JPH0995487A - Benzotriazole compound and heat-sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a protecting layer, etc., in a heat-sensitive recording material due to excellent fixity and light resistance, especially reduction in light transmissivity after fixation in a wave length region to cause light fixation. SOLUTION: This compound is shown by formula I or in formula II [(m) is 1 or 2; A is a group of formula III (R<1> and R<2> are each H, an alkyl, etc.; ring B is phenyl or naphthyl), etc., when m=1 formula I, and in formula II, etc., or a group of formula IV, etc., when m=2; X is H, an aryl, etc.; W is H, a halogen etc.; Y is H, an alkenyl, etc., in the formula I, OR<4> O (R<4> is an alkylene, an arylene, etc.), etc., in the formula II; Z is a halogen, an alkyl, etc.], etc. The compound, for example, is obtained by reacting a benzotriazole compound such as 4-t-butyl-6-sec-butyl-2-(2H-benzotriazol-2-yl)phenol, etc., with a cinnamic acid derivative obtained by reacting 2-acetyloxy-α-methylcinnamic acid with thionyl chloride, in the presence of a base.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a benzotriazole compound and a heat-sensitive recording material, and more specifically, a benzotriazole compound useful as a polymer material, a photographic material, an additive for a heat-sensitive recording material and the like, and excellent in light resistance. In particular, it relates to a heat-sensitive recording material having both light resistance and fixing property.

[0002]

2. Description of the Related Art Thermal recording has recently been developed because its recording apparatus is simple, highly reliable, and requires no maintenance. As the heat-sensitive recording material, those utilizing a reaction between an electron-donating colorless dye and an electron-accepting compound and those utilizing a reaction between a diazonium salt compound and a coupler have been widely known. As a heat-sensitive recording material, in recent years, studies have been earnestly conducted to improve properties such as (1) color density and color sensitivity (2) fastness of color material. However, heat-sensitive recording materials have the drawbacks that when exposed to sunlight for a long time or when they are posted in the office for a long time, the background part is colored by the light or the image part is discolored or faded. Was there. 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.

[0003]

An object of the present invention is to provide a benzotriazole compound which is useful as an additive for polymer materials, photographic materials, heat-sensitive recording materials, etc., and is excellent in light resistance, and particularly excellent in light resistance and fixability. It is an object of the present invention to provide a heat-sensitive recording material that is compatible with both.

[0004]

The above-mentioned object is achieved by using a benzotriazole compound represented by the general formula (I) and a thermosensitive recording material having a thermosensitive recording layer and a protective layer provided on a support. Achieved by a heat-sensitive recording material containing a benzotriazole compound represented by I).

[0005]

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In the formula, m represents 1 or 2. A is the case where m = 1 in the general formula (I)-(1) and the general formula (I)-
In (2) to (4), the following formula (1-1) is represented.

[0007]

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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 , —
It represents CN or an aryl group. Ring B represents a phenyl group or a naphthyl group. R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. When m = 2 in the general formulas (I)-(1), A represents the following formula (1-2).

[0009]

[Chemical 6]

In the formula, R ¹ , R ² and ring B are each represented by the above formula (1-
It is the same as in 1). R ³ is, -OR ^3A O-or -OCOR ^3A CO ₂ - represents a. Here, R ^3A represents an alkylene group or an arylene group.

X is represented by the general formula (I)-(1), (I)-
In (3) and (I)-(4), a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom is used, and in the general formulas (I)-(2), an alkylene group, -OR. Represents ⁴ O- or -OCOR ⁴ CO _2- . In the general formulas (I)-(1), (I)-(2) and (I)-(4), W is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom, In formulas (I)-(3), —OR ⁴ O—
Or -OCOR ⁴ CO ₂ - represents a.

Y is represented by the general formula (I)-(1), (I)-
In (2) and (I)-(3), a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom is used, and in the general formulas (I)-(4),
^{OR 4 O -, - OCOR 4} CO 2 -, - CH 2 CH 2 CO 2 R
_{^{4 OCOCH 2 CH 2 -, -}} CH 2 CH 2 OCOR 4 CO 2 C
H ₂ CH ₂ - or ^{_{-CH 2 CH 2 CON (R 5}} ) R 4 N
_{^{(R 5) COCH 2 CH 2}} - represents a. R ⁴ represents an alkylene group or an arylene group. R ⁵ represents a hydrogen atom or an alkyl group. Z represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. Among the substituents 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.

As R ¹ and R ² , 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 2 to 18 carbon atoms. −
CONR ⁷ R ^8, -CN, aryl group having 6 to 18 carbon atoms is preferable, in particular, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms Is preferred. Further, the phenyl group and naphthyl group in ring B are an alkyl group, an alkoxy group,
It may be substituted with a halogen atom. For ring B,
An alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group which may be substituted with a halogen atom and a naphthyl group are preferable, and an alkyl group having 1 to 12 carbon atoms and 1 to 12 carbon atoms are particularly preferable. May be substituted with an alkoxy group, a chlorine atom or a fluorine atom, and a phenyl group and a naphthyl group are preferable.

The substituents represented by R ¹ and R ² include
Specifically, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, hexyl 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-octylcarbamoyl group, N, N- Examples thereof include dibutylcarbamoyl group and cyano group. Specific examples of ring B include those represented by the following formula,
It is not limited to these.

[0016]

[Chemical 7]

Among the substituents represented by X, Y and W, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and a carbon atom having 3 carbon atoms
~ 12 alkenyl groups, C1-18 alkoxy groups, C6-18 aryl groups, fluorine atoms, chlorine atoms, bromine atoms are preferred, and among these,
Particularly, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group or a chlorine atom is preferable. Among the substituents represented by Z, a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms.
A 12-alkoxy group is 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.

Of the substituents represented by R ^3A , an alkylene group having 1 to 12 carbon atoms and an arylene group having 6 to 18 carbon atoms are preferable. Specific examples of the substituent represented by R ^3A _{is, -OCH 2 CH 2 O -,} - O (CH 2) 8 O -, - O
_{CO (CH 2) 4 CO 2} -, - OCH (CH 3) CH 2 O-
And the like.

A so-called bis compound having two benzotriazole rings in one molecule [m = 2 in the general formulas (I)-(1) and general formulas (I)-(2) to (I)-(4)] In the case], the substituent represented by R ⁴ has 1 to 1 carbon atoms.
A alkylene group having 12 carbon atoms or an arylene group having 6 to 12 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferable as the substituent represented by R ⁵ .

Specific examples of the above substituents are shown below, but the present invention is not limited thereto. Among the substituents represented by X, Y and W, monovalent ones include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, t-
Butyl, pentyl, hexyl, octyl, decyl, dodecyl, allyl, 2-butenyl, benzyl, α-dimethylbenzyl, methoxy, ethoxy, propyloxy, butyloxy, octyloxy Group, dodecyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxycarbonylethyl group, ethoxycarbonylethyl group, propyloxycarbonylethyl group, butyloxycarbonylethyl group, octyloxycarbonylethyl group, phenoxycarbonylethyl group, phenyl group, Examples thereof include a tolyl group, chlorine atom, fluorine atom and bromine atom, and examples of the divalent group include the following.

[0021]

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Specific examples of the substituent represented by Z include hydrogen atom, chlorine atom, methyl group, ethyl group, propyl group,
Hexyl group, methoxy group, ethoxy group, propyloxy group, octyloxy group and the like can be mentioned.

Specific examples of the benzotriazole compound represented by the general formula (I) are shown below, but the present invention is not limited thereto. These benzotriazole compounds may be used alone or in combination of two or more.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

[0028]

[Table 5]

[0029]

[Table 6]

[0030]

[Table 7]

[0031]

[Table 8]

[0032]

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[0033]

[Table 9]

Benzotriazole compound (I) of the present invention
-(1) [m = 1] is, for example, a base, an acid or a condensation product of a benzotriazole compound represented by the following general formula (II) and a cinnamic acid derivative represented by the following general formula (III). It is easily obtained by reacting in the presence of an agent.

[0035]

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

[0037]

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In the general formula (III), rings B, R ¹ and R
² has the same meaning as above. R ⁹ is a hydrogen atom, -C
OR ^10, represents a -SO ₂ R ^10. R ¹⁰ represents an alkyl group or an aryl group. X is a halogen atom, -OH, -OC
OR ^10, represents a -OSO ₂ R ^10.

When R ⁹ is other than H, the general formula (I
A benzotriazole compound represented by I) and the general formula (III)
After the reaction with the cinnamic acid derivative represented by the formula (5), hydrolysis (deprotection) gives R ⁹ = 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, for example, 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.

[0042]

[Chemical 12]

[0043]

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[0044]

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In the general formulas (IV), (V) and (VI),
R ¹ , R ² and R ⁹ have the same meanings as described above. R
¹¹ represents a hydrogen atom, an alkyl group or an aryl group. It is to be noted that the reaction was carried out at R ⁹ = H, then XCOR ¹⁰ , XS
It may be obtained by reacting with O ₂ R ¹⁰ , (R ¹⁰ CO) ₂ O or the like.
Here, X and R ¹⁰ 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 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.

Benzotriazole compound (I) of the present invention
With respect to-(2) to (4), the above (I)-(1) is also used.
It can be easily obtained by the same method as.

The benzotriazole compound represented by the general formula (I) can be used as a polymer material, a photographic material, an additive for a heat-sensitive recording material, and the like, and particularly as an additive for a heat-sensitive recording material. It is suitable. When the benzotriazole compound represented by the general formula (I) is used as an additive for a heat-sensitive recording material, when fixing the heat-sensitive recording material, the fixing light is not absorbed, that is, the fixing light is not hindered,
By shining light after image formation, it is possible to further absorb long-wave ultraviolet rays and improve the light stability of the image.
It is advantageous in that it is possible to provide a heat-sensitive recording material having excellent light resistance and having both light resistance and fixing property.

The heat-sensitive recording material of the present invention has a heat-sensitive recording layer and a protective layer, and may further have other layers such as an undercoat layer and an intermediate layer, if necessary. The heat-sensitive recording material of the present invention contains the benzotriazole compound represented by the general formula (I) of the present invention. Examples of the method of incorporating the benzotriazole compound represented by the general formula (I) into the heat-sensitive recording material include, for example, (1) a solid dispersion method of the benzotriazole compound represented by the general formula (I),
Examples include (2) a method of emulsifying and dispersing, (3) a method of dispersing a polymer, (4) a method of dispersing a latex, and (5) a method of microencapsulating. Among these, the method of microencapsulating is particularly preferable. .

The heat-sensitive recording material of the present invention contains the benzotriazole compound represented by the general formula (I) in any of the heat-sensitive recording layer, the protective layer, and other layers such as an intermediate layer and an undercoat layer. Although it may be contained, it is particularly preferably contained in the protective layer. The content of the benzotriazole compound represented by the general formula (I) in the heat-sensitive recording material of the present invention is preferably 0.05 to 3.0 g / m ² , and 0.1
˜2.0 g / m ² is more preferred. When the content is 0.
When the amount is less than 05 g / m ² , the function of adjusting the light transmission, especially after the light irradiation of the wavelength in the region necessary for fixing is finished,
It becomes difficult to reduce the light transmittance in the ultraviolet region, and the light resistance is likely to deteriorate. If it exceeds 3.0 g / m ² , the light transmission adjusting function, especially the light before irradiation in the wavelength of the region necessary for fixing The transmittance tends to be low, and the fixability is likely to be impaired.

Next, the method for incorporating the benzotriazole compound represented by the general formula (I) into the heat-sensitive recording material will be described in detail. As a method of emulsifying and dispersing, first, a benzotriazole compound represented by the general formula (I) is dissolved in oil. This oil may be solid or liquid at room temperature, or 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 and the like can be mentioned. . Specific examples include tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilaurate phthalate, dicyclohexyl phthalate, butyl oleate, 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'-ditolylethane, 2,4-di-t-amylphenol, N, N-dibutyl-2-butoxy-5-t-
High boiling oils such as octylaniline, 2-ethylhexyl hydroxybenzoate, and polyethylene glycol can be mentioned. Among these, alcohol-based, phosphoric ester-based, carboxylic acid ester-based, alkylated biphenyl, alkylated terphenyl, Alkylated naphthalene and diarylethane are preferred. further,
An anti-carbonizing agent such as hindered phenol or hindered amine may be added to the high boiling point oil. Further, as the oil, one having an unsaturated fatty acid is particularly desirable, and specific examples thereof include α-methylstyrene dimer. As α-methylstyrene dimer,
For example, there is MSD100 (trade name, manufactured by Mitsui Toatsu Chemical) or the like.

An oil solution containing a benzotriazole compound represented by the general formula (I) is added to an aqueous solution of a water-soluble polymer and emulsified and 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 also be used together.

As the water-soluble polymer, 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 maleic anhydride copolymer, polyacrylamide, polystyrene sulfonic acid, polyvinylpyrrolidone,
Examples thereof include ethylene-acrylic acid copolymer and gelatin. Of these, carboxy-modified polyvinyl alcohol is particularly preferable. Examples of the emulsion or latex of the hydrophobic polymer include styrene-butadiene copolymer, carboxy-modified styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and the like.
At this time, a conventionally known surfactant or the like may be added, if necessary, for the purpose of improving the emulsion stability.

As a method of microencapsulating the benzotriazole compound represented by the general formula (I), 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 an organic solvent that is sparingly soluble or insoluble in water, added to an aqueous solution of a water-soluble polymer, and emulsified and dispersed using a homogenizer or the like. Then, the polymer substance which becomes a microcapsule wall by heating can be prepared by forming a wall film at the oil / water interface. Specific examples of the polymer 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, styrene-acrylate copolymer resin. , Styrene-methacrylate copolymer resin, gelatin, polyvinyl alcohol and the like, and mixtures thereof. Among these, particularly preferable are microcapsules having a wall film made of polyurethane-polyurea resin. Polyurethane
A microcapsule having a wall film made of a polyurea resin is prepared by mixing a microcapsule wall precursor such as polyvalent isocyanate in a core substance to be encapsulated, emulsifying and dispersing it in an aqueous solution of a water-soluble polymer such as polyvinyl alcohol, and liquid temperature. Is produced to cause a polymer forming reaction at the oil drop interface.

Here, some of the specific examples of the polyisocyanate 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 , An isocyanate prepolymer such as an adduct of xylylene diisocyanate and trimethylolpropane, an adduct of tolylene diisocyanate and hexanetriol, etc. In addition, two or more kinds may be used in combination, if necessary. Particularly preferred is one having three or more isocyanate groups in the molecule.In the method of microencapsulation, the organic solvent for dissolving the benzotriazole compound represented by the general formula (I) is an emulsified dispersion of The oil exemplified in the method can be used, and the same applies to the water-soluble polymer.

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 during 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-A-3-25434 and JP-A-1-252953
Japanese Patent Application Laid-Open No. 302753, Japanese Patent Application Laid-Open No. 1-127
29247, Japanese Patent Application Laid-Open No. 1-2227145, Japanese Patent Application Laid-Open No. 1-243048, Japanese Patent Application Laid-Open No. 2-262649.
It is described in Japanese Patent Publication No. Specifically, N-phenylacetohydrazide, N-phenylbutyrylhydrazide,
In addition to p-t-butylphenol and 2-azidobenzoxazole, the following compounds may be mentioned.

[0060]

[Chemical 15]

In the present invention, as the color-forming component used in the heat-sensitive recording layer, conventionally known ones can be used. In particular, those utilizing the reaction of a diazonium salt compound and a coupler, or an electron-donating colorless dye and an electron are used. Those utilizing the reaction with a receptive compound are preferable, and those utilizing the reaction between the diazonium salt compound and the coupler are particularly preferable.
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. Here, the diazonium salt compound is a compound represented by the following formula, and in these formulas, the maximum absorption wavelength can be controlled depending on the position and type of the substituent of the Ar moiety.

[0062]

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

Specific examples of the diazonium salt compound in the present invention 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-te
rt-amylphenoxy) butyryl) piperazino) benzenediazonium, 2,5-dibutoxy-4-tolylthiobenzenediazonium, 3- (2-octyloxyethoxy) -4-morpholinobenzenediazonium and other acid anion salts and the following: Diazonium salt compound D-1 to
5 and the like. Particularly, hexafluorophosphate salt, tetrafluoroborate salt and 1,5-naphthalene sulfonate salt are preferable.

[0065]

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Of these diazonium salt compounds, particularly preferred compounds in the present invention are 300 to 40
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,
Examples thereof include the compounds shown in Specific Examples D-3 to D-5. The maximum absorption wavelength of the diazonium salt compound here is a spectrophotometer (manufactured by Shimadzu Corporation, MPS-200 manufactured by Shimadzu Corporation) with a coating film of each compound being 0.1 g / m ² to 1.0 g / m ^2.
0).

Specific examples of the coupler which is used in the present invention and which reacts with the above-mentioned diazonium salt under heat to give a color include 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-octylacetoacetanilide, 1-phenyl-3-methyl-5-pyrazolone, 1- (2'-octylphenyl) -3-methyl-
5-pyrazolone, 1- (2 ', 4', 6'-trichlorophenyl) -3-benzamido-5-pyrazolone, 1-
(2 ′, 4 ′, 6′-Trichlorophenyl) -3-anilino-5-pyralone, 1-phenyl-3-phenylacetamido-5-pyrazolone and C-1 to 6 shown below.
And the like. Two or more of these couplers may be used in combination to obtain a desired color hue.

[0068]

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The basic substance includes, in addition to inorganic or organic basic compounds, 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 of these 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 type compounds, diphenylmethane type compounds, thiazine type compounds, xanthene type compounds, spiropyran type compounds, among others, triarylmethane type compounds, Xanthene compounds are useful because of their high color density.

Some examples of these are 3,3-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-methylindole-
3-yl) phthalide, 3- (o-methyl-p-diethylaminophenyl) -3- (2-methylindole-3-
Yl) phthalide, 4,4′-bis (dimethylamino) benzhydrin benzyl ether, N-halophenyl leuco auramine, N-2,4,5-trichlorophenyl leuco auramine, rhodamine-B-anilinolactam,
Rhodamine (p-nitroanilino) lactam, Rhodamine-B- (p-chloroanilino) lactam, 2-benzylamino-6-diethylaminofluorane, 2-anilino-6-diethylaminofluorane, 2-anilino-3
-Methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-cyclohexylmethylaminofluorane, 2-anilino-3-methyl-6-isoamylethylaminofluorane, 2- (o-chloroanilino)-
6-diethylaminofluorane, 2-octylamino-
6-diethylaminofluorane, 2-ethoxyethylamino-3-chloro-2-diethylaminofluorane, 2
-Anilino-3-chloro-6-diethylaminofluorane, benzoylleuco methylene blue, p-nitrobenzyl leuco methylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran,
3,3′-dichloro-spiro-dinaphthopyran, 3-benzylspirodinaphthopyran, 3-propyl-spiro-
Dibenzopyran etc. are 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-point organic compound having an aromatic group and a polar group in the molecule, such as benzyl p-benzyloxybenzoate, α-naphthylbenzyl ether, β- 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 present invention, the above-mentioned diazonium salt compound, a coupler which reacts with the diazonium salt compound under heat to develop a color, a basic substance, an electron-donating colorless dye, an electron-accepting compound, and a sensitizer are used. Is not particularly limited. That is, as in the case of the compound of general formula (I),
(1) a method of dispersing and using a solid, (2) a method of dispersing and using an emulsion, (3) a method of dispersing and using a polymer,
There are (4) a method of dispersing and using latex, (5) a method of using by encapsulating microcapsules, and the like. Among them, the method of encapsulating by microcapsules is preferable from the viewpoint of preservability, and particularly diazonium salt compound. It is preferable to microencapsulate the diazonium salt compound in a color-forming system that utilizes the reaction between a dye and a coupler, and in a color-forming system that utilizes the reaction between an electron-donating colorless dye and an electron-accepting compound, an electron-donating colorless dye is used as a microcapsule. It is preferably encapsulated.

The constitution of the heat-sensitive recording material to which the present invention is applied is not particularly limited. For example, (1) a diazonium salt compound having a maximum absorption wavelength of 360 ± 20 nm is reacted with a diazonium salt compound on a support to be presented. A heat-sensitive recording material in which a heat-sensitive recording layer containing a color coupler and a heat-sensitive recording layer containing 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 are sequentially provided. , (2) Maximum absorption wavelength of 4 on the support
A thermosensitive recording layer containing a diazonium salt compound having a wavelength of 00 ± 20 nm and a coupler which reacts with the diazonium salt compound to develop a color, and a diazonium salt compound having a maximum absorption wavelength of 360 ± 20 nm and a color which reacts with the diazonium salt compound. A thermosensitive recording layer containing a coupler, and a thermosensitive recording material comprising (3) 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. Examples thereof include a heat-sensitive recording layer containing a layer, a diazonium salt compound having a maximum absorption wavelength of more than 420 nm, and a coupler which reacts with the diazonium salt compound to develop a color.

In the present invention, the above-mentioned thermosensitive recording layers may be laminated and applied, and a multicolor thermosensitive recording material can be obtained by changing the hue of each thermosensitive recording layer. The layer structure is not particularly limited, but in particular, a thermosensitive recording layer 2 in which two kinds of diazonium salt compounds having different photosensitizing wavelengths and a coupler which reacts with each diazonium salt compound upon heating to develop different hues are combined. A multicolor heat-sensitive recording material in which a layer and a heat-sensitive recording layer in which an electron-donating colorless dye and an electron-accepting compound are combined are laminated is preferable. That is,
First heat-sensitive recording layer containing an electron-donating colorless dye and an electron-accepting compound on a support, maximum absorption wavelength of 360 ± 20 nm
A second thermosensitive recording layer containing a diazonium salt compound which is a dye and a coupler which develops a color when reacted with the diazonium salt compound, a diazonium salt compound having a maximum absorption wavelength of 400 ± 20 nm and the diazonium salt compound when heated The third heat-sensitive recording layer contains a coupler that reacts to develop a color. 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 this layer are colored. Next 400 ± 20
nm light to decompose the unreacted diazonium salt compound contained in the third thermosensitive recording layer, and then the second
Sufficient heat is applied to the thermosensitive recording layer to develop a color, whereby the diazonium salt compound and the coupler contained in the layer are developed. 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. 360 ± 20
nm light is irradiated to decompose the diazonium salt compound contained in the second thermosensitive recording layer, and finally, sufficient heat for coloring the first thermosensitive recording layer is applied to develop the color. 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 heat-sensitive recording layer laminated directly on the support surface (the lowermost layer of the heat-sensitive recording layer) is not limited to the combination of the electron-donating dye and the electron-accepting dye.
For example, a diazo coloring system from a diazonium salt and a coupler that reacts with the diazonium salt to form a color, a base coloring system that develops a color by contact with a basic compound, a chelate coloring system, and a desorption reaction that reacts with a nucleophile to develop a color. Any of the above-described color-developing systems may be used. By providing two heat-sensitive recording layers each containing a diazonium salt compound having a different maximum absorption wavelength and a coupler which reacts with the diazonium salt compound to develop a color, two layers are provided on the heat-sensitive recording layer. A color thermosensitive recording material can be constructed. In the heat-sensitive recording material of the present invention, it is preferable from the viewpoint of effect that a protective layer containing the benzotriazole compound represented by the general formula (I) of the present invention is provided on these heat-sensitive recording layers.

In the present invention, in order to further improve the light resistance, the following known antioxidants can be used. For example, European Patent Publication No. 310551, German Patent Publication No. 3435443, European Publication. Japanese Patent No. 310552, JP-A-3-1214
49, European Published Patent No. 459416, JP-A-2-262654, JP-A-2-712.
62, JP-A-63-163351, US Pat. No. 4,814,262, JP-A-54-48535, JP-A-5-61166, and JP-A-5-119.
No. 449, U.S. Pat. No. 4,980,275, JP-A-63-113536, JP-A-62-26204.
7 publication, European Patent No. 223739 publication,
Examples thereof include those described in European Patent Publication No. 309402 and European Patent Publication No. 309401. Specific examples include the following.

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[0082]

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[0083]

[Chemical 21]

Furthermore, 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, 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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These antioxidants can be added to the heat-sensitive recording layer or the intermediate layer, the benzotriazole compound-containing protective layer represented by the general formula (I), and the protective layer. When these antioxidants and the like are used in combination, for example, specific examples (Q-7), (Q-45), (Q-46) or a combination of the compound (Q-10) and the compound (Q-13) is used. Can be mentioned.

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.

As the support in the present invention, plastic film, paper, plastic resin laminated paper, synthetic paper and the like can be used.

In the present invention, when heat-sensitive color-developing layers having different hues are laminated, an intermediate layer may be provided to prevent color mixture. 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.

In addition to the same water-soluble polymer compound as that of the intermediate layer, various pigments, release agents and the like can be added to the protective layer in the present invention.

[0095]

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 (9)> Salicylaldehyde 1
2.2 g, carbetoxyethylidene triphenylphosphorane 39 g, and toluene 100 ml were placed in a three-necked flask and stirred at room temperature for 1 hour, and then the solvent was concentrated.
To this concentrate, 50 ml of ethanol, 50 ml of water,
16.8 g of potassium hydroxide was added, and the mixture was stirred at 80 ° C. for 1 hour. After cooling the reaction product to room temperature, 100 ml of water and 50 ml of ethyl acetate were added to the reaction product, and after liquid separation, the aqueous layer was separated and concentrated hydrochloric acid was added until pH 1-2. Then, the precipitated crystals were filtered to obtain 16.1 g of 2-hydroxy-α-methylcinnamic acid.

16 g of the obtained 2-hydroxy-α-methylcinnamic acid and 18.4 g of acetic anhydride were placed in a three-necked flask. Into this three-necked flask, 14.2 g of pyridine was added dropwise under ice cooling. After stirring for 2 hours at room temperature, water 1
00 ml was added and concentrated hydrochloric acid was added until pH 1-2. Then, the precipitated crystals were filtered to obtain 16.8 g of 2-acetyloxy-α-methylcinnamic acid. 16.7 g of the obtained 2-acetyloxy-α-methylcinnamic acid
And 30 ml of acetonitrile and dimethylformamide 0.
5 ml and 3 ml were put into a three-necked flask, 9.9 g of thionyl chloride was added dropwise at room temperature, the mixture was stirred at 85 ° C. for 1 hour, and then cooled to room temperature. This reaction liquid was designated as "reaction liquid A".

4-t-butyl-6-sec-butyl-2
2 (3H-benzotriazol-2-yl) phenol 23.3 g, triethylamine 15.3 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 are filtered and recrystallized from methanol to give a compound 3 represented by the following formula (VII).
2.9 g were obtained.

[0099]

[Chemical formula 26]

32.8 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 10.4 g of 48% sodium hydroxide aqueous solution was added dropwise under ice-cooling at room temperature. Stir for 1 hour. After adding 200 g of ice water to this reaction solution, concentrated hydrochloric acid was added to pH 3-4.
Was added until. Then, the precipitated crystals are filtered,
Recrystallized from a mixed solvent of ethyl acetate-n-hexane,
26.6 g of the benzotriazole compound (melting point 113 to 115 ° C.) represented by the specific example (9) 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 (CDCl ₃ ) δ (TMS, ppm) 0.88 (3H, t), 1.30 (3H, d), 1.41 (9H, s), 1.62 to 1.72 (2H , M), 2.02 (3H, s), 2.92 to 3.00 (1H, m), 5.45 (1H, s), 6.84 to 6.88 (1H, dd), 6. 91 to 7.00 (1H, m), 7.20 to 7.24 (2H, m), 7.37 to 7.40 (2H, m), 7.46 (1H, dd), 7.86 to 7.91 (4H, m)

<Synthesis Example 2: Synthesis of Benzotriazole Compound Represented by Specific Example (1)> In Synthesis Example 1, 2-
Acetyloxy-α-methylcinnamic acid is used as 2-acetyloxycinnamic acid, and 4-t-butyl-6-sec-butyl-2- (2H-benzotriazol-2-yl) phenol is used as 2- (2H-benzo). Triazol-2-yl)-
A benzotriazole compound (melting point 217 to 218 ° C) represented by Specific Example (1) was obtained in the same manner as in Synthesis Example 1 except that 4-t-octylphenol was used.

<Synthesis Example 3: Synthesis of benzotriazole compound represented by Specific Example (13)> In Synthesis Example 1, 2
A benzotriazole compound represented by Specific Example (13) in the same manner as in Synthesis Example 1 except that 2-acetyloxy-3-methyl-α-methylcinnamic acid was used in place of -acetyloxy-α-methylcinnamic acid ( Mp 169-170 ° C).

<Synthesis Example 4: Synthesis of benzotriazole compound represented by specific example (45)> In Synthesis Example 1, 2
-Acetyloxy-α-methylcinnamic acid was replaced by 2-acetyloxy-3-methoxy-α-methylcinnamic acid in the same manner as in Synthesis Example 1 except that the benzotriazole compound represented by Specific Example (45) (melting point) was used. 149-150 ° C) was obtained.

<Synthesis Example 5: Synthesis of benzotriazole compound represented by Specific Example (31)> In Synthesis Example 1, 2
-Acetyloxy-α-methylcinnamic acid was replaced with 2-acetyloxy-α-benzylcinnamic acid in the same manner as in Synthesis Example 1 and the benzotriazole compound represented by the specific example (31) (melting point: 150 to 151). C) was obtained.

All "parts" in the following examples refer to parts by weight. The reflection density is measured by Macbeth's reflection densitometer R
It was measured using D918. The photo-fixing property of the diazo heat-sensitive recording layer is evaluated by the fixing operation by light irradiation for a predetermined time.
Heat of 86 mJ / mm ² was applied again to the non-printed portion, and it was confirmed that no color was developed (that is, that it was fixed).
The light resistance is evaluated by the Weather Ometer (WEATHEROMETER
CI 65: trade name, manufactured by ATLAS ELECTRIC DEVICES CO) was used for a sample irradiated at 0.9 W / m ² for 48 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 fluorescent lamp irradiation)
/ (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 solution of general formula (I)] 5.3 parts of the compound shown in the specific example (3) was added to 6.6 parts of ethyl acetate and the following formula. It was mixed with the phthalate ester solvent shown in A-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, 10 parts by weight of carboxy-modified polyvinyl alcohol (PVA21) to which 3.2 parts of 10% by weight sodium dodecylsulfonate aqueous solution was added.
7E: trade name, manufactured by Kuraray Co., Ltd.) 60 parts of an aqueous solution was prepared, the above solution was added, and the mixture was emulsified and dispersed by 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 having a maximum absorption wavelength of decomposition at 365 nm as a diazonium salt compound, dibutyl sulfate 2 .8 parts, 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 651: trade name, Ciba.
0.56 parts (manufactured by 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 Takenate D1)
7.6 parts (10N: 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., 6.5 parts of ion exchange resin Amberlite IRA68 (manufactured by Organo) and 13 parts of Amberlite IRC50 (manufactured by Organo) were added,
Stir for another hour. Thereafter, the ion exchange resin was filtered to obtain a desired capsule liquid. The average particle size of the capsule is 0.
It was 64 μm.

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(Preparation of Emulsion Dispersion of Coupler) 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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[Chemical 29]

(Preparation of coating liquid) The above diazonium salt compound encapsulating liquid, coupler emulsion dispersion, and styrene-butadiene rubber (SBR: SN307: trade name, manufactured by Sumitomo Nogatak Co., Ltd.) were respectively 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 benzotriazole compound-containing protective layer of the general formula (I), and a protective layer were successively formed in this order 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. Then, this heat-sensitive recording material was exposed to an ultraviolet lamp having an emission center wavelength of 365 nm and an output of 40 W for 15 seconds to be fixed.

Example-2 Using the compound of the specific example (9) in place of the specific example (3), an aqueous solution of carboxy-modified polyvinyl alcohol (KL-318: manufactured by Kuraray Co., Ltd.) was mixed with the surfactant Scrapph-8. A coating liquid for a benzotriazole compound-containing protective layer of the general formula (I) was obtained in the same manner as in Example 1 except that 0.3 part (manufactured by Nippon Seika Co., Ltd.) was added. The average particle size of the capsule was 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 benzotriazole compound-containing protective layer 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 compound shown in Specific Example (10) was replaced with 6.6 parts of ethyl acetate and phthalic acid shown as A-1. Mixed with 2.9 parts of ester solvent. 2.0 parts of xylylene diisocyanate / trimethylolpropane adduct (75% ethyl acetate solution Takenate D110N: Takeda Pharmaceutical Co., Ltd.) was further added to this solution as a capsule wall material, and the mixture was stirred to be uniform. Separately, 60 parts of an aqueous solution of 10% by weight polyvinyl alcohol (PVA217E: manufactured by Kuraray Co., Ltd.) to which 3.2 parts of an aqueous solution of 10% by weight sodium dodecylsulfonate was added was prepared, and 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] [Preparation of coating liquid for protective layer containing benzotriazole compound of general formula (I)] In Example 2, instead of the compound shown in Example (9), the compound shown in Example (11) was used. A thermosensitive recording material was prepared and evaluated in the same manner as in Example 2 except that 1.3 parts of the compound (R-6) was used as the reducing agent.

[Example-5] In Example 1, between the support and the diazo heat-sensitive recording layer (hereinafter referred to as heat-sensitive recording layer A), the following leuco-type heat-sensitive recording layer B and two heat-sensitive recording layers were formed. A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the intermediate layer 1 was provided therebetween and the compound of the specific example (13) was used instead of the compound of the specific example (3).

[Preparation of Liquid B for Thermal 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 gelatin (MG) to which 0.07 part of 10% sodium dodecylsulfonate aqueous solution was added.
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.

[Preparation of Liquid 1 for Intermediate Layer] 8.2 parts of a 4% by weight aqueous solution of boric acid and 14 parts by weight of 4- (nonylphenoxytrioxyethylene) butylsulfone were added to an aqueous solution of 14% by weight gelatin (# 750 gelatin: manufactured by Nitta Gelatin Co., Ltd.). 1.2 parts of a 2% by weight aqueous solution of sodium acid and 7.5 parts of a 2% by weight aqueous solution of the compound shown in d-1 were added and uniformly stirred to prepare a target coating solution.

[0128]

[Chemical 31]

[Coating] On a photographic paper support obtained by laminating polyethylene on high-quality paper, the above-mentioned heat-sensitive recording layer B, intermediate layer 1, heat-sensitive recording layer A, and benzotriazole compound-containing protective formula (I) were protected with a Meyer bar. The desired heat-sensitive recording material was obtained by sequentially applying and drying the layers and the protective layer in this order. The coating amount as solid content is 7.12 g / m ² and 3.28 g / m ² respectively.
It was g, 8.33 g, 2.50 g, 1.23 g.

[Thermal recording] Kyocera thermal head KST
Using a mold, (1) recording energy per unit area is 6
The electric power applied to the thermal head and the pulse width were determined so as to be ² mJ / mm ^2, and the thermal recording material was printed.
The recording material was exposed to a UV lamp having an emission center wavelength of 365 nm and an output of 40 W for 15 seconds, and (2) again, the applied power to the thermal head and the pulse width were determined so that the recording energy per unit area was 86 mJ / mm ² . The thermal recording material was printed. The recorded image obtained is (1)
An image was obtained in which the portion where only the recording was performed was magenta and the portion where only (2) was recorded was blue. Further, the portions where the recordings of (1) and (2) were duplicated were purple, and the unrecorded portions were gray-white.

Example-6 The following diazo color-developing heat-sensitive recording layer C was provided between the diazo heat-sensitive recording layer A of Example 5 and the compound-containing protective layer of the general formula (I), and the heat-sensitive recording was carried out. A thermosensitive recording material was prepared and evaluated in the same manner as in Example 5 except that the intermediate layer 2 was provided between the layer C and the diazo thermosensitive layer A.

[Preparation of Thermosensitive Recording Layer C] (Preparation of Diazonium Salt Compound Capsule Solution) 3.5 parts of compound e-1 having a maximum absorption wavelength of decomposition at 420 nm as a diazonium salt compound, compound 0 of e-2 9.9 parts was dissolved in 16.4 parts of ethyl acetate, 9.8 parts of isopropyl biphenyl as a high boiling point solvent was added, and the mixture was heated and uniformly mixed. As a capsule wall agent, 4.5 parts of xylylene diisocyanate / trimethylol propane adduct (75 wt% ethyl acetate solution: Takenate D110N: Takeda Pharmaceutical Co., Ltd.), 30 wt% acetic acid of xylylene diisocyanate / bisphenol A adduct Further 4.2 parts of ethyl solution was added to this solution and stirred uniformly. Separately, S
77 parts of a 6% by weight gelatin aqueous solution to which 0.36 part of kraph AG-8 (manufactured by Nippon Seika Co., Ltd.) was added, the above diazonium salt compound solution was added, and the mixture was emulsified and dispersed by a homogenizer. After 20 parts of water was added to the obtained emulsion to homogenize it, the capsule reaction was carried out for 3 hours while stirring at 40 ° C. Thereafter, the liquid temperature was lowered to 35 ° C., and ion-exchange resin Amberlite IRA68 (manufactured by Organo) 6.5
And 13 parts of Amberlite IRC50 (manufactured by Organo) are added and the mixture is further stirred for 1 hour. After that, the ion exchange resin is filtered, and 0.4 parts of a 1 wt% aqueous solution of hydroquinone is added to another part of the capsule solution, and the mixture is stirred. In this way, the target capsule liquid was obtained. The average particle size of the capsule was 0.91 μm.

(Preparation of Coupler Dispersion) 2.4 parts of compound f-1 shown below as a coupler and 2.5 parts of triphenylguanidine, 1,1- (p-hydroxyphenyl) were used.
2.5 parts of 2-ethylhexane and 3.6 parts of 4,4 '-(p-phenylenediisopropylidene) diphenol.
Parts, 3.2 parts of 2-ethylhexyl-4-hydroxybenzoate, 0.8 parts of f-2 were dissolved in 8.0 parts of ethyl acetate, and 1.0 part of pionein A41C (manufactured by Takemoto Yushi Co., Ltd.) was added. After heating, they were mixed uniformly. Separate gelatin (#
750 gelatin: manufactured by Nitta Gelatin Co., Ltd.) 10 weight aqueous solution 7
In addition to 5.0 parts, it was emulsified and dispersed by a homogenizer.
The remaining ethyl acetate was evaporated from this emulsion to obtain a target emulsified dispersion.

[0134]

Embedded image

(Preparation of Coating Liquid) The above diazonium salt compound capsule liquid, coupler emulsion dispersion, and styrene-butadiene rubber (SBR: SN307: trade name, manufactured by Sumitomo Nogatak Co.) were used in a diazonium salt compound / coupler ratio of 1. /3.2, and the weight of the styrene-butadiene rubber was mixed so as to be equal to the weight of gelatin of the coating liquid to prepare the target coating liquid.

[Preparation of coating solution for intermediate layer 2] 0.47 parts of a 2% by weight aqueous solution of sodium (4-nonylphenoxytrioxyethylene) butyl sulfonate was added to 57 parts of a 13% aqueous gelatin solution and 2 parts of the compound shown in g-1. Wt% aqueous solution 8.3
Department, PVP-k15 (trade name, manufactured by GAF Gokyo Sangyo Co., Ltd.)
2.4 parts was added and uniformly stirred to prepare a desired coating liquid.

[0137]

[Chemical 33]

[Coating] Heat sensitive recording layer B, intermediate layer 1, heat sensitive recording layer A, intermediate layer 2, heat sensitive recording layer C, and general formula ( The benzotriazole compound-containing protective layer of I) and the protective layer were sequentially applied and dried to obtain the intended multicolor heat-sensitive recording material. The coating amount as solid content was 7.12 g, 3.28 g, 8.33 g and 3.13 g per 1 m ^2, respectively.
It was g, 8.06 g, 2.50 g, 1.23 g.

[Thermal recording] Kyocera thermal head KST
Using a mold, (1) recording energy per unit area is 3
The power applied to the thermal head and the pulse width were determined so as to be 5 mJ / mm ^2, and the thermal recording material was printed.
A yellow image was recorded. (2) Place the recording material under an ultraviolet lamp with an emission center wavelength of 420 nm and an output of 40 W.
Irradiation was carried out for 0 seconds, and (3) the applied power to the thermal head and the pulse width were determined again so that the recording energy per unit area would be 66 mJ / mm ^2, and printing was performed to record a magenta image. Furthermore, (4) emission center wavelength 365n
Irradiate for 15 seconds under an ultraviolet lamp of m, output 40W,
(5) The recording energy per unit area is 90 mJ again.
The electric power applied to the thermal head and the pulse width were determined so as to be / mm ^2, and printing was performed to record a cyan image. As a result, in addition to the yellow, magenta, and cyan color-developed images, the recording area where the yellow and magenta recording overlap is red, the magenta and cyan overlapping area is blue, and the yellow and cyan overlapping area is green. And the image portion where the yellow, magenta, and cyan recordings were overlapped developed a black color. The unrecorded area was gray white.

Example-7 The compound of the specific example (29) was replaced by the compound of A-1 in place of the specific example (13) in Example 6.
A thermosensitive recording material was prepared and evaluated in the same manner as in Example 6 except that tricresyl phosphate was used instead of.

Example-8 A thermal recording material was prepared and evaluated in the same manner as in Example 6 except that the specific example (17) was used in place of the specific example (13).

Example 9 Example 8 was repeated except that 3.3 parts of the compound of Example (11) and 2 parts of the compound of Example (12) were used in place of Example (17) in Example 8. A thermal recording material was prepared and evaluated in the same manner as in.

Example-10 In Example 8, instead of the specific example (17), 0.75 part of the specific example (32), 1.5 parts of the compound of the specific example (26), and a specific example (8). A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 8 except that 3.0 parts of the compound of 2. was used.

Example-11 In Example 8, 4.0 parts of the compound of Example (29) and 2.3 parts of the compound of Example (8) were used in place of the compound of Example (17). Otherwise, a thermal recording material was prepared and evaluated in the same manner as in Example 8.

[Example 12] A thermosensitive recording material was prepared in the same manner as in Example 6 except that instead of using the intermediate layers 1 and 2 in Example 6, the following intermediate layer 3 was used. It was prepared and evaluated.

[Preparation of Liquid 3 of Intermediate Layer] 1.1 parts of the compound shown in Specific Example (3) was uniformly stirred with 0.7 part of ethyl acetate and 0.59 part of the phthalate ester solvent shown in A-1. . To this solution, 0.5 part of xylylene diisocyanate / trimethylolpropane adduct (75 wt% ethyl acetate solution: Takenate D110N: manufactured by Takeda Pharmaceutical Co., Ltd.) is added, and further stirred uniformly. Separately, a 6 wt% gelatin (MGP-9066: Nippi Gelatin Co., Ltd.) aqueous solution 3 to which 1.8 parts of a 10% sodium dodecylsulfonate aqueous solution was added 3
6.4 parts was prepared, the above-mentioned electron-donating dye precursor solution was added, and the mixture was emulsified and dispersed by a homogenizer. While stirring this emulsion dispersion at 40 ° C., the encapsulation reaction was carried out for 3 hours to obtain a target coating liquid.

[Coating] Heat sensitive recording layer B, intermediate layer 3, heat sensitive recording layer A, intermediate layer 3, heat sensitive recording layer C, and general formula ( The compound-containing protective layer of I) and the protective layer were sequentially applied and dried to obtain the intended multicolor thermosensitive recording material. The coating amount as solid content is 7.12 g per 1 m ^2, respectively.
4.58 g, 8.33 g, 4.57 g, 8.06 g,
It was 1.23 g.

Comparative Example-1 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the compound shown in B-1 was used instead of the compound of Example (3). .

[Comparative Example 2] A thermal recording material was prepared in the same manner as in Example 1 except that the protective layer containing the benzotriazole compound represented by formula (I) was not provided in Example 1. ,evaluated.

[Comparative Example 3] A thermosensitive recording material was prepared and evaluated in the same manner as in Example 2 except that the compound of B-1 was used instead of the compound of Example (9) in Example 2.

Comparative Example-4 A thermal recording material was prepared and evaluated in the same manner as in Example 2 except that the protective layer containing the benzotriazole compound of the general formula (I) was not provided in Example 2.

Comparative Example-5 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 3 except that the compound of B-1 was used instead of the compound of Example (10) in Example 3.

Comparative Example 6 A thermal recording material was prepared and evaluated in the same manner as in Example 3 except that the protective layer containing the benzotriazole compound of the general formula (I) was not provided in Example 3.

Comparative Example-7 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 6 except that the compound of B-1 was used in place of the compound of Example (11) in Example 4.

[Comparative Example-8] A thermosensitive recording material was prepared and evaluated in the same manner as in Example 6 except that the protective layer containing the benzotriazole compound of the general formula (I) was not provided in Example 4.

Comparative Example-9 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 5 except that the compound of B-1 was used instead of the compound of Example (13) in Example 5.

[Comparative Example-10] A thermosensitive recording material was prepared and evaluated in the same manner as in Example 5 except that the benzotriazole compound-containing protective layer of the general formula (I) was not provided in Example 5.

Comparative Example-11 A thermal recording material was prepared and evaluated in the same manner as in Example 6 except that the compound of B-1 was used instead of the compound of Example (13) in Example 6.

Comparative Example-12 A thermal recording material was prepared and evaluated in the same manner as in Example 6 except that the protective layer containing the benzotriazole compound of the general formula (I) was not provided in Example 6.

Comparative Example-13 A thermal recording material was prepared and evaluated in the same manner as in Example 9 except that the compound of B-1 was used instead of the compound of Example (29) in Example 7.

Comparative Example-14 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 7 except that the protective layer containing the benzotriazole compound of the general formula (I) was not provided in Example 7.

Comparative Example-15 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 8 except that the compound of B-1 was used instead of the compound of Example (17) in Example 8.

Comparative Example 16 A thermal recording material was prepared and evaluated in the same manner as in Example 8 except that the protective layer containing the benzotriazole compound of the general formula (I) was not provided in Example 8.

[Comparative Example-17] A thermosensitive recording material was prepared in the same manner as in Example 9 except that the compound of B-2 was used instead of the compounds of Examples (11) and (12) in Example 9. evaluated.

Comparative Example-18 A thermal recording material was prepared and evaluated in the same manner as in Example 9 except that the benzotriazole compound-containing protective layer of the general formula (I) was not provided in Example 9.

[Comparative Example-19] B-1 in place of the compounds of Specific Examples (32), (26) and (8) in Example 10
A thermosensitive recording material was prepared and evaluated in the same manner as in Example 10 except that the compound of 1. was used.

Comparative Example-20 A thermal recording material was prepared and evaluated in the same manner as in Example 10 except that the protective layer containing the benzotriazole compound of the general formula (I) was not provided in Example 10.

[Comparative Example-21] A thermosensitive recording material was prepared in the same manner as in Example 11 except that the compound of B-1 was used in place of the compounds of Examples (29) and (8) in Example 11.
evaluated.

[Comparative Example-22] A thermosensitive recording material was prepared and evaluated in the same manner as in Example 11 except that the benzotriazole compound-containing protective layer of the general formula (I) was not provided in Example 11.

[Comparative Example-23] A thermosensitive recording material was prepared and evaluated in the same manner as in Example 12 except that the compound of B-1 was used instead of the compound of Example (13).

Comparative Example-24 A thermal recording material was prepared and evaluated in the same manner as in Example 12 except that the benzotriazole compound-containing protective layer of the general formula (I) was not provided in Example 12.

[0172]

Embedded image

The evaluation results of Examples 1 to 12 and Comparative Examples 1 to 24 are shown in Table 10 below.

[0174]

[Table 10]

As is clear from Table 9, in all of Examples 1 to 12, the light fixing property is good, and the density of the non-printed portion is low and the light resistance of the non-image portion is excellent. I understand. Further, the residual amount of the dye in the image area is high, and the light resistance of the image area is excellent. This tendency is particularly excellent in the multicolor heat-sensitive recording material. On the other hand, Comparative Examples 1, 3,
5, 7, 9, 11, 13, 15, 17, 19, 21, 2
No. 3 was provided with a protective layer containing a known ultraviolet absorbing compound, but all had low light transmittance before photofixing and were inferior in photofixability. Comparative Examples 2, 4, 6, 8, 10, 12, 1
Nos. 4, 16, 18, 20, 22, and 24 have no protective layer containing the benzotriazole compound of the general formula (I) of the present invention, so that the fixing property is good, but the density of the non-printed portion is high. It can be seen that the light resistance of the non-image area is particularly poor.

[0176]

INDUSTRIAL APPLICABILITY As described above, the benzotriazole compound of the present invention is suitable as a polymer material, a photographic material, an additive for a heat-sensitive recording material, and the like. Since it decreases later, it is suitable for use in a protective layer or the like in a thermal recording material, and when used in the protective layer or the like, it imparts light resistance to the protective layer or the like without impairing the fixing property of the protective layer or the like. be able to. Further, the heat-sensitive recording material of the present invention contains the benzotriazole compound of the present invention so that it does not hinder fixing and has good fixability, and further, the light resistance of the heat-sensitive recording material is improved after fixing, It is possible to prevent coloring of the non-image area.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03C 1/815 B41M 5/18 T // C09K 3/00 104 101E 102S 112 (72) Inventor Adachi Keiichi, 200, Onakazato, Fujinomiya-shi, Shizuoka Prefecture Fuji Photo Film Co., Ltd.

Claims (7)

[Claims] 1. A benzotriazole compound represented by the general formula (I). Embedded image In the formula, m represents 1 or 2. A is the general formula (I)-
When m = 1 in (1) and the general formula (I)-(2)-
In (4), the following formula (1-1) is represented. Embedded image In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkenyl group, —CO ₂ R ⁶ , —CONR ⁷ R ⁸ , —CN or an aryl group. Ring B represents a phenyl group or a naphthyl group. R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. In addition, the general formula (I)-
When m = 2 in (1), A is represented by the following formula (1-2).
Represents Embedded image In the formula, R ¹ , R ² and ring B have the same meanings as in formula (1-1). R ³ is -OR ^3A O- or -OCOR
^3A CO ₂ −, wherein R ^3A represents an alkylene group or an arylene group. X is represented by the general formula (I)-(1), (I).
In-(3) and (I)-(4), a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom is used, and in general formulas (I)-(2),
Alkylene group, -OR ⁴ O-or -OCOR ⁴ CO ₂ - represents a. W in the general formulas (I)-(1), (I)-(2) and (I)-(4) is a hydrogen atom, an alkyl group,
Alkenyl group, an alkoxy group, an aryl group or a halogen atom, the general Formulas (I) - (3) are, -OR ⁴ O
- or -OCOR ⁴ CO ₂ - represents a. Y is the general formula (I)
In-(1), (I)-(2) and (I)-(3), a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom may be represented by the general formula (I)-
(4) ^{In, -OR 4 O -, - OCOR} 4 CO
_{2 -, - CH 2 CH 2} CO 2 R 4 OCOCH 2 CH 2 -, - C
_{^{H 2 CH 2 OCOR 4 CO 2}} CH 2 CH 2 - or -CH ₂ CH ₂
CON (R ⁵ ) R ⁴ N (R ⁵ ) COCH ₂ CH ₂ —.
R ⁴ represents an alkylene group or an arylene group. R ⁵ is
Represents a hydrogen atom or an alkyl group. Z represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. 2. A heat-sensitive recording material having a heat-sensitive recording layer and a protective layer provided on a support, wherein the benzotriazole compound according to claim 1 is contained. 3. The heat-sensitive recording material according to claim 2, wherein the benzotriazole compound according to claim 1 is encapsulated in microcapsules. 4. The heat-sensitive recording material according to claim 2 or 3, wherein the benzotriazole compound according to claim 1 is contained in the protective layer. 5. The heat-sensitive recording material according to claim 2, wherein the heat-sensitive recording layer contains a diazonium salt compound and a coupler that reacts with the diazonium salt compound to develop a color. 6. A heat-sensitive recording layer comprising a heat-sensitive recording layer A containing an electron-donating colorless dye and an electron-accepting compound, a diazonium salt compound and a coupler which reacts with the diazonium salt compound to produce a color. The heat-sensitive recording material according to any one of claims 2 to 4, which is a laminate of the recording layer B and the recording layer B. 7. The heat-sensitive recording layer reacts with a heat-sensitive recording layer A containing an electron-donating colorless dye and an electron-accepting compound, a diazonium salt compound having a maximum absorption wavelength of 360 ± 20 nm, and the diazonium salt compound. A heat-sensitive recording layer B containing a color coupler, and a maximum absorption wavelength of 400 ± 20 n
A thermosensitive recording layer C containing a diazonium salt compound of m and a coupler which reacts with the diazonium salt compound to develop a color.
5. The heat-sensitive recording material according to claim 2, wherein the heat-sensitive recording material and the heat-sensitive recording material are sequentially laminated.