JPH0420946B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel heterocyclic compound useful for dyeing or coloring hydrophobic fiber materials, synthetic resins, etc. More specifically, the present invention relates to the general formula () [In the formula, R ₁ and R ₂ are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an optionally substituted phenyl group, R ₃ , R ₄ , and R ₅ each represents a hydrogen atom or a lower alkyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR ₆ or -
Represents NHSO ₂ R ₆ . However, R ₆ represents a hydrogen atom, a lower alkyl group, a phenyl group which may be substituted with a halogen atom or a lower alkoxy group] and dyeing of hydrophobic fibers using the heterocyclic compound represented by This invention relates to methods for coloring synthetic resins. In the present invention, substituents for the optionally substituted alkyl group in R ₁ and R ₂ include, for example, chlorine, bromine, hydroxyl group, cyano group, -OR ₇ , -
CO ₂ R ₇ , −OCOR ₇ , −OCO ₂ R ₇ , −CSO ₂ R ₇ , −
NHSO ₂ R ₇ , −NHR ₇ , −OCONHR ₇ , −NHCOR ₇ ,
_-NHCO2R , _-SR8 , alkenyl group,

【formula】

【formula】

[expression] or

[Formula] can be given. Examples of substituents on phenyl include lower alkyl groups, lower alkoxy groups, and halogens. However, R ₃ represents the above meaning, and R ₇ is an alkyl group, a cycloalkyl group, an alkenyl group,
Represents an aralkyl group or a phenyl group (which may be substituted with a lower alkyl group, lower alkoxy group, halogen atom, lower alkanoylamino group, cyano group, or lower alkoxycarbonyl group). R ₈ represents a lower alkyl group, an optionally substituted phenyl group, a benzothiazolyl group or a benzoxazolyl group. R ₉ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower alkanoylamino group, a cyano group, or a lower alkoxycarbonyl group. n represents an integer of 1 or more. Specifically, R ₆ is, for example, methyl, ethyl, propyl, butyl, phenyl, chlorophenyl, bromphenyl, methylphenyl, ethyl phenyl, propylphenyl, butylphenyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl or butoxyphenyl. Examples include bases. Examples of R ₇ include methyl, ethyl, n-
Propyl, isopropyl, n-butyl, i-butyl, t-butyl, cyclohexyl, cyclopentyl, vinyl, -CH= _CHCH3 , -CH=C( _CH3 ) ₂ ,
-CH=CHCl, -CH=CHBr, phenyl, methylphenyl, ethyl phenyl, propylphenyl,
Methoxyphenyl, ethoxyphenyl, chlorphenyl, bromphenyl, benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, methoxybenzyl, ethoxybenzyl, chlorbenzyl, brombenzyl, phenethyl, methylphenethyl, ethylphenethyl, methoxyphenethyl,
Ethoxyphenethyl, chlorphenethyl, bromphenethyl, acetylaminophenyl, propionylaminophenyl, propylcarbonylaminophenyl, butylcarbonylaminophenyl, cyanophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, propoxycarbonylphenyl or butoxycarbonyl Examples include phenyl group. Examples of R ₈ include methyl, ethyl, propyl, butyl, phenyl, methylphenyl, ethyl phenyl, propylphenyl, butylphenyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, cyanophenyl, chlorphenyl, bromphenyl, acetylaminophenyl, Examples include enyl, propionylaminophenyl, propylcarbonylaminophenyl, butylcarbonylaminophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, propoxycarbonylaminophenyl, and butoxycarbonylphenyl groups. A compound represented by the general formula () is a compound represented by the general formula () (In the formula, R ₁ represents the above meaning) and a compound represented by the general formula () (In the formula, X, R ₂ , R ₃ , R ₄ , R ₅ represent the above-mentioned meanings.)
It can be synthesized by reacting in an inert solvent. Examples of the inert solvent include dimethylformamide, dimethylsulfoxide, acetonitrile, ethyl acetate, sulfolane, tetrahydrofuran, and toluene. The compound of general formula () is a lonnitrile dimer and the following formula or (R ₁ represents the above-mentioned meaning) can be obtained by treating the reaction product with a chlorinating agent such as thionyl chloride, phosgene, benzenesulfonyl chloride, benzotrichloride, phosphorus oxychloride, and the like. The compound of the general formula () thus obtained has excellent dyeing properties on hydrophobic fibers, and also has good dye bath stability and build-up properties. Further, it provides a dyed product having a clear color tone ranging from reddish-blue to greenish-blue and excellent in various fastnesses such as water fastness, sublimation fastness, light fastness, and washing fastness. When using the obtained compound as a dye,
First, decentralization is carried out according to the conventional method. For example, in a sand mill, naphthalene sulfonic acid formalin condensate, lignin sulfonic acid, cresol. A dispersant selected as desired from various dispersants such as anionic dispersants such as Scheffuric acid formalin condensate, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and other nonionic dispersants. It may be treated with an appropriate amount of water, and it may remain in liquid form or may be dried to form powder or granules. Synthetic fibers to which the dyeing method of the present invention can be applied include synthetic polyamide fibers, polyester fibers, and other so-called hydrophobic synthetic fibers, and semi-synthetic fibers such as g- or triacetate, which can be used alone or in combination. refers to various forms of fibrous materials 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 having vivid color tones ranging from reddish-blue to greenish-blue, 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 colored in colors ranging from reddish-blue to greenish-blue. 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 . The compounds of the present invention can also be used as dyes for various recording materials. 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 Formula (a) below 20.5 parts of the compound shown in 150 parts of acetonitrile
of N-phenethyl-2,2,4-trimethyl- dissolved in 200 parts of acetonitrile.
60.9 parts of 1,2,3,4-tetrahydroquinoline are added at room temperature. After 30 minutes, 200 parts of water is added, and the precipitate is filtered, washed with water, and dried. 38 parts of a compound of the following formula (1) is obtained. λmax: 642 nm (acetone) Color tone: Greenish blue Example 2 15 parts of the compound (a) shown in Example 1 was added to 200 parts of ethyl acetate, and to this was added N-ethyl-2, which was dissolved in 100 parts of ethyl acetate. 2,4-trimethyl-1,
29.7 parts of 2,3,4-tetrahydroquinoline are added at room temperature, and after 1 hour the precipitated solid is filtered, washed and dried. 20 parts of a compound of the following formula (2) is obtained. λmax: 643nm (acetone) Color tone: greenish blue Example 3 Formula (b) below 21.8 parts of the compound shown in 200 parts of acetonitrile
59 parts of N-phenoxyethyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline dissolved in 200 parts of acetonitrile.
at room temperature. After 1 hour, 200 parts of water is added and the precipitated solid is filtered, washed and dried. 38 parts of a compound of the following formula (3) is obtained. λmax: 639 nm (acetone) Color tone: greenish blue Example 4 Using the compound (1) obtained in Example 1, dyeing was carried out by the following procedure. a Preparation of dispersion Compound (1) 20 parts Anionic dispersant (Note 1) 20 parts Water 60 parts Total 100 parts (Note 1) Naphthalene sulfonic acid formalin condensate The above mixture was treated in a sand mill for 4 hours to form a dispersion. I got it. 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 finishing dyeing, wash and rinse using the usual method. To obtain a vivid greenish-blue dyed product with excellent color fastness. Example 5 Using the compound (2) obtained in Example 2, a dispersion is prepared according to a) of Example 4. 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 furnace Oil 7 parts Water 25 Part Viscon KM-3 (Note 3) 5 parts Total 100 parts (Note 3) Shin-Nakamura Chemical Co., Ltd.: 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 strong and vivid greenish-blue printed fabric is obtained. Example 6 Using a dispersion of the compound of Example 3 prepared according to the method of Example 4, the polyester fabric of Example 4 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 greenish blue color, while cotton fabrics are dyed with virtually no staining. Example 7 After heating and mixing 0.2 parts of the compound (14) described below in fine powder form and 100 parts of powdered ABS resin at 120°C, the mixture is passed through an extruder to form pellets. This is then molded using an injection molding machine at 230°C. A bright blue molded product is obtained that is robust to heat, light and migration. Example 8 30 parts of Sumikalon Brilliant Pink SE-RL (Sumitomo Chemical Disperse Dye) was dispersed in 170 parts of warm water,
Next, 50 parts of potassium carbonate, 10 parts of glycose, 150 parts of polyethylene glycol (MW300) and Kiprogum P
Add 570 parts of -20N (product of Nippon Chemical Co., Ltd.) 12% concentration paste to prepare a total of 1000 parts of uniform printing paste, and print on this polyester fiber cloth. Separately, 100 parts of the dispersion obtained in Example 4 was dispersed in 300 parts of hot water, and then 665 parts of Kiprogum P-20N 12% paste and 5 parts of metanitrobenzenesulfonic acid soda were added to make a total of 1000 parts of uniform printing paste. Prepare. This printing paste was overprinted on the previously printed cloth, and after drying, it was heated to 175℃ for 8 minutes.
Apply HT steam treatment. Next, it is washed with water, treated with a cleaning solution containing 2 ml of caustic soda (40°B'e), 2 g of hydrosulfite, and 1 g of nonionic detergent at 75°C for 5 minutes, and finished by washing with water. In this way, a clear pink pattern was obtained on a greenish blue background. Example 9 The compounds shown in the table below are obtained by the same method as in Examples 1 to 3.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ and R ₂ are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an optionally substituted phenyl group, R ₃ , R ₄ , and R ₅ each represents a hydrogen atom or a lower alkyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR ₆ or -
Represents NHSO ₂ R ₆ . provided that R ₆ represents a hydrogen atom, a lower alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group] A heterocyclic compound represented by the following. 2 General formula () [In the formula, R ₁ and R ₂ are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an optionally substituted phenyl group, R ₃ , R ₄ , and R ₅ each represents a hydrogen atom or a lower alkyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR ₆ or -
Represents NHSO ₂ R ₆ . provided that R ₆ represents a hydrogen atom, a lower alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group] A hydrophobic fiber characterized by using a heterocyclic compound represented by the following. dyeing method. 3 General formula () [In the formula, R ₁ and R ₂ are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an optionally substituted phenyl group, R ₃ , R ₄ , and R ₅ each represents a hydrogen atom or a lower alkyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR ₆ or -
Represents NHSO ₂ R ₆ . However, R ₆ represents a hydrogen atom, a lower alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group] Synthetic resins characterized by using a heterocyclic compound represented by How to color.