JP2576081B2 - Recording system - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive, pressure-sensitive and photosensitive pressure-sensitive recording system. More specifically, general formulas [1] to
The present invention relates to a novel chelate coloring system comprising one or more of the compounds of [5], a metal compound and a basic compound.

[0002]

2. Description of the Related Art Conventionally, many chemical coloring systems utilizing energy such as heat and pressure have been known.

[0003] In particular, a color-forming system consisting of two components, usually a colorless or pale-colored leuco dye and a color developer which comes into contact with the leuco dye, and a two-component system consisting of a metal salt of an organic acid and a polyvalent hydroxy aromatic compound. Such a chelate color forming system has been known for a long time, and is widely used for recording materials.

For example, there are heat-sensitive recording paper utilizing heat energy, pressure-sensitive recording paper utilizing pressure energy, and photosensitive pressure-sensitive recording paper utilizing light and pressure energy.

A thermal recording paper using a leuco dye is disclosed in JP-B-45-14039, and a thermal recording paper utilizing a chelate is disclosed in US Pat. No. 2,663,654. These thermal recording papers add heat energy to the thermal recording layer,
It is based on the principle that a color forming component is melted and brought into contact to form a color. The thermal recording method using a thermal head has many advantages such as non-impact, no noise at the time of recording, small size, light weight and easy maintenance, and it is used for facsimile, various printers, recorders, automatic ticket vending machines, etc. ing.

On the other hand, pressure-sensitive recording paper, for example, when a leuco dye is used, is composed of an upper paper in which a dye solution is microencapsulated and applied on a support, and a lower paper in which a developer is applied. It is based on the principle that the lower paper is opposed to apply pressure energy to break the microcapsules, and the dye transfers to and contacts the color developer layer to form color. Because it can copy many sheets, it is widely used for slips and the like. A pressure-sensitive recording paper using a leuco dye is disclosed in U.S. Pat. No. 2,711,375.
Pressure-sensitive recording paper using chelate is used for
38206 and the like.

The photosensitive pressure-sensitive recording paper is prepared by microencapsulating a leuco dye, a polymerizable monomer, and a photopolymerization initiator, coating the microcapsule on a support, and irradiating light to partially cure the microcapsule to form a latent image. To form Thereafter, the exposure sheet is made to face the receiving paper coated with the color developer, pressure energy is applied to break the uncured microcapsules, and the dye is transferred to the color developer layer, and the color is formed upon contact. .
This is a color copying system that cleverly utilizes the color development system of pressure-sensitive recording paper. The photosensitive pressure-sensitive recording paper is disclosed in JP-A-59-30.
No. 537.

[0008]

However, these various types of recording paper have a number of drawbacks, and improvements have been desired. For example, heat-sensitive recording paper loses colored characters due to light or oil such as a plasticizer, bleeds colored characters due to a solvent such as ethanol, or makes a white paper portion reversely colored and becomes unreadable. However, there were drawbacks such as the yellowing of the blank portion due to NOx gas. Among these drawbacks, a method of providing a protective layer on a heat-sensitive recording layer has been adopted for the purpose of preventing the disappearance of colored characters due to a plasticizer and a solvent and preventing the coloring of a blank portion. Although a water-soluble polymer, an ultraviolet curable resin, an electron beam curable resin and the like are used as the protective layer, the protective layer is thickened in order to increase the barrier effect because the purpose is to protect the contact with the recording layer. As a result, there is a disadvantage that the thermal conductivity to the heat-sensitive layer is reduced, and the sensitivity cannot be obtained. However, in any case, since it is a light-transmitting resin, the influence of light or the like cannot be eliminated, and light fading cannot be prevented. In the chelate type, since the formed chelate compound is a pigment, the color fastness is high in sunlight fastness, but under high temperature and high humidity due to the influence of iron contained in the base paper and polyvalent metal contained in the filler. There are drawbacks such as the formation of white paper, the inability to read colored characters due to the formation of white paper, and low color density.

The pressure-sensitive recording paper is slightly different depending on the type of developer such as activated clay, phenol resin, polyvalent metal salt of aromatic carboxylic acid, polyvalent metal salt of carboxy-modified terpene phenol resin. There are drawbacks such as disappearance of colored characters due to light or oil such as a plasticizer, and yellowing of a white paper portion due to light or NOx gas.

[0010] The photosensitive pressure-sensitive recording paper basically has the same coloring principle as the pressure-sensitive recording paper, and thus has the same problem.

At present, a recording method which is used for a part of a facsimile and the like and which can obtain an image having good storability, has been developed.
There are a recording method and a thermal transfer recording method. In these methods, an image is obtained by transferring a toner or a colored dye or pigment onto plain paper. However, when the apparatus is small, lightweight, inexpensive, easy to maintain, and the like, the heat-sensitive recording method is excellent, and pressure-sensitive recording paper is excellent in that it can be recorded directly by writing and can copy many sheets.

An object of the present invention is to develop a high-preservation recording paper excellent in oil resistance, solvent resistance, water resistance and light resistance in a heat-sensitive, pressure-sensitive and light-sensitive pressure-sensitive recording system.

[0013]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve these problems, and as a result, have found general formulas [1] to
Preservability such as oil resistance, solvent resistance, water resistance, light resistance, etc. can be improved by using a novel chelate coloring system comprising one or more of the compounds of [5], a metal compound and a basic compound as coloring components. I found

As described above, in the leuco dye coloring system, it is impossible to enhance the storability without taking physical measures such as providing a protective layer. There is the use of colored dyes and pigments depending on the method. Many dyes and pigments have a high degree of fastness, and are utilized in clothing, printed matter and the like by making use of their characteristics. Since these are colored and used as they are, the recording layer of the heat-sensitive recording paper is colored, and the pressure-sensitive recording paper is disadvantageous in that, for example, when used on the microcapsule side, the back surface of the upper paper is colored. The present inventors have paid attention to the high fastness of dyes and pigments, that is, high preservability, and made use of the characteristics, and further studied by performing chemical modification so as to match the intended recording system. Reached.

According to the present invention, the color dye is made colorless or lighter like a leuco dye, and then the colorless or lighter dye is brought into contact with another substance without heat (thermosensitive recording) or heat ( Pressure-sensitive recording) to revert to the original dye (color development). More specifically, to reduce the color of a colored dye from colorless to light, the substituent of the colored dye contributing to coloring or deep coloration may be replaced by another substituent (protecting group).
In order to suppress resonance and reduce the color, and to develop colors and records, the substituent (protecting group) once introduced in the presence of a substituent (protecting group) releasing agent with or without heat is removed. It is based on the principle that the colored dye is colored deeper by releasing, returning to the original colored dye and then reacting with other substances. Here, the colored dye having the protective substituent introduced therein is a compound of the above-mentioned general formulas [1] to [5], the substituent-eliminating agent is a basic compound, and the colored dye after the substituent has been eliminated. The substance that reacts and darkens is a metal compound. This darkening reaction is a chelate forming reaction. The present inventors have found that the above object can be completely achieved by using this coloring system. Further, the recording system of the present invention is excellent in optical readability in the near-infrared region and can be used for POS systems for thermal labels and the like.

Colored dyes can be classified into basic dyes, acid dyes, acid mordant dyes, metal complex dyes, mordant dyes, direct dyes, vat dyes, soluble vat dyes, sulfur dyes.
Azoic dyes, oxidation dyes, disperse dyes, reactive dyes, and structurally, azo dyes, anthraquinone dyes, indigoid dyes, soluble vat dyes, sulfur dyes, carbonium dyes, quinone imine dyes, phthalocyanine dyes, etc. Separated. The properties required for the compound corresponding to the dye of the present invention have, first of all, a color tone close to black after the reaction, and furthermore excellent oil resistance, solvent resistance, water resistance, light resistance, and when a substituent is introduced. Lighter colors are possible, and the recording layer becomes white, white paper does not develop color or yellow, there is no toxicity, and the cost is lower. As a result of research on compounds which satisfy these conditions among the above dyes and can be used in the recording system of the present invention, a compound having the same basic structure as a part of the mordant dye and the same dye among the above dyes, that is, quinone Only compounds represented by general formulas [1] to [5] having a hydroxyl group protected at the α-position of (carbonyl group) by a substituent were found. Other types of dyes, namely basic dyes and acid dyes, are readily soluble in water, while acidic mordant dyes are insoluble in water but use chromium for complex formation and toxicity.Metal complex dyes use chromium for complex formation. Due to toxicity and difficulty in lightening the dyes, direct dyes and soluble vat dyes are water-soluble, so vat dyes are insoluble in water but black color cannot be obtained.Sulfur dyes are insoluble in water and black color. However, azoic dyes and reactive dyes are not suitable as dyes for achieving the object of the present invention because lightening is difficult and azoic dyes and reactive dyes lack stability.

The compounds represented by the above general formulas [1] to [5] are anthraquinone, naphthoquinone, benzoquinone, benzophenone, acetophenone, and propiophenone compounds, and before introducing a substituent into the hydroxyl group of these compounds. The following compounds can be exemplified as the compounds, but the present invention is not limited thereto.

Examples of the anthraquinone compound include 1-hydroxyanthraquinone, 1,2-dihydroxyanthraquinone, 1,3-dihydroxyanthraquinone,
4-dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone, 1,6-dihydroxyanthraquinone, 1,7-dihydroxyanthraquinone, 1,8-dihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,2,4-tri Hydroxyanthraquinone, 1,2,5-trihydroxyanthraquinone, 1,2,6-trihydroxyanthraquinone, 1,
2,7-trihydroxyanthraquinone, 1,2,8-
Trihydroxyanthraquinone, 1,4,5-trihydroxyanthraquinone, 1,4,6-trihydroxyanthraquinone, 1,2,3,4-tetrahydroxyanthraquinone, 1,2,4,6-tetrahydroxyanthraquinone, 1, 2,5,6-tetrahydroxyanthraquinone, 1,2,5,8-tetrahydroxyanthraquinone, 1,2,6,7-tetrahydroxyanthraquinone, 1,2,7,8-tetrahydroxyanthraquinone, 1,3 5,7-tetrahydroxyanthraquinone, 1,4,5,7-tetrahydroxyanthraquinone, 1,2,3,5,7-pentahydroxyanthraquinone, 1,2,4,5,8-pentahydroxyanthraquinone, 1, 2,3,5,6,7-hexahydroxyanthraquinone, 1,2,2 , 5,6,8- hexa-hydroxy anthraquinone, 1,2,4,5,7,8- hexa-hydroxy-anthraquinone, 1-hydroxy-2,4
Dibromoanthraquinone, 1,2-dihydroxy-3-
Chloranthraquinone, 1,5-dihydroxy-2,6
-Dibromoanthraquinone, 1,2,3-trihydroxy-4-bromoanthraquinone, 1-hydroxy-4-
Nitroanthraquinone, 1-hydroxy-2,4-dinitroanthraquinone, 1,2-dihydroxy-3-nitroanthraquinone, 1,4-dihydroxy-5-nitroanthraquinone, 1,2,3-trihydroxy-4-nitroanthraquinone, 1,2,6-trihydroxy-4
-Nitroanthraquinone, 1-hydroxy-3-bromo-4-aminoanthraquinone, 1-hydroxy-4-aminoanthraquinone, 1,4-dihydroxy-5-anilinoanthraquinone, 1,5-dihydroxy-4,8-
Dimethylaminoanthraquinone, 1-hydroxy-4-
Acetamidoanthraquinone, 1,5-dihydroxy-
4,8-p-methoxybenzoylaminoanthraquinone.

The naphthoquinone compounds include 2-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,
4-naphthoquinone, 2-hydroxy-3-methyl-1,
4-naphthoquinone, 2-hydroxy-3-cyclohexyl-1,4-naphthoquinone, 2-hydroxy-3-benzyl-1,4-naphthoquinone, 2-hydroxy-3-chloro-1,4-naphthoquinone, 2-hydroxy- 3-nitro-1,4-naphthoquinone, 2-hydroxy-3-anilino-1,4-naphthoquinone, 2,3-dihydroxy-1,4-naphthoquinone, 2,5-dihydroxy-1,
4-naphthoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 5,8-dihydroxy-2-methyl-1,
4-naphthoquinone, 2-hydroxy-3-α-naphthylamidonaphthoquinone, 2-hydroxy-3-o-methoxyphenylamidonaphthoquinone. Examples of the benzoquinone-based compound include oxy-p-benzoquinone, 3-hydroxy-2-methyl-p-benzoquinone, and 5-hydroxy-2.
-Methyl-p-benzoquinone, 2,5-dioxy-p-
Benzoquinone.

The benzophenone compounds include 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxybenzophenone, 2,3'-dihydroxybenzophenone, 2,4
'-Dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,5-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,3 4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone.

As acetophenone and propiophenone compounds, 2'-hydroxyacetophenone, 2 ',
4'-dihydroxyacetophenone, 2 ', 5'-dihydroxyacetophenone, 2', 6'-dihydroxyacetophenone, 2 ', 3', 4'-trihydroxyacetophenone, 2'-hydroxypropiophenone, 2
', 4'-dihydroxypiophenone, 2', 4 ', 6
'-Trihydroxypropiophenone.

All the compounds before the introduction of a substituent into the hydroxyl group are dyes that are strongly colored, but the compounds of the present invention in which a substituent is introduced into the hydroxyl group and the function of the hydroxyl group is blocked are all colorless. Alternatively, it is a light-colored compound.

With respect to the relationship between the color and the chemical structure of a substance, it has long been known that the larger or more complex the molecule, the deeper the color, and the substituents also contribute to the depth of the color depending on the type. For example, as one that gives a deep color effect
_{OH, -OCH 3, -NH 2,} -NHCH 3, -N (C
H ₃ ) _{2 and the} like provide -COCH
₃ , -COC ₆ H _{5 and the} like. For example, the same applies to the above-described anthraquinone-based compound. When the α-position of quinone is substituted with -OH or the like, it absorbs long-wavelength light and becomes deep-colored, but when the -OH group is acylated, an anthraquinone nucleus is formed. Is hindered and becomes pale.

On the other hand, the hydroxyl group is the most abundant substituent in the structure of the natural or synthetic organic compound, and therefore, protection of the hydroxyl group is an indispensable reaction in the structure and synthetic studies of the compound. For this reason, protection studies have been made for a long time, and there are more than one hundred kinds of protecting groups, which are classified into silyl ether type, alkyl ether type, acetal type and ester type. Examples of the protecting group that can be used in the present invention include a trimethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group, a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a trityl group, and a tetrahydro group. Pyranyl group, 1-ethoxyethyl group, methoxymethyl group, methoxyethoxymethyl group, acetyl group, benzoyl group, p-nitrobenzoyl group, acetonide group, methylene acetal group, methoxycarbonyl group, benzyloxycarbonyl group, carbamate group Etc. can be raised. Considering the light-color effect, ease of reaction with a hydroxyl group, synthesis cost, and ease of elimination, an acetyl group, an acyl group such as a benzoyl group, an oxycarbonyl group such as a methoxycarbonyl group or a benzyloxycarbonyl group. Is most preferred.

The basic compounds usable in the present invention include amines, amides, guanidines, imidazoles, thiazoles, triazoles, thioureas, thiocarbamic acids, thiuram sulfides and morpholines. Oxazoles, piperazines, pyrazoles, carbazoles, indoles, piperidines, pyrrolidines, and the like, and specific examples include the following compounds. The present invention is not limited to this.

As amines, hexadecylamine, tribenzylamine, N, N, N ', N'-tetrabenzylethylenediamine, decamethylenediamine, tricyclohexylamine, dioctadecylamine, cyclohexyldibenzylamine, octadecylbenzylamine,
Phenyl-1-naphthylamine, N, N'-diphenyl-p-phenylenediamine, p- (p-toluenesulfonylamide) diphenylamine, 4,4'-diaminobenzanilide.

As amides, stearic acid amide, N-
Cyclohexyl-2-benzothiazolylsulfenamide, Nt-butylbenzothiazolylsulfenamide, ethylenebisstearamide, oleamide,
Methylene bis stearoamide, methylol stearoamide, o-toluene sulfonamide.

As guanidines, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1,3
-Di-p-methoxyphenylguanidine, 1,3-dicyclohexylguanidine, 1-benzyl-3-phenylguanidine, 1-p-tolyl-3-phenylguanidine, 1-o-tolylguanidine, 1,2,3-triene Phenylguanidine, 1,2,3-tricyclohexylguanidine, 1,1,3-triphenylguanidine, 1,3
-Diphenyl-2-p-tolylguanidine, 1,2-dibenzoyl-3-phenylguanidine, di-o-tolylguanidine salt of dicatecholoborate.

As imidazoles, 2-phenylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 2,4-diamino-6
[2′-Undecylimidazolyl- (1 ′)]-ethyl-S-triazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1,2-aminobenzimidazole, 2-mercaptobenz Imidazole.

As thiazoles, 2-aminobenzothiazole, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazol zinc salt, 2-mercaptobenzothiazole Cyclohexylamine salt, 2- (4'-morpholinodithio) benzothiazole, 2-aminothiazole.

As triazoles, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2
-(2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5
'-Di-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole.

As thioureas, 1,3-diphenyl-
2-thiourea, 1,3-diethyl-2-thiourea, 1,
3-dilauryl-2-thiourea, ethylenethiourea,
1,3-dibutyl-2-thiourea, 1,1,3-trimethyl-2-thiourea, 1,3-bis (dimethylaminopropyl) -2-thiourea.

As thiocarbamic acids, pentamethylenedithiocarbamic acid piperidine salt, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate.

As thiuram sulfides, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide.

The metal of the metal compound which can be used in the present invention includes chromium, aluminum, iron, nickel, tin, zinc, manganese, cobalt, lead, copper, vanadium, calcium, magnesium, silver and the like. Aluminum, iron and zinc are preferred in consideration of the properties, cost and color tone after the chelate reaction. The metal may be not only a single salt but also a double salt using two or more metals. Specific examples of compounds using these metals will be given, but the present invention is not limited thereto.

As aluminum compounds, aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum acetate, aluminum lactate, aluminum laurate, aluminum oxalate, aluminum oleate,
Aluminum stearate, aluminum acetylacetone, aluminum stearyl phosphate.

As iron compounds, iron nitrate, ferric hydroxide,
Ferric sulfate, ferric phosphate, ferric stearate, ferric myristate, ferric caproate, ferric behenate,
Ferric laurate, ferral pelargonate, ferric acetate,
Ferric citrate, ferric oxalate, iron lactate, iron benzoate, iron salicylate, ferric naphthalene, iron acetylacetone, iron dicyclopentadienyl, and ferric (2-ethylhexyl) phosphate.

As zinc compounds, zinc carbonate, zinc nitrate,
Zinc phosphate, zinc sulfate, zinc oxide, zinc acetate, zinc citrate, zinc formate, zinc lactate, zinc oleate, zinc oxalate, zinc stearate, zinc tartrate, zinc benzoate,
Zinc salicylate, zinc diethyldithiocarbamate, zinc acetylacetone, zinc stearyl phosphate.

The recording system of the present invention is manufactured by supporting the compounds of the general formulas [1] to [5], the basic compound and the metal compound, which are the color-forming components, simultaneously or separately on a support. In general, the support is applied on a support together with a binder. Further, other additives and physical treatments for satisfying the quality required according to the recording system can be performed within the ordinary technical range of the recording system. Further, when the recording system is pressure-sensitive recording paper, it has been found that the color-forming component of the present invention can be used in combination with a conventionally known leuco dye and a color-forming component composed of a developer that forms the leuco dye. Was. By taking advantage of the fact that the color development speed of the leuco dye and the color developing system, which are advantages of the leuco dye and the developer, is high, and that the color development color is rich, the color development component of the present invention can be used to achieve the desired color development. In addition, the pressure-sensitive recording paper is improved in coloring speed and excellent in storability.

When the recording system of the present invention is a thermosensitive recording paper, it is possible to use a conventionally known leuco dye together with a developer which causes the leuco dye to develop a color when heated as in the case of the pressure-sensitive recording paper. It has been found possible. Conventionally known thermosensitive recording papers containing a leuco dye and a color developing agent as coloring components generally use a heat-fusible substance having a lower melting point than the above coloring components as a sensitizer in order to improve the coloring sensitivity. The sensitizer may be used only when the color forming component of the present invention is used as a heat-sensitive color forming component.
It is effective for improving the color sensitivity.

When a recording system such as a thermosensitive recording paper or a pressure-sensitive recording paper is manufactured, an ultraviolet absorbent, a defoaming agent,
In addition to additives such as a fluorescent whitening agent, a waterproofing agent, a lubricant such as wax, and a staying agent, these additives can be used without any problem in the present invention.

The pressure-sensitive recording paper is usually prepared by encapsulating at least one of the color-forming components in a capsule, and other components separately from the capsule. In the case of the present invention, the compounds [1] to [5] and the basic compound must not be simultaneously present in the capsule. If the compound of [1] to [5] and the basic compound come into contact with each other in a dissolved state, the substituent protecting the hydroxyl group of the compound of [1] to [5] is eliminated by the basic compound, and the color is formed. Because you do. When used in combination with a leuco dye, the compound may be dissolved in a solvent together with the compounds [1] to [5] of the present invention and encapsulated, or may be separately encapsulated.

In the production of thermosensitive recording paper, it is necessary to avoid mixing and pulverizing the compounds [1] to [5] of the present invention and a basic compound at the same time. This is because, when mixed and pulverized at the same time, a partial reaction occurs and the hydroxyl-protecting groups of the compounds [1] to [5] are eliminated by the basic compound, and the slurry is colored. With this in mind, the recording system of the present invention can be manufactured using methods similar to conventional recording systems. Leuco dyes are colorless or light-colored electron-donating colorless described in paper pulp technology Times 9 , 99 (1982), literature on functional pigment chemistry (R & D report, CMC, 1981), and various patents. Although any dye can be used, the following compounds can be exemplified as typical ones.

As a triphenylmethanephthalide leuco dye, 3,3-bis (p-dimethylaminophenyl)-
6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide,
3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide.

As the fluoran leuco dye, 3-diethylamino-6-methyl-7-anilinofluoran;
(N-ethyl-p-toluidino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3-
Diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran, 3-pyrrolidino-6-methyl-
7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3-diethylamino- 7- (m-trifluoromethylanilino) fluoran, 3-Nn-dibutylamino-7- (o-chloroanilino) fluoran, 3-
(N-ethyl-N-tetrahydrofurfurylamino)-
6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino)
Fluoran, 3- (N-methyl-N-propylamino)
-6-methyl-7-anilinofluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-diethylamino-7- (o- Chloranilino)
Fluoran, 3-diethylamino-6-methyl-chlorofluoran, 3-diethylamino-6-methyl-fluoran, 3-cyclohexylamino-6-chlorofluoran, 3-diethylamino-benzo [a] -fluoran,
3-N-n-dibutylamino-6-methyl-7-anilinofluoran, 3-dimethylamino-5,7-dimethylfluoran, 3- (N-methyl-N-isobutylamino) -6-methyl- 7-anilinofluoran.

As the azaphthalide leuco dye, 3- (4
-Diethylamino-2-ethoxyphenyl) -3- (1
-Ethyl-2-methoxyindol-3-yl) -4-
Azaphthalide 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-octyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-N-cyclohexyl-N-methylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindole -3-yl) -4-azaphthalide.

3,3,6 as fluorene leuco dyes
'-Tris (dimethylamino) spiro [fluorene-
9,3'-phthalide] and 3,3,6'-tris (diethylamino) spiro [fluorene-9,3'-phthalide].

As the diphenylmethane leuco dye, 4,
4'-bis-dimethylaminobenzhydryl benzyl ether, N-halophenyl-leuco auramine, N-
2,4,5-trichlorophenyl-leuco auramine.

As phenothiazine leuco dyes, 3,7
-Bis (dimethylamino) -10-benzoylphenothiazine, 3,7-bis (dimethylamino) -10-p-
Nitrobenzoylphenothiazine, 10- (3 ', 4
', 5'-Trimethoxybenzoyl) -3,7-bis (dimethylamino) -phenothiazine.

As spiropyran-based leuco dyes, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphthopyran, 3-methyl-naphtho (6'-methoxy) Benzo) spiropyran, 3
-Propyl-spiro-dibenzopyran, 6 ', 8'-dichloro-1,3,3-trimethyl-indolino-benzospiropyranspiro [3-methylchromene-2,2'-
7'-diethylaminochromene], spiro [3-methylchromene-2,2'-7'-benzylaminochromene].

Rhodamine as a lactam leuco dye
B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine (o-chloroanilino) lactam, N-butyl-3- [bis- {4- (N-methylanilino) phenyl} methyl] carbazole.

3,7 as phenoxyzine leuco dyes
-Bis (diethylamino) -10-benzoylphenoxydine, 3-diethylamino-7 (N-methylanilino) -10-benzoylphenoxydine.

As an indolylphthalide leuco dye, 3,3-bis (1-ethyl-2-methylindole-3) is used.
-Yl) phthalide, 3,3-bis (2-methyl-1-octylindol-3-yl) phthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (1-
n-butyl-2-methylindol-3-yl) phthalide.

Developers for developing the leuco dye include literature such as information paper (Paper Industry Times, 1987), Paper Pulp Technical Times 5 , 33 (1987), and Paper Pulp Technical Times 3 , 1 (1989). And any of the electron-accepting compounds described in various patents can be used. Typical examples thereof include the following compounds.

Examples of bisphenol A include 4,4'-isopropylidenediphenol, 1,7-di (4-hydroxyphenylthio) -3,5-dioxaheptane,
4'-cyclohexylidenediphenol, 4,4'-
(1-methyl-normalhexylidene) diphenol,
2,2'-dihydroxydiphenol, 2,2'-methylenebis (4-methyl-6-tert-isobutylphenol), 4,4'-isopropylidenebis (2-te
rt-butylphenol), 4,4'-sec-butylidenediphenol, 2,2'-methylenebis (4-chlorophenol), 4,4'-isopropylidenebis (o
-Methylphenol), 4,4'-isopropylidenebis (2-chlorophenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol),
2,2'-methylenebis (4-methyl-6-tert-
Butylphenol), 4,4'-butylidenebis (6-
tert-butyl-2-methylphenol).

Examples of 4-hydroxybenzoic acid esters include benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate,
-Isopropyl hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate,
-Methylbenzyl hydroxybenzoate.

The 4-hydroxyphthalic acid diesters include dimethyl 4-hydroxyphthalate, diisopropyl 4-hydroxyphthalate, dibenzyl 4-hydroxyphthalate, and dihexyl 4-hydroxyphthalate.

Monoesters of phthalic acid include monobenzyl phthalate, monocyclohexyl phthalate, monophenyl phthalate, monomethyl phenyl phthalate, monoethyl phenyl phthalate, monoalkyl benzyl phthalate, phthalic acid Monohalogen benzyl ester, phthalic acid monoalkoxybenzyl ester.

As bis- (hydroxyphenyl) sulfides, bis- (4-hydroxy-3-tert-butyl-6-methylphenyl) sulfide, bis- (4-
(Hydroxy-2,5-dimethylphenyl) sulfide;
Bis- (4-hydroxy-2-methyl-5-ethylphenyl) sulfide, bis- (4-hydroxy-2-methyl-5-isopropylphenyl) sulfide, bis-
(4-hydroxy-2,3-dimethylphenyl) sulfide, bis- (4-hydroxy-2,5-diethylphenyl) sulfide, bis- (4-hydroxy-2,5-
Diisopropylphenyl) sulfide, bis- (4-hydroxy-2,3,6-trimethylphenyl) sulfide, bis- (2,4,5-trihydroxyphenyl) sulfide, bis- (4-hydroxy-2-cyclohexyl-5) -Methylphenyl) sulfide, bis- (2,
3,4-trihydroxyphenyl) sulfide, bis-
(4,5-dihydroxy-2-tert-butylphenyl) sulfide, bis- (4-hydroxy-2,5-diphenylphenyl) sulfide, bis- (4-hydroxy-2-tert-octyl-5-methylphenyl) Sulfide.

As 4-hydroxyphenylarylsulfones, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, Hydroxy-4'-n-butyloxydiphenyl sulfone.

As 4-hydroxyphenylarylsulfonates, 4-hydroxyphenylbenzenesulfonate, 4-hydroxyphenyl-p-tolylsulfonate, 4-hydroxyphenylmethylenesulfonate,
4-hydroxyphenyl-p-chlorobenzenesulfonate, 4-hydroxyphenyl-p-tert-butylbenzenesulfonate, 4-hydroxyphenyl-p-
Isopropoxybenzenesulfonate, 4-hydroxyphenyl-1'-naphthalenesulfonate, 4-hydroxyphenyl-2'-naphthalenesulfonate.

1,3-di [2- (hydroxyphenyl)
-2-propyl] benzenes include 1,3-di [2-
(4-hydroxyphenyl) -2-propyl] benzene, 1,3-di [2- (4-hydroxy-3-alkylphenyl) -2-propyl] benzene, 1,3-di [2
-(2,4-hydroxyphenyl) -2-propyl] benzene, 1,3-di [2- (2, -hydroxy-5-methylphenyl) -2-propyl] benzene.

Examples of 4-hydroxybenzoyloxybenzoate esters include benzyl 4-hydroxybenzoyloxybenzoate, methyl 4-hydroxybenzoyloxybenzoate, ethyl 4-hydroxybenzoyloxybenzoate, propyl 4-hydroxybenzoyloxybenzoate, Butyl 4-hydroxybenzoyloxybenzoate, isopropyl 4-hydroxybenzoyloxybenzoate, ter 4-hydroxybenzoyloxybenzoate
t-butyl, hexyl 4-hydroxybenzoyloxybenzoate, octyl 4-hydroxybenzoyloxybenzoate, nonyl 4-hydroxybenzoyloxybenzoate, cyclohexyl 4-hydroxybenzoyloxybenzoate, β- 4-hydroxybenzoyloxybenzoate
Phenethyl, phenyl 4-hydroxybenzoyloxybenzoate, 4-hydroxybenzoyloxybenzoic acid α
-Naphthyl, β-naphthyl 4-hydroxybenzoyloxybenzoate, sec-butyl 4-hydroxybenzoyloxybenzoate.

As bisphenol sulfones, bis-
(3-1-butyl-4-hydroxy-6-methylphenyl) sulfone, bis- (3-ethyl-4-hydroxyphenyl) sulfone, bis- (3-propyl-4-hydroxyphenyl) sulfone, bis- (3 -Methyl-4-hydroxyphenyl) sulfone, bis- (3-isopropyl-4-hydroxyphenyl) sulfone, bis- (3-
Ethyl-4-hydroxyphenyl) sulfone, bis-
(3-chloro-4-hydroxyphenyl) sulfone, bis- (2,3-dimethyl-4-hydroxyphenyl) sulfone, bis- (2,5-dimethyl-4-hydroxyphenyl) sulfone, bis- (3-methoxy -4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-2
'-Ethyl-4'-hydroxyphenylsulfone, 4-
Hydroxyphenyl-2'-isopropyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-3
'-Isopropyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-3'-secbutyl-4
'-Hydroxyphenylsulfone, 3-chloro-4-hydroxyphenyl-3'-isopropyl-4'-hydroxyphenylsulfone, 2-hydroxy-5-t-butylphenyl-4'-hydroxyphenylsulfone, 2-
Hydroxy-5-t-aminophenyl-4'-hydroxyphenylsulfone, 2-hydroxy-5-isopropylphenyl-4'-hydroxyphenylsulfone, 2-
Hydroxy-5-t-octylphenyl-4'-hydroxyphenylsulfone, 2-hydroxy-5-t-butylphenyl-3 -'- chloro-4'-hydroxyphenylsulfone, 2-hydroxy-5-t-butylphenyl -3'-methyl-4'-hydroxyphenylsulfone,
2-hydroxy-5-tert-butylphenyl-3'-isopropyl-4'-hydroxyphenylsulfone, 2-hydroxy-5-tert-butylphenyl-2'-methyl-4
'-Hydroxyphenylsulfone, 4,4'-sulfonyldiphenol, 2,4'-sulfonyldiphenol,
3,3'-dichloro-4,4'-sulfonyldiphenol, 3,3'-dibromo-4,4'-sulfonyldiphenol, 3,3 ', 5,5'-tetrabromo-4,4'
-Sulfonyldiphenol, 3,3'-diamino-4,
4'-sulfonyldiphenol.

As phenols, p-tert-butylphenol, p-phenylphenol, p-benzylphenol, 1-naphthol, 2-naphthol, 4-hydroxyacetophenol, 1,3-dihydroxy-6
(Α, α-dimethylbenzyl) -benzene.

The metal salts of aromatic carboxylic acids include benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, 3-sec-butyl-4-hydroxybenzoic acid,
-Cyclohexyl-4-hydroxybenzoic acid, 3,5-
Dimethyl-4-hydroxybenzoic acid, terephthalic acid,
Salicylic acid, 3-isopropylsalicylic acid, 3-ter
t-butylsalicylic acid, 3-benzylsalicylic acid, 3-
(Α-methylbenzyl) salicylic acid, 3-chloro-5-
(Α-methylbenzyl) salicylic acid, 3,5-di-te
rt-butylsalicylic acid, 3-phenyl-5- (α, α
-Methylbenzyl) salicylic acid, 3,5-di-α-methylbenzylsalicylic acid, etc., and the metals of these compounds include magnesium, aluminum, cadmium, calcium, titanium, zinc, nickel, cobalt, manganese, vanadium, Iron, copper, etc. can be raised.

The developer for the thermal recording system has been exemplified above.
The following compounds can be exemplified as the developer for the pressure-sensitive recording system. As the aromatic carboxylic acid polyvalent metal salt,
Benzoic acid, p-hydroxybenzoic acid, chlorobenzoic acid,
Bromobenzoic acid, nitrobenzoic acid, methoxybenzoic acid,
Ethoxybenzoic acid, toluic acid, ethylbenzoic acid, p-
n-propylbenzoic acid, p-isopropylbenzoic acid, 3
-Methyl-4-hydroxybenzoic acid, 3-ethyl-4-
Hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, p-tert-butylbenzoic acid, o-benzoylbenzoic acid, p-cyclohexylbenzoic acid, salicylic acid, 3-methyl-5-tert-butylsalicylic acid,
3,5-di-tert-butylsalicylic acid, 5-nonylsalicylic acid, 5-cyclohexylsalicylic acid, 3-cyclohexylsalicylic acid, cresotic acid, 3-cumylsalicylic acid, 3-phenylsalicylic acid, 3,5-di-se
c-butylsalicylic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, gallic acid, naphthoic acid, monobenzyl phthalate, monocyclohexyl phthalate, salicylosalicylic acid, 3-tert-butyl-5-α -Methylbenzylsalicylic acid, 3,5-di (α
-Methylbenzyl) salicylic acid, phthalic acid, terephthalic acid, isophthalic acid, diphenic acid, naphthalene dicarboxylic acid, naphthalic acid and the like. The metals of these compounds are magnesium, aluminum,
Cadmium, calcium, titanium, zinc, nickel, cobalt, manganese, vanadium, iron, copper and the like can be mentioned.

Examples of the activated clay include activated clay, acid clay, attapulgite, bentonite, zeolite, montmorillonite, halloysite, kaolinite, anhydrous silicic acid, anhydrous magnesium silicate and anhydrous aluminum silicate.

Examples of the phenol resin include p-phenylphenol-formaldehyde polymer, p-octylphenol-formaldehyde polymer, p-cumylphenol-formaldehyde polymer, p-tert-butylphenol-formaldehyde polymer, and p-nonylphenol-formaldehyde. Polymer, p-cyclohexylphenol-formaldehyde polymer, p-ethylphenol-formaldehyde polymer, p-propylphenol-formaldehyde polymer, p-amylphenol-
Formaldehyde polymer, p-hexylphenol-formaldehyde polymer, p-heptylphenol-formaldehyde polymer, p-decylphenol-formaldehyde polymer, p-dodecylphenol-formaldehyde polymer, p-octylphenol-acetaldehyde polymer, p -Phenylphenol-acetaldehyde polymer, p-tert-butylphenol-acetaldehyde polymer.

A polyvalent metal-modified phenol resin obtained by modifying the above phenol resin with a polyvalent metal such as zinc or a polyvalent metal salt of a carboxylated terpene phenol resin can also be used. Among these color developers, metal compounds such as polyvalent metal salts of aromatic carboxylic acids and polyvalent metal-modified phenol resins are chelate with the compounds of the general formulas [1] to [5] from which the protecting groups have been eliminated. It can be used as a metal compound to be formed.

In a conventional thermal recording system using a leuco dye and a color developer as a coloring component, a sensitizer is used to improve the coloring sensitivity. This sensitizer was also effective in a thermal recording system using the color-forming component of the present invention. The sensitizer is information paper (Paper Industry Times, 1987)
Year), non-impact printing (CMC, 198)
6 years) and various patents can be used. As typical examples, the following compounds can be exemplified.

Stearic acid and behenic acid are used as fatty acids, zinc stearate, aluminum stearate, calcium stearate, zinc palmitate and zinc behenate are used as fatty acid metal salts, and stearamide and palmitic acid are used as fatty acid amides. As the waxes, amides, oleic acid amides, ethylenebisstearamides, and coconut fatty acid amides are montan waxes and polyethylene waxes.

As carbonates, phenyl-α-naphthyl carbonate, di-p-tolyl carbonate and diphenyl carbonate are used, and as triphenyls, p-benzylbiphenyl, m-terphenyl and triphenyl are used.
Triphenylmethane is converted to hindered phenols by 2,2′-methylenebis (4-methyl-6-ter
t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.

As ethers, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (phenoxy)
Ethane, 1,2-bis (4-methylphenoxy) ethane, 1,4-bis (phenoxy) butane, 1,4-bis (phenoxy) butene, 2-naphthylbenzyl ether, 1,4-diethoxynaphthalene 1,4-dimethoxynaphthalene, 1,4-dibenzyloxynaphthalene,
Benzyl-4-methylthiophenyl ether, 4-chlorobenzyl-4'-methylthiophenyl ether, 4-
Methylbenzyl-4'-methylthiophenyl ether,
1,4-bis (phenylthio) butane, 1,4-bis (phenylthio) butene, 1,2-bis (4-methoxyphenylthio) butene, 1,3-bis (2-vinyloxyethoxy) benzene, 1, 4-bis (2-vinyloxyethoxy) benzene, p- (2-vinyloxyethoxy) biphenyl, p-aryloxybiphenyl, p-
Propagyloxybiphenyl.

As the esters, 1-hydroxy-2-
Naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid methyl ester, 2-naphthoic acid phenyl ester, benzyl p-benzyloxybenzoate, dibenzyl terephthalate, dimethyl terephthalate, dibenzoyloxymethane, 1,3-dibenzoyl Oxypropane,
Dibenzyl disulfide, 1,1-diphenylethanol, 1,1-diphenylpropanol, 1,1,
3-diphenoxy-2-propanol, p- (benzyloxy) benzyl alcohol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N-octadecylcarbamoylbenzene.

The binder that can be used in the present invention includes:
Modified polyvinyl alcohols such as completely and partially saponified polyvinyl alcohols of various degrees of polymerization, carboxy-modified polyvinyl alcohols, starch and various modified starches,
Cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, casein, gelatin, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, styrene, vinyl acetate
And polymers and copolymers of acrylamide, acrylate, and the like, polyamide resins, silicone resins, petroleum resins, terpene resins, ketone resins, cumarone resins, and the like. These natural and synthetic polymer substances are used by dissolving them in water or an organic solvent such as alcohol.
It can be used in a state of being emulsified or dispersed in a paste form in a medium such as water, and can be used in combination depending on the application.

The fillers usable in the present invention include clay, calcined clay, diatomaceous earth, talc, kaolin, calcium carbonate, basic magnesium carbonate, barium sulfate,
Natural or synthetic inorganic or organic fillers such as barium carbonate, aluminum hydroxide, zinc oxide, silica, magnesium hydroxide, titanium oxide, urea-formalin resin, polystyrene resin, phenol resin and the like can be used.
These fillers can be used in combination.

This paint was applied to an air-knife coater,
When a variety of coaters such as a coater and a roll coater are applied on an arbitrary support, a recording medium having a novel color developing system can be obtained.

Examples of the support used herein include paper such as high quality paper, medium quality paper, and coat paper, synthetic paper, and film.

[0080]

According to the present invention, a compound of the general formulas [1] to [5], which is obtained by introducing a substituent (protecting group) into a colored dye or pigment and which is made colorless or pale like a leuco dye, is subjected to either heat or pressure energy. When the basic compound is reacted by adding
The basic compound removes the substituent introduced as a protecting group to obtain the original colored dye or pigment. Next, the coloring system is a recording system in which a colored dye or pigment is reacted with a metal compound to form a chelate to further form a deep color compound.
The reason why the recording system of the present invention has high preservability excellent in oil resistance, solvent resistance, water resistance, and light resistance is that the compounds of [1] to [5], in which a pre-reaction-substituent is used, used in the above recording method. And a chelate compound formed by a metal compound and a compound having a protective substituent eliminated from the compound of-[1] to [5] after the reaction is dissolved in water, an oil, a solvent, or decomposed by light. It is considered that no reverse reaction occurs.

[0081]

EXAMPLES The present invention will be described in detail below with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.
In the description, parts and percentages indicate parts by weight and percentage by weight, respectively.

Synthesis Example 1 Methoxycarbo of 1,2-dihydroxyanthraquinone
Nylation thermometer, 300ml in 500ml three-necked flask with stirrer
Introduce ml of tetrahydrofuran and dissolve 5.0 g (0.0208 mol) of 1,2-dihydroxyanthraquinone. Next, 10 ml of pyridine are added as a catalyst. Due to the exothermic reaction, the temperature in the flask was cooled to 19 to 20 ° C., and 10 ml (0.0847 mol) of methyl chloroformate was added dropwise from a dropping funnel over 1 hour. React at room temperature for 2 hours after dropping. Thereafter, the reaction solution was placed in 5 l of water to precipitate crystals,
Filter, wash thoroughly with water and dry. Melting point 188.5-1
90.5 ° C. pale yellow crystals are obtained.

Synthesis Example 2 1,2,5,8-Tetrahydroxyanthraquinone
300ml in a 500ml three-necked flask equipped with
Add tetrahydrofuran (ml) and dissolve 5.0 g (0.0184 mol) of 1,2,5,8-tetrahydroxyanthraquinone. Next, 10 ml of pyridine are added as a catalyst. Due to the exothermic reaction, the temperature in the flask was cooled to 15 ° C, and 9.6 ml (0.0827 mol) of benzoyl chloride was added dropwise from a dropping funnel over 30 minutes. It reacts at room temperature for 7 hours after dropping. Thereafter, the reaction solution is placed in 5 l of water to precipitate crystals, which is filtered, sufficiently washed with water, and dried. Recrystallization from ethyl acetate-methyl alcohol gave a melting point of 177.5.
178.1 ° C. pale red crystals are obtained.

[Synthesis Example 3] 2-hydroxy-3-o-methoxyphenylamide naph
Toquinone acetylation thermometer, 500 ml three-necked flask with stirrer, 300
ml of pyridine and 5.0 g of 2-hydroxy-3-o-methoxyphenylamidonaphthoquinone (0.0171
Mol) is dissolved. The temperature in the flask was cooled to 15 to 20 ° C due to an exothermic reaction, and 3.8 ml of acetic anhydride (0.034
2 mol) from the dropping funnel over 30 minutes. It reacts for 4 hours at room temperature after dropping. Thereafter, the reaction solution is placed in 5 l of ice water and lowered to pH 2 with 1N hydrochloric acid. The precipitated crystals are filtered, sufficiently washed with water, and dried. Melting point 163.7-16
Light gray crystals at 4.4 ° C. are obtained.

[Synthesis Example 4] Acetyl of 2,3,4-trihydroxybenzophenone
Of thermometer, a stirrer with a 500ml three-necked flask, 300
Add pyridine of ml and dissolve 5.0 g (0.0217 mol) of 2,3,4-trihydroxybenzophenone.
Due to the exothermic reaction, the temperature in the flask was cooled to 15 to 20 ° C., and 10.9 ml (0.0977 mol) of acetic anhydride was added dropwise from a dropping funnel over 30 minutes. It reacts at room temperature for 5 hours after dropping. Then, the reaction solution is put in 5 l of ice water and 1N hydrochloric acid.
Lower to pH 2. The precipitated crystals are filtered, sufficiently washed with water, and dried. Light yellow crystals with a melting point of 118.7-119.0 ° C. are obtained.

Synthesis Example 5 Benzoyl of 2 ', 4'-dihydroxyacetophenone
Of thermometer, a stirrer with a 500ml three-necked flask, 300
Add tetrahydrofuran (ml) and dissolve 5.0 g (0.0329 mol) of 2 ', 4'-dihydroxyacetophenone. Next, 10 ml of pyridine are added as a catalyst. Due to the exothermic reaction, the temperature in the flask was cooled to 15 ° C., and 9.6 ml (0.0823 mol) of benzoyl chloride was added dropwise from a dropping funnel over 30 minutes. It reacts at room temperature for 8 hours after dropping. Thereafter, the reaction solution is placed in 5 l of water to precipitate crystals, which is filtered, sufficiently washed with water, and dried. Melting point 80.0-81.
Light yellow crystals at 0 ° C. are obtained.

Synthesis Example 6 Acetylation of 2,5-dihydroxy-p-benzoquinone Thermometer, 300 ml in a 500 ml three-necked flask equipped with a stirrer
Add ml of pyridine and dissolve 5.0 g (0.0357 mol) of 2,5-dihydroxy-p-benzoquinone. Due to the exothermic reaction, the temperature in the flask was cooled to 15 to 20 ° C, and 11.9 ml (0.107 mol) of acetic anhydride was added dropwise.
Drop over 30 minutes. It reacts at room temperature for 5 hours after dropping. Thereafter, the reaction solution is put in 5 l of ice water and pH is adjusted with 1N hydrochloric acid.
Lower to 2. The precipitated crystals are filtered, washed thoroughly with water,
dry. Light brown crystals with a melting point of 150.0-155.0 ° C. are obtained.

[Examples 1 to 9] Production method of thermosensitive recording paper Each of the materials shown in Tables 1-1 and 1-2 was blended as in the following liquids A, B and C, and each was mixed for about 3 hours with an attritor. Grind to a particle size of 3μ. Liquid A Compounds of general formulas [1] to [5] 2.5 parts 10% polyvinyl alcohol 4.2 parts Water 7.8 parts Liquid B basic compound 4.0 parts 10% polyvinyl alcohol 5 7.7 parts water 5.5 parts C liquid metal compound 6.0 parts 10% polyvinyl alcohol 15.0 parts water 9.0 parts These dispersions are mixed at the following ratio to prepare a paint. Liquid A 10.7 parts Liquid B 25.0 parts Liquid C 30.0 parts Kaolin dispersion (30%) 53.0 parts 10% polyvinyl alcohol 20.0 parts Water 31.0 parts 50 g of the above coating material / M ² of high-quality paper with an application amount of 6.0 g /
and m ^{2, and} the coating scan - Pa - calendering - processing to give a heat-sensitive recording paper.

Examples 10 to 14 Production of thermosensitive recording paper
Method Each material shown in Table 1-3 was blended as in the following liquids A, B, C, D, and E, and each was treated with an attritor for about 3 hours for a particle size of 3
Grind to a μ. Liquid A Compound of general formula [1] to [5] 2.5 parts 10% polyvinyl alcohol 4.2 parts Water 7.8 parts Liquid B leuco dye 2.0 parts 10% polyvinyl alcohol 4. 6 parts water 2.5 parts liquid basic compound 4.0 parts 10% polyvinyl alcohol 5.7 parts water 5.5 parts liquid metal compound 6.0 parts 10% polyvinyl alcohol 15.0 part 9.0 parts solution E 6.0 parts 10% developer aqueous polyvinyl - Ruaruko - 15.0 parts water 15.0 parts Le mixing these dispersions in the following proportions to paint. Liquid A 9.7 parts Liquid B 0.8 parts Liquid C 22.5 parts Liquid D 27.0 parts Liquid E 7.2 parts Kaolin Kure dispersion (30%) 53.0 parts 10% polyvinyl alcohol 20 0.0 parts water 35.0 parts The above coating material was applied to a high quality paper of 50 g / m ^{2 in} an amount of 6.0 g / m ^2.
and m ^{2, and} the coating scan - Pa - calendering - processing to give a heat-sensitive recording paper.

Examples 15 to 19 Production of Thermal Recording Paper
Method Each of the materials shown in Table 1-4 is blended as in the following liquids A, B, C and D, and each is pulverized by an attritor for about 3 hours until the particle diameter becomes 3 μm. Liquid A Compounds of general formulas [1] to [5] 2.5 parts 10% polyvinyl alcohol 4.2 parts Water 7.8 parts Liquid B basic compound 4.0 parts 10% polyvinyl alcohol 5 5.7 parts water 5.5 parts liquid metal compound C 6.0 parts 10% polyvinyl alcohol 15.0 parts water 9.0 parts liquid D sensitizer 4.0 parts 10% polyvinyl alcohol 5.7 parts 5.5 parts of water These dispersions are mixed at the following ratio to prepare a paint. Liquid A 10.7 parts Liquid B 25.0 parts Liquid C 30.0 parts Liquid D 25.0 parts Kaolin clay dispersion (30%) 53.0 parts 10% polyvinyl alcohol 20.0 parts Water 49. 0 parts The above coating material is applied to a high quality paper of 50 g / m ^{2 in} an amount of 6.0 g / m ^2.
and m ^{2, and} the coating scan - Pa - calendering - processing to give a heat-sensitive recording paper.

[Comparative Example 1] Method for producing thermosensitive recording paper Each liquid of A and B having the following composition was pulverized with an attritor for about 3 hours until the particle diameter became 3 µm. Solution A 3-Diethylamino-6-methyl-7-anilinofluorane 2.0 parts 10% polyvinyl alcohol 4.6 parts Water 2.5 parts Solution B 4,4'-isopropylidene diphenol 6.0 Parts 10% polyvinyl alcohol 15.0 parts water 15.0 parts These dispersions are mixed at the following ratio to form a paint. A solution 10.0 parts B solution 36.5 parts of kaolin clay - dispersion (30%) 50.0 parts 10% polyvinyl - Ruaruko - Le 20.0 parts Water 20.0 parts The above coating material to 50 g / m ² fine paper The coating amount is 6.0 g / m
² and a super calendar treatment to obtain a thermosensitive recording paper.

[Examples 20 to 28] Production of pressure-sensitive recording paper
Method The following upper paper and lower paper were manufactured using the materials shown in Tables 2-1 and 2-2. Manufacture of upper paper 90 parts of a 10% aqueous solution of ethylene maleic anhydride copolymer is mixed with 90 parts of diluting water, and 10 parts of urea and 1 part of resorcin are dissolved in the mixture to adjust the pH to 3.4. Separately, a 1: 1 mixed oil of alkyldiphenylethane and diisopropylnaphthalene is used as a capsule core substance in the general formulas [1] to [5].
Is dissolved 4%. 180 parts of this oil solution was added to the above aqueous solution, and emulsified to an average particle size of 4 μm.
27% aqueous solution of formaldehyde was added and the temperature was increased.
The reaction is carried out at 2 ° C. for 2 hours to form capsule walls. 28%
The solution was neutralized to pH 7.5 with an aqueous ammonia solution to obtain a microcapsule slurry. The coating amount consisting of 180 parts of this capsule slurry, 40 parts of flour starch, 85 parts of an 8% oxidized starch solution and 340 parts of water was applied to a high-quality paper of 45 g / m ^{2 in} an amount of 4.0.
g / m ² to obtain the upper paper. Production of lower paper A liquid basic compound 4.0 parts 10% polyvinyl alcohol 5.7 parts water 5.5 parts B liquid metal compound 6.0 parts 10% polyvinyl alcohol 15.0 parts water 9 0.0 parts Each of the liquids A and B having the above composition is pulverized by an attritor for about 3 hours until the particle diameter becomes 3 μm. These dispersions are mixed at the following ratio to obtain a paint. Liquid A 25.0 parts Liquid B 30.0 parts Kaolin Kure dispersion (50%) 200.0 parts Styrene-butadiene latex (48%) 20.8
Part Oxidized starch aqueous solution (20%) 75.0 parts Water 115.9 parts The amount of the above coating composition applied to 50 g / m ² high quality paper was 6.0 g / m2.
m ² to obtain a lower paper.

[Examples 29 to 33] Production of pressure-sensitive recording paper
Method The following upper paper and lower paper were manufactured using the materials shown in Table 2-3. Manufacture of upper paper 90 parts of a 10% aqueous solution of ethylene maleic anhydride copolymer is mixed with 90 parts of diluting water, and 10 parts of urea and 1 part of resorcin are dissolved in the mixture to adjust the pH to 3.4. Separately, a 1: 1 mixed oil of alkyldiphenylethane and diisopropylnaphthalene is used as a capsule core substance in the general formulas [1] to [5].
Is dissolved in 3.6% of the compound and 0.4% of the leuco dye, respectively. 180 parts of this oil solution is added to the above aqueous solution, and when emulsified to an average particle diameter of 4 μm, 27 parts of a 37% formaldehyde aqueous solution is added, the temperature is raised, and the mixture is reacted at 55 ° C. for 2 hours to form a capisel wall. 28% aqueous ammonia
The solution was neutralized to pH 7.5 to obtain a microcapsule slurry.
180 parts of this capsule slurry, 40 parts of flour starch and 8 parts
45 parts of a paint consisting of 85 parts by weight of an oxidized starch solution and 340 parts of water.
g / m ² of high-quality paper was applied so that the coating amount was 4.0 g / m ² , to obtain an upper paper. Production of lower paper A liquid basic compound 4.0 parts 10% polyvinyl alcohol 5.7 parts water 5.5 parts B liquid metal compound 6.0 parts 10% polyvinyl alcohol 15.0 parts water 9 .0 parts C solution 6.0 parts 10% color developer polyvinyl - Ruaruko - le 15.0 parts water 15.0 parts the above formulation a, B, and C each liquid attritor - about 3 hours,
Grind to a particle size of 3μ. These dispersions are mixed at the following ratio to obtain a paint. Liquid A 22.5 parts Liquid B 27.0 parts Liquid C 7.2 parts Kaolin clay dispersion (50%) 200.0 parts Styrene-butadiene latex (48%) 20.8
Part Oxidized starch aqueous solution (20%) 75.0 parts Water 114.2 parts The amount of the above coating composition applied to 50 g / m ² high quality paper is 6.0 g / part.
m ² to obtain a lower paper.

Comparative Example 2 Method for Producing Pressure-Sensitive Recording Paper Production of Upper Paper In the production of upper paper of Examples 20 to 28, 3-diethylamino- was used in place of the compounds of the general formulas [1] to [5].
Capsule slurry in the same manner as in Examples 20 to 28 except that 6-methyl-7-anilinofluoran was used.
Was manufactured to obtain upper paper. Manufacture of lower paper The developer is ground with an attritor for about 3 hours until the particle size becomes 3 μm with the following composition. p-Phenylphenol resin 10.0 parts Sodium polyacrylate 0.3 part Water 15.0 parts The above dispersion is mixed at the following ratio to prepare a paint. The above developer dispersion 37.5 parts Kaolin clay dispersion (50%) 200.0 parts Styrene-butadiene latex (48%) 20.8
Part Oxidized starch aqueous solution (20%) 75.0 parts Water 133.4 parts The amount of the above coating composition applied to a high quality paper of 50 g / m ² is 6.0 g / part.
m ² to obtain a lower paper.

The heat-sensitive recording paper and pressure-sensitive recording paper obtained in the above Examples and Comparative Examples were subjected to quality tests shown in Tables 3 and 4 below. As a result, Examples 1 to 9 had better oil resistance, light resistance, water resistance, and solvent resistance than Comparative Example 1,
When a leuco dye and a developer are used in combination, the color tone becomes black and the attained color density is increased as in Examples 10 to 14. When a sensitizer is used in combination, the storage stability is impaired as in Examples 15 to 19. Color density reached, and 10
It can be seen that the difference in color density between the second and 24 hours later becomes smaller and the color developing speed becomes faster. Example 20 with pressure-sensitive recording method
As compared with Comparative Example 2, it was excellent in oil resistance, light resistance, water resistance, and solvent resistance as compared with Comparative Example 2, but when a leuco dye and a developer were used in combination, the color tone became black as in Examples 29 to 33 and reached. It can be seen that the color density is increased.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

[0102]

[Table 7]

[0103]

[Table 8]

Evaluation: (1) Oil resistance, light resistance, and water resistance (colored portion) ○ Almost unchanged △ Slightly reduced color density × disappeared (2) Solvent resistance (blank paper portion) ○ Almost no color △ Slightly colored × Coloring Coloring and color tone: Step wedge tester 150 ° C
The color is heated and the color tone is observed with the naked eye. Color density: after 10 seconds and 24
After time, measured with a Macbeth densitometer (RD-914, using an amber filter). Coloring speed: The smaller the difference between the coloring densities after 10 seconds and 24 hours, the faster the coloring speed. Oil resistance: The coloring paper is soaked in salad oil for 24 hours, and the decrease in coloring density is visually observed. Lightfastness: Treat colored paper with a fade meter for 6 hours,
The decrease in color density is visually observed. Water resistance: The coloring paper is immersed in water at 20 ° C. for 24 hours, and the decrease in coloring density is visually observed. Solvent resistance: 95% ethanol is dropped on white paper, and after 30 minutes, the state of color development is visually observed.

[0105]

[Table 9]

Evaluation: (1) Oil resistance, solvent resistance, and light resistance (colored portion) ○ Almost no change △ Slight decrease in color density × disappearance (2) Light resistance (blank paper portion) ○ Almost unchanged △ Slightly yellow No × becomes yellow Coloring, color tone: The upper paper and the lower paper face each other and are superimposed on each other to form a color with a calendar, and the color density and color tone are visually observed. Color density is digital hunter whiteness meter
(Toyo Seiki) using an amber filter. Color density (%) = (I ₀ −I ₁ ) / I ₀ × 100 I ₀ : Reflectivity before color development I ₁ : Reflectivity after 24 hours color development Oil resistance: Coloring paper is converted to vinyl chloride containing a plasticizer The scissors are treated at 60 ° C. and 90% for 24 hours, and the decrease in color density is visually observed. Solvent resistance: The coloring paper is soaked in ethanol, and the decrease in coloring density is visually observed. Lightfastness: (1) Color-developed portion: Color-developed paper is treated with a fade meter for 6 hours, and a decrease in color-developed density is visually observed. (2) Blank paper: White paper is exposed to direct sunlight for 8 hours, and the degree of yellowing is visually observed.

[0107]

As described above, the use of a novel chelate coloring system comprising one or more of the compounds represented by the general formulas [1] to [5], a metal compound and a basic compound according to the present invention provides oil and oil resistance. A recording paper excellent in solvent, water resistance and light resistance can be supplied. Furthermore, when a leuco dye and a developer are used in combination in these color forming systems, the above-mentioned preservability and black color development,
When a recording paper excellent in high color density is used in combination with a sensitizer, it is possible to supply a recording paper excellent in the preservability, the color density and the color developing speed.

Claims (3)

(57) [Claims] 1. A recording system comprising one or more of the compounds represented by the following general formulas [1] to [5], a metal compound and a basic compound as a coloring component. Embedded image (Wherein, X represents a hydroxyl-protecting group, l is 0-3, m is 0-4, n + o is 1-2, p is 0-1, q is 0-3, r
Represents 0 to 1, s represents 0 to 2, t represents 0 to 4, u represents 0 to 5, and v represents a number of 0 to 4. R _{1 to} R ₉ represent hydrogen, an alkyl group, an alkoxy group, an acyl group, an acylamino group, an amino group, an aralkyl group, an aryl group, a nitro group, or a halogen atom, and can substitute a portion other than the OX group. R ₁₀ represents an alkyl group. ) 2. A recording system according to claim 1, comprising a leuco dye as a color-forming component and a developer for developing the leuco dye. 3. A heat-sensitive recording system comprising the color-forming component according to claim 1 and a heat-fusible sensitizer.