JPH07109423A - Color developer for electron-donating color-forming organic compound, elapsed-time indicating material, temperature indicating material, recording material, and thermal recording medium - Google Patents

Abstract

PURPOSE:To obtain the subject color developer which rapidly undergoes color forming reaction with a color-changing dye to give a colored part having high density and high shelf stability without readily losing the color in the air and which is excellent in stability in the air, by using as the constituent a compound obtained by substituting the hydrogen atom of the amino group of an amino acid by a specified group. CONSTITUTION:The color developer comprises a compound obtained by substituting the hydrogen atom of the amino group of an amino acid (e.g. phenylalanine) by an acyl group (e.g. a benzoyl group). The elapsed-time indicating material contains this color developer preferably together with a color-changing dye (e.g. 1,3-dimethyl-6-diethylaminofluoran) and a vaporizable desensitizing chemical (e.g. diethylene glycol mono-n-hexyl ether). The temperature indicating material contains this color developer preferably together with a color-changing dye and a fusible compound (e.g. lauryl alcohol).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an electron-donating color-forming organic compound, which is used for various displays and recordings by utilizing the color development of an electron-donating color-forming organic compound (for example, leuco dye). The present invention relates to a color developer that can be used to generate color, and various materials using the developer such as a time display agent, a temperature indicator, a recording material and a heat-sensitive recording material.

[0002]

2. Description of the Related Art Conventionally, in recording materials such as thermal paper,
As one of the recording methods, a method utilizing a reversible coloring mechanism of an electron-donating color-forming organic compound (hereinafter referred to as “color-changing dye”) is widely adopted. A color-changing pigment and a color-developing agent for the color-changing pigment are used in this coloring mechanism, and as the color-developing agent, clay, phenols, acids and the like are known (Yamato: Paper and Pulp Technology). Times, 14
(8), 28 (1971)). Among these, various phenolic compounds have been proposed as being useful as phenols. For example, there is a phenolic compound of JP-B-45-14039, but in general, 4,4′-isopropylidene is used. Sidiphenol (bisphenol A) is used. Further, also in the pressure-sensitive paper which is a recording material, at least one of the color-changing dye and the color-developing agent is contained in the microcapsules, and the microcapsules are destroyed by pressure to cause a color-forming reaction,
The same developer as the thermal paper is used as the developer.

Further, it is well known to utilize the color-developing reaction between the color-changing dye and the color developing agent also in the temperature indicating material, the thermochromic material, the coloring agent for writing and the aging indicator. -10180, JP-A-49-3288
5, JP-A-50-75992, and JP-A-50-811.
57, JP-A-50-105554, JP-A-50-1.
05555, JP-A-50-105556, JP-A-5
No. 0-107040, JP-A-51-31682, JP-A-49-62230, JP-A-49-78682, JP-A-48-86612, and JP-A-49-109108. In these, a compound having a phenolic hydroxyl group, or a metal salt thereof, and / or a carboxylic acid or a metal salt thereof is usually used as a developer. The temperature-indicating material and the aging indicator are used together with a desensitizing agent that inhibits the coloring reaction and suppresses the coloration. Examples of the phenolic compound include bisphenol A, phenolcarboxylic acid ester (JP-A-56-144193), 4-hydroxybenzoic acid-
Polymerizable phenol compounds such as 4'-vinylbenzyl ester (Japanese Patent Laid-Open No. 59-83693) are known.

[0004]

The color developer consisting of these phenolic compounds is unsatisfactory with respect to the reactivity with the color-changing dye, in the case of bisphenol A, since the reaction rate is slow. Also, if a color developing agent that is highly reactive to the color changing dye is used, the color changing dye and the color developing agent are mixed in the recording material, so that a color reaction occurs little by little when the recording material is stored for a long period of time, causing fogging. There is a problem of causing. The same problem occurs when the recorded matter is stored for a long period of time, and the color image may become unclear. In addition, phenolic compounds are not substances that have good stability in air. From these points, it is desirable to obtain a color developing agent that is practical and has a small number of defects such that the color forming reaction with a color changing dye can be utilized in a wide field. The present invention aims to provide a new color-developing agent for a color-changing dye, which is different from the conventionally known phenolic compound, and to provide various useful materials utilizing a color-developing reaction between the color-changing dye and the color-developing agent. To do.

[0005]

Means for Solving the Problems The present inventor has studied to obtain a stable and highly versatile new color-developing color developer capable of addressing the above-mentioned problems.
It was discovered that a compound in which hydrogen of the amino group of amino acid is replaced with an acyl group is useful as a developer, and the present invention was achieved based on that. That is, the present invention has achieved the above object by the following means. (1) A developer for a color-changing dye, which comprises a compound in which hydrogen of an amino group of amino acid is substituted with an acyl group. (2) An elapsed-time display agent containing the color-developing color developer as described in (1) above. (3) A temperature indicator containing the developer for color-changing dye as described in (1) above. (4) A recording material containing the developer for a color-changing dye as described in (1) above. (5) A heat-sensitive recording material containing the color-developing color developer as described in (1) above.

The "amino acid" as a compound constituting the developer for a color-changing dye of the present invention, in which hydrogen of amino group of amino acid is substituted with acyl group, may be an aliphatic compound, an aromatic compound or the like. It may be an aromatic compound having an alkyl group or a heterocyclic compound having an alkyl group. The amino acid may have not only one amino group and two carboxyl groups, respectively, but may have two or more amino groups, but one amino group is preferable and one carboxyl group is preferable. In the case of, those having two or more carboxyl groups are also preferable. Hereinafter, specific examples of the compound in which hydrogen of the amino group of amino acid is replaced with an acyl group will be shown.

[0007]

[Chemical 1]

[0008]

[Chemical 2]

[0009]

[Chemical 3]

[0010]

[Chemical 4]

[0011]

[Chemical 5]

The compound obtained by substituting the hydrogen of the amino group of this amino acid with an acyl group is a known method (Ruts et al .; Precision Organic Synthesis [Experimental Manual], p308 (1983)).
Can be manufactured by. For example, A14 is a dilute sodium hydroxide solution (2 mol) of 0.1 mol of phenylglycine.
g / 150 ml) under ice-cooled stirring and 0.1 mol of benzoyl chloride and dilute sodium hydroxide solution (6 g / 30 ml).
ml) solution is added dropwise. After the dropping, the solution was stirred for an additional hour, and then the solution was mixed with conc. Pour into hydrochloric acid water (50 ml). Then, the colorless precipitate was obtained by suction filtration and recrystallization from ethanol.

The color-changing dye to which the color-developing agent used in the present invention is applied is not particularly limited as long as it is a general electron-donating color-developing organic compound. This shows triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, spiropyran-based, indoleazaphthalide-based, indolephthalide-based leuco dyes, and the like, for example, malachite green lactone, crystal violet lactone, 3-diethylamino. -6,5-Dimethylfluorane, 3-cyclohexylamino-6-chlorofluorane, 2-methyl-6- (Np-tolyl-N-ethylamino) fluorane, 3-diethylamino-6-methyl-
7-chlorofluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-6-benzyloxyfluorane, 3-diethylamino-6-methylfluorane, 3-diethylamino-7-chlorofluorane,
3-Diethylamino-5-methyl-7- (N, N-dibenzylamino) fluorane, 3-diethylamino-6-
Methyl-7-anilinofluorane, 3-diethylamino-7-chloroanilinofluorane, 3-pyrrolidino-6
-Methyl-7-anilinofluorane, 3-8 diethylamino) -7- (N, N-dibenzylamino) fluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3,6-bis ( Diethylamino) fluorane-γ
-(4-nitroanilino) lactam, 3- (N-cyclohexyl-N-ethylamino) 6-methyl-7-anilinofluorane, 2,3-butylene-6-di-n-butylaminofluorane, 3- Diethyl-7- (p-toluidino) fluorane, 3-diethylamino-7- (N-methylanilino) fluorane, 3-diethylamino-6-methoxyfluorane, 1,2-benz-6-diethylaminofluorane, 3,6- Diethoxyfluorane, 3,6
-Diethoxyfluorane, 3-diethylamino-6-methyl-chlorofluorane, 1,2-benz-6-diethylaminofluorane, N-phenylrhodamine lactam, 2- [3,6-bis (diethylamino) -9- (O
-Chloroanilino) xanthyl] lactam benzoate, 2
-(Phenyliminoethanedilidene) -3,3-trimethylindolinobenzospiropyran, 1,3,3-trimethylindolino-2,2'-spiro-6'-nitro-
8'-methoxybenzopyran, 1,3,3-trimethyl-indolino-7'-chloro-β-naphthospiropyran, benzo-β-naphthoisospiropyran, xant-
β-naphthospiropyran, N-acetyl auramine, N
-Phenyl auramine, rhodamine B lactone, benzoyl leuco methylene blue, ethyl leuco methylene blue, methoxybenzoyl leuco methylene blue, 2-
N, N-dibenzylamino-6-diethylaminofluorane, 6-diethylamino-benzo [α] -fluorane, 1,3-dimethyl-6-diethylaminofluorane, 3,6-bis (diethylamino) fluorane, γ-
(4′-Nitro) anilinolactam, 2- (2-chloroalinino) -6-dibutylaminofluorane, 2-anilino-3-methyl-6- (N-ethyl-N-furfurylamino) fluorane, N- Examples thereof include 3,3-trimethylindolinobenzospirolane, di-β-naphthospiropyran, and methylleucomethylene blue, and one or more selected from these can be used.

Since the color-changing dye develops color by contacting the color-developing agent of the present invention with the above-mentioned color-changing dye, many materials such as an elapsed-time indicating material, a temperature-indicating agent, a recording material and a heat-sensitive material are produced by using this coloring mechanism. It is possible to make recording materials for use. In the elapsed time display material, which is one of the uses of the color developer of the present invention, the color change dye, the color developer of the present invention, and a volatile desensitizing agent (hereinafter referred to as “desensitizer”) are combined to obtain a color tone. It is used as an elapsed time display material that utilizes changes. This desensitizer initially suppresses the color development of the discoloring dye due to the color developing agent, and the discoloring dye usually discolors as its concentration decreases due to volatilization of the desensitizing agent. As a means, another dye may be further added to change the color tone. This elapsed time display material is effectively used as a so-called time indicator, an indirect endpoint of drug efficacy, or an endpoint indicator.

Examples of the desensitizing agent used for the time display material include alcohols such as nonyl alcohol, decanol, benzyl alcohol, phenylethyl alcohol, geraniol, citronellol, dimethyl adipate and di-iso-butyl adipate. , Dimethyl sebacate, diethyl sebacate, -n-butyl benzoate,
Benzoic acid-n-amyl, benzoic acid-n-hexyl, benzoic acid-iso-amyl, laurate-n-butyl laurate-iso-butyl laurate, la-n-amyl laurate-iso-amyl, caprin Acid-n-amyl,
Capric acid-n-heptyl, methyl myristate, geranyl acetate, tributyrin and other esters, dipentyl ketone, butylphenone and other ketones, dihexyl ether, diethylene glycol dimethyl ether, diethylene glycol mono-n-hexyl ether and other ethers can be used. It is possible to use one or more selected from these.

Furthermore, by using a compound in which the desensitizing agent itself has a medicinal component, it can be used as an indicator or indicator that directly indicates the end point of the medicinal effect. For example empentryn,
Pyrethroid insecticides such as flamethrin, etoproxyfen and resmetri, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-phthalate
Insect repellents and repellents such as iso-propyl, di-n-butyl phthalate, di-iso-butyl phthalate and N'N'-diethyl-m-toluamide, ethyl benzoate, safrole, isosaflor, eugenol, citronellol , Insecticides such as anethole and l-carvone, citral, citronellal, nerol, geraniol,
Desensitization of volatility with medicinal properties such as linalyl acetate, acetophenone, terpineol, menthone, benzyl benzoate, ethyl phenylacetate, isoamyl acetate, eucalyptol, fragrances such as cinnamic aldehyde, benzaldehyde, etc. 1 selected according to desired drug effect
One kind or two or more kinds can be used. Then, the developer of the present invention, the above-described color-changing dye and desensitizer are mixed, and a solvent such as a synthetic oil such as alkylated naphthalene, alkylated diphenylmethane, chlorinated paraffin, acetone; cotton oil, castor oil, etc. A vegetable oil; an animal oil; a mineral oil or a mixture thereof, which can be easily processed into a base material, and those which can be mixed are as described in JP-A-62-163965 and the like. , A binder, an antioxidant, an ultraviolet absorber, a dispersant, a fixing agent and the like can also be added. .

The time display material is prepared by supporting the mixture on a base material and indirectly indicates the drug efficacy time or use time. In this case, the base material may support the time display material of the present invention with a chemical such as an insecticide. The substrate to be supported in this manner is not limited to a particular material, and may be the same as various materials conventionally used in, for example, insect repellent sheets, repellent sheets, etc.,
Pulp, paper, non-woven fabric, cloth, wood, leather, polymer compounds, inorganic porous substances (silicic anhydride, silica, etc.), organic polymer substances (cellulose, polyethylene, polyvinyl alcohol, etc.), gelling substances (agar, starch) , Alginic acid, etc.), sublimable substances (adamantane, naphthalene, camphor, etc.), inorganic fibers or organic sheets or synthetic resins, metal sheets, laminated sheets made of these materials, and the like, and particularly easy to absorb the mixture. Those are preferable. The formulation can be formed by mixing or impregnating the mixture with a base material, and shaping it into a sheet, a mat, a film, a gel, a powder, a granule, a tablet mold or the like. Further, a chemical such as a chlorine-based thermoplastic resin may be kneaded with a resin that can exude from the inside of the resin. Further, it is preferable that these base materials have a color whose color tone change is easy to visually judge according to the present invention, and white is particularly preferable. Then, the elapsed time display material is made into a solution and dropped and impregnated into the above-mentioned base material, whereby the elapsed time display material (elapsed time display body) can be produced. Further, the elapsed time display material may be packaged in a transparent or semitransparent packaging material (for example, a nonwoven fabric having a basis weight of 15 to 100 g / m ² ) or the like so that the elapsed time display material is not directly exposed. Then, the elapsed-time display material can be stored for a long time by packaging it with a packaging material (for example, a PP laminate material) that prevents volatilization of the desensitizer until the time of use.

In the temperature indicator which is one of the uses of the color developer of the present invention, the color developer of the present invention can be used in combination with the color-changing dye and the fusible substance. This temperature indicator is mixed with the developer, the color-changing dye, and a substance having a property of inhibiting the color development reaction according to temperature, that is, by mixing with other components, it is possible to coagulate and dissolve at a unique temperature. And involved in the electron transfer reaction between the color-changing dye and the developer,
A temperature indicator can be obtained by combining a substance that develops a color-changing dye upon dissolution and decolorizes upon solidification. From this, the reaction of the color-changing dye in the temperature indicator is reversible,
It is possible to obtain a temperature indicator that can be used many times. The same color-changing dye as that used for the elapsed-time indicating material can be used as the color-changing dye necessary for producing the temperature indicating material. Furthermore, by combining a fusible substance having good compatibility with the two components of the color developer and the color-changing dye of the present invention, a temperature indicating material utilizing a change in color tone can be prepared. Then, the temperature indicator can be made by holding the temperature indicator on the base material or enclosing it in a container,
The same means as the above-mentioned elapsed-time display material can be used for the base material and the means for holding the color developer, the color change pigment, and the like on the base material.

In this temperature indicator, the fusible substances conventionally used to promote the reaction between the color-changing dye and the color developer include aliphatic higher alcohols, esters, fatty acids, ethers and Acid amides and the like can be used. Fats such as n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-lauryl alcohol, n-myristyl alcohol, n-cetyl alcohol, n-stearyl alcohol, n-eicosyl alcohol and n-docosyl alcohol Group higher alcohols, heptyl laurate, stearyl myristate, propyl palmitate, ethyl stearate, lauryl benzoate, dicetyl adipate, methyl myristate, butyl stearate, decyl palmitate, myristyl laurate, stearyl palmitate, stearin Acid stearyl, decyl caprate, amyl caproate,
Butyl benzoate, diethyl oxalate, dibutyl phthalate and other esters, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, crotonic acid, adipic acid, benzoic acid,
Fatty acids such as P-t-butylbenzoic acid and salicylic acid,
Ethers such as didecyl ether and didodecyl ether, ketones such as bisstearic acid amide, laurone, diheptyl ketone, stearone and benzophenone, acetamide, oleyl amide, 2-methoxyacetanilide, acetanilide caprylic acid amide, lauric acid amide Acid amides such as myristic acid amide, palmitic acid amide, stearic acid amide, acetoacetyl amide, and salicylic acid amide can be exemplified, and one or more selected from these can be used.

The temperature indicator of the present invention is mixed with the developer, color-changing dye and fusible substance of the present invention, or if necessary, a surfactant, a solvent, an antifoaming agent, a dye (a dye, a pigment, It can be prepared by mixing an extender pigment), an ultraviolet absorber, an antioxidant, an antiseptic, a fragrance, a water repellent, and the like and holding the mixture on a base material in the same manner as the above-mentioned elapsed time display material. Further, when the developer of the present invention, the color-changing dye and the fusible substance alone are used, the color development due to the solidification of the composition tends to slightly fade over time, and an agent for preventing this color fading or a vivid color A drug (coloring strength enhancer) or the like can be added. Then, a substance that accelerates or inhibits the color-developing reaction between the color developing agent of the present invention and the color-changing dye according to temperature, that is, a substance that does or does not have a desensitizing action depending on temperature is co-present in the temperature indicator. As a result, a temperature-dependent reversible temperature indicator can be obtained. For example, as described in JP-A-1-253480, butyl alcohol / acrylonitrile adduct, hexyl alcohol / acrylonitrile adduct, heptyl alcohol / acrylonitrile adduct, octyl alcohol / acrylonitrile adduct, nonyl alcohol / acrylonitrile adduct, decyl. Examples include alcohol / acrylonitrile adducts, lauryl alcohol / acrylonitrile adducts, myristyl alcohol / acrylonitrile adducts, cetyl alcohol / acrylonitrile adducts, stearyl alcohol / acrylonitrile adducts and eicosyl alcohol / acrylonitrile adducts, and these are selected. 1 or 2
More than one species can be used. Further, in this case, not only can the material be held on the base material or kneaded with the thermoplastic resin as described above, but also kneaded with a thermosetting resin or the like.

The recording material, which is one of the uses of the developer of the present invention, is a thermal paper, a light-sensitive thermal paper, or a thermal transfer which can utilize a coloring reaction by an electron transfer reaction between the developer of the present invention and a color-changing dye. Examples include paper and pressure sensitive paper. Of these recording materials, the recording material can be obtained by supporting the color developer of the present invention on the support in a form in which the color changing dye is not in contact with the support. For example, a color developer and / or a color-changing dye is made into a fine dispersion or fine droplets and supported on a substrate to prevent contact, and various recording materials can be made using the fine dispersion or fine droplets. As a method for producing a microdispersion or microdroplets (hereinafter collectively referred to as "microdroplets or the like"), US Pat. Nos. 2,505,470 and 2,505,471,
No. 2,505,489, No. 2,548,366
No. 2, No. 2,712,507, No. 2,730,45
No. 6, No. 2,730,457, No. 3,103,4
No. 04, No. 3,418, 250, No. 4, 010,
There are various forms described in prior patents such as 038. And as for the method for producing capsules, a method utilizing coacervation of a hydrophilic colloid sol described in US Pat. Nos. 2,800,457 and 2,800,458 (gelatin capsule) British Patent 86
No. 7,797, No. 950,443, No. 989,2
No. 64, No. 1,091,076, etc., or the method (nylon, saturated polyester, polyurethane) described in US Pat. No. 3,103,404, etc.

In particular, the above-mentioned various methods are used in the method of producing microdroplets used for a heat-sensitive recording material, but the electron-donating colorless dye and the accepting compound are mixed in a dispersion solvent at 10 μm.
It is used by pulverizing and dispersing to a particle size of m or less, preferably 3 μm or less. The dispersion solvent is generally a water-soluble polymer aqueous solution having a concentration of about 0.25 to 10% (starch, hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, styrene-maleic anhydride polymer, styrene-butadiene acid polymer, polyacrylamide). , Carboxymethyl cellulose, gum arabic, casein or the like or a resin diluent), and the dispersion is performed using a ball mill, a sand mill, a horizontal sand mill attritor, a colloid mill or the like. When a color developer is used in the heat-sensitive recording material of the present invention, it must be used as a composition in which an electron transfer reaction occurs between the color developer and the color-changing dye when heat is applied to develop a color. For example, the composition melts,
Addition of a fusible substance in which a color change dye and a color developer come into close contact with each other to ensure a chemical reaction in a short time, or an electron transfer reaction does not occur at room temperature, but the reaction occurs at a high temperature, which is a color change dye, that is, a color development It is preferable to use a color-changing dye that does not develop color only by contact between the agent and the color-changing dye and causes an electron transfer reaction only after being heated.

When a color-changing dye that develops color at room temperature is used for the heat-sensitive recording material, the color-changing dye or the color developer of the present invention is used as the above-mentioned minute droplets, and these minute droplets are broken during heating. The color-changing dye or the color-developing agent flows out from the microdroplets and the like, so that the color-developing agent or the color-developing dye outside the microdroplets or the like is brought into contact with the color-developing agent or the color-developing colorant to develop a color. The support used when the developer of the present invention is used for the heat-sensitive recording material supports the developer and the color-changing dye of the present invention on the surface of the base material among the base materials used for the above-mentioned elapsed time display material. It is limited to the sheet type, and the treatment on the substrate is preferably a treatment such that the developer of the present invention and the color-changing dye are retained on the surface, that is, coating / coating treatment.

Further, other auxiliary components commonly used in heat-sensitive recording materials, for example, inorganic or organic fillers such as calcium carbonate, silica, polyvinyl chloride resin powder, metal soaps such as zinc stearate, and antioxidants. ,
An ultraviolet absorber, a binder, etc. are used. The ratio of the color-changing dye and the color developer of the present invention supported on the support is 0.1 to 100 parts by weight of the color developer with respect to 1 part by weight of the color-changing dye, preferably 1 part by weight of the color-changing dye. In contrast, the color developer is 0.1 to 50 parts by weight. In this way, the color developing agent of the present invention easily reacts with the color changing dye to provide a heat-sensitive recording material suitable for high-speed recording, and the color image obtained by the reaction between the color developing agent and the color changing dye is The storage stability is remarkably excellent.

Further, the color developer of the present invention can be used as a pressure sensitive paper for a recording material. The pressure sensitive paper may have the same structure as that of the conventionally known pressure sensitive paper. The color developer of the present invention may be used in place of the color developer. That is, a pressure-sensitive paper is prepared by forming microcapsules containing a color-changing dye solution by the above-described method for producing microdroplets, applying a coating containing the microcapsules on one surface, and then developing color on contact with the color-changing dye. The lower paper coated with the coating containing the developer of the present invention on one side, and the coating containing only the developer that develops color by contact with the color-changing dye on the surface of the upper paper facing the microcapsule coating surface. And, it is composed of at least two of the middle papers having the microcapsule-containing paint applied to the surface of the lower paper opposite to the developer application surface, and combining these papers. When the microcapsules are brought into contact with each other to destroy the microcapsules by a writing pressure, a typing pressure, or the like, and a color-changing dye and a developer are brought into contact with each other, a color-forming reaction is caused to obtain a record.

Specifically, an electron-donating colorless dye is used alone or in a mixture, dissolved in a solvent and contained in a microcapsule, and then paper, wood free paper, plastic sheet,
A coloring material sheet is obtained by applying it to a transparent or opaque smooth support such as resin-coated paper. Alternatively, a color-changing dye, alone or mixed, or together with another developer, is dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and a paper with a pigment,
A developer sheet is obtained by applying it to a support such as a plastic sheet or resin coated paper.
By using the color developing agent of the present invention as a color developing agent in this pressure sensitive paper, it is possible to produce a useful pressure sensitive paper in which clear recording can be obtained with high sensitivity and storage stability of the recording is good.

[0027]

The color developer of the present invention has a rapid color-forming reaction with the color-changing dye and can form a color-developing portion having a high density. Further, since the color-developed portion obtained there does not easily disappear in air, the storage stability of the record is high. Further, this developer has a high stability in the air, and therefore, when this developer is used as an elapsed time display material, the passage of time can be easily discriminated. Further, the temperature of the temperature indicating material can be easily discriminated. Also for recording materials, clear recording with high sensitivity and high density can be obtained, and the storage stability of the recording is also high. Further, depending on the types of the color-changing dye and the desensitizing agent that are mixed or reacted, various kinds of compound A and compound B are used for the aging indicator, and B2 and B are used for the temperature indicator.
5 is various kinds of compound A and compound B1 in the heat-sensitive recording material.
B2, B4 and B5 are good. And the pressure sensitive compound A
13, A33, B1 are preferred.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. The abbreviations of the color-changing dyes used in the following examples are shown. O-DCF 1,3-Dimethyl-6-diethylaminofluorane (trade name fluoran compound O-DCF, Hodogaya Chemical Co., Ltd.) P-DCF 3,6-bis (diethylamino) fluorane-8- (4'- Nitro) anilinolactam (trade name fluoran compound P-DCF, Hodogaya Chemical Co., Ltd.) R-DCF 6-diethylamino-benzo [α] -fluorane (trade name fluoran compound R-DCF, Hodogaya Chemical Co., Ltd. TH-107 2- (2-chloroalinino) -6-diethylaminofluorane (trade name fluoran compound TH
-107, Hodogaya Chemical Co., Ltd.) GN-2 Product name: GN-2 (Yamamoto Kasei Co., Ltd.) B-63 3- (4-Dimethylamino-2-ethoxyphenyl) -3- (1-ethyl-) 2-Methylindol-3-yl) -4-azaphthalide (trade name Indoleazaphthalide compound blue 63, manufactured by Yamamoto Kasei Co., Ltd.) R-40 3,3-bis (1-n-butyl-2-methyl) Indole-3-yl) phthalide (trade name: indole azalide compound R-40, manufactured by Yamamoto Kasei Co., Ltd.)

Examples 1 to 20 1 part by weight of the color developer of the present invention, 1 part by weight of a color-changing dye and 50 parts of a fusible compound were mixed in a combination shown in Table 1 to obtain an oil at about 120 ° C. Melted in the bath, inner diameter 2mm
The temperature indicator was prepared by enclosing the temperature indicator in a glass tube. Each of the prepared temperature indicating materials was placed in water in a beaker that was stirred by a magnetic stirrer and kept at a constant temperature, and the temperature at which the color tone changed was measured by gradually increasing the temperature from 20 ° C. Then, Table 1 shows the change in color tone of each temperature indicator and the color change temperature, that is, the temperature indicated by the temperature indicator.

[0030]

[Table 1]

Example 21 1 part by weight of Compound A13 as a developer and 50 parts by weight of stearyl alcohol as a fusible compound, and O-DC
F, R-DCF, P-DCF, TH-107, GN-
Epicoat 828 was added to 5 g of a reversible temperature indicator composition containing 1 part by weight of 7 kinds of discoloring dyes of 2, B-63 or R-40.
Approximately 90 by adding 2 g (made by Yuka Shell Epoxy Co., Ltd.)
It was heated to ℃ and melted. Then, this molten solution is dropped with a Komagome pipette into 50 ml of a 2% sodium alginate aqueous solution which is heated to about 90 ° C. and stirred with a magnetic stirrer, and further stirred so as to become fine droplets. Next, to the aqueous solution of sodium alginate to which the reversible temperature indicator composition was dripped, a solution prepared by dissolving 2.5 g of Epicure U (produced by Yuka Shell Epoxy Co., Ltd.) in 5 ml of water was gradually added dropwise, and the whole amount was added. The mixture is stirred at a liquid temperature of about 90 ° C for about 1 hour. The reaction solution thus prepared was suction-filtered with a filter paper (No. 131 manufactured by Toyo Roshi Kaisha, Ltd.), the residue was washed with water, and then dried in a drier at 40 ° C. for about 3 hours to give about 8.
Microcapsules containing 5 g of the reversible color change agent were obtained. Then, as in Example 10, each of the temperature indicating materials was placed in water in a beaker which was stirred by a magnetic stirrer and kept at a constant temperature, and the temperature was gradually raised from 15 ° C. to change the color tone. Was measured. As a result, in these temperature indicating materials, the change in color tone was derived from each color-changing dye, but the indicated temperature was about 53 ° C. in almost the same manner as in Example 10.

Examples 22 to 52 1 ml of an acetone or ethanol solution containing 1 mg of the discoloring dye O-DCF shown in Table 2 and 100 mg of diethylene glycol mono-m-hexyl ether and 10 mg of the color developing agent of the present invention shown in Table 2 had a diameter of 7 cm. No. 2 filter paper (No. 2 manufactured by Toyo Roshi Kaisha, Ltd.) was impregnated and air-dried to prepare an elapsed time display material of the present invention. These were suspended in a constant temperature layer at 40 ° C. for 2 days, and then taken out and the change in color tone was visually measured. The measurement results are shown in Table 2 as "◎" that can be clearly identified and "○" that can be easily identified. Since this measurement is based on an acceleration test in which the temperature is raised to 40 ° C., the actual color development time at room temperature is considerably longer than the values in Table 2.

[0033]

[Table 2]

Examples 53 to 71 0.4 g of the color developer of the present invention shown in Table 3 is put in a mortar together with 2 g of a 5% aqueous solution of polyvinyl alcohol, and well ground and dispersed. 2 g of a dispersion of stearic acid amide (10 g of stearic acid amide dispersed in 50 ml of a 5% polyvinyl alcohol aqueous solution), 0.2 g of zinc stearate, and a dispersion of pigment (CaCO ₃ : 25 g, Z
8 g of nO: 25 g dispersed in 100 g of water) and 1 g of a color change pigment dispersion (B-63: 10 g dispersed in 50 ml of a 5% polyvinyl alcohol aqueous solution) were added and mixed well to obtain a coating liquid. 3 ml of this coating solution has a basis weight of 64 g /
m ² was applied on a high-quality paper and dried in an oven at 50 ° C. to prepare a heat-sensitive recording material. The thermosensitive recording material was equipped with a recorder C-RIA manufactured by Shimadzu Corporation, printed, and the change in color tone was observed. As the observation result, the characters formed by changing the color tone were read, and those that could be clearly identified were marked with "◎", and those that could be easily identified were marked with "○",
The results are shown in Table 3.

[0035]

[Table 3]

Examples 72-86 In Examples 72 to 83 shown in Table 4, 100 g of the developer of the present invention was dissolved in 2 ml of ethanol to obtain 13 × 18.
cm is a color-developing sheet prepared by uniformly impregnating an imitation paper of cm and air-drying, and Examples 84 to 86 are the same as Table 1 except that 1 g of the color-developing agent of the present invention is added to 5% polyvinyl alcohol aqueous solution 1
Add with 0 ml and mix well to disperse. Then, 1 ml of this dispersion is applied to a 13 × 18 cm imitation paper, and 5
A developer sheet was prepared by drying at 0 ° C. for 10 minutes. When each of the color-developing sheets was placed between the upper and lower sheets of commercially available pressure-sensitive copying paper and characters were written with a ballpoint pen to develop the color, all the color-developing sheets were colored blue as written. , And observed the readability of the colored letters. The observation results are shown in Table 4 in which clearly distinguishable ones are indicated by “◯”, and easily identifiable ones are indicated by “Δ”, and the developer used previously is described.

[0037]

[Table 4]

[0038]

INDUSTRIAL APPLICABILITY According to the present invention, there can be obtained a color developer which is brought into contact with a leuco dye to cause a favorable color development reaction. This color developing agent is stable in the air, and when it comes into contact with various leuco dyes, it gives good sensitivity and clear color development.
It can be widely used for various applications utilizing its properties. For example, when used in combination with a desensitizer, it can be used as a time-sensitive display agent. It is also useful as a temperature indicator. Further, it can be used as a developer in recording materials such as thermal paper and pressure-sensitive paper to obtain clear and good-preservation records and to reduce fog.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location D06P 1/649

Claims (5)

[Claims] 1. A developer for an electron-donating color-developing organic compound, which comprises a compound in which hydrogen of an amino group of an amino acid is substituted with an acyl group. 2. An elapsed time display agent comprising the developer for an electron-donating color-developing organic compound according to claim 1. 3. A temperature indicator containing the developer for an electron-donating color organic compound according to claim 1. 4. A recording material comprising the developer for an electron-donating color organic compound according to claim 1. 5. A heat-sensitive recording material containing the developer for an electron-donating color-developing organic compound according to claim 1.