JP3232282B2 - Reversible thermosensitive recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a reversible thermosensitive recording material. More specifically, the present invention relates to a reversible thermosensitive recording material having excellent image contrast, storage stability and heat resistance.

[0002]

2. Description of the Related Art In recent years, rewritable reversible thermosensitive recording materials have been developed in place of conventional irreversible thermosensitive recording materials. For example, JP-A-2-188293 discloses, as a reversible thermosensitive recording medium for forming and erasing an image, a color-reducing agent comprising a leuco compound and bis (hydroxyphenyl) acetic acid or a higher aliphatic amine salt thereof on a support. There has been proposed a recording medium provided with a recording layer containing. This recording medium obtains a color-developing and decoloring effect by opening and closing the lactone ring of the leuco compound. However, since this reaction is an equilibrium reaction, it cannot be said that the contrast of the image is always sufficient. Also, JP-A-6-210954 discloses that
It is possible to form and erase images with good contrast,
As a reversible thermosensitive recording material capable of maintaining a stable image over time, a colorless electron-donating dye precursor and an electron-accepting compound composed of a phenolic compound having an aliphatic hydrocarbon group having 6 or more carbon atoms are used. A reversible thermosensitive recording material is proposed. However, even with this heat-sensitive recording material, there are still problems in contrast and storage stability, and no satisfactory material has been obtained for practical use.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a reversible thermosensitive recording material having excellent image contrast and excellent image storability and heat resistance.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that substituted phenoxycarboxylic acid compounds having a group having an alkylene group having 4 or more carbon atoms as a substituent are obtained. It has been found that a reversible thermosensitive recording material having excellent image contrast, image storability and heat resistance can be obtained by using the compound as an electron accepting compound, and the present invention has been completed based on this finding. That is, the present invention provides: (1) a reversible thermosensitive recording material comprising a support provided with a thermosensitive coloring layer containing an electron-donating coloring compound, an electron-accepting compound and a binder; A reversible thermosensitive recording material, wherein a substituted phenoxycarboxylic acid compound represented by the general formula [1] is used as an electron-accepting compound that causes a reversible color change;

Embedded image (Wherein, X is a divalent group containing a hetero atom, R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a carboxyl group,
n is an integer of 1 to 4, and m is an integer of 4 to 22. ), Is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The reversible thermosensitive recording material of the present invention comprises:
In a reversible thermosensitive recording material having a thermosensitive coloring layer containing an electron-donating coloring compound, an electron-accepting compound and a binder on a support, an electron which causes a reversible hue change in the electron-donating coloring compound As the receptive compound, a substituted phenoxycarboxylic acid compound having at least one kind of a group having an alkylene group having 4 to 22 carbon atoms as a substituent is used. There is no particular limitation on the electron donating color compound used in the present invention, and colorless or pale leuco dyes such as fluoran compounds, triphenylmethane compounds and diphenylmethane compounds can be used. Such leuco dyes include, for example, 3-diethylamino-6-methyl-7-anilinofluoran,
3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isobutyl) amino-6
Methyl-7-anilinofluoran, 3- (N-propyl-N-methyl) amino-6-methyl-7-anilinofluoran, 3- (N-isopropyl-N-ethyl) amino-
6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-methyl) amino-6-methyl-7-anilinofluoran, 3- (N-isoamyl-N-ethyl)
Amino-6-methyl-7-anilinofluoran, 3-diisoamylamino-6-methyl-7-anilinofluoran, 3- (N-ethoxy-N-propyl) amino-6-methyl-7-ani Linofluoran, 3-diethylamino-
6-methyl-7- (m-trichloromethylanilino) fluoran, 3-diethylamino-6-methyl-7- (m-
(Trifluoromethylanilino) fluoran, 2-chloro-6-dimethylaminofluoran, 3-pyrrolidino-6
-Methyl-7-anilinofluoran, 2-chloro-3-
Methyl-6-diethylaminofluoran, 3-diethylamino-7,8-benzofluoran, 3-cyclohexylamino-6-chlorofluoran, 2-dibenzylamino-6-diethylaminofluoran, 2- (N-phenyl- N-methyl) amino-6- (Np-tolyl-N-ethyl) aminofluoran, 3- (Np-tolyl-N-ethyl) amino-7-methylfluorane, 3- (N-p -Tolyl-N-ethyl) amino-6-methyl-7-anilinofluoran, 3- (Np-tolyl-N-ethyl) amino-6-methyl-7- (p-methylanilino) fluoran,
3-ethyl (3-merbutyl) aminobenzofluoran,
3,7-dimethylamino-10-benzoylphenothiazine, 7- (2-chlorophenylamino) -3-diethylaminofluoran, 6-methyl-7- (2,4-dimethylphenylamino) -3-diethylaminofluoran, 3 ,
3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4- Azaphthalide, 3,3-bis [2- (4
-Dimethylaminophenyl) -2- (4-methoxyphenyl) vinyl] -4,5,6,7-tetrachlorophthalide, 3
-(4-diethylamino-6-ethoxyphenyl) -3-
(1-hexyl-2-methylindol-3-yl) -4
-Azaphthalide, 2-chloro-6-diethylaminofluoran, 3-methyl-6-diethylaminofluoran,
7- (N-octylamino) -3-diethylaminofluoran, 3-methoxy-6-methoxyfluoran, 3,3
-Bis (p-diethylaminophenyl) -6-diethylaminophthalide, 3-diamylamino-6-methyl-7-
Anilinofluoran, 3- (N-ethoxypropyl-N
-Ethyl) amino-3-diamylamino-6-methyl-
7-anilinofluoran and the like can be mentioned. One of these electron donating color compounds can be used alone, or two or more of them can be used in combination.

The electron accepting compound used in the present invention is:
A substituted phenoxycarboxylic acid compound having at least one kind of a group having an alkylene group having 4 to 22 carbon atoms as a substituent. Among such substituted phenoxycarboxylic acid compounds, a compound represented by the general formula [1] can be particularly preferably used.

Embedded image In the general formula [1], X is a divalent group containing a hetero atom, and R ¹ is a hydrogen atom, a halogen atom, a carbon atom having 1 to 4 carbon atoms.
Where n is an integer of 1 to 4 and m is an integer of 4 to 22.

In the general formula [1], examples of the divalent group containing a hetero atom represented by X include an amide group, an ester group, an ether group, a thioether group and a sulfone group. In particular,

Embedded image And the like.

In the present invention, the structural formula of a substituted phenoxycarboxylic acid compound represented by the general formula [1] which can be suitably used as an electron accepting compound is shown in Table 1 and can be used. The substituted phenoxycarboxylic acid compound represented by the general formula [1] is not limited thereto.

[0009]

[Table 1]

[0010]

[Table 2]

[0011]

[Table 3]

[0012]

[Table 4]

[0013]

[Table 5]

[0014]

[Table 6]

[0015]

[Table 7]

In the present invention, the method for producing the substituted phenoxycarboxylic acid compound used as the electron accepting compound is not particularly limited, and can be obtained by a conventionally known general production method. For example, various phenols and monohalogenated acetic acid can be easily obtained by heating and reacting in the presence of a basic compound using an appropriate solvent, or various phenols and monohalogenated acetic acid can be obtained. It can be obtained by subjecting an ester compound to a heat reaction using a suitable solvent in the presence of a basic compound, followed by hydrolysis. The substituted phenoxycarboxylic acid compound used in the present invention has a moderately high decoloring temperature as compared with a conventional electron-accepting compound, and thus has heat resistance suitable for a use environment. If the decoloring temperature is too low, the heat resistance is inferior. Conversely, if the temperature is extremely high, a load is imposed on the print head, causing a problem. However, the reversible thermosensitive recording material of the present invention has a decoloring temperature of 70 to 80 ° C. There is no possibility that such a problem will occur. There is no particular limitation on the binder used in the present invention, and a polymer compound usually used as a binder can be used. Examples of such a polymer compound include polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, polyester, aromatic polyester, polyurethane, polycarbonate, and polyacrylic acid. Examples thereof include esters, polymethacrylic acid esters, acrylic acid-based copolymers, polyvinyl alcohol, maleic acid-based copolymers, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, gelatin, and starch.

In the present invention, if necessary, a sensitizer may be used in combination. Examples of the sensitizer include fatty acid amides such as stearic acid amide, stearic acid methylolamide, oleic acid amide, palmitic acid amide, and coconut fatty acid amide, 1,2-bisphenoxyethane, and 1,2-bis (m-toluyl). Oxy) ethane, 1,4-
Dimethoxynaphthalene, 1,4-dibenzyloxynaphthalene, benzyloxythiophenyl ether, 2-benzyloxynaphthalene, 1,2-diphenyloxymethylbenzene, 1,4-diphenyloxymethylbenzene, 1,4-di (o- Tolyloxymethyl) benzene, 1,
4-di (m-tolyloxymethyl) benzene, 1,4-di
(p-tolyloxymethyl) benzene, bisphenol S
Ethers such as diallyl ether, dibenzyl oxalate, di (p-methylbenzyl) oxalate, dibenzyl terephthalate, esters such as phenyl 1-hydroxy-2-naphthoate, m-terphenyl, p-benzylbiphenyl, Examples include various waxes, condensates of aromatic carboxylic acids and amines, higher linear glycols, higher ketones, bisphenol S derivatives and the like. In the reversible thermosensitive recording material of the present invention, there is no particular limitation on the quantitative relationship between the electron donating color compound and the electron accepting compound. It is preferable to use 5 to 20 parts by weight. The binder is used in an amount of 0.1 to 20 parts by weight based on a total of 1 part by weight of the electron donating color compound and the electron accepting compound.
It is preferred to use parts by weight. To the reversible thermosensitive recording material of the present invention, if necessary, conventionally used additives can be added in order to improve coating characteristics and recording characteristics. Such additives include, for example, stabilizers, antioxidants, dispersants, ultraviolet absorbers, surfactants,
Examples include a conductive agent, a filler, and a wax. In the reversible thermosensitive recording material of the present invention, the heat-sensitive coloring layer may be formed by a commonly used method, for example, an electron-donating coloring compound, an electron-accepting compound, a binder and, if necessary, a sensitizer to be added. The dispersion can be prepared by dispersing in a medium such as a medium to prepare a dispersion, and applying the dispersion to a support and drying the dispersion. The support used in the reversible thermosensitive recording material of the present invention is not particularly limited, and examples thereof include paper, various nonwoven fabrics, woven fabrics, synthetic resin films, synthetic resin laminated paper, synthetic paper, metal foil, and glass. Can be.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In Examples and Comparative Examples, evaluation of the reversible thermosensitive recording material was performed by the following method. (1) Coloring and Decoloring Test A reversible thermosensitive recording material is printed using Shoin WD-1200U [Sharp Corporation], and the density of the printed coloring area is measured by a colorimeter CR-200 “Minolta Co., Ltd.” Is measured as a lightness index L *. The smaller the value of the lightness index L *, the higher the print color density. Further, the printed material is placed on a hot plate and heated under the conditions of 100 ° C. and a heating time of 5 seconds, and then the erased density of the erased portion is measured using a colorimeter CR-200. (2) Decoloring start temperature A reversible thermosensitive recording material is printed using Shoin WD-1200U [Sharp Corporation], and the printed material is placed on a hot plate in increments of 10 ° C from 50 to 100 ° C. After heating under the condition of a heating time of 5 seconds, the density of the printed coloring portion is measured as a lightness index L * using a color difference meter CR-200 [Minolta Co., Ltd.]. Lightness index L * of printing color development part
However, the temperature at which the initial print density is increased by 20% with respect to the lightness index L * is defined as the decoloring start temperature. (3) Storage stability test A reversible thermosensitive recording material was printed using Shoin WD-1200U [Sharp Corporation], and the density of the printed coloring portion was measured using a colorimeter CR-200 [Minolta Corporation]. And measured as a lightness index L *. Further, after the printed color-developed substrate is left at 40 ° C. and 90% RH for 10 days, the lightness index L * of the density of the printed color-developed portion is measured.

Synthesis Example 1 (Electron-accepting compound, 1,10-
[Synthesis of [N, N'-di (p-carboxymethoxyphenyl)] decanediamide) A mixed solution of 65.4 g of p-aminophenol, 47.4 g of pyridine and 200 g of dimethylformamide was mixed with 85. 8 g was added dropwise and reacted at the same temperature for 2 hours. After completion of the reaction, 200 g of water was added to precipitate crystals, which were filtered to obtain crude crystals. The obtained crude crystals were recrystallized using tetrahydrofuran to obtain 1.1
98.6 g of 0- [N, N'-di (p-hydroxyphenyl)] decanediamide were obtained. Then, the obtained 1,10- [N,
N'-di (p-hydroxyphenyl)] decanediamide 1
Ethyl monochloroacetate (18.4 g) was added dropwise at 60 ° C. to a mixture of 2.4 g, potassium carbonate (8.3 g) and dimethylformamide (120 g), and reacted at the same temperature for 3 hours. After completion of the reaction, the reaction mixture was cooled and 250 g of water was added to precipitate crystals, adjusted to pH 3 with hydrochloric acid, and filtered to obtain crude crystals. The resulting crude crystals were recrystallized from ethyl acetate to give 1.1
13.9 g of 0- [N, N'-di (p-ethoxycarbonylmethoxyphenyl)] decanediamide was obtained. The obtained 1,1
A mixture of 5.8 g of 0- [N, N'-di (p-ethoxycarbonylmethoxyphenyl)] decanediamide and 120 g of dimethylformamide was added at 60 ° C. with 25 ml of potassium hydroxide.
11.2 g of a 1% by weight aqueous solution was added dropwise and reacted at the same temperature for 2 hours. After completion of the reaction, the reaction mixture was cooled, 350 g of water was added, the pH was adjusted to 3 with hydrochloric acid, and the precipitated crystals were filtered. 100 g of dimethylformamide was added to the obtained crystals, 10.0 g of a 20% by weight aqueous solution of potassium hydrogencarbonate was added dropwise at 60 ° C., followed by cooling, and the crystals were filtered. 200 g of dimethylformamide was added to the obtained crystals and neutralized with hydrochloric acid. Then, 200 g of water was added to precipitate crystals, which were filtered to obtain crude crystals. The obtained crude crystals were recrystallized from methanol to give 1,1 having a structure represented by Table 1
4.0 g of 0- [N, N'-di (p-carboxymethoxyphenyl)] decanediamide was obtained. Melting point was 197 ° C.

Example 1 40 parts by weight of 3-dibutylamino-6-methyl-7-anilinofluoran and 2.5% by weight of polyvinyl alcohol
90 parts by weight of the aqueous solution was put in a ball mill and pulverized by rotating for 3 hours to prepare Dispersion A. Further, 1,10- [N, N′-di (p
-Carboxymethoxyphenyl)] decanediamide 100
2.5 parts by weight of a 2.5 parts by weight aqueous solution of polyvinyl alcohol and polyvinyl alcohol 4
00 parts by weight were put in a ball mill and pulverized by rotating for 3 hours to prepare a dispersion B. Further, the dispersion A6
A coating solution was prepared by mixing 5 parts by weight, 250 parts by weight of the dispersion B, 100 parts by weight of a 10% by weight aqueous solution of polyvinyl alcohol, and 200 parts by weight of water. Apply this coating solution to a thickness of 1
A 20 μm polyethylene terephthalate film was applied to a thickness of 10 μm and dried to obtain a reversible thermosensitive recording material. The lightness index L * of the color-developed portion of this reversible thermosensitive recording material was 60.1, and the lightness index L * of the decolored portion was 9
2.6. The decoloration start temperature was 70 ° C. The lightness index L * of the color-developed portion after standing at 40 ° C. and 90% RH for 10 days was 73.5. Example 2 Instead of 1,10- [N, N'-di (p-carboxymethoxyphenyl)] decanediamide, 1,10- [N, N'-di having a structure represented by the following Formula 1 is used. A reversible thermosensitive recording material was prepared in the same manner as in Example 1 except that (p-carboxymethoxyphenylcarbamoyl)] decane was used. The lightness index L * of the colored portion of this reversible thermosensitive recording material
Was 58.7, and the lightness index L * of the decolored portion was 91.9. The decoloration start temperature was 80 ° C. Also, 40
C., lightness index L of the colored portion after standing at 90% RH for 10 days
* Was 67.8.

Example 3 Instead of 1,10- [N, N'-di (p-carboxymethoxyphenyl)] decanediamide, 1,12- [N, N having a structure represented by Table 1 A reversible thermosensitive recording material was produced in the same manner as in Example 1 except that '-di (m-hydroxy-p-carboxymethoxyphenyl)] dodecanediamide was used. The lightness index L * of the color-developed portion of the reversible thermosensitive recording material is 57.7, and the lightness index L of the decolored portion is
* Was 93.1. The decoloration start temperature was 70 ° C. Further, the lightness index L * of the color-developed part after standing at 40 ° C. and 90% RH for 10 days was 69.2. Example 4 Instead of 1,10- [N, N′-di (p-carboxymethoxyphenyl)] decanediamide, 1,12-di (p-carboxymethoxyphenyl) having a structure represented by Table 1 A reversible thermosensitive recording material was produced in the same manner as in Example 1 except that (ureylene) dodecane was used. The lightness index L * of the color-developed portion of this reversible thermosensitive recording material was 59.9.
And the lightness index L * of the decolored portion was 92.3. The decoloration start temperature was 70 ° C. Also, 40 ° C, 90%
After 10 days at RH, the lightness index L * of the colored portion was 7
3.4. Example 5 Instead of 1,10- [N, N'-di (p-carboxymethoxyphenyl)] decanediamide, 1,12-di (p-carboxymethoxyphenoxy) having a structure represented by Table 1 ) A reversible thermosensitive recording material was produced in the same manner as in Example 1 except that dodecane was used. The lightness index L * of the coloring portion of this reversible thermosensitive recording material was 60.7,
The lightness index L * of the decolored portion was 90.5. The decoloration start temperature was 80 ° C. Also, at 40 ° C. and 90% RH,
The lightness index L * of the color-developed portion after standing for 0 days was 71.3.

Example 6 Instead of 1,10- [N, N'-di (p-carboxymethoxyphenyl)] decanediamide, 1,12-di [(p -Carboxymethoxyphenyl) sulfamoyl] dodecane,
A reversible thermosensitive recording material was produced in the same manner as in Example 1. The lightness index L * of the color-developed portion of this reversible thermosensitive recording material was 59.8, and the lightness index L * of the decolored portion was 91.1. The decoloration start temperature was 70 ° C. Also, at 40 ° C,
Color index lightness index L * after standing at 90% RH for 10 days
Was 70.6. Example 7 Instead of 1,10- [N, N′-di (p-carboxymethoxyphenyl)] decanediamide, 1,12-di (p-carboxymethoxyphenyl) having a structure represented by the following Table 39 is used. A reversible thermosensitive recording material was produced in the same manner as in Example 1 except that sulfonylureylene) dodecane was used. The lightness index L * of the colored portion of this reversible thermosensitive recording material
Was 60.2, and the lightness index L * of the decolored portion was 91.7. The decoloration start temperature was 70 ° C. Also, 40
C., lightness index L of the colored portion after standing at 90% RH for 10 days
* Was 69.9.

Comparative Example 1 The procedure of Example 1 was repeated, except that 4- (N-behenoylamino) salicylic acid was used instead of 1,10- [N, N′-di (p-carboxymethoxyphenyl)] decanediamide. Thus, a reversible thermosensitive recording material was produced. The lightness index L * of the colored portion of this reversible thermosensitive recording material was 63.8,
The lightness index L * of the decolored portion was 88.7. The decoloration start temperature was 60 ° C. Also, at 40 ° C. and 90% RH,
The lightness index L * of the colored portion after standing for 0 days was 84.8. Comparative Example 2 In the same manner as in Example 1 except that 4- (N-stearoylamino) phenol was used instead of 1,10- [N, N′-di (p-carboxymethoxyphenyl)] decanediamide, A reversible thermosensitive recording material was prepared. The lightness index L * of the color-developed portion of the reversible thermosensitive recording material was 80.6, and the lightness index L * of the decolored portion was 84.0. In the decolorization start temperature test, after heating at 100 ° C. for 5 seconds,
The lightness index L * of the printed coloring portion was 81.4. Also,
The lightness index L * of the colored portion after standing at 40 ° C. and 90% RH for 10 days was 88.0. Examples 1 to 7 and Comparative Example 1
Tables 2 and 3 show the results.

[0024]

[Table 8]

As can be seen from Table 2, the reversible thermosensitive recording materials of Examples 1 to 7 using the substituted phenoxycarboxylic acid compound as the electron-accepting compound have a high density of the color-developing portion and a high lightness of the decoloring portion. 70-80, having good coloring and decoloring properties
It has an appropriate decoloration start temperature of ° C., excellent heat resistance, and good storage stability. On the other hand, the reversible thermosensitive recording material of Comparative Example 1 using 4- (N-behenoylamino) salicylic acid as the electron-accepting compound has a slightly lower density in the color-developing portion and lightness in the decoloring portion, and has a lower decoloring start temperature Poor in color development / decoloration and heat resistance, and poor in storage stability. The reversible thermosensitive recording material of Comparative Example 2 using 4- (N-stearoylamino) phenol as the electron accepting compound was:
The density of the color-developed portion and the brightness of the decolored portion are low, the color-decoloring property is poor, the color does not disappear even when heated to 100 ° C., and the storage stability is also poor.

[0026]

The reversible thermosensitive recording material of the present invention contains a substituted phenoxycarboxylic acid compound as an electron accepting compound, and can form a good image contrast.
Excellent image storability and heat resistance.

Continued on the front page (72) Inventor Kazuto Onjuku 163 Morikawaramachi, Moriyama-shi, Shiga Prefecture Gunze Co., Ltd.Shiga Research Laboratory (72) Inventor Toshinori Okamoto 163 Morikawaramachi, Moriyama-shi Shiga Prefecture Inside Shiga Research Laboratory (72) Inventor Akihiro Tanaka 163 Morikawaramachi, Moriyama City, Shiga Prefecture Gunze Research and Development Department Shiga Research Laboratory (56) References JP-A-11-236558 (JP, A) JP-A-11-235874 ( JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/28-5/34 CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A reversible thermosensitive recording material comprising a support and a thermosensitive coloring layer containing an electron donating color compound, an electron accepting compound and a binder, wherein the reversible hue of the electron donating color compound is provided. A reversible thermosensitive recording material characterized by using a substituted phenoxycarboxylic acid compound represented by the general formula [1] as an electron-accepting compound causing a change. Embedded image (Wherein, X is a divalent group containing a hetero atom, R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a carboxyl group,
n is an integer of 1 to 4, and m is an integer of 4 to 22. )