JPH06328838A - Recording material - Google Patents

Abstract

PURPOSE:To improve the conservation stability, color development density and color development sensitivity of a nonimage part and image part by a method wherein a specific salicylic acid derivative or multivalent metallic salt is contained as an electron accepting compound. CONSTITUTION:A recording material contains at least one kind of a salicilic acid derevative or its multivalent metallic salt which is represented as an electron accepting compound wherein, X represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, a carboxyl group, a sulfonic group, furthermore, an alkyl group, an aryl group, an alkenyl group, an acyl group, an aralkyl group, an alkoxy carbonyl group, or a substituted compound of those. R1 and R2 may be either identical or different and are respectively hydrogen atom or alkyl group, alkenyl group, aryl group, acyl group, alkylsulfonyl group, arylsulfonyl group, aralkyl group, aryl oxyalkyl group, a substituted compound of those. R3 is hydrogen atom, acyl group, alkyl sulfonyl group, aryl sulfonyl group, carbamoyl group, thiocarbamoyl group, substituted compound of thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material using an electron-donating colorless dye and an electron-accepting compound, such as a pressure-sensitive recording material, a heat-sensitive recording material and a light- and heat-sensitive recording material, and particularly to a non-image area and an image. The present invention relates to a recording material which is excellent in storage stability of parts, and is also excellent in color density and color sensitivity.

[0002]

2. Description of the Related Art Recording materials using an electron-donating colorless dye and an electron-accepting compound are pressure-sensitive paper, thermal paper, photosensitive pressure-sensitive paper,
It is well known as an electric heat-sensitive recording paper and a heat-sensitive transfer paper.
For example, British Patent 2140449 and US Patent 44800.
No. 52, No. 4436920, Japanese Patent Publication No. 60-23992
JP-A-57-179836 and 60-12355.
For details, see No. 6, No. 60-123557, etc.

As a recording material, research has recently been earnestly conducted on (1) storage stability of an image area, and (2) improvement of characteristics such as color density and color sensitivity. Conventional electron-accepting compounds for electron-donating colorless dyes include bisphenol A, p-hydroxybenzoic acid esters, and bis- (4-
Various compounds such as hydroxyphenyl) sulfones are known. However, all of them have some drawbacks in terms of color density, color sensitivity, storage stability (weather resistance, chemical resistance, plasticizer resistance) of non-image areas and image areas. For example, bis- (3-phenyl-4-hydroxyphenyl)
Sulfone is a magic ink when used as a thermal recording material,
When a highlighter pen or the like was applied, the non-image area was poor in storability such as the background area being fogged.

The present inventors have found that specific compounds are effective in improving these characteristics.

[0005]

The object of the present invention is to have good storage stability (weather resistance, chemical resistance, plasticizer resistance), color density and color sensitivity of the non-image area and the image area. The present invention provides a recording material satisfying the above conditions.

[0006]

The above object of the present invention is to provide a recording material using an electron-donating colorless dye and an electron-accepting compound, wherein the compound represented by the following general formula (1) is used as the electron-accepting compound.
Can be achieved by a recording material containing at least one salicylic acid derivative or a polyvalent metal salt thereof.

General formula (1)

[0008]

[Chemical 2]

In the formula, X represents a hydrogen atom, a nitro group, a cyano group or a halogen atom, and further represents an alkyl group, an aryl group, an alkenyl group, an acyl group, a sulfoalkoxy group, an aryloxy group or a substituent thereof. R ₁ ,
R _{2 s} may be the same or different and each is a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group, an acyl group or a substitution product thereof, and R ₃ represents a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a thiocarbamoyl group or a substitution product thereof.

The present invention further provides, as an electron-accepting compound,
A recording material in which at least one of the salicylic acid derivative represented by the general formula (1) or a polyvalent metal salt thereof and a polyvalent metal oxide, hydroxide or carbonate is used in combination is preferable.

The present invention will be described in detail below. In the general formula (1), the group represented by X is hydrogen atom, hydroxy group, carboxyl group, alkoxycarbonyl group having 1 to 7 carbon atoms, fluorine atom, chlorine atom, bromine atom, acyl group, sulfo group, cyano group. Group, an alkyl group having 1 to 5 carbon atoms,
C1-C5 alkoxy group, allyl group, C7-C1
An aryl group having 0, an aralkyl group having 7 to 10 carbon atoms, or a cycloalkyl group having 5 to 7 carbon atoms is preferable, and particularly a hydrogen atom, a hydroxy group, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and butoxy. Carbonyl group, butylcarbonyl group, benzyloxycarbonyl group, chlorine atom, methyl group, ethyl group, propyl group, propenyl group, butyl group, octyl group, methoxy group, butoxy group, allyl group, phenyl group,
Benzyl group, n-dodecyl group, cyclododecyl group, t-
Dodecyl group, benzotriazolyl group, cyclohexyl group, α-phenylpropyl group, α-phenylethyl group,
Is more preferable. Moreover, these groups may be substituted.

In the general formula (1), the groups represented by R ₁ and R ₂ include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, and 7 carbon atoms. 20 aralkyl groups or 8 to 8 carbon atoms
20 aryloxyalkyl groups are preferred. Particularly, hydrogen atom, methyl group, ethyl group, propyl group, propenyl group, butyl group, octyl group, 2-ethylbutyl group, 4-
Phenylbutyl group, amyl group, hexyl group, n-octyl group, benzyl group, methylbenzyloxyethyl group, p
-Ethylbenzyl group, pn-propylbenzyl group, p
-Iso-propionylbenzyl group, ω-methoxyethoxybenzyl group, chlorobenzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, phenoxyethyl group, methoxyphenoxyethyl group, chlorophenoxyethyl group, methylphenoxyethyl group, 1- Methyl-2
-Phenoxyethyl group, 1-methyl-2- (methoxyphenoxy) ethyl group, 1-methyl-2- (methylphenoxy) ethyl group, 2-naphthoxyethyl group, 1-naphthoxyethyl group, 1-methyl-2- (2- The naphthoxy) ethyl group is more preferred. Moreover, these groups may be substituted.

The group represented by R ₃ is preferably a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a thiocarbamoyl group or a substitution product thereof. In particular, acetyl group, phenoxyacetyl group, p-chlorophenoxyacetyl group, cinnamoyl group, naphthoxyacetyl group, acetoacetyl group,
ω-phenoxybutyroyl group, hexanoyl group, 2-
(2 ', 4'-dimethylphenoxy) acetyl group, β-
Diethylaminopropionyl group, benzyloxycarbonyl group, diethylaminocarbonyl group, dodecanoyl group, aliphatic acyl groups such as stearoyl group, benzoyl group, furoyl group, naphthoyl group, terephthaloyl group, anisoyl group, o-carboxybenzoyl group, nitrobenzoyl group, Aromatic acyl group such as 3-butoxycarbonylbenzoyl group, thiobenzoyl group, o-N-butylcarbamoylbenzoyl group, methanesulfonyl group, butanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p-acetylbenzene Sulfonyl group, p-methoxybenzenesulfonyl group, p
-(Β-phenoxyethoxy) benzenesulfonyl group,
4-hydroxy-5-carboxybenzenesulfonyl group, alkyl or arylsulfonyl group such as naphthalenesulfonyl group, ureido group, carbamoyl group, N-butylcarbamoyl group, N-hexylcarbamoyl group, N
-A carbamoyl group which may be substituted, such as a benzylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-dibutylcarbamoyl group, an Np-carboxyphenylcarbamoyl group and a 2,4-dibutoxyphenylcarbamoyl group, is preferable. . Moreover, these may be substituted.

Particularly, R ₃ is preferably an acyl group, an arylsulfonyl group or a substituted carbamoyl group. Further, the polyvalent metal forming a salt with these salicylic acid derivatives is preferably a divalent, trivalent or tetravalent metal atom.
Especially zinc, calcium, aluminum, magnesium,
Iron, tin, etc. are preferred.

The salicylic acid derivative represented by the above general formula (1) can be synthesized by applying various known unit operations. For example, a method of reacting the corresponding halogenated sulfonylsalicylic acid derivative with a hydrazine derivative, a method of reacting with a hydrazine or a hydrazine derivative to induce a hydrazide, or a method of reacting these with an acylating agent, an alkyl or aryl (thio) isocyanate. Alternatively, various methods such as the reverse process can be used.

The reaction of the sulfonyl halide compound with hydrazine or hydrazide is very easy to proceed and can be conveniently used. Usually, a reaction at room temperature or lower or a reaction in the coexistence of an organic or inorganic base suppresses a side reaction and is convenient from the viewpoint of handling in the post-treatment. Also, hydrazide decomposition may be carried out once via sulfonic acid ester or sulfonylimidazole.

Further, in the reaction, when a solvent selected from ketone type solvents, ether compounds, halogenated hydrocarbons, alcohols, amide solvents, tertiary amines, etc. is used,
It is easy to control the reaction temperature (heating, cooling, etc.). In the recording material using the salicylic acid derivative or the polyvalent metal salt thereof according to the present invention, the colored dye is extremely stable. or,
The color density is also sufficient. For this reason, the recorded image hardly changes even when exposed to sunlight for a long time or stored in an environment of high temperature and high humidity, which is advantageous for long-term storage. In particular,
When applied to a heat-sensitive recording system, so-called discoloration does not occur even with a solvent, an oil film, etc., so that it is a very excellent material for recording images.

The salicylic acid derivative represented by the general formula (1) of the present invention is preferably the following.

[0019]

[Chemical 3]

In the general formula (2-1) or (2-2),
X represents the above group. As the group represented by R ₃ in the general formula (1), the following groups can be mentioned in more detail. _{-Y-R 4 (3-1) -YZR} 5 (3-2) -R 6 (3-3) General formula (3-1), At a (3-2) and (3-3), R ₄ , R ₅ or R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

Y represents --CO--, --SO _2- , --CS-- or a divalent group containing them. Z is -NR ₇ - shows,
R ₇ represents a group defined for R ₂ . Specific examples of the salicylic acid derivative represented by the general formula (1) of the present invention include the following compounds. 4-hydroxy-5-carboxybenzenesulfonyl hydrazide (hereinafter sometimes referred to as salicylic acid sulfonyl hydrazide), N'-methyl (salicylic acid sulfonyl hydrazide), N'-phenyl (salicylic acid sulfonyl hydrazide), N'-tolyl- ( Salicylic acid sulfonyl hydrazide), N-methyl-
N'-phenyl (salicylic acid sulfonyl hydrazide),
N'-phenethyl- (salicylic acid sulfonyl hydrazide), N-acetyl-N'-phenyl (salicylic acid sulfonyl hydrazide), N'-acetyl-N'-phenyl (salicylic acid sulfonyl hydrazide), N'-butyl-
N'-phenyl (salicylic acid sulfonyl hydrazide),
N-octyl-N'-naphthyl (salicylic acid sulfonyl hydrazide), N-benzyl-N'-phenyl (salicylic acid sulfonyl hydrazide), N'-benzyl (salicylic acid sulfonyl hydrazide), N '-(β-hydroxyethyl) (salicylic sulfonyl) Hydrazide), N'-
(P-Methoxyphenyl) (salicylic acid sulfonyl hydrazide), N '-(2,5-dichlorophenyl)-(salicylic acid sulfonyl hydrazide), N'-naphthyl (salicylic acid sulfonyl hydrazide), 3-methyl-4-hydroxy-5-carboxy Benzenesulfonyl hydrazide, 3-lauryl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-phenyl-3-methyl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-acetyl-4-hydroxy-5
-Carboxybenzenesulfonyl hydrazide, N-methyl-N'-acetyl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-benzoyl-4
-Hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-cinnamoyl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-phenoxyacetyl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N '-(ω-phenyl Butyroyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N '-(o-carboxybenzoyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-(p-carboxybenzoyl)
-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N '-(acetoacetyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide,
N '-(o-benzoylbenzoyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'
-(Terephthaloylbis) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N, N'-bis-4-hydroxy-5-carboxybenzenesulfonyl hydrazine, N '-(p-methoxybenzoyl) -4-
Hydroxy-5-carboxybenzenesulfonyl hydrazide, N '-(p-β-phenoxyethoxybenzoyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-(octanoyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide ,
N '-(pivaloyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-propionyl-N-phenyl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-acetyl-N-phenyl-4-hydroxy -5-carboxybenzenesulfonyl hydrazide, N'-acetyl-N-phenyl-3-
Lauryl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N '-(2-hydroxybenzoyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-(hydroxynaphthoyl) -4
-Hydroxy-5-carboxybenzenesulfonyl hydrazide, 4-hydroxy-5-carboxybenzenesulfonyl semicarbazide, N-phenyl-N'-4-hydroxy-5-carboxybenzenesulfonylaminoureido, N '-(tolylbenzenesulfonyl) -4 -Hydroxy-5-carboxybenzenesulfonyl hydrazide, N '-(benzenesulfonyl) -4-hydroxy-
5-carboxybenzenesulfonyl hydrazide, N'-
Naphthalenesulfonyl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N '-(butanesulfonyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-(β-styrenesulfonyl) -4-hydroxy-5-carboxy Benzenesulfonyl hydrazide, N '-(octanesulfonyl) -4-
Hydroxy-5-carboxybenzenesulfonyl hydrazide, N '-(methanesulfonyl) -4-hydroxy-
5-carboxybenzenesulfonyl hydrazide, N'-
(Hydroxybenzenesulfonyl) -4-hydroxy-
5-carboxybenzenesulfonyl hydrazide, N'-
(Methoxynaphthalenesulfonyl) -4-hydroxy-
5-carboxybenzenesulfonyl hydrazide, N-methyl-N '-(tolylbenzenesulfonyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N-acetyl-N'-(tolylbenzenesulfonyl) -4-hydroxy-5 Carboxybenzenesulfonyl hydrazide, N '-(p-dimethylaminobenzenesulfonyl) -4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-(p-N-methylcarbamoylbenzenesulfonyl) -4-hydroxy-5-
Carboxybenzenesulfonyl hydrazide, N-phenyl-N'-benzenesulfonyl-4-hydroxy-5-
Carboxybenzenesulfonyl hydrazide, N, N'-
Dimethyl-N'-benzenesulfonyl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide, N '
-Benzenesulfonyl-3-α-methylbenzyl-4-
Hydroxy-5-carboxybenzenesulfonyl hydrazide, N'-4-hydroxy-5-carbomethoxybenzenesulfonyl-4-hydroxy-5-carboxybenzenesulfonyl hydrazide.

The salicylic acid derivative and / or its polyvalent metal salt as described above can be used in combination of two or more kinds, if necessary. In the present invention, a salicylic acid derivative and /
The amount of the polyvalent metal salt used is not particularly limited, but is generally adjusted in the range of 5 to 500 parts by weight, preferably 10 to 50 parts by weight with respect to 10 parts by weight of the electron-donating colorless dye. Is desirable.

In the present invention, the electron-accepting compound (coloring agent)
As a salicylic acid derivative represented by the general formula (I) and /
Alternatively, by using a polyvalent metal salt thereof, a recording material excellent in color developability and raw storability, particularly storability of a recorded image is obtained, and by further using a metal compound, these characteristics can be improved. It can be further improved. Examples of such metal compounds include oxides of divalent, trivalent, or tetravalent metals, for example, polyvalent metals selected from zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt, manganese, iron, and the like. , Hydroxide, sulfide,
Halide, carbonate, phosphate, silicate, sulfate,
Examples thereof include nitrates and halogen complex salts, and among these, zinc compounds are particularly preferable.

Specific examples of the metal compound include zinc oxide, zinc hydroxide, zinc aluminate, zinc sulfide, zinc carbonate, zinc phosphate, zinc silicate, aluminum oxide, magnesium oxide, titanium oxide, aluminum hydroxide, Examples thereof include aluminum silicate, aluminum aluminosilicate, aluminum phosphate, magnesium aluminate, magnesium hydroxide, magnesium carbonate, magnesium phosphate and the like. Of course, these metal compounds may be used in combination of two or more kinds.

The amount of the above metal compound used is not necessarily limited, but is usually 1 to 500 parts by weight with respect to 100 parts by weight of the salicylic acid derivative represented by the general formula (I) and / or its polyvalent metal salt. , Preferably 5-300
It is desirable to adjust within the range of about parts by weight. Further, various known electron-accepting compounds may be used in combination within a range that does not impair the desired effects of the present invention. Specific examples of such electron-accepting compounds will be described below.

[0026]

[Chemical 4]

[0027]

[Chemical 5]

[0028]

[Chemical 6]

As the electron-donating colorless dye used in the present invention, conventionally known triphenylmethanephthalide compounds, fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leukoauramine compounds, rhodamine lactams. Various compounds such as a series-based compound, a triphenylmethane-based compound, a triazene-based compound, a spiropyran-based compound, and a fluorene-based compound are known.

Specific examples of the phthalides include US Reissue Patent Specification No. 23024 and US Patent Specification No. 3491111.
No. 3,491,112, No. 3,491,116 and No. 3,509,174, and specific examples of fluoranes are U.S. Pat. Nos. 3,624,107, 3,627,787.
No. 3641011, No. 3462828, No. 3
681390, 3920510, and 3959.
No. 571, specific examples of spiro dipyrans are US Pat. No. 3,971,808, and pyridine-based and pyrazine-based compounds are US Pat. Nos. 3775424, 3853.
No. 869, No. 4264318, and specific examples of the fluorene compound are described in JP-A-63-94878.

Examples thereof will be given below, but the electron-donating colorless dye used in the present invention is not limited to these.

3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p
-Dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole -3-yl)
Phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-
Bis (1,2-dimethylindol-3-yl) -6-
Dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide.

3- (2-ethoxy-4-diethylaminophenyl) -3- (1-normaloctyl-2-methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-Normal octyl-2-methylindol-3-yl) -4-azaphthalide, 3,3-bis (1-normal octyl-2)
-Methylindol-3-yl) phthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylaminophthalide, 3-p-dimethylaminophenyl-
Triarylmethane dyes such as 3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide, 4,
4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leuco auramine, N-
Diphenylmethane dyes such as 2,4,5-trichlorophenylleuco auramine, and thiazine dyes such as benzoyl leuco methylene blue and p-nitrobenzoyl leuco methylene blue.

3-methyl-spiro-dinaphthopyran, 3
-Ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho (6'-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran and other spiro dyes , Rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine (o-chloroanilino) lactam and the like.

2-methoxy-6-diethylaminofluorane, 3-methoxy-6-diethylaminofluorane,
2-t-butyl-6-diethylaminofluorane, 2-
Chloro-6-diethylaminofluorane, 2-chloro-
3-methyl-6-diethylaminofluorane, 2,3-
Dimethyl-6-diethylaminofluorane, 2-methyl-6- (N-ethyl-p-toluidino) fluorane, 2
-N-acetyl-N-methylamino-6-diethylaminofluorane, 2-N-octylamino-6-diethylaminofluorane.

2-dibenzylamino-6-diethylaminofluorane, 2-N-methyl-N-benzylamino-
6-diethylaminofluorane, 2-N-chloroethyl-N-methylamino-6-diethylaminofluorane,
2-N-dioctylamino-6-diethylaminofluorane, 2-anilino-3-methyl-6- (N-ethyl-
p-toluidino) fluorane, 2- (p-toluidino)
-3-Methyl-6- (N-ethyl-p-toluidino) fluorane, 2-anilino-3-methyl-6-diethylaminofluorane.

2-anilino-3-methyl-6-dibutylaminofluorane, 2- (2-carbomethoxy-phenylamino) -6-diethylaminofluorane, 2-anilino-3-methyl-6- (N-ethyl-) N-isoamylamino) fluorane, 2-anilino-3-methyl-6-
(N-cyclohexyl-N-methylamino) aminofluorane, 2-anilino-3-methyl-6-pyrrolidinofluorane, 2-anilino-3-methyl-6-piperidinoaminofluorane, 2- (2 , 4-dimethylanilino)
-3-Methyl-6-diethylanilinofluorane, 2-
(2,6-Dimethylanilino) -3-methyl-6-diethylanilinofluorane.

2- (o-chlorophenylamino) -6-
Diethylaminofluorane, 2- (o-chlorophenylamino) -6-dibutylaminofluorane, 2-anilino-3-methyl-6- (N-ethyl-N-tetrahydrofurfurylamino) fluorane, 2-anilino-3- Methyl-6- (N-methyl-N-n-butylamino) fluorane, 2-anilino-3-methyl-6- (N-ethyl-N-isobutylamino) fluorane, 2-diphenylamino-3-methoxy-6 -Ethyl-Np-tolylaminofluorane, 2-bis-p-tolylamino-3-methoxy-6-ethyl-Np-tolylaminofluorane, 2-bis-p-anisylamino-3-methoxy-6
-Ethyl-N-p-tolylaminofluorane.

2-anilino-3-methyl-6- (N-methyl-Nn-hexylamino) fluorane, 2-anilino-3-methyl-6- (N-ethyl-Nn-hexylamino) fluorane , 2-anilino-3-methyl-6
-(N-ethyl-N-cyclopentylamino) fluorane, 2-anilino-3-methyl-6-N-ethyl-N-
[3- (p-Ethylphenoxy) propyl] aminofluorane, 2-anilino-3-methyl-6-N-propyl-N- [3- (p-methoxyphenoxy) propyl] aminofluorane, 2-anilino- 3-methyl-6-N-
Propyl-N-3-ethoxypropylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-
Fluorane dyes such as 3-ethoxypropylaminofluorane. From the viewpoint of improving the storage stability or adjusting the hue, it is usually preferable to use two or more of them.

The electron-donating colorless dye used in the present invention is, of course, not limited to these dyes. The electron-accepting compound according to the present invention can be used in combination with conventionally known compounds such as phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins and metal complexes.

Examples of these are Japanese Examined Patent Publication Nos. 40-9309 and 45-14039, JP-A-56-140483, 48-51510, 57-210886 and 58.
-87089, 59-11286, 60-76
No. 795, No. 61-95988, etc.

Examples of these are, for example, bisphenol A, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) heptane, 1,1-bis (4- Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)
-2-ethylhexane, 1,1-bis (3-chloro-4)
-Hydroxyphenyl) -2-ethylbutane, bis (3
-Allyl-4-hydroxyphenyl) sulfone, 1,7
-Bis (4-hydroxyphenylthio) -3,5-dioxaheptane, sulfonylanilide salicylate, (4-
Hydroxyphenyl)-(4-isopropoxyphenyl) sulfone, 4-hydroxybenzoic acid benzyl ester, 2,4-dihydroxybenzoic acid-β-phenoxyethyl ester, 2,4-dihydroxybenzoic acid-α-methyl-β- ( 3-methoxyphenoxy) ethyl ester, 1,3-bis (4-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2-phenylpropane, 3,5-bis (α-methylbenzyl) salicylic acid zinc Etc.

When the compound of the present invention is used in a thermal paper, it is disclosed in JP-A-62-114989 and JP-A-1-87729.
It takes the form as described in No. 1 specification. Specifically, the electron-donating colorless dye and the electron-accepting compound are pulverized and dispersed in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less. As the dispersion medium, an aqueous polymer solution having a concentration of about 0.5 to 10% is generally used, and the dispersion is performed using a ball mill, a sand mill, a horizontal sand mill, an attritor, a colloidal mill or the like.

The ratio of the commonly used electron-donating colorless dye to the electron-accepting compound has been described above. At that time, a thermofusible substance may be contained in the thermosensitive coloring layer in order to improve the thermal response. As a heat fusible substance,
Aromatic ethers, thioethers, esters and / or aliphatic amides or ureides are typical examples.

Examples of these are disclosed in JP-A-58-57989,
58-87094, 61-58789, 62.
-109681, 62-2132674, 63-
151478, 63-235961, JP-A-2-
No. 184489 and No. 2-215585.

Examples of heat-fusible substances are phenethyl biphenyl ether, benzyloxynaphthalene, benzyl biphenyl, 1,2-diphenoxyethane, 1,2-
Di-m-tolyloxyethane, 1-phenoxy-2-p
-Methoxyphenoxyethane, 1-p-methoxyphenoxy-2-o-chlorphenoxyethane, 1,2-di-
p-fluorophenoxyethane, 1,3-di-p-methoxyphenoxypropane, 1,2-di-p-methoxyphenoxypropane, 1-phenoxy-2-p-methoxyphenoxypropane, 1-p-methoxyphenoxyethoxy- 2-p-methoxyphenoxyethane, 1,2-di-p-methoxyphenylthioethane, p-methoxybenzyloxytolylmethane, (4-methoxybenzyloxy)-(3-methyl-4-chlorophenyl) methane, p
-Chlorobenzyloxy-p-ethoxyphenylmethane and the like.

These are used at the same time as the electron-donating colorless dye or at the same time as being finely dispersed at the same time as the electron-accepting compound. The amount of these used is 20% or more with respect to the electron accepting compound and 30
It is added in a weight ratio of 0% or less, especially 40% or more and 150%
The following are preferred. If necessary, additives are added to the coating liquid thus obtained in order to meet various requirements. As an example of the additive, an oil-absorbing substance such as an inorganic pigment or polyurea filler is dispersed in a binder in order to prevent the recording head from being soiled during recording, which further enhances the releasability of the head. For fatty acids,
Metal soap or the like is added. Therefore, in general, in addition to electron-donating colorless dyes and electron-donating compounds that directly contribute to color development, heat-fusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers, defoamers, conductive agents, fluorescent dyes, An additive such as a surfactant is coated on the support to form the recording material.

If necessary, a protective layer may be provided on the surface of the heat-sensitive recording layer. Two or more protective layers may be laminated if necessary. In addition, in order to correct the curl balance of the support or to improve the chemical resistance from the back side,
You may apply the coating liquid similar to a protective layer on the back surface. An adhesive may be applied to the back surface, and release paper may be further combined to form a label. These are already well known in the art.

Usually, the electron-donating colorless dye and the electron-accepting compound are dispersed and applied in a binder. Water-soluble binders are generally used, and polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride. Examples thereof include acid copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, gelatin and the like. Also, for the purpose of imparting water resistance to these binders, adding a water resistance agent,
A hydrophobic polymer emulsion, specifically, styrene-butadiene rubber latex, acrylic resin emulsion, vinylidene chloride latex, or the like can be added.

The obtained heat-sensitive coating liquid is applied to high-quality paper, high-quality paper having an undercoat layer, synthetic paper, plastic film and the like. At this time, it is particularly preferable from the viewpoint of dot reproducibility to use a support having a smoothness of 500 seconds or more, particularly 800 seconds or more as defined by JIS-8119. As the pigment for the case where the undercoat layer containing a pigment as a main component is provided on the support, all the general organic or inorganic pigments can be used, but in particular,
Oil absorption specified by JIS-K5101 is 40cc / 10
It is preferably 0 g or more, and specifically calcium carbonate, barium sulfate, titanium oxide, talc, wax stone, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, urea formalin resin powder, polyethylene resin powder and the like. Can be mentioned.

When these pigments are coated on the support, the above-mentioned heat-fusible agent can be used together. The amount of pigment is 2 g / m ² or more, preferably 8 g / m ² or less.

As the binder used in the undercoat layer,
Examples thereof include water-soluble polymers and water-soluble binders, and the binders may be used alone or in combination of two or more. As the water-soluble polymer, methyl cellulose, carboxymethyl cellulose, hydroxytyl cellulose, starches, gelatin, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, Examples thereof include polyvinyl alcohol and polyacrylamide.

As the water-soluble binder, synthetic rubber latex or synthetic resin emulsion is generally used.
Examples thereof include styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion. The amount of binder used is 3 for pigments.
-100% by weight, preferably 5-50% by weight. Wax, decoloring inhibitor, surfactant, etc. may be added to the undercoat layer. When adding a heat-fusible agent, 1-5 g /
About m ² is preferable.

Examples of pigments used as additives in the recording material of the present invention include kaolin, calcined kaolin, talc, wax, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, lithopone, and amorphous. Silica, colloidal silica, calcined stone, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate,
Examples thereof include barium sulfate, mica, microballoons, synthetic aluminum silicate, urea-formalin filler, polyester particles, and cellulose filler.

Examples of the metal soap include higher fatty acid polyvalent metal salts such as zinc stearate, aluminum stearate, calcium stearate and zinc oleate. Further, in the present invention, it is preferable to use a wax having a melting point of 40 to 120 ° C. together from the viewpoint of the head matching property with respect to the facsimile. The wax having a melting point of 40 to 120 ° C. is preferably paraffin wax, polyethylene wax, carnauba wax, microcrystalline wax, candelia wax, montan wax, and fatty acid amide wax, and particularly, paraffin having a melting point of 50 to 100 ° C. Wax, montan wax and methylol stearamide are preferred.

The wax is used in an amount of 5 to 200% by weight, preferably 20 to 150% by weight of the electron-donating colorless dye.
Is.

As the hindered phenol compound, a phenol derivative in which one or more of at least 2-position or 6-position is substituted with a branched alkyl group is preferable. UV absorbers include cinnamic acid derivatives, benzophenone derivatives,
Benzotriazole phenol derivatives and the like, for example, butyl α-cyano-β-phenylcinnamate, o-benzotriazole phenol, o-benzotriazole-p-chlorophenol, o-benzotriazole-2,4-di-te.
rt-butylphenol, o-benzotriazolyl-
2,4-di-tert-octylphenol and the like.

As the waterproofing agent, N-methylol urea,
Water-soluble initial condensates such as N-methylol melamine and urea-formalin, dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic crosslinking agents such as boric acid and borax,
Examples include blend heat treatment of polyacrylic acid, methyl vinyl ether-maleic acid copolymer, isobutylene-maleic anhydride copolymer, and the like.

Materials used for the protective layer include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, gelatins, gum arabic. , Casein, styrene-
Maleic acid copolymer hydrolyzate, styrene-maleic acid copolymer half ester hydrolyzate, isobutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivative, polyvinylpyrrolidone, sodium polystyrene sulfonate, sodium alginate, etc. Water-soluble polymers and water-insoluble polymers such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex and vinyl acetate emulsion are used.

Further, for the purpose of improving the matching property with the thermal head, a pigment, a metal soap, a wax, a waterproofing agent and the like may be added to the protective layer. Further, when the protective layer is coated on the thermosensitive coloring layer, a surfactant may be added to obtain a uniform protective layer. As the surfactant, a sulfosuccinic acid-based alkali metal salt or a fluorine-containing surfactant is used. Specifically, sodium salts such as di- (n-hexyl) sulfosuccinic acid and di- (2-ethylhexyl) sulfosuccinic acid, or ammonium salts are preferable, but anionic surfactants are effective.

When used for pressure-sensitive paper, US Pat.
No. 05470, No. 25054571, No. 250548
No. 9, No. 2548366, No. 2712507, No. 2
No. 730456, No. 2730457, No. 310340
It can take various forms as described in prior patents such as No. 4, No. 3418250 and No. 4010038. Most commonly it consists of at least a pair of sheets containing separately an electron donating colorless dye and an electron accepting compound.

Regarding the method for producing capsules, US Pat.
Nos. 800457 and 2800458, methods utilizing coacervation of hydrophilic colloid sol, British Patents 867797, 950443 and 9
There are methods described in 89264 and 1091076.

Generally, an electron-donating colorless dye is used alone or in a mixture, and a synthetic oil such as a solvent (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, chlorinated paraffin, etc .; cotton oil,
A coloring agent sheet by dissolving it in vegetable oil such as castor oil; animal oil; mineral oil or a mixed oil thereof, including it in microcapsules, and coating it on paper, high-quality paper, plastic sheet, resin coated paper, etc. To get

Further, the electron-accepting compound and, if necessary, the additives are singly or mixed and dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and together with the pigment, paper, plastic sheet, resin coated paper, etc. A color developer sheet is obtained by applying it to the support.

As the binder, it is preferable to use a carboxy-modified styrene-butadiene latex in combination with a water-soluble polymer from the viewpoint of light resistance and water resistance. Further, as the pigment, it is preferable to use calcium carbonate having an average particle diameter of 5.0 μm or less in an amount of 60% by weight or more based on all pigments from the viewpoint of color developing ability.

The use amount of the electron-donating colorless dye and the electron-accepting compound depends on the desired coating thickness, the form of the pressure-sensitive recording paper, the capsule manufacturing method, and other conditions, and may be appropriately selected according to the conditions. A person skilled in the art can easily determine this usage amount.

[0067]

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

Examples 1 to 4 2-anilino-3-methyl- which is an electron-donating colorless dye
6-N-methyl-N-n-butylaminofluorane, compounds used in Examples 1 to 4 below, which are electron accepting compounds, zinc oxide, and 2-naphthylbenzyl ether which is a heat-fusible compound. 20g of each 5% of 100g
Disperse with a polyvinyl alcohol (Kuraray PVA105) aqueous solution overnight in a ball mill to obtain a volume average particle size of 2 μm.
And On the other hand, calcined kaolin (Anisilex-93)
80 g of a 0.5% solution of sodium hexametaphosphate 160
It was dispersed with a homogenizer together with g.

Example 1. N'-cinnamoyl-N- (4
-Hydroxy-5-carboxybenzenesulfonyl) hydrazine Example 2. N'-toluenesulfonyl-N- (4-hydroxy-5-carboxybenzenesulfonyl) hydrazine Example 3. N'-anilinocarbonyl-N- (4-hydroxy-5-carboxybenzenesulfonyl) hydrazine Example 4. A 1: 1 mixture of the compound of Example 1 and 4-β-methoxyphenoxyethoxysalicylic acid.

Dispersing as described above, each dispersion was prepared by dispersing 5 g of an electron-donating colorless dye dispersion and 20 g of an electron-accepting compound dispersion.
A mixture of 10 g of 2-naphthylbenzyl ether dispersion and 22 g of calcined kaolin dispersion was added, and 4 g of zinc stearate emulsion and 5 g of an aqueous solution of 2% (2-ethylhexyl) sodium sulfosuccinate were added to obtain a coating liquid. . This coating liquid, dry coating amount wood free paper weighing 50 g / m ² was coated with a wire bar such that the 6 g / m ^2, to obtain a coated paper subjected to calendering treatment.

The coated paper obtained as described above was used as a thermal head (KLT-216-8MPD manufactured by Kyocera Corp.).
1) and with a thermal printing experimental device having a pressure roll of 100 kg / cm ² immediately before the head, a head voltage of 24
While using a pressure roll under the conditions of V and a pulse cycle of 10 ms, printing was performed with a pulse width of 1.0, and the print density was measured with a Macbeth reflection densitometer RD-918. The color density of each example was good as follows.

[0072]

Further, the image portion colored black with a fluorescent pen or the like was not erased, and the non-image portion on a white background was not fogged by the solvent. Also, the non-image area was marked with red magic ink, but the red color did not change.

[0074]

The recording material of the present invention has a storage stability (weather resistance, chemical resistance, plasticizer resistance) of the non-image area and the image area,
Good color density and color sensitivity.

Claims (2)

[Claims] 1. A recording material using an electron-donating colorless dye and an electron-accepting compound, containing at least one of a salicylic acid derivative represented by the following general formula (1) or a polyvalent metal salt thereof as an electron-accepting compound. A recording material characterized by: General formula (1) In the formula, X represents a hydrogen atom, a hydroxy group, a nitro group, a cyano group, a halogen atom, a carboxyl group or a sulfo group,
Further, it represents an alkyl group, an aryl group, an alkenyl group, an acyl group, a sulfoalkoxy group, an aryloxy group, an allyl group, an aralkyl group, an alkoxycarbonyl group or a substitution product thereof, and R ₁ and R ₂ may be the same or different. Often represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an aralkyl group, an aryloxyalkyl group or a substituted product thereof, and R ₃ is a hydrogen atom, an acyl group or an alkyl group. It represents a sulfonyl group, an arylsulfonyl group, a carbamoyl group, a thiocarbamoyl group or a substitution product thereof. 2. As the electron-accepting compound, at least one of the salicylic acid derivative represented by the general formula (1) or a polyvalent metal salt thereof and a polyvalent metal oxide, a polyvalent metal hydroxide or a polyvalent metal salt. The recording material according to claim 1, further comprising a metal carbonate.