JPH0565355B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coloring method, and more specifically, the present invention relates to a coloring method, and more specifically, a method in which a colored object is supported with a compound represented by general formula (1) and a compound represented by general formula (2), and a compound represented by general formula (1) and a compound represented by general formula The present invention relates to a method of forming a colored image on a colored object by subjecting the compound represented by (2) to a contact or heating contact reaction to develop color. [In the formula, A is O, NH, (OR ₁ ) ₂ (wherein, R ₁ is a lower alkyl group, preferably an alkyl group having 1 to 5 carbon atoms) or

[Formula] (wherein R ₂ is an alkylene group), and Z represents an aromatic compound residue or a heterocyclic compound residue that can form a conjugated system with C═NH. ] R(-NCO) _n (2) [In the formula, R represents an aromatic compound residue or a heterocyclic compound residue that may have a substituent, and m represents an integer of 1 or more. ] Traditionally, as a method of forming colored images on the surfaces of paper, films, sheets, molded products, and other various objects, printing, patterning, or coloring using colorants such as ink, ink, dyes, paints, paints, etc. However, apart from these methods, the surface of the object to be colored on which a colored image is to be applied is given color-forming characteristics in advance, and then some kind of energy or auxiliary substance necessary for coloring is applied to the surface of the object to be colored. There is a method of developing color by adding it externally to form a desired colored image. The latter method of developing color on the surface of a colored object is rapidly progressing as a method for converting and recording various information into visible images, especially with the development of the information society in recent years. For example, there are known thermal coloring methods in which a chemical coloring layer is provided on the surface of a support and color recording is performed using thermal energy, or pressure sensitive coloring methods in which color recording is performed using pressure energy. Such a coloring method is not limited to the information industry, but can be widely applied to coloring, patterning, etc. of various everyday items or industrial items. A number of leuco dyes from the group of phthalides, fluorans, phenothiazines, etc. are known as typical coloring agents used to impart coloring characteristics to the surface of such objects to be colored. Coloring methods using these leuco dyes have been widely put into practical use mainly for heat-sensitive recording and pressure-sensitive recording because of their excellent coloring properties. However, the colored images obtained by this method often have the defect of poor light fastness and fading after relatively short exposure to light, as typified by, for example, crystal violet lactone. Furthermore, the colored images obtained by the method using leuco dyes have poor chemical resistance and are easily erased by chemicals contained in foods and cosmetics, plasticizers contained in vinyl chloride resin, erasers, etc. It has The present inventors have published Japanese Patent Application Laid-Open No. 55-152749,
-109255 publication, 57-83557 publication, 57-
The present invention was achieved as a result of research focusing on the characteristics of carboxamide-type azomethine pigments obtained from various imino group-containing compounds and isocyanate compounds, which are known from the inventions of Publication No. 83558 and others. In the present invention, a compound represented by the general formula (1) (hereinafter referred to as color former A
) and a normally colorless or light-colored compound represented by the general formula (2) (hereinafter abbreviated as color former B) that develops color upon contact or heating contact with color former A, and on the object to be colored. Provided is a method for forming a desired colored image on an object to be colored by bringing color forming agent A and color forming agent B into contact or by heating contact reaction to develop color. Coloring according to the present invention can be achieved very easily by supplying energy such as heat and pressure or by supplying solvents for coloring agent A and coloring agent B. By appropriately selecting color former A and color former B, various colors such as red, orange, yellow, and brown can be produced.
The light fastness of the colored image obtained is extremely excellent. Furthermore, the colored images obtained are resistant to many chemicals. Thus, the present invention provides a novel coloring method that provides colored images with excellent storage stability. The object to be colored in the present invention refers to solid objects of various shapes made of natural or synthetic organic and inorganic materials on which a colored image is to be applied, such as paper, film, board, laminate, leather, pipe, and molded material. It is of good quality. In the recording material, paper, film, etc., which are commonly called supports because they support recording, are also included in the object to be colored in the present invention. The colored image referred to in the present invention refers to color former A and color former B.
refers to images of various hues and shapes formed by the reaction of Includes a wide range of colors. Although it usually has a certain shape, either fixed or amorphous, it is acceptable even if the entire surface is colored and has no shape. The coloring agent A used in the present invention consists of one or more compounds represented by the general formula (1). general formula
Z in (1) represents an aromatic compound residue or a heterocyclic compound residue that can form a conjugated system with C=NH,
Examples of aromatic compound residues include benzene ring, naphthalene ring, biphenyl ring, anthracene ring, indene ring, fluorene ring, phenanthrene ring, acenaphthene ring, etc., and derivatives thereof; examples of heterocyclic groups include: Furan ring, thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, triazine ring,
Thiazine ring, benzofuran ring, benzothiophene ring, indole ring, indazole ring, benzimidazole ring, benzothiazole ring, quinoline ring,
Quinazoline ring, carbazole ring, acridine ring,
Examples include naphthoquinone rings, anthraquinone rings, and derivatives thereof. A typical example of the compound represented by the general formula (1) is 3-
iminoisoindolin-1-one, 3-imino-
4,5,6,7-tetrachloroisoindoline-
1-one, 3-imino-4,5,6,7-tetrabromoisoindolin-1-one, 3-imino-
4,5,6,7-tetrafluoroisoindolin-1-one, 3-imino-5,6-dichloroisoindolin-1-one, 3-imino-4,5,7
-Trichloro-6-methoxy-isoindoline-
1-one, 3-imino-4,5,7-trichloro-6-methylmercapto-isoindoline-1-
on, 3-imino-6-nitroisoindoline-
1-one, 3-imino-isoindoline-1-spiro-dioxolane, 1,1-dimethoxy-3-
imino-isoindoline, 1,1-diethoxy-
3-imino-4,5,6,7-tetrachloroisoindoline, 1-ethoxy-3-imino-isoindoline, 1,3-diiminoisoindoline,
1,3-diimino-4,5,6,7-tetrachloroisoindoline, 1,3-diimino-6-methoxyisoindoline, 1,3-diimino-6-cyanoisoindoline, 1-imino-naphthalic acid imide , 1-imino-diphenimide, 7-amino-2,3-dimethyl-5-oxopyrrolo[3,
4b] pyrazine, 7-amino-2,3-diphenyl-5-oxopyrrolo[3,4b] pyrazine, and the like. It is said that the compound represented by the general formula (1) can have the following isomeric structure depending on the conditions (PEClark et, ab, J.Chem.Soc.3593<1953
>). Therefore, for the compound structure represented by general formula (1), for example, when A is OR, the following two types of isomers are expected. Therefore, although the above-mentioned compound names may be expressed by different names depending on the case, they are all included in general formula (1) for the above-mentioned reasons. Among the compounds represented by general formula (1), particularly important compounds are 3-imino-isoindolin-1-one compounds that may have a halogen substituent and 3-imino-isoindolin-1-one compounds that may have a halogen substituent. For example, 3-imino-4,5,6,7-tetrachloroisoindolin-1-one is a 1,3-diimino-isoindolin-based compound. It can be obtained by hydrolyzing chlorophthalonitrile in an acetone-water mixed solvent using ammonia and hydrogen peroxide as catalysts, and can also be obtained by, for example, 1,3-diimino-
4,5,6,7-tetrachloroisoindoline is obtained by reacting tetrachlorophthalonitrile with formamide in the presence of an alkali metal alcoholate or alkali metal hydroxide. Color forming agent B used in the present invention consists of one or more compounds represented by general formula (2). general formula
Representative examples of the compound represented by (2) include phenyl isocyanate, o-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, p-bromophenyl isocyanate, p-nitrophenyl isocyanate, o-Methyl phenyl isocyanate, p-methoxy phenyl isocyanate, 2,4,6-trichlorophenyl isocyanate, 2,6-dichloro-4-nitrophenyl isocyanate, 2-methyl-4-nitrophenyl isocyanate enyl isocyanate, 2,5-dimethoxy-4
-Nitrophenyl isocyanate, 4-nitro-
Phenyl isocyanates that may have substituents such as 2-bromo-6-cyanophenyl isocyanate, p-trifluoromethylphenyl isocyanate, p-dimethylaminophenyl isocyanate, 4-N-phenyl isocyanate Diphenyl isocyanates that may have substituents such as nylcarbamoyl-phenyl isocyanate, 4'-chloro-4-isocyanato diphenyl ether, diphenylsulfone-2-isocyanate, p-isocyanatobenzene, etc. monoisocyanate, p-
phenylene diisocyanate, m-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,
5-tolylene diisocyanate, 2-nitrobenzene-1,4-diisocyanate, chlorobenzene-3,5-diisocyanate, 2,5-dimethylbenzene-1,4-diisocyanate, 2-methoxybenzene-1 , 4-diisocyanate,
2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxybenzene-1,4
-diisocyanate, 2,5-dibutoxybenzene-1,4-diisocyanate, 2-chloro-5
-methoxybenzene-1,4-diisocyanate, 2-chloro-5-ethoxybenzene-1,4
- diisocyanate, phenyl diisocyanates that may have substituents such as 2,5-diethoxybenzene-1,4-diisocyanate,
4.4'-diphenyl diisocyanate, 3,3'-dichloro-4,4'-diphenyl diisocyanate,
3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, 3,3'-dinitro-4,
4'-diphenyl diisocyanate, 3-nitro-
4,4'-diphenyl diisocyanate, 3,3'-
Diethoxy-4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, diphenyl sulfide-4,4'-diisocyanate Diphenylsulfone-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylamine, 4,4'-benzophenone diisocyanate, 4,4'-azobenzene diisocyanate,
4,4'-Stilbene diisocyanate, 3,3'-
Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-dimethyl-3,3'-diisocyanate diphenyl urea, 2-methyl-4,4'-azobenzene diisocyanate, 2-methoxy −
4,4'-Azobenzene diisocyanate, 2,5
-dimethyl-4,4'-azobenzene diisocyanate, 3-methyl-2'-methoxy-azobenzene-4,4'-diisocyanate, 3-chloro-2'-
Methyl-azobenzene-4,4'-diisocyanate, 2-chloro-azobenzene-4,3'-diisocyanate, 2-methylazobenzene-4,3'-
Diisocyanate, 2-methoxyazobenzene-
4,3'-diisocyanate, 2,4-azobenzene diisocyanate, 5-methoxyazobenzene-2,4-diisocyanate, 3,3',5,5'-
Diphenyl diisocyanate that may have substituents such as tetramethyldiphenylmethane-4,4'-diisocyanate, as well as 2,8-dibenzothiophene diisocyanate and 3,7-dibenzofurone diisocyanate. , 2,7-fluorenone diisocyanate, 2,7-carbazole diisocyanate, dibenzothiophene-3,7-diisocyanate, 2,7-fluorene diisocyanate, 2,7-acridine diisocyanate,
2,7-acridone diisocyanate, 3,6-
Anthorone diisocyanate, 1,4-naphthalene diisocyanate, 1,5-anthraquinone diisocyanate, 1,4-anthraquinone diisocyanate, 3,8-pylene diisocyanate,
3,10-perylene diisocyanate, 2,8-diphenylene oxide diisocyanate, 5,8-
quinoline diisocyanate, 2,8-chrysene diisocyanate, 4,7-benzimidal diisocyanate, 2,6-pyridine diisocyanate, 2,5-pyridine diisocyanate, triphenylmethane triisocyanate, Tris (4-
phenyl isocyanate) thiophosphate,
Examples include polymethylene polyphenyl isocyanate. There are various methods for supporting color former A and color former B on the surface of the object to be colored. Which method is used varies depending on the type of object to be colored, its purpose, and whether coloring is done by thermal energy or pressure energy. The most common method is color former A and color former B
This is a method in which the pigment is dispersed in a medium containing a suitable binder, applied to the surface of the object to be colored, and dried. As a binder, polyvinyl alcohol, modified starch, casein, gelatin, gum arabic, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, maleic anhydride-styrene copolymer, isobutylene-maleic anhydride copolymer, styrene-butadiene copolymer Known binders such as polymers, acrylic polymers, olefin polymers, and vinyl chloride polymers are used, and these binders are used in the form of aqueous solutions, emulsions, or solutions in suitable organic solvents. Furthermore, when a skin layer and a top layer are laminated on a base fabric, such as in the case of synthetic leather, coloring agent A and coloring agent B can be dispersed in the skin layer and/or the top layer. Similar methods can be used for laminates and other laminate products. The object to be colored is film, thread,
In the case of a sheet or the like, a method of forming into a film, thread, etc. using a forming raw material mixed with a coloring agent can also be adopted. Various additives can be added together with the coloring agent. The types of additives used vary depending on the type of object to be colored, the intended use, and whether coloring is done by heat-sensitive or pressure-sensitive methods. Examples of some typical additives are as follows. One feature of the present invention is that the reaction between color forming agent A and color forming agent B proceeds extremely easily. A reaction catalyst can optionally be added. As the catalyst, conventionally known reaction catalysts for isocyanate compounds and active hydrogen-containing compounds are used, such as tertiary amines such as triethylenediamine, organic metal salts such as dibutyltin dilaurate, and carboxylic acid derivatives such as monomethylphthalic acid. When using a heat-sensitive coloring method, a coloring agent that is solid at room temperature is often used, but a sensitivity improver is sometimes used to aid the flow of the coloring agent during heating coloring and to effectively proceed with the reaction. Sensitivity enhancers are generally thermoplastic substances with melting points around 40 to 200℃.
It is desirable that the color former mixes well with or dissolves in at least one of the color formers in a molten state, and upon heat color development, it facilitates the contact reaction of the color former by lowering the melting point of the color former or dissolving it. Examples of such additives include N,N-diphenylformamide, stearamide, diphenyl, triphenylmethane, stearanilide, and the like. In addition, pigments or fillers such as talc, clay, silica, titanium oxide, and calcium carbonate are sometimes used to improve whiteness and surface properties. In addition, various waxes, higher fatty acids, or derivatives of higher fatty acids may be used to prevent unintended color development (fogging) during storage. In order to cause color former A and color former B to react in contact with each other in the object to be colored, the color is developed by externally applying energy such as heat or pressure, or by externally adding a solvent that dissolves at least one of the color formers. This is achieved by bringing at least one of the agents into a fluid state. The most common and effective color development method is one using thermal energy. Thermal energy is usually applied by direct heating methods such as a thermal pen, hot plate, flame, or heating furnace, but it may also be supplied as light energy or electrical energy and converted into thermal energy on the object to be colored. . In any case, until a colored image is formed, measures are taken to prevent unintentional color development due to contact between color former A and color former B, and at the time of color development, at least one of the color formers is supplied with appropriate external energy or solvent. A colored image is obtained by causing one to flow and cause a contact reaction. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples. “Part” in Examples
Unless otherwise specified, "parts by weight" means "parts by weight". Example 1 (Liquid A) 1,3-diimino-4,5,6,7-
Tetrachloroisoindoline 1 part 5% polyvinyl alcohol aqueous solution 2 parts Water 2 parts The above composition was ground in a ball mill for 24 hours, and then 3 parts of 20% polyvinyl alcohol aqueous solution were added and mixed. (Liquid B) 2,5-dimethoxybenzene 1,4-
Diisocyanate 1 part 5% polyvinyl alcohol aqueous solution 2 parts Water 2 parts The above composition was ground in a ball mill for 24 hours, and then 3 parts of 20% polyvinyl alcohol aqueous solution were added and mixed. A coating liquid was prepared by mixing liquid A and liquid B at a ratio of 2:1. This coating solution was applied to 50 g/m ² of high-quality paper using a coating rod and dried so that the coating weight after drying was 3 g/m ² , and smoothed with a supercalender to obtain thermal paper. As a result of printing on the thus obtained thermal paper using Thermal Typer STT-401KC (thermal printer manufactured by Sanyo Electric Co., Ltd.), a clear reddish-black printed image was obtained. Dioctyl phthalate was dropped onto the colored image thus obtained, but the print did not disappear even after one month had passed. In addition, to test the light resistance of the colored image, it was left outdoors for 15 days and exposed to sunlight, but the print did not fade. For comparison, when dioctyl phthalate was dropped onto a print image obtained by similarly developing color using crystal violet lactone (leuco dye) and bisphenol A using a known method, the print completely disappeared immediately. When left outdoors for 15 days, the print faded to the point where it was difficult to read. Example 2 (Liquid A) 3-imino-4,5,6,7-tetrachloroisoindolin-1-one 1 part N,N-diphenylformamide 1 part Polyvinyl alcohol 5% aqueous solution 4 parts Water 4 parts Above composition The material was ground in a ball mill for 2 hours. (Liquid B) 4,4'-diphenylmethane diisocyanate 1 part N,N-diphenylformamide 1 part 5% polyvinyl alcohol aqueous solution 4 parts Water 4 parts The above composition was ground in a ball mill for 2 hours. Mix liquid A, liquid B, and a 20% polyvinyl alcohol aqueous solution in a ratio of 2:2:1 to make a coating liquid, and apply this coating liquid onto a wooden board so that the thickness after drying is approximately 5μ. Dry. When this wooden board was pressed with a hot plate at 160° C. for 10 seconds (pressure: 1 kg/cm ² ) from above the coated surface, color developed and a yellow colored image was obtained. Ethanol was dropped onto this colored area, but almost no discoloration was observed. Example 3 (Liquid A) 3-imino-isoindolin-1-one 1 part N,N-diphenylformamide 1 part Ethylcellulose 5% aqueous solution 4 parts Water 4 parts The above composition was ground in a ball mill for 2 hours. (Liquid B) 3,3'-dimethyl-4,4'-diphenyl diisocyanate 1 part N,N-diphenylformamide 1 part Ethylcellulose 5% aqueous solution 4 parts Water 4 parts The above composition was heated in a ball mill for 2 hours. Shattered. Liquid A, liquid B, and copolymer emulsion of methyl methacrylate and butyl acrylate (solid content
45%) in a ratio of 4:4:1 to obtain a coating liquid,
This coating solution was applied onto nearly white synthetic leather so that the film thickness after drying was approximately 5 μm, and then dried. When this leather was heated to 130°C for 5 seconds, a red to orange colored image was obtained. Example 4 (Liquid A) 1,3-diiminoisoindoline
1 part Stearamide 1 part Ethyl cellulose 5% aqueous solution 4 parts Water 4 parts The above composition was ground in a ball mill for 2 hours. (Liquid B) 4,4'-benzophenone diisocyanate 1 part Stearamide 1 part Ethyl cellulose 5% aqueous solution 4 parts Water 4 parts The above composition was ground in a ball mill for 2 hours. Liquid A, liquid B, and copolymer emulsion of methyl methacrylate and butyl acrylate (solid content
45%) in a ratio of 4:4:1 to obtain a coating liquid. After drying this coating liquid on an aluminum plate, the film thickness is approx.
It was applied to a thickness of 5μ and dried. 150 this board
When heated to ℃ for 5 seconds, a reddish-yellow color was obtained. Example 5 (Liquid A) 1,1-dimethoxy-3-imino-
4,5,6,7-tetrachloroisoindoline 1 part N,N-diphenylformamide 1 part 5% polyvinyl alcohol aqueous solution 4 parts Water 4 parts The above composition was ground in a ball mill for 2 hours. (Liquid B) 2,7-fluorene diisocyanate
1 part N,N-diphenylformamide 1 part 5% polyvinyl alcohol aqueous solution 4 parts Water 4 parts The above composition was ground in a ball mill for 2 hours. A coating liquid was prepared by mixing liquid A, liquid B, and a 20% polyvinyl alcohol aqueous solution in a ratio of 2:2:1.
Apply this coating liquid on high-quality paper, and after drying, the coating amount is 9 g/
It was applied in an amount of ² m2 and dried. Press a hot plate at 160°C onto this paper for 10 seconds from above the coated surface (pressure: 1
Kg/cm ² ), a brown colored image was obtained. Example 6 Example 5 except that 1,3-diimino-4,5,6,7-tetrachloroisoindoline was used as color former A and 1,5-naphthalene diisocyanate was used as color former B. When an experiment was carried out in the same manner as in Example 5, an orange to brown colored image was obtained on the piece of paper. Example 7 In Example 5, 7-amino-2,3-dimethyl-5-oxopyrrolo[3,
4b] An experiment was conducted in the same manner as in Example 5 except that 2,5-diethoxybenzene 1,4-diisocyanate was used as pyrazine and color former B, and a brown colored image was obtained on the paper piece. Example 8 Example 5 except that 1,3-diimino-4,5,6,7-tetrachloroisoindoline was used as color former A and 4,4'-benzoanilide diisocyanate was used as color former B. When an experiment was conducted in the same manner as in Example 5, a brown colored image was obtained on the paper piece. Example 9 In Example 5, 1,3-diimino-isoindoline was used as color former A, and 2,6 was used as color former B.
- When an experiment was conducted in the same manner as in Example 5 except that dichlorophenyl isocyanate was used, a pale yellow colored image was obtained on the paper piece. Example 10 An experiment was carried out in the same manner as in Example 5, except that 1,3-diimino-isoindoline was used as color former A and diphenylsulfone 4,4'-diisocyanate was used as color former B. However, a pale yellow colored image was obtained on the piece of paper. Example 11 In Example 5, 1-iminonaphthalimide was used as color former A, and tris(4-imide) was used as color former B.
When an experiment was carried out in the same manner as in Example 5 except that thiophosphate (phenylisocyanate) was used, a yellow colored image was obtained on the paper piece. Example 12 Liquids A and B were obtained in exactly the same manner as in Example 5,
Mix in the same way to create a coating liquid, and apply it on high-quality paper.
It was coated and dried so that the coating amount after drying was 9 g/m ² . When a dibutyl phthalate solution was partially applied onto this piece of paper, a brown colored image was obtained where the solution was applied.

Claims (1)

[Claims] 1. A coloring material is characterized in that a compound represented by the general formula (1) and a compound represented by the general formula (2) are supported on an object to be colored, and the compounds are brought into contact with each other by heating to develop color. A method of coloring objects to be colored. [In the formula, A represents O, NH, (OR ₁ ) ₂ (in the formula, R ₁ is a lower alkyl group) or [formula] (in the formula, R ₂ is a lower alkylene group), and Z is >C
=Represents an aromatic compound residue or a heterocyclic compound residue that can form a conjugated system with NH. ] R(-NCO) _n (2) [In the formula, R represents an aromatic compound residue or a heterocyclic compound residue that may have a substituent, and m represents an integer of 1 or more. ]