JPS60215866A - Production of polyester fiber having fine recessed parts - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyester fibers having fine particles on the fiber surface. The present invention also relates to a method for producing polyester fibers having improved color development, texture, and water absorption.

Aromatic polyesters such as polyethylene terephthalate are widely used in fibers, films, and other molded products because of their excellent mechanical performance, light resistance, and chemical resistance. However, aromatic polyester fibers have the disadvantage that compared to other fibers such as acetic acid, rayon, wool, and silk, the surface of the fibers is smoother, making it difficult to obtain a deep color effect, and they also have a slimy feel unique to synthetic fibers. There is.

It also has the disadvantage of not being absorbent.

Conventionally, methods for improving the color development of polyester fibers include forming a thin film of a component having a refractive index smaller than that of the polyester fibers on the fiber surface to lower the reflectance, and spinning by mixing inert fine particles with T-. A known method is to apply elution treatment to give the fiber surface fine irregularities to increase the efficiency of light entering the fiber. However, the former has disadvantages such as poor durability against bending and peeling when subjected to kneading action, while the latter has the disadvantage of increasing back pressure during melt spinning and causing IlI of the running yarn guide, although it improves color development.
It has the disadvantage of causing a decrease in I, and has problems such as insufficient dyeability and low water absorption.

The inventors of the present invention have conducted extensive studies in order to eliminate the above-mentioned drawbacks, create a polyester fiber that can create deep colors by forming minute concavities on the fiber surface, and have improved texture and water absorbency. Result 1 The present invention was completed. That is, 1 the present invention is obtained by adding 0.3 to 20% by weight of a vinyl polymer containing t-10 mole or more of a vinyl unsaturated sulfonic acid or a salt thereof to an aromatic polyester having ethylene terephthalate as a main repeating unit. The method for producing polyester fibers having fine concave portions is characterized in that the vinyl polymer is eluted from a textile product using an alkaline aqueous solution.

The polyester fiber of the present invention has a large number of fine four-part shapes ranging from ovals to vertical stripes extending in the direction of the fiber axis on the surface, and is therefore characterized by excellent deep color development, improved texture, and water absorption. has.

In the method of the present invention, the aromatic polyester is defined as one in which the main acid component is terephthalic acid or its ester-forming derivative;
The main glycol component consists of ethylene glycol, but the acid components include oxalic acid, 1 malonic acid, and maleic acid.

Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, or ester-forming derivatives thereof, phthalic acid, isophthalic acid,
S-C alkali metal) sulfoisophthalic acid, siphenic acid, 1,4-naphthalene dicarboxylic acid, 2,6-natuthalene dicarboxylic acid, 1,2-bis(phenoxy)ethane-P, P'-dicarboxylic acid, etc. An aromatic dicarboxylic acid or an ester-forming derivative thereof may be included as a copolymerization component. In addition, the acid component has a P-
(Oxycarboxylic acids such as 2-hydroxyethoxy9benzoic acid or ester-forming derivatives thereof may also be included.

Glycol components include 20% or less of propylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanedio-/
'1114-Cyclohexane dimetatool, 1.10-
Decamethylene glycol, 4,4'-dihydroxybisphenol, 1,4-bis(β-hydroxyethoxy)
Benzene, 2,5-naphthalenediol, glycols obtained by adding ethylene oxide to these glycols, polyethylene glycols, and the like can be included.

Next, the vinyl polymer contained in the method of the present invention c,
It is a vinyl polymer containing 1:10 mole or more of vinyl sulfonic acid or its salt. As the vinyl unsaturated sulfonic acid or its salt.

In addition, unsaturated hydrocarbons or their salts such as styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, (methyl)allylsulfonic acid, (meth)acrylic acid sulfoethyl ester, (meth)acrylic acid sulfonate Sulfoalkyl ester of (meth)acrylic acid such as butyl ester, (meth)acrylic acid sulfopropyl ester i
Examples of te include a salt thereof, 2-acrylamido-2methylpropanesulfonic acid or a salt thereof.

In the present invention, those having an aromatic ring, such as styrene sulfonic acid, vinylbenzyl sulfonic acid, or a salt thereof, and forming a salt are preferable. It should be noted that alkali metals and alkaline earth metals are preferable as those that form a salt with the vinyl unsaturated sulfonic acid.

The vinyl polymer is copolymerized with other polymerizable unsaturated vinyl monomer units along with the monomer unit consisting of the above-mentioned vinyl unsaturated sulfonic acid or its salt 〇Other polymerizable unsaturated vinyl monomers Examples include conjugated diene monomers such as butadiene and isoprene; styrene, α-methylstyrene,
Aromatic vinyl monomers such as chlorostyrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, and their esters; acrylamide and methacrylamide N-alkyl substituents; vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide, vinylidene chloride, and vinylidene bromide; vinyl esters such as vinyl acetate and vinyl propionate; Examples include unsaturated vinyl compounds containing oxyalkylene compounds. Examples of the unsaturated vinyl compound include esters such as heptacrylic esters, methacrylic esters, and itaconic esters of polyoxyalkylene glycol; N of acrylamide and methacrylamide;
Substituents, polyoxyalgylene, recall mono(meth)allyl ether, etc.;F can be mentioned. Among these monomers, unsaturated vinyl compounds containing polyoxyalkylene monomers are particularly preferred.

The polyoxyalkylene resin of the unsaturated vinyl compound has an average molecular weight of 20 (on L-1, preferably 400 or more and 5
,000 or less. If the average molecular weight is less than 200, it is unsuitable because the spinning operability during fiber production will deteriorate, particularly the nozzle back pressure during spinning will increase.

On the other hand, if the average molecular weight exceeds 5,000, the monopolymerization rate decreases during polymerization of the vinyl polymer, and the vinyl polymer cannot be obtained efficiently, which is not preferable. Examples of polyoxyalkylene studs include polyoxyethylene glycol,
Examples include polyoxypropylene glycol, polytetrahydrofuran, and copolymers thereof, and those containing oxyethylene units are particularly preferred. Further, one end of these polyoxyalkylene groups may be an OH group or may be bonded to another organic group other than the polymerizable unsaturated group via an ether bond, an ester bond, or the like.

In the present invention, the vinyl polymer has a monomer unit composed of a vinyl unsaturated sulfonic acid or a salt thereof in its constituent units of 10 moles or more, preferably 15 moles or more and 90 moles or more.
It is desirable that the monomer unit content be less than 10%. If the monomer unit is less than 10 moles, unevenness will not occur on the fiber surface, and if it is more than 90 moles, the spinning property when making fibers will be reduced. I don't like it.

Furthermore, when the vinyl polymer is a monomer consisting of an unsaturated vinyl compound containing a polyoxyalkylene compound in its constituent units, it is at least 3 mol, preferably 5 mol.
Must contain more than molti.

By containing 3 or more moles of the monomer, long-term fiber formability, especially an increase in nozzle back pressure during spinning, can be improved.

Note that any method can be used to obtain the vinyl copolymer, and examples thereof include ordinary radical addition polymerization such as emulsion polymerization, suspension polymerization, and solution polymerization, and ionic polymerization. In addition to these methods, it is of course possible to adopt a method of introducing the monomer unit by sulfonating the vinyl polymer.

In the present invention, the vinyl polymer having the above structure must be blended in an amount of 0.3 to 20% by weight based on the resulting polyester. When the amount is less than 0.3% by weight, fine particles cannot be obtained on the fiber surface, and when it is more than 20% by weight, spinning operability becomes poor.

Further, the yarn physical properties of the obtained fibers are deteriorated, which is not preferable.

Further, in the present invention, any method can be adopted to blend the vinyl polymer into the polyester. For example, a method in which a vinyl polymer is mixed during the polymerization of polyester, or a method in which the vinyl polymer is added to the molten polyester and stirred and mixed after the completion of the 5-polymerization. Examples include a method in which a polyester pellet and a vinyl copolymer are stirred and mixed in an extrusion molding machine or a spinning machine.

Further, the composition of the present invention may contain other arbitrary additives such as antioxidants, ultraviolet absorbers, flame retardants, pigments, etc., but this does not impede the effects of the present invention in any way.

To remove a portion of the polyester fiber thus obtained, the polyester fibers are subjected to stretching heat treatment or false twisting as necessary. can be done.

Examples of the alkali compounds used here include sodium hydroxide, potassium hydroxide, tetramethylammonium, hydroxide, sodium carbonate, potassium carbonate, and the like. Among them, sodium hydroxide1. Potassium hydroxide is particularly preferred. The concentration of such an aqueous solution of an alkali compound varies depending on the type of alkali compound, processing conditions, etc., but is usually preferably in the range of 0.01 to 40% by weight. The treatment temperature is preferably in the range of room temperature to 100°C, and the treatment time is usually in the range of 1 minute to 4 hours. Further, it is appropriate that the amount to be eluted and removed by treatment with the aqueous solution of the alkali compound is in the range of 2 to 30% by weight.

By treating with an alkaline aqueous solution in this manner, a large number of the above-mentioned fine recesses can be easily formed. In addition, the minor axis of the four parts is about 0.01 to 1.0μ.

The major axis is 0.1 to 5.0 μ, preferably the minor axis is 0.05
-0.5μ, long axis 0.3-3.0μ. The cross-sectional form of the fiber may be solid, hollow, irregularly shaped solid, or irregularly hollow.

Hereinafter, the present invention will be specifically illustrated by examples.

In the examples, parts and q mean parts by weight (qbt).

In addition, evaluation of bathochromic property, water droplet absorption rate, and dry touch of Examples was performed by the following method.

Evaluation method (1) Bathochromic property: Silk material that has been subjected to weight loss treatment is dyed with 20% of DiaX Black HG-FS (dispersible dye from Mitsubishi Kasei)
Bath ratio 1:100° 6 at 130°C with towf water teaching solution
After staining for 0 minutes, reduction washing was performed.

Then, the L value of the dried knitted fabric was measured using a Hunter type color difference meter. The lower the L value, the deeper the color tone.

(2) JI for silk fabric treated to reduce water droplet absorption rate
A container for measuring the water droplet absorption rate using the SL-1018A method. A low value indicates high water absorption.

(3) Dry touch: Evaluation was made by touching the weight-reduced silk fabric with the hands.

Example 1 1000 parts of 1v dimethyteterephthalate and 700 parts of ethylene glycol were heated at 150°C using zinc acetate dihydrate as a catalyst.
Transesterification reaction is carried out while raising the temperature to ~230°C, and then methoxypolyethylene glycol/L/(20mol/L/)
Sevenoarylethe* (PEG (20) A E Toki t
) 85 R Sodium styrene sulfonate (S
PSS) was added to the bic=fii polymer obtained from 15 parts, and the mixture was heated to 0 at 275°C using antimony dioxide as a catalyst.
．． A polycondensation reaction was carried out under a reduced pressure of 1 wmHf to obtain a vinyl polymer-containing polyester having an intrinsic viscosity of 0.631 measured with a 674 mixed solution of phenol/tetrachloroethane.This was spun using an extrusion spinning machine. The obtained undrawn yarn was drawn according to a conventional method to obtain long fibers of 75 tennies/I/36 filament. This was knitted into an interlock, scoured, and treated under boiling conditions with a 209/l aqueous sodium hydroxide solution to obtain a silk fabric with a weight loss of 20 inches.

Fig. 1 shows a scanning electron micrograph of the surface of the fiber extracted from this silk fabric, magnified 4000 times.

As is clear from FIG. 1, there are many fine recesses. The obtained silk had a deep black color and an L value of 13.
It's 3 and it's hot. In addition, the water droplet absorption speed is 3 seconds, showing high water absorption, and it also gives a dry texture. It has been certified. In addition, polyester tv obtained without adding vinyl polymer t-
In the case of the knitted fabric, the L value of the fabric dyed black was 15.7, and the water droplet absorption rate was 300 seconds or more.

Comparative Example 1 When polyethylene terephthalate was synthesized from 1000 parts of dimethyl terephthalate and 700 parts of ethylene glycol according to the polyester synthesis method of Example 1, 150 parts of 30 parts of fine silica powder with an average particle size of 40 mμ was added at the end of the transesterification reaction. A polyester containing finely powdered silica having an intrinsic viscosity of 0.627 was obtained by adding a solution dispersed in 100% ethylene glycol.

This was spun using the same extrusion spinning machine as in Example 1 under the same conditions. The obtained undrawn yarn was treated in the same manner as in Example 1 to 75
A 5f Neil 36 filament was made into rope, and the material was subjected to weight reduction treatment and evaluated. The bathochromic property (L value 13.4) and dry touch of this material were almost the same as those of the silk fabric of Example 10, but the water droplet absorption rate was 180 seconds, indicating that the water absorbency was significantly inferior to that of the silk fabric of Example 1. Understood.

Examples 2-6. Comparative Example 2 A knitted fabric was obtained using the vinyl polymer used in Example 1 and having the composition shown in Table 1 in the same manner as in Example 1. The evaluation results are shown in Table 1.

Table 1 As is clear from Table 1, 5PSS in vinyl polymers
Unless it is 10mol/% or more, a fiber surface with improved bathochromic properties, water absorption, and dry touch cannot be obtained.

On the other hand, with PEG(20)AE, it was found that spinnability deteriorates unless the ratio is 3 or more.

Examples 7-10. Comparative Examples 3 to 4 A knitted fabric was obtained in the same manner as in Example 1, except that the addition (2) shown in Table 2 was added to the composition of the vinyl polymer used in Example 1.

The evaluation results are shown in Table 2.

Table 2 Umbrella 5PSS/PEG (20) AE and 15/85 (mole ratio) As is clear from Table 2, when the vinyl polymer content is less than 0.3, the fiber after reduction treatment is used. It was found that almost no copolymer was present on the surface, and on the other hand, when the vinyl copolymer content exceeded 20%, the spinnability was markedly reduced and spinning was difficult.

[Brief explanation of drawings]

FIG. 1 is a scanning electron micrograph of the fiber of the present invention obtained in Example 1, magnified 4000 times. Patent applicant: Toyobo Co., Ltd. Haya 11! l Procedures Amendment Document July 4, 1985 16 Case Description 1982 Patent Application No. 69849 2 Title of Invention Method for Manufacturing Polyester Fibers Having Fine Concave Parts 3 Relationship with the Person Who Makes the Amendment Case Patent Application 2-2-8 Dojimahama, Kita-ku, Osaka-shi, Column 5 of "Detailed Description of the Invention" of the Specification, Contents of Amendment (1) "Motsu" in the 3rd line of page 4 of the specification has been replaced with "Mochi, Power". "It has excellent anti-pilling properties." ■ Insert the following sentence between the third and fourth lines from the bottom of page 11. ``The polyester fiber obtained by employing the method of the present invention having the above-mentioned structure has a large number of fine depressions on the fiber surface, has excellent deep color development, water absorption, and has a dry touch texture. and has excellent anti-pilling properties.'' (3) Insert the following sentence under the last line of page 16. Example 11 A vinyl-based polymer co-produced polyester was obtained in the same manner as in Example 1, and after spinning, it was stretched 4 times, heat treated, and cut to obtain a spun yarn by a conventional method. There was no problem at all.The obtained spun yarn was knitted into a jersey knitted fabric,
It was treated under boiling conditions with a 20 g/l aqueous sodium hydroxide solution, washed with water, and dried. As a result, the knitted fabric with 20% integrity was measured according to J15107EiA (ICI pilling test method) and was found to be grade 5. Comparative Example 5 In Example 11, the same procedure as in Example 111 was carried out except that water containing vinyl polymer (1) did not contain vinyl polymer instead of diester (°C) x normal polyester (+1) was used. , The result of the I-P-IJ-K test is 1.
It was class. ”

Claims (2)

[Claims] (1) Polyester (V) obtained by adding 0.3 to 20% by weight of a vinyl polymer containing 10 moles or more of vinyl unsaturated sulfonic acid or its salt to an aromatic polyester whose main repeating unit is ethylene terephthalate.
A method for producing polyester fibers having fine recesses, which comprises subjecting fibers or textile products to elution treatment of the vinyl polymer using an alkaline aqueous solution. (2) Vinyl polymer is vinyl unsaturated sulfonate 1
Production of a polyester fiber having fine recesses according to claim (1), characterized in that an unsaturated vinyl compound having 0 to 97 mol and a polyoxyalkylene group is bonded thereto. Law.