JPH0653988B2 - Method for producing polyester-based synthetic fiber having fine pores - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyester fiber having fine recesses on the fiber surface. More specifically, it relates to a method for producing polyester fibers having special fine pores, exhibiting improved color depth and vividness when dyed, and having a particularly improved dry feel.

(Prior Art) Conventionally, there have been many attempts to improve texture and bathochromic property by imparting fine irregularities to polyester fibers.

For example, a method is known in which fine particles of an inert substance as disclosed in JP-B-43-14186 and the like are contained and then a part of the surface is eluted with a solvent. Another method is Japanese Patent Publication Sho-39-52
A method is known in which an easily-eluting polymer is blended and then eluted as disclosed in Japanese Patent Publication No. 14-242242.

As another means, a so-called internal particle method is known in which any one of a carboxylic acid component, an oligomer and a phosphorus compound is reacted with a metal compound during the polyester production reaction to form fine particles. Further, physical methods such as plasma treatment and rubbing with a rough surface are also known.

(Problems to be Solved by the Invention) A conventionally known method for eluting a fiber containing fine particles with a solvent is how to miniaturize the particles to be used and how to uniformly disperse the particles into primary particles. The point is that a complicated device is required and the amount of particles that can be contained in the polyester to prevent agglomeration is limited, and the surface of the obtained fiber has a relatively large number of flat portions between the concave portions. Although existing and a tactile improvement effect can be seen, the bathochromic effect is insufficient. In order to obtain a sufficient bathochromic effect, it is necessary to reduce the particle size to 50 mμm or less and evenly disperse the particles. Will be enough.

On the other hand, in the case of the method of blending the easily eluted substance, there are cases where the spinning equipment becomes complicated and the elution ability changes due to the passage of time during kneading. In addition, the easy-to-use eluate used may reduce the physical properties of the obtained yarn and affect the dyeing fastness,
At present, there is no satisfactory product. Although the surface-roughening technology by the internally generated particle method can obtain uniform fine unevenness after elution, it has a bathochromic effect due to the fact that the recesses are shallow and the recess edge is not relatively sharp as in the case of adding ultrafine particles. Has an extremely large effect, but cannot give a sufficient dry feeling or squeaky feeling to the touch.

Further, plasma irradiation and a physical surface roughening method using a rough surface are not sufficient in view of slow processing speed and uniform processing, and are difficult to industrialize.

(Means for Solving Problems) Technical means for solving the above problems, that is, the constitution of the present invention, comprises a dicarboxylic acid mainly containing terephthalic acid or an ester-forming derivative thereof and at least one glycol. Synthetic fiber made of polyester synthesized by reaction to form a glycol ester of dicarboxylic acid and / or a low polymer thereof and a second step of polycondensing the reaction product In doing so, the polyester having a mean particle diameter of 0.2 to 1.0 μm and a fine particle of the inert material at an arbitrary stage up to the start of the reaction in the second step of polycondensing the reaction product is added to the polyester.
The amount of the zirconium compound and the phosphorus compound added is 5 to 3% by weight, and the amount of the zirconium compound and the phosphorus compound added is 80 at the zirconium atom conversion with respect to the polyester produced by the zirconium compound at any stage until the synthesis of the polyester is completed.
˜2500 ppm and the zirconium compound and the phosphorus compound are added so that the phosphorus compound is 0.5 to 2.5 times the mol of the zirconium, and then the polyester obtained is completed and melt-spun. A method for producing a polyester-based synthetic fiber having fine pores, which comprises subjecting the obtained fiber or fiber product to an elution treatment with an alkaline aqueous solution.

In the method of the present invention, the polyester means that the main acid component is terephthalic acid or an ester-forming derivative thereof and the main glycol component is ethylene glycol, and the acid component is 20 mol% or less of acid, malonic acid, maleic acid, and glutaric acid. Acid, adipic acid, sebacic acid, 1,
Aliphatic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid and 2,5-norbornanedicarboxylic acid or ester-forming derivatives thereof, phthalic acid, isophthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 1 , 4-naphthalenedicarboxylic acid, 2,6
-Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 1,2-bis (phenoxy) ethane-P, P'-dicarboxylic acid or their ester-forming derivatives can be included as copolymerization components. 20 mol% of the acid component
The following oxycarboxylic acids such as P- (2-hydroxyethoxy) benzoic acid or ester-forming derivatives thereof may also be included.

As a glycol component, 20% or less of propylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,10-
Decamethylene glycol, 4,4'-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy)
Benzene, 2,5-naphthalene diol These glycols may include ethylene glycol-added glycol, polyethylene glycol and the like.

In the present invention, the above-mentioned first step reaction for reacting an acid component with a glycol component to produce a glycol ester of dicarboxylic acid and / or a low polymer thereof and a second step reaction for polycondensing the reaction product. In producing a synthetic fiber composed of polyester synthesized by and, it is important to add the fine particles of the inert substance at any stage up to the start of the reaction in the second stage for polycondensing the reaction product.

The effect of the fine particles of the inert substance on the formation of the surface fine structure of the fiber according to the present invention and the conditions for adding the fine particles of the inert substance will be described.

It has been conventionally known that it is effective to impart irregularities of 0.3 to 0.8 μm corresponding to the wavelength of visible light to the fiber surface as a means for improving bathochromism.

As a result of further studies on the bathochromic property and the fiber surface shape, the inventors found that the size of the fine recesses, particularly the recess width in the direction perpendicular to the fiber axis, is important for the bathochromic property, and It has been found that the existing flats have an unfavorable effect on the bathochromic properties. Further, it is known that it is effective to roughen the fiber surface or to form a modified cross-section yarn for the purpose of removing the slippery touch characteristic of the synthetic fiber of the polyester fiber.

The inventors have found that the width of the concave portion on the fiber surface (the width of the concave portion in the outer peripheral direction perpendicular to the fiber axis is hereinafter referred to as the concave portion width)
I examined the tactile effect and obtained interesting results. That is, when the width of the concave portions on the fiber surface becomes 0.5 μm or less, the effect of removing the touchy feeling that is slippery (hereinafter referred to as imparting a dry feeling) is remarkably disappeared, which is due to the synergistic effect with the number of fine concave portions that can exist. The width of the recess is 1.
When it is 0 μm, it is most effective in giving a dry feeling.
In addition, it is important that the edge of the recess, that is, the critical line between the recess and the average portion, is sharper as a factor of the shape of the recess that affects the feel. The sharp shape of the concave edge is related to the ease with which the micropore-forming agent and the base polyester are compatible. When it is difficult to adapt, a sharp edge is more likely to be formed and the rate of dissolution with the polyester is preferably high.

In the present invention, as means for achieving the above-mentioned object, inactive particle particles having an average primary particle diameter of 0.2 to 1.0 μm are used as means for forming a relatively rough surface recess. The inert substance particles in the method of the present invention are not so well compatible with polyester, and are important because they have the property that the edges of the recesses are sharp and partial peeling occurs at the interface between the particles and polyester during stretching after spinning. Requirements. Kaolin, talc, titanium oxide, silicon oxide, magnesium hydroxide, aluminum hydroxide, aluminum oxide, calcium carbonate, barium carbonate, barium sulfate, calcium hydroxide and the like are useful as the inert substance particles used here, but fibers For the purpose of reducing the metal abrasion in the process after spinning without impairing the transparency of No. 1, kaolin, talc and calcium carbonate, which have a refractive index close to that of polyester and low hardness, are preferable. The fine particles of the inert substance may be added at any stage after the dispersion in alkylene glycol, from the end of the esterification reaction, which is the first-step reaction, to the start of the polycondensation reaction, which is the second-step reaction.

In the present invention, the average particle diameter of the inactive substance fine particles is 0.2 to 1.
It is important that the average primary particle size is 0.2 μm or less, and if the average width of the primary particles is 0.2 μm or less, the recess width effective for touch cannot be obtained. It is necessary to increase the addition concentration because it is necessary to generate more, and if high concentration addition is adopted here, it is not possible to sufficiently raise the degree of polymerization due to the thickening effect of particle addition at the time of high concentration addition, There is a drawback that the physical properties of the obtained drawn yarn deteriorate.

When the particle size exceeds 1.0 μm, the particles are clogged in the filter during spinning, resulting in an increase in nozzle back pressure over time, spinning for a long time is not possible, and loss due to nozzle replacement becomes large, resulting in cost reduction. Not only is it unfavorable, but the physical properties of the obtained stretched yarn after the weight reduction is significantly reduced.

In the present invention, the addition amount of such inactive substance fine particles needs to be in the range of 0.5 to 3% by weight with respect to the produced polyester, and the addition amount of the inactive substance fine particles is 0.5% by weight. If the amount is less than 100%, the dry feeling is not sufficiently imparted. If the amount exceeds 3% by weight, the secondary particles increase and the coarse particles cause an increase in the nozzle back pressure during spinning and a decrease in the final yarn physical properties. It is inconvenient.

Furthermore, in order to achieve the present invention, it is important to add the zirconium compound and the phosphorus compound at any stage until the synthesis of the polyester is completed. That is, in order to further achieve the present invention, it is necessary that the formation of the recesses by the above-mentioned inert substance fine particles and the recesses formed by the internally generated particles of the zirconium compound and the phosphorus compound are present at the same time.

The effect of the internally generated particles on the formation of the surface microstructure of the fiber according to the present invention and the conditions for generating the internally generated particles will be described.

A method for producing internally generated particles is disclosed in, for example, JP-A-56-132039.
In the case of producing by a conventional method such as Japanese Patent Publication, it was necessary to strictly control the polymerization conditions in order to produce coarse particles and scale in the polymerization vessel, and to control the amount and particle size of produced particles. .

As a result of research on various combinations of the above problems, the inventors have found that internally generated particles produced from a zirconium compound and a phosphorus compound achieve the object of the present invention.

That is, the recess width of the recess formed after eluting the internally generated particles of the fiber according to the present invention with the alkaline solution is 0.2 to
It has a thickness of 0.5 μm and a depth of 0.05 to 0.2 μm and needs to be uniformly formed on the fiber surface.

Any zirconium compound can be used as long as it is soluble in the reaction system. Tetra-n is typical
-Propio zirconate, tetraisopropio zirconate, tetra-n-butyl zirconate, tetra-n-
Zirconium alkoxide such as amyl zirconate,
Zirconyl acetate, Zirconyl formate, Zirconyl tartrate,
Examples thereof include organic acid zirconyl salts such as zirconyl oxalate, zirconyl stearate and zirconyl benzoate, and inorganic acid zirconyl salts such as zirconyl chloride, zirconyl bromide, zirconyl carbonate and ammonium zirconyl carbonate.

The addition amount of these zirconium compounds is preferably set in the range of 80 to 2500 ppm in terms of zirconium atom based on the produced polyester, and when the addition amount is less than 80 ppm, the production amount of fine particles is small and the bathochromic property and the texture are improved. This is not preferable because the effect of is not obtained. On the other hand, if it exceeds 2500 ppm, the bathochromic property reaches a saturated state, rather coarse particles are generated, which causes a rise in back pressure and the polymer color deteriorates, which is not preferable. Especially preferred amount is 200-1500p
pm. The zirconium compound may be added in either solid or liquid form, but it is most preferable to add it as an alkylene glycol solution in order to uniformly disperse the produced particles. When it is added in a solid state, it is preferable to add it to the reaction system by enclosing it in a polyester vessel.

The phosphorus compound has a unique effect of controlling the concentration and size of particles precipitated by the zirconium compound and is the most characteristic component of the present invention together with the zirconium compound.

As such a phosphorus compound, a pentavalent phosphorus compound is preferable, and phosphoric acid, phosphonic acid and their derivatives are more preferable. Specific compounds include phosphoric acid, alkali metal salts of phosphoric acid, phosphoric acid trimethyl ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester,
Phosphoric acid triphenyl ester, phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid monoethyl ester, phosphoric acid diethyl ester, phosphoric acid monobutyl ester, phosphoric acid dibutyl ester, phosphonic acid, phosphonic acid alkali metal salt, methylphosphonic acid , Methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, benzinephosphonic acid diethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester,
Examples include diethylphosphonoethylpropionate,
These may be used alone or in combination of two or more. In particular, a combination of two or more kinds is preferable in that the control range of the particle size is widened.

Since these phosphorus compounds control the concentration and particle size of the insoluble particles formed by the zirconium compound as described above, the addition amount should be determined in consideration of the addition amount of zirconium, and confirmed by experiments. By the way, it was confirmed that the addition effect of the phosphorus compound is effectively exhibited by setting the addition amount so that the Zr / P molar ratio falls within the range of 0.5 to 2.5. However, when the amount of the phosphorus compound is too small, the insoluble particles formed in the polymer cannot be sufficiently miniaturized, the bathochromic effect of the final product is insufficient, and the stability of the polymer is reduced, which is preferable. Absent. On the other hand, if the amount is too large, the polymerization rate decreases, which is industrially disadvantageous. In addition, the softening point and stability of the polymer are lowered, which is not preferable.

The phosphorus compound may be added at any time until the synthesis of the polyester is completed, as in the case of adding zirconium, but it is added after the completion of the esterification reaction, which is the first step reaction, in order to reduce the formation of ether bonds. Is preferred. For the same reason, it is preferable to add the zirconium compound after the addition.

The polyester thus obtained is melt-extruded and spun by a conventional method, stretch-heat-set, woven and knitted to form a cloth, and an elution treatment is carried out with an alkaline solution to remove a part of the polyester fiber. Examples of the alkaline compound used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate and potassium carbonate. Of these, sodium hydroxide and potassium hydroxide are particularly preferable. The concentration of the aqueous solution of the alkaline compound varies depending on the type of the alkaline compound, the treatment conditions and the like, but is usually preferably 0.01 to 4.0% by weight. The treatment temperature is preferably room temperature to 100 ° C., and the treatment time is usually 1 minute to 4 hours. Further, the amount of the fiber or cloth partially eluted and removed by the treatment with the aqueous solution of the alkali compound is appropriately in the range of 2 to 30% by weight.

By thus treating with an alkaline aqueous solution, a large number of fine recesses can be easily formed on the surface of the fiber.

The cross-sectional shape of the fiber of the present invention may be solid, hollow, modified solid, modified hollow. Further, if necessary, it may be used as a spun yarn after being spun and drawn, followed by bulking such as false twisting or after drawing, and then made into short fibers.

(Examples) The present invention will be specifically described below with reference to Examples. In the Examples, "part" and "%" mean "part by weight" and "% by weight", respectively.

Example 1 1000 parts of terephthalic acid, 676 parts of ethylene glycol, 1.8 parts of triethylamine, 0.4 parts of antimony trioxide and Kaonri (Engelhard ASP-072 refractive index; 1.56 average particle size 0.3 μm) ethylene glycol slurry. (200g of kaolin was added per 1 part of ethylene glycol, mixed with a stirrer for 24 hours, and then 10wt% with a centrifugal classifier.
169.5 parts (having a kaolin concentration of 2% by weight with respect to the produced polyester) were charged in an autoclave and replaced with nitrogen, and then pressurized to a gauge pressure of 2.5 kg / cm ² to obtain 2
The esterification reaction was carried out while continuously removing water produced at 40 ° C. from the distillation column. 120 minutes after the start of the reaction, the pressure was released and a product having an esterification rate of 95% was obtained. 53.3 parts by volume of a 0.1 mol / concentration zirconium acetate solution in ethylene glycol was added to this product (addition of 1000 ppm in terms of zirconium atom to the produced polyester),
Then, an ethylene glycol solution of trimethylphosphate having a concentration of 100 g / 8.0 parts by volume (twice the mole of zirconium) was added, and the mixture was stirred at the same temperature for 10 minutes at normal pressure and heated to 240 ° C for polycondensation. Transfer to the reactor and take 60 minutes to gradually raise the pressure of the reaction system while raising the temperature to 275 ° C.
The polycondensation reaction was further carried out at the same temperature and the same pressure for 100 minutes at 0.1 mmHg. The polyester thus obtained was melt-extruded at a spinning temperature of 285 ° C. to obtain an undrawn yarn of 150 denier and 36 filament.

The undrawn yarn was drawn 3.0 times to obtain a drawn yarn of 50 denier and 36 filaments, and the drawn yarn was 103 warps /
A woven fabric having a plain weave structure with a pitch and a weft density of 86 / inch was obtained. The woven fabric was scoured and preset, and then treated in an aqueous solution of 60 g / sodium hydroxide at a temperature of 90 ° C. for 57 minutes to give a woven fabric having a weight loss ratio of 23% by weight. 20% owf of the same cloth of Dionyx Black HG-FS (disperse dye of Mitsubishi Kasei)
After dyeing with an aqueous dispersion at a bath ratio of 1: 100 at a temperature of 130 ° C. for 60 minutes, reduction washing was performed.

Then, the fabric was stretch-set at 160 ° C. for 30 seconds to obtain a final cloth. The cloth was measured for L value with a hunter type color difference meter, and at the same time, 10 people who were experts in polyester fabric weighed the texture and classified into 5 grades (5 for dry feeling, 1 for slimy cloth ; Regular polyester filament cloth) and judged. The results are shown in Table 1.

Example 2 The same as Example 1 except that the amount of the kaolin / ethylene glycol slurry used in Example 1 was 42.4 parts (kaolin concentration of 0.5% by weight based on the produced polyester) and the amount of ethylene glycol was 805 parts. Yarn and weaving were performed, and the obtained cloth was alkali-reduced and dyed, and the cloth was evaluated. The results are shown in Table 1.

Example 3 A cloth was obtained in the same manner as in Example 1 except that the amount of the zirconium acetate ethylene glycol solution of Example 1 was 5.33 parts and the amount of trimethyl phosphate ethylene glycol solution was 0.8 parts by volume. The fabric was evaluated. The results are shown in Table 1.

Comparative Example 1 The kaolin / ethylene glycol slurry of Example 1 was added to 0.
And the amount of ethylene glycol added was 822 parts, and the fabric was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 A fabric was produced and evaluated in the same manner as in Example 1 except that the amounts of the zirconium acetate ethylene glycol solution and the trimethyl phosphate ethylene glycol solution in Example 1 were each 0 parts. The results are shown in Table 1.

(Effects of the Invention) According to the present invention, the bathochromic properties of polyester fibers, which according to the prior art cannot be achieved without sacrificing the quality of the fibers, can be obtained without degrading the quality. In addition, a polyester fiber having an extremely improved dry feeling can be easily and stably produced. The polyester fiber obtained by the present invention is slightly coarse (0.4 to 1.5 .mu.m concave width, 0.05 to 0.5 .mu.m concave depth) due to the particles of the inert material, but has concave edges with sharp edges. A dry feeling is given, and
Fine (concave width of 0.2 to 0.5 μm, depth of 0.05 to 0.2 μm) concaves due to internally generated particles are evenly distributed on the fiber surface, so that there are few flat parts on the fiber surface. Since it has a special surface fine structure for improving the bathochromic effect, it is suitable for various kinds of clothing.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area // D06M 101: 32

Claims (1)

[Claims] 1. A first-step reaction for reacting a dicarboxylic acid mainly comprising terephthalic acid or an ester-forming derivative thereof with at least one glycol to form a glycol ester of dicarboxylic acid and / or a low polymer thereof. And in producing a synthetic fiber composed of a polyester synthesized by the reaction of the second step of polycondensing the reaction product, at any stage until the reaction of the second step of polycondensing the reaction product is started. Average particle size 0.2-1.0μ
The amount of the zirconium compound and the phosphorus compound added is 0.5 to 3% by weight with respect to the polyester that produces the inactive substance fine particles of m, and zirconium compound and phosphorus compound are added at any stage until the synthesis of the polyester is completed. The zirconium compound and the phosphorus compound are added so that the amount of the zirconium atom is 80 to 2500 ppm and the phosphorus compound is 0.5 to 2.5 times the mol of the zirconium with respect to the polyester produced by the compound, and then the polyester is synthesized. The method for producing a polyester-based synthetic fiber having fine pores, which comprises melt-spinning the polyester obtained by completing the above step and subjecting the obtained fiber or fiber product to an elution treatment with an alkaline aqueous solution.