JPH0776309B2 - Anthraquinone compound and method for dyeing or printing fiber material using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel anthraquinone compound in the field of dyeing or printing a fiber material as a reactive dye.

2. Description of the Related Art It has been widely practiced to dye or print a fiber material with a bright blue color using a fiber-reactive anthraquinone compound.

Problems to be Solved by the Invention Due to recent changes in technical and economic conditions in the demand industry, existing fiber-reactive anthraquinone compounds cannot always meet all the needs of the demand industry. For example, looking at the dyeing performance, which is one of the basic required performances of dyes, many unsatisfactory points have been found.

Means for Solving the Problems In order to find a novel anthraquinone compound having performance capable of responding to the sophistication of needs as described above, the present inventors have found that the type and number of the dye matrix, and the fiber-reactive group As a result of diligent studies on the types and types of linking groups connecting them, the linking sites, etc., the inventors have found compounds having specific properties by optimally combining specific ones, and completed the present invention.

That is, the present invention has the following general formula (I) in the form of a free acid. [Wherein R is hydrogen, methyl or ethyl, R ₁ and R ₂ are independently of each other hydrogen, methoxy, methyl, sulfo or chloro,
Z is vinyl or --CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali), l is 0, 1 or 2, and A is the formula (II). (In the formula, R ₃ , R ₄ and R ₅ are independently of each other hydrogen, methyl,
Ethyl, methoxy or ethoxy, m is 0 or 1, and n
Represents 0, 1 or 2. ) Or formula (III) (In the formula, p represents 0, 1, 2 or 3) and represents a divalent group. ] An anthraquinone compound represented by and a method for dyeing or printing a fiber material using the anthraquinone compound.

In the above general formula (I), when Z is —CH ₂ CH ₂ L, L corresponds to a group known as a group capable of leaving by the action of an alkali, and examples thereof include sulfate and thiosulfate. Examples include fert, acetoxy and chloro. Preferred Z is the case of β-sulfatoethyl, in which vinyl may be partially mixed.

A corresponds to a divalent group represented by the formula (II) and the formula (III), in particular, among them, R ₃ , R ₄ and R ₅ in the formula (II) are each independently hydrogen or methyl, m is 0 or 1, n
Is preferably 0 or 1, and p in the formula (III) is 0, 1 or 2.

It is preferable that l is balanced with the number of water-soluble groups such as sulfo substituted at positions other than the anthraquinone ring in the formula (I), and it is particularly preferable that l is 0 or 1.

The compound of the present invention is preferably an alkali metal or alkaline earth metal salt, and particularly preferably a sodium or potassium salt.

The compound of the present invention has the following formulas (IV) to (VI) [Wherein l, A, R, R ₁ , R ₂ and Z have the above-mentioned meanings, and X is a group capable of temporarily protecting amino such as hydrogen or acetyl. ] It can manufacture with a compound shown by and a cyanuric chloride or a cyanuric fluoride by a conventional method.

For example, first, the compound of the formula (IV) and the compound of the formula (V) are subjected to a known Ullmann condensation reaction, and at that time, X in the compound of the formula (V) used may temporarily protect an amino group such as acetyl. When it is a group, by subjecting it to a hydrolysis reaction in the presence of an alkali or an acid, and then changing X to hydrogen, the following formula (VII) [In the formula, 1 and A have the above-mentioned meanings. ] An organic dye residue of the compound of formula (I) (pigment base)
Can be manufactured.

Then, by condensing this with cyanuric chloride or cyanuric fluoride, the following formula (VIII) [In the formula, Y represents chloro or fluorine. ] The compound shown by these can be manufactured, By condensing this with a compound of Formula (VI) and Formula (VII) in arbitrary order,
Compounds of formula (I) can be prepared.

Examples of the compound of formula (IV) include 1-amino-4-bromoanthraquinone-2-sulfonic acid and 1-amino-4-
Bromoanthraquinone-2,6- or 2,7-disulfonic acid,
1-amino-4-bromoanthraquinone-2,5,8-trisulfonic acid may be mentioned.

Examples of the compound (V) of the formula include 2,4,6-trimethyl-3,5-diaminobenzenesulfonic acid and 5-methyl-2,4.
-Diaminobenzenesulfonic acid, 1,8- or 1,4-diaminocyclohexane, 2- or 4-methyl-1,8-diaminocyclohexane, 5,5-dimethyl-1,3-diaminocyclohexane, 4-aminomethyl- 2-amino-5-methylbenzenesulfonic acid, 4 or 5-aminomethyl-2-
Aminobenzenesulfonic acid, 5-aminomethyl-8-amino-2,4-dimethylbenzenesulfonic acid, 6-aminomethyl-2-amino-8-methoxybenzenesulfonic acid, 8-aminomethyl-2-amino-5- Methylbenzenesulfonic acid, 4-aminomethyl-2-amino-5-methoxybenzenesulfonic acid, 5-aminomethyl-2-aminobenzene-1,4-disulfonic acid, 4-aminomethyl-2-amino-5-ethylbenzene Sulfonic acid, m- or p-phenylenediamine, 2,4- or 2,5-diaminotoluene, 2,4,6-trimethyl-1,3-phenylenediamine, 2,4- or 2,5-diaminobenzenesulfone Examples thereof include compounds in which one of the acid or amino groups is protected with a group such as acetyl. Among them, amino-aminomethylsulfonic acids substituted with 0 to 2 methyls, phenylenediamines substituted with 0 to 8 methyls, and cyclohexylenediamines substituted with 0 to 2 methyls, or in some cases, A compound in which a part of the amine group of is protected with a group such as acetyl is preferred.

The above-mentioned starting compound is an acid and / or salt depending on reaction conditions,
In particular, it is used in the form of an alkali metal salt or an alkaline earth metal salt.

The anthraquinone compound produced by the present invention can be made into a liquid product by removing an inorganic salt and optionally adding a stabilizer or a dyeability improving agent, or by evaporating the liquid product or the reaction solution. For example, it can be made into a powder product by mist drying, and can also be made into a liquid product or a powder product through salting-out separation by addition of an electrolyte by a generally known method.

The anthraquinone compounds according to the invention can be used as fiber-reactive dyes and can dye fiber materials, for example materials containing hydroxy groups or carboxylic acid amide groups.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulosic fiber materials or regenerated products thereof and polyvinyl alcohol. Cellulosic fiber materials are cotton, as well as other vegetable fibers such as linen,
Hemp, jute and ramie fibers are preferred. Regenerated cellulose fibers are, for example, viscose staples and filament viscose.

Carbonamide group-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hair, silk, leather, polyamide 6,6,
Polyamide 6, polyamide 11 and polyamide 4.

For dyeing, a method depending on the reactive group of the fiber reactive dye can be applied.

For example, in the case of cellulosic fibers, dyeing is carried out using the dye of the present invention and an acid binder such as caustic soda, sodium carbonate, phosphate, silicate or sodium hydrogen carbonate. The dyeing method can be selected according to the nature of the fiber and the physical shape,
For example, an exhaust method, a printing method, a cold pad-batch-up method or the like can be adopted.

In the case of the exhaust method, sodium carbonate, sodium triphosphate,
It is carried out at a relatively low temperature in a dyebath containing Glauber's salt or salt in the presence of an acid binder such as caustic soda. In the case of printing processes, pastes or emulsified pastes such as sodium alginate or starch ether and sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, sodium triphosphate, sodium trichloroacetate or the corresponding potassium or alkaline earth compounds Along with the alkaline or alkali-releasing agents, if desired, is applied to the fibers with the addition of conventional printing aids or dispersants such as urea, dried and heat-treated, especially in the presence of steam. It can be dyed by In the case of cold pad-batch-up dyeing, caustic soda alone, or sodium silicate, sodium carbonate or sodium triphosphate as an acid binder is used in combination, and in some cases, sodium hydroxide or sodium chloride is added, and if desired, urea or the like is added. At around room temperature with the addition of a solubilizer or penetrant, pad on the fiber and wind it up on a roll.
It can be dyed by leaving it for 8 hours or overnight and washing with water and drying.

The compound of the present invention is characterized in that it exhibits excellent performance on fiber materials, and is particularly suitable for dyeing cellulosic fibers. It has a high exhaustion rate and sticking rate, extremely excellent build-up property, level dyeing property and detergency property, and even if there is some variation in dyeing conditions such as temperature, bath ratio and salt concentration, it has almost no effect on dyeing property. Not only is it excellent in light resistance, sweat light resistance, sweat resistance, oxidation water decomposition resistance, washing resistance, chlorine resistance, etc.

Next, the present invention will be described in more detail with reference to Examples. In the text, parts indicate parts by weight.

Example 1 1-Amino-4- (4-aminomethyl-2-sulfoanilino) anthraquinone-2-sulfonic acid (27.8 parts), cyanuric chloride (9.3 parts) and 1-aminobenzene-8-β-sulfatoethylsulfone (14.1 parts) were added to water. In a medium, successively condensed by a conventional method, and then reacted with 24.5 parts of 1-amino-4- (4-aminomethyl-2-sulfoanilino) anthraquinone-2-sulfonic acid at 60 to 70 ° C. under weak acidity, After salting out, the following formula in the form of free acid The atraquinone compound shown by was obtained.

Example 2 1-amino-4- (4-aminomethyl-2-of Example 1)
Sulfoanilino) anthraquinone-2-sulfonic acid, 1
Using the compounds in the first and second columns of the following table in that order in place of -aminobenzene-8-β-sulfurethylsulfone, the corresponding anthraquinone compounds were obtained in the same manner as in Example 1. It was The color tone on cotton of these compounds is as shown in the third column.

Example 3 1-Amino-4- (3-amino-2,4,6-trimethyl-
5-sulfoanilino) anthraquinone-2-sulfonic acid
56.8 parts, cyanuric chloride 9.3 parts in an aqueous medium, PH 6 ~ 7, 20 ~
Condensate at 30 ℃, salt out, and use the following formula in the form of free acid. An anthraquinone compound represented by

Next, 24.5 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone and the obtained anthraquinone compound are reacted at 60 to 70 ° C. under weak acidity and salted out to obtain a free acid form. formula An anthraquinone compound represented by

Example 4 1-amino-4- (3-amino-2,4,6-trimethyl-5-sulfoanilino) anthraquinone-2-of Example 3
Instead of sulfonic acid and 1-aminobenzene-3-β-sulfatoethylsulfone, the compounds in columns 1 and 2 of the following table were used in that order, respectively, according to the method according to Example 3 An anthraquinone compound was obtained. The color tone on cotton of these compounds is as shown in the third column.

Dyeing Example 1 0.1, 0.3, and 0.6 parts of the anthraquinone compound described in Example 1 were each dissolved in 200 parts of water, and 20 parts of Glauber's salt was added to the cotton.
Add 10 parts and raise the temperature to 60 ° C. After 30 minutes, 3 parts of carbonate carbonate is added and dyeing is carried out at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a bright blue dyed product having various fastnesses, particularly fastness to sunlight and sweat, and having good build-up properties.

This compound also has excellent solubility and has good levelness and dyeing reproducibility.

Dyeing example 2 0.3 part of the anthraquinone compound described in No. 5 of Example 4 is dissolved in 200 parts of water, 20 parts of Glauber's salt is added, 10 parts of cotton is added, and the temperature is raised to 60 ° C. Then, after 20 minutes, 3 parts of sodium phosphate tribasic are added. Dye at that temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a bright blue dyed product having various fastnesses.

Dyeing example 3 Color paste composition Anthraquinone compound described in Example 3 5 parts Urine 5 parts Sodium alginate (5%) Original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts Color paste having the above composition is mercerized After printing on processed cotton broad cloth, intermediate drying, steaming at 100 ° C for 5 minutes, washing with hot water, soaping, hot water washing and drying to finish.

In this way, a vivid blue print with excellent fastness was obtained.

Dyeing Example 4 The compounds shown in Examples other than the anthraquinone compound used in Dyeing Examples 1, 2 and 3 are also carried out by the method of Dyeing Examples 1, 2 or 3 and similar results are obtained.

Claims (5)

[Claims] 1. The following general formula (I) in the form of a free acid. [Wherein R is hydrogen, methyl or ethyl, R ₁ and R ₂ are independently of each other hydrogen, methoxy, methyl, sulfo or chloro,
Z is vinyl or --CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali), l is 0, 1 or 2, and A is the formula (II). (In the formula, R ₃ , R ₄ and R ₅ are independently of each other hydrogen, methyl,
Ethyl, methoxy or ethoxy, m is 0 or 1, and n
Represents 0, 1 or 2. ) Or formula (III) (In the formula, p represents 0, 1, 2 or 3) and represents a divalent group. ] The anthraquinone compound shown by these. 2. The compound according to claim 1, wherein Z is vinyl or β-sulfatoethyl. 3. A divalent group represented by the formula (II), wherein R ₃ , R ₄ and R _{5 are}
Are independently hydrogen or methyl, and m is 0 or 1,
The compound according to claim 1 or 2, wherein n is 0 or 1. 4. The compound according to claim 1 or 2, wherein the divalent group is represented by the formula (III) and p is 0.1 or 2. 5. The following general formula (I) in the form of a free acid. [Wherein R is hydrogen, methyl or ethyl, R ₁ and R ₂ are independently of each other hydrogen, methoxy, methyl, sulfo or chloro,
Z is vinyl or --CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali), l is 0, 1 or 2, and A is the formula (II). (In the formula, R ₃ , R ₄ and R ₅ are independently of each other hydrogen, methyl,
Ethyl, methoxy or ethoxy, m is 0 or 1, and n
Represents 0, 1 or 2. ) Or formula (III) (In the formula, p represents 0, 1, 2 or 3) and represents a divalent group. ] The method of dyeing or printing the textile material characterized by using the anthraquinone compound shown by these.