JPH08252981A - Thermal recording material - Google Patents

Abstract

PURPOSE: To obtain excellent lightfastness of a recording material or an image section usable for a block copy film of a photosensitive material to be exposed at an ultraviolet region, by providing a layer which contains a specified compound and an organic nucleophilic reagent, on a support body. CONSTITUTION: In formulas I, II, II, and IV, n is 1 or 2, R1 represents -COR, when n = 1, -CO- when n=2, or -CO-R9 -CO-. R2 -R5 represent a hydrogen atom, an alkyl group, a cycloalkyl group. R, represents a hydrogen atom, a halogen atom, and an alkyl group. R7 represents an alkyl group, an aryl group, an aralkyl group. R8 represents an alkylene group, an arylene group, -O-X-O-. An organic nucleophilic reagent is of a general nucleophilic reagent in organic synthetic chemistry having -OH, -NH, -SH, -PH as a partial structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording material having a spectral absorption in the ultraviolet region, and particularly excellent in light resistance of a recording material or an image area which can be used as a block film of a light-sensitive material exposed in the ultraviolet region. Thermal recording material.

[0002]

2. Description of the Related Art Recording materials having spectral absorption in the visible region have already been used as pressure-sensitive paper, heat-sensitive paper, light-sensitive pressure-sensitive paper, current-sensitive heat-sensitive recording paper and heat-sensitive transfer paper, which contain an electron-donating colorless dye and an electron-accepting compound. Are known. For example British Patent 2140
No. 449, U.S. Pat.
No. 0, JP-B-60-23992, JP-A-57-179.
No. 836, No. 60-123556, No. 60-1235.
Details on No. 57 etc. However, almost no recording material having spectral absorption in the ultraviolet region has been known. As a recording material, in recent years, studies have been earnestly conducted on (1) enhancement of absorption in the ultraviolet region (2) improvement of properties such as storage stability of non-image area and image area, but there have been various problems. In particular, in order to provide a recording material which can be used as a block film of a light-sensitive material exposed in the ultraviolet region or a recording material having excellent light resistance in the image area, the ultraviolet region before and after heating (about 300 to 4) is provided.
It is desired that the difference in absorbance at 20 nm) be large, that the reaction proceed rapidly by heating, and that the amount of ultraviolet absorber produced be large.

[0003]

The present invention relates to a heat-sensitive recording material having a spectral absorption in the ultraviolet region, and particularly to a light-proof property of a recording material or an image portion which can be used as a block film of a light-sensitive material exposed in the ultraviolet region. And a heat-sensitive recording material excellent in

[0004]

The object of the present invention is to provide a support with the following general formula (1), (2), (3) or (4).
This is achieved by a heat-sensitive recording material characterized in that a layer containing a compound represented by and an organic nucleophile is provided. General formula (1)

[0005]

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General formula (2)

[0007]

[Chemical 6]

General formula (3)

[0009]

[Chemical 7]

General formula (4)

[0011]

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In the general formulas (1) to (4), n is 1
Or 2 for R₁ Is -COR when n = 1₇ , N
= 2, -CO- or -CO-R₉ -CO- table
You R₂ ~ R_Five Is a hydrogen atom, alkyl group, cycloalkyl
Group, aryl group, aralkyl group, alkenyl group, halo
Gen atom, or -OR₁₁Represents R₂ ~ R_Five The archi
Group is an alkoxy group, an aryloxy group, an alkyl group.
It has a substituent such as a thiol group and an aryloxycarbonyl group.
can do. R₆ Is a hydrogen atom, a halogen atom,
Alkyl group, aryl group, alkoxy group, aryloxy
Group, an aralkyloxy group, or an aralkyl group is represented by R₇ 
Is an alkyl group, aryl group, aralkyl group, alkoxy
A group, an aryloxy group, or an aralkyloxy group,
R₈ Is an alkylene group, an arylene group, -O-X-O-,
Or- (CH₂ )_p-CO-Y-X-Y-CO- (C
H₂ )_q-Is R₉ Is a direct bond, alkylene group, aral
A kylene group or an arylene group, p and q are 0 to 4
A number, X is an alkylene group which may contain an oxygen atom,
Y is a direct bond to an aralkylene or arylene group.
, -O-, or -NR_Ten-Is R_TenIs a hydrogen atom,
Or an alkyl group, R ₁₁Is a hydrogen atom, alkyl group, ara
Alkyl group, aryl group, alkenyl group, cycloalkyl
Group, or -CO-R₇ Represents In the above substituents
R₂ ~ R_Five At least one of them is -OR₁₁, Or R
₈ Represents -O-X-O-.

More specifically, among the groups represented by R _{2 to} R ₅ , hydrogen atom, alkyl group having 1 to 8 carbon atoms, phenyl group, aralkyl group having 7 to 9 carbon atoms, and 3 carbon atoms.
The alkenyl group of -5, -OR < ₁₁ >, or a halogen atom is preferable. Particularly, it is preferable that R ₃ and / or R ₄ represents OR ₁₁ in terms of high ε, high reactivity, or absorption long-wavelength. As R _{2 to} R ₅ , hydrogen atom, methyl group,
Ethyl group, isopropyl group, t-butyl group, t-amyl group, t-octyl group, sec-butyl group, sec-amyl group, sec-hexyl group, benzyl group, α-methylbenzyl group, α, α-dimethyl group A benzyl group, an allyl group, a phenyl group, a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, a chlorine atom and a bromine atom are preferable. Among the groups represented by R ₆ , a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms are preferable, and particularly, a hydrogen atom, a chlorine atom, a methyl group, an ethyl group. , A methoxy group, an ethoxy group, an acetyl group, or a methoxycarbonyl group is preferable.

1 to 8 carbon atoms in the group represented by R _7.
Alkyl group, C 6-10 aryl group, C 1-8 alkoxy group, or C 6-1
Aryloxy group of 0 is preferable, and particularly, methyl group, ethyl group, propyl group, butyl group, octyl group, methoxy group, ethoxy group, butoxy group, phenyl group, tolyl group,
Anisyl group, chlorophenyl group, dichlorophenyl group,
A nitrophenyl group, a naphthyl group and a phenyloxy group are preferred. Among the groups represented by R ₈ , an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 10 carbon atoms, —O
-X-O -, - (CH 2) p -CO-Y-X-Y-CO
- (CH _{2) q} - are preferable, an alkylene group having 1 to 8 carbon atoms, phenylene group preferred as R _9, p,
q is an integer of 0 to 4, X is preferably an alkylene group which may contain an oxygen atom, Y is preferably a direct bond, or —O—. R
Of the groups represented by ₁₀ and R ₁₁ , a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable, and a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or an n-butyl group is particularly preferable.

Typical examples of the phenylbenzotriazole derivative according to the present invention include, but are not limited to, the following compounds.

[0016]

[Chemical 9]

[0017]

[Chemical 10]

[0018]

[Chemical 11]

[0019]

[Chemical 12]

[0020]

[Chemical 13]

The organic nucleophile according to the present invention refers to a general nucleophile in synthetic organic chemistry having —OH, —NH, —SH, —PH, etc. as a partial structure, such as phenols, alcohols, Examples thereof include alkylamines, arylamines, thiophenols, mercaptans, sulfinic acids, active methylene compounds, oximes, hydroxamic acids and hydroxylamine. Among these, mercaptans, sulfinic acids, oximes and hydroxamic acids and salts thereof are preferable, oximes and hydroxamic acids are particularly preferable, and compounds represented by the following general formula (5) or (6) are preferable. General formula (5)

[0022]

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General formula (6)

[0024]

[Chemical 15]

In the above formula, R ₁₂ and R ₁₄ are an alkyl group, an alkoxy group, an aryl group or an aryloxy group which may have a substituent, and R ₁₃ and R ₁₅ are a hydrogen atom, an alkyl group, or Represents an aryl group.

In the above formula, examples of the substituent of the alkyl group and the alkoxy group represented by R ₁₂ and R ₁₄ include an alkoxy group, an aryl group, an aryloxy group, a halogen atom, a pyridyl group and a dialkylamino group. Examples of the substituent of the aryl group and aryloxy group represented by R ₁₂ and R ₁₄ include an alkyl group, an alkoxy group, a halogen atom, a cyano group and a nitro group. Of the groups represented by R ₁₂ and R ₁₄ , an alkyl group having 1 to 8 carbon atoms, and 1 to 8 carbon atoms
8 alkoxy group, alkoxy-substituted alkyl group, alkoxy-substituted alkyloxy group, phenyl-substituted alkyl group,
Phenyl-substituted alkyloxy group, phenoxy-substituted alkyl group, phenoxy-substituted alkyloxy group, dialkylamino-substituted alkyl group, phenyl group, phenoxy group, chloro-substituted phenyl group, nitro-substituted phenyl group, tolyl group,
Anisyl group, dichloro-substituted phenyl group, chloro-substituted phenoxy group, nitro-substituted phenoxy group, toluoxy group, anisoxy group, and dichloro-substituted phenoxy group are preferable. Among the groups represented by R ₁₃ and R ₁₅ , a hydrogen atom, a methyl group, an ethyl group and a phenyl group are preferable.

Specific examples of the organic nucleophile according to the present invention include acetohydroxamic acid, propanohydroxamic acid, butanohydroxamic acid, octanohydroxamic acid,
Methoxycarbohydroxamic acid, butoxycarbohydroxamic acid, 2-ethoxyethoxycarbohydroxamic acid, benzyloxycarbohydroxamic acid, α-chloroacetohydroxamic acid, α-dimethylaminoacetohydroxamic acid, α-phenylacetohydroxamic acid, α-
Phenoxyacetohydroxamic acid, N-methylacetohydroxamic acid, N-methylpropanohydroxamic acid, N
-Methylbutanohydroxamic acid, N-methyl-α-chloroacetohydroxamic acid, N-methyl-α-dimethylaminoacetohydroxamic acid, N-methyl-α-phenylacetohydroxamic acid, N-methyl-α-phenoxyacetohydroxamic acid Acid, benzohydroxamic acid, phenoxycarbohydroxamic acid, benzosulfohydroxamic acid, p-chlorobenzohydroxamic acid,

P-Methylbenzohydroxamic acid, p-methoxybenzohydroxamic acid, p-nitrobenzohydroxamic acid, m-nitrobenzohydroxamic acid, (2,4
-Dichlorobenzo) hydroxamic acid, salicylhydroxamic acid, N-methyl-benzohydroxamic acid, N-methyl-p-chlorobenzohydroxamic acid, N-methyl-p
-Nitrobenzohydroxamic acid, N-methyl-p-methoxybenzohydroxamic acid, benzophenone oxime,
Diphenylglyoxime, cyclohexanone oxime,
2-hexanone oxime, N-phenylhydroxylamine, N-ethyl-N-phenylhydroxylamine,
N-benzyl-N-phenylhydroxylamine, didodecylamine, 4-benzyloxythiophenol, 2
-Mercapto-5-octylthio-1,3,4-thiadiazole, 2-mercapto-5-benzylthio-1,
Examples thereof include 3,4-thiadiazole, 2-mercapto-5-butylthio-1,3,4-thiadiazole, 2-mercaptobenzoxazole, dodecylbenzenesulfinic acid, and sodium dodecylbenzenesulfinate, but are not limited thereto. is not. These can be used in combination of two or more.

When heated, the organic nucleophile of the present invention reacts with a compound having a benzotriazole group in the molecule to cause a deprotection reaction of the ester part. However, the nucleophile is activated and the benzotriazole derivative is activated. For this purpose, a base or an acid may be used in combination. The base may be an inorganic or organic base, or a compound that decomposes when heated to release an alkaline substance. Representative examples include organic ammonium salts, organic amines, amides, ureas, thioureas, thiazoles, pyrroles, pyrimidines, piperazines,
Examples of nitrogen-containing compounds include guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, pyridines and the like. Specific examples thereof include tricyclohexylamine, tribenzylamine, dioctadecylbenzylamine, allylurea, thiourea, 2-benzylimidazole, 4-phenylimidazole, 2-undecylimidazoline, 2,4,5-trifuryl-2. -Imidazoline,
1,2-diphenyl-4,4, -dimethyl-2-imidazoline, triphenylguanidine, dicyclohexylguanidine, tricyclohexylguanidine, guanidine trichloroacetate, N, N'-dibenzylpiperazine,
Examples include morpholine trichloroacetate and 2-aminobenzothiazole.

The method of using the compounds of the general formulas (1) to (4) and the organic nucleophile of the present invention is not particularly limited, and a method of solid-dispersing them, a method of emulsifying-dispersion or microencapsulation. The method of doing is mentioned. The compound finely divided by these methods can be contained in any of the heat-sensitive recording layer, protective layer, intermediate layer, undercoat layer and backcoat layer.

The amount of the compound of the general formula (1), (2), (3) or (4) of the present invention to be used is not particularly limited,
0.1 to 15.0 g / m ² is preferable, especially 0.2 to 1
0.0 g / m ² is preferred. General formula (1) of the present invention,
The ratio of the compound of (2), (3) or (4) to the organic nucleophile is such that the organic compound is 1.0 mol of the compound of the general formula (1), (2), (3) or (4). The nucleophile is preferably used in an amount of 0.5 to 20 equivalents, and particularly preferably 1.0 to 10 equivalents.

In the heat-sensitive recording material of the present invention, conventionally known electron-donating colorless dyes, electron-accepting compounds, and sensitizers (heat-fusible substances) can be used. For details of these, Japanese Patent Publication No. 59-53193 and Japanese Patent Laid-Open No. 59-53
197463, JP 62-114989 A, JP 3-288688 A, JP 1-237 A.
189, JP-A-58-57989, and 58.
-87094, 61-58789, 6
No. 2-109681, No. 62-132674, No. 63-151478, and No. 63-23596.
It is described in Japanese Patent Publication No. 1 and the like.

In the heat-sensitive recording material of the present invention, conventionally known aromatic diazonium salt compounds, couplers and organic base compounds which react with the aromatic diazonium salt compound when heated can also be used. Details of these are described in JP-A-2-136286 and JP-A-62-1.
No. 46678, JP-A No. 61-291183, and the like.

As the wall material of the microcapsule used in the present invention, polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, Etc. In the present invention, two or more of these polymer substances may be used in combination. Among the above-mentioned polymer substances, polyurethane, polyurea, polyamide, polyester, polycarbonate and the like are preferable, and polyurethane and polyurea are particularly preferable. Details of a preferable method for producing microcapsules and microcapsules which can be preferably used in the present invention are described in JP-A-59-222716 and US Pat. No. 37268.
No. 04, No. 3,796,696, and JP-A-3-28868.
No. 8 publication and the like. Further, a plasticizer may be added for the purpose of controlling the glass transition point of the microcapsules. The details are described in JP-A-61-277490.

As the water-soluble polymer compound used in the present invention, conventionally known compounds can be used. Specifically, polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl pyrrolidone, ethylene-maleic anhydride copolymer, styrene-
Examples thereof include maleic anhydride copolymer, isobutylene-maleic salicylic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivative, casein, gelatin and the like. Further, for the purpose of imparting water resistance to these binders, a water resistance agent such as polyamide epichlorohydrin may be added. Further, use of a hydrophobic polymer emulsion, specifically, styrene-butadiene rubber latex, acrylonitrile-butadiene latex, or various emulsions of polyvinyl acetate, polyacrylic ester, ethylene-vinyl acetate copolymer, etc. You can

In the present invention, additives can be added appropriately depending on the purpose. Examples of additives include organic and inorganic pigments, metal soaps, waxes, antistatic agents, ultraviolet absorbers, defoamers, conductive agents, fluorescent dyes, surfactants and the like.

The pigment used in the present invention includes:
Kaolin, calcined kaolin, talc, wax stone, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, lithopone, amorphous silica, colloidal silica, calcined stone ko, silica, magnesium carbonate,
Titanium oxide, alumina, barium carbonate, barium sulfate,
Examples thereof include mica, microballoons, urea-formalin filler, polyester particles, and cellulose filler. Examples of the metal soap used in the present invention include higher fatty acid polyvalent metal salts such as zinc stearate, aluminum stearate, calcium stearate and zinc oleate.

In the present invention, an anti-fading agent may be added if necessary. For more information on this,
JP-A-61-283589 and 61-28359.
No. 0 and No. 61-283591.

Examples of the support used in the present invention include acidic paper, neutral paper, high quality paper, pigment coated paper, plastic film laminated paper, plastic film and synthetic paper. Among these, neutral paper, plastic film laminated paper, and synthetic paper are preferable, and specifically, heat-extracted pH 6-9 neutral paper sized with a neutral sizing agent such as alkyl ketene dimer, polyethylene resin laminated paper, polyethylene terephthalate. Examples thereof include films, polyethylene terephthalate film, polypropylene synthetic paper, polyethylene terephthalate synthetic paper, and the like. The thickness of the support is preferably 20 to 200 μ, and particularly preferably 50 to 100 μ. Corona discharge treatment can be carried out, if necessary, at the time of coating on these supports.

[0040]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. In Examples,% represents% by weight unless otherwise specified.

Example 1 20 g each of the compound of Specific Example (1), benzohydroxamic acid as an organic nucleophile, and 2-benzyloxynaphthalene as a heat-fusible compound were added to 100 g of 5% polyvinyl alcohol (Kuraray Co., Ltd.). Made PVA
105) Dispersed with an aqueous solution by a ball mill all day and night to give a volume average particle size of 3μ. On the other hand, calcined kaolin (Ani
80 g of silex-93) was dispersed with a homogenizer together with 160 g of a 0.5% solution of sodium hexametaphosphate. 5 g of the dispersion liquid of the compound of the specific example (1), 10 g of the dispersion liquid of benzohydroxamic acid, 5 g of the dispersion liquid of 2-benzyloxynaphthalene, and 22 g of the dispersion liquid of calcined kaolin were mixed, and further 4 g of zinc stearate emulsion. A coating solution was obtained by adding 5 g of a 2% aqueous solution of sodium (2-ethylhexyl) sulfosuccinate. This coating liquid was weighed on 50 g / m ² of neutral paper and the dry coating amount was 6 g / m 2.
^The coating material was coated with a wire bar so as to have a value of ^2, and subjected to a calendar treatment to obtain a recording material of the present invention. This recording material,
Using a thermosensitive static color development tester, heat recording was performed at 140 ° C. for 5 seconds. The absorbance of the recorded area and the non-recorded area was measured by a spectrophotometer (UV2200 type, manufactured by Shimadzu Corporation) to obtain 360.
nm is 0.68 in the recorded part and 0.1 in the non-recorded part.
It was below. As described above, the heat-sensitive recording material of the present invention can record in the ultraviolet region.

[Example-2] A specific example (1) of Example-1
A thermosensitive recording material was prepared and evaluated in the same manner as in Example-1 except that the compound of Specific Example (9) was used instead of. The absorbance of the recording portion was 1.45 at 350 nm.

Example 3 Compound of Specific Example (1) 9.
0 g, 5.0 g of the compound of the specific example (9) and 13.7 g of benzohydroxamic acid as an organic nucleophile were added to phthalated gelatin 1
It was dispersed by a ball mill together with 0 g of an aqueous solution all day and night to give a volume average particle diameter of 3 μm. This dispersion is weighed 100 g /
m ² on the surface of polyethylene terephthalate support whose surface was treated by corona discharge, the dry coating amount was 24.5 g /
A heat sensitive recording material of the present invention was obtained by coating with a wire bar to give m ² and calendering. When this heat-sensitive recording material was allowed to stand in an oven at 130 ° C. for 30 seconds, it exhibited spectral absorption in the ultraviolet region of 340 to 370 nm,
The absorbance at 360 nm before heating was 0.18, while the absorbance after heating was 1.76.

Example 4 Compound of Specific Example (9) 3.
0 g and 5.1 g of phenethylcumene as an oil were dissolved and stirred in 17.5 g of ethyl acetate at 40 ° C. After lowering the liquid temperature to 25 ° C, MR-200 (trade name of Nippon Polyurethane Co., Ltd.) was used as a capsule wall material in this solution.
7.2 g and D-110N (trade name of Takeda Pharmaceutical Co., Ltd.) 9.6 g were added and stirred uniformly. Separately, p-
Sodium dodecylbenzene sulfonate (surfactant)
58 g of a 5.8% gelatin aqueous solution containing 0.17 g was prepared, and the above solution was added and emulsified and dispersed by a homogenizer. Ion-exchanged water (70 g) and diethylenetriamine (0.5 g) were further added to this emulsion, and the mixture was stirred while stirring to 65
The temperature was raised to ° C and the encapsulation reaction was carried out for 3 hours to obtain the target capsule liquid. Next, as an emulsion stabilizer, 3- (bis-p
-Dihydroxyphenylmethyl) heptane 3.0 g, bis (5-t-butyl-4-hydroxy-2-methylphenyl) thioether 2.0 g, tricyclohexylguanidine as a base 1.0 g, benzohydroxamic acid 1 as an organic nucleophile 0.5 g was dissolved in 10.5 g of ethyl acetate. This was added to 27 g of a 7% aqueous gelatin solution containing 0.18 g of sodium p-dodecylbenzenesulfonate, and the mixture was further heated to 40 ° C. and stirred to evaporate ethyl acetate to obtain an emulsified dispersion liquid. The above-prepared capsule liquid and emulsion dispersion were mixed in a ratio of 1: 3 parts by weight and stirred to obtain a coating liquid. Apply this coating solution to cellulose triacetate (TAC)
It was coated on the support of No. 2 with a wire bar and dried to obtain the heat-sensitive recording material of the present invention.

The recording energy of this recording material was 110 mJ / mm ² or 1 using a thermal head (KST, manufactured by Kyocera Corporation).
The applied power and pulse width were determined so as to be 30 mJ / mm ^2, and the heat-sensitive recording material was heat-recorded. Recording part 350
The absorbance at nm is 0.89 at 110 mJ / mm ² ,
It was 1.28 at 130 mJ / mm ² . This recorded image also had good light resistance.

Example-5 Compound of Specific Example (9) 3.
0 g and compound (A) 15.0 as an electron-donating colorless dye
g was dissolved in 20.0 g of ethyl acetate and stirred at 40 ° C. After lowering the liquid temperature to 25 ° C., 1.0 g of MR-200 (trade name of Nippon Polyurethane Co., Ltd.) and D-110N (trade name of Takeda Pharmaceutical Co., Ltd.) as capsule wall materials were added to this solution. 0 g was added and stirred uniformly.
This was added to 58 g of a 6.0% gelatin aqueous solution and emulsified and dispersed by a homogenizer. After adding 70 g of ion-exchanged water and 0.5 g of tetraethylenepentamine to this emulsion, the temperature was raised to 50 ° C. with stirring and the encapsulation reaction was carried out for 3 hours to obtain a target capsule liquid.

[0047]

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Next, as an electron accepting compound, 3- (bis-
3.0 g of p-dihydroxyphenylmethyl) heptane,
Bis (5-t-butyl-4-hydroxy-) as a sensitizer
2.0 g of 2-methylphenyl) thioether, 1.0 g of tricyclohexylguanidine as a base, 1.5 g of benzohydroxamic acid as an organic nucleophile and 1 g of ethyl acetate.
It was dissolved in 0.5 g. This was emulsified and dispersed with 27 g of a 7% gelatin aqueous solution to which 0.18 g of sodium p-dodecylbenzenesulfonate was added. The liquid thus obtained was stirred at 40 ° C. and ethyl acetate was evaporated to obtain an emulsified dispersion liquid. The above-prepared capsule liquid and emulsion dispersion were mixed in a ratio of 1: 3 parts by weight and stirred to obtain a coating liquid. This coating solution was applied onto a support of cellulose triacetate (TAC) with a wire bar and dried to obtain a heat-sensitive recording material of the present invention (application amount of the compound of Specific Example (9): 0.33 g / m ^2). ).

This thermal recording material was recorded by using a thermal head (a thermal head KST type manufactured by Kyocera Co., Ltd.) by setting the applied power and the pulse width so that the recording energy per unit area was 130 mJ / mm ² . Absorption was obtained in the ultraviolet region of 340 to 420 nm in the recording portion, and the absorbance was 1.12 when measured with an optical densitometer (manufactured by Macbeth (with UV filter)). Further, the light resistance of the obtained recorded image was also good.

Example 6 As electron-donating colorless dye
2-anilino-3-methyl-6-N, N-dibutylami
Nofluorane, bisphenol as electron-accepting compound
A, β-naphthylbenzyl ether as a sensitizer
20 g to 100 g of 5% polyvinyl alcohol (Kuraray
PVA105) Aqueous solution is dispersed with ball mill all day and night
To obtain each dispersion having a volume average particle size of 1.5 μm.
Was. Also, 80 g of calcium carbonate was added to sodium hexametaphosphate.
Disperse with a homogenizer together with 160 g of 0.5% solution.
Then, a pigment dispersion liquid was obtained. Each of these dispersions has an electron donating property.
Dispersion liquid 5 g of colorless dye, dispersion liquid 10 of electron-accepting compound
g, sensitizer dispersion 10 g, calcium carbonate dispersion 5
A coating solution was obtained by mixing at a ratio of g. The basis weight of the obtained coating liquid
50 g / m² 6g / m dry coating amount on high quality paper² In
Apply it with a wire bar and dry in an oven at 50 ° C
did. Same as the one shown in Example 1 on this thermosensitive recording layer
Dry coating amount of 6g / m ² So that the wire
The recording material of the present invention coated with a bar and subjected to calendar processing
Got paid. This recording material is used as a thermal head (Kyocera stock
Unit area by using the company thermal head KST type)
Recording energy per unit is 20 mJ / m² So that
The applied voltage and pulse width were determined and recorded.

[Example-7] 12 g of 2-anilino-3-methyl-6-N-ethyl-N-isobutylaminofluorane as an electron-donating colorless dye and Takenate D-110N (Takeda Pharmaceutical Co., Ltd. as a capsule wall agent) Company name) 20g to 1-phenyl-1-xylylethane 12g
And methylene chloride were added to a mixed solvent of 20 g and dissolved. This solution was added to 60 g of an 8% aqueous solution of polyvinyl alcohol (PVA217E manufactured by Kuraray Co., Ltd.) and water 20.
It is mixed with an aqueous solution to which g is added, and is 10,000 rpm using an ace homogenizer (trade name of Nippon Seiki Co., Ltd.)
And emulsified for 5 minutes. 120 g of water was added to this emulsion, and 4
The reaction was carried out at 0 ° C. for 3 hours to obtain a capsule liquid having a volume average particle size of 1.0 μ. 3,5- (1-
Phenethyl) zinc salicylate 5 g, benzyl p-hydroxybenzoate 2 g, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane 8 g 1-phenyl-1-
It was dissolved in 1 g of xylylethane and 7 g of ethyl acetate. This solution was mixed with 37 g of an 8% aqueous solution of polyvinyl alcohol (PVA217E manufactured by Kuraray Co., Ltd.), 35 g of water, and sodium dodecylbenzenesulfonate (surfactant) 0.2.
g aqueous solution and mixed with an ace homogenizer (trade name of Nippon Seiki Co., Ltd.) at 10,000 rpm,
The mixture was emulsified for 5 minutes to obtain an emulsified dispersion having a volume average particle size of 1.5μ.

Electron-donating colorless dye capsule solution 5.0
g, 10.0 g of an electron-accepting compound emulsified dispersion, and 5.0 g of ion-exchanged water were mixed to prepare a coating liquid. A transparent polyethylene terephthalate support (thickness 7
5 μ) was coated on one surface so that the solid content was 6 g / m ² , and dried to form a heat-sensitive recording layer. On this thermosensitive recording layer, the same coating solution as in Example 5 was applied at a dry coating amount of 5 g / m ^2.
To obtain a recording material of the present invention. A thermal head (a thermal head KST type manufactured by Kyocera Corp.) was used for this recording material, and the applied voltage and pulse width were determined so that the recording energy per unit area was 65 mJ / m ² .

Comparative Example 1 A recording material was prepared in the same manner as in Example 6 except that the coating liquid of Example 1 was not applied on the thermosensitive recording layer.

[Comparative Example 2] A recording material was prepared in the same manner as in Example 7 except that the coating liquid of Example 5 was not applied on the thermosensitive recording layer.

After exposing the thermosensitive recording materials of Examples 6 and 7 and Comparative Examples 1 and 2 to direct sunlight for 2 days, the absorbance of the recording portion was measured by an optical densitometer (using a Macbeth blue filter). . Table 1 shows the results.

[0056]

[Table 1]

It can be seen from Table 1 that the light resistance of the recording portion is improved by overcoating the compound having spectral absorption in the ultraviolet region of the present invention.

[0058]

According to the present invention, a recording material having a spectral absorption in the ultraviolet region can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kunihiko Oga 200 Onakazato, Fujinomiya-shi, Shizuoka Prefecture Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. A substrate represented by the following general formula (1):
Thermosensitive recording material characterized by comprising a layer containing a compound represented by (2), (3) or (4) and an organic nucleophile, represented by the general formula (1): General formula (2) General formula (3) General formula (4) In the general formulas (1) to (4), n represents 1 or 2, R ₁ represents —COR ₇ when n = 1, and n—2 when n = 2.
CO-, or an -CO-R ₉ -CO-. R ₂ ~ R
₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a halogen atom, or -OR ₁₁ . R ₆ is a hydrogen atom, a halogen atom,
An alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an aralkyl group, an alkoxycarbonyl group, an acyl group, or a cyano group, and R ₇ is an alkyl group, an aryl group, an aralkyl group, an alkoxy group,
An aryloxy group or an aralkyloxy group is replaced by R ₈
Alkylene group, an arylene group, -O-X-O-, or _{- (CH 2) p -CO-} Y-X-Y-CO- (CH
₂ ) _q- , R ₉ is a direct bond, an alkylene group, an aralkylene group, an arylene group, or -O-X-O- is p,
q is an integer of 0 to 4, X is an alkylene group which may contain an oxygen atom, an aralkylene group, or an arylene group, Y is a direct bond, -O-, or -NR _10- , R ₁₀
Is a hydrogen atom or an alkyl group, R ₁₁ is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkenyl group,
Cycloalkyl group, or a -CO-R _7,. In the above substituent, at least one of R _{2 to} R ₅ is
OR ₁₁ or R ₈ represents —O—X—O—.