JPH0363997B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-insoluble dye suitable for dyeing hydrophobic fibers or coloring synthetic resins. More specifically, the present invention relates to the general formula () [In the formula, A is a cyano group, a carbo-lower alkoxy group, a carbamoyl group, an N-lower alkylcarbamoyl group optionally substituted with a lower alkoxy group, a lower alkyl group, or an N- optionally substituted with a lower alkoxy group. phenylcarbamoyl group, acetyl group, benzoyl group, 4-nitrophenyl group or 4-cyanophenyl group; X represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group; n is the number 1 or 2, Y is a hydrogen atom, lower alkyl group, lower alkoxy group, halogen atom, group NHSO ₂ R ₅ , group -
NHCOR ₅ (here, R ₅ represents a phenyl group optionally substituted with a C ₁ -C ₁₂ alkyl group, lower alkyl group or lower alkoxy group), R ₁ represents an optionally substituted alkyl group, cyclo The alkyl group, alkenyl group, R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a lower alkyl group. ] It is a water-insoluble dye shown by Examples of the substituent A include cyano, acetyl, benzoyl, 4-nitrophenyl, 4-cyanophenyl, and carbamoyl, as well as carbo-lower alkoxy, such as carbomethoxy, carboethoxy, carbo-n-propoxy, carbo-n-butoxy,
Carboisopropoxy group, N-lower alkylcarbamoyl optionally substituted with lower alkoxy group, such as N-methyl, N-ethyl, N-propyl, N-butyl, N-(3-methoxypropyl), N-( N-phenylcarbamoyl optionally substituted by a lower alkyl group or a lower alkoxy group, e.g. -Phenyl, N-(4-methylphenyl), N-(2-methylphenyl), N-(4-ethylphenyl), N-
(4-methoxyphenyl), N-(4-ethoxyphenyl), or N-(4-butoxyphenyl)-carbamoyl groups, and cyano group is particularly preferred. Examples of the substituent X include chlorine, methyl, ethyl, methoxy, ethoxy, and butoxy; examples of the substituent Y include methyl, ethyl, methoxy,
In addition to ethoxy, propoxy, chlorine, and bromine groups, -
Examples include NHCOR ₅ and -NHSO ₂ R ₅ . Here, specific examples of R ₅ include methyl, ethyl, n
-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2,2-dimethylpropyl, 1-methylbutyl, n-hexyl, 1-ethylpentyl, 2,2-dimethylpentyl, octyl, nonyl, decyl, undecyl, Phenyl, 2
-,3- and 4-methylphenyl, 2-,3-
and 4-ethylphenyl, 4-propylphenyl, 4-methoxyphenyl, and 4-ethoxyphenyl. Substituents for the optionally substituted alkyl group in R ₁ include -OH, -CN, -OR ₆ , -
OCOR ₆ , −OCOOR ₆ , −OSO ₂ R ₆ , −COOR ₆ , −
NHSO ₂ R ₆ , -NHR ₆ , -OCONHR ₆ , alkenyl group, cycloalkyl group, or phenyl group (which may be substituted with lower alkyl, lower alkoxy, or halogen) can be mentioned. put it here
R ₆ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or a phenyl group (which may be substituted with lower alkyl, lower alkoxy, or halogen). R ₁ may further represent the following formula. (In the formula, Z represents O or S, and B represents a hydrogen atom, lower alkyl or lower alkoxy.) The dye of the formula () is a dye of the general formula () (wherein A, This isoindoline derivative may exist in tautomeric form) with the general formula () (In the formula, Y, R ₁ , R ₂ , R ₃ , R ₄ have the same meanings as above.) Obtained by reacting the amine represented by the formula in an organic solvent in the presence of a catalytic amount of an acid. . Examples of the organic solvent at this time include acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, naphthalene, and tetrahydrothiophene-s.
-dioxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are used. Examples of acids used as catalysts include sulfuric acid, phosphoric acid, hydrogen chloride, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, trienesulfonic acid, benzenesulfonic acid, and methanesulfonic acid. The reaction temperature is 90-150°C, preferably 110-130°C. The compound thus obtained dyes polyester in vivid reddish-blue to greenish-blue tones, and provides dyed products with excellent fastness to light, fastness to sublimation, and fastness to water. 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 synthetic polyamide fibers, polyester fibers, and other so-called hydrophobic synthetic fibers, and semi-synthetic fibers such as di- or triacetate, and these may be used alone or in combination. Furthermore, it refers to various forms of fiber 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 . 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 9.3 parts of the compound represented by N-ethyl-2,2,
A mixture of 11.2 parts of 4-trimethyl-1,2,3,4-tetrahydroquinoline, 40 parts of acetic anhydride, and 2 drops of concentrated sulfuric acid was stirred at 120°C for 2 hours while keeping it warm. material(
After confirming the disappearance of a) by chromatography, the solution is cooled, filtered, washed with methanol, washed with water, and dried. 8.2 parts of compound (1) having the following structural formula are obtained. λmax 633nm (DMF) Color tone: greenish blue Example 2 9.3 parts of the compound (a) shown in Example 1, N
-β-Phenoxyethyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline 16.3
1 part, 40 parts of acetic anhydride, and 2 drops of concentrated sulfuric acid at 120°C.
After stirring while keeping warm for 2 hours, cool, filter, wash, and dry. 11.2 parts of compound (2) having the following structural formula are obtained. λmax 630nm (DMF) Color tone: greenish blue Example 3 Formula (b) below 10 parts of the compound represented by N-n-butyl-2,
2,4-trimethyl-7-acetylamino-1,
2,3,4-tetrahydroquinoline 16.1 parts, O-
A mixture of 60 parts of dichlorobenzene and 2 drops of concentrated sulfuric acid.
Stir at 130°C for 1 hour. After cooling, filter and wash. 12.0 parts of compound (3) of the following formula is obtained. λmax 640nm (DMF) Color tone: greenish blue Example 4 Formula (c) below 10 parts of the compound represented by, 15 parts of N-ethyl-2-methyl-1,2,3,4-tetrahydroquinoline,
A mixture of 50 parts of propionic anhydride and 0.1 part of chloroacetic acid is stirred at 130°C for 1 hour. After cooling, filter, wash and dry. 9.5 parts of compound (4) of the following formula are obtained. λmax 582 nm (DMF) Color tone: reddish blue Example 5 Dyeing was carried out using the compound (1) obtained in Example 1 by the following procedure. a Dispersion preparation 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. Examples 6 to 47 The compound shown in (a) in Example 1 and N-ethyl-2,2,4-trimethyl-1,
Using the following compounds () and () as raw materials instead of 2,3,4-tetrahydroquinoline,
The corresponding compound is obtained by reacting in the same manner.

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[Table] Example 48 Using the compound (2) obtained in Example 2, a dispersion is prepared according to a) of Example 5. 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 Total balance 100 parts (Note 2) Half emulsion base paste composition Kerosene 70 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 49 Using a dispersion of the compound of Example 3 prepared according to the method of Example 5, the polyester fabric of Example 5 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, whereas cotton fabrics are dyed with virtually no staining. Example 50 0.2 parts of the compound obtained in Example 15 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 blue molded product is obtained that is robust to heat, light and migration.

Claims (1)

[Claims] 1 General formula () [In the formula, A is a cyano group, a carbo-lower alkoxy group, a carbamoyl group, an N-lower alkylcarbamoyl group optionally substituted with a lower alkoxy group, a lower alkyl group, or an N- optionally substituted with a lower alkoxy group. phenylcarbamoyl group, acetyl group, benzoyl group, 4-nitrophenyl group or 4-cyanophenyl group; X represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group; n is the number 1 or 2, Y is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a group NHSO ₂ R ₅ , a group -
NHCOR ₅ (here, R ₅ represents a phenyl group optionally substituted with a C ₁ -C ₁₂ alkyl group, lower alkyl group or lower alkoxy group), R ₁ represents an optionally substituted alkyl group, cyclo The alkyl group, alkenyl group, R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a lower alkyl group. ] A water-insoluble dye represented by