JPS642687B2 - - Google Patents

Description

[Detailed description of the invention] (a) Industrial application field The present invention relates to a method for producing polyester fibers, more specifically, a process in which special linear micropores are formed by post-processing.
The present invention relates to a method for producing polyester fibers capable of producing a woven or knitted fabric that has a natural silk-like feel, particularly a natural semi-woven silk-like dry feel and squeaky feel, and is excellent in fibrillation resistance.

(b) Prior Art Polyester fibers have many excellent properties and are therefore widely used in woven and knitted fabrics.

However, woven and knitted fabrics made of polyester fibers lack a dry feel and a squeaky feel, which is significantly different from the excellent dry feel and squeaky feel of natural silk fabrics, especially natural semi-wrought silk fabrics.

Advances in production and processing technology for polyester fiber woven and knitted materials have made it possible to obtain woven and knitted materials that are quite similar to silk woven and knitted materials in terms of fullness, drapability, and repellency. There is a big difference in feel, which is one of the decisive differences between silk woven and knitted fabrics and polyester fiber woven and knitted fabrics.

The dry feeling and squeaky feeling mentioned here refers to the dry feeling and squeaky feeling that is peculiar to half-wrought silk woven and knitted fabrics among silk woven and knitted fabrics, and is in contrast to the slimy feeling that polyester fiber woven and knitted fabrics have. Quantitative measurement is difficult and is generally based on the touch of the fabric manufacturer.

(c) Purpose of the Invention The present inventor has developed a raw material for polyester fibers in order to eliminate the slimy feeling in polyester fiber woven and knitted fabrics and to provide polyester woven and knitted fabrics that exhibit an excellent dry feel and squeaky feel similar to semi-kneaded silk. As a result of extensive research from the perspective of yarn modification, we have developed a woven or knitted fabric by melt-spinning an improved polyester fiber obtained by melt-spinning a polyester blended with a polyester such as sodium alkyl sulfonate and a non-reactive organic sulfonate metal salt. After that, by subjecting the fiber to alkali weight reduction treatment, a large number of streak-like micropores oriented in the fiber axis direction can be formed on the surface and inside of the fiber.
We found that the resulting woven and knitted fabrics exhibit an excellent dry and squeaky feeling, probably due to the formation of such streaky micropores that cause creaks between the fibers, and we have already proposed (e.g. Unexamined Japanese Patent Publication 1987-
Publication No. 144237).

However, the polyester fibers having streak-like micropores obtained in this way tend to fibrillate due to physical external forces such as friction, and the fibrillated parts appear white, so they cannot be used for various purposes. In the past, there were problems that limited its use, for example, in the field of high-twist jersey textiles.

The inventor of the present invention has conducted extensive research in an effort to provide polyester fibers that do not have the above-mentioned drawbacks of fibrillation and can provide polyester woven and knitted fabrics that have excellent dry and squeaky sensations. It has been found that the above object can be achieved by using a higher fatty acid metal salt such as calcium stearate in combination with a polyester and a non-reactive organic sulfonic acid metal salt. Although the reason for this is not clear, due to the special interaction between the organic sulfonic acid metal salt and the higher fatty acid metal salt, the dispersion state of the organic sulfonic acid metal salt inside the polyester fiber changes to the dispersion state of the higher fatty acid metal salt. The adhesive force at the interface between the polyester and the organic sulfonic acid metal salt dispersed inside the polyester fiber, which becomes finer due to the action of the surfactant of the higher fatty acid metal salt, is increased by the action of the higher fatty acid metal salt. This is thought to be related to improvements in performance.

The present invention was completed as a result of further studies based on these findings.

(d) Structure of the Invention In other words, the present invention involves melt-spinning polyester to produce fibers, and at any stage until the end of melt-spinning, an organic sulfonic acid metal salt that is non-reactive with the polyester and a carbon number This is a method for producing polyester fiber characterized by adding 8 to 32 higher fatty acid metal salts.

The polyester in the present invention is a polyester having terephthalic acid as the main acid component and at least one type of glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as the main glycol component. The main target is

It may also be a polyester in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/or a part of the glycol component is replaced with the above-mentioned glycol other than the main component or other diol component. It may also be made of polyester.

Examples of difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid,
Diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, 5-
Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as sodium sulfoisophthalic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. In addition, examples of diol compounds other than the above-mentioned glycols include cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S.
Examples include aliphatic, alicyclic, and aromatic diol compounds such as, and polyoxyalkylene glycols.

Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as glycerin, trimethylolpropane, and pentaerythritol may be copolymerized to the extent that the polyester is substantially linear (usually 1 mol % or less). .

Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, usually terephthalic acid and ethylene glycol are directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are transesterified. The first stage reaction is to react with terephthalic acid to produce a glycol ester and/or its low polymer, and the first stage reaction product is heated under reduced pressure until the desired degree of polymerization is achieved. It is produced by a second step of polycondensation reaction.

The organic sulfonic acid metal salt to be mixed with the above polyester is not particularly limited as long as it is non-reactive with the polyester, but for example, an organic sulfonic acid metal salt represented by the following general formula RSO ₃ M Salt is preferably used.

In the above formula, R is an alkyl group having 3 to 30 carbon atoms, or an aryl group or alkylaryl group having 7 to 40 carbon atoms, and when R is an alkyl group or an alkylaryl group, the linear or branched side It may have a chain. M is a metal, preferably an alkali metal or an alkaline earth metal. Such an organic sulfonic acid metal salt does not need to be a single compound, and may be a mixture of sulfonic acid metal salts having various alkyl groups or alkylaryl groups, for example.

Preferred specific examples of such organic sulfonic acid metal salts include sodium stearyl sulfonate,
Examples include sodium octylsulfonate, sodium dodecylsulfonate, mixtures of sodium alkylsulfonates with an average carbon number of 14, mixtures of sodium alkylsulfonates with an average carbon number of 15, sodium dodecylbenzenesulfonate, etc. can.

The amount of the organic sulfonic acid metal salt added is preferably in the range of 0.3 to 30 parts by weight per 100 parts by weight of polyester. If the amount added is less than 0.3 parts by weight, the dry feel and squeaky feel of the final polyester fiber obtained will not be sufficient, and if it is more than 30 parts by weight, the processability in the mixing process with polyester, melt spinning process, etc. will be poor. So I don't like it. Particularly preferred is a range of 0.5 to 7 parts by weight.

The organic sulfonic acid metal salt may be added at any stage before the polyester melt spinning process is completed; for example, it may be added to the polyester raw materials, added during the polyester synthesis, or added during the synthesis. It may be added between after the completion of melt spinning and before melt spinning. In any case, it is preferable to mix them in a molten state after addition.

Carbon number 8 used in combination with the above organic sulfonic acid metal salt
~32 higher fatty acid metal salts include, for example, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pendadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, pehenic acid, lignoceric acid,
Cerotic acid, heptacanoic acid, montanic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, arachidonic acid, lithium, sodium, potassium, rubidium, cesium, perylium, magnesium, calcium, strontium of ricanic acid, barium, radium,
Zinc, cadmium, mercury, cobalt, cerium,
Manganese, nickel salts and the like can be mentioned, among which particularly preferred examples include calcium stearate, magnesium stearate, zinc stearate, calcium montanate, magnesium montanate and zinc montanate. These higher fatty acid metal salts may be used alone or in combination of two or more.

The amount of the higher fatty acid metal salt added is preferably in the range of 0.001 to 5 parts by weight per 100 parts by weight of polyester. If the amount added is less than 0.001 part by weight, the fibril resistance of the final polyester fiber obtained will be insufficient; as the amount is increased, the fibril resistance will improve, but if it is used in excess of 5 parts by weight, the fibril resistance will be insufficient. This is not preferable because the fibrillation resistance does not show a significant improvement, and on the contrary, the viscosity of the polyester fibers decreases, coloration, and haze increase. Especially 0.01
A range of 1.0 parts by weight is preferred. .

The higher fatty acid metal salt may be added at any stage until the melt spinning of the polyester is completed, similar to the addition time of the organic sulfonic acid metal salt. The organic sulfonic acid metal salt and the higher fatty acid metal salt may be added at the same time or at different times, and the order of addition may be arbitrary.

Preferred addition methods include, for example, a method of simultaneously adding an organic sulfonic acid metal salt and a higher fatty acid metal salt as a glycol diluted mixture during the second stage reaction of the polyester production; A polyester containing a higher fatty acid metal salt (higher fatty acid metal salt) and a higher fatty acid metal salt (or an organic sulfonic acid metal salt), or a polyester containing an organic sulfonic acid metal salt and a polyester containing a higher fatty acid metal salt are mixed in powder form, either as is or once. A method in which a polyester containing an organic sulfonic acid metal salt (or a higher fatty acid metal salt) and a higher fatty acid metal salt (or an organic sulfonic acid metal salt) are turned into chips and fed to a spinning process, or a polyester containing an organic sulfonic acid metal salt and a higher Polyester containing fatty acid metal salts and a polyester containing fatty acid metal salts are combined in a molten state, mixed using a static mixer, extrusion screw, etc., and supplied to the spinning process as is or once chipped, polyester, organic sulfonic acid metal salt, and higher fatty acid metal salt Mix each of the three in powder form,
A method for supplying the polyester, an organic sulfonic acid metal salt, and a higher fatty acid metal salt to the spinning process either as they are or once they are turned into chips.The polyester, the organic sulfonic acid metal salt, and the higher fatty acid metal salt are combined in a molten state and mixed using a static mixer, extrusion screw, etc. Examples include a method of chipping it and supplying it to the spinning process.

There is no need to employ any special method to melt-spun the thus obtained mixture consisting of the polyester, organic sulfonic acid metal salt, and higher fatty acid metal salt, and any melt-spinning method for polyester fibers can be employed. The polyester fibers obtained in this case may be solid fibers having no hollow portions or hollow fibers having hollow portions. Further, the outer shape and the shape of the hollow portion in the cross section of the fiber may be circular or irregular. Furthermore, even if it is a core-sheath type composite fiber consisting of the above-mentioned polyester mixture and ordinary polyester, with the polyester mixture as a sheath component and ordinary polyester as a core component, two layers or two layers consisting of the above-mentioned polyester mixture and ordinary polyester are used. It may also be a multilayer side-by-side type composite fiber as described above.

The polyester fiber obtained in this way is
After carrying out stretching heat treatment or false twisting as necessary, or by further treating it with an aqueous solution of an alkali compound after making it into a fabric, a part of it is removed and the fibers are coated on the fiber surface and inside in the fiber axial direction. It is possible to provide a polyester fiber knitted fabric in which a large number of streak-like micropores oriented in a direction are formed, which exhibits a dry feeling and squeaky feeling comparable to natural silk, especially natural semi-wrought silk, and which has significantly improved fibril resistance. .

Examples of the alkali compounds used in such alkali treatment include sodium hydroxide, potassium hydroxide, tetramethine ammonium hydroxide, sodium carbonate, potassium carbonate, and the like.

The concentration of the aqueous solution of the alkali compound described above varies depending on the type of alkali compound, processing conditions, etc.
Usually the range of 0.01 to 40% by weight is preferable, especially 0.1
A range of ~30% by weight is preferred. Processing temperature is room temperature ~
The temperature is preferably in the range of 100°C, and the treatment time is usually in the range of 1 minute to 4 hours. In addition, the amount of alkaline compound eluted and removed by treatment of the aqueous solution is:
A preferable range is 2% by weight or more based on the weight of the fiber.

The polyester fiber obtained by the method of the present invention may contain optional additives, such as catalysts, color inhibitors, heat resistant agents, flame retardants, fluorescent brighteners, matting agents, colorants, etc., as necessary. May be included.

(e) Effect of the invention As explained above, in the present invention, when producing polyester fiber, an organic sulfonic acid metal salt that is non-reactive with polyester and a carbon number of 8 to 32
The final polyester woven or knitted fabric after alkali treatment has a dry feel, squeakiness, and depth comparable to natural silk, especially natural semi-wrought silk. In addition to exhibiting gloss, the fibrillation resistance of the fabric is significantly improved compared to when a higher fatty acid metal salt is not used in combination.

(f) Examples The following examples will be further explained. Parts and % in Examples indicate parts by weight and % by weight, and the fibril resistance of the resulting polyester fibers was measured by the following method.

<Fibril resistance> Using a Gakushin type flat abrasion machine for abrasion fastness testing, a test cloth dyed gray was tested 300 times under a load of 500g using dioset made of 100% polyethylene terephthalate fiber as the friction cloth. After surface wear, the degree of discoloration was determined using a gray scale for discoloration. The case where the wear resistance was extremely low was rated as 1st grade, and the case where it was extremely high was rated as 5th grade. For practical purposes, a grade 4 or above is required.

Example 1 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, and 0.06 parts of calcium acetate monohydrate were placed in a transesterification tank, and the temperature was raised from 140°C to 230°C over 4 hours in a nitrogen gas atmosphere to produce methanol. The transesterification reaction was carried out while distilling it out of the system. Subsequently, 0.05 part of trimethyl phosphate and 0.04 part of antimony trioxide were added to the resulting reaction product, and the mixture was transferred to a polymerization vessel. Next, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and at the same time, over 1 hour and 30 minutes.
The temperature was raised from 230℃ to 285℃. In this depressurization process, when the degree of vacuum reaches 30 mmHg, 1.0 part of sodium alkyl sulfonate having 8 to 20 carbon atoms and an average of 14 carbon atoms, calcium stearate,
A mixture of 0.2 parts and 1.0 parts of ethylene glycol was added. Polymerization was carried out for 3 hours at a polymerization temperature of 285°C under reduced pressure of 1 mmHg or less to obtain a polymer having an intrinsic viscosity of 0.640 and a softening point of 263°C. After the reaction was completed, the polymer was made into chips according to a conventional method.

This chip was dried using a conventional method, and a spinneret with 36 circular spinning holes with a hole diameter of 0.3 mm was used.
The mixture was melt-spun at 290°C and then drawn at a draw ratio of 3.5 times according to a conventional method to obtain a raw yarn of 75 denier/36 filaments.

This yarn has S twist of 2500T/m and Z twist of 2500T/m.
The highly twisted yarn was then subjected to a steam treatment at 80° C. for 30 minutes to stop the twist.

This anti-twist, highly twisted yarn has a warp density of 47 threads/cm and a weft density of 32.
A satin jersey fabric was woven by alternately arranging two S and Z twists at a thread/cm ratio.

The obtained greige was subjected to a relaxing treatment for 20 minutes at boiling temperature using a rotary washer to create a texture, and after presetting using a conventional method, it was treated with a 3.5% aqueous sodium hydroxide solution at boiling temperature to achieve a weight loss rate of 20. % fabric was obtained.

This fabric is made from Kayalon Polyester in the usual manner.
Gray (Hodogaya Chemical Co., Ltd. product) 60 at 130℃ with 3.5% owf
After staining for minutes, 70°C in an aqueous solution containing 1 g of sodium hydroxide and 1 g of hydrosulfite.
A gray dyed cloth was obtained by reduction washing for 20 minutes.

This fabric exhibited an excellent dry feel and squeaky feel comparable to natural semi-woven silk, a deep and calm luster, and a high-quality color tone. The fibril resistance after 300 rubbings was good at grade 4-5.

Example 2 The same procedure as in Example 1 was carried out except that zinc stearate was used in place of the calcium stearate used as the higher fatty acid metal salt in Example 1.

The obtained fabric exhibited an excellent silk-like dry feel and squeaky feel, and its fibril resistance was good at grade 4 to 5.

Example 3 The same procedure as in Example 1 was carried out except that 0.1 part of magnesium stearate was used in place of 0.2 part of calcium stearate used as the higher fatty acid metal salt in Example 1.

The obtained fabric had excellent dry feel and squeaky feel, and good fibril resistance of grade 4 to 5.

Example 4 The same procedure as in Example 1 was carried out except that 0.3 part of calcium montanate was used in place of the calcium stearate used as the higher fatty acid metal salt in Example 1.

The fabric obtained had a dry touch that was superior to, but not inferior to, semi-woven silk. Fibril resistance is 4
It was in good condition.

Example 5 Same as Example 1 except that 2 parts of sodium dodecylbenzenesulfonate was used in place of the sodium alkylbenzenesulfonate used as the organic sulfonic acid metal salt in Example 1, and the amount of calcium stearate used was 0.6 parts. I did the same.

The obtained fabric had a silk-like dry feel and squeaky feeling, and the fibril resistance was grade 4 and passed.

Example 6 Intrinsic viscosity containing 1.0% sodium alkylsulfonate having an average carbon number of 14 was prepared in the same manner as in Example 1 except that calcium stearate used as the higher fatty acid metal salt in Example 1 was not used.
0.650 and a softening point of 263°C was obtained.

100 parts of these chips were dried in a conventional manner and placed in a Nauta mixer (manufactured by Hosokawa Iron Works) along with 0.2 part of separately dried calcium stearate powder.
After dry blending for 10 minutes, the mixture was melt-kneaded at 285°C using a twin-screw extruder to form chips.

Using this chip, the following steps were carried out in the same manner as in Example 1: chip drying, melt spinning, stretching, strong twisting, twist stopping, weaving,
Texturing, presetting, alkali reduction treatment, dyeing, and reduction cleaning were performed.

A semi-woven silk-like fabric with a good, mild luster and a pronounced dry and squeaky feel was obtained. The fibril resistance of this fabric was good at grade 4-5.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the calcium stearate used as the higher fatty acid metal salt in Example 1 was not used.

Although the obtained fabric had a good dry touch without sliminess, its fibril resistance was poor at grade 3, and it could not be used as a satin jersey fabric.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the calcium stearate used as the higher fatty acid metal salt in Example 5 was not used.

The resulting fabric had an excellent dry feel and squeaky feel, but its fibril resistance was poor at grade 2-3.

Claims (1)

[Scope of Claims] 1. When manufacturing fibers by melt spinning polyester, an organic sulfonic acid metal salt that is non-reactive with the polyester and a carbon number 8 to 32 metal salt are added at any stage until the melt spinning is completed. A method for producing polyester fiber characterized by adding a higher fatty acid metal salt. 2. The method for producing polyester fibers according to claim 1, wherein the amount of the organic sulfonic acid metal salt added is 0.3 to 30 parts by weight per 100 parts by weight of polyester. 3 The organic sulfonic acid metal salt has the following general formula RSO ₃ M [wherein R is an alkyl group having 3 to 30 carbon atoms or an aryl group or alkylaryl group having 7 to 40 carbon atoms, and M is an alkali metal or an alkylar earth group] Indicates metal. ] The method for producing a polyester fiber according to claim 1 or 2, which is an organic sulfonic acid metal salt represented by: 4. Production of the polyester fiber according to any one of claims 1 to 3, wherein the added amount of the metal salt of a higher fatty acid having 8 to 32 carbon atoms is 0.001 to 5 parts by weight per 100 parts by weight of polyester. Law.