JPH0819627B2 - Dyeing method for polyester fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for dyeing polyester fibers, and more specifically, the polyester fibers are treated with an aqueous metal salt solution and then dyed with a vegetable dye. The present invention relates to a method for dyeing polyester fibers.

[Conventional technology]

Polyester fibers are fibers that do not have a functional group that binds to the dye, and are difficult to dye due to the fact that the fiber structure is dense and hydrophobic, so carrier dyeing is performed using dyes with low molecular weight.・ High pressure dyeing is common.

However, the color tone of the obtained dyed product is pastel and less vivid than that of natural fiber. As a method for eliminating the above-mentioned drawbacks, a so-called "cationic dyeable polyester" technique in which a functional group that bonds with a dye is introduced by copolymerizing 5-sulfoisophthalate has been developed and commonly used.

On the other hand, the diversification and individualization of clothing materials in recent years is remarkable. This is not the case with dyed fabrics. That is, in recent years, clothing materials are required to have not only economic and practical values but also mental and cultural values.
Among them, in dyed woven and knitted fabrics, in addition to mere clear and unsharp shades, there are also demands for unique and complex colors that are completely different from the ones that appeal to the senses. Examples of the dyed product having the above-mentioned properties include a cloth dyed by a so-called "vegetation dyeing" method with a plant dye of ancient Japan. However, dyeing with the above-mentioned vegetable dyes,
Limited to natural fibers such as silk and wool, synthetic fibers,
In particular, it was completely impossible with fibers having low dyeability such as polyester fibers.

The present inventors have made various attempts to achieve the above object. For example, a third component such as polyethylene glycol component
It is an attempt to impart easy dyeability to the polyester fiber by introducing the components, and further an attempt by the above-mentioned "cationic dyeing technique".

In the case of the former, the mobility of the rigid polyester molecular chain is improved, it becomes easy to dye, and the dyeability with the vegetable dye is expressed, but the degree of dyeing (coloring) is low and the dyeing fastness is insufficient. .

The latter has improved the degree of dyeing as compared with the former, but has extremely poor dyeing fastness, and there is a limit to the extension of cation dyeing technology, and further, a drastic solution is needed.

[Problems to be Solved by the Invention]

The present invention provides a method for dyeing a polyester fiber that can be dyed in a variety of unique and deep colors, which cannot be obtained by a conventional polyester fiber, and specifically, Is an extremely versatile and calm color such as "vegetation dyed" even with polyester fibers, the dyeing fastness of the dyed fabric is excellent, and the mechanical properties of the fibers constituting the dyed fabric are excellent. The present invention provides a polyester dyeing method that solves all the problems in terms of color, practicality, and production, such as the fact that the dyeing operation is easy, the multifilaments that make up the woven or knitted fabric can be easily obtained. The purpose is to

[Means for solving the problem]

The present invention treats 5-sulfoisophthalate copolyester fiber with an aqueous solution of a salt of at least one metal selected from the group consisting of iron, copper and aluminum, and then dyes it with a vegetable dye. A method for dyeing a polyester fiber, which comprises:

The dyeing mechanism of the above-mentioned dyeing is still being clarified and is not always clear, but when at least one metal selected from the group consisting of iron, copper and aluminum is used, this metal becomes a fiber and a dye. It is presumed that it contributes greatly to the stable binding of the dye, and as a result, even the vegetable dye develops a sufficient color at room temperature and the dyeing fastness is dramatically improved.

The at least one metal salt selected from the group consisting of iron, copper and aluminum in the present invention is not particularly limited as long as it is water-soluble, but examples of the anion include halide ion, acetate ion and sulfate ion. , Phosphate ion, oxalate ion and nitrate ion can be mentioned, and more preferable results can be obtained by using sulfate ion and chloride ion (Cl ^-1 , Cl ₂ ^-2 ).

When the temperature of the aqueous solution of the metal salt is high, more preferable results can be obtained.

The pH of the aqueous solution depends on the dye and metal salt used.
It may be set appropriately, for example, the dye is safflower and the metal salt is Cu.
Staining with SO ₄ gives more favorable results under acidic conditions (pH 2-5).

At this time, a swelling agent may be added in order to swell the dense structure of the polyester fiber and further enhance the color developability.
Examples of the swelling agent used include acetone, methanol, phenol, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, benzyl benzoate and mixtures thereof.

The plant dyes that can be used in the present invention are not necessarily limited, and the plant dyes used for so-called "vegetation dyeing", for example, safflower, madder, purple root, indigo,
Yellowfin, turmeric, caryas, gardenia, sen, kunugi,
Dyes such as cloves, wheel plums, plums, gobaishi, and rockwood can be used. Besides this, more common flowers,
Wild grasses, vegetables, fruits, etc., such as mandarin orange and onion soup, can also be used, so the range of use is extremely wide.

Further, regarding the dyeing method, a sufficient dyeing product can be obtained by performing each treatment once, and may be performed a plurality of times when deep color dyeing is required. Furthermore, since the dyeing is sufficiently possible even under normal pressure, it is not necessary to use a complicated and large-sized dyeing device, and the dyeing can be performed very easily.

The polyester fiber used in the present invention is a fiber mainly composed of a polyester composed of terephthalic acid and an alkylene glycol having 2 to 6 carbon atoms, and a dicarboxylic acid other than terephthalic acid or a carbon number other than terephthalic acid as long as the object of the present invention is not impaired. It may be a fiber obtained by copolymerizing 2 to 6 diols other than alkylene glycol in an amount of less than 20 mol% each. Particularly, those made of polyethylene terephthalate are preferable.

The 5-sulfoisophthalic acid salt of the present invention includes
5-sulfoisophthalic acid alkali metal salts and 5-sulfoisophthalic acid quaternary phosphonium salts are mentioned. The type of alkali metal ion and phosphonium ion is not particularly limited, but examples of the alkali metal include sodium, potassium, lithium and the like, and as the phosphonium, tetraalkylphosphonium, tetraarylphosphonium, among them, tetramethylphosphonium, tetraethylphosphonium, tetra. Butylphosphonium,
Tetraphenylphosphonium or the like is preferable, and particularly in the case of tetrabutylphosphonium, even if the proportion of copolymerization is increased, troubles due to the viscosity effect in the polymerization and the spinning process are eliminated, and the polymer can be polymerized (high [η], It is more preferable because the color developability and the fiber strength can be made compatible with each other.

As the fiber physical properties of the fiber used for dyeing of the present invention, it is not necessary to pay particular attention to it, and it is sufficient to have the same level as that of a normal polyester fiber.
Approximately 40% normally drawn yarn, and high-speed spun products with elongation of 40-80% can also be used.
It is preferably 5 g / denier or more, more preferably 3.0 g / denier.

The shrinkage rate is preferably 20% or less, 5 to 15
% Is more preferable.

Further, when the sublimation is required, the sublimation can be imparted by false twisting, and it can be used as a spun yarn after spinning after forming staple fibers.

Next, regarding the structure and form of the woven or knitted fabric, it is not necessary to make any special measures.
For twill weaves and knits, basic weft knitting and warp knitting as well as various complicated weaving can be used. Various interwoven,
A knitted fabric can also be used as the woven or knitted fabric of the present invention.

In the dyeing method of the present invention, a main constituent component is alkylene terephthalate, and in a copolyester obtained by copolymerizing 5-sulfoisophthalic acid metal salt, the metal of the metal salt is a group consisting of iron, copper, and aluminum. At least one selected from, and the polyester having a content of the metal salt of 0.1 to 20 mol% may be dyed with a vegetable dye, wherein the main constituent is alkylene terephthalate. Is a polyester mainly composed of terephthalic acid and an alkylene glycol having 2 to 6 carbon atoms, and is a dicarboxylic acid other than terephthalic acid or a diol other than alkylene glycol having 2 to 6 carbon atoms as long as the object of the present invention is not impaired. May be copolymerized in an amount of less than 20 mol%. Usually, the intrinsic viscosity measured at 25 ° C in o-chlorophenol is 0.3 or more, preferably
It is a polyester of 0.35 to 1.2. This polyester can be obtained by a well-known melt polymerization method.

The metal of the 5-sulfoisophthalic acid metal salt to be copolymerized is at least one selected from the group consisting of iron, copper, and aluminum. Iron can be divalent or trivalent,
Copper may be monovalent or divalent. Aluminum is trivalent.

The proportion of 5-sulfoisophthalic acid metal salt to be copolymerized is preferably 0.1 to 20 mol%, more preferably 0.4 to 10 mol% with respect to alkylene terephthalate which is a main constituent. When it is less than 0.1 mol%, the improvement of light resistance and washing durability is insufficient, while when it exceeds 20 mol%, the physical properties inherent to the main constituent alkylene terephthalate are significantly lost, which is not preferable.

The sulfonic acid part of the 5-sulfoisophthalic acid component is iron,
The proportion of at least one metal salt selected from the group consisting of copper and aluminum may be equal to or less than the proportion of the entire 5-sulfoisophthalic acid component to be copolymerized.

The sulfonic acid part of the 5-sulfoisophthalic acid component is iron,
The counterion other than at least one metal selected from the group consisting of copper and aluminum is usually an alkali metal ion or a quaternary phosphonium salt.

The formed 5-sulfoisophthalic acid metal salt contains anion other than sulfonate anion, such as halide ion such as fluoride ion, chloride ion, bromide ion, iodide ion and acetate ion. Good. Furthermore, one or more sulfonate anions derived from 5-sulfoisophthalic acid, one or more of the above-mentioned metals, and one or more anions other than sulfonate anions derived from 5-sulfoisophthalic acid form a complex. It may be formed.

The metal salt of 5-sulfoisophthalic acid may be 0.1 to 20 mol% of 5-sulfoisophthalic acid alkali metal salt and / or 5-sulfoisophthalic acid quaternary phosphonium salt.
It is formed by reacting a copolyester mainly composed of copolymerized alkylene terephthalate with an aqueous solution of at least one metal salt selected from the group consisting of iron, copper and aluminum. The types of the alkali metal salt and the fourth phosphonium salt are not particularly limited, and the above-mentioned ones are preferably used.

The at least one metal salt selected from the group consisting of iron, copper and aluminum in the present invention is not particularly limited as long as it is water-soluble, and the above anion is preferably used.

Impregnating these metal salts into the polyester,
A sulfonic acid of at least one metal selected from the group consisting of iron, copper and aluminum in a polyester whose main constituent is alkylene terephthalate by exchanging sodium ion and / or quaternary phosphonium ion with the metal ion. A copolyester having a salt copolymerized can be obtained. If it is difficult to impregnate with the metal salt, it is preferable to heat.

Usually, the impregnation with the metal salt is carried out by boiling the metal salt aqueous solution under normal pressure.

At this time, the swelling agent may be added so that the metal salt can more easily enter the inside of the polymer.

When the polyester thus obtained is thoroughly washed with water, a vegetable dye dyeable polyester is obtained. The vegetable dye-dyeable polyester thus obtained is 2
When a metal ion having a valency of more than 5 is used as the counter ion of the sulfonic acid of the 5-sulfoisophthalic acid component, a very large thickening effect is exhibited when the polymer is melted. The viscosity of the polymer can be increased to facilitate molding.

Further, in order to produce a polyalkylene terephthalate in which a metal ion having a valence of 2 or more is used as a counter ion of sulfonic acid of a 5-sulfoisophthalic acid component, the metal salt of 5-sulfoisophthalic acid is added at the time of polymerization. Then,
A three-dimensional knitted structure of polymer chains is generated by ionic crosslinking.

Therefore, since the viscosity of the molten polymer is significantly increased, stirring for increasing the degree of polymerization and the generated polymer could not be discharged from the polymer manufacturing apparatus,
According to the method of the present invention, a polymer having a high degree of polymerization can be obtained, so that it can be used as a fiber, a film or a resin.

[Action]

In order to activate the polyester fiber that is originally inactive to the dye, a functional group that binds to the dye is required as in the "cationic dyeing" technology described above, and this bond is extremely stable. Need to be made
As a concrete measure, when dyeing a polyester fiber, if the fiber is previously treated with an aqueous solution of at least one metal selected from the group consisting of iron, copper, and aluminum, and then the dyeing treatment is performed. If
Surprisingly, not only the plant dyes develop sufficient color at room temperature, but also the dyeing fastness, which has been a problem with the conventional techniques, is dramatically improved, and the dyeing fastness is improved to a sufficiently practical level.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples.

The definition of the evaluation method used in the present invention is as follows.

(Coloring property) A cloth made of multifilaments used in the present invention was treated with an aqueous solution of a metal salt, then dyed with a vegetable dye, washed with water and dried, and used as a sample for determination of coloration property. In the color development determination, the degree of color development (dark or light) was qualitatively determined with the naked eye. In addition, when the metal salt aqueous solution was not treated, the evaluation was performed in the same manner.

 The evaluation criteria are as follows.

◯: The degree of dyeing of the tubular knit that has been subjected to the dyeing treatment is sufficient.

Δ: The degree of dyeing is insufficient and the dye is slightly light.

X: Not dyed at all.

(Dyeing fastness) (a) Washing fastness The dyed woven or knitted fabric was visually evaluated in accordance with JIS L-0844-73 A-2 for the degree of discoloration of the dyed fabric.

The judgment was made according to the grades, and the grades were 1 to 5 grades, and 3.5 grades or higher were accepted.

(B) Light fastness A dyed woven or knitted fabric is treated with xenon arc JIS L-0843.
-71 It was judged with the naked eye according to the third exposure method. The content of the judgment was the same as that of the wash fastness.

(Strength and Elongation) The stress-elongation curve of the multifilament constituting the woven or knitted fabric was obtained at room temperature in a vertical tensile test, and the strength at the point where the stress was maximized was the fineness (denier) of the multifilament.
The value divided by was taken as the strength, and the elongation up to the point where the stress was maximized was taken as the elongation.

(Comprehensive Evaluation) Good: Color development, dyeing fastness, and fiber properties after dyeing are all good, and it can be used practically enough.

Δ: There is room for further improvement in terms of color developability and dyeing fastness.

X: There is no color development, and it is difficult to dye with a vegetable dye.

Reference Example 1 5 g of tetrabutylphosphonium 5-sulfoisophthalate copolymerized with 2 g each of polyethylene terephthalate fibers (single yarn fineness: 1.1 denier, intrinsic viscosity: 0.60) was added to an aqueous solution containing 2% by weight of the following metal salts and 1% by weight of acetic acid. Soak,
It was treated at 100 ° C. for 1 hour. This fiber was thoroughly washed with water and dried, and then the amount of element in the fiber was measured.

 The results are shown in Table 1.

Examples 1 to 3, 3-1 to 3-3, Comparative Examples 1 and 5
~ 9 Polyethylene terephthalate fiber copolymerized with 5 mol% tetrabutylphosphonium 5-sulfoisophthalate (single yarn fineness: 1.1 denier, intrinsic viscosity 0.60), polyethylene terephthalate fiber copolymerized with 5 mol% sodium 5-sulfoisophthalate (monomer Fiber fineness 1.1 denier, intrinsic viscosity 0.42, and polyethylene glycol (number average molecular weight)
Polyethylene terephthalate fiber (single yarn fineness 1.
1 denier and an intrinsic viscosity of 0.64) were made into fabrics and treated with metal salts in the same manner as in Reference Example 1. This was immersed in an aqueous solution of 2% by weight of safflower dye, 1.5% by weight of acetic acid, and 1% by weight of tannic acid at a bath ratio of 70 times, and the temperature was raised to 100 ° C. over 20 minutes at normal pressure. This was washed and dried, and then the L value was measured with a color difference calculator on the digital side (manufactured by Suga Test Instruments Co., Ltd.). 5 in total
Each time the cloth was washed under the following conditions, the cloth was washed and dried at each washing, and the L value was measured in the same manner as described above. The results are shown in Table 2.

In addition, for washing, 70 ° C water 2, detergent Zab (Kao Corporation)
10 g of fabric) and 20 g of cloth were placed in a beaker and stirred for 20 minutes.

As described above, the dye copolymer does not drop when washed with 5-sulfoisophthalic acid, but the dye drops when polyethylene glycol is copolymerized.

The strength and elongation of the fibers used in this fabric before and after dyeing was
Shown in the table. However, the strength and elongation after dyeing are those before washing.

Examples 4 to 10, Comparative Examples 10 to 23 and 10-1 to 10-7 Polyethylene terephthalate fibers shown in Table 4 were used as cloths, and an aqueous solution containing 2% by weight of the metal salt shown in Table 5 and 1% by weight of acetic acid. And was treated at 100 ° C. for 1 hour.

After thoroughly washing this fiber with water, it was dipped in an aqueous solution of 2% by weight of rack dye, 1.5% by weight of acetic acid and 1% by weight of tannic acid at a bath ratio of 70 times, and kept at 100 ° C. for 20 minutes under normal pressure. This is washed and dried, and then a xenon tester (XW-20, manufactured by Shimadzu Corporation) with a blue scale compliant with JIS L0841.
Type) and exposed to a current of 20 A for 20 hours to examine the light resistance. The light fastness was evaluated on a scale of 8 on the degree of color change of the dyed fabric as compared with the degree of color change on the blue scale (Grade 1 shows the worst and Grade 8 shows the best).

 The results are shown in Table 5.

Examples 11 to 18 and Comparative Examples 24 to 37 Using dimethyl terephthalate and ethylene glycol, transesterification and polycondensation were carried out according to a conventional method to obtain a polyethylene terephthalate polymer. At this time, 5-sulfoisophthalic acid salt or polyethylene glycol (number average molecular weight = 20,00
A polymer in which 0) was copolymerized was also prepared. The obtained polymer chips were dried at 140 ° C. for 5 hours, and then melt-extruded at 285 ° C. After cooling and solidification, an oil agent was applied and the film was wound at 400 m / min. Subsequently, it was stretched by heat treatment (preheated by a preheated roller at 80 ° C., stretched and heat set by a plate heater at 160 ° C.), and then wound through a cooling roller to obtain a 75 denier, 24-filament multifilament.

The obtained multifilament polymer is shown in Table 6.

The drawn yarn was cylindrically knitted, dipped in an aqueous solution of a surfactant [Monogen (manufactured by P & G Co., Ltd.)] at 50 ° C. to remove the spinning oil, washed with water and dried. Then, the sample was set at 180 ° C. for 1 minute to prepare a dyeing sample. The tubular knitting operation was performed in two cases, that is, after the treatment with an aqueous solution of a metal salt, followed by washing with water and drying, and the case of dyeing without treatment with a metal salt. The metal salt aqueous solution treatment was performed by using an aqueous solution of cupric sulfate 2% by weight and acetic acid 1% by weight at a bath ratio of 100 times and boiling for 1 hour. Also, for dyeing, safflower dye was used at 2% owf and the bath ratio was 100
It was dipped in double and boiled for 30 minutes.

The tubular knitted fabric that had been subjected to the dyeing operation was washed with water and dried, and then evaluated for color developability, dyeing fastness and strength and elongation.

 The results are shown in Table 7.

As is clear from Table 7, comparative examples having no functional group
In the fibers of 24 and 25, no coloring due to the vegetable dye is observed. Further, in the fibers of Comparative Examples 34 to 36 copolymerized with polyethylene glycol, if the copolymerization ratio is increased, the color developability is improved, but it is still not sufficient, and even if an aqueous metal salt solution treatment is performed. The dyeing fastness is insufficient.

On the other hand, in the knitted product obtained by copolymerizing 5-sulfoisophthalic acid salt and treated with an aqueous solution of a metal salt, for example, the knitted products of Examples 11 to 13, the color developability, the dyeing fastness, and the fiber physical properties after dyeing are very good. is there.

Particularly, in the case of the fibers of Examples 14 to 18 in which the copolymerization component is tetrabutylphosphonium 5-sulfoisophthalate,
Even if the proportion of copolymerization is increased, the decrease in fiber physical properties is small,
It was extremely favorable.

Example 19, Comparative Example 38 Using the polymer 8 and using a spinneret having a tri-lobal type discharge hole, a spinning and drawing operation was performed in the same manner as in Example 11, and 75 denier composed of filaments having a triangular cross-section was formed. , A multifilament of 36 filaments was obtained. A woven fabric having a basis weight of 100 g / cm ^{2 made} of satin weave using the multifilaments as warps and wefts was prepared by a known method and used as a dyeing sample. The metal salt aqueous solution treatment and the dyeing treatment were carried out in the same manner as in Example 11.

Examples of color development, dyeing fastness and fiber properties after dyeing
Evaluation was made in the same manner as 11. Table 8 shows the results.

The woven fabric of Example 19 exhibited a good feel of silky touch, and had good colorability and good fiber physical properties after dyeing.

On the other hand, the woven fabric of Comparative Example 38 had room for improvement in dyeing fastness.

[Effects of the Invention] By the dyeing method of the present invention, or by using the dyeable polyester of the present invention, the dye does not detach even by washing, and has good light resistance, for example, "vegetable dyeing". It is possible to provide a polyester fiber having a color appealing to the sensibilities as described above.

That is, according to the present invention, for example, it is possible to obtain a polyester fiber dyed with a vegetable dye, which has a color that is said to be unrepresentable with a synthetic fiber such as a retro tone or a trad tone, and the dyeing fastness of the dyed product is high. A dyed polyester which is extremely good and can be sufficiently put to practical use, has excellent mechanical properties of a woven or knitted product after dyeing, has practical properties, and is easily manufactured and produced. It is possible to provide a system fiber.

Claims (1)

[Claims] 1. A 5-sulfoisophthalate copolyester fiber is treated with an aqueous solution of a salt of at least one metal selected from the group consisting of iron, copper and aluminum, and then treated with a vegetable dye. A method for dyeing a polyester fiber, which comprises dyeing.