JPS5854085A - Coloring method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] The present invention relates to a new coloring method, more specifically, at least one C=NH represented by the general formula (1).
A color former having a group A H 1 1 (wherein A represents 0, NH or (OR+)n, R1 is a lower alkyl group at C1 to C4, n is an integer of 1 or 2, 2 is C= N) represents an aromatic ring group or a heterocyclic group capable of forming a conjugated system with I) and an incyanato compound R2(NCO)m(II) represented by the general formula (II) (wherein R2 has a 1j1 substituent (m represents an integer from 1 to 4) are dispersed and mixed in a vehicle.

This is catalytically reacted with the other adduct of the residue, either directly or through a solvent or solid medium, if necessary under heating, to form a colored compound NC0NHR2 1 1 (in the formula, B is O, NCONT(R2, or (OR1)n
in.

R1, R2+n as defined above) in the vehicle phase and in different planes.

Generally, plastic molded products, films, sheets, rubber (including synthetic rubber), leather (including artificial leather, synthetic leather, vinyl chloride rubber, etc.), ink, synthetic fibers, etc. are colored in advance. The methods used include mixing pigments or dyes blended to give the desired color into the object to be colored, or coating or forming a dye layer on the object to be colored. These methods can be said to be preferable when producing large quantities of one model or when producing large quantities of molded products with the same color tone, but if it is necessary to change the color tone of each part, it is difficult to produce a small number of products. In this case, it cannot be said to be a preferable method when creating patterns of various colors.

The method of the present invention differs from these methods in its total heat concept, by first mixing and dispersing either the color former A or the incyanate compound into the object to be colored, and then adding this to the other material. Isocyanate compound (color former B
The purpose of the present invention is to provide a new coloring method that can color a desired portion and a desired amount in a desired color by contacting it with a coloring agent A or a coloring agent A.

By the method of the present invention, it is possible to perform color development treatment on 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 color development can be performed on the material to be colored. Color forming agent A (6
It becomes colored only after contact reaction with color former B). Moreover, the colored matter formed here is a new compound that is chemically bonded to the coloring agent embedded in the coated colored matter, and this is also firmly fixed in the colored matter. ing. 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 vehicle used in the present invention refers to a vehicle that is itself colored by dispersing and retaining coloring agent A or B, and dispersing and retaining a colored substance after coloring treatment.
t@/I7 (Plastic molded products such as lums, sheets, foams, etc., synthetic fibers, synthetic leather, etc.)
Liquid and powdered materials such as molding raw materials such as chips and pellets, coating materials, and film forming materials such as printing and dyeing pastes are also included. For dispersing the color former into the vehicle, a method suitable for the properties and characteristics of the vehicle and the color former to be mixed, such as powder mixing, heating bath melt mixing, solution or slurry mixing using a solvent, is selected. Mixers include kneaders, extruders, whole mills, shakers, etc. The most suitable method is selected depending on the characteristics of each mixer. Examples of selected vehicles include polyethylene, polypropylene, 2j? polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate 1. J? Thermoplastic resins such as lyacrylate ester, polymethacrylate ester, polystyrene, polyamide, 4-hylyester, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylonitrile, polycellulose acetate, and silicone resin are suitable, but of course thermosetting It is also possible to use color-forming resins if the dispersion of the coloring agent in 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 of reacting color formers dispersed and mixed in these resins with other color formers to develop color: resins containing each color former; wax, etc. are contacted and heated to develop color; one color former is mixed with a solvent etc. The resin molding containing the coloring agent is immersed in the solution, and the reaction is carried out at room temperature or under heating.
In addition to the method of color development, a method of directly contacting a color former in a gaseous, liquid, or solid state and reacting to develop 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, 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, zolobionitrile, and pezonitrile, esters such as methyl acetate and ethyl acetate, ketones such as acetone methyl ethyl ketone and cyclohexanone, and other trimethyl sulfoxide, trimethyl formamide, anisole, hyridine, and nitrobenzene. etc. can be mentioned. In addition to these, waxes, oligomers, plasticizers, and the like can also be used.

The coloring agent A used in the present invention is a compound represented by the general formula (1) and having at least one >C-+ group in its structure, and examples of the aromatic ring group represented by 2 are: benzene ring, naphthalene ring, biphenyl ring, anthracene ring, i/denjo, nluolene term, phenanthrene ring, acenaphthene ring, etc., and derivatives thereof; as a series of heterocyclic groups, indazole ring, indazole ring, coumaron ring, benzimidacylon ring, benzothiophene ring,
Benzoxyzole ring, benzothiazole ring, pe/shiimidazole ring, pyridine ring, quinoline ring, isoquinoline ring, quinazoline ring, acridine ring, phenaso/Pj1,
Pyrazone ring, oxazine ring, xandene ring, purine ring,
- Dipenzofuran ring, nope/-zopyrrole ring, anthraquinone ring, etc., and derivatives thereof. Specific examples thereof include the following compounds.

3-iminoisoindolin-1-one, 3-imino-4
, 5,6,7-tetrachloroisoindolin-1-one, 3-imino-4,5,6,7-titrapromoinindolin-1-o/l 3-(mino-4,5,6,7 -tetrafluoroisoindolin-1-one, 3-imino-
5,6-dichloroisoindolin-1-one, 3-imino-4゜5.7-)lichloro-6-methoxyisoindolin-1-one, 3-imino-4,5,7-)lichloro- 6-methylmercaptoyfindolin-1-one, 3-imino-6-nitroisoindolin-1-one,
1.1-dimethoxy-3-imino-isoindoline, 1
．． 1-jethoxy-3-imino-4,5,6,7-titrachloroisoindoline, 1,3-diiminoisoindoline, 1-13-diimino-4,5,6,7-tetrachloroisoindoline, 1,3-diimino-6-medoxyisoinodrine, 1,3-siimino-6-tuanoisoindoline, 7-aminol 2,3-dimethyl-5-oxopyrrolo(3,4b,)virazino, 7-amino -2,3-
diphenyl-5-oxopyrrolo[3,4b: birazino,
These include 1-iminosifenoic acid imide, 1-iminosifenoic acid imide, and the like.

It is said that the compound represented by the general formula (1) can take the following isomeric structure depending on the conditions (P, F,
C1ark et, al+ J, Cham,
See, +3593 (1953)).

Therefore, for the compound structure represented by general formula (I), for example, when A is OR, three types of isomers are expected.

Margin below 1 1 R Therefore, although the above-mentioned compound names may be expressed by different names depending on the case, these are all included in the general formula (1) for the above-mentioned reasons.

The color forming agent B used in the present invention is an isocyanate compound represented by the general formula (n), and specific examples thereof include the following compounds.

Phenyl isocyanate, p-chlorophenylisocyanate, 3.4-dichlorophenylisocyanate, α-naphthyl isocyanate, 2.4-tolylene diisocyanate, 2.6-)lylene diisocyanate, sophenylmethanezoisocyanate, 3. Azomethyl-4,4'
-diphenylzoisocyanate, 3. Ryo-Fukuroro 4
14'-zophenyl diisocyanate, 1,5-naphthalene diisocyanate), 4,4'-diphenyl diisocyanate, p-phenylene diisocyanate, 2゜7-
Diisocyanatofluorene, 3,5-diisocyanatochlorobenzene, diphenylthioether-4,4'
-Diisocyanate, 4,4! -diinocyanatopenzanilide, 2,5-dichloro0-p=7enine/diisocyanate, 2,5-zomethyl-p-phenyleneynoisocyanate, 4゜isoisocyanate azobenzene, 4.4'- Diisocyanate benzophenone,
3.6-Diisocyanatoacridine, 4e 4'-
Examples include zoisocyanate sophenyl sulfone.

The present invention will be explained in detail below with reference to Examples.

It goes without saying that the scope of the invention is not limited to these examples.

Example 1 Coloring solutions A and B were prepared by dispersing mixtures having the following compositions for 30 minutes using a stirrer containing glass beads.

Part A 3-Imino-4,5,6,7-tetrachloroisosodrine-1-one---------------10 parts Polystyrene resin-----=----- -----, 20
Part methylene chloride---------
---------70 parts B liquid 3.3'-dimethyl-4,4'-diphenyl diisocyanate --------------, -------5
Sound b paraffin wax -----, ------45 parts cyclohexane ------50 parts Apply fAiM to art paper using an applicator and dry to a colorless thickness of about 10 microns. A film was obtained. Next, a methylene chloride solution containing 2.5% paraffin wax is applied thereon and dried. Further, liquid B was applied thereon in the same manner and dried to form a heat-sensitive coloring film. When this product was heated with an iron at 170° C. for 5 seconds, the heated portion was colored bright red.

Example 2 A mixture having the following composition was stirred and mixed using a powerful stirring gun to prepare a uniform dispersion containing a color former.

3-Imino-5,6-cycloindolin-1-one ---1--,, ---------------
----------5 parts 30 parts Polyurethane resin DMF solution - 100 parts Toluene
----1--30 parts of this dispersion g!
L was applied onto a polyester nonwoven fabric and dried under reduced pressure at 80 to 100°C to obtain a sheet-like product. Next, a 5-titoluene solution of toluylene-2,4-diisocyanate was applied onto the sheet and dried by heating at 130°C for 20 minutes. The sheet was colored bright yellow and had good light resistance, solvent resistance, A synthetic leather-like material with a film having excellent chemical resistance was obtained.

Example 3 A vulcanized molded product (50 x 50 in length and width, 3 sheets thick) of styrene putaso emulsion containing 1.3-diiminoisoindoline t-5 weight percentage was prepared. This product was immersed in a benzene solution containing 10% by weight of 3,3'-dimethyl-4,47-sophenyl soisocyanate prepared separately and treated at 80°C for 5 minutes. Coloring starts immediately after soaking υ,
After 5 minutes, the color turned bright orange. After the treatment, the surface was washed with n-hexane and dried to obtain a colored molded product.

This product was colored bright orange and showed excellent light fastness test results.

Example 4 7-Amino-2,3-dimethyl-5-oxopyrrolo(3
, 4b) 5 parts of pyrazine were heat-melted and mixed with 7100 parts of polystyrene, and a film with a thickness of about 30 microns was prepared by extrusion molding. On the other hand, a solution having the following composition was prepared and 1,5-naphthalene diisocyaner) --
--5 parts styrene butadiene block co. 7--2
Part 5 Penzen----------------------
---------- 70 parts was coated on art paper using an applicator and dried to prepare coated paper coated with styrene-butadiene block copolymer.

When the above-mentioned 4 Listrein films were layered on the coated paper prepared in this way and heat-sealed using heat-sealing, the heat-sealed area turned into a very bright yellow V.
C layer was colored. This heat-sealed product exhibited excellent light resistance and abrasion resistance.

Patent Applicant: Asahi Kasei Kogyo Co., Ltd. Patent Attorney Akira Aoki Patent Attorney Kazuyuki Nishidate 1) Honorable Patent Attorney Akira Yamaguchi Procedural Amendment (Voluntary) December 16, 1980 Commissioner of the Japan Patent Office Wakasugi Mr. Kazuo 1. Indication of the case 1980 Patent Application No. 146999 2. Name coloring method of the invention 3. Relationship with the case of the person making the amendment Patent applicant name (003) Asahi Kasei Kogyo Co., Ltd. 4. Agent address Tokyo Shizukou Toranomon Building, 8-10 Toranomon-chome, Minato-ku 105 Telephone (504) 0721 5, Subject of amendment 1) “Claims” column of the specification 2) Detailed description of one invention in the specification” Column 6, Contents of amendment 1) The scope of claims is amended as shown in the attached sheet.

2) Page 3 of the specification, line 7 to line 5 below, [contact reaction,
It relates to the general formula (I[[)... '' and add the following after it.

"This invention relates to a new method for coloring a vehicle by producing a colored compound in the vehicle phase and on the surface of the vehicle through a contact reaction." 7. Amended Patent List of Attached Documents Claims 1 copy (2) 2. Patent Scope of claims 1. At least one >C represented by general formula (1)
= Compound having NH group NH''1 1 (wherein A represents O, NH or (OR,)n, R,
is a lower alkyl group from CI to C4, n is an integer of 1 or 2, Z represents an aromatic ring group or a heterocyclic group that can form a conjugated system with C=NH) or is represented by the general formula (It) Isocyanate compound R2 (NGO) m (II) (in the formula, Hiki is an aromatic compound residue that may have a substituent, m is 1
(representing an integer of ~4) incorporated into the vehicle, the remaining other compound (II) or (1
) to produce a colored compound in a vehicle phase.

(1) Spontaneous writing of procedural amendments) December 17, 1980 Mr. Kazuo Wakasugi, Director General of the Chiang Xu Office ■, Indication of the case 1982 Patent Application No. 146999 2, Method of coloring the name of the invention 3, Case of the person making the amendment Relationship between: Patent applicant name (003) Asahi Kasei Kogyo Co., Ltd. 4. Agent address: Shizuko Toranomon Building, IO, 8-chome, Toranomon, Minato-ku, Tokyo 105 Telephone: (504) 0721 5. "Invention Column 6 of ``Detailed explanation of ``, content of amendment ■) Specification, page 12, line 20, [triphenyl sulfone, etc.]. ] is replaced with ``totrhenyl sulpon, triphenylmethane triisocyanate, tris(4-phenylisocyanate thiophosphate), 4
．． 4',4''-trimethyl-3,3',3''-1-diisocyanate-2,,4,6-triphenyl cyanurate, 2.4,4'-diphenyl ether triisocyanate, polymethylene polyphenyl Isocyanate, 2.
Examples include adducts of diisocyanates such as 4-tolylene diisocyanate and trimethylolpropane and compounds containing active hydrogen groups. ” he corrected.

2) Add the following sentence after line 12 on page 16.

"Example 5 1,3-diimino,4,5,6,7-tetrac(2) coroisoindoline 1 part styrene butadiene broth copolymer - 2 parts toluene
10 parts A mixture having the above composition was ground in a ball mill for 2 hours to obtain a coating liquid. This coating liquid was applied onto art paper so that the coating amount after drying was approximately 5 g/rr+, and then dried. A 75% ethyl acetate solution (trade name:
A solution obtained by diluting Coronate L) with an equal amount of ethyl acetate was added dropwise, dried, and then heated to 150° C. for 10 seconds, resulting in the area where the isocyanate was added colored orange. ” That’s all (3)

Claims (1)

[Claims] 1. At least one C represented by general formula (I)
=N) Compound having a T group NH 1 1 (wherein A represents O, Nf (or (OR+)n), R1 is a lower alkyl group of C1 to C4, n is an integer of 1 or 2, 2 is represents an aromatic ring group or a heterocyclic group capable of forming a conjugated system with C=NH) or an incyanato compound R2(NC'O)m(It) represented by the general formula (II) (wherein R2 is a substituent (m represents an integer from 1 to 4) contained in a vehicle, the other aromatic compound residue (I
A coloring method characterized by subjecting I) or (1) to a catalytic reaction to produce a colored compound represented by the general formula (2) in a vehicle phase. NC0NHR2 1 1 (In the formula, B is O, NC0N) (R2 or (OR1) n
T6, R1+ R2+ n is the term p defined in soil.
It is. )