JPH0143640B2 - - 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 the general formula ()
or a coloring agent B represented by () R ₁ (NCO) _n () R ₁ (NCO-HR') _n () (wherein R ₁ is an aromatic compound residue that may have a substituent, R' represents an isocyanate-blocked compound residue having active hydrogen, and m is 1 to 4.
(representing an integer of
The present invention relates to a new method for coloring a binder by causing a catalytic reaction, if necessary under heating, to produce a colored compound in the binder phase and on its surface.

Generally, plastic molded products, films, sheets, rubber (including synthetic rubber), leather (artificial leather,
(including synthetic leather, PVC leather, etc.), ink, paint, synthetic fibers, etc., by mixing pre-colored pigments or dyes mixed to the desired color into the material to be colored. Alternatively, a method of coating or dyeing the object to be colored 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 of the same color tone, but when it is necessary to change the color tone of each part or when producing a wide variety of products in small quantities, This method cannot be said to be preferable when creating patterns of various colors.

The method of the present invention is completely different in concept from these methods, and involves mixing either a colorless coloring agent A or an isocyanate compound into the object to be colored in advance.
A new coloring agent that can be dispersed and then brought into contact with another isocyanate compound (referred to as coloring agent B) or coloring agent A to color a desired portion and amount in a desired color. The present invention provides a method.

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 colored waste material, waste liquid, etc. from the coloring process are not discharged, which is very advantageous in terms of operation and pollution prevention measures.

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 powdered products such as plastic molded products such as foams and pipes, molded products such as synthetic fibers and synthetic leather, molding raw materials such as chips and pellets, and film forming materials such as paints and printing dye pastes. . For dispersing the color former into the binder, a method suitable for the nature and properties of the binder and the color former to be mixed is selected, such as powder mixing, heating melt mixing, solution or slurry mixing using a solvent. Mixers include kneaders, extruders, ball mills, sheakers, etc. The most suitable method is selected depending on the characteristics of each mixer. Specific examples of selected binders include polyethylene, polypropylene, polyvinyl chloride,
Suitable thermoplastic resins include polyvinylidene chloride, polyvinyl acetate, polyacrylic ester, polymethacrylic ester, polystyrene, polyamide, polyester, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylonitrile, polycellulose acetate, and silicone resin. Of course, thermosetting resins can also be used if the dispersion of the color former into the resin is appropriately selected. Additives (e.g. plasticizers, waxes, oligomers,
It is also possible to add a high boiling point solvent, etc.). Of course, each of the above-mentioned substances can be used not only alone, but also in a mixed system.

There are two methods for coloring by reacting color formers dispersed and mixed in these resins with the other color former: a method in which resins containing each color former; wax, etc. are contacted and heated; 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 and reacting with the color former in the form of a gas, liquid, or solid. A method of 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 vehicle. Specifically, n-hexane, n-decane,
Aliphatic and aromatic hydrocarbons such as cyclohexane, tetralin, decalin, benzene, toluene, xylene, chlorinated organic solvents such as chloroform, carbon tetrachloride, dichloromethane, monochlorobenzene, dichlorobenzene, acetonitrile, propionitrile, bezonitrile Examples include nitriles such as methyl acetate and ethyl acetate, esters such as acetone methyl ethyl ketone and cyclohexanone, and dimethyl sulfoxide, dimethyl formamide, anisole, pyridine, and nitrobenzene. In addition to these, waxes, oligomers, plasticizers, resins, etc. can also be used.

The coloring agent A used in the present invention is a compound represented by the general formula () having at least one >C=NH group in its structure, and an example of the aromatic ring group represented by Z is benzene. rings, naphthalene rings, biphenyl rings, anthracene rings, indene rings, fluorene rings, phenanthrene rings, acenaphthene rings, etc., and derivatives thereof; examples of heterocyclic groups include indole rings, indazole rings,
Coumarone ring, benzimidazolone 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, Examples include purine ring, dibenzofuran ring, dibenzopyrrole ring, anthraquinone ring, and derivatives thereof. Specific examples thereof include the following compounds.

3-imino-1,2-benzo[d]thiazoline-1,1-dioxide, 6-chloro-3-imino-1,2-benzo[d]thiazoline-1,1-dioxide, 5,6-dichloro- 3-imino-1,
2-benzo[d]thiazoline-1,1-dioxide, 4,5,6,7-tetrachloro-3-imino-1,2-benzo[d]thiazoline-1,1-dioxide, 4,5,6 ,7-tetrabromo-3-
imino-1,2-benzo[d]thiazoline-1,
1-dioxide, 4,5,6,7-tetrafluoro-3-imino-1,2-benzo[d] thiazoline-1,1-dioxide, 3-imino-6-nitro-1,2-benzo[d] ]Thiazoline-1,1-
Dioxide, 3-imino-methoxy-1,2-benzo[d]thiazoline-1,1-dioxide,
4,5,7-trichloro-3-imino-6-methylthio-1,2-benzo[d]thiazoline-1,
1-dioxide, 3-imino-1,2-naphtho[2,3-d]thiazoline-1,1-dioxide,
5-bromo-3-imino-1,2-naphtho[2,
3-d] thiazoline-1,1-dioxide and the like.

Color former B used in the present invention has the general formula ()
Specific examples of the isocyanate compound represented by the formula include the following compounds.

That is, phenyl isocyanate, p-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, α-naphthyl isocyanate,
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-diisocyanatofluorene, 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'-diisocyanato azobenzene, 4,4'-diisocyanato benzophenone,
3,6-diisocyanatoacridine, 4,4'-
Diisocyanate diphenyl sulfone triphenylmethane triisocyanate, tris(4-phenyl isocyanate thiophosphate), 4,4',
4″trimethyl 3,3′,3″-triisocyanate 2,4,6-triphenyl cyanurate, 2,
4,4′ diphenyl ether triisocyanate, polymethylene polyphenyl isocyanate,
These include adducts of diisocyanates and compounds containing active hydrogen groups, such as adducts of 2,4-tolylene diisocyanate and trimethylolpropane.

Another example of the color forming agent B used in the present invention is what is 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,
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 this isocyanate diegenerator include:
Isocyanates are microencapsulated in polystyrene, wax, etc., and the isocyanate is 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 category.

The above-mentioned coloring agents A and B are dispersed separately or together in a vehicle containing a solvent, additives, etc., and are applied or molded by a conventional method 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 color development is caused by the reaction of color formers A and B to produce a new colored compound C. This is due to the formation of this colored compound. The chemical structure of this colored compound is represented by, for example, the general formula () or, if m in () is 1, the general formula ().

(In the formula, Z and R ₁ 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 color phase, etc. However, the heating temperature is approximately 80℃~
The preferred range is 250°C and heating time from several seconds to several tens of minutes.

EXAMPLES Hereinafter, the present invention will be explained more 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 following examples, "parts" are "parts by weight"
shows.

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

Thermosensitive color former mixture 3-imino-1,2-benzo[d]thiazoline-
1,1-dioxide...4.5 parts 3,3'-dimethyl-4,4'-diphenyl diisocyanate-MEK oxime block...5.5 parts Vinyltoluene-butane diene resin...20 parts Ethylcyclohexane...70 parts This heat-sensitive color former The mixed solution was applied onto art paper using an applicator and dried to obtain heat-sensitive coloring paper having a colorless coloring agent-containing coating layer on the surface with a thickness of about 20 microns. It was observed that this product turned yellow when heated with an iron for 5 seconds at 200°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.

Solution A 3-imino-1,2-benzo[d]thiazoline-
1,1-dioxide...10 parts Polystyrene resin...20 parts Methylene chloride...70 parts Part B 2,4-tolylene diisocyanate...5 parts Paraffin wax...45 parts Methylene chloride...50 parts First, apply Part A using an applicator. It was applied onto art paper and dried to create a colorless coating approximately 20 microns thick. Next, apply paraffin wax on top of this.
A methylene chloride solution containing 2.5% was applied and dried.
Further, liquid B was applied thereon in the same manner and dried to form a coloring agent film. This one is 170℃, 5
After heating the iron for a few seconds, the heated part turned yellow.

Example 3 A mixture having the following composition was stirred using a strong stirrer to obtain color forming agent-containing mixtures A and B.

Solution A 6-chloro-3-imino-1,2-benzo[d]
Thiazoline-1,1-dioxide...5 parts Polyurethane resin...25 parts Methyl ethyl ketone...70 parts Part B 4,4'-diphenylmethane diisocyanate-cyclohexanone oxime block...5 parts Vinyl chloride resin...25 parts Methyl ethyl ketone...70 parts These A and B solutions were mixed at a ratio of 1:1, and this mixed solution was applied onto polyurethane leather and dried to obtain a heat-sensitive coloring material. When this product was heated with an iron for 5 seconds at 190°C, the heated area turned yellow.

Example 4 A sheet of polystyrene resin containing 5% by weight of 3-imino-1,2-benzo[d]thiazoline-1,1-dioxide (50 x 50 mm in length and width,
2 mm thick). This product was immersed in a toluene solution containing 10% by weight of separately prepared tolylene diisocyanate (2:8 mixture of 2,6 and 2,4) and treated at 50°C for 30 minutes.
The treated molded article was colored yellow. After processing, n
- The colored molded product was washed with hexane, dried, and used as a sample for light resistance measurement. This product showed excellent light resistance.

Example 5 3-imino-1,2-benzo[d]thiazoline-
1,1-dioxide 1 part 5% aqueous solution of polyvinyl alcohol 2 parts 2 parts water This composition was ground in a ball mill for 2 hours, then 2 parts of 20% aqueous polyvinyl alcohol solution was added to form a coating solution, and this coating solution was applied onto art paper. , and dried so that the weight after drying was approximately 5 g/m ² .
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. When the mixture was dried and then heated to 150°C for 10 seconds, the area where the isocyanate was dropped turned 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 the general formula ()
An isocyanate compound represented by R ₁ (NCO) _n () (wherein R ₁ is an aromatic compound residue that may have a substituent, m represents an integer from 1 to 4) and /
or blocked isocyanates represented by the general formula () R ₁ (NCO-HR') _n () (wherein R' represents a residue of an isocyanate block compound having active hydrogen, and R ₁ and m are A coloring method characterized in that a colored compound is produced in a binder phase by contacting or heating catalytically reacting (as defined).