JP4576924B2 - Reactive dye composition and dyeing or printing method using the composition - Google Patents

Description

  The present invention relates to a reactive dye composition and a dyeing or printing method using the composition.

The reactive dye represented by the following formula (I ′) is a known compound described in Japanese Patent Publication No. 62-1036.

  The reactive dye represented by the following formula (II) is a known compound described in, for example, Japanese Patent Publication No. 3-10669.

｛式（Ｄ１）中、Ｘ_１は塩素原子又はフッ素原子を表す。Ｘ_２は下式（Ｘ_２’）、（Ｘ_２’’）又は（Ｘ_２’’’）で示される基を表す。
−Ｎ（Ｒ）−Ａ （Ｘ_２’）
−Ｎ（Ｒ）−Ａ_１−ＳＯ_２Ｚ_３ （Ｘ_２’’）
−Ｎ（Ｒ）−Ａ_２−ＳＯ_２Ｚ_３ （Ｘ_２’’’）
（式中、Ｒは水素原子、炭素数１〜４の直鎖状アルキル基又はフェニル基を表す。Ａはフェニル基を表す。該フェニル基における１〜２個の水素原子は、炭素数１〜４のアルキル基、スルホン酸基、−ＮＨＣＯＣＨ（Ｂｒ）ＣＨ_２Ｂｒ及び−ＮＨＣＯＣ−（Ｂｒ）＝ＣＨ_２からなる群より選ばれる１〜２個の置換基で置換されていてもよい。Ａ_１はフェニレン基を表す。Ａ_２は炭素数２〜４の直鎖状アルキレン基又は−（ＣＨ_２）_２Ｏ（ＣＨ_２）_２−基を表す。Ｚ_３は−ＣＨ＝ＣＨ_２基又は−ＣＨ_２ＣＨ_２Ｌ_３を表す。Ｌ_３はアルカリの作用で脱離する基を表す。）｝ [In the formula (II), D represents a group represented by the following formula (D1) or (D2).

{In Formula (D1), X ₁ represents a chlorine atom or a fluorine atom. X ₂ represents a group represented by the following formula (X ₂ ′), (X ₂ ″) or (X ₂ ′ ″).
_{-N (R) -A (X 2} ')
_{-N (R) -A 1 -SO 2} Z 3 (X 2 '')
_{-N (R) -A 2 -SO 2} Z 3 (X 2 ''')
(In the formula, R represents a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a phenyl group. A represents a phenyl group. 1-2 hydrogen atoms in the phenyl group represent 1 to 2 carbon atoms. 4 alkyl group, a sulfonic acid group, optionally substituted with one to two substituents selected from -NHCOCH (Br) _CH 2 Br and -NHCOC- (Br) = group consisting of CH ₂ .A ₁ Represents a phenylene group, A ₂ represents a linear alkylene group having 2 to 4 carbon atoms or a — (CH ₂ ) ₂ O (CH ₂ ) ₂ — group, and Z ₃ represents a —CH═CH ₂ group or —CH. .L ₃ representing the ₂ CH ₂ L ₃ represents a group capable of leaving by the action of an alkali.)}

｛式（Ｄ２）中、Ｔは水素原子又は塩素原子を表す。｝］

{In formula (D2), T represents a hydrogen atom or a chlorine atom. }]

The reactive dye represented by the following formula (X) is known as Reactive Black 5.

A reactive dye composition containing a reactive dye represented by the formula (I ′) and a dye represented by the formula (II) is described in Patent Document 1.
Patent Document 2 describes a reactive dye composition containing a reactive dye represented by the formula (I ′), a reactive dye represented by the formula (X), and a yellow to orange reactive dye.
Further, Patent Document 3 discloses a reactive dye composition containing a reactive dye represented by the formula (II), a reactive dye represented by the formula (X), and a yellow to orange reactive dye.
Patent Document 4 discloses a reactive dye composition comprising a reactive dye represented by the formula (I ′), a reactive dye represented by the formula (II), and a yellow to red dye.

Japanese Patent No. 3405135 Special table 2003-518143 gazette Japanese Patent No. 3383068 JP-A-11-335576

However, the above-mentioned known reactive dye composition is not necessarily related to the dyeing performance such as dyeing reproducibility and the balance of dyeing fastness, particularly the light fastness, sweat sunfastness, chlorine fastness and wet fastness. It is not satisfactory.
For example, when the cellulose fiber material is dyed dark blue or black using the reactive dye composition described in Patent Document 1, there is a problem that the build-up property is unsatisfactory depending on the temperature and time at the time of dyeing.
Moreover, when the reactive dye composition described in patent documents 2-4 was used, there existed a problem that the fastness of sweat sunlight and chlorine fastness of the obtained dyeing | staining were not necessarily satisfied.
Furthermore, with the diversification of the types and forms of fiber materials, there is a problem that the hue is different due to differences in the front and back of the dyeing and the weaving method. Development of dark blue to black reactive dyes having good capacity is desired.
The object of the present invention is to provide a dark blue to black reactive dye that has an excellent balance of fastness to sweat and sunlight and particularly good compatibility when dyed with a yellow reactive dye or a red reactive dye. There is to do.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a specific reactive dye composition, and have completed the present invention.
That is, (a) of the present invention is a reactive dye represented by the following formula (I) in the form of the free acid, and a reactive dye represented by the following formula (II) in the form of the free acid. A reaction comprising one or more reactive dyes selected from reactive dyes represented by the following formulas (III) to (IX) and a reactive dye represented by the following formula (X) in the form of a free acid: A dye composition is provided.
Further, (b) of the present invention provides a method for dyeing or printing a fiber material, characterized by using the reactive dye composition of (i) above.

［式（Ｉ）中、Ｙ_１は−ＳＯ_２ＣＨ＝ＣＨ_２又は−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_１を表す。Ｌ_１はアルカリの作用で脱離する基を表す。Ｘは塩素原子又はフッ素原子を表す］

[In Formula (I), Y ₁ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₁ . L ₁ represents a group capable of leaving by the action of an alkali. X represents a chlorine atom or a fluorine atom]

［式（ＩＩ）中、Ｄは、下式（Ｄ１）又は（Ｄ２）で表される基を表す。

[In the formula (II), D represents a group represented by the following formula (D1) or (D2).

{In Formula (D1), X ₁ represents a chlorine atom or a fluorine atom. X ₂ represents a group represented by the following formula (X ₂ ′), (X ₂ ″) or (X ₂ ′ ″).
_{-N (R) -A (X 2} ')
_{-N (R) -A 1 -SO 2} Z 3 (X 2 '')
_{-N (R) -A 2 -SO 2} Z 3 (X 2 ''')
(In the formula, R represents a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a phenyl group. A represents a phenyl group. 1-2 hydrogen atoms in the phenyl group represent 1 to 2 carbon atoms. 4 alkyl group, a sulfonic acid group, optionally substituted with one to two substituents selected from -NHCOCH (Br) _CH 2 Br and -NHCOC- (Br) = group consisting of CH ₂ .A ₁ Represents a phenylene group, A ₂ represents a linear alkylene group having 2 to 4 carbon atoms or a — (CH ₂ ) ₂ O (CH ₂ ) ₂ — group, and Z ₃ represents a —CH═CH ₂ group or —CH. .L ₃ representing the ₂ CH ₂ L ₃ represents a group capable of leaving by the action of an alkali.)}

{In formula (D2), T represents a hydrogen atom or a chlorine atom. }

［式（ＩＩＩ）中、Ｄ_３はフェニル基又はナフチル基を表す。該フェニル基及びナフチル基における１〜３個の水素原子は、スルホ基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、−ＳＯ_２ＣＨ＝ＣＨ_２及び−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_４からなる群より選ばれる１〜３個の置換基で置換されていてもよい。Ｌ_４はアルカリの作用で脱離する基を表す。
Ｒ_１はメチル基又はカルボキシル基を表す。ベンゼン環の炭素原子に結合するＹ_３は水素原子、スルホン酸基、−ＳＯ_２ＣＨ＝ＣＨ_２又は−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_５を表す。Ｌ_５はアルカリの作用で脱離する基を表す。上記のＬ_４及びＬ_５は、互いに同一でもよく、異なってもよい。
但し、Ｙ_３が水素原子又はスルホン酸基を表す場合は、Ｄ_３はフェニル基又はナフチル基を表す。該フェニル基及びナフチル基における水素原子は、−ＳＯ_２ＣＨ＝ＣＨ_２及び−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_４からなる群より選ばれる置換基で置換されている。

Wherein (III), _{D 3} represents a phenyl group or a naphthyl group. 1 to 3 hydrogen atoms in the phenyl group and naphthyl group are a sulfo group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, —SO ₂ CH═CH ₂ and —SO ₂ CH _2. It may be substituted with 1 to 3 substituents selected from the group consisting of CH ₂ L ₄ . L ₄ represents a group capable of leaving by the action of an alkali.
R ₁ represents a methyl group or a carboxyl group. Y ₃ bonded to the carbon atom of the benzene ring represents a hydrogen atom, a sulfonic acid group, —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₅ . L ₅ represents a group capable of leaving by the action of an alkali. L ₄ and L ₅ may be the same as or different from each other.
However, if Y ₃ represents a hydrogen atom or a sulfonic acid group, D ₃ represents a phenyl group or a naphthyl group. Hydrogen atom in the phenyl group and naphthyl group _is substituted with a substituent selected from the group consisting of -SO ₂ CH = CH 2 and _{-SO 2 CH 2 CH 2 L 4} .

[In Formula (IV), R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents a cyano group, a carbamoyl group, or a sulfomethyl group.
X ₃ represents a chlorine atom or a fluorine atom. Y ₄ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₆ , and L ₆ represents a group capable of leaving by the action of an alkali. ]

［式（Ｖ）中、ｍ_１は１〜３の整数を表す。Ｘ_４は塩素原子又はフッ素原子を表す。アゾ基が結合したベンゼン環の炭素原子に結合するＲ_４及びＲ_５は、それぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、アルキルカルボニルアミノ基又はウレイド基を表す。Ｒ_６は水素原子又は炭素数１〜４のアルキル基を表す。
Ｙ_５は−ＳＯ_２ＣＨ＝ＣＨ_２又は−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_７を表す。Ｌ_７はアルカリの作用で脱離する基を表す。］

Wherein (V), _{m 1} represents an integer of 1 to 3. X ₄ represents a chlorine atom or a fluorine atom. R ₄ and R ₅ bonded to the carbon atom of the benzene ring to which the azo group is bonded are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonylamino group, or a ureido Represents a group. R ₆ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ₅ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₇ . L ₇ represents a group capable of leaving by the action of an alkali. ]

［式（ＶＩ）中、Ｒ_７はアミノ基又はアルキルカルボニルアミノ基を表す。Ｒ_９は水素原子又はスルホン酸基を表す。Ｙ_６は−ＳＯ_２ＣＨ＝ＣＨ_２又は−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_８を表す。Ｌ_８はアルカリの作用で脱離する基を表す。Ｒ_８は下式（ＶＩ’）で示される基を表す。ｔは０又は１を表す。］

[In the formula (VI), R ₇ represents an amino group or an alkylcarbonylamino group. R ₉ represents a hydrogen atom or a sulfonic acid group. Y ₆ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₈ . L ₈ represents a group capable of leaving by the action of an alkali. R ₈ represents a group represented by the following formula (VI ′). t represents 0 or 1; ]

[In the formula (VI ′), R ₁₀ represents a hydrogen atom or a sulfonic acid group. Y ₇ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₉ . L ₉ represents a group capable of leaving by the action of an alkali. ]

[In the formula (VII), m ₂ represents 0 or 1. R ₁₁ and R ₁₂ bonded to the carbon atom of the benzene ring to which the azo group is bonded are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, or —SO 2. _{2 represents} CH = CH ₂ or —SO ₂ CH ₂ CH ₂ L ₁₀ . L ₁₀ represents a group capable of leaving by the action of an alkali. R ₁₃ represents an acetyl group, a carboxyethylcarbonyl group, or the following formula (VII ′)

In the formula (VII ′), X ₅ and X ₆ are each independently a chlorine atom, a fluorine atom or the following formula

Represents a group represented by In the formula (VII ″), R ₁₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ₈ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₁₁ , and L ₁₁ represents a group capable of leaving by the action of an alkali.
_{However, if R 13} represents an acetyl group or a carboxyethyl _group, one or more of _{R 11} and _{R 12} represents an _{-SO 2} CH = CH 2 or _{-SO 2 CH 2 CH 2 L 10} . ]

［式中、Ｙ_９が結合したベンゼン環の炭素原子に結合するＲ_１５及びＲ_１６は、それぞれ独立に炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。Ｒ_１７及びＲ_１８はナフタレン環の炭素原子に結合し、それぞれ独立に水素原子又はスルホン酸基を表す。Ｒ_１９及びＲ_２０は、それぞれ独立に水素原子、アミノ基又はヒドロキシ基を表す。
Ｙ_９は−ＳＯ_２ＣＨ＝ＣＨ_２基又は−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_１２基を表す。Ｌ_１２はアルカリの作用で脱離する基を表す。］

[Wherein, R ₁₅ and R ₁₆ bonded to the carbon atom of the benzene ring to which Y ₉ is bonded each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. R ₁₇ and R ₁₈ are bonded to the carbon atom of the naphthalene ring and each independently represents a hydrogen atom or a sulfonic acid group. R ₁₉ and R ₂₀ each independently represents a hydrogen atom, an amino group or a hydroxy group.
Y ₉ represents a —SO ₂ CH═CH ₂ group or a —SO ₂ CH ₂ CH ₂ L ₁₂ group. L ₁₂ represents a group capable of leaving by the action of an alkali. ]

[Wherein, D ₄ represents a phenyl group, a naphthyl group, a group represented by the following formula (IX ′) or a group represented by the following formula (IX ″). One or two hydrogen atoms in the phenyl group and naphthyl group are substituted with one or two sulfonic acid groups, respectively.
D ₅ represents an acetyl group, a propionyl group or a group represented by the following formula (IX ′ ″). However, when the above D ₅ represents an acetyl group or a propionyl group, D ₄ represents a group represented by the above formula (IX ') or (IX''). ]

（式中、Ｙ_１０は−ＳＯ_２ＣＨ＝ＣＨ_２又は−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_１３を表す。Ｙ_１1は−ＳＯ_２ＣＨ＝ＣＨ_２又は−ＳＯ_２ＣＨ_２ＣＨ_２Ｌ_１4を表す。Ｌ_１３及びＬ_１4は、それぞれ独立にアルカリの作用で脱離する基を表す。Ｘ_７は塩素原子又はフッ素原子を表す。）

(In the formula, Y ₁₀ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L _13. Y ₁₁ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₁₄ . L ₁₃ and L ₁₄ each independently represent a group capable of leaving by the action of alkali, and X ₇ represents a chlorine atom or a fluorine atom.)

(In the formula, R ₂₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₂₂ bonded to the carbon atom of the benzene ring to which Y ₁₂ is bonded is a hydrogen atom, a chlorine atom, a sulfonic acid group, or a carbon number of 1 .X ₈ representing a to 4 alkyl groups represents _{.Y 12} is _{-SO 2} CH = CH 2 or _-SO 2 _CH 2 _CH 2 _{L 15} representing a chlorine atom, a fluorine atom or a morpholino group _{.L 15} is alkaline Represents a group capable of leaving by action)]]

（Ｘ）

(X)

_{(Wherein, Y 13} and _{Y 14,} the _{.L 16} representing a _{-SO 2} CH = CH 2 group or _-SO 2 _CH 2 _CH 2 _{L 16} groups each independently represent a group capable of leaving by the action of an alkali. )

The dark blue to black reactive dye composition of the present invention (I) has good compatibility when dyed with a yellow reactive dye or a red reactive dye.
In addition, according to the dyeing or printing method of the present invention (b), a dark blue to black dyeing having an excellent balance of light fastness, sweat sunfastness and chlorine fastness can be obtained.

Hereinafter, the present invention will be described in detail.
In (i) and (b) of the present invention, L _{1 to} L ₁₆ represent a group capable of leaving by the action of an alkali. Examples of the group capable of leaving by the action of alkali include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, a halogen atom and a pyridinio group. One to two hydrogen atoms in the pyridinio group may be substituted with one to two substituents selected from the group consisting of a halogen atom, a carboxy group and a ureido group.

As L _{1 to} L ₁₆ in the reactive dyes represented by the formulas (I) to (X), a sulfate group is particularly preferable.

D in the formula (II) represents the above-described (D1) group or (D2) group. When the above D is (D1) group, _{X 1} is a chlorine atom or a fluorine atom, _{X 2} represents formula (X2 ') ~ (X2'''). Preferred X2 ′ is that R is a hydrogen atom and A is a phenyl group. The hydrogen atom in the phenyl group is substituted with a sulfonic acid group. Preferable X ₂ ″ includes a fiber reactive group in which R is a linear alkyl group having 1 to 4 carbon atoms. Preferred examples of X ₂ ′ ″ include a fiber reactive group in which R is a hydrogen atom or a phenyl group, and A ₂ is an ethylene group or a — (CH ₂ ) ₂ O (CH ₂ ) ₂ — group. it can.
When D in the formula (II) is a group represented by (D2), T represents a hydrogen atom or a chlorine atom. Preferred T is a chlorine atom.

D ₃ in the formula (III) represents a phenyl group or a naphthyl group. 1-3 hydrogen atoms on the phenyl group and naphthyl group, respectively, a sulfonic acid group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon _atoms, -SO ₂ CH = CH 2 group and - It may be substituted with 1 to 3 substituents selected from the group consisting of SO ₂ CH ₂ CH ₂ L ₄ groups.
Preferred D ₃ is a naphthyl group in which two hydrogen atoms are substituted with two sulfonic acid groups, or two hydrogen atoms are one —SO ₂ CH═CH ₂ group or —SO ₂ CH ₂ CH. ₂ L ₄ group and a phenyl group substituted with one methyl group or methoxy group.

R ₂ in formula (IV) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferred R ₂ is an alkyl group having 1 to 4 carbon atoms. R ₃ in formula (IV) represents a cyano group, a carbamoyl group or a sulfomethyl group. Preferred R ₃ is a carbamoyl group. X ₃ in formula (IV) represents a chlorine atom or a fluorine atom. Preferred X ₃ is a chlorine atom.

M1 in Formula (V) represents an integer of ₁ to 3. R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl (preferably having 1 to 4 carbon atoms) carbonylamino group, or a ureido group.
As a preferable reactive dye in the formula (V), m ₁ is 3, a dye in which one of R ₄ and R ₅ is a hydrogen atom, and the other of R ₄ and R ₅ is a ureido group, or m ₁ is 2 And a dye in which one of R ₄ and R ₅ is a hydrogen atom, and the other of R ₄ and R ₅ is an alkyl (C 1-4) carbonylamino group.
X ₄ represents a chlorine atom or a fluorine atom. Preferred X ₄ is a chlorine atom.

（ＸＸＩＩ）
［式中、Ｙ_５は、上記と同じ定義である。］ A preferred reactive dye (V) is a reactive dye represented by the following formula (XXII).

(XXII)
[Wherein Y ₅ has the same definition as above. ]

R ₇ in the reactive dye (VI) represents an amino group or an alkyl (preferably having 1 to 4 carbon atoms) carbonylamino group. R ₈ in the formula (VI) represents a hydrogen atom or a group represented by the above formula (VI ′). When R ₈ represents a group represented by the above formula (VI ′), preferred R ₇ is an amino group.
A preferred reactive dye (VI) is a dye represented by the following formula (XI) or (XII).

［式中、Ｙ_６及びＲ_７は上記と同じ定義である。］

[Wherein Y ₆ and R ₇ have the same definitions as above. ]

[Wherein Y ₆ , Y ₇ , R ₉ and R ₁₀ have the same definitions as above. ]

R ₁₁ and R ₁₂ in Formula (VII) are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, —SO ₂ CH═CH ₂ group or — Represents the SO ₂ CH ₂ CH ₂ L ₁₀ group. Preferable R ₁₁ and R ₁₂ are each independently a hydrogen atom, a methyl group, a methoxy group, a sulfonic acid group, a —SO ₂ CH═CH ₂ group or a —SO ₂ CH ₂ CH ₂ OSO ₃ H group.

When _{R 13} in formula (VII) is an acetyl group or a carboxyethyl _group, at least one of _{R 11} and _{R 12} represents _{-SO 2} CH = CH 2 group or _-SO 2 _CH 2 _CH 2 _{L 10} groups .
Preferable reactive dye (VII) includes dyes represented by the following formulas (XIII) to (XV).

[Wherein, m ₂ , R ₁₄ , X ₆ and Y ₈ have the same definitions as above. ]

R ₁₅ and R ₁₆ in Formula (VIII) each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Preferred R ₁₅ and R ₁₆ are a hydrogen atom, a methyl group or a methoxy group.
Preferred reactive dyes (VIII) include the following reactive dyes (XVI) or (XVII). Particularly preferred reactive dyes (VIII) include the following reactive dyes (XVI).

［式中、Ｙ_９、Ｒ_１９及びＲ_２０は上記と同じ定義である。］

[Wherein Y ₉ , R ₁₉ and R ₂₀ have the same definitions as above. ]

［式中、Ｒ_１５〜Ｒ_１９及びＹ_９は、上記と同じ定義である。］

[Wherein R _{15 to} R ₁₉ and Y ₉ have the same definitions as above. ]

When D ₅ in Formula (IX) is an acetyl group or a propionyl group, D ₄ represents a group represented by Formula (IX ′) or (IX ″).

[Wherein Y ₁₀ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₁₃ . Y ₁₁ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₁₄ . L ₁₃ and L ₁₄ each independently represent a group capable of leaving by the action of an alkali. ]

  The reactive dye represented by the formula (IX) is preferably a dye represented by the following formula (XVIII), the following formula (XIX) or the following formula (XX).

［式中、Ｘ_７及びＹ_１１は、それぞれ上記と同じ定義である。］

[Wherein, X ₇ and Y ₁₁ have the same definitions as above. ]

［式中、Ｘ_８及びＹ_１２は、それぞれ上記と同じ定義である。］

[Wherein, X ₈ and Y ₁₂ each have the same definition as above. ]

As the reactive dye in the formula (X), a dye represented by the following formula (XXI) is preferable.

  The reactive dye (I), the reactive dye (II), the reactive dyes (III) to (IX) and the reactive dye (X) in the composition of the present invention (a) are, for example, those in the form of a free acid and salts thereof However, alkali metal salts, alkaline earth metal salts, and mixtures containing them are preferred, sodium salts, potassium salts or lithium salts, and mixtures containing two or more of these salts Is particularly preferred.

The method for producing the reactive dye in the composition of the present invention is not particularly limited.
For example, the reactive dyes of formula (I) and formulas (III) to (IX) can be produced by a combination of diazotization reaction and coupling reaction. The reactive dyes of formula (II) and formula (X) are known compounds.

  The reactive dye composition of the present invention comprises one or more reactive dyes selected from the group consisting of the reactive dye (I), reactive dye (II), reactive dyes (III) to (IX), and reactive dye (X). The preparation method is not particularly limited. For example, each reactive dye may be obtained by mixing in advance before dyeing, or may be obtained by mixing in a dye bath at the time of dyeing.

  In the composition of the present invention comprising the reactive dye (I), the reactive dye (II), one or more reactive dyes selected from the group of the reactive dyes (III) to (IX), and the reactive dye (X) The weight ratio of the reactive dye (I) to the reactive dye (II) is 95-5: 5-95, and the weight ratio of the reactive dye (I) to the reactive dye (X) is 95-5: 5-95. One or more reactive dyes selected from the group consisting of reactive dyes (III) to (IX), wherein the weight ratio of reactive dye (II) to reactive dye (X) is 95-5: 5-95 The weight ratio of reactive dye (I), reactive dye (II) and reactive dyes (III) to (IX) is selected from the group consisting of one or more reactive dyes and reactive dye (X). The composition which is the range of 0.1-50 weight part is preferable.

The reactive dye composition of the present invention comprises an inorganic salt (eg, salt); a dispersant; a dissolution improver such as a naphthalene derivative or an anthraquinone derivative; a dust scattering inhibitor; a pH stabilizer; a hard water such as a polyphosphate. Softening agent; antifoaming agent; water;
The reactive dye composition of the present invention is not particularly limited in its form, and may be powdery, granular, or liquid (aqueous).

The reactive dye composition of the present invention is useful as a reactive dye for dyeing or printing fiber materials. Such a fiber material is not particularly limited as long as it contains a hydroxy group and / or an amide group. For example, natural or regenerated cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, and blended materials containing them can be exemplified.
Examples of natural cellulose fibers include cotton, linen, hemp, jute and ramie fibers. A preferred natural cellulose fiber is cotton.
Examples of the regenerated cellulose fiber include rayon, polynosic, cupra fiber, tencel (trade name), tufcell (trade name), modal (trade name), Celtima (trade name), and the like.
Examples of natural or synthetic polyamide fibers include wool, silk, polyamide-6,6, polyamide-6, polyamide-11, and polyamide-4.
Examples of blended materials containing these include blended materials of the above-mentioned fiber materials, blended materials of the above-mentioned fiber materials and synthetic fibers such as polyester, nylon, and acrylic.

The reactive dye composition of the present invention can be dyed or printed on the above-described fiber material by a method according to physical and chemical properties. Specifically, for example, a method of dyeing or printing on the above-described fiber by a method such as an exhaust dyeing method, a cold batch up method, a continuous dyeing method, or a printing method can be given.
For example, in the case of dyeing on cellulose fibers by exhaust dyeing method, in the presence of alkali such as sodium carbonate, sodium bicarbonate, sodium tribasic phosphate and caustic soda, neutral salt such as sodium salt and salt is added as necessary, Furthermore, the method of dyeing | staining at the temperature of about 30-100 degreeC etc. which combine a solubilizing agent, a penetrating agent, a leveling agent, etc. as needed is illustrated. The addition of the above alkali or neutral salt may be performed at once or may be performed in divided portions.
When dyeing on cellulose fiber by cold batch up method, after padding with neutral salt such as mirabilite and salt and alkali such as caustic soda and sodium silicate, it is left at a fixed temperature in sealed packaging material. The method of doing is illustrated.
When dyeing cellulose fibers by continuous dyeing method, one-phase padding that is treated by steaming or dry heat after padding at room temperature or elevated temperature by a known method in the presence of alkali such as sodium carbonate or sodium bicarbonate Or after immersing the fibers in a padding solution in which the composition of the present invention is dissolved, neutral salt such as mirabilite or salt and alkali such as sodium hydroxide or sodium silicate are padded and steamed or dry-heated The two-phase padding method etc. which are processed by this are illustrated.

  When printing on cellulose fibers, printing with a paste containing alkali such as baking soda in one phase and then steaming at a high temperature of 80 ° C. or higher, or a two-phase neutral or slightly acidic printing paste Examples of the method include a method of performing a steaming or a dry heat treatment after printing with the like, after passing through an alkaline bath containing an electrolyte, or after overpassing with an alkaline electrolyte-containing padding solution. The printing paste may contain a paste and / or an emulsifier such as sodium alginate and starch ether, and may contain a print paste and / or a dispersant such as urea, if necessary.

  Examples of the alkali used when dyeing or printing the composition of the present invention on cellulose fibers include, for example, alkali metal hydroxides, water-soluble basic salts of alkali metals or alkaline earth metals and inorganic or organic acids, Examples thereof include compounds that liberate alkali in a heated state. Preferred are alkali metal hydroxides and alkali metal salts of weak to moderate strength inorganic or organic acids, hydroxides such as sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate. Is more preferable. Specific examples of such alkali include sodium carbonate, sodium bicarbonate, tribasic sodium phosphate, sodium hydroxide, sodium silicate, potassium hydroxide, sodium formate, potassium carbonate, primary sodium phosphate, secondary sodium phosphate, Examples include sodium trichloroacetate.

In the case of exhaust dyeing on a synthetic or natural polyamide fiber or polyurethane fiber, after exhausting the composition of the present invention under pH control in an acidic to slightly acidic dye bath, 60 to 120 Examples thereof include a method of changing the pH from neutral to alkaline at about ° C. If necessary, leveling agents, etc. (condensation products of cyanuric chloride and aminobenzene sulfonic acid, condensation products of cyanuric chloride and aminonaphthalene sulfonic acid, addition products of stearylamine and ethylene oxide, etc.) may be used. Good.

  In order to obtain a desired hue, the composition of the present invention can be used by mixing with other dyes as long as the characteristics of the present invention are not impaired. The dye to be used as a mixture is not particularly limited as long as it is a reactive dye. For example, as a reactive group, a sulfatoethylsulfone group, a vinylsulfone group, a monochlorotriazine group, a monofluorotriazine group, a mononicotinic acid triazine group, Mention may be made of dyes having at least one dichlorotriazine group, difluoromonochloropyrimidine group and trichloropyrimidine group. Further, Sumifix, Sumifix HF, Sumifix Supra, Remazol, Levafix, ReaNova, Procion, Cibacron, Basilen, Dreamarene, Kayacion, Kayelon React, etc. JP-A-56-128380, JP-A-57-2365, JP-A-59-15451, JP-A-59-96174, JP-A-60-123559, JP-A-60. -229957, JP-A-60-260654, JP-A-60-141765, JP-A-61-155469, JP-A-61-225256, JP-B-62-1036, 63-22566 No. 1, JP-A-1-185370, JP-A-3-770, JP-A-5-32907, JP-A-5-247366, JP-A-6-287463, and JP-A-2001-2952. The dye etc. which are described in are illustrated.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to said example. In the examples, “%” and “parts” represent “% by weight” and “parts by weight” unless otherwise specified.

（１） Example 1
Expressed in the form of the free acid, the following formula (1)

(1)

（２） In the form of a free acid, 500 parts of the dye represented by the following formula (2)

(2)

290 parts of a dye represented by the formula (3)

（３）
で示される染料１０部、及び、遊離酸の形で表すと、下式（４）

(3)
When expressed in the form of 10 parts of a dye and a free acid, the following formula (4)

（４）

(4)

When 200 parts of the dye represented by is mixed, an amber reactive dye composition is obtained.
0.30 g of the composition thus obtained and 5.0 g of anhydrous sodium sulfate are put into a dyeing apparatus (bath ratio 1:20, bath temperature is 60 ° C.) in which 5 g of knitted fabric made of cotton fibers is set. The knitted fabric was treated at 60 ° C. for about 20 minutes, and then 2.0 g of sodium carbonate was put into the bath, and the knitted fabric was dyed at 60 ° C. for 60 minutes and then washed. Washing fastness, sweat light fastness, chlorine fastness and light fastness were good, and a uniform and dark amber dyeing without spots was obtained. Moreover, the reproducibility of the dyeing was also good.

Example 2
400 parts of the dye represented by the above formula (1), 380 parts of the dye represented by the above formula (2), 10 parts of the dye represented by the above formula (3), 200 parts of the dye represented by the above formula (4), and Expressed in the form of the free acid, the following formula (5)

（５）

(5)

When 10 parts of the dye represented by is mixed, an amber reactive dye composition is obtained.
0.40 g of the composition thus obtained and 5.0 g of anhydrous sodium sulfate were put into a dyeing apparatus (bath ratio 1:20, bath temperature 60 ° C.) in which 5 g of knitted fabric made of cotton fibers was set. After the charging, the knitted fabric was treated at 60 ° C. for about 20 minutes. Then, 2.0 g of sodium carbonate was charged into the bath, and the knitted fabric was dyed at 60 ° C. for 60 minutes and then washed. Washing fastness, sweat light fastness, chlorine fastness and light fastness were good, and a uniform and dark amber dyeing without spots was obtained. Moreover, the reproducibility of the dyeing was also good.

Examples 3-8
A dye composition was obtained in the same manner as in Example 1 using the following dyes (6) to (11) in place of the dye (2) used in Example 1, and the dye composition was used to obtain Example 1 When dyeing in the same manner, a uniform dark blue dyeing without spots is obtained.

（６）

(6)

（７）

(7)

（８）

(8)

（９）

(9)

（１０）

(10)

（１１）

(11)

（１２） Example 9
Expressed in the form of the free acid, the following formula (12)

(12)

180 parts of the dye represented by the above formula (1), 200 parts of the dye represented by the above formula (2), 20 parts of the dye represented by the above formula (3), and the above formula (4) When 400 parts of the dye represented by is mixed, an amber reactive dye composition is obtained.
0.40 g of the composition thus obtained and 5.0 g of anhydrous sodium sulfate are put into a dyeing apparatus (bath ratio 1:20, bath temperature is 60 ° C.) set with 5 g of knitted fabric made of cotton fibers. The knitting was treated for about 20 minutes at 60 ° C., and then 2.0 g of sodium carbonate was put into the bath. Further, the knitted fabric was dyed at 60 ° C. for 60 minutes and then washed. Washing fastness, sweat light fastness, chlorine fastness and light fastness were good, and a uniform and dark amber dyeing without spots was obtained. Moreover, the reproducibility of the dyeing was also good.

Examples 10-24
Instead of the dye used in Example 9, the following dyes (13) to (30) were used in the number of parts described in Table 1 below to obtain a dye composition in the same manner as in Example 9, and the dye composition was used. When dyed in the same manner as in Example 9, a uniform dark blue to black dyed product without spots is obtained.

（１３）

(13)

（１４）

(14)

（１５）

(15)

（１６）

(16)

（１７）

(17)

（１８）

(18)

（１９）

(19)

（２０）

(20)

（２１）

(21)

（２２）

(22)

（２３）

(23)

（２４）

(24)

（２５）

(25)

（２６）

(26)

（２７）

(27)

（２８）

(28)

（２９）

(29)

（３０）

(30)

Example 25
200 parts of the reactive dye composition obtained in Example 2 was dissolved in hot water, cooled to 25 ° C., 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium bicarbonate were added, and water was further added. In addition, the total amount was 1000 parts at 25 ° C., and the cotton fabric was padded using this solution as a padding solution. The fabric was dried at 120 ° C. for 2 minutes and then steamed at 100 ° C. for 5 minutes to fix the dye. . A dyed product having a uniform deep amber color and good washing fastness, sweat sunlight fastness, chlorine fastness and light fastness was obtained. Even when the above staining was repeated, the reproducibility of the staining was good.

Example 26
Using the reactive dye composition obtained in Example 2, a color paste having the following composition was prepared.

  This color paste was printed on mercerized cotton broad, and after intermediate drying, steaming was performed at 100 ° C. for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying. A uniform dark print was obtained. Various fastnesses of the obtained printed matter are good.

Example 27
30 g of the reactive dye composition obtained in Example 2 is dissolved in hot water and then cooled to 25 ° C. To this dye solution, 15 g of 32.5% caustic soda solution and 150 g of 50 ° Baume water glass are added, and water is added at 25 ° C. to make the total amount 1000 g. The cotton fabric is padded with this solution as a padding solution. . The padded cotton fabric is rolled up, sealed with a polyethylene film, left at room temperature of 25 ° C. for 20 hours, then washed in a conventional manner, dried and finished. Various fastnesses are good, and a uniform and dark blue-colored dyeing is obtained.

The composition of the present invention (I) is useful as a reactive dye when dyeing cellulose fibers such as cotton in a dark to black color.
According to the dyeing method of the present invention (b), a variety of fastnesses of various color fastness to black are obtained.

Claims (5)

Reactive dye represented by the following formula (I) in the form of the free acid, reactive dye represented by the following formula (II) in the form of the free acid, and represented by the following formula (3) in the form of the free acid. And a reactive dye composition comprising a reactive dye represented by the following formula (X) in the form of a free acid.

[In Formula (I), Y ₁ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ L ₁ . L ₁ represents a group capable of leaving by the action of an alkali. X represents a chlorine atom or a fluorine atom. ]

[In the formula (II), D represents a group represented by the following formula (D1) or (D2).

{In Formula (D1), X ₁ represents a chlorine atom or a fluorine atom. X ₂ represents a group represented by the following formula (X ₂ ′), (X ₂ ″) or (X ₂ ′ ″).
_{-N (R) -A (X 2} ')
_{-N (R) -A 1 -SO 2} Z 3 (X 2 '')
_{-N (R) -A 2 -SO 2} Z 3 (X 2 ''')
(In the formula, R represents a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a phenyl group. A represents a phenyl group. 1-2 hydrogen atoms in the phenyl group represent 1 to 2 carbon atoms. 4 alkyl group, a sulfonic acid group, optionally substituted with one to two substituents selected from -NHCOCH (Br) _CH 2 Br and -NHCOC- (Br) = group consisting of CH ₂ .A ₁ Represents a phenylene group, A ₂ represents a linear alkylene group having 2 to 4 carbon atoms or a — (CH ₂ ) ₂ O (CH ₂ ) ₂ — group, and Z ₃ represents a —CH═CH ₂ group or —CH. .L ₃ representing the ₂ CH ₂ L ₃ represents a group capable of leaving by the action of an alkali.)}

{In formula (D2), T represents a hydrogen atom or a chlorine atom. }

(3)

(X)
_{(Wherein, Y 13} and _{Y 14,} independently of one _{another, .L 16} representing a -SO ₂ CH = CH 2 group or _-SO 2 _CH 2 _CH 2 _{L 16} groups represent a group capable of leaving by the action of an alkali .) In reactive dye of the formula (II), D is a group represented by the formula (D1), _'is a group represented by, X _2' X 2 is X ₂ A in is substituted with a sulfonic acid group The reactive dye composition according to claim 1, which is a phenyl group. In reactive dye of the formula (II), D is a group represented by the formula (D1), 'is a group represented by, X _{2' X 2} is X _{2 'R} is the' 1 to 4 carbon atoms The reactive dye composition according to claim 1, which is a linear alkyl group. In reactive dye of the formula (II), D is a group represented by the formula (D1), 'is a group represented by, X _2' X ₂ is X _{2 '' 'R} is a hydrogen atom or in' The reactive dye composition according to claim 1, which is a phenyl group, and A ₂ is ethylene or — (CH ₂ ) ₂ O (CH ₂ ) ₂ —. A method for dyeing or printing a fiber material, wherein the reactive dye composition according to any one of claims 1 to 4 is used.