JP3446663B2 - Thermal recording medium - Google Patents

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 which is excellent in color developability, image storability and blank sheet stability.

[0002]

2. Description of the Related Art In general, a heat-sensitive recording material is prepared by grinding and dispersing a colorless or light-colored dye precursor, which is an electron-donating compound, and a developer, which is an electron-accepting compound, into fine particles. , Binder, filler, sensitizer,
A coating solution obtained by adding lubricants and other auxiliaries is applied to a support such as paper, synthetic paper, film, plastic, etc., and color is developed by an instant chemical reaction by heating with a thermal head, hot stamp, laser light, etc. Get the record. These thermosensitive recording media are applied to a wide range of fields such as measurement recorders, computer terminal printers, facsimiles, automatic ticket vending machines, and bar code labels. In recent years, high-speed printing and high-speed image formation have become possible with the diversification of recording devices and the development of higher performance, and higher quality is required for the recording sensitivity and storability of thermal recording media. ing.

As a method for satisfying this demand, it has been proposed to use a sensitizer in addition to a dye and a color developer. For example, when the developer is a phenolic compound represented by bisphenol A, p-benzylbiphenyl (JP-A-60-82382) and p-benzyloxybenzoate benzyl (JP-A-57-201691). , Benzylnaphthyl ether (JP-A-58-87094) and the like are used as the optimum sensitizer. When a sensitizer is used, the sensitizer first melts when heated, and it dissolves the dye and developer to mix them and induce a color reaction at the molecular level. It is important to consider agents and dyes and developers.

In JP-B-04-38599, a sensitizer aromatic ether is added to a developer 4-hydroxy-4'-methyldiphenyl sulfone, and JP-B-03-69318.
In the publication, a thermal recording material is proposed in which a sensitizer naphthalene 1,4 substituted derivative is combined. With these combinations, although the color development sensitivity is good when the applied energy is high, the applied energy is low or the speed is high. In the case of printing with (1), a sufficient color density was not obtained, and it was insufficient for practical use in a device that requires them. Further, when the color development sensitivity is usually improved by the addition of a sensitizer, there is a problem that the heat resistance of the white paper part is deteriorated.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a thermosensitive recording medium which has high color development sensitivity even with low applied energy, and has improved image storability in a printed portion and ground color stability (moisture resistance, heat resistance) in a blank portion. Is to provide.

[0006]

The present invention provides an aminosulfonyl group (-) represented by the following general formula (1) as a developer and a sensitizer represented by the following general formula (2) in a thermosensitive color developing layer.
The present invention provides a heat-sensitive recording material containing an aromatic compound having SO ₂ NH ₂ ).

[0007]

[Chemical 3]

[0008]

[Chemical 4]

[0009] (wherein, ^{R 1} represents a hydrogen atom, a methyl group, indicates to the chlorine atom.)

In the present invention, at least one kind of compound represented by the general formula (1) is used as a color developer. When R ¹ is a methyl group, the heat resistance of the blank area is good, and when it is a hydrogen atom, the color development sensitivity is high, which is preferable. From the viewpoint of storage stability, R ¹ is preferably in the p position with respect to the sulfone group.

In the present invention, Ru using at least one compound represented by the general formula (2) as a sensitizer.

[0012] Formula (2) Specific examples of the compound represented by the below (2 2) - (2-4) is exemplified <br/> is Ru. Above all, (2-2) or (2-4) is preferably used since the effect when the compound (1) is used as a color developer is good.

[0013]

[Chemical 5]

[0014]

[0015]

[0016]

In the present invention, the content of the sensitizer represented by the general formula (2) is the developer represented by the general formula (1).
If the amount is less than 0.01 part with respect to 1 part, the sensitizing effect is not sufficient, and if the amount is more than 5 parts with respect to 1 part of the color developer, sufficient color density cannot be obtained. Therefore, the general formula (2)
It is desirable to use the sensitizer represented by the above in a ratio of 0.01 to 5 parts with respect to 1 part of the developer represented by the general formula (1). More preferably, it is desirable to use it in a ratio of 0.01 to 2 parts.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION To manufacture the thermosensitive recording medium of the present invention, various conventionally known manufacturing methods can be used. Specifically, it can be manufactured by the following method. That is, the developer, the dye precursor, and the sensitizer are atomized by a pulverizer or an emulsifier such as a ball mill, an attritor, and a sand grinder, and various fillers and various additives are added and dispersed in an aqueous solution of a water-soluble binder. As a paint, and use this as an air knife coater, blade coater,
A thermosensitive recording medium can be obtained by coating on an arbitrary support with various coaters such as a roll coater.

The heat-sensitive recording method utilizing the color-forming reaction between the electron-donating compound and the electron-accepting compound in the present invention includes, for example, a combination of a dye precursor and a developer, a combination of a diazonium salt and a coupler, iron and the like. Examples of the combination of a transition element and a chelate compound, a combination of an aromatic isocyanate compound and an imino compound, and the like, the combination of a dye precursor and a developer is excellent in color density and recording sensitivity. The heat-sensitive recording material utilizing the coloring reaction between the dye precursor and the color developer will be described in detail.

Various known compounds can be used as the dye precursor used in the present invention. These may be used alone or in admixture of two or more, and are selected depending on the intended use and required characteristics. Specific examples include the following compounds, but the invention is not limited thereto.

(1) Triarylmethane compound 3,3'-bis (4-dimethylaminophenyl) -6-
Dimethylaminophthalide <Product Name: Crystal Violet Lactone, CVL>, 3- (4-Dimethylamino-
2-Methylphenyl) -3- (4-dimethylaminophenyl) phthalide, 3,3'-bis (2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl) -4,5,6 , 7-Tetrachlorophthalide <NI
R-Black>, 3,3′-bis (4-dimethylaminophenyl) phthalide <MGL>, 3- (4-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3 -(4-Dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3'-bis (4-ethylcarbazole-3)
-Yl) -3-dimethylaminophthalide, 3,3'-bis (1-ethyl-2-methylindol-3-yl) phthalide <indolyl red>, 3,3'-bis (2-phenylindole- 3-yl) -5-dimethylaminophthalide, tris (4-dimethylaminophenyl) methane <LCV> and the like can be mentioned. (2) Diphenylmethane compound 4,4-bis (dimethylamino) benzhydrin benzyl ether, N-halophenyl-leuco auramine, N
-2,4,5-trichlorophenyl leuco auramine etc. are mentioned. (3) Xanthene compound Rhodamine B-anilinolactam, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-butylaminofluorane, 3-diethylamino-7-anilinofluorane <Green-2 >, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-dibutylamino-7- (2-chloroanilino)
Fluoran <TH-107>, 3-diethylamino-7
-(3-trifluoromethylanilino) fluorane <B
rack-100>, 3-diethylamino-6-methyl-7-anilinofluorane <ODB>, 3-dibutylamino-6-methyl-7-anilinofluorane <ODB-.
2>, 3-piperidino-6-methyl-7-anilinofluorane, 3- (N-isoamyl-N-ethylamino)-
6-methyl-7-anilinofluorane <S-205>,
3- (N-ethyl-N-tolylamino) -6-methyl-
7-anilinofluorane, 3- (N-cyclohexyl-
N-methylamino) -6-methyl-7-anilinofluorane <PSD-150>, 3-diethylamino-6-chloro-7- (β-ethoxyethylamino) fluorane,
3-diethylamino-6-chloro-7- (γ-chloropropylamino) fluorane, 3-cyclohexylamino-6-chlorofluorane <OR-55>, 3-diethylamino-6-chloro-7-anilinofluorane, 3-
(N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7
-Phenylfluorane and the like. (4) Thiazine-based compounds such as benzoyl leuco methylene blue and p-nitrobenzoyl leuco methylene blue. (5) Spiro compound 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3-benzylspirodinaphthopyran, 3
-Methylnaphtho- (6'-methoxybenzo) spiropyran and the like can be mentioned. (6) Pentadiene compound 1,1,5,5-tetrakis (4-dimethylaminophenyl) -3-methoxy-1,4-pentadiene, 1,
1,5,5-tetrakis (4-dimethylaminophenyl) -1,4-pentadiene and the like can be mentioned.

In the present invention, the developer represented by the general formula (1) may be used alone or in combination with one or more known developers which have been conventionally used. Examples of the developer that can be used in the present invention include 2,2-bis (4-hydroxyphenyl) propane, 1,7-di (4-hydroxyphenylthio) -3,5-dioxaheptane, 4,4′- Bisphenols such as cyclohexylidene diphenol, 4-
Benzyl hydroxybenzoate, ethyl 4-hydroxybenzoate, normal propyl 4-hydroxybenzoate, 4
-Isopropyl hydroxybenzoate, 4-hydroxybenzoic acid esters such as butyl 4-hydroxybenzoate, dimethyl 4-hydroxyphthalate, diisopropyl 4-hydroxyphthalate, dibenzyl 4-hydroxyphthalate, dihexyl 4-hydroxyphthalate, etc. 4-
Phthalic acid monoesters such as hydroxyphthalic acid diesters, phthalic acid monobenzyl ester, phthalic acid monocyclohexyl ester, phthalic acid monophenyl ester, and phthalic acid monomethylphenyl ester, bis (4
-Hydroxy-3-tert-butyl-6-methylphenyl) sulfide, bis (4-hydroxy-2,5-dimethylphenyl) sulfide, bis (4-hydroxy-)
Bishydroxyphenyl sulfides such as 2-methyl-5-ethylphenyl) sulfide, 4-hydroxy-
4-hydroxyphenyl aryl sulfones such as 4'-isopropoxydiphenyl sulfone and 4-hydroxy-4'-normal propoxydiphenyl sulfone, 4-
4 such as hydroxyphenylbenzenesulfonate, 4-hydroxyphenyl-p-tolylsulfonate, 4-hydroxyphenyl-p-chlorobenzenesulfonate
-Hydroxyphenyl aryl sulfonates, 1,3
-Di [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,3-di [2- (4-hydroxy-3)
1,3-di [2- (hydroxyphenyl) -2-propyl] benzenes such as -methylphenyl) -2-propyl] benzene, benzyl 4-hydroxybenzoyloxybenzoate, methyl 4-hydroxybenzoyloxybenzoate, 4-hydroxybenzoyloxybenzoic acid esters such as ethyl 4-hydroxybenzoyloxybenzoate, normal propyl 4-hydroxybenzoyloxybenzoate, isopropyl 4-hydroxybenzoyloxybenzoate and butyl 4-hydroxybenzoyloxybenzoate, bis ( 3-tert-butyl-4-hydroxy-6-methylphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone, bis (3-
Propyl-4-hydroxyphenyl) sulfone, bis (3-isopropyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, 2-
Bishydroxyphenylsulfones such as hydroxyphenyl-4′-hydroxyphenylsulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (3-bromo-4-hydroxyphenyl) sulfone, p-
Phenols such as tert-butylphenol, p-phenylphenol, p-benzylphenol, 1-naphthol, 2-naphthol, benzoic acid, p-tert
-Butylbenzoic acid, trichlorobenzoic acid, 3-sec-
Aromatic such as butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, terephthalic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert-butylsalicylic acid Examples thereof include metal salts of carboxylic acids.

In the present invention, the sensitizer represented by the general formula (2) and one or more known sensitizers conventionally used can be used in combination. Specific examples thereof will be shown below, but the present invention is not limited thereto. Stearic acid amide, palmitic acid amide, methoxycarbonyl-N-stearic acid benzamide, N-benzoylstearic acid amide, N-eicosanoic acid amide, ethylenebisstearamide, ethylenebisstearic acid amide, behenic acid amide, methylenebisstearic acid Amide, methylolamide, N-methylolstearic acid amide, dibenzyl terephthalate, dimethyl terephthalate, dioctyl terephthalate, benzyl p-benzyloxybenzoate, phenyl 1-hydroxy-2-naphthoate, dibenzyl oxalate, oxalic acid-diester -P-methylbenzyl, oxalic acid-di-p-chlorobenzyl, 2-naphthylbenzyl ether, m-terphenyl, p-benzylbiphenyl, tolylbiphenyl ether, di (p-methoxyphenoxy) Ethyl) ether, 1,2-di (3-
Methylphenoxy) ethane, 1,2-di (4-methylphenoxy) ethane, 1,2-di (4-methoxyphenoxy) ethane, 1,2-di (4-chlorophenoxy) ethane, 1,2-diphenoxy Ethane, 1- (4-methoxyphenoxy) -2- (2-methylphenoxy) ethane,
p-methylthiophenylbenzyl ether, 1,4-di (phenylthio) butane, p-acetotoluidide, p-
Examples include acetophenetide, N-acetoacetyl-p-toluidine, di (-biphenylethoxy) benzene, p-di (vinyloxyethoxy) benzene, 1-isopropylphenyl-2-phenylethane and the like.

Further, the heat-sensitive recording material of the present invention may contain a storage stabilizer for stabilizing the storage. Specific examples of the storage stabilizer include 1,1,3-tris (2
-Methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-)
Hydroxy-5-cyclohexylphenyl) butane,
4,4'-butylidene bis (2-tert-butyl-5)
-Methylphenol), 4,4'-thiobis (2-te
hindered such as rt-butyl-5-methylphenol), 2,2′-thiobis (6-tert-butyl-4-methylphenol), 2,2′-methylenebis (6-tert-butyl-4-methylphenol) Phenol compound, 4-benzyloxy-4 ′-(2-methylglycidyloxy) diphenyl sulfone, sodium 2,
2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and the like can be mentioned. These storage stabilizers are usually used in an amount of 0.1 to 10 parts by weight per 1 part by weight of the dye precursor. .

Specific examples of the binder used in each layer in the thermosensitive recording medium of the present invention include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, carboxy modified polyvinyl alcohol, and aceto. Acetyl group modified polyvinyl alcohol, silicon modified polyvinyl alcohol, isobutylene-
Water-soluble binder such as alkali salt of maleic anhydride copolymer, alkali salt of styrene-maleic anhydride copolymer, alkali salt of ethylene-maleic anhydride copolymer, alkali salt of styrene-acrylic acid copolymer, styrene-butadiene copolymer Examples thereof include latexes such as polymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers, water-dispersible binders such as urea resins, melamine resins, amide resins and polyurethane resins. At least one kind of these binders is used in the range of 15 to 80% by weight based on the total solid amount of the thermosensitive recording layer, the protective layer, the intermediate layer or the underlayer.

As the filler, activated clay, clay,
Calcined clay, diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, barium carbonate, titanium oxide, zinc oxide, silicon oxide, inorganic filler such as aluminum hydroxide, urea-formalin resin, polystyrene resin, phenol resin, An organic filler such as a bowl-shaped styrene-butadiene rubber resin is used.

In addition, a heat fusible substance may be added for the purpose of preventing head wear and sticking.
Examples thereof include animal waxes such as beeswax and shellac wax, vegetable waxes such as carnauba wax, mineral waxes such as montan wax, petroleum waxes such as microcrystalline wax, higher fatty acid polyhydric alcohol ester, and stearin. Higher fatty acid amide such as acid amide, higher fatty acid metal salt such as zinc stearate, calcium stearate, higher amine, condensate of fatty acid and amine, condensate of aromatic and amine, synthetic paraffin, chlorinated paraffin, oxidized paraffin, higher grade Examples thereof include straight-chain glycols, dialkyl 3,4-epoxyhexahydrophthalates, synthetic waxes such as polyethylene and polyethylene oxide.

Further, a dispersant such as sodium dioctylsulfosuccinate, an ultraviolet absorber such as a benzophenone type or a triazole type, a surfactant, a defoaming agent, a fluorescent brightening agent, a water resistant agent, a lubricant, an antioxidant and the like are desired. It is used according to.

Papers such as high-quality papers, medium-quality papers, coated papers and recycled papers are mainly used as the support in the thermosensitive recording medium of the present invention, but various non-woven fabrics, plastic films, synthetic papers, metal foils, etc. Alternatively, a composite sheet in which these are combined is optionally used.

The thermosensitive recording medium of the present invention can be manufactured by a conventionally known method using the various materials as described above. The method for preparing the coating liquid for each layer of the thermosensitive recording medium is not particularly limited, and generally, water is used as a dispersion medium, and a binder, a filler added as necessary, a lubricant, etc. are mixed and stirred. In the case of a heat-sensitive recording layer, a dye precursor and a color developer are added for adjustment.

The dye precursor and the developer are separately pulverized and dispersed in an aqueous system by a sand grinder, an attritor, a ball mill or the like, and then mixed to obtain an aqueous coating composition, or the dye precursor and the developer. A method of obtaining an aqueous paint after microencapsulating one of the agents is known. The use ratio of the dye precursor and the developer is appropriately selected according to the type of the dye precursor and the developer to be used and is not particularly limited, but is generally 0.5 with respect to 1 part by weight of the dye precursor. -50 parts by weight, preferably 2
About 10 parts by weight of the developer is used.

The method for forming each layer of the thermosensitive recording medium is not particularly limited, and air knife coating, varibar blade coating, pure blade coating,
Rod blade coating, short dwell coating, curtain coating, die coating, etc. can be appropriately selected. For example, after coating the support for the thermal recording layer coating liquid and drying, further coating the protective layer coating liquid with the thermal recording layer. It is formed by a method such as coating and drying on top. The coating amount of the thermal recording layer coating liquid is 2 to 12 g as a dry weight.
/ M ² , preferably about 3 to 10 g / m ² , and the coating amount of the coating liquid for the intermediate layer or the protective layer is 0.1 to 15 by dry weight.
g / m ² approximately, it is preferably adjusted in the range of about 0.5~7g / m ^2.

The heat-sensitive recording material of the present invention may be provided with a back coat layer on the back surface side of the support, if necessary, to further improve the storage stability. Furthermore, after each layer is formed, it is subjected to smoothing treatment such as super calendering, or the back surface of the thermosensitive recording material is treated with an adhesive to process it into an adhesive label, a magnetic thermosensitive recording layer, a coating layer for printing, and a thermal transfer thermosensitive material. Various known techniques in the field of producing a thermosensitive recording medium, such as providing a recording layer, can be added depending on the application.

[0034]

EXAMPLES The present invention will be described in detail below with reference to specific examples. However, the present invention is not limited to this embodiment. In addition, "part" and "%" in an example show "weight part" and "weight%", respectively, unless there is particular notice.

-Production of Thermosensitive Recording Material- [Example 1] The thermosensitive recording material of the present invention has a color developer of 4-
Hydroxy-4′-methyldiphenyl sulfone, 3-dibutylamino-6-methyl-7-anilinofluorane <ODB-2> as a dye precursor, and compound (2-4) as a sensitizer. . First, a dye dispersion (solution A), a developer dispersion (solution B), and a sensitizer dispersion (solution C) having the following formulations were each made to have an average particle diameter of 1 μm using a sand grinder.
It was ground to m. (Liquid A: Dye dispersion) 3-dibutylamino-6-methyl-7-anilinofluorane 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts (solution B: developer dispersion) ) 4-Hydroxy-4'-methyldiphenyl sulfone 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts (C liquid: sensitizer dispersion) compound (2-4) 6.0 parts 10 % Polyvinyl alcohol aqueous solution 18.8 parts Water 11.2 parts Next, the dispersions of A liquid, B liquid, C liquid and kaolin clay were mixed at the following ratios to prepare a heat-sensitive paint. A liquid: Dye dispersion 9.2 parts B liquid: Developer dispersion 36.0 parts C liquid: Sensitizer dispersant 36.0 parts Kaolin clay (50% dispersion) 12.0 parts This heat-sensitive paint Coating amount on one side of 50 g / m ² base paper 4.
The sheet was coated and dried so as to have a weight of 0 to 4.5 g / m ² , and this sheet was processed with a super calender so that the smoothness was 500 to 600 seconds to prepare a heat sensitive recording material.

Example 2 As the sensitizer for the liquid C in Example 1, the compound (2-2) was used instead of the compound (2-4).
A thermosensitive recording medium was prepared in the same manner as in Example 1 except that was used.

Example 3 In Example 3, as a sensitizer,
It is an example using the compound (2-2) and the compound (2-4). Similar to Example 1, 4-hydroxy-4′-methyldiphenyl sulfone developer dispersion, <ODB-2
> Dispersion, compound (2-2) and compound (2-4) sensitizer dispersion. Next, the dispersions were mixed and stirred at the following ratios to prepare a heat-sensitive paint. Solution A: Dye dispersion 9.2 parts Solution B: Developer dispersion 36.0 parts Solution C: sensitizer [compound (2-4)] Dispersant 14.4 parts Solution D: sensitizer [compound (2-2)] Dispersant 21.6 parts Kaolin clay (50% dispersion liquid) 12.0 parts

[Example 4] The same procedure as in Example 1 was repeated except that 4-hydroxydiphenylsulfone was used in place of 4-hydroxy-4'-methyldiphenylsulfone as the developer for the liquid B in Example 1. A thermosensitive recording medium was prepared.

[Embodiment 5] As a developer for the solution B in Embodiment 1, 4-hydroxydiphenylsulfone was used in place of 4-hydroxy-4'-methyldiphenylsulfone, and C was used.
A thermosensitive recording medium was prepared in the same manner as in Example 1 except that the compound (2-2) was used in place of the compound (2-4) as the liquid sensitizer.

Example 6 In Example 6, 4 was used as a color developer.
In this example, compound (2-2) and compound (2-4) were used as a sensitizer with -hydroxydiphenyl sulfone. In the same manner as in Example 1, the developer dispersion of 4-hydroxydiphenyl sulfone, the dispersion of <ODB-2>, and the sensitizer dispersion of compound (2-2) and compound (2-4) were treated. . Next, the dispersions were mixed and stirred at the following ratios to prepare a heat-sensitive paint. Solution A: Dye dispersion 9.2 parts Solution B: Developer dispersion 36.0 parts Solution C: sensitizer [compound (2-4)] Dispersant 14.4 parts Solution D: sensitizer [compound (2-2)] Dispersant 21.6 parts Kaolin clay (50% dispersion liquid) 12.0 parts

Example 7 Example 4 was repeated except that 4-chloro-4′-hydroxydiphenylsulfone was used in place of 4-hydroxy-4′-methyldiphenylsulfone as the developer for the liquid B in Example 1. A thermosensitive recording medium was prepared in the same manner as in 1.

[Example 8] 4-chloro-4'-hydroxydiphenylsulfone was used in place of 4-hydroxy-4'-methyldiphenylsulfone as the developer of solution B in Example 1, and the sensitizer of solution C was used. As a thermal recording material, the same procedure as in Example 1 was carried out except that the compound (2-2) was used in place of the compound (2-4).

[Embodiment 9] In Embodiment 6, as a developer,
This is an example in which compound (2-2) and compound (2-4) were used as -sensitizer with -chloro-4'-hydroxydiphenyl sulfone. In the same manner as in Example 1, 4-chloro-
4'-hydroxydiphenyl sulfone color developer dispersion,
The dispersion of <ODB-2>, the sensitizer dispersion of the compound (2-2) and the compound (2-4) were treated. Next, the dispersions were mixed and stirred at the following ratios to prepare a heat-sensitive paint. Solution A: Dye dispersion 9.2 parts Solution B: Developer dispersion 36.0 parts Solution C: sensitizer [compound (2-4)] Dispersant 14.4 parts Solution D: sensitizer [compound (2-2)] Dispersant 21.6 parts Kaolin clay (50% dispersion liquid) 12.0 parts

[Comparative Example 1] Example 1 was repeated except that ethylene bis stearamide <armowax> was used in place of the compound (2-4) in the sensitizer dispersion liquid (C liquid) in Example 1. A thermosensitive recording medium was prepared in the same manner as in.

Comparative Example 2 Example 4 was repeated except that ethylene bisstearamide <armowax> was used in place of the compound (2-4) in the sensitizer dispersion liquid (C liquid) of Example 4. A thermosensitive recording medium was prepared in the same manner as in.

[Comparative Example 3] Example 7 was repeated except that ethylene bis stearamide <armowax> was used in place of the compound (2-4) in the sensitizer dispersion liquid (C liquid) in Example 7. A thermosensitive recording medium was prepared in the same manner as in.

-Evaluation of Thermal Recording Material- [Coloring Method] The thermal recording material produced was used as TH manufactured by Okura Electric Co., Ltd.
Recording was performed on the prepared thermal recording medium using a PMD (a thermal recording paper printing tester, equipped with a thermal head manufactured by Kyocera Corp.) with an applied energy of 0.25 and 0.33 mj / dot. Then, the image densities of the recorded portion and the blank portion were measured with a Macbeth densitometer (RD-914, using an amber filter). Using this as a test sample, the following tests were conducted.

[Moisture resistance test]: Applied energy 0.33
Humidity 90% RH for test sample printed in mj / dot
After leaving at -40 ° C. for 24 hours, the densities of the printed area and the blank area were measured with a Macbeth densitometer.

[Heat resistance test]: Applied energy 0.33
The test sample printed with mj / dot was left at 60 ° C. for 24 hours, and the densities of the printed part and the blank part were measured with a Macbeth densitometer.

The results of the color development and storage stability tests are shown in Table 1 and Table 2, respectively. A larger value in the printed part indicates a better image storability, and a smaller value in a blank part indicates a better ground color stability.

[0051]

[Table 1] Table 1. Results of color development test

Note) The values in Table 1 represent (Macbeth value of printed area) / (Macbeth value of blank area). Table 2 is the same.

[0053]

[Table 2] Table 2. Results of image storability test

As is clear from the above results, Examples 1 to 3 using 4-hydroxy-4'-methyldiphenyl sulfone as the color developer and the compound represented by the general formula (2) as the sensitizer. In comparison with Comparative Example 1 using the conventional sensitizer, the sensitivity is remarkably improved at low applied energy. Furthermore, even if the sensitivity is increased, it is excellent in moisture resistance and heat resistance. Examples 4 to 6 in which 4-hydroxy-diphenyl sulfone was used as the developer and the compound represented by the general formula (2) was used as the sensitizer were compared with Comparative Example 2 in which the conventional sensitizer was used. It can be seen that the sensitivity is remarkably improved at low applied energy. Furthermore, even if the sensitivity is increased, the moisture resistance is excellent. 4-chloro- as a developer
Examples 7 to 9 in which 4'-hydroxydiphenyl sulfone was used as the sensitizer and the compound represented by the general formula (2) was used.
In comparison with Comparative Example 3 using the conventional sensitizer, the sensitivity is markedly improved at low applied energy. Furthermore, even if the sensitivity is increased, it is excellent in moisture resistance and heat resistance.

[0055]

The heat-sensitive recording material of the present invention contains the compound represented by the general formula (2) as a sensitizer when the compound represented by the general formula (1) is used as a developer. As a result, the dye precursor has sufficient ability to develop color even with low applied energy. Further, this heat-sensitive recording material is very useful because it is very excellent in the image storability of the recording portion and the moisture resistance and heat resistant background color stability of the blank portion.

Continuation of the front page (56) Reference JP-A-9-109556 (JP, A) JP-A-4-135788 (JP, A) JP-A-58-166098 (JP, A) JP-A-59-225989 (JP , A) JP 10-236003 (JP, A) JP 10-264526 (JP, A) JP 9-207443 (JP, A) JP 9-142034 (JP, A) JP 9-76633 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) B41M 5 / 28-5 / 34

Claims (4)

(57) [Claims] 1. A thermosensitive recording medium having a thermosensitive recording layer comprising, on a support, a colorless or light-colored dye precursor and a developer which reacts upon heating to develop the color of the dye precursor. A heat-sensitive recording material comprising a compound represented by the following general formula (1) as an agent and a compound represented by the following general formula (2) as a sensitizer. [Chemical 1] [Chemical 2] (However, R ¹ represents a hydrogen atom, a methyl group, or a chlorine atom.
You ) 2. The heat-sensitive recording material according to claim 1, wherein the developer is 4-hydroxy-4′-methyldiphenyl sulfone. 3. The heat-sensitive recording material according to claim 1, wherein the developer is 4-hydroxydiphenyl sulfone. 4. The heat-sensitive recording material according to claim 1, wherein the developer is 4-chloro-4′-hydroxydiphenyl sulfone.