JPS59129264A - Tricyanostyryl compound and its use in dyeing and coloring - Google Patents

Abstract

NEW MATERIAL:A tricyanostyryl compd. of formula I (where R<1> is H, lower alkyl or halogen; R<2> is 2-10C alkylene; R<3> is benzimidazolyl, benzoxazolyl or benzothiazolyl which may be substituted with lower alkyl, lower alkoxyl, halogen, nitro or cyano). EXAMPLE:Compd. of formula II. USE:To dye hydrophobic fibers, especially polyester fiber in bright reddish orange to bluish red color. PREPARATION:The compd. of formula I is prepared by reacting a compd. of formula III (where R<1-3> are the same as in I ) with tetracyanoethylene in an inert solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a tricyanostyryl compound represented by the general formula q) and a method for dyeing hydrophobic fibers or a method for coloring synthetic resin using the same.

R'' (in the formula, I is a hydrogen prefix, a lower alkyl group, a lower alkoxy group, or a halogen group).
The alkylene group R3 is a lower alkyl group, a lower alkoxy group, and a halogen compound represented by the general formula (1) is, for example, USP 2.803,640 and USP 2,889.
It can be produced by the following methods (Δ) and (B) shown in No. 835.

(A) General formula 11! + (In the formula, R, R and R3 each have the same meaning as defined above.) A compound represented by the following formula is reacted with a cyanide salt in an inert solvent, and then oxidized with an oxidizing agent.

(S) A compound represented by the general formula (■) (wherein, 1*R2 and R3 each have the same meaning as above) is reacted with tetracyanoethylene in an inert solvent.

The compounds obtained in this way have vivid color tones ranging from reddish-orange to bluish-red.

The obtained compound is dispersed according to a conventional method for use as a dye. For example, in a nodomil, anionic dispersants such as naphthalene sulfonic acid formalin condensate, lignin sulfonic acid, cresol-Shaffer acid formalin condensate, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, etc. It may be treated with a dispersant selected as desired from various dispersants such as ionic dispersants and water in an appropriate amount, and it may be processed in a liquid state or dried to form a powder or granules.

Synthetic fibers to which the dyeing method of the present invention can be applied include acrylic fibers, modacrylic fibers, synthetic polyamide fibers, polyester fibers, so-called hydrophobic synthetic fibers, and semi-synthetic fibers such as G or triacetate. Refers to various types of cedar fiber materials mixed with or mixed with natural fibers of ponds. Among these, it is particularly suitable for polyester fibers and mixed products of polyester fibers and natural or recycled cellulose fibers.

Dyeing methods in the present invention include dip dyeing, continuous dyeing, textile printing, and transfer printing. In particular, the compound of the present invention is an extremely suitable dye for dyeing and continuous dyeing of mixed products of polyester fibers and cellulose fibers, since stains on cellulose fibers can be easily removed.

In textile printing, it is particularly suitable as a background dye for ordinary direct printing and alkaline resist discharge printing.

The compound of the present invention is also useful as a special coloring agent for synthetic resins, and it is possible to obtain various colored synthetic resins having clear color tones ranging from reddish orange to bluish red, which are robust with respect to light, heat and migration. can.

Examples of synthetic resins that can be colored with the compound of the present invention include polystyrene-based, polyolefin-based, polyacrylate-based, polyvinyl acetate-based, polyvinyl chloride-based, polyamide-based, polycarbonate-based, polyacetal-based,
Examples include polyester resins, acrylonitrile-lyrustine copolymer K (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin 1), and the like.

In order to color a synthetic resin using the compound of the present invention, for example, the required amount of the compound of the present invention represented by the general formula (1) is blended with the synthetic resin, kneaded, and then compression molding, injection molding, calendering, etc. By using pressure molding methods such as molding methods and extraction molding methods, it is possible to obtain robust molded products such as films, plates, and pipes that are colored in colors ranging from reddish orange to bluish red.

Further, if desired, in addition to the compound of the present invention represented by general formula (I), one or two kinds of known colorants and additives such as organic pigments, inorganic pigments, lubricants, ultraviolet absorbers, and antioxidants are added. Preferable results can be obtained even when the above are added in combination.

USP 2,889,385 describes compounds similar to the compounds of the present invention;
Compared to the compound specifically described in SP 2,889,835, it is particularly excellent in light fastness and dyeing MEQ properties.

The results of the comparative test are shown below.

Table-1 (note) 0 staining method: method described in Example 3.

O Light fastness: JIS L-0842-7 Part 0 Dyeing rate: Compounds are extracted from the dyed material using monochlorobenzene, and quantitative determination is made using the spectroscopic absorption method; the dyed dye is determined as a percentage of the dye used. Calculated.

Hereinafter, the present invention will be explained in detail with reference to Examples. In the Examples, "parts" represent parts by weight, and "color tone" represents the color tone of the polyester-based material.

Example 1 47.1 parts of the compound represented by the following formula (1) was mixed with 1 part of dimethylformamide.
Dissolved in 50 parts and then 80% (by weight) of NaCN
Gradually add 195 parts of the aqueous solution. At this time, heat is generated, so the reaction vessel is cooled with water, and the temperature is lower than 40'C, then at room temperature).
Continue stirring with a trowel for 1 hour. Next, 19.2 parts of bromine was gradually added at room temperature, and stirring was continued for an additional hour.
Dilute the reaction solution with 50 parts. Filter, then wash with water and dry. 43.7 parts of the compound represented by the following formula (2) are obtained.

λmax5 Q 3 nm (in acetone) 2 tones: yellowish scarlet Example 2 40.9 parts of the compound represented by the following formula (3) was mixed with 1 part of dimethylformamide.
50 parts, and then gradually add 15.8 parts of tetracyanoethylene at room temperature.

After adding the entire amount of tetracyanoethylene, the temperature was raised to 60°C and the urine was kept at this temperature for 1 hour. Then, the reaction solution was cooled to room temperature and diluted with 750 parts of water. The following procedure was carried out in the same manner as in Example 1 to obtain a dark red solid 4 having a green luster of the following formula (4).
2.4 parts are obtained. λmax 51Qnm (in acetone) Example 8 Compound (2) obtained in Example 1 and compound (4) obtained in Example 2 were used for staining by the following procedure.a) Preparation of dispersion Compound (2) ) or (4) 20 parts (Note 1) Anionic dispersant 20 parts Water 60 parts Total 1
00 parts (Note 1 > Naphthalene sulfonic acid formalin condensate) The above mixture was treated in a sand mill for 4 hours to obtain a dispersion.

b) Staining 3 parts of the dispersion obtained in a) are placed in a dyeing pot together with 3000 parts of water and adjusted to pH 5 using acetic acid. Next, 100 parts of polyester fabric was added to this and heated at 130"C for 6
Perform staining for 0 minutes. After the dyeing is finished, washing and rinsing are carried out in a conventional manner, followed by drying. A dyed product with excellent light fastness and dyeing rate was obtained.

Example 4 A pond was prepared in the same manner as in Example 1 using 398 parts of the compound of formula (5) instead of compound (1). 25.6 parts of the compound of formula (6) are obtained.

'Amax 500 nm (in 7 setone) Color tone: Scarlet Examples 5 to 27 In Example 1, the compound shown in Table 2 was used as a nail material in place of compound (1), and the corresponding compound was obtained by reacting in the same manner.

-R1 Table 2 Example 28 Using the compound (6) obtained in Example 4, a dispersion liquid is prepared according to a) of Example 8. Using this dispersion, a printing paste having the following composition is prepared.

(Printing paste composition) Above dispersion 3 parts Roof emulsion base paste (Note 2) 60 parts Tartaric acid
o, a part Sodium chlorate 0.2 part Water Remainder total 100 parts (Note 2) Half emulsion base glue composition Kerosene
70 parts Total 100 parts (Note 3) Shin-Nakamura Chemical Co., Ltd. product; Emulsifier 80 parts of an emulsion made by mixing the above in a high-speed mixer! : Maypro Gum N)' 70 parts of 12% paste (manufactured by Grinara Co., Ltd.) was mixed to obtain /)-fuemulsion base paste.

Using the dyeing paste thus obtained, hand printing is performed on polyester cloth. The fabric is then dried and subjected to superheated steam treatment at 175C for 7 minutes. Thereafter, washing and drying are performed using a conventional method. A robust and clear scarlet colored printed fabric is obtained.

Example 29 A part of the printed surface of the cloth printed according to Example 28 is hand-printed with a resist dyeing paste having the following composition. Superheated steam treatment, washing and drying are then carried out according to Example 28. A white resist dye with extremely little contamination of the resist paste stamped area can be obtained.

(Resist paste composition) Potassium carbonate 7 parts Glycerin 5 parts Maprogum NP 12% paste 60 parts Water
28 parts total 100 parts Example 30 Compound of Example 4 prepared according to the method of Example 3 (6
) Continuous staining is carried out as follows using the dispersion liquid. A marbling-like scarlet dyed product of a polyester fiber/cotton blend with extremely little staining on cotton is obtained, and its various fastnesses are extremely good.

(Padding liquid composition) Above dispersion 4 parts 1% sodium alginate aqueous solution 1 part water
95 parts total 100 parts A polyester/cotton blend Boblin cloth (65:85) is soaked in the above-prepared putting liquid, and then patterned uniformly with a mangle so that the pick-up is 60%. After drying the fabric with hot air, it is subjected to thermosol treatment at 210'C for 60 seconds.

Subsequently, after padding again with an aqueous solution of sulfurium carbonate 596, steaming is performed at 100° C. for 30 seconds, and then washing is performed with hot water and water.

Example 31 Using a dispersion of the compound of Example 17 prepared according to the method of Example 8, dyeing is carried out using 100 parts of polyester cloth and 100 parts of cotton cloth in place of 100 parts of the polynisder cloth of Example 3. After dyeing is finished, the temperature of the dye bath is cooled to 60"C,
Add 6 parts of sodium carbonate to the dye bath and keep the bed temperature at 60°C for 1 hour. Next, the cloth to be dyed is taken out and washed with hot water and water. Polyester fabric is dyed in a vivid and robust bluish-red color.

Example 32 After heating and mixing 0.2 parts of the compound (6) obtained in Example 4 in the form of fine powder and 100 parts of powdered ABS resin at 120'C,
Create pellets through an extruder. This is then molded at 230°C using an injection molding machine. A bright scarlet colored molding is obtained which is robust to heat, light and migration.

Example 33 0.2 part of the compound obtained in Example 1 in fine powder form and powder P E
After thoroughly drying 100 parts of T resin, the mixture was mixed and molded at 290°C using an injection molding machine.

A scarlet-colored molding is obtained that is resistant to heat, light and migration.

Claims (1)

[Claims] (11 General formula (1) (wherein, R' is a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom P, and R2 has 1 to 10 carbon atoms.
R3 represents a lower alkyl group, a lower alkoxy group, a benzimidazolyl group, a benzoxasilyl group or a benzthiazolyl group which may be substituted with a halogen atom, a nitro group or a cyano group. ) Tricyanostyryl compound. (2) General formula (T) (wherein, R1 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom; R2 is an alkylene group having 1 to 10 carbon atoms; R3 is a lower alkyl group, a lower alkoxy group, or a halogen atom; tricyanostyryl compound (representing a benzimidazolyl group, benzoxasilyl group, or benzthiazolyl group which may be substituted with an atom, a nitro group, or a cyano group)). Textile dyeing method. (3) General formula (I) E' (In the formula, R1 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom 'f-1R2 has 1 to 1 carbon atoms.
The alkylene group up to 0, R represents a lower alkyl group, a lower alkoxy group, a halogen group, a benzimidazolyl group, a benzoxasilyl group or a benzthiazolyl group which may be substituted with a nitro group or a cyano group. ) A method for coloring synthetic resins, characterized by using one or more of the tricyanostyryl compounds shown in the following.