JPH10100542A - Thermal recording material - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide a thermosensitive recording material having excellent storage stability of a recorded image. SOLUTION: In a heat-sensitive recording material provided on a support with a thermosensitive coloring layer mainly composed of a leuco dye and a developer for coloring the leuco dye upon heating, the following general formula is used as the developer:
One of the phenolic compounds represented by (1a) and the like is used. (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.)

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 using a leuco dye and a developer capable of developing the leuco dye when heated, and more particularly to a heat-sensitive recording material having excellent storage stability of recorded images.

[0002]

2. Description of the Related Art In general, there are various recording materials utilizing a color development reaction by heat, pressure or the like between a colorless or pale color electron donating compound (leuco dye) and a color developer which develops a color when the leuco dye is contacted. Proposed. One such heat-sensitive recording material is disclosed in JP-B-43-4160 and JP-B-45-14.
No. 039 and JP-A-48-27736, which require no complicated processing such as development and fixing, can be recorded in a relatively simple device in a short time, and generate little noise. Because of their advantages such as lower cost and the like, they are widely used as recording materials for electronic computers, facsimile machines, ticket vending machines, label printers, recorders and the like.
As the color-forming dye used in the heat-sensitive recording material, for example, a colorless or light-colored leuco dye having a lactone, lactam or spiropyran ring is used, and as a developer, an organic acid or a phenolic compound is conventionally used. Thermal recording materials using this leuco dye and a developer are widely used because of their high image density and high whiteness of the background. On the other hand, in recent years, as the demand for the heat-sensitive recording method has increased, the demand for improving the preservability of recorded images against chemicals, light, heat, water, and the like has been increasing. It is strongly desired.

[0003]

In order to cope with high storage stability of recorded images, high-reliability color developers such as those disclosed in JP-A-58-82788 and JP-A-60-158 are available.
No. -13852 discloses a phenol sulfone compound,
JP-A-61-47292 discloses a metal benzoate,
Further, substituted salicylic acid compounds have been proposed in Japanese Patent Application Laid-Open No. 62-169681, etc., but a heat-sensitive recording material using these compounds as a color developer is not sufficient in terms of fastness to a plasticizer in an image area, water and the like. It is still not enough. SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has as its object to provide a heat-sensitive recording material having excellent storage stability of a recorded image.

[0004]

According to the present invention, first, there is provided a thermosensitive recording layer comprising, as a main component, a leuco dye and a developer for developing the leuco dye upon heating on a support. The present invention provides a heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (1-a) as a color developer.

Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) Secondly, in the heat-sensitive recording material described in the first item, the general formula (1- A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (1-b) in place of the phenolic compound represented by a).

Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.) Third, in the heat-sensitive recording material described in the first item, a general formula is used as a color developer. A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (2-a) instead of the phenolic compound represented by (1-a).

Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) Fourth, in the heat-sensitive recording material described in the first item, the general formula (1- A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (2-b) instead of the phenolic compound represented by a).

Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.) Fifth, in the heat-sensitive recording material described in the first item, a general formula is used as a color developer. A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (3-a) instead of the phenolic compound represented by (1-a).

Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) Sixth, in the heat-sensitive recording material described in the first item, the general formula (1- A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (3-b) instead of the phenolic compound represented by a).

Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.) Seventh, in the heat-sensitive recording material described in the first aspect, a general formula is used as a color developer. A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (4-a) instead of the phenolic compound represented by (1-a).

Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) Eighth, in the heat-sensitive recording material described in the first item, the general formula (1- A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (4-b) instead of the phenolic compound represented by a).

Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.) Ninth, in the thermosensitive recording material described in the first item, a general formula is used as a developer. A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (5-a) instead of the phenolic compound represented by (1-a).

Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) Tenthly, in the heat-sensitive recording material described in the first aspect, the general formula (1- A heat-sensitive recording material characterized by using a phenolic compound represented by the following general formula (5-b) in place of the phenolic compound represented by a).

Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.)

Hereinafter, the present invention will be described in detail. As described above, the present invention relates to a heat-sensitive recording material provided with a thermosensitive coloring layer mainly composed of a leuco dye and a developer for coloring the leuco dye when heated on a support, wherein a general formula (1-
In this method, any of the phenolic compounds represented by a) to (5-b) is used, whereby a recorded image having excellent storage stability can be obtained.

[0006]

Embodiments of the present invention will be described below. First, the general formula (1-
Tables 1 to 10 show specific examples of the phenolic compounds represented by a) to (5-b). However, the present invention is not limited to these exemplified compounds.

[0007]

[Table 1]

[0008]

[Table 2]

[0009]

[Table 3]

[0010]

[Table 4]

[0011]

[Table 5]

[0012]

[Table 6]

[0013]

[Table 7]

[0014]

[Table 8]

[0015]

[Table 9]

[0016]

[Table 10]

Next, as the leuco dye used in the present invention, a leuco dye generally known in this type of leuco-based recording material is used alone or in combination of two or more. For example, triphenylmethanephthalide, triallylmethane, fluoran, phenothiazine, thiofluoran, xanthene, indophthalyl, spiropyran, azaphthalide, chromenopyrazole, methine, rhodamine anilinolactam, rhodamine Dye leuco compounds such as lactams, quinazolines, diazaxanthenes and bislactones are preferably used. Specific examples of such a leuco dye include the following.

3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p
-Cimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6
-Chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6-
Chlorfluoran, 3-dimethylamino-5,7-dimethylfluoran, 3- (N-methyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3- (N
-Methyl-N-isobutylamino) -6-methyl-7-
Anilinofluoran, 3- (Np-tolyl-N-ethylamino) -6-methyl-7-anilinofluoran, 3
-(N-methyl-N-amylamino) -6-methyl-7-
Anilinofluoran, 3- (N, N-di-n-amylamino) -6-methyl-7-anilinofluoran, 3- (N
-Methyl-N-cyclohexylamino) -6-methyl-
7-anilinofluoran, 3- (N-methyl-N-is
o-propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-iso-propylamino) -6-methyl-7-anilinofluoran, 3- (N-
Ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran, 3-diethylamino-
7,8-benzfluorane, 3-diethylamino-7-
Chlorofluorane, 3-diethylamino-7-methylfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl -7
-(M-trichloroanilino) fluoran, 3-diethylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran,
3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-
(2 ′, 4′-dimethylanilino) fluoran, 3-
(N, N-diethylamino) -5-methyl-7- (N, N
-Dibenzylamino) fluoranbenzoylleucomethylene blue, 6'-chloro-8'-methoxybensoindolinosspiropyran, 6'-bromo-8'-methoxybenzoindolinospiropyran, 3- (2'-hydroxy-4 ' -Dimethylaminophenyl) -3- (2'-methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-
Methoxy-5'-nitrophenyl) phthalide, 3- (2 '
-Hydroxy-4'-diethylaminophenyl) -3-
(2-methoxy-5'-methylphenyl) phthalide, 3-
(2-methoxy-4'-dimethylaminophenyl) -3-
(2'-hydroxy-4'-chloro-5'-methylphenyl) phthalide, 3-morpholino-7- (N-propyltrifluoromethylanilino) fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran , 3-
Diethylamino-5-chloro-7- (N-benzyl-trifluoromethylanilino) fluoran, 3-diethylamino-5-chloro-7- (α-phenylethylamino)
Fluoran, 3- (N-ethyl-Np-toluidino)-
7- (α-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylethyl) fluoran, 3-diethylamino-5-methyl-
7- (α-phenylethylamino) fluoran, 3-diethylamino-7-piperidinoaminofluoran, 2-chloro-3- (N-methyltoluidino) -7- (p-N-butylanilino) fluoran, 3,6 -Bis (dimethylamino) fluorenespiro (9,3 ')-6-dimethylaminophthalide, 3- (N-ethyl-N-cyclohexylamino) -5,6-benzo-7-α-naphthylamino-4-
Bromofluorane, 3-diethylamino-6-chiro-
7-anilinofluoran, 3- (N-ethyl-N-2-
Ethoxypropylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tetrafurfurylamino) -6-methyl-7-anilinofluoran, 3-
Diethylamino-6-methyl-7-mesitidino-4 ′,
5'-benzofluoran, 3- (p-dimethylaminophenyl) -3- {1,1-bis (p-dimethylaminophenyl) ethylene-2-yl} phthalide, 3- (p-dimethylaminophenyl)- 3- {1,1-bis (p-dimethylaminophenyl) ethylene-2-yl} -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3
-(1-p-dimethylaminophenyl-1-phenylethylene-2-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (1-p-dimethylaminophenyl-1
-P-chlorophenylethylene-2-yl) -6-dimethylaminophthalide, 3- (4'-dimethylamino-
2'-methoxy) -3- (1 "-p-dimethylaminophenyl-1" -p-chlorophenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide, 3- (4'-dimethylamino-2 '-Benzyloxy) -3- (1 "-p-dimethylaminophenyl-1" -phenyl-1 ", 3"-
Butadiene-4 "-yl) benzophthalide, 3-dimethylamino-6-dimethylamino-fluorene-9-spiro-3 '-(6'-dimethylamino) phthalide, 3,3-
Bis {2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl} -4,5,6,7-tetrachlorofluoride, 3-bis {1,1-bis (4-pyrrolidino Phenyl) ethylene-2-yl {-5,6-dichloro-4,7-dibromophthalide, bis (p-dimethylaminostyryl) -1-naphthylenesulfonylmethane, bis
(p-dimethylaminostyryl) -1-p-tolylsulfonylmethane and the like.

The phenolic compound represented by the general formula (1) is used as a color developer. If necessary, various other electron-accepting compounds such as a phenolic compound and thiophenol may be used. Compounds, thiourea derivatives, organic acids and metal salts thereof can be used in combination,
Specific examples include the following, but are not limited thereto.

4,4'-isopropylidene diphenol, 4,4'-isopropylidenebis-o-methylphenol, 4,4'-sec-butylidenebisphenol, 4,4'-isopropylidenebis (2-tert −
(Butylphenol) zinc p-nitrobenzoate, 1,3
5-tris (4-tert-butyl-3-hydroxy-
2,6-dimethylbenzyl isocyanuric acid, 2,2-
(3,4'-dihydroxyphenyl) propane, bis (4
-Hydroxy-3-methylphenyl) sulfide, 4 (β
-(P-methoxyphenoxy) ethoxy) salicylic acid,
1,7-bis (4-hydroxyphenylthio) -3,5-
Dioxaheptane, 1,5-bis (4-hydroxyphenylthio) -3-oxapentane, monobenzyl phthalate monocalcium salt, 4,4'-cyclohexylidenediphenol, 4,4'-isopropylidenebis
(2-chlorophenol), 2,2'-methylenebis (4
-Methyl-6-tert-butylphenol), 4,
4′-butylidenebis (6-tert-butyl-2-methylphenol), 1,1,3-tris (2-methyl-4
-Hydroxy-5-cyclohexylphenyl) butane,
4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-diphenolsulfone,
-Isopropoxy-4-hydroxydiphenylsulfone, 4-benzyloxy-4-hydroxydiphenylsulfone, 4,4'-diphenolsulfoxide, isopropyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, benzyl protocatechuate, stearyl gallate , Lauryl gallate, octyl gallate, 1,3-
Bis (4-hydroxyphenylthio) propane, N, N '
-Diphenylthiourea, N, N'-di (m-chlorophenyl) thiourea, salicylanilide, methyl bis (4-hydroxyphenyl) acetate, benzylbis (4-hydroxyphenyl) acetate, 1,3-bis (4- (Hydroxyphenyl) benzene, 1,4-bis (4-hydroxyphenyl)
Benzene, 2,4'-diphenol sulfone, 3,3 '
-Diallyl-4,4'-hydroxyphenylsulfone,
3,4-dihydroxy-4′-methyldiphenyl sulfone, zinc 1-acetyloxy-2-naphthoate, zinc 2-acetyloxy-3-naphthoate, zinc 2-acetyloxy-1-naphthoate, α, α- Bis (4-hydroxyphenyl) -α-methyltoluene, an antipyrine complex of zinc thiocyanate, tetrabromobisphenol A,
Tetrabromobisphenol S, 4,4'-thiobis
(2-methylphenol), 4,4′-thiobis (2-chlorophenol) and the like.

In order to obtain the heat-sensitive recording material of the present invention, a heat-sensitive coloring layer containing a leuco dye, a color developer and an auxiliary component described below may be provided on a support, and various conventional binders may be used. Can be used as appropriate. Specific examples of such a binder include the following.

Polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylate copolymer, acrylamide / acrylate / Methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene /
In addition to water-soluble polymers such as sulfonic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein, polyvinyl acetate, polyurethane, polyacryl esdel, polymethacrylate, vinyl chloride / vinyl acetate Emulsions such as copolymers, ethylene / vinyl acetate copolymers, and latexes such as styrene / butadiene / acrylic copolymers.

Further, in the present invention, various heat-fusible substances can be used in combination as a sensitivity improver. Specific examples thereof include the following, but are not limited thereto. Absent.

Fatty acids such as stearic acid and behenic acid, fatty acid amides such as stearic acid amide and barmitic acid amide, zinc stearate, aluminum stearate;
Fatty acid metal salts such as calcium stearate, zinc palmitate, zinc behenate, p-benzylbiphenyl, diphenyl, triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene, β
-Phenyl naphthoate, phenyl 1-hydroxy-2-naphthoate, methyl 1-hydroxy-2-naphthoate,
Diphenyl carbonate, guaiacol carbonate, dibensil terephthalate, dimethyl terephthalate,
1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dibenzyloxynaphthalene, 1,2
-Diphenoxyethane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-methylphenoxy)
Ethane, 1,4-diphenoxybutane, 1,4-diphenoxy-2-butene, 1,2-bis (4-methoxyphenylthio) ethane, dibenzoylmethane, 1,4-diphenylthiobutane, 1,4- Diphenylthio-2-butene, 1,3-bis (2-vinyloxyethoxy) benzene, 1,4-bis (2-vinyloxyethoxy) benzene, p- (2-vinyloxyethoxy) biphenyl, p-
Aryloxybiphenyl, p-propargyloxybiphenyl, dibenzoyloxymethane, dibenzoyloxypropane, dibenzylcis sulfide, 1,1-diphenylethanol, 1,1-diphenylpropanol, p
-Benzyloxybenzyl alcohol, 1,3-phenoxy-2-propanol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N-octadecylcarbamoylbenzene, 1,2-bis (4-methoxyphenoxy) propane, 1,5- Bis (4-methoxyphenoxy) -3-oxapentane, dibenzyl oxalate,
Bis oxalate (4-methylbenzyl), bis oxalate (4
-Chlorobenzyl) and the like.

When obtaining a heat-sensitive recording material, if necessary, additional components commonly used in this type of heat-sensitive recording material, such as a filler, a surfactant, a lubricant, and a pressure coloring inhibitor, can be used in combination. . In this case, as a filler, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, kaolin, talc, surface-treated inorganic fine powder such as calcium and silica, Organic fine powders such as urea-formalin resin, styrene / methacrylic acid copolymer, polystyrene resin, vinylidene chloride resin and the like can be mentioned. As the lubricant, higher fatty acids and their metal salts, higher fatty acid amides, higher fatty acids Examples include esters, animal, vegetable, mineral or petroleum waxes.

In the present invention, if necessary, an intermediate layer may be provided between the support and the thermosensitive coloring layer, and the above-mentioned various fillers, expandable and non-expandable fine hollow particles, etc. are added to the binder. In addition, the intermediate layer can be formed by bonding and supporting.

[0027]

The present invention will be described more specifically with reference to the following examples. The parts and percentages shown below are based on weight.

[Examples 1-1 to 1-4] Each mixture having the following composition was separately dispersed in a glass mayonnaise bottle using a glass ball in a ball mill for 2 days.
Solution], [solution B] and [solution C]. [Solution A] 3-N, N-dibutylamino-6-methyl-7-anilinofluoran 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts [Solution B] Developer shown in Table 6 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts [Solution C] Silicon dioxide 20 parts Water 80 parts Next, [Solution A] 10 parts, [Solution B] 30 parts, [Solution C] 10 parts and zinc stearate dispersion liquid (Concentration: 30%) 10 parts were mixed to prepare a thermosensitive coloring layer forming liquid. This thermosensitive coloring layer-forming solution was applied to the surface of a commercially available high-quality paper (basis weight: 52 g / m ² ) so that the dye adhesion after drying was 0.5 g / m ^2, and dried to form a thermosensitive coloring layer. Next, the surface smoothness is 500 to
The heat-sensitive recording material of the present invention was prepared by calendering the surface of the layer to 600 seconds. A total of four types of heat-sensitive recording materials were produced in the same manner as above except that only the developer of [liquid B] was changed to that shown in Table 11.

Comparative Example A heat-sensitive recording material was produced in the same manner as in Example 1, except that the following [Solution E] was used instead of the [Solution B] in Example 1-1. [Solution E] 4,4'-dihydroxydiphenylsulfone 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts

The heat-sensitive recording materials of Examples and Comparative Examples obtained as described above were heated in a 150 ° C. heat block at 2 kg / kg.
Printing was carried out under the conditions of cm ² and 1 second, and each of the printed samples was tested for water resistance and plasticizer resistance. Table 11 shows the results. The test conditions and the measurement of the color density and the background density are as follows. <Plasticizer resistance test> The density of the color-developed portion and the background after the test sample was immersed in di (2-ethylhexyl) adipic acid for 16 hours was measured. <Water resistance test> After the test sample was immersed in tap water for 16 hours, the density of the color-developed portion and the background portion was measured. <Coloring density and background density> The color image and background density before and after each test were measured using a Macbeth densitometer RD-918.

[0031]

[Table 11]

From Table 11, it can be seen that the plasticizer resistance and water resistance test results of the examples are very good, and are excellent in water resistance and plasticizer resistance.

Examples 2-1 to 2-4 Examples 1-1 to 1-2
In 1-4, only the developer of [Liquid B] was changed to those shown in Table 12, and all other conditions were the same to produce a total of four types of heat-sensitive recording materials. The obtained heat-sensitive recording material was printed by a heat block at 150 ° C. under the conditions of ² kg / cm ² and 1 second as described above, and each printed sample was tested for water resistance and plasticizer resistance. Table 12 shows the results. The test conditions and the measurement of the color density and the background density are the same as described above.

[0034]

[Table 12]

From Table 12, it can be seen that the plasticizer resistance and water resistance test results of the examples are very good, and are excellent in water resistance and plasticizer resistance.

[Examples 3-1 to 3-4] Examples 1-1 to 1-4
In 1-4, only the developer of [Liquid B] was changed to those shown in Table 13, and all other conditions were the same to produce a total of four types of heat-sensitive recording materials. The obtained heat-sensitive recording material was printed by a heat block at 150 ° C. under the conditions of ² kg / cm ² and 1 second as described above, and each printed sample was tested for water resistance and plasticizer resistance. Table 13 shows the results. The test conditions and the measurement of the color density and the background density are the same as described above.

[0037]

[Table 13]

From Table 13, it can be seen that the plasticizer resistance and water resistance test results of the examples are very good, and are excellent in water resistance and plasticizer resistance.

[Examples 4-1 to 4-4] Examples 1-1 to 4-4
In 1-4, only the developer of [Liquid B] was changed to those shown in Table 14, and all other conditions were the same to produce four types of heat-sensitive recording materials. The obtained heat-sensitive recording material was printed by a heat block at 150 ° C. under the conditions of ² kg / cm ² and 1 second as described above, and each printed sample was tested for water resistance and plasticizer resistance. Table 14 shows the results. The test conditions and the measurement of the color density and the background density are the same as described above.

[0040]

[Table 14]

From Table 14, it can be seen that the plasticizer resistance and water resistance test results of the examples were very good and excellent in water resistance and plasticizer resistance.

[Examples 5-1 to 5-4] Examples 1-1 to 1-5
In 1-4, only the developer of [Liquid B] was changed to those shown in Table 15, and all other conditions were the same to produce a total of four types of heat-sensitive recording materials. The obtained heat-sensitive recording material was printed by a heat block at 150 ° C. under the conditions of ² kg / cm ² and 1 second as described above, and each printed sample was tested for water resistance and plasticizer resistance. Table 15 shows the results. The test conditions and the measurement of the color density and the background density are the same as described above.

[0043]

[Table 15]

From Table 15, it can be seen that the plasticizer resistance and water resistance test results of the examples are very good, and are excellent in water resistance and plasticizer resistance.

[0045]

As described above, the above-mentioned general formula is used as a developer.
Even with the heat-sensitive recording material using any of the phenolic compounds represented by (1-a) to (5-b), a recorded image excellent in storage stability, particularly excellent in water resistance and plasticizer resistance Is obtained.

Claims (10)

[Claims] 1. A thermosensitive recording material comprising a support and a thermosensitive coloring layer comprising a leuco dye and a color developing agent for coloring the leuco dye upon heating as a main component.
A heat-sensitive recording material using the phenolic compound represented by (1-a). Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) 2. A thermosensitive recording material comprising a support having thereon a thermosensitive coloring layer mainly composed of a leuco dye and a color developing agent for coloring the leuco dye when heated, wherein the following general formula is used as the color developing agent.
A heat-sensitive recording material using the phenolic compound represented by (1-b). Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.) 3. A thermosensitive recording material comprising a support and a thermosensitive coloring layer comprising a leuco dye and a color developing agent for coloring the leuco dye upon heating as a main component.
A heat-sensitive recording material using the phenolic compound represented by (2-a). Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) 4. A heat-sensitive recording material comprising a support and a thermosensitive coloring layer comprising a leuco dye and a color developing agent for coloring the leuco dye upon heating as a main component.
A heat-sensitive recording material using the phenolic compound represented by (2-b). Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.) 5. A heat-sensitive recording material comprising a support and a thermosensitive coloring layer comprising a leuco dye and a developer for coloring the leuco dye upon heating as a main component.
A heat-sensitive recording material using the phenolic compound represented by (3-a). Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) 6. A thermosensitive recording material comprising a support having thereon a thermosensitive coloring layer comprising a leuco dye and a color developing agent for coloring the leuco dye upon heating as a main component.
A heat-sensitive recording material characterized by using the phenolic compound represented by (3-b). Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.) 7. A heat-sensitive recording material comprising a support having thereon a thermosensitive coloring layer mainly comprising a leuco dye and a developer for developing the leuco dye upon heating, wherein the developer has the following general formula:
A heat-sensitive recording material using the phenolic compound represented by (4-a). Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) 8. A heat-sensitive recording material comprising a support and a thermosensitive coloring layer containing a leuco dye and a developer for coloring the leuco dye upon heating as a main component.
A heat-sensitive recording material using the phenolic compound represented by (4-b). Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.) 9. A heat-sensitive recording material comprising a support and a thermosensitive coloring layer comprising a leuco dye and a developer for coloring the leuco dye upon heating as a main component.
A heat-sensitive recording material using the phenolic compound represented by (5-a). Embedded image (In the formula, m represents an integer of 1 to 3, and n represents an integer of 1 to 11.) 10. A thermosensitive recording material comprising a support having thereon a thermosensitive coloring layer comprising a leuco dye and a color developing agent for coloring the leuco dye upon heating as a main component, the following general formula (5-b) A heat-sensitive recording material characterized by using a phenolic compound represented by the formula (1). Embedded image (In the formula, p represents an integer of 1 to 3, and q and r each represent an integer of 1 to 11.)