JPH0615952A - Pressure-sensitive recording material - Google Patents

Abstract

PURPOSE:To obtain a heat-sensitive recording material with less blushing of the base surface under a high temp. and high humidity condition and with high water resistance by laminating a heat-sensitive color developing layer contg. an electron-donative color developing dye, terpene diphenol and an epoxy resin on a substrate. CONSTITUTION:A color developing dye, terpene diphenol, an epoxy resin of formula I (wherein n is an integer of 1-25) each with a specified amt. are separately ground and dispersed with a binder or if necessary, other additives by using a dispersing machine such as a ball mill and then, they are mixed together to prepare a heat-sensitive color developing layer coating liq. This heat-sensitive color developing coating liq. is applied on a substrate such as a paper, a plastic sheet and a synthetic paper by means of a bar coater etc., and is dried to laminate a heat-sensitive color developing layer and to obtain a heat-sensitive recording material. As the practical example of the above described color developing dye, fluoran compd., triarylmethane compd. etc., can be cited. The terpene diphenol as the color developing compd. is obtd. by reacting a terpene resin with phenol in the presence of a Friedel-Crafts type catalyst.

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, and more particularly to a heat-sensitive recording material excellent in storage stability of color images and whiteness of the background.

[0002]

2. Description of the Related Art A heat-sensitive recording material using a colorless or light-colored color-forming substance and a color-developing substance capable of coloring the color-forming substance under heat is disclosed in JP-B-43-4160 and JP-B-451403.
It was announced in No. 9 and has been put to practical use. Generally, in a heat-sensitive recording material, a leuco dye and a color developer such as a phenolic substance are separately dispersed in fine particles, and then both are mixed, and a binder, a sensitizer, a filler, a lubricant, etc. are added thereto. It forms a coating liquid by adding an agent and is applied to a support such as paper, film, synthetic paper, etc. Color recording by a chemical reaction that occurs when one or both of the leuco dye and the developer melt and contact by heating. And a sheet-like heat-sensitive recording material is usually prepared. A thermal printer or the like having a built-in thermal head is used for coloring such a thermal recording sheet. Compared to other recording methods, this heat-sensitive recording method is (1) no noise is generated during recording, (2) there is no need for developing and fixing, (3) maintenance-free, (4)
It is widely used in the field of facsimiles, computer output, printers such as calculators, recorders for medical measurement, ticket vending machines, thermosensitive recording labels, etc. due to the fact that machines are relatively inexpensive. .

[0003] Among these fields of use, labels are being used with the expansion of POS systems in retail stores, supermarkets, etc., and their use is increasing in train tickets for station automation systems. However, their use is a major drawback in that the color image disappears or fades due to contact with plastic sheets or water wetting.

As a method for solving such a drawback, a method of coating an aqueous emulsion of a chemically resistant resin on the heat-sensitive recording layer (JP-A-54-128347) and a method of coating a water-soluble polymer compound such as polyvinyl alcohol. (Actual development No. 50-125354), or a method of using a bisphenol derivative for the purpose of improving water resistance and storability of a color image (JP-A-57-195691, JP-A-57-20519).
1), a method using a novolac epoxy resin (Japanese Patent Laid-Open No. 2-289378), etc. have been proposed, but no sufficiently satisfactory effect has been obtained.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art. That is,
To provide a heat-sensitive recording material having high water resistance and high plasticizer property, which is unlikely to be discolored or discolored due to wetness of a color image or contact with a plastic film or the like, has little background fog under high temperature and high humidity conditions. It is in.

[0006]

The inventors of the present invention have completed the present invention as a result of various studies to achieve the above object. That is, the present invention provides a color-forming recording material comprising a colorless or light-colored electron-donating color-forming dye and an acidic substance, and at least terpene diphenol as the color-developing compound and an epoxy resin represented by the general formula (1). The present invention provides a heat-sensitive recording material containing one or more kinds.

[0007]

[Chemical 2]

(In the formula (1), n represents an integer of 1 to 25.) The color-developing compound used in the present invention, terpene diphenol or α-pinene resin, β-pinene resin, dipentene resin. It is obtained by reacting a terpene resin such as the above with phenol in the presence of a Friedel-Crafts type catalyst. It has physical properties such as molecular weight = about 324 and melting point = about 85 ° C., and although its structure has not been sufficiently clarified, it is considered that the compound represented by the following formula is the main component. These terpene diphenols can be easily obtained from the market.

[0009]

[Chemical 3]

Further, the epoxy resin used in the present invention contains bisphenol A represented by the formula (2) and epichlorohydrin in the presence of caustic soda as epichlorohydrin /
By adjusting the molar ratio of bisphenol A / caustic soda to carry out the reaction, a desired epoxy resin represented by the formula (1) having n can be produced.

[0011]

[Chemical 4]

As another method, in the epoxy resin represented by the formula (1), a low molecular weight epoxy resin in which n is less than 1 and the bisphenol A represented by the formula (2) are combined with the low molecular weight epoxy resin / bisphenol. An epoxy resin having n of 1 to 25 can be produced by adjusting the molar ratio of A and reacting.

The preferred softening point of the compound of the formula (1) is an epoxy resin having a softening point of 60 to 150 degrees, particularly preferably 80 to 120 degrees. If the softening point is too high, the effect of improving storability may be lowered, and if the softening point is too low, the whiteness of the thermal recording paper may be lowered.

In the heat-sensitive recording material of the present invention, the ratio of the color-developing compound terpene diphenol to the color-developing compound is in the range of 2: 1 to 1:10, preferably 1: 1. ~ 1: 5. The epoxy resin represented by the formula (1) is contained in the heat-sensitive recording material in an amount of 1 to 50% by weight, preferably 2 to 30% by weight. It may be contained in an intermediate layer provided between the coloring layer and a protective layer provided on the thermosensitive coloring layer. As a result, a heat-sensitive recording paper having improved plasticizer resistance and oil resistance and free from background fog can be obtained.

In the heat-sensitive recording material of the present invention, the terpene diphenol and the epoxy resin represented by the formula (1), a color-forming compound as shown below, a binder and other color-developing compound as required. The heat-sensitive color forming layer is prepared by using a combination of the above, a filler, a heat-fusible compound, a surfactant and the like.

Examples of the color-forming compound are generally used for pressure-sensitive recording paper and heat-sensitive recording paper and are not particularly limited. Specific examples include the following compounds. Fluoran compounds; 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-
6-dibutylaminofluorane, 2-anilino-3-methyl-6- (N-methyl-N-cyclohexylamino)
Fluoran, 2-anilino-3-methyl-6- (N-ethyl-N-isopentylamino) fluorane, 2-anilino-3-methyl-6-isobutylethylaminofluorane, 2-anilino-3-methyl-6 -[N-ethyl-
N- (3-ethoxypropyl) amino] fluorane, 2
-Anilino-3-methyl-6- (N-ethyl-N-hexylamino) fluorane, 2-anilino-3-methyl-
6-dipentylaminofluorane, 2-anilino-3-
Methyl-6- (N-methyl-N-propylamino) fluorane, 2-anilino-3-methyl-6- (N-ethyl-N-tetrahydrofurylamino) fluorane, 2-
(P-Chloroanilino) -3-methyl-6-diethylaminofluorane, 2- (p-fluoroanilino) -3-
Methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6- (p-toluidinoethylamino) fluorane, 2- (p-toluidino) -3-methyl-6-
Diethylaminofluorane, 2- (o-chloroanilino) -6-diethylaminofluorane, 2- (o-chloroanilino) -6-dibutylaminofluorane, 2-
(3,4-Dichloroanilino) -6-diethylaminofluorane, 2- (o-fluoroanilino-6-diethylaminofluorane, 2- (o-fluoroanilino) -6
-Dibutylaminofluorane, 2-anilino-3-methyl-6-piperidinofluorane, 2-anilino-3-methyl-6-pyrrolidinofluorane, 2-ethoxyethylamino-3-chloro-6-diethylamino Fluoran,
2-anilino-3-chloro-6-diethylaminofluorane, 2-chloro-6-diethylaminofluorane, 2
-Methyl-3-chloro-6-diethylaminofluorane, 2-methyl-6-diethylaminofluorane, 2-
Octylamino-6-diethylaminofluorane, 2-
Phenyl-6-diethylaminofluorane, 2-phenethyl-3-methyl-6- (p-toluidinoethylamino) fluorane, etc.,

Triarylmethane compound; 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3 -(P-Dimethylaminophenyl) -3-
(1,2-Dimethylaminoindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2
-Methylindol-3-yl) phthalide, 3- (p-
Dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis ( 1,2-Dimethylindole-
3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3- (2-phenylindol-3-yl)- 5-dimethylaminophthalide, 3-p-
Dimethylaminophenyl-3- (1-methylpyrrole-
2-yl) -6-dimethylaminophthalide, etc.

Spiro compounds; 3-methylspiro-dinaphthopyran, 3-ethylspirodinaphthopyran, 3,
3'-Dichlorospirodinaphthopyran, 3-benzylcypyrrodinaphthopyran, 3-propylspirobenzopyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, 1,3,3-trimethyl-6-nitro-8 ' −
Diphenylmethane compounds such as methoxyspiro (indoline-2,2'-benzopyran); N-halophenyl-leuco auramine, 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ae, N-2,4,5-
Trichlorophenyl leuco auramine and other thiazine compounds; benzoyl leuco methylene blue, p-nitrobenzoyl leuco methylene blue and other lactam compounds;
Rhodamine-B-anilinolactam, Rhodamine B-p
-Fluorene compounds such as chloranilinolactam;
3,6-bis (dimethylamino) fluorene spiro (9,3 ′)-6-′dimethylaminophthalide, 3,6
-Bis (dimethylamino) fluorene spiro (9,
3 ')-6'-pyrrolidinophthalide, 3-dimethylamino-6-diethylaminofluorenspiro (9,3')
-6′-pyrrolidinophthalide] and the like. These color forming compounds may be used alone or as a mixture.

The color-developing compound that can be used in combination is also generally used for pressure-sensitive recording paper and heat-sensitive recording paper and is not particularly limited. Specific examples include α-naphthol, β-naphthol, p-octylphenol, 4-t-octylphenol, pt-butylphenol, p-phenylphenol, 1,1′-bis (p-hydroxyphenyl) propane, 2, 2-bis (p-hydroxyphenyl) propane (bisphenol A), 2,2'-bis (p-hydroxyphenyl) butane, 1,1'-bis (p-hydroxyphenyl) cyclohexane, 4,4'-thiobisphenol , 4,4'-cyclohexylidene diphenol,
4,4'-sulfonyldiphenol, 4,4'-sulfonyl-bis (2-allylphenol), 2,2'-bis (2,5-dibromo-4-hydroxyphenyl) propane, 4,4'-isopropyi Redene bis (2-t-butylphenol), 2,2'-methylenebis (4-chlorophenol), 4-hydroxy-4'-isopropoxydiphenyl sulfone, bis (4-hydroxyphenyl) methyl acetate, bis (4-hydroxy) Phenolic compounds such as phenyl) butyl acetate, bis (4-hydroxyphenyl) benzyl acetate, benzyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, dibenzyl 4-hydroxyphthalate, dimethyl 4-hydroxyphthalate,
Ethyl 5-hydroxyisophthalate, 3,5-di-t-
Examples include aromatic carboxylic acid derivatives such as butylsalicylic acid and 3,5-di-α-methylbenzylsalicylic acid, aromatic carboxylic acids or polyvalent metal salts thereof.

(C) Examples of binders Methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, cellulose, polyvinyl alcohol (PVA), carboxy group-modified polyvinyl alcohol, sulfonic acid group-modified polyvinyl alcohol, polyvinylpyrrolidone, poly Water-soluble acrylamide, polyacrylic acid, starch and its derivatives, casein, gelatin, aqueous isoprene rubber, alkali salt of styrene / maleic anhydride copolymer, alkali salt of iso (or diiso) butylene / maleic anhydride copolymer, etc. Or polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polystyrene, polyacrylate, polyurethane, styrene / butadiene (SB) copolymer Polymers, carboxylated styrene / butadiene (SB) copolymers, styrene / butadiene / acrylic acid copolymers, water-soluble emulsions such as composite particles of colloidal silica and acrylic resin, and the like are used.

Examples of Other Additives Examples of fillers include calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, talc, clay, alumina, magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, polystyrene. Resin, urea-formalin resin and the like.

Examples of the heat-fusible compound include waxes such as animal and vegetable wax, polyethylene wax, and synthetic wax, higher fatty acids, higher fatty acid amides, higher fatty acid metal salts, acetylated aromatic amines, aromatic ether compounds, and aromatics. Group sulfonic acid esters, biphenyl derivatives, etc.
It is possible to use those which are solid at room temperature and have a melting point of about 80 ° C. or higher.

Specific examples of these compounds include caproic acid amide, capric acid amide, palmitic acid amide,
Stearic acid amide, oleic acid amide, erucic acid amide, linoleic acid amide, N-methyl stearic acid amide, stearic acid anilide, N-methyl oleic acid amide, benzanilide, linoleic acid anilide, N-ethylcaprylic acid amide, N-butyllaurin Acid amide, N-
Octadecylacetamide, N-oleinacetamide, N-oleinbenzamide, N-stearylcyclohexylamide, erucic acid amide, methylolbehenic acid amide, methylolstearic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide, p-acetotoluidide, polyethylene Glycol,
1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-
Methoxyphenoxy) ethane, 1,2-bis (3,4-
Dimethylphenyl) ethane, 1-phenoxy-2- (4
-Chlorophenoxy) ethane, 1-phenoxy-2-
(4-methoxyphenoxy) ethane, 1- (2-methylphenoxy) -2- (4-methoxyphenoxy) ethane, terephthalic acid dibenzyl ester, oxalic acid dibenzyl ester, oxalic acid di (4-methylbenzyl) ester , P-benzyloxybenzoic acid benzyl ester,
p-benzylbiphenyl, m-terphenyl, 1,5-
Bis (p-methoxyphenoxy) -3-oxa-pentane, 1,4-bis (2-vinyloxyethoxy) benzene, p-biphenyl-p-tolyl ether, benzyl-
Examples of such compounds include p-methylthiophenol, phenylmesitylene sulfonate, and 4-methylphenylmesitylene sulfonate.

In addition, lubricants such as zinc stearate, calcium stearate and aluminum stearate, various surfactants, defoaming agents, ultraviolet absorbers and the like are added as required.

The heat-sensitive recording material of the present invention is prepared by using the above-mentioned material by the following method, for example. That is, by a conventional method, a color-forming compound, a terpene diphenol, and a compound represented by the formula (1) are separately added to a dispersing machine such as a ball mill, an attritor, or a sand mill together with a binder or, if necessary, other additives. After crushing and dispersing, the compound of formula (1) may be mixed with a color-forming compound or a color-developing compound in advance for dispersion to prepare a heat-sensitive color-developing layer coating solution, paper or plastic sheet. 1 to 20 g / m ^{2 by} dry weight on a support such as synthetic paper.
To obtain a heat-sensitive recording material of the present invention by coating with a bar coater, a blade coater or the like (the ratio of the color-forming compound to the color-developing compound is usually 2: 1 to 1:10 by weight). .

If necessary, an intermediate layer may be provided between the thermosensitive color developing layer and the support, or an overcoat layer may be provided on the thermosensitive color developing layer. The heat-sensitive recording material of the present invention containing the terpene diphenol and the compound of the formula (1) has excellent storage stability of a color image as compared with the conventionally known heat-sensitive recording material.

[0027]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples, "part" indicates part by weight.

Example 1 A mixture [A] liquid, a [B] liquid, and a [C] liquid were prepared by pulverizing and dispersing a mixture having the following composition using a sand grinder so as to have an average particle diameter of 2 μm or less. did. [A] liquid: 2-anilino-3-methyl-6-dibutylaminofluorane 25 parts 25% PVA aqueous solution 20 parts water 55 parts [B] liquid: terpene diphenol 25 parts 25% PVA aqueous solution 20 parts water 55 parts [ C] liquid: Epoxy resin No. 1. 25 parts 25% PVA aqueous solution 20 parts water 55 parts Epoxy resin No. 1 used here has a softening point 9 in which the average n of the formula (1) is 5.4 and the epoxy equivalent is 920.
It is an epoxy resin at 8 ° C.

Next, the respective preparation solutions were mixed in the following ratios to prepare a coating solution for the thermosensitive color developing layer, which was applied onto a high quality paper having a basis weight of 50 g / m ^{2 so} that the dry weight was about 13 = g / m ^2. Then, it was dried to obtain the heat-sensitive material of the present invention. [A] liquid 6 parts [B] liquid 24 parts [C] liquid 20 parts 50% calcium carbonate dispersion 20 parts 25% PVA aqueous solution 15 parts water 15 parts

Example 2 Epoxy resin No. 1 of the liquid [C] of Example 1 was used. Epoxy resin No. 1 instead of No. 1 2 was used in the same manner as in Example 1 to obtain a heat-sensitive recording material of the present invention. Epoxy resin No. 2 is an epoxy resin having a softening point of 68 ° C. and an average n of the formula (1) of 2.1 and an epoxy equivalent of 475.

Example 3 Epoxy resin No. 1 of the liquid [C] of Example 1 was used. Epoxy resin No. 1 instead of No. 1 In the same manner as in Example 1 except that No. 3 was used, a thermosensitive recording material of the present invention was obtained. Epoxy resin No. 3 is an epoxy resin having a softening point of 83 ° C. and an average n of the formula (1) of 3.4 and an epoxy equivalent of 650.

Example 4 Epoxy resin No. 1 of the liquid [C] of Example 1 was used. Epoxy resin No. 1 instead of No. 1 4 was used in the same manner as in Example 1 to obtain a heat-sensitive recording material of the present invention. Epoxy resin No. No. 4 is an epoxy resin having a softening point of 89 ° C. and an average n of the formula (1) of 3.7 and an epoxy equivalent of 700.

Example 5 Epoxy resin No. 1 of the liquid [C] of Example 1 was used. Epoxy resin No. 1 instead of No. 1 5 was used in the same manner as in Example 1 to obtain a heat-sensitive recording material of the present invention. Epoxy resin No. 5 has an average n of formula (1) of 12.6 and an epoxy equivalent of 200.
It is an epoxy resin having a softening point of 128 ° C. which is 0.

Example 6 A 25% 2- (o-chloroanilino) -6-dibutylaminofluorane dispersion obtained by similarly pulverizing and dispersing was used in place of the liquid [A] of Example 1. A thermal recording material of the present invention was obtained in the same manner as in Example 1.

Example 7 25% 2-anilino-3-methyl-6- (N-ethyl-N-isopentylamino) obtained by pulverizing and dispersing in the same manner as in Example 1 instead of the liquid [A]. A thermal recording material of the present invention was obtained in the same manner as in Example 1 using the fluoran dispersion liquid.

Example 8 25% 2-anilino-3-methyl-6- (N-methyl-N-cyclohexylamino) fluorane obtained by pulverizing and dispersing in the same manner as in Example 1 instead of the liquid [A]. Using the dispersion liquid, a thermal recording material of the present invention was obtained in the same manner as in Example 1.

Example 9 When preparing the coating solution for the thermosensitive color developing layer of Example 1, [D] solution of the following pulverized composition solution [D] solution: N-methylolstearic acid amide 25 parts 25% PVA aqueous solution 20 parts water 55 parts In the same manner as in Example 1 except that 20 parts were added, a heat-sensitive recording material of the present invention was obtained.

Example 10 Solution [E] of the following pulverized composition solution when preparing the coating solution for thermosensitive color developing layer of Example 1 [E] solution: 4-methylphenylmesitylene sulfonate 25 parts 25% PVA aqueous solution 20 parts water 55 parts Was added in the same manner as in Example 1 to obtain a heat-sensitive recording material of the present invention.

Example 11 When preparing the coating solution for the thermosensitive color developing layer of Example 1, [F] solution of the following pulverized composition solution [F] solution: p-benzylbiphenyl 25 parts 25% PVA aqueous solution 20 parts water 55 parts 20 parts In addition, a thermal recording material of the present invention was obtained in the same manner as in Example 1.

Comparative Example 1 A thermal recording material for comparison was obtained in the same manner as in Example 1 without using the liquid [C].

Comparative Example 2 25% 2,2-bis (p-hydroxyphenyl) obtained by similarly pulverizing and dispersing in place of the liquid [B] of Example 1
A thermal recording material for comparison was obtained in the same manner as in Example 1 except that propane was used.

Using the heat-sensitive recording material of the present invention and the heat-sensitive recording material for comparison which were obtained as described above, the following quality evaluation test was carried out.

Table 1 Quality performance test results Color density ¹⁾ Heat resistance ²⁾ Moisture resistance ³⁾ Water resistance ⁴⁾ Plasticizer resistance ⁵⁾ Example 1 1.33 100% 100% 100% 93% Example 2 1. 35 100% 100% 100% 90% Example 3 1.34 100% 100% 100% 90% Example 4 1.33 100% 100% 100% 91% Example 5 1.31 100% 100% 100% 95 % Example 6 1.32 100% 100% 100% 88% Example 7 1.38 100% 100% 100% 95% Example 8 1.37 100% 100% 100% 93% Example 9 1.46 100 % 100% 100% 92% Example 10 1.45 100% 100% 100% 94% Example 11 1.45 100% 100% 100% 93% Comparative Example 1 1.35 100% 100% 100% 40% Comparative Example 2 1.24 100% 100% 50% 96%

1) Image Density The density when printed on a sample with a thermal printer (D-805P) manufactured by Ishida Koki Co., Ltd., the value measured by a Macbeth reflection densitometer RD-914 type. 2) Heat resistance The residual rate (%) of the color image part measured by Macbeth reflection densitometer after leaving the sample color-developed by the thermal printer in a thermostat at 60 ° C. for 24 hours. 3) Moisture resistance The residual rate (%) of the color image portion measured by a Macbeth densitometer after leaving the sample colored by the above thermal printer in a humidity chamber at 40 ° C and 90% relative humidity for 24 hours. 4) Water resistance A value measured by the Macbeth reflection densitometer by immersing a sample colored by the above thermal test printer in tap water at room temperature for 2 hours and then air-drying. 5) Plasticizer resistance A sample printed by the above thermal printer is sandwiched from both sides with a PVC wrap film, and 3
Value measured by the above Macbeth reflection densitometer on the printed part after being left at 25 ° C. for 24 hours under the load of 0 g / cm ^2.

As can be seen from the table, the heat-sensitive recording material of the present invention is excellent in storability of color images such as heat resistance, moisture resistance, water resistance and plasticizer resistance.

[0046]

EFFECT OF THE INVENTION A heat-sensitive recording material excellent in storage stability of a color image is obtained.

Claims (1)

[Claims] 1. A color-forming recording material comprising a colorless or light-colored electron-donating color-forming dye and an acidic substance, and at least terpene diphenol as the color-developing compound and an epoxy resin represented by the general formula (1). A heat-sensitive recording material comprising one or more kinds. [Chemical 1] (In the formula (1), n represents an integer of 1 to 25.)