JPH07330652A - Color-developing recording material - Google Patents

Abstract

PURPOSE:To provide a new compound capable of forming a colored image excellent in plasticizer resistance and oil resistance and stable even to contact with, e.g. a packaging material made of an organic polymer material or hand cream applied to the human's hand in the case of a label, etc., produced according to the heat sensitive recording method. CONSTITUTION:A tetraphenylethane derivative of the formula (R<1> to R<3> are each H, an alkyl, an alkenyl, an aralkyl, an acyl, phenacyl or cinnamyl provided that all of R<1> to R<3> are not H), e.g. 1,2,2-tris(4-hydroxyphenyl)-1-(4- methoxyphenyl)ethane. The compound of the formula can be synthesized, e.g. by reacting a dialkylsulfuric acid, an alkyl halide, etc., with a tetrakisphenol such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane in the presence of an alkali.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording material containing a novel tetraphenylethane derivative as a developer.

[0002]

2. Description of the Related Art A recording material utilizing color development due to a reaction between a color forming dye and a color developer can be recorded in a short time by a relatively simple device without performing complicated processing such as development and fixing. It is widely used as heat-sensitive recording paper for output recording of printers or pressure-sensitive copying paper for forms for simultaneously copying several sheets. As these recording materials, materials that rapidly develop color, retain the whiteness of an uncolored portion (hereinafter referred to as “background”), and have high color fastness of the image and background are demanded. Furthermore, in recent years, it has come to be used in large quantities in fields where the reliability of recorded images such as labels is important, and it is used for plasticizers and oils and fats contained in organic polymer materials used for packaging. There has been a strong demand for recording materials having a colored image with high storage stability. Therefore, various problems such as the development of various auxiliaries such as a color forming dye, a color developing agent and a storage stabilizer have been studied, but no satisfactory one has been found yet.

Similar to the compounds of the present invention are:
Thermosensitive recording materials using a tetraphenol compound as a color developer are disclosed in Japanese Patent Publication Nos. 4-69555 and 6-434. However, in any case, it cannot be said that the storage stability of the image is still sufficient.

[0004]

As described above, in recording materials, improvement in storage stability of colored images, particularly plasticizer resistance and oil and fat resistance, has been awaited in recent years. An object of the present invention is to provide a color developer which is excellent in storage stability of a colored image and which solves the above problems.

[0005]

The present invention is a recording material containing at least one tetraphenylethane derivative represented by the following general formula (I).

[0006]

[Chemical 2]

In the above formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an acyl group, a phenacyl group or a cinnamyl group. Has 1 to 1 carbon atoms
5 is preferably a linear or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group,
Examples thereof include n-butyl group, isobutyl group, t-butyl group, n-pentyl group and neopentyl group.

The alkenyl group is preferably a linear or branched alkenyl group having 3 to 5 carbon atoms, for example, propenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group and the like. Is mentioned.

The aralkyl group has an alkylene chain having 1 to 5 carbon atoms, and the phenyl group which it has may be substituted with an alkyl group, a halogen atom or the like. For example, a 4-position methyl group, 3-position methyl group, 2-position methyl group, 4-position chloro group, 3-position chloro group, 2-position chloro group may have a substituent benzyl group, phenethyl group, α-
Examples thereof include a methylbenzyl group.

As the acyl group, a benzoyl group which may be substituted with a halogen atom, an alkyl group or the like, for example,
Examples thereof include a benzoyl group, a 4-methylbenzoyl group, a 4-chlorobenzoyl group, a 2-fluorobenzoyl group, a 3-methylbenzoyl group, an acetyl group, a propionyl group, a butyryl group and a cinnamoyl group.

The following can be exemplified as the compound represented by the general formula (I) of the present invention. (1) 1,2,2-tris (4-hydroxyphenyl) -1- (4-methoxyphenyl) ethane
Melting point (° C) 223-229 (2) 1,2,2-tris (4-hydroxyphenyl) -1- (4-isopropoxyphenyl) ethane
Melting point (° C) 108-116 (3) 1- (4-ethoxyphenyl) -1,2,2-
Tris (4-hydroxyphenyl) ethane
Melting point (° C) 188-193 (4) 1,2-bis (4-hydroxyphenyl)-
1,2-bis (4-methoxyphenyl) ethane
Melting point (° C) 224-227 (5) 1- (4-benzyloxyphenyl) -1,
2,2-tris (4-hydroxyphenyl) ethane
Melting point (° C) 207-210 (6) 1- (4-hydroxyphenyl) -1,2,2
-Tris (4-methoxyphenyl) ethane
Melting point (° C) 132-137 (7) 1,2,2-tris (4-benzyloxyphenyl) -1- (4-hydroxyphenyl) ethane
Melting point (° C) 183-186 (8) 1- (4-allyloxyphenyl) -1,2,
2-tris (4-hydroxyphenyl) ethane
Melting point (° C) 195-198 (9) 1- (4-benzoyloxyphenyl) -1,
2,2-tris (4-hydroxyphenyl) ethane
Melting point (° C) 139-141 (10) 1,2,2-tris (4-hydroxyphenyl) -1- (4-n-propoxyphenyl) ethane
Melting point (° C) 207-210 (11) 1- (4-butyloxyphenyl) -1,2,
2-tris (4-hydroxyphenyl) ethane (12) 1,2,2-tris (4-hydroxyphenyl) -1- (4-pentyloxyphenyl) ethane (13) 1,1-bis (4-hydroxyphenyl) ) −
2,2-bis (4-methoxyphenyl) ethane (14) 1,1-bis (4-ethoxyphenyl) -2,
2-bis (4-hydroxyphenyl) ethane (15) 1,2-bis (4-ethoxyphenyl) -1,
2-bis (4-hydroxyphenyl) ethane (16) 1,2,2-tris (4-hydroxyphenyl) -1- (4-isopentyloxyphenyl) ethane (17) 1,2,2-tris (4 -Hydroxyphenyl) -1- (4-phenethyloxyphenyl) ethane (18) 1- (4-butyryloxyphenyl) -1,
2,2-Tris (4-hydroxyphenyl) ethane (19) 1,2,2-Tris (4-hydroxyphenyl) -1- (4-propionyloxyphenyl) ethane (20) 1- [4- (4- Methylbenzyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl) ethane (21) 1- [4- (2-methylbenzyloxy) phenyl] -1,2,2-tris (4-hydroxy) Phenyl) ethane (22) 1- [4- (3-methylbenzyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl) ethane (23) 1- [4- (4-chlorobenzyloxy) Phenyl] -1,2,2-tris (4-hydroxyphenyl) ethane (24) 1- [4- (2-chlorobenzyloxy) phenyl] -1,2,2-tris (4-hydr) Kishifeniru) ethane (25) 1- [4- (3-chloro-benzyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl) ethane (26) 1- [4- (2-butenyloxy) phenyl]
-1,2,2-Tris (4-hydroxyphenyl) ethane (27) 1- [4- (3-butenyloxy) phenyl]
-1,2,2-Tris (4-hydroxyphenyl) ethane (28) 1- [4- (2-pentenyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl)
Ethane (29) 1- [4- (3-pentenyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl)
Ethane (30) 1- [4- (4-Pentenyloxy) phenyl] -1,2,2-tris (4-hydroxyphenyl)
Ethane (31) 1- (4-methallyloxyphenyl) -1,
2,2-tris (4-hydroxyphenyl) ethane (32) 1- (4-cinnamyloxyphenyl) -1,
2,2-Tris (4-hydroxyphenyl) ethane (33) 1- (4-cinnamoyloxyphenyl)-
1,2,2-tris (4-hydroxyphenyl) ethane

The compound represented by the general formula (I) is, for example, a dialkyl sulfuric acid, an alkyl halide, an alkenyl halide, with respect to tetrakisphenols such as 1,1,2,2-tetrakis (4-hydroxyfer) ethane.
It is synthesized by reacting an aralkyl halide or an acid halide in the presence of an alkali.

Examples of the alkali used include hydroxides of alkali metals or alkaline earth metals such as caustic soda, caustic potash, lithium hydroxide and calcium hydroxide, and carbonates of alkali metals such as sodium carbonate, potassium carbonate and lithium carbonate. Salt etc. are mentioned.

The organic solvent used is B, such as water-insoluble benzene, toluene, xylene, chlorobenzene, etc.
TX-based solvents, ketone-based solvents such as methyl isobutyl ketone, diethyl ketone, ethyl methyl ketone, and cyclohexanone, ester-based solvents such as ethyl acetate, butyl acetate, and amyl acetate can be used alone or in combination. The reaction is more preferably carried out in a water-organic solvent bilayer system.

The reaction temperature is generally -20 ° C to 100 ° C.
C. is preferable, and more preferably 20 to 90.degree.

The compound of the present invention can be used in any application as long as it is a recording material using a color forming dye.
It can be used for heat-sensitive recording paper or pressure-sensitive copying paper.

When the compound of the present invention is used in a thermal recording paper, it may be used in the same manner as a known developer. For example, each of the compound of the present invention, an auxiliary agent and a color forming dye is water-soluble. The dispersion is dispersed in an aqueous solution of the agent, the dispersions are mixed, coated on a support such as paper, and dried.

In addition to the method of incorporating in the color-forming layer as described above, in the case of a multilayer structure, it may be incorporated in any layer such as a protective layer or an undercoat layer. In this case, the ratio of the compound of the present invention to the color forming dye is 0.1 to 5 parts by weight based on 1 part by weight of the color forming dye.
The ratio is parts by weight, preferably 0.2 to 2 parts by weight.

As the above-mentioned auxiliaries, an image stabilizer, a sensitizer, a filler, a dispersant, an antioxidant, a desensitizer, an anti-adhesive agent, a defoaming agent, a light stabilizer, a fluorescent whitening agent, etc. may be used, if necessary. Can be included.

The sensitizer may be optionally selected and used, for example, higher fatty acid amide, benzamide, stearic acid anilide, acetoacetic acid anilide, thioacetanilide, dibenzyl oxalate, dimethyl phthalate, dibenzyl terephthalate, dibenzyl isophthalate, bis. (Tert-butylphenol) s, 4,4′-dihydroxydiphenylsulfone diethers, 1,2-bis (phenoxy)
Ethane, 1,2-bis (4-methylphenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 2
-Naphthol benzyl ether, diphenylamine, carbazole, 2,3-di-m-tolylbutane, 4-benzylbiphenyl, 4,4'-dimethylbiphenyl, m-
Examples include terphenyl and di-β-naphthylphenylenediamine.

Examples of the filler include clay, talc, kaolin, satin white, titanium oxide, calcium carbonate, magnesium carbonate, barium sulfate, magnesium silicate, aluminum silicate and the like.

Examples of the dispersant include sulfosuccinic acid esters such as dioctyl sodium sulfosuccinate, sodium dodecylbenzene sulfonate, sodium salt of lauryl alcohol sulfate, and fatty acid salts.

Examples of the color image stabilizing agent include salicylic acid derivatives, metal salts of oxynaphthoic acid derivatives (particularly zinc salts), and other water-insoluble zinc compounds.

As the antioxidant, 2,2'-methylenebis (4-methyl-6-tert-butylphenol),
2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-propylmethylenebis (3
-Methyl-6-tert-butylphenol), 4,4'-
Thiobis (2-tert-butyl-5-methylphenol)
Examples of the desensitizer include aliphatic higher alcohols, polyethylene glycol, guanidine derivatives and the like.

As the anti-tacking agent, stearic acid,
Examples thereof include zinc stearate, calcium stearate, carnauba wax, paraffin wax, ester wax and the like.

Examples of the color-forming dye used with the compound of the present invention include leuco dyes such as fluorane-based, phthalide-based, lactam-based, triphenylmethane-based, phenothiazine-based and spiropyran-based dyes. The dye is not limited to these, and any color-forming dye can be used without limitation as long as it is a color-forming dye that develops color when brought into contact with a developer that is an acidic substance.

Among these dyes, the fluoran type dyes include 3-diethylamino-6-methyl-7-anilinofluorane and 3-dibutylamino-6-methyl-7.
-Anilinofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluorane,
3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isopentylamino) -6-methyl-7-anilinofluorane, 3 -Diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-5-
Methyl-7-dibenzylaminofluorane, 3- (N-
Ethyl-p-toluidino) -6-methyl-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3-
(N-ethyl-N-isobutylamino) -5,6 benzofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, and 3-piperidino-6-methyl-7-.
Anilino fluoran etc. can be illustrated.

Further, other developers can be used in combination with the compound of the present invention, for example, bisphenol A,
4,4'-sec-Butylidene bisphenol, 4,4'-
Bisphenol compounds such as cyclohexylidene bisphenol, 2,2′-dihydroxydiphenyl, pentamethylene-bis (4-hydroxybenzoate), 1,7
-Sulfur-containing bisphenol compounds such as di (4-hydroxyphenylthio) -3,5-dioxaheptane, benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, 4-hydroxybenzoic acid 4-hydroxybenzoic acid esters such as isopropyl, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, chlorobenzyl 4-hydroxybenzoate, methylbenzyl 4-hydroxybenzoate, diphenylmethyl 4-hydroxybenzoate, benzoic acid Benzoic acid metal salts such as zinc acidate and zinc 4-nitrobenzoate, 4-
Hydroxy-4'-methyldiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone,
Hydroxydiphenylsulfones such as 4-hydroxy-4′-butoxydiphenylsulfone, dimethyl 4-hydroxyphthalate, dicyclohexyl 4-hydroxyphthalate, 4-hydroxyphthalic acid diesters such as diphenyl-4-hydroxyphthalate, 2-hydroxy Hydroxynaphthoic acid esters such as -6-carboxynaphthalene, hydroxyacetophenone, p-phenylphenol, benzyl 4-hydroxyphenylacetate, p-benzylphenol, hydroquinone-monobenzyl ether, and tribromomethylphenyl sulfone. Examples thereof include tribromomethyl sulfones.

The compounds of the present invention can be used in pressure-sensitive copying paper in the same manner as in the case of using known image storage stabilizers, color developers or sensitizers. For example, the color-forming dye microencapsulated by a known method is dispersed with an appropriate dispersant and coated on paper to prepare a color-forming sheet.
A developer sheet can be produced by applying the dispersion liquid of the developer of the present invention to paper, and pressure sensitive copying paper is produced by combining both sheets thus produced.

The pressure-sensitive copying paper to be produced is an upper paper having microcapsules containing an organic solvent solution of a color forming dye coated and carried on the lower surface and a lower paper having a developer coated and carried on the upper surface. Or a so-called self-content paper in which the microcapsules and the color developer are coated on the same paper surface.

Hereinafter, the present invention will be described in more detail with reference to examples. A. Synthesis of tetraphenol derivative (Examples 1 to 3) A tetraphenol derivative was synthesized as follows.
The compound was identified by H ¹ -NMR spectrum, IR spectrum and mass spectrum.

(Example 1) Synthesis of 1,2,2-tris (4-hydroxyphenyl) -1- (4-methoxyphenyl) ethane (compound (1)) 200 ml of water was placed in a 500 ml four-diameter flask, To this, 2 g of caustic soda was added and dissolved. Into this 1,
20 g of 1,2,2-tetrakis (4-hydroxyphenyl) ethane (hereinafter referred to as “TEP”), 200 ml of methyl isobutyl ketone and 6.4 g of dimethylsulfate were added, and the mixture was heated under reflux for 2 hours. After the reaction was completed, the aqueous layer was separated, the organic layer was washed with 100 ml of water twice, and the solvent was distilled off under reduced pressure to obtain a brown oily substance. This was purified by column chromatography to obtain 14 g of compound (1). mp: 223
-229 ° C yield 68%

Example 2 Synthesis of 1- (4-benzyloxyphenyl) -1,2,2-tris- (4-hydroxyphenyl) ethane (Compound (5)) 200 ml of water was put into a 500 ml four-dimensional flask. Then, 2 g of caustic soda was added thereto and dissolved. Into this TEP
20 g and 200 ml of methyl isobutyl ketone were added, and 6.4 g of benzyl chloride was added to this while stirring.
The mixture was added dropwise over a period of time, and after the addition was completed, the mixture was heated under reflux for 3 hours. After the reaction was completed, the aqueous layer was separated, the organic layer was washed twice with 100 ml of water, and the solvent was distilled off under reduced pressure to obtain a brown oily substance. Purification by column chromatography gave 13.5 g of compound (5). mp: 207-210 ° C Yield 57%

(Example 3) Synthesis of 1- (4-benzoyloxyphenyl) -1,2,2-tris- (4-hydroxyphenyl) ethane (compound (9)) 200 ml of water was put into a 500 ml four-dimensional flask. Then, 2 g of caustic soda was added thereto and dissolved. Into this TEP
20 g and 200 ml of methyl isobutyl ketone were added, and further, 7.1 g of benzoyl chloride was added thereto at room temperature.
It was added dropwise over 0 minutes. After the reaction, the aqueous layer was separated, the organic layer was washed twice with 100 ml of water, and the solvent was distilled off under reduced pressure to obtain an off-white solid. This was purified by column chromatography to obtain 18 g of compound (9). mp:
139-141 ° C Yield 72%

B. Preparation of thermosensitive recording paper (Example 4) Dye dispersion (liquid A) 3-dibutylamino-6-methyl-7-anilinofluorane 7.0 g Polyvinyl alcohol 15% aqueous solution 30.0 g Filler (calcium carbonate) 13. 5 g Pure water 49.5 g Developer dispersion (B liquid) Compound of the present invention 14.0 g Polyvinyl alcohol 15% aqueous solution 30.0 g Filler (calcium carbonate) 6.5 g Pure water 49.5 g Filler dispersion (C liquid) Filler (calcium carbonate) 20.5 g Polyvinyl alcohol 15% aqueous solution 30.0 g Pure water 49.5 g Mixtures having the above compositions are sufficiently ground with a sand grinder to prepare dispersion liquids A, B and C. Prepared. 1 part by weight of solution A, 1 part by weight of solution B and 2 parts by weight of solution C were mixed to prepare a coating solution containing the compound of the present invention. This coating solution was applied to white paper using a wire rod (No. 12), dried, and calendered to prepare a heat-sensitive recording paper.

Comparative Example 1 In the liquid B of Example 4, 2,2-bis (4-hydroxyphenyl) propane (B was used instead of the compound of the present invention.
PA) was used to prepare a thermosensitive recording paper.

C. Plasticizer resistance test of thermal recording paper (Example 5) For each thermal recording paper prepared in Example 4 and Comparative Example 1, a thermal paper color test device (TH-P manufactured by Okura Electric Co., Ltd.) was used.
MD type), printing voltage 22V, pulse width 1.8m
A checkerboard pattern was developed under the condition of s, and the developed part and the undeveloped part (background) were measured with a Macbeth reflection densitometer RD-514 (filter used: # 106). Then, a vinyl chloride wrap film was adhered to the checkered pattern-developed surface, and the plasticizer resistance test was conducted by leaving the film at room temperature for 7 days. Macbeth reflection densitometer R
It was measured with D-514 (same as above).

As a result of measuring the color density of the color-developed part and the uncolored part before the test, the plasticizer resistance was calculated by the following formula and expressed as a residual rate. The results are summarized in Table 1.

[0039]

[Equation 1]

D. Oil resistance test of thermosensitive recording paper (Example 6) Using the test paper colored in a checkered pattern in Example 5, 1 μl of a 10% n-hexane solution of salad oil was attached to the coloring surface using a microsyringe. . After confirming that the solvent, n-hexane, was volatilized, it was placed in a dark box and left for 7 days. Macbeth reflection densitometer RD-
514 (Id.). The oil resistance is represented by the residual rate by the same formula as the plasticizer resistance, and is summarized in Table 1.

[0041]

[Table 1]

From the above table, it can be seen that the larger the residual rate, the more stable the image after each storage stability test. Further, the smaller the value of the uncolored portion, the less the stain on the background. That is, it can be said that the compound of the present invention is an excellent color developer having excellent plasticizer resistance and oil resistance, and having no background stain.

[0043]

INDUSTRIAL APPLICABILITY The compound of the present invention is a novel compound for improving the storage stability of color images, particularly plasticizer resistance and oil resistance, and a recording material using the same. When it is used, it has a characteristic that an extremely stable color-developed image can be retained even in an environment where it comes into contact with a packaging material made of an organic polymer material, and even against a hand cream applied to a human hand.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B41M 5/30 C07C 69/035 9546-4H 69/773 9546-4H

Claims (2)

[Claims] 1. A tetraphenylethane derivative represented by the general formula (I). [Chemical 1] (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an acyl group, a phenacyl group or a cinnamyl group.
¹ and R ² and R ³ are not hydrogen atoms at the same time. ) 2. A recording material comprising a normally colorless to light-colored color-forming substance and at least one of the tetraphenylethane derivative according to claim 1.