JPH0363995B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a tricyanostyryl compound represented by the general formula () and a method for dyeing hydrophobic fibers or coloring synthetic resins using the same. (In the formula, R ¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R ² represents an alkyl group having 5 or more carbon atoms or a cycloalkyl group that may have a substituent.) General formula The optionally substituted alkyl group having 5 or more carbon atoms represented by R ² in parentheses is a linear or branched alkyl group having 5 or more carbon atoms, preferably 12 or less, and the substituent is, for example, a halogen atom. In addition, -OCO-R ⁶ , -OCOOR ⁶ , -
OSO ₂ −R ⁶ , group −COOR ⁶ , group −NHCOR ⁶ , group −
NHSO ₂ R ⁶ , group -NHR ⁶ , group -NR ⁶ R ⁷ , group -
Examples include OCONHR ⁶ , the group -OR, an aromatic residue, a cycloalkyl group or an alkenyl group, and other groups. However, R ⁶ can be an aromatic residue, an alkyl group, a cycloalkyl group, an alkenyl group, or an aralkyl group, and in these groups, the phenyl group can be further substituted with a halogen atom, nitro group, lower alkoxy group, or lower alkyl group. may be replaced. For example, the compound represented by the general formula () is
The following (A) shown in USP2803640 and USP2889335,
It can be manufactured by method (B). (A) General formula () (In the formula, R ¹ and R ² each have the same meaning as above.) The compound represented by the formula is reacted with a cyanide salt in an inert solvent, and then oxidized with an oxidizing agent. (B) General formula () (In the formula, R ¹ and R ² each have the same meaning as above.) A compound represented by the following is reacted with tetracyanoethylene in an inert solvent. The compounds obtained in this way have vivid color tones ranging from scarlet to bluish red. The obtained compound is dispersed according to a conventional method before its use as a dye. For example, in a sand mill, anionic dispersants such as naphthalene sulfonic acid formalin condensate, lignin sulfonic acid, cresol-schefate formalin condensate, or nonionic dispersants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, etc. It may be treated with a dispersant selected from various dispersants such as a dispersant as desired and an appropriate amount of water, and it may remain in a liquid state or may be 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 and other so-called hydrophobic synthetic fibers, and semi-synthetic fibers such as di- or triacetate. It refers to various forms of fiber materials that are mixed together or mixed with other natural fibers. 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 because stains on cellulose fibers can be easily removed. In textile printing, it is particularly suitable as a base dye for alkaline resist discharge printing in addition to ordinary direct textile printing. The compound of the present invention is also useful as a coloring agent for synthetic resins, and it is possible to obtain various colored synthetic resins with vivid color tones ranging from reddish-orange to bluish-red, which are robust with respect to light, heat, and migration properties. can. Synthetic resins suitable for coloring 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, polyester-based resins, and Examples include acrylonitrile-styrene copolymer (AS resin) and acrylonitrile-butadiene-styrene copolymer (ABS resin). 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 () is blended with the synthetic resin, kneaded, and then subjected to compression molding, injection molding, or calendar molding. Film,
It is possible to obtain solid molded products such as plates and pipes that are colored in colors ranging from reddish orange to bluish red. If desired, in addition to the compound of the present invention represented by the general formula (), one or more of known colorants and additives such as organic pigments, inorganic pigments, lubricants, ultraviolet absorbers, and antioxidants may be added. Favorable results can also be obtained by adding and using . USP2889335 describes compounds similar to the compound of the present invention, but the compound of the present invention is
Compared to the compound specifically described in USP2889335, it is particularly superior in both light fastness and dyeing reproducibility. The results of the comparative test are shown below.

[Table] Hereinafter, the present invention will be explained in more detail with reference to Examples. In the Examples, unless otherwise specified, parts represent parts by weight, and color tones represent those on polyester fibers. Example 1 Below formula (1) 29.2 parts of the compound shown in dimethylformamide
150 parts and then gradually add 19.5 parts of a 30% (by weight) aqueous solution of NaCN. At this time, heat is generated, so the reaction vessel is cooled with water to keep it below 40°C, and stirring is continued for 1 hour at room temperature. Next, 19.2 parts of bromine is gradually added at room temperature, and stirring is continued for an additional hour.
Next, dilute the reaction solution with 750 parts of water. Filter, then wash with water and dry. 26.0 parts of a solid compound of the following formula (2) is obtained. λmax505nm (in acetone), color tone: Scarlet Example 2 Below formula (3) 23.0 parts of the compound shown in dimethylformamide
150 parts, and then gradually add 15.3 parts of tetracyanoethylene at room temperature. After adding the entire amount of tetracyanoethylene, the temperature is raised to 60°C and kept at this temperature for 1 hour. Then cool to room temperature and add water
Dilute the reaction solution with 750 parts. Thereafter, the same procedure as in Example 1 was carried out to obtain 24.8 parts of a reddish-black solid of the compound of formula (4). λmax 510 nm (in acetone), color tone: bluish red Example 3 Dyeing was carried out using the compound (2) obtained in Example 1 and the compound (4) obtained in Example 2 by the following operation. a Preparation of dispersion Compound (2) or (4) 20 parts Anionic dispersant ⁽ Note ¹⁾ 20 parts Water 60 parts Total 100 parts (Note 1) Naphthalene sulfonic acid formalin condensate Treat the above mixture in a sand mill for 4 hours A dispersion liquid was obtained. b. Staining Add 3 parts of the dispersion obtained in a) to a dyeing pot with 3000 parts of water and adjust the pH to 5 using acetic acid. Next, 100 parts of polyester fabric was added to this, and 130 parts of
Perform staining for 60 min at °C. After the dyeing is finished, washing and rinsing are carried out in a conventional manner, followed by drying. Lightfastness,
A dyed product with excellent dyeing rate can be obtained. Example 4 The same procedure as in Example 1 was carried out except that 30.5 parts of the compound of formula (5) was used in place of compound (1) in Example 1. 28.7 parts of the compound of formula (6) are obtained. λmax500nm (in acetone), color: scarlet. Examples 5 to 54 In Example 1, the compounds shown in Table 2 were used as raw materials in place of compound (1) and reacted in the same manner as in Example 1 to obtain the corresponding compounds.

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[Table] Example 55 Using the compound (6) obtained in Example 4, a dispersion is prepared according to a) of Example 3. Using this dispersion, a printing paste having the following composition is prepared. (Printing paste composition) Above dispersion 3 parts Half emulsion base paste (Note 2) 60 parts Tartaric acid 0.3 parts Sodium chlorate 0.2 parts Water Balance Total 100 parts (Note 2) Half emulsion base paste composition Kerosene 70 parts Water 25 parts Viscon KM-8 ⁽ Note ³⁾ 5 parts Total 100 parts (Note 3) Shin-Nakamura Chemical Co., Ltd. product; Emulsifier Emulsion made by mixing the above in a high-speed mixer
Mix 30 parts with 70 parts of Maypro Gum NP 12% paste (Greenough product) to make a half emulsion base paste. Using the dyeing paste thus obtained, hand printing is performed on polyester cloth. The cloth is then dried and subjected to superheated steam treatment at 175°C for 7 minutes. Thereafter, washing and drying are performed using a conventional method. A robust and vivid scarlet colored printed fabric is obtained. Example 56 A part of the printed surface of the cloth printed according to Example 55 is manually printed with a resist dyeing paste having the following composition. Next, Example 49
Perform superheated steam treatment, washing and drying according to the following. A white resist dye with extremely little contamination of the resist paste stamped area can be obtained. (Resist dye composition) Potassium carbonate 7 parts Glycerin 5 parts Maprogum NP 12% paste 60 parts Water 28 parts Total 100 parts Example 57 Using a dispersion of the compound of Example 22 prepared according to the method of Example 3, the following was prepared. Perform continuous staining. A marbling-like scarlet-colored 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 Polyester/cotton blended poplin cloth (65:35) was soaked in the padding liquid prepared above, and then picked up to 60%. Squeeze it evenly with a mangle. After drying the cloth with hot air, perform thermosol treatment at 210°C for 60 seconds. Subsequently, it is padded again with a 5% aqueous sodium carbonate solution, then steamed at 100°C for 30 seconds, and then washed with hot water and water. Example 58 Using a dispersion of the compound of Example 17 prepared according to the method of Example 3, the polyester fabric of Example 3 was prepared.
Dyeing is performed using 100 parts of polyester and 100 parts of cotton cloth instead of 100 parts. After dyeing, the temperature of the dye bath is set to 60℃.
6 parts of sodium carbonate was added to the dye bath and kept at 60°C for 1 hour. Next, the cloth to be dyed is taken out and washed with hot water and water. Polyester fabrics are dyed in a vivid and strong bluish-red color, whereas cotton fabrics are dyed with virtually no staining. Example 59 A dispersion liquid is prepared using the compound (2) of Example 1 and the compound (4) of Example 2 as follows. (Dispersion liquid composition) Compound (2) of Example 1 15 parts Compound (4) of Example 2 15 parts Lignosulfonic acid dispersant 65 parts Naphthalene sulfonic acid formalin condensate 5 parts Water 200 parts Total 300 parts The above was sand milled. for 6 hours to prepare a dispersion. This dispersion is then spray-dried to obtain a dispersible powder composition. If dyeing is carried out in accordance with Example 58 except that 2 parts of this powder composition is replaced with the compound of Example 17, a solid polyester fiber dyed product with a moderate reddish color and good white leaving property on cotton is obtained. Example 60 0.2 part of the compound obtained in Example 22 in fine powder form and powder
After heating and mixing 100 parts of ABS resin at 120°C, pellets are created through an extruder. This is then molded using an injection molding machine at 230°C. A bright scarlet colored molding is obtained which is resistant to heat, light and migration. Example 61 0.2 parts of the compound obtained in Example 22 in fine powder form and powder
After thoroughly drying 100 parts of PET resin, mix and mold with an injection molding machine at 290℃. A scarlet-colored molding is obtained which is resistant to heat, light and migration.

Claims (1)

[Claims] 1 General formula () (In the formula, R ¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R ² represents an alkyl group having 5 or more carbon atoms or a cycloalkyl group that may have a substituent.) Tricyanostyryl compound. 2 General formula () (In the formula, R ¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R ² represents an alkyl group having 5 or more carbon atoms or a cycloalkyl group that may have a substituent.) 1. A method for dyeing hydrophobic fibers, the method comprising using one or more tricyanostyryl compounds. 3 General formula () (In the formula, R ¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R ² represents an alkyl group having 5 or more carbon atoms or a cycloalkyl group that may have a substituent.) 1. A method for coloring synthetic resins, the method comprising using one or more tricyanostyryl compounds.