JPH0841372A - Dye composition and dyeing method using the same - Google Patents

Abstract

PURPOSE:To obtain a dye compsn. which dyes fibers such as polyester, nylon, acetate, silk, and wool fibers in turkish blue to emerald green by compounding a specific copper phthalocyanine colorant with a dispersant. CONSTITUTION:This compsn. contains as the main components a copper phthalocyanine colorant of the formula [wherein Cu-Pc is a copper phthalocyanine residue; R is alkoxy or (alkoxyalkoxy-substd.) alky; Z<+> is an H io, an alkali metal ion, or an ammonium ion (NH4<+> or <+>NH3-R); n is 2-4; and m is 0-1] having a particle size of 2mum or lower and an anionic dispersant pref. in a wt. ratio to the colorant of 0.5-5. Emerald green is obtd. by incorporating a fluorescent yellow disperse dye pref. in a wt. ratio to the colorant of 0.01-10 into the compsn. Exhaustion dyeing is pref. for dyeing with the compsn., and carrier dyeing is esp. pref. for dyeing polyester fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper phthalocyanine dye composition capable of dyeing a textile product in a beautiful turquoise blue to emerald green color and a dyeing method using the same. The present invention relates to a dye composition suitable for dyeing synthetic fibers, especially polyester fibers, in a clear turquoise blue color with a good dyeing ratio and a dyeing method using the same. The present invention also relates to a dye composition and a dyeing method capable of advantageously dyeing polyester fibers which are difficult to dye, for example, ultrafine fibers, heterogeneous shrinkage mixed fibers and other processed fibers.

[0002]

2. Description of the Related Art Conventionally, it has been very difficult to dye synthetic fibers, particularly polyester fibers, in a fast and beautiful turquoise blue to emerald green color. In fact, we are not aware of the beautiful turquoise to emerald green dyed polyester fibers. JP-A-53-24489 describes a method of mainly dyeing cellulose fibers using an aqueous preparation containing a specific copper phthalocyanine dye, and at the same time, dyeing polyester fibers well. However, in our test, not only the polyester fiber can not be dyed deeply, but also uniform dyeing cannot be easily obtained.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a dye composition for dyeing synthetic fibers such as polyester and nylon, semi-synthetic fibers such as acetate fibers, and other nitrogen-containing dyes such as silk and wool into turquoise jade blue to emerald green. . In particular, it is an object of the present invention to develop a dye composition capable of dyeing processed yarns such as ultrafine fibers which are difficult to dye, high-speed spun fibers, and different-shrink mixed fiber into turquoise blue to emerald green. Another object of the present invention is to develop a method for dyeing polyester fibers to a fast turquoise blue to emerald green.

[0004]

The present invention provides the following general formula [I] having a particle size of 2 μm or less.

[0005]

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[In the formula, Cu-Pc represents a (m + n) -valent residue of copper phthalocyanine, R represents an alkoxy group or an alkyl group which may be substituted with an alkoxyalkoxy group, and Z ⁺ represents a hydrogen ion or an alkali. Metal ions,
NH ₄ ⁺ or ⁺ NH ₃ —R (wherein R has the same meaning as above) represents an ammonium ion, n represents a number of 2 to 4, and m represents a number of 0 to 1. ] A dye composition comprising a copper phthalocyanine dye and an anionic dispersant as main components and a method for dyeing synthetic fibers using the same are summarized.

Hereinafter, the present invention will be described in detail. In the general formula [I], examples of the alkoxy group represented by R or the alkyl group which may be substituted with an alkoxyalkoxy group include a C _{1 to} C ₁₂ linear alkyl group. Specifically, a methyl group, an ethyl group, an n-propyl group,
iso-propyl group, n-butyl group, iso-butyl group, amyl group, sec-hexyl group, 2-ethylhexyl group, n-octyl group, iso-nonyl group, n-decanyl group, n-undecanyl group, sec- Undecanyl group,
Examples thereof include n-dodecanyl group and sec-dodecanyl group.

As the alkoxy group or the alkyl group substituted with an alkoxyalkoxy group, methoxyethyl group, methoxypropyl group, methoxyhexyl group, ethoxyethyl group, ethoxyoctyl group, propoxyethyl group, isopropoxyethyl group, butoxyethyl group. Group, butoxybutyl group, isobutoxypropyl group, butoxypropyl group, amyloxypropyl group, amyloxybutoxy group, hexyloxypropyl group, octyloxyethyl group, 2'-ethylhexyloxypropyl group, 2'-
Examples thereof include an ethylhexyloxybutyl group, a methoxyethoxypropyl group, an ethoxyethoxypropyl group, a methoxyethoxyamyl group, a propoxypropoxypropyl group and a butoxyethylpropyl group. An alkoxyalkyl group having 4 to 12 carbon atoms, particularly preferably 6 to 10 carbon atoms, or an alkoxyalkoxyalkyl group is preferable.

The number of sulfonamide groups represented by n in the general formula [I] is 2.3 to 3.2 on average, preferably 2.5 to 3.0. And m is 0.5 on average
The following is preferably 0.3 or less. Examples of the alkali metal ion represented by Z include lithium ion, sodium ion and potassium ion.

As the anionic dispersant, lignin sulfonic acid, 2-naphthalene sulfonic acid-formaldehyde condensation product salt, phenol or cresol sulfonic acid-
A salt of a condensation product of urea-formaldehyde is mentioned, and a ligninsulfonic acid-based dispersant is particularly preferable. The amount of the anionic dispersant is preferably 0.5 times or more, particularly preferably 1.0 times or more by weight of the copper phthalocyanine dye represented by the general formula [I]. There is no particular upper limit of the amount added, but a triple amount is sufficient, and addition of 5 times or more does not change the effect.

The dye composition of the present invention is manufactured as follows. A copper phthalocyanine dye and an anionic dispersant in an amount of 0.5 times by weight or more of the copper phthalocyanine dye are suspended in water and finely ground in a sand mill or a pearl mill until the particle size becomes 2 μm, particularly preferably 1 μm. When the particle size is larger than 2 μm, the dyeing rate is remarkably reduced, which is not preferable. To obtain a powdery composition, water is distilled off from the finely pulverized water slurry liquid using a spray dryer.

In order to obtain an emerald green color in the present invention, the fluorescent yellow disperse dye compounded with the copper phthalocyanine dye represented by the general formula [I] is, for example, one of the following general formulas [II] to [VII]. Included are the dyes shown. However, it is not particularly limited to these dyes.

[0013]

[Chemical 3]

(In the formula, R ² and R ³ represent a C ₁ -C ₃ alkyl group or an allyl group, and R ³ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group.

[0015]

[Chemical 4]

(In the formula, R ² , R ³ and R ⁴ have the same meanings as described above.)

[0017]

Embedded image

(In the formula, R ² , R ³ and R ⁴ have the same meanings as described above.)

[0019]

[Chemical 6]

(In the formula, R ² , R ³ and R ⁴ have the same meanings as described above.)

[0021]

[Chemical 7]

(Wherein R ⁴ has the same meaning as described above,
R ⁵ represents a C ₂ -C ₃ alkylene group, and R ⁶ represents C ₁
It represents an alkyl group of -C _3. )

[0023]

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(In the formula, R ⁷ represents a C ₁ -C ₃ alkoxy group, R ⁸ represents a C ₁ -C ₄ alkyl group which may be substituted with a hydroxyl group, and X represents an oxygen atom or a sulfur atom. The ratio of the yellow disperse dye having fluorescence to be added is preferably 0.01 to 10 times by weight, particularly preferably 0.2 to 2 times by weight of the copper phthalocyanine dye represented by the general formula [I].

The fibers to be dyed with the dye composition of the present invention include polyester fibers, acetate fibers, other polyamide fibers, polyurethane fibers, nitrogen-containing fibers such as silk and wool, and particularly ordinary polyethylene terephthalate and poly Butylene terephthalate, polyester fiber made of polycondensation product of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, or mixed fiber of fibers such as cotton, wool, rayon, polyamide, polyurethane and the above polyester fiber Products include.

As the polyester fiber, it is possible to dye from 1 to 5 denier regular fiber called regular fiber to 1 to 0.1 denier fine denier fiber. Further, as a method for dyeing these fibers, exhaust dyeing method, continuous dyeing method,
The printing method is applied, but the exhaust dyeing method is particularly preferable.

Further, in the exhaust dyeing method, various leveling agents or ultraviolet absorbers may be used in combination. In the case of exhaust dyeing, the dyeing conditions include a dyeing temperature of 125 to 140 ° C. and a dyeing time of 30.
Normal conditions of ~ 120 minutes are taken. Carrier dyeing is preferred as a dyeing method for dyeing a dye composition mainly composed of a copper phthalocyanine dye and an anionic dispersant in the present invention and a green dye composition in which a yellow disperse dye is added to the dye composition, especially polyester fiber. Bring results.

Carriers used include C _{5 to} C
Mention may be made of ₁₅ N-alkylphthalimides, C _{1 to} C ₅ benzoates, C _{1 to} C ₃ dialkyl terephthalates, C ₁ or C ₂ alkylnaphthalenes, di- or trichlorobenzenes. In the present invention, the amount of the above-mentioned carrier added at the time of dyeing is generally preferably 0.1 to 10 g per liter of dyeing bath. If 0.1g or less,
There is no effect of deep-colored dyeing, and if it is 10 g or more, the dyeing rate decreases. Particularly preferably, it is about 1 to 5 g. These carriers can be added as is,
It may also be used in the form of an aqueous emulsion.

Among the above carriers, especially C _{5 to} C ₁₅ N
-Alkylphthalimides are particularly suitable. Upon dyeing, by adding an amino acid or a derivative of an amino acid together with a carrier, decomposition of the copper phthalocyanine dye is suppressed and advantageous dyeing is performed. Examples of the amino acids used include neutral amino acids, for example, glycine, alanine, aminobutyric acid, aminocaproic acid, etc., acidic amino acids, such as aspartic acid, glutamic acid, etc. and basic amino acids, such as lysine, arginine, etc., among them, glycine, Alanine and glutamic acid are preferred.

[0030] The amino acid alkyl amino groups C ₁ -C _4, hydroxyalkyl group C ₁ ~C _4, C ₁ ~
It may be substituted with a C ₄ alkoxy C ₁ -C ₄ alkyl group. The amount of these amino acids and their derivatives to be used is usually 0.02 to 2.0 g / l, preferably 0.2 to 2.0 in the dye bath from the viewpoint of the effect of preventing the decomposition of the copper phthalocyanine dye.
It is in the range of 1.0 g / l. In addition to this, a usual dyeing aid can be added if necessary.

[0031]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1

[0032]

[Chemical 9]

10 g of copper phthalocyanine dye represented by and lignin sulfonic acid type anionic dispersant Ultrazin
e NA (registered trademark) (Norway BORREGAAR
DIM company) 30g, 60g water slurry liquid AIM
EX CO. Six-cylinder sand grinder made by LTD (MO
The average particle size was ground to 1 μm with DEL 6TSG-1 / 4) to prepare an aqueous paste solution. Water was distilled off from this with a spray dryer to obtain a powder composition containing 25% by weight of Cu-Pc dye.

On the other hand, polyester different shrinkage mixed woven cloth (Agante (registered trademark) 10 g manufactured by Teijin Ltd. was put in a pot made of 300 C stainless steel, and then the powder dye composition 0.
2 g, C _{9 to} C ₁₆ mixed alkylphthalimide 0.4
g, 0.1 g of glycine, and 100 cc of water, and a dye liquor adjusted to pH 8 with diluted sodium hydroxide was added.
Next, the temperature was raised to 135 ° C over 45 minutes, and at this temperature 60
After dyeing for a minute, reduction washing was performed under the following conditions. That is Na
OH 2 g / l, hydrosulfite 2 g / l, Hostapearl SC-LFB (registered trademark) (manufactured by Hoechst Japan) 1 g / l, bath ratio 1:30, 80 ° C., 10
It was washed for a minute. Then, the product was washed with water and dried to obtain a very clear turquoise blue dyed product. This vividness is based on the anthraquinone type clear turquoise blue dye C.I. I. Disperse
It was surprisingly superior to the dyed fabric using B-60.

Comparative Example 1 Dyeing was carried out in the same manner as in Example 1 except that N-alkylphthalimide and glycine were not used, the pH of the dyeing bath was adjusted to 8.0. Comparative Example 2 Using the same N-alkylphthalimide as in Example 1,
The pH of the dyebath was adjusted to 5.0, and all other dyeing was carried out according to Example 1.

Comparative Example 3 0.2 g of the powder composition prepared in Example 1 was used in Japanese Patent Laid-Open No. 53-2.
Dyeing was carried out according to Example 1 of the present application, except that 0.5 g of the 10% aqueous dye preparation described in Example 1 (C) of 4489 was used.

With respect to Example 1 and Comparative Examples 1 to 3, the dyeing rate, levelness and stain degree of the dyeing container were evaluated. The evaluation method is shown below. Dyeing rate: The dyeing rate on the dyed cloth is expressed as a dyeing utilization rate. Dimethylformamide was used as the dye dyed on the dyed cloth, and the mixture was completely extracted at 130 ° C. The dyeing ratio of Example 1 was set to 100 (standard), and the comparison value was calculated as the dyeing ratio. Level dyeability: It was visually evaluated whether the dyed fabric was dyed uniformly.

◯: Good leveling property x: Poor leveling property (no value as a product) Contamination degree of dyeing container: Contamination degree of copper phthalocyanine dye in a stainless container was visually evaluated and the contamination degree was evaluated. It is not polluted. Δ: Somewhat contaminated. X: Remarkably contaminated. These results are summarized in Table-1.

[0039]

[Table 1]

Example 2 0.4 g of a dye composition containing 25% by weight of the copper phthalocyanine dye described in Example 1, 25% by weight of a fluorescent yellow dye represented by the following structural formula [a], and a lignin-based anionic dispersant. Dyeing was carried out according to the procedure described in Example 1 with 0.8 g of a green composition consisting of 0.4 g of a dye composition consisting of 75% by weight.

[0041]

[Chemical 10]

As a result, a green dyeing product having good levelness and remarkably excellent sharpness was obtained. Example 3 In Example 1, the polyester fiber was replaced with polyester /
Dyeing was performed according to Example 1 except that the nylon (80/20) was replaced with 10 g. As a result, a turquoise-blue dyed product having surprisingly excellent sharpness and good levelness was obtained.

Example 4 In Example 1, the polyester fiber was replaced with polyester /
Dyeing was performed according to Example 1 except that triacetate (60/40) was replaced with 10 g. As a result, a turquoise-blue dyed product having surprisingly excellent sharpness and good levelness was obtained. Examples 5 and 6 The carrier and amino acid used in Example 1 were (i) n-propylbenzoic acid ester and glutamic acid, or (ii) di-ethylterephthaloic acid ester and N, N-.
Staining was performed according to Example 1 except that dihydroxyethylglycine was replaced. As a result, a vivid turquoise blue dyeing having good dyeability and good levelness was obtained.

Examples 7 to 14 Dyeing was carried out according to the method described in Example 1 except that the copper phthalocyanine dye used in Example 1 was replaced with the copper phthalocyanine dye described in Table 2. As a result, a remarkably vivid turquoise blue dyeing product having a good dyeing rate and excellent levelness was obtained.

[0045]

[Table 2]

Examples 15-21 All Example 2 except that the fluorescent yellow dyes used in Example 2 were replaced by the fluorescent yellow dyes listed in Table-3.
Staining was performed according to the method described. As a result, a remarkably vivid green dyeing product having a good dyeing ratio and excellent levelness was obtained.

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

Industrial Applicability According to the present invention, it is possible to give a beautiful and clear turquoise blue dyeing to synthetic fibers, nitrogen-containing fibers, and especially polyester fibers. Further, by using a fluorescent yellow disperse dye together, emerald green dyeing can be performed. In addition, the obtained Turquoise blue to emerald green dyeing is durable and has excellent leveling properties, and it is a beautiful Turkish jade blue to emerald green that has not been easily found in ultra-fine polyester fibers or polyester-processed fibers that are difficult to dye. It can be dyed.

Claims (6)

[Claims] 1. The following general formula [I] having a particle size of 2 μm or less: [In the formula, Cu-Pc represents a (m + n) -valent residue of copper phthalocyanine, R represents an alkoxy group or an alkyl group which may be substituted with an alkoxyalkoxy group, and Z
⁺ Is hydrogen ion, alkali metal ion, NH ₄ ⁺ , or
⁺ NH ₃ —R (wherein R has the same meaning as described above), an ammonium ion, n is a number of 2 to 4, and m is a number of 0 to 1. ] The dye composition which has a copper phthalocyanine dye shown by these, and an anionic dispersant as a main component. 2. The dye composition according to claim 1, wherein the anionic dispersant is present in an amount of 0.5 to 5 times the weight of the copper phthalone dye. 3. 0.01 per weight of copper phthalocyanine dye
The dye composition according to claim 1 or 2, wherein a yellow disperse dye having a fluorescence amount of about 10 times is blended. 4. A method for dyeing a polyester fiber, which comprises using the dye composition according to claim 1. 5. 125-140 ° C. in the presence of a carrier
The dyeing method according to claim 4, wherein the dyeing is exhaustion dyeing. 6. A pH of 9 to 7, 125 ° C. to 140 ° C. in the presence of a carrier and amino acids and / or amino acid derivatives.
The dyeing method according to claim 4, wherein the dyeing is performed with.