JPH0643549B2 - Polyester composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a polyester composition, more specifically, a fiber having hydrophilicity such as antistatic property, sweat absorbing property, antifouling property, etc., which is excellent in durability.
The present invention relates to a polyester composition that can be easily formed into a molded product such as a film or a sheet.

<Prior Art> Since polyester has many excellent properties, it is widely used as a molding material for fibers, films, sheets and the like. However, since polyester is hydrophobic, its use is restricted in fields requiring hydrophilicity such as antistatic property, sweat absorption property, and antifouling property.

BACKGROUND ART Conventionally, attempts have been made to impart hydrophilicity to polyester so as to exhibit functionality such as antistatic property, sweat absorption property, antifouling property, and the like, and many proposals have been made so far.
For example, as one of attempts to impart antistatic properties to polyester fibers, a method of blending polyoxyalkylene glycol with polyester is known. However, in order to exert sufficient antistatic control on the polyester fiber by this method, a large amount of polyoxyalkylene glycol of 15 to 20% by weight is required, and the obtained antistatic polyester fiber has physical properties, especially thermal properties. Significantly deteriorated and cannot be used.

In order to solve this drawback, polyoxyalkylene glycol, polyoxyalkylene glycol / polyamide block copolymer, polyoxyalkylene glycol / polyester block copolymer, etc. which are substantially insoluble in polyester are used. A method of blending an ionic compound is also known. According to this method, it is possible to reduce the total amount of the antistatic agent used and obtain an antistatic polyester fiber having a relatively small decrease in physical properties. However, even the antistatic polyester fiber obtained by this method has the drawback that the dyeing fastness is liable to be chemically reduced, and the alkali widely used to improve the feel of the polyester fiber. When the weight reduction treatment is applied, it is usually performed after the weight reduction of 20% by weight or more of alkali, which is necessary for the development of silky feel.
There is a drawback that the antistatic property is easily lost in the dyeing process at a temperature of ~ 135 ° C, and it cannot be used in this application.

Furthermore, by melt-spinning a polyester in which a small amount (up to 3% by weight at most) of an antistatic agent composed of a substantially insoluble polyoxyalkylene glycol and a sulfonic acid metal salt into the polyester is melt-spun into a hollow fiber, an antistatic agent is obtained. A method has been proposed in which most of them are coagulated and localized around the hollow portion of the fiber, and the texture can be improved by alkali reduction treatment.
However, in order to impart sufficient antistatic property to the polyester fiber by such a method, it is necessary to strictly control the spinning conditions and the like to control the bleed-out of the antistatic agent to the periphery of the hollow portion, which results in a high spinning cost. Become. In addition, since the hollow portion is present, there is a drawback that the depth of color and sharpness when dyed are lowered.

On the other hand, a method has been proposed in which an antistatic agent is localized at a high concentration in the core / sheath composite fiber to enable alkali weight loss treatment, but the drawback is that the fiber manufacturing cost is significantly increased because it is a composite fiber. is there.

On the other hand, attempts have been made to impart hydrophilic properties such as antistatic property, sweat absorbing property, antifouling property, etc. to the polyester resin by a post-processing method, and many methods have been proposed so far. For example, a method of attaching a hydrophilic polymer compound to the fiber surface (eg, Japanese Patent Publication Sho
53-47435), a method of polymerizing a polymerizable monomer having a hydrophilic group on the fiber surface to form a film (eg, JP-A-53-130396), and the like. Such a method often loses its effect after repeated severe washing treatments, and if the amount of treatment agent is increased to increase the durability even a little, the texture will become rough and hard and the dyeing fastness will be poor. There are problems such as getting worse. Further, for example, thin fabrics, such as women's dresses and blouses, which require a soft texture, are often subjected to alkali weight reduction treatment in the case of polyester fibers. However, the above post-processing method has many problems such as difficulty in exerting a durable processing effect.

As described above, the solid fibers of the material-modified antistatic polyester that withstands high alkali weight loss have not yet been obtained by the conventional technology, and there is a limit in the post-processing technology. It is strongly desired to introduce solid antistatic polyester fibers by material modification that can withstand high alkali weight loss processing with a weight loss rate of about 20% by weight or more.

<Objects of the Invention> As is clear from the above, the object of the present invention is excellent in anti-static property, sweat absorption property, and anti-static property, for example, for high alkali weight reduction processing and washing processing which is severely repeated. It is an object of the present invention to provide a polyester composition capable of giving a molded article such as a fiber exhibiting hydrophilicity such as stain resistance.

The present inventor has made earnest studies to solve the above-mentioned drawbacks and to provide a hydrophilic polyester fiber having excellent mechanical properties, alkali resistance and washing resistance. As a result, the polyoxyalkylene glycol actually used in the conventional antistatic polyester fiber is substantially a linear polymer, and therefore, when the molecular weight is increased in order to increase the durability against hot water and washing, it is accompanied by it. Since the melt viscosity exponentially increases, it was difficult to disperse the polyester into a long streak when blended with polyester and melt-spun, and as a result, good antistatic property was not exhibited. Focusing on this point, the present inventor has focused on a method of modifying polyoxyalkylene glycol to have a high molecular weight and a low melt viscosity type. Further, the high molecular weight and low melt viscosity of the polyoxyalkylene glycol can be achieved by the branched polyglycerin polyether such as the alkylene oxide adduct of polyglycerin, and the branched polyglycerin can be obtained. It has been found that polyester fibers containing a specific kind of polyether exhibit dramatically superior antistatic durability. That is, the polyester fiber containing the specific polyglycene phosphorus polyether compound dispersed therein has practically sufficient strength and fibril resistance even if it is subjected to a high alkali weight reduction process with a weight reduction rate of about 20% by weight or more necessary for improving the feeling. In addition to having physical properties such as heat resistance and heat resistance, good antistatic property and its washing durability are maintained even after dyeing, and the color clarity and fastness of dyed products are also good. It has been found that even if the solid fiber is used as the antistatic polyester fiber without forming the type composite fiber, it has an extremely high potential. Also,
It was found that the polyester fiber thus obtained has not only excellent antistatic property but also excellent sweat absorption property (wicking property) and antifouling property. The present inventor has completed the present invention as a result of further studies based on these findings.

<Structure of the Invention> The present invention comprises (a) 100 parts by weight of an aromatic polyester and (b) the following general formula (I). (In the formula, X is independently a hydrogen atom, a hydrocarbon group or an acyl group, A is an alkylene group having 2 to 4 carbon atoms, m is independently an integer of 30 to 500, and n is an integer of 2 to 6. The present invention relates to a polyester composition containing 0.2 to 30 parts by weight of a polyglycerin polyether compound represented by the formula (1).

The aromatic polyester referred to in the present invention is an aromatic polyester having an aromatic ring as a chain unit of a polymer, and is a reaction of a bifunctional aromatic carboxylic acid or its ester-forming derivative with a diol or its ester-forming derivative. It is a polymer obtained by.

Examples of the bifunctional aromatic carboxylic acid referred to here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, and 2,6.
-Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid 4,4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4 ' Examples thereof include -p-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, β-hydroxyethoxybenzoic acid and p-oxybenzoic acid, and terephthalic acid is particularly preferable.

Two or more kinds of these bifunctional aromatic carboxylic acids may be used in combination. If the amount is small, a difunctional aliphatic carboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, or a bifunctional alicyclic carboxylic acid such as cyclohexanedicarboxylic acid together with these difunctional aromatic carboxylic acids. , 5-sodium sulfoisophthalic acid and the like can be used alone or in combination of two or more.

Further, as the diol compound, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-
Preferable examples are aliphatic diols such as 1,3-propanediol, diethylene glycol and trimethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof. Also,
If the amount is small, polyoxyalkylene glycol having both ends or one end unblocked can be copolymerized with these diol compounds.

Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, and polyols such as glycerin, trimethylolpropane, and pentaerythritol can be used as long as the polyester is substantially linear.

Specific preferred aromatic polyesters include polyethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-
In addition to bis (phenoxy) ethane-4,4'-dicarboxylate, etc., polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate,
Copolymerized polyesters such as polybutylene terephthalate / decanedicarboxylate can be used. Among them, polyethylene terephthalate and polybutylene terephthalate, which have well-balanced mechanical properties and moldability, are particularly preferable.

Such aromatic polyester can be synthesized by any method. For example, polyethylene terephthalate will be described. Either direct esterification reaction of terephthalic acid and ethylene glycol, transesterification reaction of lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or terephthalic acid and ethylene oxide will be described. The reaction is carried out to produce a glycol ester of terephthalic acid and / or a low polymer thereof in the first stage reaction, and then the product is heated under reduced pressure to carry out a polycondensation reaction until a desired degree of polymerization is reached. It is easily produced by the reaction of.

In the composition of the present invention, the above aromatic polyester is added to the following general formula (I) The polyglycerin polyether compound represented by is blended. In the general formula (I), X is independently a hydrogen atom, a hydrocarbon group or an acyl group, and the hydrocarbon group is preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an alkylaryl group, and The acyl group is preferably an alkanoyl group, alkenoyl group, cycloalkylcarbonyl group, arylcarbonyl group or alkylarylcarbonyl group. A is an alkylene group having 2 to 4 carbon atoms, and specific examples thereof include an ethylene group, a propylene group and a tetramethylene group. It may be a mixture of two or more kinds, for example, a copolymer having an ethylene group and a propylene group. m represents the degree of polymerization of alkylene oxide per branch and must be independently an integer in the range of 30 to 500. When m is less than 30, it does not exhibit durable antistatic, sweat absorption, and antifouling properties, and m is 5
If it exceeds 00, the melt viscosity of the polyglycerin polyether compound becomes excessive, so that the dispersibility of the polyglycerin polyether compound in polyester becomes poor, and good antistatic property, sweat absorption property, and antifouling property are obtained. I can't get it. A more preferable range of m is 50 to 300, and a particularly preferable range.
80 to 200. n is a positive integer indicating the degree of polymerization of polyglycerin and must be in the range of 2 to 6. When n is 1, the anti-thickness effect is insufficient and thus the durable antistatic property, sweat absorption property, and antifouling property are not exhibited, and when n is 7 or more, the polyglycerin polyether compound in the polyester is Due to poor dispersibility, good anti-static properties, sweat absorption and antifouling properties can no longer be obtained.

Preferred specific examples of such polyglycerin polyether compounds include the following.

X: independently H or R ' The above polyglycerin polyether may be used alone or in combination of two or more kinds.

The amount of the polyglycerin polyether compound added is
It is in the range of 0.2 to 30 parts by weight with respect to 100 parts by weight of the aromatic polyester. If the amount is less than 0.2 parts by weight, the hydrophilicity is insufficient and sufficient antistatic property, sweat absorbing property, and antifouling property cannot be exhibited. Further, even if the amount is more than 30 parts by weight, the effect of improving the antistatic property, the sweat absorbing property and the antifouling property is no longer recognized, and the mechanical properties of the composition obtained on the contrary are impaired.

The polyester composition of the present invention may contain an organic or inorganic ionic compound in order to improve the antistatic property. Preferred examples of the organic ionic compound include sulfonic acid metal salts and sulfonic acid quaternary phosphonium salts represented by the following general formulas (II) and (III).

RSO ₃ M (II) In the formula, R represents an alkyl group having 3 to 30 carbon atoms or an aryl group having 7 to 40 carbon atoms, and M represents an alkali metal or an alkaline earth metal. When R is an alkyl group in the above formula (II), the alkyl group may be linear or may have a branched side chain. M is an alkali metal such as Na, K or Li or an alkaline earth metal such as Mg or Ca, with Li, Na and K being preferred. Such sulfonic acid metal salts may be used alone or in combination of two or more. Preferred specific examples include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, sodium alkyl sulfonate mixture having an average number of carbon atoms of 14, sodium dodecyl benzene sulfonate (hard type, soft type),
Examples thereof include lithium dodecylbenzene sulfonate (hard type, soft type), magnesium dodecyl benzene sulfonate (hard type, soft type).

RSO ₃ PR ₁ R ₂ R ₃ R ₄ (III) In the formula, R is the same as the definition of R in the above formula (II), and R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups or aryl groups. Of these, a lower alkyl group, a phenyl group or a benzyl group is preferable. Such sulfonic acid quaternary phosphosnium salts may be used alone or in combination of two or more. Preferred specific examples include tetrabutylphosphonium alkylsulfonate having an average number of carbon atoms of 14, tetraphenylphosphonium alkylsulfonate having an average number of carbon atoms of 14, and butylalkylsulfonate having an average number of carbon atoms of 14. Triphenylphosphonium, tetrabutylphosphonium dodecylbenzenesulfonate (hard type, soft type), tetraphenylphosphonium dodecylbenzenesulfonate (hard type, soft type), benzyltriphenylphosphonium dodecylbenzenesulfonate (hard type, soft type) Etc. can be given.

As inorganic ionic compounds, potassium iodide, sodium chloride, calcium chloride, sodium thiocyanate,
Preferable examples include potassium thiocyanate, lithium thiocyanate, and cesium thiocyanate.

Such organic or inorganic ionic compounds may be used alone or in combination of two or more, and the compounding amount thereof is preferably in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the aromatic polyester. If it is less than 0.05 parts by weight, the effect of improving the antistatic property is small,
If the amount exceeds the range, the mechanical properties of the composition will be impaired.

Any method may be adopted for blending the polyglycerin polyether compound and, if necessary, the organic and / or inorganic ionic compound, and both may be blended with the aromatic polyester at the same time or in any order. You can That is, at any stage until the molding of the aromatic polyester is completed, for example, before the polycondensation reaction of the aromatic polyester is started, during the polycondensation reaction, at the end of the polycondensation reaction and still in the molten state, the powder state , At the molding stage, etc.
Both may be melt-mixed in advance and then added, divided into two or more times, or both may be separately mixed in advance with the aromatic polyester and then mixed before molding. Furthermore, when it is added before the middle stage of the polycondensation reaction, it may be added after being dissolved or dispersed in a solvent such as glycol.

The composition of the present invention may contain an antioxidant and an ultraviolet absorber, and it is preferable to do so. In addition, a flame retardant, a fluorescent whitening agent, a matting agent, a coloring agent, other additives, etc. may be added as required.

When the polyester composition of the present invention is used for fiber applications, any yarn-making conditions can be adopted without any trouble. For example, a method of spinning at a speed of 500 to 2500 m / min, drawing and heat treatment, a method of spinning at a speed of 1500 to 5000 m / min, and performing drawing and false twisting simultaneously or subsequently, 50
Any spinning conditions such as a method of spinning at a high speed of 00 m / min or more and omitting the drawing step may be adopted depending on the application. Also,
The heat treatment of the obtained fiber or fibrous material at a temperature of 100 ° C. or higher is effective for stabilizing the structure and for the polyglycerin polyether compound contained in the composition and the ionic compound contained as necessary. It is preferable because it promotes the migration to the vicinity of the surface. Furthermore, relaxation heat treatment and the like can be used together if necessary.

Further, the composition of the present invention can be used for film and sheet applications, and in this case, any molding condition can be adopted without any trouble. For example, arbitrary conditions such as a method of drawing the film-forming yarn in one direction and a method of drawing in two or more stages are used. Also, 100 films, sheets, etc.
It is preferable to perform the heat treatment at a temperature of 0 ° C. or higher for the reasons described above.

<Effects of the Invention> Molded articles such as fibers obtained from the polyester composition of the present invention exhibit excellent antistatic property, sweat absorption property, and antifouling property even after repeated washing and heat treatment such as ironing and pressing. Therefore, it is a very suitable material for applications in which washing and heat treatment are frequently performed and antistatic property, sweat absorption property, and antifouling property are required.

In recent years, uniforms used in various workplaces, work clothes called uniforms, work clothes worn in industrial work, clothing such as white coats used in medical, food-related workplaces, etc., used in hospitals, hotels, etc. Sheets, bedding covers, bedding such as yukata, sleeping clothes, etc., and table cloths used at restaurants, various banquets, gatherings, etc. are called linens, and are rented where they are used. In many cases, this weight is increasing year by year, and these product fields are also called linen supply fields. What is required of products in this field is that they are clean and can be comfortably used or worn from the side of using the product, while from the side of renting the product, the product after use is The stains do not easily come off, the stains do not redeposit during washing, the product does not deteriorate even after repeated washing, ironing, pressing, etc., and comfort is maintained. The content of comfort varies depending on the application and place of use, but it is typical that it absorbs sweat that has been worn while wearing it (sweat absorbing property) or does not generate static electricity (antistatic property). Therefore, it is easy to remove stains on these linen supply products,
Soil does not reattach during washing, that is, it has antifouling properties, has sweat absorption and antistatic properties, and even if these performances are repeatedly washed, even after repeated heat treatment such as ironing and pressing after washing, the initial It is desirable that the product of the composition of the present invention has antifouling property, sweat absorption property, and antistatic property.
Moreover, since it has excellent washing resistance and heat resistance, it can be suitably used.

In addition, as is well known, polyester fibers are often subjected to alkali weight reduction processing for the purpose of improving the texture, but the fibers of the polyester composition of the present invention have antistatic, sweat-absorbing and antifouling functions. It is not affected at all by such alkali weight reduction processing, and the deterioration of mechanical properties due to alkali weight reduction is extremely small, so it is possible to improve the texture by alkali weight reduction treatment, and it can be used for female inner wear such as lingerie, lining, dust-free clothing, etc. It can be used not only in the field but also in the field of anti-static, sweat absorption, and antifouling, and is extremely useful.

Furthermore, according to the polyester fiber made of the composition of the present invention, a conventional composite fiber type (one in which an antistatic agent is localized at a high concentration in the core portion of the core-sheath composite fiber to enable alkali treatment) and Compared to the hollow fiber type (an antistatic polyester resin in which the antistatic agent is localized around the hollow part of the polyester hollow fiber to enable alkali treatment), there is no need to perform special spinning, and the spinning cost is reduced. , It is remarkably superior in terms of diversification of brands (easy cross-section, fine denier), color depth and sharpness of dyed products.

<Examples> Examples will be further described below. Parts and% in the examples indicate parts by weight and% by weight, respectively, and the antistatic property, water absorption property and antifouling property of the obtained polyester fiber were measured by the following methods.

(1) Antistatic property The sample was left in the atmosphere of temperature 20 ° C and relative humidity 65% for one day or more in advance to adjust the humidity, and then 10 KV was applied to the electrode using a static onest meter, and the temperature was kept at 20 ° C. Relative humidity
Measure the half-life (seconds) of the sample electrostatic voltage at 65%.

(2) Water absorption speed (according to JIS-L1018) The sample is stretched horizontally, one drop (0.04cc) is dropped from a height of 1 cm above the sample, and water is completely absorbed by the sample and reflected light is observed. Measure the time (in seconds) until it runs out.

(3) Antifouling property (i) Contamination treatment Put 300cc of the contamination liquid of the following composition in the pot of the color pet dyeing tester (manufactured by Nippon Dyeing Machinery), and immerse the sample of 10cm x 13cm sandwiched in the holder into it. The mixture was stirred at 50 ° C for 100 minutes.

Contaminated liquid composition The composition of the artificial soiling liquid is as follows.

Artificial dirt liquid After the above treatment, the sample was lightly washed and then sandwiched between filter papers to remove excess contamination. This contamination treatment, washing with water and treatment for removing excess contaminated liquid were repeated 4 times. Then, half of the contaminated sample was washed for 10 minutes in a warm water of 40 ° C. containing 2 g / mL of Marcel soap under a weak condition of a home washing machine. Thereafter, the stainability and removability were determined by the following methods.

(ii) Determination of contamination and removability Macbeth MS-2020 (Instrumental Color System)
(Produced by Limited) and E ^* of the CIE colorimeter by a conventional method ^.
Was calculated, and the stainability and removability were calculated by the following formulas.

ΔE ^* _A = E ^* _1- E ^* ₂ ΔE ^* _B = E ^* _1- E ^* _{3 In the} above formula, ΔE ^* _A : Contamination property ΔE ^* _B : Removability E ^* ₁ : Before contamination treatment E ^* E ^* ₂ of sample: E ^* E ^* ₃ of sample after contamination treatment: E ^* E of sample after washing treatment ^* (4) Washing-heat treatment Antistatic, water absorption rate and antifouling washing-durability to heat treatment The washing treatment and heat treatment for investigating the property were as follows.

(i) Washing treatment Using a household washing machine (National NA-680L), 2 g of new enzyme Zab (manufactured by Kao) / 30 solution (bath ratio 1:30)
Put the sample, put the sample and wash at 40 ℃ for 10 minutes with automatic swirling water flow. After that, dehydration, warm water at 40 ℃ 30 (bath ratio 1:30)
Rinse with hot water for 5 minutes, dehydrate, and then rinse with overflow water for 10 minutes.
It was made for a minute and dehydrated. The above washing was treated once and this was repeated as many times as necessary.

(ii) Heat treatment 1 in a hot air dryer at a temperature of 170 ° C in an air atmosphere
It was treated for 1 minute, and this was treated once.

Therefore, the repetition of washing to heat treatment means 1
This means that the heat treatment is performed once after performing the washing once, and the washing to heat treatment are performed once, and the combination is repeated a necessary number of times.

Examples 1 to 4 and Comparative Example 1 100 parts dimethyl terephthalate, 60 ethylene glycol
Parts, calcium acetate monohydrate 0.06 parts (0.066 mol% relative to dimethyl terephthalate) and cobalt acetate tetrahydrate 0.009 parts as tanning agent (0.007 relative to dimethyl terephthalate)
(Mol%) charged in a transesterification can, and under a nitrogen gas atmosphere 4
The temperature was raised from 140 ° C to 220 ° C over a period of time, and the produced methanol was distilled out of the system to carry out a transesterification reaction.
After completion of the transesterification reaction, 0.058 parts of trimethyl phosphate as a stabilizer (0.080 mol% based on dimethyl terephthalate) and 0.024 of dimethylpolysiloxane as a defoaming agent.
Added some. Then, after 10 minutes, 0.04 part of antimony trioxide (0.027 mol% relative to dimethyl terephthalate) was added,
Simultaneously expelling excess ethylene glycol, 240 ℃
After the temperature was raised to, it was transferred to a polymerization vessel. Then the following chemical formula (Average molecular weight 16500, m is about 93 as an average value) oleic acid ester of polyglycerin polyether (esterification number 2, melting point 52 ° C.) is added in the amount shown in Table 1, and subsequently added. The pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and at the same time, the temperature was raised from 240 ° C to 280 ° C over 1 hour 30 minutes. Irganox is used as an antioxidant after polymerization for 2 hours at a polymerization temperature of 280 ° C under a reduced pressure of 1 mmHg or less.
0.410 parts of 1010 (manufactured by Ciba-Geigy) was added under vacuum, and then polymerization was carried out for another 30 minutes. The polymer obtained had an intrinsic viscosity in the range of 0.645 to 0.655 and a softening point in the range of 260 to 263 ° C. This polymer was made into chips by a conventional method.

These chips are dried by a conventional method, melt-spun at 285 ° C using a spinneret having 24 circular spinning holes with a hole diameter of 0.3 mm, and then the elongation of the resulting drawn yarn is 30%. Using a heating roller at a draw ratio of 80 ° C. and a plate heater at a temperature of 160 ° C., a drawing heat treatment was carried out to obtain a drawn yarn of 75 denier / 24 filament.

The drawn yarn thus obtained was made into a knitted fabric, and refined and preset (180 ° C. × 45 seconds) by a conventional method to obtain a knitted fabric A. After presetting, a knitted fabric B having a weight loss rate of 20% was obtained by treating with a 3.5% sodium hydroxide aqueous solution at a boiling temperature.

Next, the knitted fabric A and the knitted fabric B were subjected to hot water treatment (pure dyeing model) at 130 ° C. for 60 minutes with pure water, and then subjected to final set (160 ° C. × 45 seconds) according to a conventional method.

Using the obtained knitted fabric A and knitted fabric B, antistatic property (charge voltage half-life (abbreviated as electrification voltage half-life (abbreviated as LH ₂₅ )) after washing-heat treatment 0 times (abbreviated as LH ₀ ) and selection-25 heat treatment repeated (abbreviated as LH ₂₅ ) Seconds)), water supply speed (seconds) and antifouling property. The results are shown in Table 1.

Examples 5 and 6 In Example 3, a polyglycerin polyether compound was used, and 10 minutes after 10 minutes from the time when the degree of vacuum reached 3 mmHg in the pressure reduction process of the polymerization reaction, 8 carbon atoms were added.
Example 3 was repeated except that sodium alkylsulfonate having an average carbon number of 14 and having a carbon number of -20 was added under vacuum in the amount shown in Table 1. The results are as shown in Table 1.

Examples 7 and 8 The procedure of Examples 5 and 6 was repeated, except that the sodium alkylsulfonate used in Examples 5 and 6 was replaced with tetrabutylphosphonium dodecylbenzenesulfonate. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 5 was repeated, except that the polyglycerin polyether compound used in Example 5 was replaced with polyoxyethylene glycol having an average molecular weight of 20000. The results are shown in Table 1.

Comparative Example 3 Instead of the polyglycerin polyether compound used in Example 5, the following chemical formula was used. The same procedure as in Example 6 was carried out except that an oleic acid ester of glycerin polyether represented by the formula (average molecular weight: 18,000, m: average value: about 135) was used. The results are shown in Table 1.

Example 9 The following chemical formula was used instead of the polyglycerin polyether compound used in Example 5. The same procedure as in Example 5 was carried out except that an oleic acid ester of polyglycerin polyether represented by the formula (average molecular weight 35,000, m is about 99) (esterification number 4, melting point 49 ° C.) was used. The results are as shown in Table 1.

Comparative Example 4 The following general formula was used instead of the polyglycerin polyether compound used in Example 5. The same procedure as in Example 5 was carried out except that an oleic acid ester of polyglycerin polyether represented by the formula (average molecular weight 35,000, m is about 66) was used. The results are shown in Table 1.

Example 10 Instead of the polyglycerin polyether compound used in Example 5, the following chemical formula (Average molecular weight 70,000, m is about 200 as an average value) The same as in Example 5 except that a polyglycerin polyether compound in which 4 out of 8 terminal hydroxyl groups of the polyglycerin polyether is phenoxy-capped is used. went. The results are as shown in Table 1.

Claims (1)

[Claims] Claims: (a) 100 parts by weight of an aromatic polyester (b) The following general formula (I) (In the formula, X is independently a hydrogen atom, a hydrocarbon group or an acyl group, A is an alkylene group having 2 to 4 carbon atoms, m is independently an integer of 30 to 500, and n is an integer of 2 to 6. A polyester composition comprising 0.2 to 30 parts by weight of a polyglycerin polyether compound represented by the formula (1).