JPS58104959A - Coloring method - Google Patents

Abstract

PURPOSE:To color a molded polymer article in an arbitrary color, in high efficiency, by mixing and dispersing a specific color developing agent, an isocyanate and a blocked isocyanate in a binder, heating and melting the dispersion, and using the resultant colored compound as the colorant. CONSTITUTION:A liquid mixture of a heat-sensitive color-developing agent is prepared by mixing and dispersing (A) a color developing agent of formulaI(Z is aromatic ring group which can form a conjugated system with C=NH; R1 is residue of aromatic compound or heterocyclic compound which can form a conjugated system with C=N)[e.g. 1-(benzimidazolin-2'-imino)-3-iminoisoindoline] and (B) an isocyanate of formula II (R2 is residue of aromatic compound or heterocyclic compound; m is 1-4) (e.g. 3,4-dichlorophenylisocyanato-methyl ethyl ketoxime) and/or blocked isocyanate of formula III (R3 is residue of the compound blocking isocyanate having active hydrogen) in (C) a binder. The liquid is applied to the article to be colored, and colored by heating. The colored compound of formula IV is formed in the above mixture by the heat-treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new coloring method, and more specifically, a coloring agent A represented by the general formula (I). (represents an aromatic ring group or a heterocyclic group that can form a system, and R1 represents an aromatic compound or a heterocyclic compound residue that can form a conjugated system with adjacent C-N)
and the coloring agent BR2 (formerly or (I[[))
NCO) m (■) R2 (NGO-HR 夛m (III) (wherein, the position represents an aromatic compound or a heterocyclic compound residue, R3 represents an incyanate-blocked compound residue having an active hydrogen, m represents an integer from 1 to 4) is dispersed and mixed in a binder, and this is mixed with the other coloring agent directly or through a medium (including the same binder), if necessary under heating. A catalytic reaction is carried out, and the general formula (IV)
This invention relates to a novel method for coloring a binder by forming a colored compound 1 -R1 represented by the formula (wherein Z, R1 and Λ are as defined above) in and on the binder phase.

Generally, plastic molded products, films, sheets, rubber (including synthetic rubber), leather (including artificial leather, synthetic leather, PVC leather, etc.), ink, paint, synthetic fibers, etc. are colored in advance. Methods include mixing pigments or dyes blended to give the desired color onto the object to be colored, or applying or dyeing the mixture into the object to be colored. 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 if it is necessary to change the color tone for each part, it is difficult to produce a large variety of products in small quantities. case,
This is not a preferable method when creating patterns of various colors.

The method of the present invention differs from these methods in the total heat concept, and is similar to the former method in that the colorless color formers A and B are mixed and dispersed in a binder in advance, and the whole or By partially heating to a predetermined temperature, colors and patterns can be freely developed and completed, or colorless color formers A or incyanato compounds and/or
Alternatively, one of the blocked compounds is mixed and dispersed in the object to be colored, and then this is mixed with the other incyanato compound and/or its pro-blocking compound (referred to as color former B) or color former A. The present invention provides a new coloring method that allows a desired portion and a desired amount to be colored in a desired color by contacting with a desired color.

By the method of the present invention, it is possible to perform color development 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 all color development can be performed 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 a very high resistance to physical and mechanical stress, and the color develops within or on the surface of the colored material, and 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 if necessary, heating elements (thermal heads, heating rolls, heating presses, heating furnaces, lasers, electron beams, etc.) can be used to By operating in conjunction with a computer, it is possible to color the entire surface, develop letters, numbers, pictures, etc. as desired, and the range of applications is extremely wide.
In addition to coloring and patterning printed materials, leather (
(artificial leather, synthetic leather/leather, vinyl leather, etc.), textiles,
It can be used in a wide range of applications, from cloth and paper to coloring and patterning glass, ceramics, and metal surfaces.

The binder used in the present invention refers to a binder that is itself colored 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 textile dyeing pastes.

One of the desirable properties of the binder required here is:
The color formers A and B can be dispersed well, and the color formers A and B can exhibit enough fluidity to undergo a sufficient contact reaction under conditions of heating and color development.

For dispersing the color former into the binder, a method suitable for the nature and properties of the binder and the color former that can be mixed is selected, such as powder mixing, heating melt mixing, solution or slurry mixing using a solvent. Mixers include kneaders, extruders, ball mills, shakers, 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, polyvinyl alcohol, polyvinyl acetate, polyvinyl alcohol, polycellulose acetate, polymethacrylate, polyacrylate, polyester, polyacrylonitrile, polyamide, polyurethane, polycarbonate, polychloroprene, polyacetal, silicone resin, etc. The following resins are suitable, and these resins can be used alone or as a mixture. Also, for the purpose of providing liquidity.
It is also possible to add additives (eg, oligomers, waxes, plasticizers, high-boiling solvents, etc.) to these resins. In this case, the resin is not limited to thermoplastic resins, and thermosetting resins can also be used. Also, depending on the purpose, these high boiling point solvents, oligomers, waxes, etc. can be used alone as a binder.

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 in which one color former is dissolved in a solvent, etc., a resin molded article containing the color former is immersed in the solution, and the reaction takes place at room temperature or under heating. In addition to the method of color development, a method of directly contacting, reacting, and coloring with a color former in a gaseous, liquid, or solid state 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, and benzonitrile, esters such as methyl acetate and ethyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and other dimethyl sulfoxide, dimethyl formamide, anisole, pyridine, and nitrobenzene. etc. can be mentioned. In addition to these, waxes, oligomers, plasticizers, rosins, etc. can also be used.

The coloring agent A used in the present invention is represented by the general formula (H),
A compound having a >C=NH group and a >C-N-group in its structure, and examples of the aromatic ring group represented by 2 and R7 include a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, and an indene ring. , fluorene ring, phenanthrene ring, acenaphthene ring, etc., and their derivatives; examples of heterocyclic groups include indole ring, indazole ring, chroman ring, benzimodacylone ring, benzothiophene ring, benzoxazole ring, benzoxazole ring, etc. Thiazole ring, benzimidazole ring, pyridine ring, quinoline ring, isoquinoline ring, quinazoline ring, acridine ring, phenazine ring, pyrazine ring, oxazine ring, xanthine ring, purine ring, dibenzofuran ring, dibenzopyrrole ring, anthraquinone ring, etc. and their Examples include derivatives. 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'-)dichlorophenylimino)-3-iminoisoindoline, 1-(2'-cyano-4'-nitrophenylimino)-3-iminoisoindoline, 1-(2'-chloro-5'-cyanophenyl imino)-3-iminoisoindoline, 1-(2',6'-dichloro-4'-nitrophenylimino)-3-iminoisoindoline, 1-
(2',5'-dimethoxyphenylimino)-3-iminoisoinviridi, 1-(2',5'・-shed:xyphenylimino)-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'-dichlorobenzothia) Zolyl-2'-imino)-3-iminoisoindoline, 1-(
6'-Methylbenzothiazolyl-2-imino)-3-iminoisoindoline, 1-(4'-phenylaminophenylimino)-3-iminoisoin, viridi, 1-
(p-phenylazo7°°“′(ゝ′・□・j,)13
-"i/4V'"1'・1-(naphthyldi1.1'-imino)-3-iminoisoindoline, 1-(anthraquinone-1'-i1'mino)-3-iminoisoindoline, 1 -(5'-chloroanthraquinone-1
1-imino)-3-iminoisoindoline, 1-(N-
Ethylcarbazolyl-3'-imino)-3-iminoisoindoline, 1-(naphthoquinone-1'-imino)-3
-iminoisoindoline, 1-(viridyl-4'-imino)-3-iminoisoindoline, 1-(benzimidacylone-6'-imino)-3-iminoisoindoline,
1-(1'-Methylbenzimidacylon-6'-imino)-3-iminoisoindoline, 1-(7'-chlorobenzimidacylon-5'-imino)-3-iminoisoindoline, 1- (Benzimidazolyl-2'-imino)-3-iminoisoindoline, 1-(Benzimidazolyl-2'-imino)-3-imino-4,5°6.7
-titrachloroisoindoline, 1-(2',4'-dinitrophenylhydrazone)-3-iminoisoindoline, 1-(indabril-3'-imino)-3-iminoisoindoline, 1-(bendazolyl-3' −Imino)
-3-imino-4,5,6,7-titrapromoinindoline, l-(bendazolyl-3'-imino)-3=imino-4,5,6,7-titrafluoroisoindoline, l-(benz imidazolyl-2'-imino)-3-imino-4,7-cythiatetrahydroisoindoline, 1
-(4'5'-dicyanoimidazolyl-21-imino)
Examples include -3-imino-5°6-dimethyl-4,7-biradiisoindoline.

The coloring agent B used in the present invention is an isocyanate compound represented by the general formula (II), and specific examples thereof include:
For example, phenyl incyanate, p-chlorophenyl isocyanate, 3,4-dichlorophenylisocyanate, α-naphthyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
diphenylmethane diisocyanate, ), 3.3'-dimethyl-4,4'-diphenyl diincyanate, 3.3
'-Dichloro-4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4゜4'-diphenyl diisocyanate, p-phenylene diisocyanate, 2,7-dicyanatofluorene, 3.5
-diisocyanatochlorobenzene, diphenylthioether-4,4'-diisocyanate, 4,4'-diisocyanatobenzanilide, 2,5-dichloro-p-
Phenyl diisocyanate, 2,5-dimethyl-p-
phenylene diisocyaner), 4.4'-diisocyanatoazobenzene, 4.4'-diisocyanatobenzophenone, 3.6-diitsocyanatoacridine, 4.
Examples include 4'-diisocyanate diphenyl sulfone.

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

RNCO+HQ −→ d crystal HCOQRNHCOQ
Niblock Isocyanate HQ Niblocking Agent Specific examples of such blocking agents include phenol,
Phenols such as cresol, ε-caprolactam,
Lactams such as γ-butyrolactam, oximes such as MEK oxime and cyclohexanone oxime, alcohols such as methanol, ethanol, and methyl lactate, and active methylene compounds such as dimethyl malonate, which have active hydrogen groups in their structures. In addition to the above, these include mercaptan-based, acid amide-based, imide-based, amine-based, imidazole-based, urea-based, carbamate-based, imine-based, and sulfite-based compounds.

In addition to the above, this category also includes what can be called sysocyanate generators that generate isocyanate compounds under the conditions of use, although they are not blocked isocyanates in the true sense of the word. Examples of such isocyaner generators include polystyrene 1. Isocyanates are micro-packaged with wax or the like, and the isocyanate is regenerated by heating above the melting point. Another example is a compound that generates isodoanate upon thermal decomposition, such as amine imide and TDI dimer, which are included in this category. ~ The above-mentioned color formers A and B are each separately or together dispersed in a binder 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 completely developed. This coloring phenomenon is caused by the reaction of coloring agents A and B to produce a new colored compound C.

The chemical structure of this colored compound C is represented by general formula (IV). 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., but the heating temperature is approximately 80°C to 25°C.
The preferable range is 0° C. and the heating time 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 following examples, "parts" indicate "parts by weight."

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

Thermosensitive color former mixture 1-(benzimidazolyl-2'-imino)-3-iminoisoindoline...4.7 parts 3.4-dichlorophenylisocyanate-methyl ethyl ketoxime...5°3 parts Vinyl toluene butadiene resin...20 parts Ethylcyclohexane...70
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 layer 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 Mixtures having the following compositions were each dispersed for 30 minutes using a stirrer containing glass beads to obtain color forming agent solutions A and B4:
Prepared.

Solution A 1-(indabrylue 31-imino)-3-imino-4
,5,6,7-titrachloroutindoline
・ ・ ・ ・ ・ ・ ・
・10 parts polystyrene resin ・・・・・・・・・20
1 part chloroform 70111B liquid α-naphthyl isocyanate 5 parts paraffin wax 45 parts chloroform
...50 parts First, Liquid A was applied onto art paper using an applicator and dried to form a coating film with a thickness of about 20 microns. Next, add 2.5% rose wax on top of this.
A chloroform solution containing was applied and dried. Further, liquid B was applied thereon in the same manner and dried to form a three-layer heat-sensitive coloring film. The heated part of this product was colored orange by applying an iron at 200°C for 5 seconds.

Example 3 Mixtures having the following compositions were each dispersed for 30 minutes using a stirrer containing glass beads to form a color former-containing mixture A.
, B was created.

Part A 1-(4',5'-dicyanoimidazolyl-27-imino)-3-imino-5,6-dimethyl-4°7-biradiisoindoline 10 parts Polyurethane resin
・・・・・・20 parts DMF-MEK (1: 1
)Mixed solvent: 70 parts B-liquid p-methylphenylisocyanate-ε-caprolactam pro, -tsuk compound: 10 parts Vinyl chloride resin: 20 parts MEK
70 parts of these canned solutions A and B 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. This one is 190℃,
5 seconds 1: Due to the ironing effect, the heated part was colored orange.
Sheet of polystyrene resin containing 5% by weight of -imino)-3-iminoisoindoline (50 cranes in height x 25 cranes in width)
2 m thick) was created. 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.

Patent Applicant: Asahi Kasei Kogyo Co., Ltd. Patent Attorney: Akira Aoki Patent Attorney: Kazuyuki Nishidate Patent Attorney: Kazuyuki Nishidate 1) Honorable Patent Attorney: Akira Yamaguchi (Written Procedural Amendment) Ken 2 January 8, 1980 Commissioner of the Japan Patent Office Wakasugi Mr. Kazuo 1, Indication of the case 1982 Inter-Patent No. 202394 2, Method of coloring the name of the invention 3, Person making the amendment, Relationship to the case Patent applicant name (003) Asahi Kasei Corporation 4, Agent address Tokyo Shizukou Toranomon Building, 8-10 Toranomon-chome, Miyakominato-ku 105 Telephone (504) 0721 5, Subject of amendment 1) "Claims" column of the specification 2) "Detailed description of the invention" of the specification " column 6, content of amendment 1) The scope of claims is amended as shown in the attached sheet.

2) (a) Page 3, line 19 of the specification to page 4, line 6, “
Under heating...as defined above)" is subjected to a contact reaction under heating and corrected as colored compound j.

(b) Page 17, lines 12-13, [Due to the formation of a new colored compound C. The chemical structure of this colored compound C is the general formula (■)'', which is corrected as follows.

r due to the formation of new colored compounds. -The chemical structure of the second colored compound is, for example, general formula (Im) or (II
For the case where m in I) is 1, the general formula % is: (where Z, R, and I are as defined above) 17,
Amended list of attached documents Claims 1 copy 2, Claim 1, Compound 1 N - R represented by general formula (1).

(In the formula, Z represents an aromatic ring group or a heterocyclic group that can form a conjugated system with C-NH, and R1 represents an aromatic compound or a heterocyclic compound residue that can form a conjugated system with adjacent C-N. )
and isocyanate compound R2 represented by general formula (n) (
N GO) m (TI) (wherein, R2 represents an aromatic compound or a heterocyclic compound residue, and m is 1 to 4
) and/or blocked isocyanates R2 (NGO-H) represented by the general formula (III) (where R, I
represents an isocyanate-blocked compound residue having active hydrogen (m and m are as defined above);
Or, a coloring method characterized by producing a colored compound in a binder phase through a heating contact reaction.

Procedural amendment (1) January 10, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office■, Indication of the case 1982 Patent Order No. 202394 2, Method of coloring the name of the invention 3, Person making the amendment Relationship with the case Patent Applicant name (003) Asahi Kasei Kogyo Co., Ltd. 4. Agent address: Shizuko Toranomon Building, 8-10 Toranomon-chome, Minato-ku, Tokyo. 105 Telephone: (504) 0721 5. "Explanation" column 6, contents of amendment (1) Page 15, line 12 of the specification, insert the following sentence between "enylsulfone" and "etc.".

'% F triphenylmethane triisocyanate, tris(4-phenylisocyanate thiophosphate),
4.4',4"trimethyl 3.3'3"-triisocyanate 2,4.6-triphenyl cyanurate, 2.4
．． Adducts of diisocyanates and compounds containing active hydrogen groups, such as 4'' diphenyl ether triisocyanate, polymethylene polyphenylisocyanate, adducts of 2,4-tolylene diisocyanate and trimethylolpropane.

(2) Insert the following Example 5 next to the 8th line of page 21. .

"Example 5 1-(Benzimidazolyl-2'-imino)-3-iminoisoindoline 1 part polyvinyl alcohol 5%
Aqueous Solution DB Water 2 parts This composition was ground in a ball mill for 2 hours, then 2 parts of a 20% polyvinyl alcohol aqueous solution was added to make a coating liquid, and this coating liquid was coated on art paper with a dry weight of about 5 g/rrr.
I covered it with heavy cloth to dry it. A solution obtained by diluting an adduct of tolylene diisocyanate and trimethylolpropane (75% ethyl acetate solution (trade name: Corone) L) with an equal amount of ethyl acetate was applied onto the coated surface of the art paper thus obtained. was added dropwise, dried, and then heated to 150° C. for 10 seconds, resulting in the area where incyanate was dropped colored yellow. 1 or more

Claims (1)

[Claims] 1. A compound represented by the general formula (1) H 1 "I N-R1 (wherein Z represents an aromatic ring group or a heterocyclic group capable of forming a conjugated system with C-NH; , river represents an aromatic compound or a heterocyclic compound residue capable of forming a conjugated system with adjacent C-N), and an isocyanate compound R2 represented by general formula (II).
(NGO) 171 (II) (wherein R2 represents an aromatic compound or a heterocyclic compound residue, m is 1-
4) and/or blocked isocyanates R2(NG O-HR3)rn(I[[) (in the formula, R
3 represents an incyanate-blocked compound residue having active hydrogen, and R2 and m are as defined above).
V) Organic metal compound 1 NR represented by V). (wherein Z, R1 and R2 are as defined above) in a binder phase.