JP2001355187A - Method for producing aliphatic polyester-based fiber- containing fibrous structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aliphatic polyester-based fibrous structure excellent in high color fastness, a soft feeling and color developing properties and further having biodegradability. SOLUTION: This method for producing the aliphatic polyester-based fiber- containing fibrous structure is characterized by carrying out reduction washing treatment after dyeing at <=70 deg.C temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fibrous structure containing an aliphatic polyester fiber. More specifically, the present invention relates to a method for producing an aliphatic polyester fiber-containing fiber structure which suppresses hydrolyzability, is excellent in coloring property and sharpness, and has good color fastness.

[0002]

2. Description of the Related Art Thermoplastic synthetic fibers typified by polyester fibers or polyamide fibers have excellent mechanical strength, chemical resistance, heat resistance, and high elongation characteristics, and are used for clothing, industrial use, and materials. Is widely used mainly.

[0003] Among them, polyethylene terephthalate (P
ET) fiber is excellent in W & W (wash and wear property), dimensional stability and color fastness, and has various characteristics by weight reduction by alkali treatment. I have.

On the other hand, polyester fibers, especially PET fibers, have a high degree of crystallinity and are difficult to dye.
Staining under high pressure (125 ° C to 135 ° C) is required. In addition, the refractive index of the fiber is higher than other fibers, the surface reflection increases, and the color development and clarity of the dyed product are lower than those of natural fibers or other synthetic fibers. There were restrictions on deployment.

[0005] On the other hand, aliphatic polyester fibers, which are attracting attention as biodegradable fibers that are friendly to the global environment, are characterized by having a lower refractive index than aromatic polyester and being similar to natural fibers. The coloring and sharpness are remarkably improved. On the other hand, as a disadvantage, in a wet heat treatment at a high temperature or under alkaline conditions, hydrolysis is particularly likely to occur, and the fiber strength tends to be greatly reduced.

[0006] Therefore, in order to improve the color fastness, PE
There are also many problems, such as the fact that reduction cleaning under alkaline conditions at 80 ° C. to 90 ° C., which is employed in T fibers, cannot be used.

Therefore, a dyed fabric made of biodegradable fiber which is excellent in deep color and color development like natural fiber, has a soft feeling and can cope with environmental problems can be obtained, but the dyeing fastness is insufficient. It is not the actual situation.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fiber structure containing an aliphatic polyester fiber which is excellent in deep color and color development and which has biodegradability. An object of the present invention is to provide a method for producing an aliphatic polyester fiber-containing fiber structure capable of obtaining a structure.

[0009]

The present invention has the following structure to solve the above-mentioned problem.

(1) A method for producing a fibrous structure containing an aliphatic polyester fiber, wherein a reduction washing treatment after dyeing is performed at a temperature of 70 ° C. or less.

(2) The method for producing an aliphatic polyester fiber-containing fiber structure according to the above (1), wherein the reduction washing treatment is performed under an acidic condition.

(3) The aliphatic polyester-based fiber according to (1) or (2), wherein the aliphatic polyester is a polyester containing L-lactic acid and / or D-lactic acid as a main component. A method for producing a fibrous structure.

(4) The above-mentioned (1), wherein the fibrous structure containing aliphatic polyester fibers comprises a fabric containing 30% by weight or more of aliphatic polyester.
The method for producing the aliphatic polyester fiber-containing fiber structure according to any one of (1) to (3).

That is, in the present invention, the fiber structure containing an aliphatic polyester fiber is dyed with a disperse dye, and then the dyeing fastness is improved by reduction washing.
Preferably, the treatment is carried out under acidic conditions to suppress a decrease in strength, and furthermore, treatment unevenness due to reduction cleaning (uneven dyeing).
It was clarified that there was no dyeing and that the color fastness was improved.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The aliphatic polyester fibers in the present invention are used in the form of multifilament yarns, short fibers such as staples, and spun yarns. When the fiber structure is a fabric, the aliphatic polyester fibers are mainly used. It is formed as. By forming a fibrous structure mainly composed of aliphatic polyester fibers, the soft feeling, deep color and biodegradability, which are the objects of the present invention, can be exhibited.

The melting point of the aliphatic polyester resin which is a raw material of the aliphatic polyester fiber of the present invention is preferably 130 ° C. or higher. When the melting point is less than 130 ° C,
Since the fibers are fused and integrated in the heat setting step and the dyeing processing step at the time of drawing, the passability in various steps is reduced, and the quality of the product is also deteriorated. Preferably, the melting point of the aliphatic polyester is at least 150 ° C, more preferably at least 160 ° C.
Here, the melting point means a peak temperature of a melting peak obtained by DSC measurement.

The aliphatic polyester used in the present invention preferably has a refractive index of 1.30 to 1.50, and specifically includes polylactic acid, polyglycolic acid, and poly-3-hydroxypropionate. Polyoxyacids such as poly-3-hydroxybutyrate and poly-3-hydroxybutyrate valerate, polycondensates of aliphatic dicarboxylic acids and aliphatic diols such as polyethylene succinate and polybutylene succinate, polycaprolactone and Examples thereof include, but are not limited to, polyesters obtained by ring-opening polymerization of an aliphatic cyclic ester such as polypivalolactone, and blends, copolymers, and modified products thereof. .

Among them, preferable polymers from the viewpoint of high melting point and high heat resistance include L-lactic acid and / or D-lactic acid.
Polylactic acid, which is a polyester having lactic acid as a main repeating unit, may be mentioned. As a method for producing polylactic acid, a two-stage lactide method in which L-lactic acid and / or D-lactic acid is used as a raw material to once produce lactide as a cyclic dimer, and then ring-opening polymerization is performed, and L-lactic acid and / or Alternatively, there is a one-step direct polymerization method in which D-lactic acid is used as a raw material to directly perform dehydration condensation in a solvent. The polylactic acid used in the present invention may be obtained by any production method. In the case of the polymer obtained by the lactide method, since the cyclic dimer contained in the polymer is vaporized at the time of melt spinning and causes thread spots, the cyclic dimer contained in the polymer before the melt spinning is obtained. It is desirable that the body content be 0.5% by weight or less. In the case of the direct polymerization method, since there is substantially no problem caused by the cyclic dimer, it can be said that it is more preferable from the viewpoint of the spinning property.

The average molecular weight of the polylactic acid is usually at least 50,000, preferably at least 100,000, more preferably 1
0 to 300,000. When the average molecular weight is lower than 50,000, the strength physical properties of the fiber are undesirably reduced. If it exceeds 300,000, the melt viscosity becomes too high, and melt spinning may be difficult.

Further, the polylactic acid in the present invention may be a copolymerized polylactic acid obtained by copolymerizing other components having an ester-forming ability in addition to L-lactic acid and D-lactic acid. As copolymerizable components, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-
In addition to hydroxycarboxylic acids such as hydroxycaproic acid, compounds containing a plurality of hydroxyl groups in a molecule such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, polyethylene glycol, glycerin, and pentaerythritol or derivatives thereof, and adipine Compounds containing a plurality of carboxylic acid groups in the molecule, such as acid, sebacic acid, and fumaric acid, and derivatives thereof are included. However, in order not to impair the fiber strength, it is desirable that 70 mol% or more of the fiber is composed of lactic acid units.

In order to reduce the melt viscosity, aliphatic polyester polymers such as polycaprolactone, polybutylene succinate and polyethylene succinate, and polyethylene glycol, polypropylene glycol and poly (ethylene-propylene) glycol copolymers can be used. Aliphatic polyether polymers can be used as internal plasticizers or as external plasticizers. Further, inorganic fine particles and organic compounds as a matting agent, a deodorant, a flame retardant, a yarn friction reducing agent, an antioxidant, a coloring pigment and the like can be added as required.

The cross-sectional shape of the fiber may be a round cross-section, a flat cross-section, hollow, triangular, multi-lobed cross-section such as five- or eight-leaf cross-section, and may be ordinary yarn or extra-fine yarn. .

The fibrous structure of the present invention contains an aliphatic polyester-based fiber. As another material, a synthetic fiber (synthetic fiber, regenerated fiber) such as aromatic polyester, polyamide, polyacrylonitrile, polyurethane Or, rayon or the like, or cotton, silk, or wool as a natural fiber may be mixed. The other materials to be mixed may be one kind or a plurality of kinds, and the form may be any form such as a filament mixed fiber, a composite processed yarn, a mixed spinning, a ply twist, and a long and short composite. In this case, it is preferable to contain the aliphatic polyester fiber in an amount of 30% by weight or more, since characteristics of the aliphatic polyester such as dyeability, coloring property, and soft feeling can be utilized.

Further, the fiber structure in the present invention is a fiber such as raw staple cotton or a staple fiber bundle, a spun yarn, or a filament, a yarn, a fabric, or a product.
The fabric may be in the form of a woven fabric, a knitted fabric, a nonwoven fabric, or the like.

In addition, aliphatic polyester fibers are dyeable with disperse dyes, and both fibers can be dyed at a time if they are polyester, acetate or polyamide fibers. Is more effective. The dyeing temperature of the aliphatic polyester fiber is usually from 100 ° C. to 120 ° C., but slightly differs depending on the polymer type and the dye concentration.

In general, PET fibers are subjected to reduction washing after dyeing for the purpose of dyeing fastness. As the condition of the reduction cleaning, the treatment is performed at 80 to 90 ° C. under alkaline conditions.
By this treatment, the unfixed dye on the fiber surface is reduced and removed, and the wet fastness and friction fastness are improved.

When the aliphatic polyester fiber of the present invention is subjected to the same reduction washing, color unevenness occurs or the strength decreases due to hydrolysis, and the tear strength decreases as a fabric characteristic. The color unevenness is caused by the temperature unevenness of the processing solution, but in the heating method, when the temperature is increased through a heater,
Some temperature change will inevitably occur. Further, since it is necessary to suppress the decrease in the strength, in the present invention, the temperature of the reducing agent treatment liquid for the reduction cleaning is set to 70 ° C. or less. Further, it is preferably used that the treatment is performed under an acid having a relatively low hydrolysis rate.

As the reducing agent, a sulfinic reducing agent such as hydrosulfite, sodium hyposulfite, sodium hydride sulfite, thiourea dioxide, Superlite C (N
aHSO ₂ · CH ₂ O · 2H ₂ O) or NaHSO ₂ ·
Tin-based reducing agents such as CH ₂ O · 2H ₂ O and Zn (HSO ₂ CH ₂ O) ₂ include stannous chloride. As other reducing agents, alkali metals and organic substances such as formic acid and oxalic acid can also be used.

Among them, hydrosulfite and NaHS
O ₂ · CH ₂ O · 2H ₂ O and Zn (HSO ₂ CH ₂ O) ₂ have a high effect of improving the fastness and are preferably used.

Although the processing temperature and the processing time for washing with the reducing agent vary depending on the dye concentration used, the processing temperature is preferably 70 ° C. or lower, and more preferably around 60 ° C. The processing time is 5 to 30 minutes, preferably 10 to 20 minutes.

The concentration of the reducing agent is preferably from 0.2 to 6 g / l, more preferably from 0.5 to 2 g / l. The pH under acidity is preferably from 1.5 to 5, and preferably from 2 to 4.

The pH can be adjusted using either an organic acid or an inorganic acid. Although it is preferable to use a surfactant for the purpose of enhancing the cleaning effect, a nonionic or anionic surfactant may be used in combination.

After washing, if necessary, as a functional agent,
A finish such as a water repellent, a softener, or an antistatic agent may be provided.

[0035]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (1) Colorimetry Using a spectral colorimeter manufactured by Minolta Co., color unevenness (visual judgment) and color development (L *) were measured with a D65 light source and a viewing angle of 10 degrees. (2) Dyeing fastness The washing fastness of the sample after dyeing was determined according to JIS-L084.
4. The rub fastness is JIS-L0849 and the light resistance is JIS
-Evaluated according to L0842. (3) Tear strength Tear strength was measured according to JIS L1096 (Pendulum method).

Examples 1 to 8 and Comparative Examples 1 to 12 A polylactic acid chip (weight average molecular weight: 180,000) having a melting point of 172 ° C., 250 ° C., and a melt viscosity at 1000 sec ⁻¹ of 1550 poise was set to 60 ° C. It was dried for 48 hours in a vacuum dryer. Using the dried chips, the spinneret and discharge rate were changed at a spinning temperature of 250 ° C. using a normal spinning machine, and the undrawn yarn was wound at a speed of 1350 m / min. Subsequently, the undrawn yarn was drawn at a temperature of 80 ° C. and a heat setting temperature of 120 ° C. using a normal hot roll-hot roll drawing machine.
The drawn yarn was stretched at a temperature of ° C. such that the elongation of the drawn yarn became 35%, and a drawn yarn was obtained.

The obtained drawn yarn is 167 dtex-75f
(Single yarn fineness: 2.2 dtex). Using this drawn yarn, a 3/3 twill fabric in which both warp and weft are polylactic acid was woven.

As Comparative Examples 7 to 12, polyethylene terephthalate (PET: manufactured by Toray Industries, Inc.) having the same fineness was spun, drawn and woven by a usual method.

Next, as a dyeing / finishing process, (1)
Refining, (2) set, (3) staining, and (4) reduction washing were performed.

However, the processing temperature of the reduction cleaning is 60 to 80.
C., and two levels of treatment under alkaline and acidic conditions. (1) Refining: (90 ° C. × 20 minutes) Grand Up US-20 0.2 g / l (manufactured by Sanyo Chemical Co., Ltd .: nonionic surfactant) Sodium carbonate 1.0 g / l (2) Set: pin tenter Polylactic acid: 150 ° C. × 45 seconds, PET: 180 ° C. × 45 seconds (3) Dyeing: High-temperature dyeing machine Polylactic acid: 120 ° C. × 45 minutes, PET: 130 ° C. × 45 minutes Dyeing and auxiliaries (Blue) Samaron Blue GSL -400 0.25%, 1% (Disperse dye manufactured by Dystar Co., Ltd.) PH-500 (PH regulator) Bath ratio: 1:20 (Rubine) Kayalon Poly. Rubine BLS-200 0.5% (Nippon Kayaku Co., Ltd.)
Disperse Dye) PH-500 (PH adjuster) Bath ratio: 1:20 (4) Reduction washing A method: Reduction washing under alkaline conditions Sodium hydroxide 0.5 g / l Hydrosulfite 2.0 g / l Gran Up US-20 0.2 g / l Temperature / time: 60 ° C., 70 ° C., 80 ° C. × 20 minutes Washed thoroughly with water, washed with water and dried.

Method B: Reduction washing under acidic conditions Acetic acid (90%) 2.0 g / l Superite C 2.0 g / l Granup US-20 0.2 g / l Temperature / time: 60 ° C., 70 ° C. , 80 ° C × 20 minutes, thoroughly washed with hot water, washed with water and dried.

The pH of the method A for the reduction washing was 11.6, and the pH of the method B was 3.7.

Color unevenness (visual judgment) and coloring (L *)
And the results are shown in Table 1.

As shown in Table 1, the examples of the present invention in which the reduction cleaning temperature is 70 ° C. or less have no color unevenness, and have a small change in coloring (L *) with respect to the processing temperature.

On the other hand, when the reduction washing temperature is 80 ° C. as in Comparative Examples 3 to 6, the occurrence of color unevenness is recognized, and the reduction in color developability is unfavorable.

Further, the PET fibers of Comparative Examples 7 to 11 showed almost no change in color unevenness at 80 ° C., indicating a tendency different from that of polylactic acid fibers.

Table 2 shows the color fastness and tear strength. Although the color fastness is not much different between 60 and 80 ° C., the acid reduction washing is slightly more effective. Also, the tear strength is P
ET fiber does not decrease in strength, but polylactic acid fiber has 8
Since the 0 ° C. treatment shows a tendency to decrease, it is preferably 70 ° C. or lower in the present invention, and the acidic side is more effective than the alkali side because it has less hydrolysis.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

EFFECTS OF THE INVENTION In the dyed product of the aliphatic polyester fiber-containing fiber structure, by using the method of the present invention, high dyeing fastness is obtained, and excellent coloring property, sharpness and deepness unique to the fiber are obtained. It is possible to obtain a fibrous structure having a softness that has never been seen before in terms of color and texture, and at the same time, having biodegradability.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H057 AA01 AA02 CA08 CA11 CB16 CB34 CB59 CC03 DA01 DA17 HA01 HA05 JA10 JB03

Claims (4)

[Claims] 1. A method for producing a fibrous structure containing an aliphatic polyester fiber, wherein a reduction washing treatment after dyeing is performed at a temperature of 70 ° C. or less. 2. The process for producing an aliphatic polyester fiber-containing fabric according to claim 1, wherein the reduction washing treatment is performed under acidic conditions. 3. The method according to claim 1, wherein the aliphatic polyester is L-lactic acid and / or
The method for producing a fibrous structure containing an aliphatic polyester fiber according to claim 1 or 2, wherein the polyester is a polyester containing D-lactic acid as a main component. 4. The aliphatic material according to claim 1, wherein the aliphatic polyester fiber-containing fiber structure is made of a fabric containing 30% by weight or more of aliphatic polyester. A method for producing a polyester fiber-containing fiber structure.