JPH08209019A - Blue color-based disperse dye mixture - Google Patents

Abstract

PURPOSE: To obtain the subject mixture having excellent pH-dependence, color rendering, built up property and temperature dependence by mixing a monoazo dye with a specific amount of azo-based dye. CONSTITUTION: This mixture is obtained by mixing (A) 1 pt.wt. of monoazo dye of formula I (R<1> is a 1-5C alkyl or allyl) with (B) 0.1-0.5 pts.wt. (preferably 0.3-1.0 pt.wt.) of azo-based dye of formula II-IV (R<2> is a halogen; R<3> is H or methoxy, etc.; R<4> is H or a 1-5C alkyl, etc.; R<5> is a 1-5C alkyl or allyl; R<6> , R<9> , R<12> , R<13> and R<17> are each a 1-5C alkyl; R<7> and R<10> are each H or a halogen; R<8> is H or methyl, etc.; R<11> is nitro or formyl; R<14> is a 1-5C alkyl or a 1-3C alkoxymethyl, etc.; R<15> and R<16> are each a 1-5C alkyl, a 1-3C alkoxy or a 2-3C alkoxymethyl, etc.).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to disperse dye mixtures. Specifically, the pH dependence is extremely excellent,
The present invention relates to a blue disperse dye mixture having improved color rendering properties and excellent dyeing properties (build-up properties) during dyeing and temperature dependence.

[0002]

2. Description of the Related Art Monoazo dyes represented by the following general formula [1] have remarkably excellent pH dependence, but have insufficient color rendering properties. On the other hand, dyeing properties (build-up properties) and dyeing temperature dependency also need to be improved, especially in the field of medium density dyeing.

[0003]

[Chemical 6]

(In the formula, R ¹ represents a C ₁ -C ₅ alkyl group or an allyl group.) On the other hand, the dyes represented by the following general formulas [2], [3], [4] and [5] are color rendering. The dyeing properties are remarkably excellent, but the sharpness is remarkably inferior, and the pH dependence is slightly inferior to the dyes represented by the general formula [1], and the dyeing property (build-up property) in the medium density dyeing field. Is not enough and needs improvement.

[0005]

[Chemical 7]

(In the formula, R ² represents a halogen atom, and R ^2
3 is a hydrogen atom, a methoxy group, an ethoxy group or C _{1 to} C ₃
Represents an alkoxy C ₂ or C ₃ alkoxy group, R ⁴ represents a hydrogen atom, a C _{1 to} C ₅ alkyl group or an allyl group, R ⁵ represents a C _{1 to} C ₅ alkyl group or an allyl group, and R ⁶ represents C represent ₁ -C ₅ alkyl group. )

[0007]

Embedded image

(In the formula, R ⁷ represents a hydrogen atom or a halogen atom, R ⁸ represents a hydrogen atom, a methyl group, an ethyl group or a halogen atom, and R ⁹ represents a C ₁ -C ₅ alkyl group.)

[0009]

[Chemical 9]

(Wherein R ¹⁰ represents a hydrogen atom or a halogen atom, R ¹¹ represents a nitro group or a formyl group, and R
¹² and R ¹³ each independently represent a C _{1 to} C ₅ alkyl group, and R ¹⁴ is a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₃ alkoxymethyl group, or a C _{1 to} C ₃ alkoxy C ₂ or C ₃ alkoxy group. Represents a methyl group. )

[0011]

[Chemical 10]

(Wherein R ¹⁵ and R ¹⁶ represent a C ₁ -C ₅ alkyl group, C ₁ -C ₃ alkoxy C ₂ or C ₃ alkyl group, and R ¹⁷ represents a C ₁ -C ₅ alkyl group. )

[0013]

DISCLOSURE OF THE INVENTION The present inventors have aimed to develop a blue-based disperse dye having excellent pH dependence and excellent color rendering and dyeing properties (build-up properties). 1), [2], [3], [4], and [5], the present invention has been achieved through repeated research and attention.

[0014]

The present invention is represented by the following general formulas [2], [3], [4] and [5] with respect to 1 part by weight of a monoazo dye represented by the following general formula [1]. 0.1 to 1 or 2 or more kinds of azo dyes selected from dyes
A gist is a blue disperse dye mixture prepared by mixing 1.5 parts by weight and a dyeing method using the same.

[0015]

[Chemical 11]

(In the formula, R ¹ represents a C ₁ -C ₅ alkyl group or an allyl group.)

[0017]

[Chemical 12]

(In the formula, R ² represents a halogen atom, and R ^2
3 is a hydrogen atom, a methoxy group, an ethoxy group or C _{1 to} C ₃
Represents an alkoxy C ₂ or C ₃ alkoxy group, R ⁴ represents a hydrogen atom, a C _{1 to} C ₅ alkyl group or an allyl group, R ⁵ represents a C _{1 to} C ₅ alkyl group or an allyl group, and R ⁶ represents C represent ₁ -C ₅ alkyl group. )

[0019]

[Chemical 13]

(In the formula, R ⁷ represents a hydrogen atom or a halogen atom, R ⁸ represents a hydrogen atom, a methyl group, an ethyl group or a halogen atom, and R ⁹ represents a C ₁ -C ₅ alkyl group.)

[0021]

Embedded image

(In the formula, R ¹⁰ represents a hydrogen atom or a halogen atom, R ¹¹ represents a nitro group or a formyl group, and R
¹² and R ¹³ each independently represent a C _{1 to} C ₅ alkyl group, and R ¹⁴ is a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₃ alkoxymethyl group, or a C _{1 to} C ₃ alkoxy C ₂ or C ₃ alkoxy group. Represents a methyl group. )

[0023]

[Chemical 15]

(In the formula, R ¹⁵ and R ¹⁶ represent a C ₁ -C ₅ alkyl group, C ₁ -C ₃ alkoxy C ₂ or C ₃ alkyl group, and R ¹⁷ represents a C ₁ -C ₅ alkyl group. ) Hereinafter, the present invention will be described in detail.

The above general formulas [1], [2], [3],
In [4] and [5], R ¹ , R ⁴ , R ⁵ , R ⁶ ,
^{R 9, R 12, R 13} , R 14, C 1 ~C 5 alkyl group represented by R ^15, R ¹⁶ and R ¹⁷ may be either linear or ^{branched, R 1, R 4, R} 5, R ⁹ , R ¹² and R ¹³ are C _{2 to} C
₄ (linear) alkyl group, R ⁶ and R ¹⁴ are preferably a methyl group or an ethyl group, and R ¹⁷ is preferably a methyl group.
The halogen atom represented by R ² , R ⁷ , R ⁸ and R ¹⁰ is preferably a chlorine atom or a bromine atom.

C ₁ -C ₃ alkoxy C represented by R ³
_A methoxyethoxy group as the ₂ or C ₃ alkoxy group,
Examples thereof include a methoxypropoxy group, an ethoxyethoxy group, an ethoxypropoxy group, a propoxyethoxy group, and (i) propoxy (n) propoxy group. The C ₁ -C ₃ alkoxymethyl group, C ₁ -C ₃ alkoxy C ₂ or C ₃ alkoxymethyl group represented by R ¹⁴ is a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethoxymethyl group, a methoxypropoxy group. Methyl group,
Examples thereof include an ethoxyethoxymethyl group, an ethoxypropoxymethyl group, (i) propoxyethoxymethyl group and a propoxypropoxymethyl group, with a methoxymethyl group and an ethoxymethyl group being particularly preferable.

The C ₁ -C ₃ alkoxy C ₂ or C ₃ alkyl group represented by R ¹⁵ and R ¹⁶ is methoxyethyl group, ethoxyethyl group, ethoxypropyl group, (i)
Examples thereof include a propoxypropyl group, but a methoxyethyl group and an ethoxyethyl group are particularly preferable.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The dye represented by the general formula [1] and the general formulas [2], [3], [4] and [5] in the present invention.
The compounding ratio of the dye represented by the following formula is as follows: 1 part by weight of the monoazo dye represented by the general formula [1], the general formula [2], [3],
0.1 to 1.5 parts by weight, preferably 0.3 to 1.0 parts by weight, of one or more azo dyes selected from the group consisting of the dyes represented by [4] and [5]. is there. When two or more dyes represented by the general formula [2], [3], [4] or [5] are used, the ratio of one kind to the other kind is 1: 0.1 to 3, It is preferably 1: 0.5 to 2.

The dyes represented by the above general formulas [1] to [5] are synthesized according to known methods. The dye mixture of the present invention comprises conventional polyethylene terephthalate, polybutylene terephthalate, other terephthalic acid and 1,4-bis-
A polyester fiber made of a polycondensation product with (hydroxymethyl) cyclohexane is dyed in a blue color with good levelness and reproducibility. Examples of the form of the article to be dyed include yarn made of polyester fiber, knitted fabric, or mixed fiber product with fibers such as cotton, silk, wool, rayon, polyamide, and polyurethane.

To dye polyester fibers with the dye of the present invention, the general formulas [1], [2], [3], and
Since the dyes represented by [4] and [5] are insoluble or sparingly soluble in water, a condensate of naphthalenesulfonic acid and formaldehyde as a dispersant, a higher alcohol sulfuric acid ester, a higher alkylbenzene sulfonate, etc. can be prepared by a conventional method. Can be used to prepare a dyeing bath or printing paste dispersed in an aqueous medium, and can be carried out by dipping or printing.

For example, in the case of dip dyeing, polyester fibers or a mixture thereof can be dyed with excellent fastness by applying a normal dyeing treatment method such as a high temperature dyeing method and a thermosol dyeing method. In that case, if a well-known acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath, a better result can be obtained. Further, the pH of the dyeing bath is preferably adjusted to a range of usually 5.0 to 8.5. And the dyeing temperature is, for example,
It is about 120 to 140 ° C.

The disperse dye mixture of the present invention exhibits particularly excellent dyeability and temperature dependency when applied to the dip dyeing method. The dyeing conditions in exhaust dyeing are not particularly limited. For example, the dyeing temperature is about 120 to 140 ° C., the dyeing time is about 30 to 60 minutes, and the pH of the dyeing bath is 4 to 8.5.
It is a degree. It should be noted that due to the hue adjustment, the excellent characteristics of the disperse dye mixture of the present invention will not be impaired even if other blue disperse dyes are added up to about 10% by weight. Further, in order to obtain a desired color tone, a yellow dye or a red dye may be added. Further, various leveling agents and ultraviolet absorbers may be used in combination.

[0033]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. Example 1 A blue disperse dye mixture comprising 35 g of a dye represented by the following structural formula (1-1) and 15 g of a dye represented by the following structural formula (2-1).

[0034]

Embedded image

Lignin sulfonic acid formalin condensate 1
50 g and 650 g of water were mixed, wet-milled with a sand grinder, and spray-dried. To 0.05 g and 0.25 g of this powdery disperse dye mixture, 0.08 g of nonionic leveling agent DIASERVER (registered trademark) LR-PSL (product of Mitsubishi Chemical Co., Ltd.) and 150 ml of water were added to prepare a dyeing bath. PH 4.5 and pH with acetic acid / sodium acetate system or potassium dihydrogen phosphate / disodium hydrogen phosphate system
Adjusted to 7.5 respectively, 5 g of polyester fabric was put therein, and exhaust dyeing was carried out at 130 ° C. and 120 ° C. for 1 hour, followed by soaping, washing with water and drying to obtain a relatively sharp blue dyed product.

The resulting dyed fabric was evaluated for pH dependence, build-up property, temperature dependence and color rendering properties according to the following methods. The results are shown in Table 1. pH dependence: 13 at pH 4.5 with 0.05 g of dye
The density of the dyed cloth when dyed at 0 ° C. × 60 minutes was set to 100, and the density of the dyed cloth when dyed at pH 7.5 was shown as a relative value. The density is measured by a color difference meter
h (registered trademark) Spectrometer, MS-20
From the reflectance of the dyed product according to 20), the K / S value was obtained.

Build-up property: When dyed with 0.05 g of dye at 130 ° C. for 60 minutes at pH 4.5, the density of the dyed fabric is 100, and 0.25 g of dye is used under the same conditions. The density of the dyed cloth was shown as a relative value. Temperature dependence: 13 at pH 4.5 with 0.25 g of dye
The density of the dyed cloth when dyed at 0 ° C. × 60 minutes was set to 100, and the density of the dyed cloth when dyed at 120 ° C. × 60 minutes under the same conditions was shown as a relative value. Color rendering: 130 ° C at pH 4.5 using 0.25g of dye
The difference between the hue of the dyed cloth and the hue of the dyed cloth under the standard C light source was used as a reference, and the difference from the hue under the standard C light source was visually judged.

Comparative Example 1 The dye represented by (2-1) in Example 1 was not used, and the amount of the dye represented by (1-1) used was 35 g to 5 g.
Dyeing was performed according to Example 1 except that the amount was changed to 0 g. The results are shown in Table 1.

Comparative Example 2 According to Example 1, except that the dye represented by (1-1) was not used and the amount of the dye represented by (2-1) used was changed from 15 g to 50 g. And dyed. The results are shown in Table 1.

Examples 2 and 3 Dyeing was carried out according to the method of Example 1 except that the compounding amounts of the dyes (1-1) and (2-1) in Example 1 were changed as shown in Table 1. I did. The results are shown in Table 1.

[0041]

[Table 1]

Examples 4 to 26 Tables as dyes [dye (A)] represented by the general formula [1]
35 parts by weight of the dye described in 2 and the general formula [2],
Dyeing was carried out according to Example 1 using a dye mixture consisting of 15 parts by weight of the dye or dye mixture [dye (B)] shown in Table 2 as the dye represented by [3] and [4]. . In any of the examples, the evaluation results of the obtained dyed fabrics were excellent as follows. pH dependency: 100 Build-up property: 430 or more Temperature dependency: 85 or more Color rendering: Very slightly reddish to almost no change.

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

[0048]

[Table 7]

[0049]

[Table 8]

[0050]

[Table 9]

[0051]

[Table 10]

[0052]

[Table 11]

[0053]

The blue disperse dye mixture of the present invention is excellent in pH dependency, build-up property and temperature dependency, and also has good color rendering properties.

Claims (5)

[Claims] 1. To 1 part by weight of a monoazo dye represented by the following general formula [1], the following general formulas [2], [3] and [4]
And a blue disperse dye mixture containing 0.1 to 1.5 parts by weight of one or more azo dyes selected from the dyes represented by [5]. Embedded image (In the formula, R ¹ represents a C ₁ -C ₅ alkyl group or an allyl group.) (In the formula, R ² represents a halogen atom, R ³ represents a hydrogen atom, a methoxy group, an ethoxy group or a C _{1 to} C ₃ alkoxy C ₂ or C ₃ alkoxy group, R ⁴ represents a hydrogen atom,
C ₁ -C ₅ represents an alkyl group or an allyl group, and R ⁵ is C
_{1 to} C ₅ represents an alkyl group or an allyl group, and R ⁶ is C ₁
~C represents a ₅ alkyl group. ) [Chemical 3] (In the formula, R ⁷ represents a hydrogen atom or a halogen atom, and R ^7
8 represents a hydrogen atom, a methyl group, an ethyl group or a halogen atom, and R ⁹ represents a C ₁ -C ₅ alkyl group. ) [Chemical 4] (In the formula, R ¹⁰ represents a hydrogen atom or a halogen atom, and R ^10
11 represents a nitro group or a formyl group, R ¹² and R ¹³ each independently represent a C _{1 to} C ₅ alkyl group, and R ¹⁴ represents a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₃ alkoxymethyl group or C _{1 to} C ₃ alkoxy represents a C ₂ or C ₃ alkoxymethyl group. ) [Chemical 5] (In the formula, R ¹⁵ and R ¹⁶ are C _{1 to} C ₅ alkyl groups, and C ₁ to
C ₃ alkoxy represents a C ₂ or C ₃ alkyl group, R ¹⁷
Represents a C ₁ -C ₅ alkyl group. ) 2. In the general formula [1], R ¹ is a C ₂ -C ₄ alkyl group, in the general formula [2], R ² is a chlorine atom or a bromine atom, and R ³ is a methoxy group or ethoxy group. R ⁴ and R ⁵ are C ₂ -C ₄ alkyl groups, R ⁶
Is a methyl group or an ethyl group, and in the general formula [3], R ⁷
And R ⁸ are hydrogen atoms, R ⁹ is a C ₂ -C ₄ alkyl group, and in the general formula [4], R ¹² and R ¹³ are C ₂ -C ₄
An alkyl group, R ¹⁴ is a methyl group, an ethyl group, a methoxymethyl group or an ethoxymethyl group, and has the general formula [5]
The blue disperse dye mixture according to claim 1, wherein R ¹⁵ and R ¹⁶ are methoxyethyl groups or ethoxyethyl groups, and R ¹⁷ is a methyl group. 3. A monoazo dye 1 represented by the general formula [1].
0.3 to 1.0 part by weight of one or two or more kinds of azo dyes selected from the dyes represented by the general formulas [2], [3], [4] and [5] per part by weight. The blue disperse dye mixture according to claim 1 or 2, which is blended. 4. A monoazo dye 1 represented by the general formula [1].
0.3 to 0.3 parts by weight of the dye represented by the general formula [2] is added to parts by weight.
The blue disperse dye mixture according to claim 1 or 2, which is blended in an amount of 1.0 part by weight. 5. A dyeing method for polyester-containing fibers, which comprises using the blue disperse dye mixture according to any one of claims 1, 2, 3, 4 and 5.