JP2872387B2 - Disperse dye composition and method for dyeing hydrophobic fiber - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a disperse dye composition and a method for dyeing hydrophobic fibers.

2. Description of the Related Art In recent years, polyester fiber materials have been increasingly used as interior materials for automobiles due to their excellent heat resistance and light resistance. With respect to this, even more excellent light fastness has been required for a disperse dye as a colorant. Light fastness is conventionally performed at a temperature of 63 ± 3 ° C specified in JIS-L0842.
For example, it is required to have a light fastness that can withstand exposure at a high temperature of 83 ± 3 ° C. for 300 to 600 hours. In addition, in automotive interior applications, for automotive seats, a polyester fiber material is stretched on a heat-resistant urethane foam. Is required.

Generally, among the disperse dyes, those having relatively good light fastness are anthraquinone-based dyes and quinophthalone-based dyes, but they generally have poor coloring power. In addition, azo-based disperse dyes having an advantage of excellent coloring power generally tend to have lower light fastness than anthraquinone-based and quinophthalone-based dyes. In particular, as the interior materials for automobiles as described above, light-colored to dark-colored dyeings are required, and it is strongly desired to develop disperse dyes having excellent coloring power and excellent light-fastness from light to dark colors. ing.

Problems to be Solved by the Invention Currently, dyeing with a disperse dye having excellent light fastness for automotive interior materials is anthraquinone-based for light colors,
Further, a dye partially containing a quinophthalone-based dye is used, and a dye partially mixed with an azo dye is used for a medium-dark color. However, the color value of a light color dye is inferior, and if a dyed product having a medium dark hue is to be obtained, the use amount of the dye is remarkably increased and the cost is extremely high. Even if a dyed product having a medium dark hue is obtained, its light fastness is at a poor level. In addition, azo disperse dyes used as dyes for medium and dark colors tend to have poor light fastness of dyed products in light colors.

Means for Solving the Problems Under severe conditions such as automotive interior use, the present inventors have conducted intensive studies on a disperse dye having a high light fastness to withstand a light fastness test from a light color to a dark color range, and as a result, It has been found that by simultaneously using the disperse dyes, a dyed article having excellent light fastness in a range from light to dark such as beige or brown, orange, orange or green can be obtained, and the present invention has been achieved. Things.

That is, the present invention provides: 1. A disperse dye composition containing the following (A) yellow disperse dye and (B) red disperse dye and / or (C) blue disperse dye.

(A) Yellow disperse dye: a mixture of the compounds represented by the formulas (1), (2) and (3).

(In the formula, X ₁ and X ₂ each independently represent a hydrogen atom, a chlorine atom or a bromine atom, and R ₁ represents a lower alkyl group or an allyl group.) (Wherein, R ₂ represents alkyl (C ₁ -C ₄ ) or phenyl, respectively) (In the formula, Z ₁ , Y ₁ , and Y ₂ each independently represent a benzene ring or a naphthalene ring in which a hydrogen atom or a halogen atom may be substituted with a ring A carboxylate group.) ) Red disperse dye: a mixture of at least two or more compounds selected from the group of compounds represented by formulas (4), (5), (6) and (7).

(Wherein, R ₃ is a methyl group or an ethyl group, R ₄ is a cyanoethyl group, or an acetoxyethyl group, and R ₅ is an acetoxyethyl group, a lower alkoxy (C _1-4 ) alkyl group, or a lower alkoxy (C ₁ -C _{1) 4} ) represents an ethoxyethyl group, respectively.) (Wherein, R ₆ represents an alkyl (C _1-6 ) group substituted with a hydroxyl group, a phenoxy group, or a phenyl group) (In the formula, R ₇ represents a hydrogen atom, a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted alkyl group, an alkyl-substituted aminosulfonyl group, an alkoxyalkyl-substituted aminosulfonyl group, or an acyloxy group.
(In the above, the substituent of the alkoxy group is a carboalkoxy group or an acyl group, and the substituent of the alkyl group is a carboalkoxy group.) R ₈ represents a hydrogen atom or a methyl group, respectively. ) (C) Blue disperse dye: Formula (8), Formula (9) and Formula (1)
A mixture of at least two or more compounds selected from the group of compounds represented by 0).

(In the formula, one of Y ₃ and Y ₄ is NH ₂ , the other is OH, and R ₉ is a bromine atom, and n is an integer of 1 to 3, respectively.) (In the formula, R ₁₀ represents a hydroxyethyl group, a hydrogen atom or a chlorine atom, Z ₂ Z ₃ represents one of NO ₂ and the other represents OH.) (In the formula, Y ₅ represents an oxygen atom or an imino group, and R ₁₁ represents an optionally branched lower alkoxyalkyl group or a lower alkoxyalkoxyalkyl group.) 2. The disperse dye according to the above item 1. Dyeing method of hydrophobic fiber characterized by using composition 3. Yellow disperse dye of (A) described in the above item 1 and (B)
A red disperse dye and / or a blue disperse dye (C).

The present invention relates to a dye and a dye composition in which a dyed product dyed with a disperse dye is discolored and discolored when exposed to sunlight, whereas a dyed product dyed in a light to dark color is exposed to sunlight under the same conditions. It is a formulation that can obtain high lightfast dyes and dye compositions as a result even after irradiation.

In the present invention, fading refers to a case where the density of a dyed product decreases, and discoloration refers to a case where the hue of the dyed product changes.

Conventionally, the formula (2) is generally used for a yellow dye component. (Wherein, R ₂ represents the same meaning as described above). (Wherein, Z ₁ , Y ₁ and Y ₂ have the same meanings as described above). When these conventional disperse dyes are used, the lightfastness of the dyed product is excellent in the light-colored field, but the color value is inferior, and the cost is high when trying to obtain a medium-dark color hue. Becomes In addition, the dyed product dyed in a medium dark color has large fading and discoloration, and it is difficult to obtain a sufficiently satisfactory light fastness. On the other hand, the compound of the formula (1) is excellent not only in light resistance but also in curry value. What is more excellent is that the yellow component obtained by mixing the formulas (1), (2) and (3) is added to the red component of the formulas (4), (5), (6) and (7). By mixing and using the blue component dyes of formulas (8), (9) and (10), beige, brown,
This is the point that extremely excellent light fastness was obtained in a wide range from light to dark colors such as orange, orange and green. Lightfastness of a dyed product obtained by adding formulas (2) and (3) to formula (1) and using the formulas (2) and (3) instead of the components to mix the red component and the blue component in the same manner The robustness was clearly inferior. This is surprising.

This means that a combination of the compounds of the formulas (1), (2) and (3) and a red dye and / or a blue dye has almost no fading and no discoloration after irradiation treatment and obtains apparently excellent light fastness. It is thought that it is possible. Further, by using the compound as a yellow compound of the formulas (1), (2) and (3), the curry value in a medium-dark color is high, so that the amount of the dye used can be small, and the cost merit is extremely large.

In the present invention, the expressions (1), (2) and (3) are
The mixing ratio is preferably (95-30): (5-70):
(5-70), more preferably (90-60): (10-40):
(10 to 40).

The general formula (4) used as the red disperse dye compound has no limitation on the mixing ratio of the formulas (5), (6) and (7). For example, the dye of the formula (4): the dye of the formula (5): the formula (6) Dyes) = (5-30) :( 95-70) :( 95-70). Dye of Formula (4): Dye of Formula (6): Dye of Formula (7) = (5-30):
A ratio of (95-70) :( 95-70) is preferred. Similarly, the dye of the formula (4): the dye of the formula (5): the dye of the formula (6): the dye of the formula (7) = (5 to 30): (95 to 70): (95 to 70):
A ratio of (95-70) is preferred.

Further, the blue disperse dye compound comprises a disperse dye obtained by mixing formulas (8), (9) and (10).

As the blue disperse dye compound, there is no particular limitation on the mixing ratio of formula (7) and formula (8) or / and formula (9). Further, the mixing ratio of the dyes (A), (B) and (C) varies depending on the color tone to be dyed, and is not particularly limited.
The disperse dye composition of the present invention may be prepared by subjecting individual compounds to fine particle treatment separately by a conventional method and then mixing them in a desired mixing ratio or by mixing the compounds represented by the formulas (1) to (9) Is mixed in advance in a desired ratio, and the mixture is subjected to micronization treatment by a conventional method.

As described above, there is almost no discoloration after irradiation in the light fastness test, a small decrease in density after irradiation, and an extremely excellent light fastness can be obtained. Further, in the dyeing of polyester fibers, a dyed article having more excellent light resistance can be obtained by using an ultraviolet absorber in combination. The following can be mentioned as the ultraviolet absorber that can be used in the present invention.

2- (2'-hydroxyphenyl) -5-chloro-benzotriazole 2- (2'-hydroxy-4'-methylphenyl)-
5-chloro-benzotriazole 2- (2'-hydroxy-3'-tert-butyl-
5'-methylphenyl) -5-chloro-benzotriazole 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole 2- (2'-hydroxy-3'-5'-ditert-butylphenyl) benzotriazole 2- (2'-hydroxy-3 ', 5'-ditert-
Amylphenyl) benzotriazole 2,2'-hydroxy4,4'-dimethoxybenzophenone 2,2'-hydroxy-4'-methoxybenzophenone 2,2'-hydroxy4,4'-diethoxybenzophenone bis (5-benzoyl- 4-Hydroxy-2-methoxyphenyl) methane These compounds can be used alone or in combination of two or more. The amount of addition is not particularly limited, but is preferably 0.5 to 8.0% by weight based on the weight of the fibers used. These ultraviolet absorbers are subjected to a fine particle treatment by a conventional method, and then added to a dye bath as needed.

In the present invention, the dyeing method can be performed according to a method known per se. For example, in the case of dyeing polyester fiber, first, acetic acid or acetic acid and sodium acetate are added to a dyeing bath containing an amount of the disperse dye composition of the present invention and an ultraviolet absorber as needed to obtain a required concentration. The pH is adjusted to 4-7 with an aqueous pH buffer solution. If necessary, a small amount of a known sequestering agent, leveling agent, etc. is added to the dyeing bath, and then the material to be dyed is charged, and the temperature of the dyeing bath is gradually increased while stirring (for example, in one minute). 1-3 ° C), 10
At a predetermined temperature of 0 ° C or more (for example, 110 to 140 ° C), usually 30
Stain for ~ 90 minutes. This dyeing time can be shortened depending on the state of dyeing. The bath ratio is usually 1:30. The dyes obtained by subjecting the compounds of the formulas (1) to (9) to micronization are each added directly to water at the ratio described above to prepare a dyeing bath, and dyeing is performed in the same manner as described above. You can also. After the dyeing is completed, it is cooled, washed with water, reduced and washed if necessary, washed with water and dried to finish. In the case of printing, a dispersion of finely divided dye is kneaded with a known paste, printed on a cloth, dried, and then subjected to steaming or drying treatment. In this case, a benzophenone-based ultraviolet absorber is preferably used. In the present invention, examples of the hydrophobic fiber include a polyester fiber and an acetate fiber, and a preferable one is a polyester fiber.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the description, parts and% mean parts by weight and% by weight, respectively.

Micronization Example 1 The following formulas (11), (12), (13), (14), (15), (16), (17), (18), (19) and For each of the dyes (primary powders) represented by the formula (20), 15
Parts, Demol N20 parts (Kao dispersant), Demol C15 parts (Kao dispersant) and water 80 parts are separately mixed, finely divided using a sand grinder until the maximum diameter becomes 5 μm or less, and dried. Thus, fine particles of each dye were obtained.

Micronization Example 2 For the ultraviolet absorbers represented by the following formulas (21), (22), and (23), 30 parts of each of the drug substance, 20 parts of Demol N (a Kao dispersant), and 10 parts of Demol C (a dispersion of Kao) Agent) and water 4
0 parts were separately mixed, and finely divided into particles having a maximum diameter of 5 μm or less using a sand grinder to obtain each liquid fine particle-shaped ultraviolet absorber.

Micronization Example 3 5.3 parts of the dye (primary powder) represented by the formula (11), 1.6 parts of the formula (12), 1.6 parts of the formula (13), and 0.2 part of the formula (14)
Parts, 0.5 parts each of formulas (15), (16) and (17), formula (1
8), (19), (20) 1.6 parts each, Demol N 20 parts,
15 parts of Demol C and 80 parts of water are mixed to form fine particles 1
In the same manner as described above to obtain fine particles.

Micronization Example 4 4.8 parts of the dye (primary powder) represented by the formula (11), 1.0 part of the formula (12), 1.0 part of the formula (13), and the formulas (18) and (1)
9) and (20), 2.7 parts of each, 20 parts of Demol N, 15 parts of Demol C, and 80 parts of water were mixed and treated in the same manner as in Example 1 of micronization to obtain micronized products.

Example 1 The dyes of formulas (11) to (20) prepared in Example 1 for micronization (the amounts used are shown in Table 1) and 2 parts of the ultraviolet absorbent of formula (21) prepared in Example 2 for micronization were used Create a dye bath of 3,000 parts of the dye dispersion containing acetic acid and sodium acetate
The pH was adjusted to 5. Brushed polyester fiber fabric for dyeing bath 10
0 parts were charged, and the temperature was raised from 60 ° C at a rate of 1 ° C every minute to 130
Stained at 60 ° C for 60 minutes, reduced, washed and dried in the usual manner. The obtained dyed product was beige.

As Comparative Example 1, the compounds of Formula (11), Formula (13), Formula (14) and Formula (20) were omitted, and the compound of Formula (12) was dyed in the same manner as described above to obtain a dyed product. .

Further, as Comparative Example 2, Expressions (11), (12), and (14)
The compound of the formula (20) was omitted, and the compound of the formula (20) was dyed in the same manner as described above to obtain a dyed product.

Further, as Comparative Example 3, a dyed product was obtained by omitting the compounds of the formulas (11), (14) and (20) and using the compounds of the formulas (12) and (13) in the same manner as described above. Was.

The amount of the dye used was adjusted so that the dyeing density of the dyed product in the example and the comparative example became the same.

Examples 2 to 4 The dyes of the formulas (11) to (20) prepared in the micronization example 1 (the amounts used are shown in Tables 2 to 4) and the dyes of the formula (21) prepared in the micronization example 2 A polyester cloth was dyed in the same manner as in Example 1 using an ultraviolet absorbent. In Comparative Examples 4 to 12, the compounds of the formulas (11), (14) and (20) were omitted, and the dyes were similarly dyed using the compounds of the formulas (12) and (13).
(The dyes used and the amounts used are shown in Tables 2 to 4.) Adjustments were made so that the dyeing densities of the dyed materials in the examples and the comparative examples matched.

Examples 1, 2, 3, 4 as shown in Tables 1, 2, 3, and 4
Each of them had better light fastness than the comparative examples. In particular, it was remarkably excellent in a medium dark color.

The same concentration was obtained at about 50% of the amount of the dye used in the comparative example.

[Test method for light fastness] A dyed product lined with urethane foam was irradiated with a fade meter (black panel temperature 83 ° C ± 3 ° C, 300 hours) using a carbon arc lamp to determine the discoloration of the irradiated part according to JIS L-0804. Was evaluated by the gray scale for discoloration.

Example 5 A polyester cloth was dyed in the same manner as in Example 1 except that the finely divided ultraviolet absorber of the formula (22) was used instead of the finely divided ultraviolet absorber of the formula (21) to obtain a beige dyed product. Was.

The light fastness of this dyed product was excellent as in Example 1.

Example 6 A polyester cloth was dyed in the same manner as in Example 1 except that, in place of the formula (21), 4 parts of the finely divided ultraviolet absorbent of the formula (23) were used, to obtain a beige dyed product.

 The lightfastness of this dyed product was excellent.

Example 7 A polyester cloth was dyed in the same manner as in Example 1 without using an ultraviolet absorbent to obtain a beige dyed product. The lightfastness of this dyed product was excellent.

Example 8 Formulas (11), (12), and (1) prepared in Example 1 for micronization were prepared.
3) Contains the dyes of formulas (14), (15), (16), and (17) (the amounts used are shown in Table 5) and 2 parts of a finely divided ultraviolet absorber of formula (21) A dye bath of 3000 parts of the dye dispersion was prepared, and a polyester cloth was dyed in the same manner as in Example 1. The dyed product had a dark orange color and had excellent light fastness.

As Comparative Example 13, the compounds of the formulas (11) and (14) were omitted, dyed in the same manner as above, and the light fastness was compared. The results are shown in Table-5. Example 8 was excellent in light resistance. Further, the dyeing concentrations of both dyed materials were adjusted to be equal, but the amount of dye used in Example 8 was about the same as that of Comparative Example 13.
The economic effect was remarkable, as low as 40%.

Example 9 Microparticulation 30 containing 0.283 parts of the finely divided dye prepared in Example 3 and 2 parts of the finely divided ultraviolet absorbent of the formula (21).
A dye bath of the dye dispersion of 00 parts was prepared, and a polyester cloth was dyed in the same manner as in Example 1. The dyed product exhibited a beige color, and its light fastness was equivalent to that of Example 1 and was excellent.

Example 10 Micronization 3000 containing 2.2 parts of the micronized dye prepared in Example 4 and 2 parts of the micronized UV absorber of the formula (21)
In the same manner as in Example 1, a polyester cloth was dyed. The dyed product exhibited a green color, and its light fastness was excellent.

On the other hand, Table 6 shows Comparative Example 14 in which the compound of the formula (11) was omitted and adjusted so that the dyeing concentration of the dyed product became equivalent. As a result, the present invention was excellent not only in light fastness but also in economy.

Example 11 Formulas (11), (12), and (1) prepared in Example 1 for micronization were prepared.
3), 0.35 parts, 0.05 parts, and 0.3 parts of the finely divided dyes of Formula (15), Formula (16), Formula (18), Formula (19), and Formula (20), respectively.
A dye bath of 3,000 parts of a dye dispersion containing 05 parts, 0.06 parts, 0.06 parts, 0.2 parts, 0.2 parts, and 0.2 parts was prepared, and a polyester cloth was dyed in the same manner as in Example 1. The dyed product was brown, and its light fastness was excellent.

Example 12 Formulas (11), (12), and (1) prepared in Example 1 of micronization were prepared.
3), Equation (14), Equation (15), Equation (16), Equation (17), Equation (1
8) and 1.15 parts of the finely divided dyes of the formula (19),
0.2 parts, 0.2 parts, 0.15 parts, 0.5 parts, 0.5 parts, 0.5 parts, 0.6 parts,
Create a dye bath of 3000 parts of the dye dispersion containing 0.6 parts,
A polyester cloth was dyed in the same manner as in Example 1. The dyed product exhibited a deep reddish color, and its light fastness was excellent.

Examples 13 to 16 Dyeing was carried out in the same manner as in Example 2 except that the dyes shown in Table 7 were used instead of the dyes of the formula (11) in Example 2 to obtain brown (medium) dyed products. Was. When the light fastness was tested, it showed excellent light fastness as shown in Table-7.

Examples 17 to 19 Instead of the dye of the formula (12) in Example 2, the dye shown in Table 8 was used, and the other steps were followed to dye in the same manner as in Example 2 to obtain a brown (medium color) dyed product. Was. When the light fastness was tested, it was found to have excellent light fastness as shown in Table-8.

Examples 20 to 25 In place of the dye of the formula (13) in Example 2, the dyes shown in Table 9 were used and dyed in the same manner as in Example 2 to obtain a brown (medium color) dyed product. . When the light fastness was tested, it showed excellent light fastness as shown in Table-9.

Examples 26 to 29 Dyeing was performed in the same manner as in Example 2 except that the dyes shown in Table 10 were used instead of the dyes of the formula (14) in Example 2 to obtain brown (medium) dyed products. Was. When the light fastness was tested, it had excellent light fastness as shown in Table-10.

Examples 30 to 41 Dyeing was carried out in the same manner as in Example 2 except that the dyes shown in Table 11 were used instead of the dye of the formula (15) in Example 2 to obtain brown (medium color) dyed products. . When the light fastness was tested, it had excellent light fastness as shown in Table-11.

Example 42 A brown (medium) dyed product was obtained by dyeing in the same manner as in Example 2 except that the dye shown in Table 12 was used instead of the dye of the formula (18) in Example 2. When the light fastness was tested, it had excellent light fastness as shown in Table-12.

Examples 43 to 46 Dyeing was carried out in the same manner as in Example 2 except that the dyes shown in Table 13 were used instead of the dyes of the formula (19) in Example 2 to obtain brown (medium color) dyed products. . When the light fastness was tested, it had excellent light fastness as shown in Table-13.

Examples 47 to 49 Brown (medium) dyed products were obtained in the same manner as in Example 2 except that the dyes shown in Table 14 were used instead of the dyes of the formula (20) in Example 2. . When the light fastness was tested, it had excellent light fastness as shown in Table-14.

Effect of the Invention It is possible to obtain a dyed product having high light fastness in a wide range from light to dark, such as beige, brown, red, orange, and green.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09B 67/22 C09B 29/40 C09B 5/02-5/22 C09B 57/00 C09B 29/085 C09B 1 / 50-1/54 CA (STN)

Claims (3)

(57) [Claims] A disperse dye composition comprising the following (A) a yellow disperse dye and (B) a red disperse dye or / and (C) a blue disperse dye. (A) Yellow disperse dye: a mixture of compounds represented by formulas (1), (2) and (3). (In the formula, X ₁ and X ₂ each independently represent a hydrogen atom, a chlorine atom or a bromine atom, and R ₁ represents a lower alkyl group or an allyl group.) (In the formula, R ₂ represents an alkyl (C ₁ -C ₄ ) or phenyl group.) (In the formula, Z ₁ , Y ₁ , and Y ₂ each independently represent a hydrogen atom or a halogen atom, and ring A represents a benzene ring or a naphthalene ring that may be substituted with a carboxylic ester group.) ) Red disperse dye: a mixture of at least two or more compounds selected from the group of compounds represented by formulas (4), (5), (6) and (7). (Wherein, R ₃ is a methyl group or an ethyl group, R ₄ is a cyanoethyl group, an acetoxyethyl group, R ₅ is an acetoxyethyl group, a lower alkoxy (C ₁ -C ₄ ) alkyl group or a lower alkoxy (C ₁ -C 4 ₄ ) represents an ethoxyethyl group.) (In the formula, R ₆ represents an alkyl (C _1-6 ) group substituted with a hydroxyl group, a phenoxy group, or a phenyl group.) (In the formula, R ₇ represents a hydrogen atom, a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted alkyl group, an alkyl-substituted aminosulfonyl group, an alkoxyalkyl-substituted aminosulfonyl group, or an acyloxy group.
(In the above, the substituent of the alkoxy group is a carboalkoxy group,
Or an acyl group, and the substituent of the alkyl group is a carboalkoxy group. ) R ₈ represents a hydrogen atom or a methyl group. ) (C) Blue disperse dye: Formula (8), Formula (9) and Formula (1)
A mixture of at least two or more compounds selected from the group of compounds represented by 0). (In the formula, one of Y ₃ and Y ₄ is NH _{2, the} other is OH, R ₉ is a bromine atom, and n is an integer of 1 to 3, respectively.) (In the formula, R ₁₀ represents a hydroxyethyl group, a hydrogen atom or a chlorine atom, one of Z ₂ and Z ₃ represents NO ₂ , and the other represents OH.) (In the formula, Y ₅ represents an oxygen atom or an imino group, and R ₁₁ represents an optionally branched lower alkoxyalkyl group or a lower alkoxyalkoxyalkyl group.) 2. A method for dyeing a hydrophobic fiber, comprising using the disperse dye composition according to claim 1. 3. A hydrophobic fiber comprising the yellow disperse dye (A) and the red disperse dye (B) and / or the blue disperse dye (C) according to claim 1. Dyeing method