JPH1121465A - Disperse dye composition - Google Patents

Abstract

(57) [Summary] [Problem] To provide a disperse dye composition which gives a dyed blue color having excellent build-up properties, levelness properties, etc. and excellent hue clarity when dyeing polyester fiber. I do. A composition comprising a compound represented by the general formula (I) and a compound represented by the general formula (II). Embedded image Embedded image (Wherein, R1 is hydrogen, halogen, alkyl, etc., R2 is hydrogen, alkyl, etc., R3 is alkyl, etc., A is alkylene, R4 is hydrogen, alkyl, etc., and R5 and R6 are phenyl, alkoxy, etc. Represents an optionally substituted alkyl, respectively.)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a blue disperse dye composition containing a specific thiophenazo compound, and a method for coloring a hydrophobic material using the same.

[0002]

2. Description of the Related Art Conventionally, as a blue disperse dye composition for coloring a hydrophobic material such as a hydrophobic fiber material, a disperse dye composition containing a thiophenazo compound and an anthraquinone compound (see, for example, -41461 and JP 5-2
No. 63002) or a disperse dye composition containing a thiophene azo compound and another azo compound (for example,
Japanese Patent Application Laid-Open No. 8-209019) is known.

[0003]

However, when a hydrophobic material, for example, a polyester fiber material is dyed blue using such a conventional disperse dye composition, the dyeability in a high dye concentration range (so-called dyeing property). Build-up properties), the levelness of the resulting dyed product and the sharpness of the hue, etc., are not satisfactory.

On the other hand, in recent years, a polyester fiber material called a new synthetic fiber has been developed by various fiber manufacturers as a sensible material having a new texture unique to synthetic fibers, which is not found in natural fibers, and has become established in the market. However, even if these new synthetic fibers are dyed with a conventional disperse dye composition, there is a problem that a dyed material which can sufficiently satisfy levelness, build-up property and sharpness of hue cannot be obtained.

[0005] Therefore, not only when the polyester fiber material is dyed blue, but also when the new synthetic fiber is dyed, the build-up property is excellent, and the uniform dyeing property and the sharpness of the hue are excellent. It has been desired to develop a disperse dye which gives a dyed product.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a disperse dye composition containing a specific thiophenazo compound and a specific heterocyclic compound is obtained. By dyeing using a material, not only when dyeing polyester fiber material for the first time, but also when dyeing new synthetic fiber, it has excellent build-up properties and excellent leveling properties and sharpness of hue. And found that an excellent blue dyed product was obtained, and completed the present invention.

That is, the present invention provides (i) (a) one or more compounds in the thiophenazo compound group represented by the following general formula (I), and (b) a compound represented by the following general formula (II). A disperse dye composition comprising: a compound group; a compound group represented by the following general formula (III); and at least one compound selected from three compound groups represented by the following general formula (IV): And (ii) a method for coloring a hydrophobic material using the composition.

[0008]

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(In the formula, R ₁ represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkylcarbonylamino group, and R ₂ represents a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkyl group. Represents a good lower alkoxy group, R ₃ represents a hydrogen atom or a lower alkyl group which may be substituted, and A represents a lower alkylene.)

[0010]

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(Wherein R ₄ is a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms or a carbon atom having 1 to 4 carbon atoms)
R ₅ and R ₆ are each independently a carbon atom which may be substituted by one kind of substituent selected from the group consisting of a phenyl group, a phenoxy group and an alkoxy group having 1 to 6 carbon atoms. Represents an alkyl group of Formulas 1 to 12. )

[0012]

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(Wherein X represents a nitrogen atom or a —CH— group, R ₇ represents an alkyl group having 1 to 10 carbon atoms,
R ₈ and R ₉ independently represent an alkyl group having 1 to 6 carbon atoms, and R ₁₀ is a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Represents a group. )

[0014]

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(Wherein R ₁₁ is substituted with a hydrogen atom, an allyl group, or a substituent selected from the group consisting of a phenyl group, a cyano group and an alkoxycarbonyl group having 2 to 7 carbon atoms. Represents an alkyl group having 1 to 6 carbon atoms, and R ₁₂ and R ₁₃ each independently represent one kind of a substituent selected from the group consisting of a phenyl group, a phenoxy group and an alkoxy group having 1 to 6 carbon atoms. This represents an optionally substituted alkyl group having 1 to 20 carbon atoms.) Hereinafter, the present invention will be described in detail.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The disperse dye composition of the present invention comprises one or more compounds of the above (a) and at least one compound of the above (b). Specifically, a) one or more compounds in the thiophenazo compound group represented by the general formula (I) and one or more compounds in the compound group represented by the general formula (II) blend,
B) a mixture of one or more compounds in the thiophenazo compound group represented by the general formula (I) and one or more compounds in the compound group represented by the general formula (III);
C) a mixture of one or more compounds in the thiophenazo compound group represented by the general formula (I) and one or more compounds in the compound group represented by the general formula (IV);
One or more compounds in the group of thiophenazo compounds represented by the general formula (I), one or more compounds in the group of compounds represented by the general formula (II), and
A mixture with one or more compounds in the compound group represented by I), e) one or more compounds in the thiophenazo compound group represented by the general formula (I), and a compound represented by the general formula (II)
A mixture of one or more compounds in the compound group represented by formula (I) and one or more compounds in the compound group represented by formula (IV); One or more compounds in the azo compound group, one or more compounds in the compound group represented by the general formula (III), and one or more compounds in the compound group represented by the general formula (IV) A mixture of the above compounds, and g) one or more compounds of the thiophenazo compound group represented by the general formula (I) and one or more compounds of the compound group represented by the general formula (II) A mixture of the above compound, one or more compounds in the compound group represented by the general formula (III), and one or more compounds in the compound group represented by the general formula (IV) .

Next, the definitions of the symbols in the above general formulas will be described below. In the definitions of A and R _{1 to} R ₁₃ , alkyl, alkoxy and alkylene may be linear. Alternatively, it may be branched.

The thiophenazo compound used in the composition of the present invention is represented by the general formula (I), wherein R ₁ is a hydrogen atom, a halogen atom (such as a bromine atom or a chlorine atom), alkyl group (alkyl group having 1 to 4 carbon atoms), or lower alkyl (alkyl of 1 to 4 carbon atoms) carbonyl amino group, R ₂ is hydrogen atom, optionally substituted lower alkyl (carbon Numbers 1-4
Alkyl) group or an optionally substituted lower alkoxy (alkoxy having 1 to 4 carbon atoms) group.

Examples of the substituent of the lower alkyl group in R ₂ include hydroxy, alkoxy having 1 to 4 carbon atoms, and halogen atom (bromine atom, chlorine atom and the like). Specific examples of the lower alkyl group which may be substituted include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
Methoxyethyl, ethoxyethyl, hydroxyethyl,
Chloroethyl and the like can be mentioned. Examples of the substituent of the lower alkoxy group in R ₂ include alkoxy having 1 to 4 carbon atoms and a halogen atom (bromine atom, chlorine atom and the like). Specific examples of the lower alkoxy group which may be substituted include methoxy, ethoxy, methoxymethoxy, ethoxyethoxy, chloromethyloxy, chloroethyloxy and the like. R ₂ is preferably a hydrogen atom or an unsubstituted lower alkyl group.

In the general formula (I), R ₃ represents a hydrogen atom or a lower alkyl group which may be substituted, and the lower alkyl group is preferably, for example, methyl, ethyl, n-propyl. And an unsubstituted alkyl group having 1 to 4 carbon atoms such as isopropyl, n-butyl, isobutyl and sec-butyl. Furthermore, A
Represents a lower alkylene group, and the alkylene group preferably has 1 to 4 carbon atoms. As A, ethylene is particularly preferred.

General formula used in the composition of the present invention
In the compound represented by (II), R _FourIs a hydrogen atom, salt
A hydrogen atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms or charcoal
Represents an alkoxy group having a prime number of 1 to 4. Of these, hydrogen
An atom or an alkyl group having 1 to 2 carbon atoms is particularly preferred.
Where R_FiveAnd R₆Are, independently of each other,
Group consisting of an enoxy group and an alkoxy group having 1 to 6 carbon atoms
May be substituted by one kind of substituent selected from
Represents an alkyl group having 1 to 12 carbon atoms. None of these
A substituted alkyl group is preferable.
To 10 are preferred. R_FiveAnd R₆Is particularly preferably
It is a linear alkyl group having 1 to 6 carbon atoms.

General formula used in the composition of the present invention
In the compound represented by (III), X represents a nitrogen atom or a -CH- group. R ₇ represents an alkyl group having 1 to 10 carbon atoms, and among them, a branched one is preferable.
In the formula, R ₈ and R ₉ independently represent an alkyl group having 1 to 6 carbon atoms, and among them, a linear one is preferable. In the formula, R ₁₀ represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a hydrogen atom is particularly preferable.

General formula used in the composition of the present invention
In the compound represented by (IV), R ₁₁Is a hydrogen atom,
Ryl group or phenyl group, cyano group and 2 to 2 carbon atoms
1 selected from the group consisting of 7 alkoxycarbonyl groups
Alkyl having 1 to 6 carbon atoms which may be substituted with
Represents a kill group, particularly preferably a hydrogen atom or an allyl group.
is there. R₁₂And R₁₃Are, independently of each other,
Group consisting of an enoxy group and an alkoxy group having 1 to 6 carbon atoms
May be substituted by one kind of substituent selected from
Represents an alkyl group having 1 to 20 carbon atoms, but is an unsubstituted alkyl
Alkyl or phenyl substituted alkyl.
Good. R₁₂And R₁₃Are independently of each other
When it is a kill group, one of these groups has 1 to 4 carbon atoms.
An alkyl group, and the other is an alkyl group having 7 to 15 carbon atoms
Is preferable, and furthermore, among them, the carbon number is 7 to
It is particularly preferred when the 15 alkyl groups are branched.

The method for producing the thiophenazo compound (I) used in the composition of the present invention is not particularly limited.

[0025]

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The amines represented by the formula (II) are diazotized according to a conventional method, and the resulting diazotized solution is converted into the following general formula (VI)

[0027]

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(Wherein A, R ₁ , R ₂ and R ₃ have the same meanings as described above), and can be obtained by coupling with an aniline in a conventional manner.

Compounds (II), (III) and (IV)
Are, for example, JP-A-55-34288 and JP-A-
No. 6-41459, Japanese Patent Application Laid-Open No. 62-273265 or Japanese Translation
It can be obtained according to a known method described in JP-A-502776.

The disperse dye composition of the present invention may contain two or more thiophenazo compounds (I). In addition to the compound (I), two or more compounds (II) ), Which may contain two or more compounds (III) and two or more compounds (IV).

The disperse dye composition of the present invention may further contain other disperse dyes as long as its effect is not impaired, and may further include an anionic dispersant, a nonionic dispersant, and the like. May contain an auxiliary agent such as a dispersant, extender, pH adjuster, dispersing and leveling agent, builder, organic solvent, and resin binder. Here, specific examples of the anionic dispersant include, for example, formalin condensates of naphthalene sulfonic acids, lignin sulfonic acids, and formalin condensates of cresol-shaferic acid, and the like. Specific examples include polyoxyethylene alkyl ethers,
Examples thereof include polyoxyethylene alkyl phenyl ethers.

In the disperse dye composition of the present invention, the preferable content ratio of each compound is the above-mentioned compound (a), that is,
The thiophenazo compound represented by the general formula (I) is obtained by combining the thiophenazo compound represented by the general formula (I) with the compound of the above (b), that is, the compound represented by the general formula (II), And a compound represented by the general formula (I
It is contained in an amount of 1 to 99% by weight based on the total weight of the compound represented by V). In particular, the thiophenazo compound (I) preferably contains 20 to 95% by weight, more preferably 50 to 90% by weight, based on the total weight of the thiopheneazo compound (a) and the compound (b). Those containing are particularly preferred.

In the present invention, the thiophenazo compound (I) of the above (a) is mixed with at least one compound of the above (b), that is, the compound (II), the compound (III) and the compound (IV). The method of dyeing is not particularly limited. For example, when the dye is used as a disperse dye, it may be mixed before dyeing or may be mixed at the time of dyeing. As the former method, for example, a mixture of the compounds of the above (a) and (b) and, if necessary, the above dispersant and the like are preliminarily mixed with the mixture, and then, in an aqueous medium or the like,
A method of dispersing, and a method of separately dispersing each of the above compounds (a) and (b) to which the above-described dispersant and the like are added as necessary, and then mixing them can be exemplified. . Examples of the latter method include, for example, a method in which the above-mentioned dispersant and the like are added as necessary, and each compound separately dispersed is added to a dye bath.

The form of the disperse dye composition of the present invention is not particularly limited, and may be a powder, a granule, or a liquid.

The disperse dye composition of the present invention can color a hydrophobic material, and can be used, for example, as a disperse dye for dyeing or printing a hydrophobic fiber material. Here, as the hydrophobic fiber material, specifically, polyester fiber, triacetate fiber, diacetate fiber, polyamide fiber, polycarbonate fiber, and the like,
Examples thereof include blended and woven products thereof, and blended and woven products of natural fibers such as cellulosic fibers, wool and silk, and the above-mentioned synthetic fibers of polyester fibers or less.

The disperse dye composition of the present invention is particularly useful for dyeing or printing polyester fiber materials, and is also useful for dyeing or printing new synthetic fibers. Here, as the new synthetic fiber, among the polyester-based fiber materials, for example,
Polyester fiber such as polycondensate of polyethylene terephthalate, polybutylene terephthalate, terephthalic acid and the like and 1,4-bis (hydroxymethyl) cyclohexane, for example, ultrafine fiber yarn of 1 denier or less (fine denier, ultramicro Fibres, etc.), modified cross-section yarns, different shrinkage blended yarns, and the like. They may be composed of mixed or interwoven fabrics of extra-fine fiber yarns and yarns of normal thickness, or may be blended or interwoven products with fibers other than the new synthetic fiber. Good.

When these hydrophobic materials are used for dyeing or printing, the form is not particularly limited, and may be in the form of yarn or fiber.
Further, it may be in the form of a nonwoven fabric.

In the method for coloring the hydrophobic material of the present invention, the disperse dye composition of the present invention may be used according to a conventional method, and other conditions are not particularly limited. For example, when dyeing a polyester fiber material, if necessary, a dye bath in which the disperse dye composition of the present invention is dispersed in an aqueous medium may have p.
After adding an H adjuster, a dispersing leveling agent, etc., the polyester fiber material is immersed in it, and the pressure is 100 ° C. or higher, preferably 1 ° C.
A method of dyeing at 05 to 140 ° C. for 30 to 60 minutes can be used. Alternatively, a method of dyeing at around 95-100 ° C in the presence of a carrier such as o-phenylphenol or methylnaphthalene, or padding of a hydrophobic fiber material or the like to a dyeing bath, steaming at 100 ° C or more, or performing dry heat treatment. Methods can also be mentioned. In printing, there may be mentioned a method in which the disperse dye composition of the present invention is kneaded together with a paste, printed on a hydrophobic fiber material or the like, dried, then steamed or subjected to dry heat treatment.

The disperse dye composition of the present invention is used not only as a disperse dye for dyeing or printing the above-mentioned hydrophobic fiber material, but also as a dye for ink jet, a dye for sublimation transfer type thermal recording and the like. Can also.

[0040]

EFFECT OF THE INVENTION By using the disperse dye composition of the present invention, in the coloring of a hydrophobic material, for example, in the dyeing or printing of a hydrophobic fiber material, the build-up property is excellent, and the leveling property and the sharpness of the hue are excellent. Good dyeing is also obtained.

[0041]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
In the examples, parts and% indicate parts by weight and% by weight, respectively.

The thiophenazo compounds represented by the formula (I) used in the following examples are shown below. In the compounds shown in Table 1 below, A in the general formula (I) represents all ethylene groups.

[0043]

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[0044]

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[0045]

[Table 1]

The compound represented by the formula (II) is shown below.

[0047]

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The compound represented by the formula (III) is shown below.

[0049]

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[0050]

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The compound represented by the formula (IV) is shown below.

[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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Example 1 0.7 parts of the thiophenazo compound represented by the formula (1), 0.3 part of the compound represented by the formula (19), and 3 parts of a formalin condensate of naphthalenesulfonic acid were dispersed in 6 parts of water. A disperse dye composition was obtained. The obtained disperse dye composition
20 parts, 1.2 parts of acetic acid and 4.8 parts of sodium acetate were added to the dyeing bath, and the bath ratio was set to 1:30. Then, 100 parts of tetron tropical (a polyester fiber fabric manufactured by Toray Industries, Inc.) was immersed in the bath according to a conventional method. When dyed at about 130 ° C. for about 60 minutes, the resulting dyed product was a uniform blue dyed product without spots, and the hue sharpness was good. In addition, when the obtained disperse dye composition was similarly dyed using 30 parts, the obtained dyed product was dyed a remarkably deep blue compared to the dyed product obtained by dyeing using 20 parts of the disperse dye composition. It was found that the build-up property of the present disperse dye composition was good.

Examples 2 to 8 Instead of using 0.3 part of the compound represented by the formula (19) in Example 1, each of the compounds represented by the formulas (20) to (26) is shown in Table 2 below. A disperse dye composition was obtained by dispersing in water according to Example 1 except that the indicated parts by weight were used. Example 1 Using the Disperse Dye Composition Obtained
As a result, the obtained dyed product was a uniform blue dyed product without spots, and the hue sharpness was good. The build-up properties were also good.

[0059]

[Table 2]

Comparative Example 1 Instead of using 0.7 parts of the thiophenazo compound represented by the formula (1) in Example 1, the following formula (27) was used.

[0061]

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A disperse dye composition was obtained by dispersing in water according to Example 1, except that 0.7 part of the thiophenazo compound represented by the following formula was used. Using the obtained disperse dye composition, dyeing was carried out in the same manner as in Example 1. The obtained dyed product was poor in levelness, in which spots were observed, and had extremely poor hue clarity. Moreover, the disperse dye composition
The darkness of the blue color of the dyed product obtained by dyeing using 30 parts is almost not different from the blue color of the dyed product obtained by dyeing using 20 parts, and the build-up property is poor. all right.

Comparative Example 2 To 1.0 part of the compound represented by the above formula (19), 3 parts of a formalin condensate of naphthalenesulfonic acid was added and dispersed in 6 parts of water to obtain a disperse dye composition. When dyeing was performed in the same manner as in Example 1 using the obtained disperse dye composition, the density of the obtained dyed product was considerably light.

Examples 9 to 15 Examples 1 to 7 are the same as Examples 1 to 7, except that 100 parts of a new synthetic fiber Toraysee (Microfiber polyester fiber woven fabric manufactured by Toray Industries, Inc.) was used instead of using Tetron tropical. As a result, each of the obtained dyed products was a uniform blue dyed product without spots, and had a good hue clarity. The build-up properties were also good.

Comparative Example 3 Instead of using the disperse dye composition obtained in Example 1,
Except for using the disperse dye composition obtained in Comparative Example 1, when dyeing the new synthetic fiber fiber Toraysee in accordance with Example 8, the density of the obtained dyed product was considerably light, and levelness was extremely poor. there were.

Example 16 Instead of using 0.7 part of the thiophenazo compound represented by the formula (1) and 0.3 part of the compound represented by the formula (19), 0.8 part of the thiophenazo compound represented by the formula (1)
A disperse dye composition was obtained according to Example 1, except that 0.1 part of the compound represented by 9) and 0.1 part of the compound represented by the formula (25) were used. When dyeing was performed in the same manner as in Example 1 using the obtained disperse dye composition, the obtained dyed product was
It was a uniform blue dyed product without spots, and the hue sharpness was also good. The build-up properties were also good.

Examples 17 to 33 Instead of using the compound represented by the formula (1),
~ Except for using each of the compounds represented by formula (18)
When a disperse dye composition was obtained in accordance with Example 1 and dyed using this composition in the same manner as in Example 1, similarly, blue dyeings excellent in levelness, sharpness of hue, etc. were obtained. can get.

Claims (6)

[Claims] (1) one or more compounds of a thiophenazo compound group represented by the following general formula (I); and (b) a compound group represented by the following general formula (II); The compound group represented by III) and the following general formula (I)
A disperse dye composition comprising at least one compound selected from the group consisting of three compounds represented by V). Embedded image (Wherein, R ₁ represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkylcarbonylamino group,
R ₂ represents a hydrogen atom, a lower alkyl group which may be substituted or a lower alkoxy group which may be substituted; R ₃ represents a hydrogen atom or a lower alkyl group which may be substituted; Represents a lower alkylene group. ) (Wherein R ₄ represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₅ and R ₆ are each independently a phenyl group , A phenoxy group and an alkyl group having 1 to 12 carbon atoms which may be substituted by one kind of substituent selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms.) (Wherein, X represents a nitrogen atom or a -CH- group, R ₇
Represents an alkyl group having 1 to 10 carbon atoms, and R ₈ and R ₉
Represents, independently of each other, an alkyl group having 1 to 6 carbon atoms,
R ₁₀ represents a hydrogen atom, a chlorine atom, a bromine atom, a carbon number of 1 to 4
Represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms. ) (In the formula, R ₁₁ is a hydrogen atom, an allyl group, or a carbon atom which may be substituted with one substituent selected from the group consisting of a phenyl group, a cyano group, and an alkoxycarbonyl group having 2 to 7 carbon atoms. It represents the number 1-6 alkyl group, R ₁₂ and R
₁₃ independently represent a C1-20 alkyl group which may be substituted by one kind of substituent selected from the group consisting of a phenyl group, a phenoxy group and a C1-6 alkoxy group. ) 2. The disperse dye composition according to claim 1, wherein the compound (a) is contained in an amount of 1 to 99% by weight based on the total weight of the compound (a) and the compound (b). 3. The disperse dye composition according to claim 2, wherein the compound (a) is contained in an amount of 20 to 95% by weight based on the total weight of the compound (a) and the compound (b). 4. The disperse dye composition according to claim 3, wherein the compound (a) is contained in an amount of 50 to 90% by weight based on the total weight of the compound (a) and the compound (b). 5. A method for coloring a hydrophobic material, comprising using the disperse dye composition according to claim 1. 6. The coloring method according to claim 5, wherein the hydrophobic material is a new synthetic fiber.