JPH045698B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is 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 ethylene group or an alkylene group having 3 to 10 carbon atoms. R ³ represents a case where R ² is an ethylene group. is a phenyl group having a substituent, and R ² has 3 to 3 carbon atoms.
When it is an alkylene group of 10, it is a phenyl group which may have a substituent. ) In the general formula (), the alkylene group represented by R ² preferably has 4 to 10 carbon atoms, and the substituent for the phenyl group in R ³ is, for example, an alkylene group having 1 to 9 carbon atoms. alkyl group,
Examples include an alkoxy group, an alkenyloxy group, a cyclohexyl group, a phenyl group, a nitro group, and a halogen atom. Further, the number of substituents on the phenyl group may be two or more, and in that case, the substituents may be the same or different. For example, the compound represented by the general formula () is as follows:
As shown in (A) or (B), USP2803640 and
It can be manufactured according to the method shown in USP2889335. (A) General formula () (In the formula, R ¹ , R ² and R ³ have the same meanings 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 , R ² and R ³ have the same meanings 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 desirably selected from various dispersants such as dispersants 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 fibers, and semi-synthetic fibers such as di- or triacetate. Alternatively, it refers to various forms of fiber materials mixed and further mixed with other natural fibers. Among these, it is particularly suitable for polyester fibers and mixed products of polyester fibers and natural or regenerated 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 that can be colored with the compound of the present invention include polystyrene, polyolefin, polyacrylate, polyvinyl acetate,
Examples include polyvinyl chloride, polyamide, polycarbonate, polyacetal, and polyester resins, as well as acrylonitrile-styrene copolymers (AS resins) and acrylonitrile-butadiene-styrene copolymers (ABS resins). 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 light fastness and dyeing rate. The results of the comparative test are shown below.

[Table] The present invention will be explained in detail with reference to Examples below.
In the examples, parts and % represent parts by weight and weight % unless otherwise specified, and color tone represents the color tone on the polyester fiber. Example 1 The following formula () 39.8 parts of the compound shown in dimethylformamide
Dissolve in 150 parts and then 19.5 parts of a 30% aqueous solution of NaCN
gradually add portions. 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. then water
Dilute the reaction solution with 750 parts. Filter, then wash with water and dry. 37.2 parts of a dark red solid with a green luster of the compound of formula (2) below are obtained. λmax502nm (in acetone), color tone: yellowish scarlet Example 2 Below formula (3) 33.6 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 750 ml of water.
Dilute the reaction solution with 50 parts. Thereafter, the same procedure as in Example 1 was carried out to obtain 36.1 parts of a dark red solid with green luster of the compound of formula (4). λmax 509 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 of Example 20 parts Anionic dispersant (Note 1) 20 parts Water 60 parts 100 parts (Note) Naphthalene sulfonic acid formalin condensate The above mixture was treated in a sand mill for 4 hours to obtain a dispersion. Ta. b. Staining Add 3 parts of the dispersion obtained in step 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 heated to 130℃.
Perform staining for 60 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. Examples 4 to 45 In Example 1, the compounds shown in Table 2 were used as raw materials in place of the compound of formula (1) and reacted in the same manner to obtain the corresponding compounds.

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[Table] Example 46 Using the compound obtained in Example 6, a dispersion is prepared according to Example 3 a. 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 Remaining 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) Emulsifier manufactured by Shin-Nakamura Chemical Co., Ltd. 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. Then dry this cloth,
Perform superheated steam treatment at 175°C for 7 minutes. After washing and drying in a conventional manner, a robust and vivid scarlet colored printed fabric is obtained. Example 47 A part of the printed surface of the cloth printed according to Example 46 is manually printed with a resist dyeing paste having the following composition. Next, Example 46
After superheated steam treatment, washing and drying according to
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 48 Using a dispersion of the compound of Example 4 prepared according to the method of Example 3, the following was prepared. Perform continuous staining. A marbling-like scarlet dyed product of a polyester fiber/cotton blend with extremely little staining on cotton is obtained, and the 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 49 Using a dispersion of the compound of Example 16 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 50 A dispersion liquid is prepared using the compound (2) of Example 1 and the compound (4) of Example 2 in the following manner. (Dispersion composition) Compound of Example 1 15 parts Compound 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 treated in a sand mill for 6 hours. , prepare a dispersion. This dispersion is then spray-dried to obtain a dispersible powder composition. If dyeing is carried out in accordance with Example 49, except that 2 parts of this powder composition is replaced with the compound of Example 16, a solid polyester fiber dyed product with a moderate reddish color and good white leaving property on cotton is obtained. Example 51 0.2 part of the compound obtained in Example 6 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 52 0.2 parts of the compound obtained in Example 1 in fine powder form and powder
After thoroughly drying 100 parts of PET resin, the mixture is mixed and molded using 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 ethylene group or an alkylene group having 3 to 10 carbon atoms. R ³ represents an ethylene group when R ² is an ethylene group. is a phenyl group having a substituent, and R ² has 3 to 3 carbon atoms.
When it is an alkylene group of 10, it is a phenyl group which 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 ethylene group or an alkylene group having 3 to 10 carbon atoms. R ³ represents when R ² is an ethylene group. is a phenyl group having a substituent, and R ² has 3 to 3 carbon atoms.
When it is an alkylene group of 10, it is a phenyl group which may have a substituent. ) A method for dyeing hydrophobic fibers, the method comprising using one or more of the tricyanostyril compounds shown in the following. 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 ethylene group or an alkylene group having 3 to 10 carbon atoms. R ³ represents when R ² is an ethylene group. is a phenyl group having a substituent, and R ² has 3 to 3 carbon atoms.
When it is an alkylene group of 10, it is a phenyl group which may have a substituent. ) A method for coloring synthetic resins, characterized by using one or more tricyanostyryl compounds shown in the following.