JP2785365B2 - Monoazo compound and method for dyeing or printing hydrophobic fiber material using the same - Google Patents

Description

The present invention relates to a novel monoazo compound and to a method for dyeing or printing hydrophobic fibers, in particular polyesters or materials produced therefrom, using the same.

(Related Art) In recent years, with the trend toward higher-grade clothing for consumers, there is a strong demand for disperse dyes having excellent dyeing properties and dyeing properties, wide dyeing suitability and good fastness. Against this background, in the case of hydrophobic fiber-centered materials dyed with disperse dyes,
Various post-processing such as softening, antistatic, and improving texture have been performed to increase the added value.However, since these post-processing are performed at high temperatures, the dye bleeds, the wet fastness, In particular, there was a problem that the washing fastness was reduced.

For example, JP-A-63-132969 discloses the following structural formula The monoazo dye represented by the following, JP-A-60-112857, the following structural formula Is further disclosed in JP-A-63-156864, the following structural formula Are disclosed, but these dyes cannot be said to have sufficient performance to solve the above demands and problems.

(Problems to be Solved by the Invention) The present invention is a monoazo dye which is capable of dyeing or printing hydrophobic fibers, particularly polyester fibers, with excellent dyeing properties, and has good dyeing properties such as leveling properties and wide dyeability. So,
Excellent fastness to lightfastness, sublimation, etc., especially wet fastness.Especially studying monoazo dyes that can provide dyeing with excellent washing fastness even after post-processing the obtained dyed fabric. As a result, the present invention has been completed.

(Means for Solving the Problems) The present invention provides the following general formula (I) Wherein X is a hydrogen atom, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acylamino, halogeno or formula -NH-CO-NHQ
(Where Q means a hydrogen atom, C ₁ -C ₄ alkyl or phenyl), Y is a hydrogen atom or halogeno, R ₁ is a hydrogen atom or C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy Carbonyl, C ₁ -C ₄ alkylcarbonyloxy, C ₁ -C ₄
Alkoxycarbonyloxy, phenyl, phenoxy,
Represents C ₁ -C ₆ alkyl or C ₈ -C ₅ alkenyl optionally substituted by benzoyloxy or cyano. In addition, Y and R ₁ can form a 5- or 6-membered ring with the nitrogen atom and the two carbon atoms connecting them. R ₂ is a linear or branched C ₂ -C ₄ alkylene optionally substituted with hydroxy, W ₁ , W ₂ , W ₃ , Z ₁ ,
Z ₂ and Z ₃ each independently represent a hydrogen atom, chloro, bromo,
C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl or nitro, D is thienyl, thiazolyl,
A substituted or unsubstituted heterocyclic or carbocyclic residue of the isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, benzoisothiazolyl, pyrazolyl, imidazolyl or phenyl series and B is Carbonyl, carbonyloxy, oxycarbonyloxy, imino, -O-, -S-, -CH = N-, -SO
_2- , Or a linear or branched C ₁ -C ₆ alkylene or a formula -A ₁ -E ₁ -A ₂ -E ₂ -A _3-wherein A ₂ , A ₂ and A ₃ are each independently a direct bond Alternatively, carbonyl, carbonyloxy, oxycarbonyloxy, imino, -O-, -S
-, - CH = N -, - SO 2 -, Wherein E ₁ and E ₂ each independently represent a direct bond or a linear or branched C ₁ -C ₆ alkylene, but when A ₁ is not a direct bond, E ₁ is also not a direct bond; _{When 3} is not a direct bond, E ₂ is also not a direct bond, and when A ₂ is a direct bond, E ₁ and E ₂ are not simultaneously a direct bond. ) Represents a linking group. However, when D is substituted or unsubstituted heterocyclic residues benzothiazolyl system, B represents -S- and linear or branched C ₁ -C ₆ linking groups other than alkylene. And a method for dyeing or printing a hydrophobic fiber material characterized by using the same.

In the general formula (I), examples of the substituent in the case of a carbocyclic or heterocyclic residue having a D substituent, for example, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or C ₁ - C ₄ alkylthio, phenyl, electronegative groups such as chloro,
Halogeno such as bromo, trifluoromethyl, cyano,
Nitro, acyl, benzoyl, methoxycarbonyl, C ₁ -C ₄ alkoxycarbonyl, such as ethoxycarbonyl,
C ₁ -C ₄ alkylsulfonyl, phenylsulfonyl, phenoxysulfonyl, include arylazo such as sulfonamides or phenylazo, any two adjacent substituents may further one fused ring together on the the ring, for example phenyl ring or Cyclic imides can be formed.

Of these, benzothiazolyl groups unsubstituted or mono- or polysubstituted by methyl, methoxy, chlorine, bromine, methylsulfonyl or nitro, or unsubstituted or cyano, methylsulfonyl, ethylsulfonyl, chlorine, bromine, formyl, acetyl, Benzoyl, carboethoxy, carbomethoxy, methoxy, or ethoxy-substituted phenyl groups are preferred, especially benzothiazolyl groups unsubstituted or mono- or disubstituted by chlorine, bromine or methoxy, or unsubstituted or nitro. A phenyl group mono- or tetra-substituted by chlorine, bromine, cyano, methylsulfonyl, ethylsulfonyl or methyl is preferred.

When X is a group of formula -NH-CO-NHQ, this indicates, for example, ureido, methylureide, ethylureide or phenylureide, and when X means acylamino, it may be, for example, a group of the formula is there.

-NH-V-R (wherein, V is -CO- or -SO ₂ - means, and R
Is a substituted or unsubstituted alkyl or phenyl. ) As the acyl group represented by -VR, acetyl, propionyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, phenylcarbonyl, 2-methoxycarbonylethylcarbonyl, 2-ethoxycarbonylethylcarbonyl, methoxycarbonyl, ethoxycarbonyl Phenoxycarbonyl, methoxyethylcarbonyl, hydroxyethylcarbonyl, methylsulfonyl or ethylsulfonyl.

X is preferably a hydrogen atom, methyl, methoxy,
It is chloro, promo, acetylamino, propionylamino or ureido, particularly preferably a hydrogen atom, methyl, chloro or acetylamino.

As Y, chloro, bromo, and hydrogen are preferable, and hydrogen is particularly preferable.

C ₁ -C ₆ alkyl represented by R ₁ is linear or branched, and preferably has C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylcarbonyloxy, C ₁ -C ₄ alkoxycarbonyl, phenyl.

R ₁ and Y, together with the nitrogen atom and the two carbon atoms to which they are attached, can form a 5- or 6-membered ring, which may optionally further comprise, as another heteroatom, an oxygen atom May be contained. Such ring substituents are, for example, hydroxy, methyl, methoxy, chloro or phenyl. Preferably, R ₁ and Y, together with the nitrogen atom and the two carbon atoms to which they are attached,
Form a 6-membered ring which is unsubstituted or has 1 to 4 methyls. Therefore, preferably, R ₁ and Y form a dihydroquinoline or tetrahydroquinoline having 0 to 4 methyl groups in which the nitrogen atom to which they are bonded and the benzene ring bonded to the azo group are combined. W _1, W _2, and
W ₃ is preferably independently a hydrogen atom, chloro, methyl, or methoxy, and particularly preferably a hydrogen atom.

Z ₁ , Z ₂ , and Z ₃ each independently represent a hydrogen atom, chloro,
It is preferably methyl, methoxy, methoxycarbonyl or nitro, and particularly preferably all are hydrogen atoms.

Examples of the linking group represented by B include carbonyl, -O-,
-S- or a linear or branched C ₁ -C ₆ alkylene, and B is a group represented by the formula -A ₁ -E ₁ -A ₂ -E _2-
Preferred A ₁ , A ₂ and A _{3 in the} case of A ₃ — (A ₁ , A ₂ , A ₃ , E ₁ and E ₂ have the above-mentioned meanings) include a direct bond, carbonyloxy and- O-.

The monoazo compound represented by the general formula (I) can be produced by a method known per se. For example, an amine derivative represented by the following general formula (II) D-NH ₂ (II) (wherein D represents the above-mentioned meaning) is diazotized to give the following general formula (III) (Wherein, X, Y, R ₁ , R ₂ , W _1-3 , B and Z _1-3 represent the above-mentioned meanings).

The coupling component represented by the general formula (III) can be prepared by a known method, for example, the following general formula (IV) _(Wherein, W 1 to 3, _{B, Z 1 to 3} are as defined above.) Compound with general formula _{(V) Hal-R 2 -Hal} (V) ( wherein represented by, R ₂ Represents the above-mentioned meaning, and Hal represents a chlorine atom or a bromine atom.) With a dihalogen compound represented by the following general formula (VI) (Wherein Hal, R ₂ , W _1-3 , B, Z _1-3 represent the above-mentioned meanings), and the compound represented by the following general formula (VII) (Wherein, X, Y and R ₁ have the same meanings as described above).

The monoazo compound represented by the general formula (I) of the present invention has a wide dyeing suitability and is useful as a disperse dye for a hydrophobic fiber material, particularly a polyester fiber material. For example,
The dye compound dispersion can be obtained by pulverizing the compound of the present invention into fine particles in an aqueous medium together with a suitable dispersant, for example, a condensate of nafuritalenesulfonic acid and formaldehyde, ligninsulfonic acid, and the like. The dye dispersion is
It can be used as it is or as a powder by spray drying or the like. Dyeing is performed by immersing the hydrophobic fiber material in an aqueous dyeing bath, and applying a pressure of 105 ° C. or more, preferably 110 ° C. or more.
It can be performed at ~ 140 ° C. Alternatively, dyeing is carried out at a relatively high temperature in the presence of a carrier such as o-phenylphenol or trichlorobenzene, for example, at the boiling state of water, or the dye dispersion is padded on a cloth, and the dyeing is carried out at 150 to 230 ° C for 30 to 30 ° C.
It is also possible to dye by so-called thermosol dyeing, which is a dry heat treatment for 60 seconds.

On the other hand, in the case of printing, the dye dispersion can be kneaded with an appropriate paste, padded onto a cloth, and then subjected to steaming or thermosol treatment for dyeing. A solvent dyeing method using an organic solvent such as trichlorethylene or perchlorethylene as a dyeing medium is also possible.

The obtained dyed product can be subjected to various post-processing such as softening processing, water repellency processing, texture improvement processing, antistatic processing, and sanitary processing as necessary, and various fastnesses even after the post-processing, In particular, it has a feature that the washing fastness does not decrease.

A dyed product obtained by dyeing or printing a hydrophobic fiber material, particularly a polyester fiber material, using the compound of the present invention represented by the above general formula (I) has various properties such as light fastness, sublimation fastness and wet fastness. It is excellent in fastness, and has a feature that washing fastness does not decrease even after heat setting or post-processing. For example, when a polyester fiber material is dyed in a deep color (JIS 2/1 density) and then heat-set, the washing fastness is remarkably superior to existing dyes.

Further, the compound (I) of the present invention has excellent dyeing properties, particularly excellent dyeing power and build-up properties, and also has good dyeing properties, so that a dyed product having a dark color and no uneven dyeing can be easily obtained. . In the case of clothing such as sportswear, the compound (I) of the present invention is used for dyeing such clothing, since it is essential that deep color dyeing is desired and that washing is frequently carried out so that the washing fastness is excellent. In particular, it demonstrates outstanding performance. Further, it may be used in combination with other dyes, and good results such as improvement of dyeability and modification of color tone can be expected.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, parts are parts by weight.

Example 1 56 parts of 2-chloro-4-nitroaniline was added to 100% of 78% sulfuric acid.
While maintaining the temperature at 35 to 40 ° C., 110 parts of 43% nitrosylsulfuric acid was added for diazotization. The obtained diazo liquid was washed with N-ethyl-N-2- (4-benzylphenoxy)
Glacial acetic acid-methanol containing 100 parts of ethylaniline (25:
It added to the solution of 2) keeping 0-5 degreeC. After adding sodium carbonate to adjust the pH to 8, the mixture was washed excessively and washed with the following structural formula (1) The compound represented by was obtained. Λmax of the compound in DMF
Was 514 nm.

1.0 part of the compound represented by the formula (1) was atomized and dispersed in an aqueous medium together with 3.0 parts of a condensate of naphthalenesulfonic acid and formaldehyde. 10 parts of tetron jersey (polyester cloth, product of Teijin Limited) is immersed in a dye bath containing 0.6 part of a powder obtained by drying the dye dispersion,
Staining was performed at 0-135 ° C for 60 minutes. Then, the dyed product was treated with 3 parts of caustic soda, 3 parts of hydrosulfite, 3 parts of betaine-type amphoteric surfactant and 3,000 parts of water.
After performing a reduction washing treatment at 10 ° C. for 10 minutes, washing with water and drying, a red dyed product was obtained, and its light fastness, sublimation and wet fastness were excellent.

The obtained dyed product was subjected to a soft antistatic treatment according to the following method.

In a pad tank, a pad solution having a composition of 10 g / Sumitex Softener LK-1 (softening agent manufactured by Sumitomo Chemical Co., Ltd.) and 5 g / Sumistat F-1 (antistatic agent manufactured by Sumitomo Chemical Co., Ltd.) was added. After preparing and immersing the dyed material in this solution,
It was squeezed evenly to a weight gain of 80%. After immersing the dyed material in the solution again and squeezing in the same manner, perform intermediate drying at 80 ° C. for 2 minutes,
Then, heat set was performed at 170 ° C. for 1 minute.

When the washing fastness of the post-processed dyed product thus obtained was measured, excellent results were obtained.

N used as a coupling component in this example
-Ethyl-N-2- (4-benzylphenoxy) ethylaniline is obtained by mixing excess N-ethylaniline with 2- (4-
(Benzyl) phenoxyethyl bromide is reacted by heating, and the residue obtained by removing unreacted N-ethylaniline by distillation is purified.

Example 2 85 parts of 2-amino-6-chlorobenzothiazole was 59%
Dispersed in 200 parts of phosphoric acid, and keeping the temperature at -5 to 0 ° C, the diazo solution obtained by adding 22 parts of sodium nitrite was converted to N-methyl-N-3- [4- (2-phenoxyethoxy) Phenoxy] propylaniline was added to a glacial acetic acid-methanol (25: 2) solution containing 113 parts while maintaining the temperature at 0 to 5 ° C.
Add 500 parts of ice water, wash the precipitated crystals, and wash with the following structural formula (2) The compound represented by To 1.3 parts of the compound represented by the formula (2), 3.7 parts of lignin sulfonic acid was added and atomized and dispersed, and 35 parts of hot water and 60 parts of a half emulsion paste having the following composition were mixed to prepare a printing paste.

O / W emulsion 300 parts Maypro gum NP12% paste 694 parts Sodium chlorate 4 parts Tartaric acid 2 parts Total 1,000 parts Using this printing paste, print on polyester cloth in Tetron Tropical (manufactured by Teijin Limited), dry and press The mixture was steamed and fixed at 170 ° C. for 7 minutes using a high-temperature steamer.
Flexible / antistatic processing was performed in this order. The red dyeing thus obtained is excellent in light fastness, sublimation and wet fastness,
In particular, the washing fastness was excellent.

N used as a coupling component in this example
-Methyl-N-3- [4- (2-phenoxyethoxy)
Phenoxy] propylaniline can be obtained from N-methylaniline and 3- [4- (2-phenoxyethoxy) phenoxy] propyl chloride in the same manner as described in Example 1.

Examples 3 to 98 According to the method described in Example 1 or 2,
The compounds shown in the table were synthesized, and the polyester cloth was dyed using the compounds to obtain a dyed product having a color tone shown in the table.

The washing fastness of each of these dyed products was excellent.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yosuke Yamamoto 3-1-198 Kasuganaka, Konohana-ku, Osaka-shi, Japan Sumitomo Chemical Industries Co., Ltd. (72) Inventor Hideo Hattori Kasuga-hi, Konohana-ku, Osaka-shi, Osaka Naka 3-chome No. 98 Sumitomo Chemical Co., Ltd. (72) Inventor Junichi Yahamachi 3-1-1 Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (58) Investigated field (Int .Cl. ⁶ , DB name) C09B 29/06-29/095 CA (STN)

Claims (10)

(57) [Claims] 1. A compound represented by the following general formula (I) Wherein X is a hydrogen atom, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acylamino, halogeno or formula -NH-CO-NHQ
(Where Q means a hydrogen atom, C ₁ -C ₄ alkyl or phenyl), Y is a hydrogen atom or halogeno, R ₁ is a hydrogen atom or C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy Carbonyl, C ₁ -C ₄ alkylcarbonyloxy, C ₁ -C ₄
Alkoxycarbonyloxy, phenyl, phenoxy,
Represents C ₁ -C ₆ alkyl or C ₃ -C ₅ alkenyl which may be substituted by benzoyloxy or cyano. In addition, Y and R ₁ can form a 5- or 6-membered ring with the nitrogen atom and the two carbon atoms connecting them. R ₂ is a linear or branched C ₂ -C ₄ alkylene optionally substituted with hydroxy, W ₁ , W ₂ , W ₃ , Z ₁ ,
Z ₂ and Z ₃ each independently represent a hydrogen atom, chloro, bromo, C ₁
-C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl or nitro, D is thienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, Benzoisochi Azolyl,
A substituted or unsubstituted heterocyclic or carbocyclic residue of pyrazolyl, imidazolyl or phenyl series, and B is carbonyl, carbonyloxy, oxycarbonyloxy, imino, -O-, -S-, -CN = N- , -SO ₂
-, - NH-C (O ) -, - OSO 2 -, - NH-C (O) -O
-Or linear or branched C ₁ -C ₆ alkylene or a formula -A ₁ -E ₁ -A ₂ -E ₂ -A _3-wherein A ₁ , A ₂ and A ₃ are each independently Direct bond or carbonyl, carbonyloxy, oxycarbonyloxy, imino, -O-,-
S -, - CH = N - , - SO 2 -, - NH-C (O) -, - OSO
Represents _2- or -NH-C (O) -O-, E ₁ and E
₂ is each independently a direct bond or a linear or branched C
If represents the ₁ -C ₆ alkylene, if A ₁ is not a direct bond E ₁ is also not a direct bond, if A ₃ is not a direct bond E ₂ is also not a direct bond, further A ₂ is a direct bond Is E ₁
And E ₂ is not a direct bond simultaneously. ) Represents a linking group represented by However, when D is a benzothiazolyl-substituted or unsubstituted heterocyclic residue,
B represents -S- and linear or branched C ₁ -C ₆ linking groups other than alkylene. ] The monoazo compound shown by these. (2) D is unsubstituted or C ₁ -C ₄ alkyl, C _1-
C ₄ alkoxy, C ₁ -C ₄ alkylthio, chloro, bromo,
Trifluoromethyl, is cyano, nitro, Ashiri, benzoyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkylsulfonyl, phenylsulfonyl, to have been replaced by a sulfonamide or arylazo, or two adjacent substituents together Thienyl, thiazolyl, isothiazolyl, 1,2,4-
The monoazo compound according to claim 1, which is thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, benzoisothiazolyl, pyrazolyl, imidazolyl or phenyl. 3. A benzothiazolyl group wherein D is unsubstituted or mono- or polysubstituted by methyl, methoxy, chlorine, bromine, methylsulfonyl or nitro, or unsubstituted or cyano, methylsulfonyl, ethylsulfonyl, chlorine, bromine, formyl The monoazo compound according to claim 1, which represents a phenyl group mono- or polysubstituted by, acetyl, benzoyl, carboethoxy, carbomethoxy, methoxy, or ethoxy. 4. A benzothiazolyl group wherein D is unsubstituted or monosubstituted or disubstituted by chlorine, bromine or methoxy, or unsubstituted or nitro, chlorine, bromine,
The monoazo compound according to claim 1, which represents a phenyl group mono- to tetra-substituted by cyano, methylsulfonyl, ethylsulfonyl or methyl. 5. The monoazo compound according to claim 1, wherein X is hydrogen, methyl, methoxy, chlorine, bromine, acetylamino, propionylamino or ureide. 6. The method according to claim 1, wherein Y is bromine, chlorine or hydrogen.
The monoazo compound according to any one of claims 1 to 5. 7. R ₁ is an unsubstituted or hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylcarbonyloxy, C ₁ -C ₄ alkoxy C ₁ substituted with carbonyl or phenyl -
Monoazo compound according to claim 1 is a C ₄ alkyl. 8. The monoazo compound according to claim 1, wherein B is carbonyl, —O—, —S—, or a linear or branched C ₁ -C ₆ alkylene. 9. B is a linking group represented by the formula -A ₁ -E ₁ -A ₂ -E ₂ -A _3- , wherein A ₁ , A ₂ and A ₃ are each independently a direct bond, carbonyloxy or-. The monoazo compound according to any one of claims 1 to 8, which represents O-. 10. A method for dyeing or printing a hydrophobic fiber material, comprising using the monoazo compound according to any one of claims 1 to 9.