -CO
R⁹Or -SO_TwoR^TenRepresents R⁹And R^TenIs an alkyl
Represents a group or an aryl group. R^FourIs a hydrogen atom, alkyl
Represents a group, an aryl group or an alkenyl group. R^ThreeAnd R
^FourIs 4 to 7-membered which may be linked to each other to contain a hetero atom.
May be an alkylene group. R^FiveIs a hydrogen atom, alkyl
Group, alkenyl group, alkoxy group, aryl group or halo
Represents a gen atom. In the general formula (I)-(1),
When m = 2, A is the same as the two substituents shown in Chemical formula 3
It represents a divalent substituent in which amino groups are linked to each other. Embedded imageWhere R¹, R^Two, R^ThreeAnd R^FiveIs the same as in
It is. R is an alkylene group, an arylene group, -COR
^4aCO- or -SO_TwoR^4aSO_TwoRepresents-. R^4aIs
Is the same as in. 2. A recording material having a recording layer and a protective layer provided on a support, the recording material comprising the benzotriazole compound according to claim 1. 3. The recording material according to claim 2, wherein the benzotriazole compound according to claim 1 is encapsulated in microcapsules. 4. A thermosensitive recording layer wherein the recording layer contains a diazonium salt compound and a coupler that reacts with the diazonium salt compound to develop a color, and / or a thermosensitive recording layer containing an electron-donating colorless dye and an electron-accepting compound. The recording material according to claim 2, which is a layer.