JPH0135752B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new color forming method, and more specifically, a color forming agent A represented by the general formula (). (In the formula, Z represents an aromatic ring group or a heterocyclic group that can form a conjugated system with C=NH, and R ₁ represents an adjacent C=N
represents an aromatic compound or heterocyclic compound residue capable of forming a conjugated system with); and a coloring agent B R ₂ (NCO) _n () R ₂ (NCO-HR ₃ ) represented by the general formula () or (). _n () (wherein R ₂ represents a residue of an aromatic compound or a heterocyclic compound, R ₃ represents a residue of an isocyanate block compound having active hydrogen, and m represents an integer from 1 to 4). dispersed in the binder,
Binder by mixing the coloring agent with another coloring agent directly or through a medium (including the same binder), and causing a contact reaction with heating if necessary to generate a colored compound in the binder phase and on the phase surface. Concerning a novel colored method.

Generally, plastic molded products, films, sheets, rubber (including synthetic rubber), leather (artificial leather,
For coloring synthetic leather, salt-pigmented leather, etc.), ink, paint, synthetic fibers, etc., pre-colored pigments or dyes mixed to the desired color may be mixed onto the material to be colored. Alternatively, a method of coating or dyeing the colored material has been adopted. These methods can be said to be preferable when producing large quantities of one model or producing large quantities of molded products with the same color tone, but when it is necessary to change the color tone for each part or when producing a wide variety of products in small quantities, there are various This method cannot be said to be preferable when creating a pattern with different color tones.

The method of the present invention is completely different in concept from these methods, and is similar in technique to the former method, in which colorless coloring agents A and B are mixed and dispersed in a binder in advance, and then the entire or partial By heating to a predetermined temperature, colors and patterns can be developed freely, or by adding either colorless color former A or an isocyanate compound and/or its blocked compound to the colored object in advance. By mixing and dispersing the mixture and then contacting it with another isocyanate compound and/or its blocked compound (referred to as color former B) or color former A, the desired portion and amount can be mixed and dispersed. The present invention provides a new coloring method that allows colors to be colored.

By the method of the present invention, it is possible to perform coloring treatment on various polymer molded products at the final stage of the manufacturing process, and not only can colored products that meet market needs be efficiently produced, but also all coloring can be done on the colored material. It becomes colored only when it comes into contact with the coloring agent A (or coloring agent B) mixed therein. Furthermore, the colored matter formed here is a new compound that is chemically bonded to the coloring agent embedded in the colored material, and is also firmly fixed in the colored material. Therefore, this colored material has very high resistance to physical and mechanical stress. Further, the color is developed in the object to be colored or on the surface of the object to be colored, and the color does not develop in the processing medium. This means that no colored waste, waste liquid, etc. are discharged during the coloring process, which is very advantageous in terms of operation and pollution prevention measures. The method is also very versatile compared to conventional methods, and can be heated by heating elements (heating heads, heating rolls, heating presses, heating furnaces, heating sources such as lasers, electron beams, etc.), if necessary. By operating in conjunction with a computer, it is possible to color the entire surface and develop characters, numbers, patterns, etc. as desired, and its range of applications is extremely wide-ranging. With this method, vinyl tiles, vinyl cloth,
In addition to coloring and patterning printed materials, by rolling or applying a binder containing this coloring agent, it can be applied to leather (artificial leather, synthetic leather, vinyl leather, etc.), fibers, cloth, paper, glass, ceramics, etc.
It can be used in a wide range of applications, including coloring and patterning metal surfaces.

The binder used in the present invention refers to a material that is colored by itself by dispersing and retaining coloring agent A or B, and dispersing and retaining a colored substance after coloring treatment. It also includes liquid and powder products such as plastic molded products such as foams and pipes, synthetic fibers, synthetic leather molded products, molding raw materials such as chips and pellets, and film forming materials such as paints and printing and dyeing pastes.

One of the preferable properties of the binder required here is that it can disperse color formers A and B well, and that it can exhibit enough fluidity to cause a sufficient contact reaction between color formers A and B under heating conditions for color development.
The dispersion of the coloring agent into the binder can be carried out by powder mixing, heated melt mixing, solution or slurry mixing using a solvent, etc., depending on the properties of the binder and the coloring agent to be mixed,
A method that suits the properties is selected. Mixers include kneaders, extruders, pole mills, sheakers, etc., and the most suitable method is selected depending on the characteristics of each.

Specific examples of binders used in the method of the present invention include polystyrene, polyvinyl chloride,
Polyethylene, polypropylene, polybutadiene, polyisoprene, polyvinyltoluene, polyvinyl acetate, polyvinyl alcohol, polyacetate cellulose, polymethacrylate, polyacrylate, polyester, polyacrylonitrile, polyamide, polyurethane, polycarbonate, polychloroprene, polyacetal, silicone Resins such as resins are suitable, and these can be used alone or as a mixture. In addition, additives (for example,
(oligomers, waxes, plasticizers, high boiling point solvents, etc.)
It is also possible to add In this case, the resin is not limited to thermoplastic resins, and thermosetting resins can also be used. Further, these high boiling point solvents, oligomers, waxes, etc. alone can be used as binders depending on the purpose.

In addition to the method of dispersing color formers A and B in the same binder and causing the color formers to develop by heating and contact, there are methods in which color formers dispersed and mixed in these resins, etc. are reacted with another color former, and color formers A and B are dispersed in the same binder and colored by contact with heat. A method of contact heating resin, wax, etc. containing a coloring agent to develop color, one coloring agent is dissolved in a solvent, etc.
In addition to methods such as immersing a resin molded product containing a color former in the solution and reacting and developing color at room temperature or under heating, there is also a method of directly contacting the color former in a gaseous, liquid, or solid state, reacting, and developing color. can also be performed. The solvent used here is preferably a substance that is inert to the color former, dissolves the color former, and does not attack the binder. Specifically, aliphatic and aromatic hydrocarbons such as n-hexane, n-decane, cyclohexane, tetralin, decalin, benzene, toluene, and xylene, chloroform, carbon tetrachloride, dichloromethane, monochlorobenzene, dichlorobenzene, etc. Chlorinated organic solvents, nitriles such as acetonitrile, propionitrile, benzonitrile, esters such as methyl acetate, ethyl acetate, ketones such as acetone, methyl ethyl ketone, cyclohexanone, other dimethyl sulfoxide, dimethyl formamide, anisole, pyridine, nitrobenzene, etc. can be given. In addition to these, waxes, oligomers, plasticizers, rosins, etc. can also be used.

The color former A used in the present invention is represented by the general formula (), and has a structure in which >C=NH group and >C
=NR ₁ group, examples of aromatic ring groups represented by Z and R ₁ include benzene ring, naphthalene ring, biphenyl ring, anthracene ring, indene ring, fluorene ring, phenanthrene ring, acenaphthene ring, etc. Examples of heterocyclic groups include indole rings, indazole rings,
Chroman ring, benzimodazolone ring, benzothiophene ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, pyridine ring, quinoline ring, isoquinoline ring, quinazoline ring, acridine ring, phenazine ring, pyrazine ring, oxazine ring, xanthene ring , a purine ring, a dibenzofuran ring, a dibenzopyrrole ring, an anthraquinone ring, and derivatives thereof. Specific examples thereof include the following compounds.

1-phenylimino-3-iminoisoindoline, 1-(3'-chlorophenylimino)-3-iminoisoindoline, 1-(2',5'-dichlorophenylimino)-3-iminoisoindoline, 1-
(2′,4′,5′-trichlorophenylimino)-3-
iminoisoindoline, 1-(2'-cyano-4'-
Nitrophenylimino)-3-iminoisoindoline, 1-(2'-chloro-5'-cyanophenylimino)-3-iminoisoindoline, 1-(2',
6′-dichloro-4′-nitrophenylimino)-3
-Iminoisoindoline, 1-(2',5'-dimethoxyphenylimino)-3-iminoisoindoline, 1-(2',5'-diethoxyphenylimino)-
3-iminoisoindoline, 1-(2'-methyl-
4'-Nitrophenylimino)-3-iminoisoindoline, 1-(5'-chloro-2'-phenoxyphenylimino)-3-iminoisoindoline, 1
-(4'-N,N-dimethylaminophenylimino)
-3-iminoisoindoline, 1-(3'-N,N
-dimethylamino-4'-methoxyphenylimino)-3-iminoisoindoline, 1-(2'-methoxy-5'-N-phenylcarbamoylphenylimino)-3-iminoisoindoline, 1-(2 ′-Chloro-5′-trifluoromethylphenylimino)
-3-iminoisoindoline, 1-(5',6'-dichlorobenzothiazolyl-2'-imino)-3-iminoisoindoline, 1-(6'-methylbenzothiazolyl-2'-imino) )-3-iminoisoindoline, 1-(4'-phenylaminophenylimino)
-3-iminoisoindoline, 1-(p-phenylazophenylimino)-3-iminoisoindoline, 1-(naphthyl-1'-imino)-3-iminoisoindoline, 1-(anthraquinone-1') -imino)-3-iminoisoindoline, 1-(5'-chloroanthraquinone-1'-imino)-3-iminoisoindoline, 1-(N-ethylcarbezolyl-3'-imino)-3- iminoisoindoline, 1
-(naphthoquinone-1'-imino)-3-iminoisoindoline, 1-(pyridyl-4'-imino)-3-
iminoisoindoline, 1-(benzimidazolone-6′-imino)-3-iminoisoindoline,
1-(1'-methylbenzimidazolone-6'-imino)-3-iminoisoindoline, 1-(7'-chlorobenzimidazolone-5'-imino)-3-iminoisoindoline, 1-(benz imidazolyl
2′-imino)-3-iminoisoindoline, 1-
(Benzimidazolyl-2'-imino)-3-imino-4,5,6,7-tetrachloroisoindoline, 1-(2',4'-dinitrophenylhydrazone)
-3-iminoisoindoline, 1-(indazolyl-3'-imino)-3-iminoisoindoline,
1-(indazolyl-3'-imino)-3-imino-
4,5,6,7-tetrabromoisoindoline,
1-(indazolyl-3'-imino)-3-imino-
4,5,6,7-tetrafluoroisoindoline, 1-(benzimidazolyl-2'-imino)-3
-imino-4,7-dithiatetrahydroisoindoline, 1-(4'5'-dicyanoimidazolyl-2'-
imino)-3-imino-5,6-dimethyl-4,
Examples include 7-pyradiisoindoline.

Color former B used in the present invention has the general formula ()
An isocyanate compound represented by, for example, phenyl isocyanate,
p-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, isocyanic acid α
-naphthyl, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,
3'-dichloro-4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate,
4,4'-diphenyl diisocyanate, p-phenylene diisocyanate, 2,7-diisocyanate fluorene, 3,5-diisocyanate chlorobenzene, diphenylthioether-4,4'-
Diisocyanate, 4,4'-diisocyanatobenzanilide, 2,5-dichloro-p-phenylene diisocyanate, 2,5-dimethyl-p-phenylene diisocyanate, 4,4'-diisocyanate Natoazobenzene, 4,4'-diisocyanatobenzophenone, 3,6-diisocyanatoacridine, 4,4'-diisocyanatodiphenylsulfone, triphenylmethane triisocyanate, tris(4-phenylisocyanate) 4,4′,4″-trimethyl 3,3′,
3″-triisocyanate 2,4,6-triphenyl cyanurate, 2,4,4′ diphenyl ether triisocyanate, polymethylene polyphenyl isocyanate, adduct of 2,4-tolylene diisocyanate and trimethylolpropane Examples include adducts of diisocyanates such as and active hydrogen group-containing compounds.

Another example of the color forming agent B used in the present invention is one generally called a blocked isocyanate represented by the general formula (). A blocked isocyanate is an addition compound of an isocyanate and a compound having an active hydrogen group called a blocking agent (also called a masking agent).

RNCO+HQ→RNHCOQ RNHCOQ: Blocking isocyanate HQ: Blocking agent Specific examples of such blocking agents include phenols such as phenol and cresol, lactams such as ε-caprolactam and γ-butyrolactam, MEK oxime, and cyclohexanone oxime. Oximes, methanol, ethanol,
Alcohols such as methyl lactate, active methylene compounds such as dimethyl malonate, and other substances with active hydrogen groups in their structures, in addition to the above examples, mercaptans, acid amides, imides, amines, imidazole, and urea. type, carbamate type, imine type,
These are compounds such as sulfites.

In addition to the above, this category also includes substances that are not blocked isocyanates in the true sense of the word, but which generate isocyanate compounds under the conditions of use. Examples of such isocyanate diegenerators include isocyanates microencapsulated with polystyrene, wax, etc., which are regenerated by heating above the melting point. Another example is a compound that generates isocyanate upon thermal decomposition, such as amine imide and TDI dimer, which are included in this field.

The above-mentioned color formers A and B are dispersed separately or together in a binder containing a solvent, additives, etc., and are coated or molded in a conventional manner to form a colored phase on a substrate. By scanning and heating this colored phase at a predetermined temperature and for a predetermined time using a heating element, for example, a desired color and pattern can be developed. This coloring phenomenon is caused by the reaction of coloring agents A and B to produce a new colored compound.
The chemical structure of this colored compound is, for example, the general formula () or when m in () is 1, the chemical structure is the general formula () (wherein Z, R ₁ and R ₂ are as defined above). The heating color development conditions vary depending on the structure of color formers A and B, the type of binder used, the presence or absence of additives, the type, the shape of the coloring phase, etc., but the approximate heating temperature is 80°C to 250°C, heating time The preferred range is from several seconds to several tens of minutes.

EXAMPLES Hereinafter, the present invention will be explained specifically and in detail with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples. In addition, in the examples below, "parts" indicate "parts by weight."

Example 1 A mixture having the following composition was dispersed for 30 minutes using a stirrer containing galam beads.

Thermosensitive color former mixture 1-(benzimidazolyl-2'-imino)-3-iminoisoindoline...4.7 parts 3,4-dichlorophenyl isocyanate-methyl ethyl ketoxime...5.3 parts Vinyltoluene-butadiene resin...20 parts Ethylcyclohexane 70 parts This heat-sensitive coloring agent mixture was applied onto art paper using an applicator and dried to obtain heat-sensitive coloring paper having a colorless coating phase containing a coloring agent and having a thickness of about 20 microns. It was observed that this product turned yellow when heated with an iron for 5 seconds at 210°C.

Example 2 Color forming agent solutions A and B were prepared by dispersing mixtures having the following compositions for 30 minutes using a stirrer containing glass beads.

A Solution 1-(indazolyl-3'-imino)-3-imino-
4,5,6,7-tetrachloroisoindoline
...10 parts Polystyrene resin 20 parts Chloroform 70 parts B Liquid isocyanate-α-naphthyl ...5 parts Paraffin wax ...45 parts Chloroform 50 parts First, apply liquid A onto art paper using an applicator and dry it. A coating film with a thickness of approximately 20 microns was created. Next, a chloroform solution containing 2.5% Parawax was applied onto this and dried. Further, Solution B was applied thereon in the same manner and dried to form a three-layer heat-sensitive coloring film. This one is 200℃,
The heated part was colored orange by heating the iron for 5 seconds.

Example 3 Mixtures having the following compositions were each dispersed for 30 minutes using a stirrer containing glass beads to create color former-containing mixtures A and B.

Solution A 1-(4',5'-dicyanoimidazolyl-2'-imino)-3-imino-5,6-dimethyl-4,7-
Pyradiisoindoline ...10 parts Polyurethane resin ...20 parts DMF-MEK (1:1) mixed solvent ...70 parts B Liquid p-methylphenylisocyanate-ε-caprolactam block ...10 parts Vinyl chloride resin ...20 parts MEK ...70 parts Mix each solution A and B at a ratio of 1:1, apply this mixed solution on polyurethane leather, dry it,
A thermosensitive coloring material was obtained. When this product was heated with an iron at 190°C for 5 seconds, the heated area was colored orange.

Example 4 1-(5',6'-dichlorobenzothiazolyl-2'-
5% by weight of (imino)-3-iminoisoindoline
Containing polystyrene resin sheet (50cm long x 50cm wide)
25mm x thickness 2mm). This product was immersed in a separately prepared toluene solution containing 10% by weight of diphenylmethane diisocyanate and treated at 50°C for 30 minutes. The treated molded article was colored yellow.

Example 5 1-(Benzimidazolyl-2'-imino)-3-iminoisoindoline 1 part 5% aqueous polyvinyl alcohol 2 parts water 2 parts This composition was ground in a ball mill for 2 hours, then 2 parts 20% aqueous polyvinyl alcohol This coating solution was applied onto art paper so that the weight after drying was about 5 g/m ² and dried. On the coated surface of the art paper thus obtained, a solution obtained by diluting a 75% ethyl acetate solution of tolylene diisocyanate and trimethylolpropane adduct (trade name: Coronate L) with an equal amount of ethyl acetate was dropped. , dried, and then heated to 150℃ for 10 seconds.
The area where the isocyanate was dropped was colored yellow.

Claims (1)

[Claims] 1. Compound represented by general formula () (In the formula, Z represents an aromatic ring group or a heterocyclic group that can form a conjugated system with C=NH, and R ₁ represents an adjacent C=N
represents an aromatic compound or a heterocyclic compound residue capable of forming a conjugated system with), and an isocyanate compound represented by the general formula () R ₂ (NCO) _n () (wherein R ₂ is an aromatic compound or represents a heterocyclic compound residue, m represents an integer of 1 to 4) and/
or blocked isocyanates represented by the general formula () R ₂ (NCO-HR ₃ ) _n () (wherein R ₃ represents an isocyanate blocked compound residue having active hydrogen, and R ₂ and m are the above-mentioned A coloring method characterized in that a colored compound is produced in a binder phase by contacting or heating contact reaction with (as defined in ).