JPH1072787A - Vegetable dyeing of polyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the calm color expression of a color tone equal to that of natural fibers without carrying out the metallic mordanting treatment by dyeing polyester fibers with a vegetable dye under specific dyeing conditions. SOLUTION: The vegetable dyeing is carried out under conditions of a pH of a dye bath within the range of 2-6 and a dyeing temperature of (glass transition temperature Tg +10 deg.C) to 160 deg.C to provide a color tone equal to that of natural fibers when dyeing polyethylene terephthalate fibers, polyester fibers, etc., copolymerized with adipic acid, etc., and dyeable with a disperse dye under atmospheric pressure with a vegetable dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing plant fibers with a plant dye, and more particularly, to a method for dyeing polyester fibers with a plant dye dye without performing metal mordant treatment under specific dyeing conditions. The present invention relates to a method for plant dyeing of polyester fiber.

[0002]

2. Description of the Related Art In recent years, as the ecology trend, which is gentle to people and nature, has been increasing, traditional Japanese plant dyes have been reexamined due to the calm color tone and natural taste of natural pigments. Conventionally, plant dyeing has been limited to application to natural fibers such as silk, cotton, and wool, and has not been applied to synthetic fibers such as polyester fibers, but recently, synthetic fibers such as polyester fibers have been used. Attempts have also been made to dye plants and plants. For example, a cation-dyeable polyester fiber obtained by copolymerizing 5-sulfoisophthalate is converted into a salt of at least one metal selected from the group consisting of iron, copper and aluminum. And dyeing with a vegetable dye (Japanese Patent Application Laid-Open No. 7-40881) or a method of dyeing a regular polyester fiber with a natural dye at a high temperature of 130 ° C. after mordant treatment [Fibre Society of Japan Proceedings G-174 (199
5)] has been proposed.

[0003] However, in addition to conventional plant dyeing of natural fibers, metal mordant treatment is indispensable in plant dyeing of the synthetic fibers, and wastewater is regulated by the Water Pollution Control Law, the Poisonous Substances Control Law, and the like. The use of harmful compounds such as iron, copper, tin, titanium and aluminum is not necessarily an ecological dyeing method that is friendly to humans and the earth.

[0004]

DISCLOSURE OF THE INVENTION The present invention is widely and widely used by using natural dyes such as plant dyes and the like, and can be dyed in the same shade as natural fibers. Provided is a method for dyeing plant fibers of polyester fibers, which can obtain plant fiber-dyed polyester fibers capable of expressing colors such as a calm color tone and natural taste by natural dyes such as plant dyes without performing metal mordant treatment. With the goal.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that, when dyeing a polyester fiber with a plant dye, under specific conditions,
Even without performing the metal mordant treatment, it can be dyed to the same concentration as in the case of performing the metal mordant treatment, and also in the dyeing fastness, a level not inferior to that obtained by performing the metal mordant treatment is obtained. I learned. And, as a result of various examinations of the characteristics of the obtained dyed cloth, the characteristics of the spectral reflectance curve are different from those of the natural or synthetic fiber plant-dyed products of the conventional metal mordant treatment, the curve is more gentle, and therefore softer for humans. I clarified that it gives a color tone. The present invention has been completed as a result of repeated and repeated studies based on the above findings.

That is, in the present invention, when dyeing a polyester fiber with a plant dye, the dyeing temperature is set to (Tg + 1).
0) to 160 ° C. (where Tg is the glass transition point of the polyester) and a dyeing bath with a pH of 2 to 6, which is a method for plant dyeing polyester fibers.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The polyester constituting the polyester fiber of the present invention contains terephthalic acid as a main acid component and is selected from at least one glycol, preferably ethylene glycol, trimethylene glycol and tetramethylene glycol. The main object is a polyester containing at least one alkylene glycol as a main glycol component. Further, a polyester in which a part of the terephthalic acid component is replaced by another bifunctional carboxylic acid component, and / or a polyester in which a part of the glycol component is replaced by a diol component other than the above glycol component. You may.

The bifunctional carboxylic acids other than terephthalic acid used herein include, for example, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid , 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, etc.
Functional carboxylic acids can be mentioned.

The diol compounds other than the above-mentioned glycols include, for example, cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A,
Examples thereof include aliphatic, alicyclic, and aromatic diol compounds such as bisphenol S, and polyoxyalkylene glycol.

The above polyester may be synthesized by any method. For example, if polyethylene terephthalate is described, usually, terephthalic acid and ethylene glycol are directly subjected to an esterification reaction, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is subjected to a transesterification reaction with ethylene glycol, or A first stage reaction of reacting terephthalic acid with ethylene oxide to form a glycol ester of terephthalic acid and / or a low polymer thereof; and heating the reaction product of the first stage under reduced pressure to obtain a desired product. Can be produced by a second-stage reaction in which a polycondensation reaction is carried out until the degree of polymerization is reached.

The above-mentioned polyester may contain a matting agent, an ultraviolet absorber, an anti-acetylation agent and the like, which is rather preferable from the viewpoint of dyeing fastness such as light fastness. is there. In addition, additives such as a catalyst, a stabilizer, an anti-coloring agent, a flame retardant, a fluorescent brightener, an antistatic agent, a heat-resistant agent, a colorant, and inorganic particles may be contained as necessary.

The polyester fiber of the present invention may be a solid fiber having no hollow portion, a hollow fiber having a hollow portion, and the outer shape and the shape of the hollow portion in the cross section of the polyester fiber. May be circular or irregular. Further, the fineness may be arbitrary. Further, fine pores may be present on the surface of the polyester fiber, and this is rather preferable from the viewpoint of a gentle color tone. As a method of forming these fine pores on the fiber surface, for example,
44064, JP-B-61-31231, and JP-B-60-43858 can be exemplified.

Further, as the polyester fiber of the present invention, a polyester fiber of a normal pressure disperse dye dyeable type can be used.
Since the dyeing can be performed to a certain degree, the decomposition of the plant dye is reduced, which is rather preferable. As the normal pressure disperse dye dyeable polyester fiber, for example, adipic acid or polyoxyethylene glycol is used in an amount of 0.1 to 20.
Mol% copolymerized polyester, high-speed spinning (for example,
(Spinning at a spinning speed of 3,000 to 6,000 m / min).

The fiber properties of the above polyester fibers are not particularly limited, and those of the same level as ordinary polyester fibers are sufficient. For example, the elongation is 15 to 40.
% Of a normal drawn yarn, more preferably an elongation of 40 to 80%.
% High-speed spun products, and the strength level is 2.
It is preferably at least 5 g / denier, more preferably 3.
0 g / denier or more. The shrinkage rate is 2
0% or less is preferable, and 5 to 15% is more preferable. Furthermore, when bulkiness is required, bulkiness can be imparted by false twisting, and after forming staple fibers, spun and used as a spun yarn.

The polyester fiber may be in the form of a yarn such as the multifilament or spun yarn, but is preferably a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric. The structure and form of the woven or knitted fabric need not be specially devised.For example, in the woven structure, plain weave, satin weave, twill weave, etc. Can be used. In addition, various types of interwoven fabrics and interwoven fabrics can also be used as the woven or knitted fabric of the present invention.

The metal mordant treatment referred to in the present invention includes a pre-mordant method in which treatment with a metal mordant is performed and then plant dyeing is performed, and a post-mordant method in which the plant is dyed and treated with a metal mordant. As the metal mordant, water-soluble metal salts are usually preferably used, and among them, sulfate, chloride, nitrate of at least one metal selected from the group consisting of copper, iron, aluminum, titanium, tin and chromium Inorganic salts, such as
Organic carboxylate such as acetate and succinate, and water-soluble salt such as complex salt such as ethylenediaminetetraacetic acid complex are particularly preferably used. The temperature and time for performing the metal mordant treatment need not be particularly limited. For example, the temperature condition is appropriately selected in the range of room temperature to 160 ° C., but many plant dyes are vulnerable to heat and oxidation. Therefore, the reaction is usually carried out in the range of room temperature to 100 ° C. In the present invention, it is not necessary to perform the above-described metal mordant treatment. When the metal mordant treatment is performed, the spectral reflectance curve of the obtained plant dyeing cloth becomes sharp, and a soft and human-friendly color tone cannot be obtained. In addition, since it uses harmful metal compounds regulated by the Water Pollution Control Law and the Poisonous Toxic Substances Control Law, it is not friendly to people or the earth and is not ecological.

As the plant dyes used in the present invention, natural dyes obtained from the natural world such as plants, animals and microorganisms, such as plant dyes for plant dyes and natural dyes for food, are used without any limitation. Among them, as plant dyes for plant dyeing, for example, safflower, madder, purple navy blue, indigo,
Yellowfin, turmeric, karyas, gardenia, asen, kunugi,
Examples include cloves, plum wheels, plums, gobishi, rockwood, and the like, as well as general flowers, vegetables, fruits, and the like, specifically, mandarin orange and onion juice. Examples of natural pigments for food include “List of Food Additives Other than Chemical Synthetic Products, First Edition,” edited by the Food Chemistry Division of the Ministry of Health and Welfare, Ministry of Health and Welfare [Social Health Publishing, Tokyo (198
And 9) natural dyes described in 9)].

Specific examples of the above natural pigments for food include annatto pigment, paprika pigment, gardenia yellow pigment, carrot carotene pigment, cochineal pigment, lac pigment, madder pigment, red cabbage pigment, perilla pigment, purple corn pigment, elderberry Pigment, boinsen berry pigment, grape skin pigment, grape juice pigment, hibiscus pigment, purple potato pigment, safflower pigment, kouryan pigment, onion pigment,
Examples include cocoa pigment, rosewood pigment, tamarind pigment, spirulina blue pigment, chlorophyll, red beet pigment, red malt pigment, red malt yellow pigment, turmeric pigment, gardenia blue pigment and the like. The above plant dyes can be used alone or in combination of two or more.

The amount of the plant dye used may be arbitrarily selected as desired, but is usually 10 to 200% by weight, preferably 50 to 150% by weight, based on the polyester fiber. The bath ratio of this plant dye is usually 1: 1:
20 to 1: 200, preferably 1: 100 to 1: 200
It is.

In the dyeing method of the present invention, when the polyester fiber is dyed with the plant dye, when the glass transition point of the polyester is defined as Tg, (Tg + 1
0) to 160 ° C., the pH of the dyeing bath must be in the range of 2 to 6. At this time, it is not necessary to perform a metal mordant treatment. If the dyeing temperature is too low, the dyeing will be insufficient and no luminous density will be obtained, while if this temperature is too high, the plant dye will be decomposed. The dyeing temperature is preferably from 95 to 135C, more preferably from 98 to 130C. Further, the pH of the dyeing bath is in the range of 2 to 6 as described above. If the pH is out of this range, the amount of dyeing is extremely reduced, and the luminous density cannot be obtained. The pH of the dye bath is preferably from 2.5 to 5.5, more preferably from 4 to 5.

The polyester fiber plant-dyed by the plant dyeing method of the present invention is not only dyed to a sufficient luminous density without metal mordant treatment, but is also a natural fiber dyed plant-dyed by conventional metal mordant treatment. In comparison with synthetic fibers and synthetic fibers, the spectral reflectance curve is gentler, and gentle and soft color expression can be achieved. In addition, since it is not necessary to use harmful metal compounds regulated by the Water Pollution Control Law and the Poisonous Substances Control Law, ecological fibers that are truly friendly to humans and the earth can be provided. Therefore, the present invention is extremely useful from baby clothing to elderly clothing, particularly for inner uses that directly touch the skin. In addition, to enable gentle color expression that cannot be expressed with synthetic dyes,
Combined with the excellent physical properties, functionality and sensitivity of the polyester fiber, it can be widely used for clothing such as outerwear, middleler, innerwear, etc., as well as for household and non-clothing. Furthermore, the antibacterial, deodorant, insect repellent and other functions of the plant dye can be exhibited.

[0022]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The parts and percentages in the examples are:
Unless otherwise specified, weight is based, and color development is
It was measured by the following method. The color development of the dyed woven or knitted fabric was measured using a Macbeth MS-2020 colorimeter [Instrumental Color System Limited].
manufactured by Stem Limited) and C
L ^* , a ^* , b ^* and color development K / S of the IE color system were measured. The higher the K / S, the higher the color development.

Examples 1-5, Comparative Examples 1-3 Polyethylene terephthalate (titanium diacetylate content;
(0.5%) multifilament (circular solid yarn, 75 denier / 24 filaments, Tg; 80 ° C.) was knitted such that the total denier was 300 denier, and knitted into a knitted fabric. According to the usual method, the obtained knitted fabric
After refining and presetting, 100% owf of green leaf liquor was used as a plant dye, bath ratio 1: 140, pH2,
Under conditions of 3,4,5,6,1,7,8, 130 ° C and 6
Staining was performed for 0 minutes. The obtained dyed cloth was soaped and dried according to a conventional method, and then evaluated for color development. The color development K / S was measured at a measurement wavelength of 420 nm. Table 1 shows the results.

[0024]

[Table 1]

Examples 6 to 7 In Example 2, instead of the green leaf liquor used as the plant dye, an Indian indigo liquor and a western madder liquor were used, respectively.
Using 50% owf and 100% owf, bath ratio 1: 1
Dyeing treatment was performed at 130 ° C. for 60 minutes under the conditions of 40 and pH 4.0. Thereafter, the same procedure as in Example 2 was performed. In addition, the chromogenic K / S was 600 nm when stained with Indian indigo,
Those stained with western madder were measured at a measurement wavelength of 440 nm. Table 2 shows the results.

[0026]

[Table 2]

Examples 8-10 Normal pressure obtained by high-speed spinning at 4,000 m / min using polyethylene terephthalate (titanium diacetate content: 0.3%) obtained by copolymerizing adipic acid at 14.5 mol%. Disperse dye dyeable polyester multifilament (Marunouchi, 7
Using a 5 denier / 24 filament, Tg; 52 ° C.), the knitted fabric was knitted so that the total denier was 300 denier. The obtained knitted fabric is refined and preset according to a conventional method, and then, as a plant dye, green leaf liquor, Indian indigo liquor, and western madder liquor are respectively 100% owf, 50% owf and 1%.
Dyeing treatment was performed at 98 ° C. for 60 minutes under the conditions of a bath ratio of 1: 140 and a pH of 4.0 using 00% owf. The obtained dyed cloth was soaped and dried according to a conventional method, and then evaluated for color development. Table 3 shows the results.

Reference Examples 1 to 3 Prior to the plant dyeing performed in Examples 8 to 10, aluminum sulfate anhydrous 25% owf was used as a metal mordant, a bath ratio of 1:50 and a temperature of 98 ° C. for 60 minutes. After mordant treatment, it was washed with water and dried. Thereafter, Examples 8 to 10
In the same manner as described above, plant dyeing, soaping, and drying treatment were performed, and the color development was evaluated. Table 3 shows the results.

[0029]

[Table 3]

Examples 11 to 12 and Comparative Examples 4 and 5 Dyeing was carried out in the same manner as in Example 2 except that the dyeing temperature was variously changed. Table 4 shows the results.

[0031]

[Table 4]

[0032]

According to the dyeing method of the present invention, it is possible to dye a polyester fiber in the same shade as a natural fiber with a plant dye without using a metal mordant treatment. A plant-dyed polyester fiber capable of expressing colors such as a calm color tone and a natural taste over a wide range up to a natural dye such as a plant dye is obtained.

Claims (2)

[Claims] When dyeing a polyester fiber with a plant dye, the dyeing temperature is (Tg + 10) to 160 ° C. (where Tg is the glass transition point of the polyester), and the pH of the dyeing bath is 2 to 6. A method for plant dyeing of polyester fibers, characterized in that: 2. The method according to claim 1, wherein the polyester fiber is a normal pressure disperse dyeable polyester fiber.