JP2865846B2 - Antistatic polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention has an antistatic property with excellent durability even under low-temperature and low-humidity conditions, and has no problem such as whitening even during high alkali weight reduction processing. The present invention relates to an antistatic polyester fiber capable of improving feeling.

<Prior Art> Conventionally, attempts have been made to impart hydrophilicity to polyester fibers to exhibit functionality such as antistatic properties, 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 (for example, Japanese Patent Publication No. 39-5214).
However, in order for the polyester fiber to exhibit sufficient antistatic properties by this method, a large amount of polyoxyalkylene glycol as much as 15 to 20% by weight is required, and the obtained antistatic polyester fiber has physical properties, particularly thermal properties. It deteriorates drastically, and is inferior in use due to poor washing fastness.

In order to solve this drawback, polyoxyalkylene glycol which is substantially incompatible with polyester, polyoxyalkylene glycol / polyamide block copolymer,
A method of using a polyoxyalkylene glycol / polyester block copolymer or the like and further blending an organic or inorganic ionic compound has been proposed (for example, JP-B-44-31828, JP-B-60-11944). , JP
53-80497, JP-A-60-39413). According to this method, the total amount of the antistatic agent used can be reduced, and an antistatic polyester fiber having a relatively small decrease in physical properties can be obtained. However, the antistatic polyester fiber obtained by this method also has the disadvantage that the color fastness is easily reduced chemically, and furthermore, the alkali weight reduction which is generally widely performed for improving the feeling of the polyester fiber. When the treatment is carried out, especially when the weight loss of 20% by weight or more is required for the alkali weight loss required for the expression of silky feeling, the antistatic property is usually obtained by a dyeing process at a temperature of 120 to 135 ° C. It has the disadvantage that it is easily lost and cannot be used in this application.

Furthermore, a polyester containing a small amount (at most 3% by weight) of an antistatic agent composed of a polyoxyalkylene glycol and a metal sulfonic acid salt substantially incompatible with the polyester is melt-spun into hollow fibers to thereby obtain a control. A method has been proposed in which most of the electric agent is aggregated and localized around the hollow portion of the fiber to improve the feeling by alkali reduction treatment (Japanese Patent Publication No. 60-56802). However, in order to impart sufficient antistatic properties to the polyester fiber by such a method, it is necessary to control bleed-out of the antistatic agent to the vicinity of the hollow portion by strictly controlling the thread-forming conditions and the like. In addition, when a high alkali weight loss treatment exceeding 15% by weight is performed, the antistatic property is easily lost by dyeing. In addition, since the hollow portion exists, there is a disadvantage that the color depth and sharpness when dyed are reduced.

In addition, a high concentration of an antistatic agent consisting of a polyoxyalkylene glycol and a metal sulfonic acid salt, which are substantially incompatible with polyester, is localized at a high concentration on the core of the core-in-sheath type conjugate fiber. (For example, Japanese Patent Publication No. 61-6883, Japanese Patent Application Laid-Open No. 55-1220)
No. 20, JP-A-61-28016). According to this method, an antistatic polyester fiber having relatively excellent antistatic properties can be obtained even when a high alkali weight reduction processing with a weight reduction rate of about 25% by weight or more is performed. However, such fibers are also about
Under a low temperature condition of less than 20 ° C. or a low humidity condition of less than 40% relative humidity, there is a disadvantage that sufficient antistatic property cannot be exhibited.

On the other hand, about 3 to 30% by weight of a high molecular weight ethylene oxide copolymer having an average molecular weight of 20,000 or more and about 70%
An antistatic composition comprising up to 97% by weight has been proposed (JP-A-64-26674).
It is disclosed that 2-dodecylene oxide may be used. However, in this method, since an ethylene oxide copolymer having a high molecular weight such as 20,000 or more is used as an antistatic agent, when applied to an aromatic polyester, the bleed-out property of the antistatic agent is suppressed and sufficient. The antistatic initial performance cannot be obtained. Further, since the ethylene oxide copolymers specifically disclosed are all random copolymers and are water-soluble to water-dispersible, a composition containing such an ethylene oxide copolymer is treated as a fiber. However, they have poor antistatic durability such as hot water resistance, alkali resistance, and washing resistance, and are not practical.

On the other hand, attempts have been made to impart antistatic properties and the like to polyester fibers 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 (for example, Japanese Patent Publication No. 53-47435), a method of polymerizing a polymerizable monomer having a hydrophilic group on the fiber surface to form a coating ( For example, JP-A-53-13
No. 0396, etc.), but the fiber obtained by such a method often loses its effect when repeated severe washing treatment is performed, and the amount of the treatment agent applied is increased in order to increase the durability even a little. If it does so, there are problems such as a rough feel and poor color fastness. Further, for example, polyester fabrics are often subjected to weight loss treatment with alkali for thin fabrics and the like that require a soft hand, such as women's dresses and blouses. However, the above-mentioned post-processing method has many problems such as difficulty in exhibiting a durable processing effect.

The present inventors have conducted studies to provide an antistatic polyester fiber having excellent mechanical properties and alkali resistance and washing resistance, and have studied water-soluble polyesters generally used in conventional antistatic polyester fibers. Instead of oxyethylene glycol, water-insoluble polyoxyethylene-based polyether, which has been made water-insoluble by specifically copolymerizing ethylene oxide with a specific higher olefin oxide, is used to achieve high alkali weight reduction processing and high-temperature hot water. The inventor of the present invention has filed an application to find that polyester fibers having excellent antistatic properties, sweat absorption properties, antifouling properties and the like can be obtained with respect to the treatment, and further to the harshly repeated washing treatments and the like (Japanese Patent Laid-Open No. 43252/1990). issue). According to this method, even if a solid fiber is used instead of a hollow fiber, the alkali weight loss rate is 20% by weight.
As described above, the practical required characteristics such as washing durability of ₃₀ or more washings (L ₃₀ ), visual infectious color and abrasion resistance are good. But,
Even in such a method, in order to impart sufficient antistatic property and its washing durability to the polyester fiber, it is necessary to control the dispersion of the antistatic agent by strictly controlling the spinning conditions. In the case where an alkali weight reduction rate of 25% by weight or more, which is necessary for further increasing the weight, is performed, there is a disadvantage that the antistatic effect is reduced. Furthermore, if there is a portion to which pressure is applied before the weight reduction processing, a problem that the portion looks white when the portion is fibrillated and dyed during weight reduction (hereinafter sometimes referred to as pressure loss whitening) is likely to occur. It turned out that. This pressure loss whitening is a phenomenon in which, if there are pin marks, scratches, and the like imparted in processing steps performed before alkali weight reduction such as weaving, knitting, refining, and presetting, the portion appears whitish after alkali weight loss and dyeing. This is a serious drawback of woven and knitted products. Incidentally, even in the solid fibers and hollow fibers of the polyester containing an antistatic agent composed of the water-soluble polyoxyalkylene glycol and the metal sulfonate, when the alkali weight loss rate is high, the above-mentioned pressure loss whitening phenomenon occurs, It was also found that the degree was larger than that of the polyester containing an antistatic agent comprising the water-insoluble polyoxyethylene-based polyether. In the pressure loss whitening phenomenon, in the case of solid fibers and hollow fibers, the degree of whitening decreases as the amount of the water-insoluble polyoxyethylene-based polyether and the amount of the metal sulfonic acid salt mixed with polyester are reduced. If the amount of water-insoluble polyoxyethylene-based polyether to be added to the polyester is reduced, hydrophilicity and hygroscopicity are reduced, and the antistatic durability, especially under low temperature and low humidity conditions, is insufficient. Becomes As described above, whitening of pressure loss and antistatic durability under low temperature and low humidity conditions are contradictory problems.

As mentioned above, at low temperatures of less than about 20 ° C and relative humidity
Antistatic polyester fibers that have been modified to provide antistatic durability under low humidity conditions of less than 40% and even after high alkali weight loss treatment have not yet been proposed. It is rare.

<Object of the Invention> Based on the present situation, the present invention has an antistatic property with excellent durability even under conditions of low temperature and low humidity against severely repeated washing treatments and the like, and the weight loss rate is about An object of the present invention is to provide a polyester fiber which has no problem such as whitening even at the time of high alkali weight reduction processing of 25% by weight or more and can improve the feeling.

<Structure of the Invention> The present inventors have solved the above-mentioned problem by using the water-insoluble polyoxyethylene-based polyether disclosed in the above-mentioned prior patent and its peripheral compounds, and the water-insoluble polyoxyethylene-based polyether. The study was repeated for the fiber structure using the blended polyester. As a result, by forming the core of the core-sheath type conjugate fiber from an aromatic polyester in which a water-insoluble polyoxyethylene-based polyether having a specific molecular structure is blended with an ionic compound, the above-described pressure loss whitening phenomenon Antistatic polyester fiber with sufficient antistatic properties and antistatic properties even under low-temperature and low-humidity conditions, with sufficient weight reduction processing durability and washing durability can be obtained, and the intended purpose can be achieved. Was found.

The excellent antistatic durability under low temperature and low humidity conditions is due to the fact that the polyester at the core of the sheath-core conjugate fiber has extremely excellent hydrophilicity and hygroscopicity, and also contains hot water, alkaline aqueous solution, and washing water. It is considered to be produced as a result of localizing and dispersing a specific water-insoluble polyether having a very low dissolution and elution property with respect to the polyester matrix and an excellent interface affinity with the polyester matrix at a high concentration. The present invention has been completed as a result of repeating experiments based on such findings.

That is, the present invention relates to a core-sheath type composite fiber whose core and sheath components are both made of aromatic polyester, wherein the core component is a poly (A) which simultaneously satisfies (a) the following (i) and (ii) with respect to the aromatic polyester. At most 10 oxyethylene polyethers
% By weight and (b) the ionic compound is present in an amount of 0.1 to 5% by weight, and the core / sheath area composite ratio is 5/95 to 50/50, and the polyoxyethylene-based polyether present in the core component is present. And the ionic compound, the total amount C (% by weight), the outer peripheral length L ₀ of the composite fiber in a cross section perpendicular to the fiber axis, and the outer peripheral length L ₁ of the figure formed by the core portion are:
An antistatic polyester fiber characterized by satisfying the following formula (II).

(I) Non-random copolymerizable polyoxyethylene polyether represented by the following general formula (I).

(Ii) The average molecular weight is 5000-16000.

The aromatic polyester used as the base of the sheath and the core in the present invention is an aromatic polyester having an aromatic ring in a chain unit of a polymer, and is composed of a difunctional aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or A polymer obtained by a reaction with the ester-forming derivative.

The bifunctional aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6
-Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid ,Four,
4'-diphenylisopropylidene dicarboxylic acid, 1,2-
Bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5
-Anthracenedicarboxylic acid, 4,4'-p-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, etc., and terephthalic acid is particularly preferred.

Two or more 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, dodecandioic acid, or a difunctional alicyclic carboxylic acid such as cyclohexanedicarboxylic acid may be used together with these difunctional aromatic carboxylic acids. An acid, 5-sodium sulfoisophthalic acid and the like can be used alone or in combination of two or more.

The diol compounds include ethylene glycol,
Propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,
Preferred are aliphatic diols such as 3-propanediol, diethylene glycol and trimethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, aromatic diols such as bisphenol A and bisphenol S, and mixtures thereof. Can be. If the amount is small, a polyoxyalkylene glycol having both ends or one end unblocked can be copolymerized with these diol compounds. Further, as long as the polyester is substantially linear, polycarboxylic acids such as trimellitic acid and pyromellitic acid, and polyols such as glycerin, trimethylolpropane and pentaerythritol can be used.

Specific preferred aromatic polyesters include polyethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyethylene-terephthalate.
In addition to 1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate, etc. Can be given. Among them, polyethylene terephthalate and polybutylene terephthalate, which are well-balanced in mechanical properties, moldability and the like, are particularly preferred.

Such an aromatic polyester is synthesized by any method. For example, when polyethylene terephthalate is described, terephthalic acid and ethylene glycol are directly reacted, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene oxide are reacted. The first step is a reaction to form a glycol ester of terephthalic acid and / or a low polymer thereof, and the second step is heating the product under reduced pressure to carry out a polycondensation reaction until a desired degree of polymerization is obtained. Easily produced by the reaction of

The polyester as described above may contain other thermoplastic polymers, for example, polyamides such as nylon-6, polyolefins such as polyethylene and polystyrene, etc., to such an extent that the physical properties of the polyester are not impaired. It is preferable to use the same polyester as the polyester used for the sheath portion and the core portion, but different polyesters may be used as long as they have an affinity.

In the antistatic polyester fiber of the present invention, a water-insoluble polyoxyethylene-based polyether is blended with the aromatic polyester in the core. The term “water-insoluble” as used in the present invention means that 5 g of a sample is put in 100 g of pure water, stirred at 100 ° C. for 60 minutes, allowed to cool to room temperature, and then JIS standard 5 type A
90% by weight or more is filtered out when natural filtration is performed using a filter paper.

As such a water-insoluble polyoxyethylene-based polyether, polyoxyethylene in which a polyoxyethylene block represented by the following general formula (I) is used as a main chain and the molecular chain end of the polyoxyethylene is blocked with a specific oxyalkylene component: A system polyether is preferably used.

Z (CH ₂ CH ₂ O) ₁ R ¹ O _m R ² ] _k (I) In the above formula, Z is a residue of an organic compound having 1 to 6 active hydrogens, and is represented by methanol, propanol, butanol, Phenol, ethylene glycol, bisphenol
A, residues of hydroxy group-containing compounds such as propylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, diglycerin, pentaerythritol, sorbitol, and 1 such as ethylenediamine, hexamethylenediamine, diethylenetriamine Examples thereof include residues of secondary and secondary amines, and among them, a hydroxyl group compound having a molecular weight of 300 or less is preferable. R ¹ is an unsubstituted alkylene group or a substituted alkylene group having 6 or more carbon atoms, among which a substituted alkylene group having 6 to 50 carbon atoms is preferable, and an alkylethylene group having 6 to 50 carbon atoms is more preferable. . Preferred specific examples of such R ^1, cyclohexylene group, phenylethylene group, hexyl ethylene group, methyl - can be mentioned hexyl ethylene group - pentyl ethylene group, heptyl ethylene group, methyl. R ¹ may be a mixture of two or more of the above.

R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent acyl group having 2 to 40 carbon atoms, and examples of the hydrocarbon group include an alkyl group, an alkenyl group and a cycloalkyl group. , An aryl group, an alkylaryl group and a hydroxyalkyl group are preferred. The acyl group is preferably an alkanoyl group, an alkenoyl group, a cycloalkylcarbonyl group, an arylcarbonyl group or an alkylarylcarbonyl group. k is an integer of 1 to 6 corresponding to the number of active hydrogen atoms of the organic compound serving as a source of Z. l needs to be an integer such that k × l is 70 or more, and may be the same or different between molecules or within a molecule. When the value of k × l is less than 70, the initial performance of antistatic property, hot water durability and washing durability of the finally obtained polyester fiber become insufficient. Also, k × l
As the value of 大 き く increases, the antistatic property and its durability are improved, but when this value exceeds 300, the remarkable improvement of the antistatic property and its durability is no longer recognized, and rather, the polyoxyethylene-based polyether Since water insolubilization tends to be difficult, l is preferably an integer such that the value of k × l is 300 or less. A more preferred range of k × l is in the range of 80-200. m is an integer of 1 or more, and may be the same or different between molecules or within a molecule, but all m must be an integer of 1 or more in k branches bonded to Z. When there is a branch where m is 0, the antistatic durability of the finally obtained polyester fiber becomes insufficient. Sequence of CH ₂ CH ₂ O units and R ¹ O units constituting such polyoxyethylene polyether, polyoxyethylene blocks consisting of CH ₂ CH ₂ O units constitute the main chain, the polyoxyethylene chains R ^{1 at the} end
It is necessary to take an arrangement in which the O unit forms a block of one unit or two or more units and is localized. Only by adopting such a specific structure can a high degree of water insolubilization and a high level of hygroscopicity of the polyoxyethylene-based polyether be enabled by introduction of a small amount of R ¹ O units, and a high antistatic property can be obtained. And its durability can be achieved. When the CH ₂ CH ₂ O unit and the R ¹ O unit are randomly arranged, the object of the present invention is not achieved.

The molecular weight of the above-mentioned water-insoluble polyoxyethylene-based polyether is in the range of 5,000 to 16,000. When the molecular weight is less than 5,000, the polyether is difficult to take a streaky dispersion form of a sufficient length in the polyester fiber, so that the initial antistatic performance becomes insufficient, and even if the R ¹ O unit is increased no matter how much. It is difficult to prevent the polyoxyethylene-based polyether from dropping into hot water, hot alkali, washing water, etc., and both the antistatic property and the durability of the finally obtained polyester fiber become insufficient. .

When the molecular weight exceeds 16,000, the melt miscibility of the polyoxyethylene-based polyether in the aromatic polyester is rapidly deteriorated, and the dispersibility is deteriorated. Since the antistatic property and physical properties are poor, and the above-mentioned whitening phenomenon of pressure loss is remarkably generated, this is a practically impossible area. Further, the increase in molecular weight also results in poor antistatic properties under low temperature and low humidity conditions. This is presumably because the thermal motion of the polyoxyethylene-based polyether in the polyester matrix is reduced, and the antistatic performance due to ionic conduction is reduced particularly at low temperatures. Among them, the preferred molecular weight range of the polyoxyethylene polyether is 55
00-14000.

In addition, the water-insoluble polyoxyethylene-based polyether described above has a specific hydrophilicity-hydrophobic balance described below in addition to satisfying the requirements described above, and exhibits particularly excellent antistatic durability and is excellent. Moldability and mechanical properties are obtained, and when subjected to an alkali weight reduction treatment of 20% by weight or more, the antistatic washing resistance is remarkably improved.
The effect of reducing the rate of alkali weight loss, the effect of improving visual infectious color, and the effect of improving abrasion resistance are remarkably recognized, and are extremely useful in practice.

That is, a value α expressed by the following formula (III) indicating the hydrophilic-hydrophobic balance of the water-insoluble polyoxyethylene-based polyether. However, it is preferable to satisfy the following conditions or.

When condition k = 1, 0.4 <α <3.0 When condition k = 2-6, 0.23 <α <3.0 The molecular term on the right side of the above formula (III) is the weight of the hydrophobic group in the polyoxyethylene polyether. And the denominator represents the weight of the hydrophilic group in the polyoxyethylene-based polyether. The denominator term 44 corresponds to the molecular weight of CH ₂ CH ₂ O unit.

In the above conditions and the inequality, the hydrophilicity-
When the value of the hydrophobic relational expression is below the lower limit, the water durability of the antistatic polyester fiber tends to decrease, and the antistatic weight loss processing durability and washing durability tend to decrease.

Conversely, when the value of the hydrophilicity-hydrophobic relational expression exceeds the upper limit, the hydrophilicity of the first polyoxyethylene-based polyether first decreases, and the initial performance of the hydrophilicity is insufficient, Even before the weight reduction processing, the antistatic property, particularly under low-temperature and low-humidity conditions, tends to decrease. Second, the miscibility between the polyoxyethylene-based polyether and the aromatic polyester is reduced, and the interface affinity between the polyester matrix and the water-insoluble polyether dispersoid tends to be reduced. When there is a portion to which is added, the fiber in that portion often becomes fibrillated by the raw material, and the dyeing is likely to be whitened. In addition, when an alkali weight loss treatment with a large weight loss rate is performed, the visual infectious color decreases and even if a sufficient amount of dye is dyed, the luminous density is small (appears whitish) and the abrasion resistance is low. It is likely to be defective (fibers are fibrillated by friction and the dyed fabric is whitened).

The preferred range of α is the following condition and range.

0.5 <α <1.5 for condition k = 1, 0.24 <α <1.5 for condition k = 2-6 Under the above conditions, the lower limit of the hydrophilic-hydrophobic relationship differs depending on the value of k because k = In the case of 1, only one end of the polyoxyethylene main chain is blocked with the (R ¹ O) _m component, whereas in the case of k = 2 to 6, all ends of the polyoxyethylene main chain are (R ¹ O) It is essentially related to being blocked by the _m component. As the water-insoluble polyoxyethylene-based polyether in the present invention, those having k = 2 to 6 are preferable.

Such a polyoxyethylene-based polyether comprises a first-stage reaction in which an active hydrogen compound is reacted with ethylene oxide, a second-stage reaction in which the product is reacted with an olefin oxide having 6 or more carbon atoms, and, if necessary, the product. Can be synthesized by a third step reaction in which the hydroxyl terminal group is blocked with a hydrocarbon group or an acyl group. The olefin oxide used at this time,
Nonene oxide, cyclohexene oxide and α-olefin oxides having 12 to 40 carbon atoms are particularly preferred.

Table 1 shows particularly preferred specific examples of such polyoxyethylene polyethers. Note that R ¹ is a mixture of alkyl ethylene groups having an alkyl group shown in parentheses and is represented by the average number of carbon atoms.

Specific examples other than H in R ² in the compounds shown in Table 1 _{^{R 2 = -CH 3, -C 6}} H 5, -CH 2 C 6 H 5, -C 12 H 25, -C
_{18 H 37, -C 18 H 35} , C 11 H 23 CO-, C 17 H 33 CO-, C 17 H 35 CO
-And the like are preferable. Such polyoxyethylene-based polyethers may be used alone or in combination of two or more.

The blending amount of the polyoxyethylene-based polyether is at most 10% by weight, preferably 2 to 7% by weight, based on the aromatic polyester constituting the core component of the sheath-core conjugate fiber. When the blending amount exceeds 10% by weight, the antistatic property of the finally obtained polyester fiber no longer shows a remarkable improvement, and the mechanical properties, heat resistance and light resistance of the obtained fiber are rather impaired. In addition, the alkali weight loss rate, visual infection colorability, pressure loss whitening property, etc. all deteriorate.

In the antistatic polyester fiber of the present invention, for the aromatic polyester of the core, together with the water-insoluble polyoxyethylene-based polyether described above, in order to improve the antistatic property, an ionic compound is used. Mix. As the ionic compound, an organic sulfonate which is substantially non-reactive with the aromatic polyester is preferable. As the organic sulfonic acid salt, for example, an organic sulfonic acid metal salt and an organic sulfonic acid quaternary phosphonium salt can all be used. Among them, the following general formulas (IV) to (IV) are preferable.
The compound represented by (VII) can be mentioned.

RSO ₃ M ... (IV) RSO ₃ PR ₁ R ₂ R ₃ R ₄ ... (V) R ₅ O (R ₆ O) _n (CH ₂ ) _p SO ₃ M ... (VI) R ₅ O (R ₆ O) _n in _{(CH 2) p SO 3 PR} 1 R 2 R 3 R 4 ... (VII) above formulas, R is an aryl group or an alkylaryl group of the alkyl group or having 7 to 40 carbon atoms of 3 to 30 carbon atoms When R is an alkyl group, it may be linear or branched. M is an alkali metal, and among them, Li, Na, and K are preferable. R ₁ , R ₂ , R ₃ and R ₄ are an alkyl group or an aryl group, and among them, a lower alkyl group, a phenyl group or a benzyl group is preferable. R ₅ represents a monovalent hydrocarbon group, such as an alkyl group, a cycloalkyl group,
Aryl or alkylaryl groups are preferred. R ₆ is an alkylene group, preferably an alkylene group having 2 to 4 carbon atoms. Specific examples include an ethylene group, a propylene group, and a tetramethylene group. A mixture of two or more,
For example, a copolymer of an ethylene group and a propylene group may be used. Among them, an ethylene group is particularly preferred. n is a positive integer indicating the degree of polymerization, and preferably ranges from 1 to 100, and particularly preferably ranges from 2 to 30. p is an integer of 2 to 4.

Preferred specific examples of the compound represented by the above (IV) include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, a mixture of sodium alkyl sulfonates having an average of 14 carbon atoms, t-butylbenzene sulfone Lithium oxide, sodium dodecylbenzenesulfonate (hard type, soft type), lithium dodecylbenzenesulfonate (hard type, soft type), potassium dodecylbenzenesulfonate (hard type, soft type), sodium dibutylnaphthalenesulfonate, dibutyl And lithium naphthalene sulfonate.

Preferred specific examples of the compound represented by the above (V) include a tetrabutylphosphonium salt of an alkylsulfonic acid having an average of 14 carbon atoms, and an average of 14 carbon atoms.
Is a tetraphenylphosphonium salt of an alkylsulfonic acid, a butyltriphenylphosphonium salt of an alkylsulfonic acid having an average of 14 carbon atoms, tetrabutylphosphonium dodecylbenzenesulfonate (hard type, soft type), tetradodecylbenzenesulfonate Examples thereof include phenylphosphonium (hard type and soft type) and benzyltriphenylphosphonium dodecylbenzenesulfonate (hard type and soft type).

Preferred specific examples of the compound represented by the above (VI) include C ₈ H ₁₇ O (CH ₂ CH ₂ O) ₇ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) CH ₃ O (CH ₂ CH ₂ O ) ₉ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) CH ₃ O (CH ₂ CH ₂ O) ₂₃ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ) ₂₃ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₂₃ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) C ₁₆ H ₃₃ O (CH ₂ CH) ₂ O) ₃₀ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) CH ₃ O (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ CH ₂ CH ₂ SO ₃ Na (or Li) C ₆ H ₅ O (CH ₂ CH ₂ O) ₂₂ CH ₂ CH ₂ CH ₂ SO ₃ Na (or Li) C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ SO ₃ K (or Li) C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₅ CH ₂ CH ₂ SO ₃ Na (or Li) and the like.

Preferred specific examples of the compound represented by the above (VII) include a metal salt in a preferred specific example of the compound represented by the above (VI), a tetra-n-butylphosphonium salt,
Examples thereof include tetraphenylphosphonium salts, n-butyltriphenylphosphonium salts, and compounds converted to phenyltri-n-butylphosphonium salts.

The organic sulfonates (IV) to (VII) may be used alone or in combination of two or more.

Further, among the organic sulfonates represented by the above formulas (IV) to (VII), (1) a compound which gives a transparent composition when quenched after being melt-mixed with the polyester and / or (2) the water Compounds that are substantially miscible with the insoluble polyoxyethylene-based polyether are more preferred because they provide particularly good antistatic properties and improve their durability. As such a compound which gives a transparent composition when quenched after being melt-mixed with the polyester, R in the above formula (IV) is an alkylphenyl group having 10 to 40 carbon atoms and M is
Preferred examples include a compound represented by Li or Na, a compound represented by the above formula (IV), wherein R is an alkylnaphthyl group having 14 to 40 carbon atoms, and a compound represented by the above formula (V). Examples of the compound substantially miscible with the water-insoluble polyoxyethylene-based polyether include the compounds represented by the above formulas (VI) and (VII).

Further, among the above-mentioned organic sulfonates, a compound in which R is an alkylphenyl group having 10 to 40 carbon atoms and M is Li or Na in the above formula (IV),
In addition to the excellent antistatic properties and durability of the finally obtained polyester fiber, it gives an alkali weight loss rate similar to that of the unmodified polyester, and further provides visual infectious color and fibril resistance after alkali weight reduction treatment. It is particularly preferable because it is much superior to others in that it gives As specific examples, sodium dodecylbenzenesulfonate (hard type, soft type), lithium dodecylbenzenesulfonate (hard type, soft type), sodium t-butylbenzenesulfonate, lithium t-butylbenzenesulfonate, dibutylbenzenesulfone And sodium dioctylbenzenesulfonate, lithium dioctylbenzenesulfonate, and the like.

Further, in addition to the compounds represented by the above general formulas (IV) to (VII), quaternary ammonium salts such as stearyltrimethylammonium chloride, distearyltrimethylammonium chloride, dodecylpyridium chloride and the like can be used as organic ionic compounds. , Sulfates such as sodium lauryl sulfate, sodium oleyl sulfate, sodium octyl sulfate, and phosphates such as sodium octanol phosphate, sodium lauryl phosphate, and diethanolamine lauryl phosphate. It is also possible to use.
Further, an inorganic ionic compound may be used, and examples thereof include potassium iodide, sodium chloride, calcium chloride, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, and cesium thiocyanate.

The organic or inorganic ionic compounds may be used alone or in a combination of two or more.

It is necessary that the amount of the ionic compound is in the range of 0.1 to 5% by weight, preferably 0.2 to 3% by weight, based on the aromatic polyester constituting the core component. If the compounding amount exceeds 5% by weight, if there is a portion to which pressure is applied before the weight reduction processing, fibrillation of the fiber in that portion is promoted due to the weight reduction, and the dyed cloth is whitened and cannot be put to practical use. On the other hand, if it is less than 0.1 part by weight, the effect of improving the antistatic property of the obtained polyester fiber is small.

In the antistatic polyester fiber of the present invention, the core / sheath area composite ratio is 5/95 to 50/50, and the water-insoluble polyoxyethylene-based polyether and ionic compound present in the core component are mixed. need summed amount C (wt%), the length L ₁ of the outer periphery of the shape forming the length L ₀ and the core component of the outer periphery of the fiber in a cross-section perpendicular to the fiber axis satisfies the following formula (II) There is.

When the core / sheath area composite ratio exceeds 50/50, the polyester portion constituting the sheath subdivision becomes thin, and the physical properties such as strength, fibril resistance and heat resistance are inferior. The durability, the color clarity and the fastness of the dyed product are at an insufficient level, making them impractical. Conversely, core /
When the area composite ratio of the sheath is less than 5/95, the effect of the polyoxyethylene-based polyether and the ionic compound blended in the core of the polyester fiber is not sufficiently exhibited, and the antistatic property, especially at low temperatures and low Poor antistatic properties under humidity conditions. In the above formula (II), If the value of is less than 2.2, the antistatic property becomes poor even before the reduction processing. vice versa, When the value exceeds 5, no further improvement in the antistatic property of the obtained polyester fiber is recognized, and the mechanical properties, heat resistance, light resistance and the like of the obtained polyester fiber are rather deteriorated. In addition, since the interfacial adhesiveness between the core and the sheath decreases, the sheath of the composite fiber becomes fibrillated due to friction and the dyed fabric whitens, and in particular, when there is a portion where pressure is applied before weight reduction processing, the In some cases, fibrillation of a part of the fibers is promoted by the raw material, and the dyed cloth is whitened and cannot be put to practical use.

Is more preferably 2.5 to 4.0.

In the antistatic polyester fiber of the present invention,
The alkali weight loss treatment is not an essential step, and may or may not be carried out depending on the application to be used. In the case of performing the alkali weight loss treatment, the amount to be reduced by the alkali weight loss treatment is the total blending amount C of the polyoxyethylene polyether and the ionic compound present in the polyester at the core of the polyester fiber after the alkali weight loss treatment. (% By weight), the outer peripheral length L ₀ of the composite fiber in the cross section perpendicular to the fiber axis of the polyester fiber obtained by weight reduction, and the outer peripheral length L ₁ of the figure formed by the core portion
Preferably satisfies the aforementioned equation (II).

Further, the aromatic polyester of the core and the sheath of the antistatic polyester fiber of the present invention may contain an antioxidant, a heat stabilizer, an ultraviolet absorber and the like, and it is preferable to do so. is there. In addition, if necessary, a flame retardant, a fluorescent whitening agent, a matting agent, a coloring agent, inert fine particles and other optional additives may be blended.

The antioxidant suppresses the thermal decomposition of the polyoxyethylene-based polyether polymer due to high temperature, low discharge speed, and long residence time in the melt spinning process of the fiber, etc., and makes the polyoxyethylene-based polyether polymer water-soluble and alkali-resistant. It is possible to prevent the occurrence of a decrease in the properties and the like. The type of the antioxidant used in the present invention is not limited as long as it has an antioxidant ability. Preferred antioxidants used in the present invention include hindered phenol compounds, thiopropionate compounds, phosphite compounds and the like. Even if only one kind is used alone, two or more kinds are mixed. May be used. The amount of the antioxidant is preferably in the range of 0.02 to 3% by weight based on the aromatic polyester. When the compounding amount is less than 0.02% by weight, the effect of inhibiting the thermal decomposition of the polyoxyethylene-based polyether polymer is insufficient. No further improvement is observed due to saturation, and the mechanical properties, hue, etc. of the resulting fiber are rather impaired.

In producing the antistatic polyester fiber of the present invention, a water-insoluble polyoxyethylene-based polyether, an organic and / or inorganic ionic compound, and, if necessary, an antioxidant are added to the aromatic polyester at the core. To do so, the above components can be blended simultaneously or in any order with the aromatic polyester by any method. That is, at any stage until the spinning of the polyester fiber is completed, for example, before the start of the polycondensation reaction of the aromatic polyester, during the polycondensation reaction, at the end of the polycondensation reaction and when the polycondensation reaction is still in the molten state, Alternatively, in the spinning step or the like, each of the aromatic polyester and the additive component may be melt-mixed in advance and added in a single operation, or may be added in two or more portions, and each additive component may be separately added in advance. After blending with the aromatic polyester, these may be mixed before spinning or the like. Furthermore, when the additional component is added before the middle stage of the polycondensation reaction, it may be added by dissolving or dispersing in a solvent such as glycol.

The cross-sectional shape of the outer periphery of the antistatic polyester fiber of the present invention and the shape of the figure formed by the core portion may be any shape according to the purpose of the woven or knitted fabric, such as bulkiness, tension, waist, feeling, and gloss. For example, in addition to a circular cross section, a triangle, a flat, a square, a pentagon, a star, a hexagon, a boomerang, and the like can be exemplified. Also, the core component and the sheath component do not need to be concentric, and may have a shape in which the center of the core is deviated.Also, the cross-sectional shape of the outer periphery and the shape of the figure formed by the core portion are also
The shapes may be the same or different.

For the antistatic polyester fiber of the present invention, the above-mentioned aromatic polyester is used on the sheath side and the water-insoluble polyoxyethylene-based polyether, organic and / or inorganic ionic Using an aromatic polyester compounded with a compound and, if necessary, at least one antioxidant such as the phosphite-based compound,
It can be produced under any yarn-making conditions without any hindrance. For example, melt spinning at a speed of 500 to 2500 m / min, stretching,
Method of heat treatment, melt spinning at a speed of 1500 to 5000 m / min,
A method of performing stretching and false twisting simultaneously or successively, 5000
Any spinning conditions can be adopted in a method such as melt spinning at a high speed of m / min or more and omitting the stretching step depending on the application. In addition, the resulting fiber or woven or knitted fabric produced from this fiber is heat-treated at a temperature of 100 ° C or higher to stabilize the structure and polyoxyethylene-based polyether contained in the fiber, and if necessary, It is also preferable to promote proper alignment by transferring various additives. Further, relaxation heat treatment or the like can be used as needed.

If necessary, the antistatic polyester fiber of the present invention or the woven or knitted fabric produced from this fiber may be subjected to appropriate post-hydrophilization processing, and it is preferable to do so. As the post-hydrophilization processing, for example, a method of treating with an aqueous dispersion of a polyester polyether block copolymer composed of terephthalic acid and / or isophthalic acid or a lower alkyl ester thereof, a lower alkylene glycol, and a polyalkylene glycol. Alternatively, a method in which a hydrophilic monomer such as acrylic acid or methacrylic acid is graft-polymerized, and then the resultant is sodium-chlorinated can be preferably used.

<Effect of the Invention> The antistatic polyester fiber of the present invention has sufficient antistatic properties even under low-temperature and low-humidity conditions, and can exhibit antistatic properties even in a low-temperature or dry environment and is extremely useful. . Also, the antistatic property is not affected by the repeated washing process. Furthermore, even when a high alkali weight loss treatment such as a weight loss rate of 25% by weight is performed, the decrease in visual infectious color and fibril resistance is extremely small. Because there is no problem that the fibers of the fibers become fibrillated due to weight loss and the dyed fabric whitens,
It can be used not only in the field of women's inner use such as lingerie, lining, dust-free clothing, etc., but also as a power-supply surface material that requires a high degree of feeling improvement by alkali weight reduction treatment.

<Examples> Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Parts and% in Examples and Comparative Examples indicate parts by weight and% by weight, respectively. Further, the frictional electrostatic voltage of the obtained antistatic polyester fiber, the visual infectious color and fibril resistance of the dyed cloth, and the pressure whitening of the weight-reduced dyed cloth were measured by the following methods.

(1) Friction band voltage i) Apparatus and material Rotary drum type friction band voltage measuring device (rotary static tester), oscilloscope, friction cloth: Cotton broad 30 /-scouring bleaching without glue ii) Adjustment of test piece Roll-in type: 3.8 cm × 30cm Gold type: 4.0cm × 8.0cm Take 3 pieces vertically each. In addition, three cotton broads (30 /-) of friction cloth are sampled vertically and 2.5 cm x 14.0 cm.

iii) Test operation Humidity control: Leave in a desiccator at 40 ± 2% RH or 30 ± 2% RH for a day or more.

Measurement room atmosphere: 40 ± 2% RH (20 ± 2 ℃), 30 ± 2% R
H (10 ± 2 ℃) Specimen: 1 stack Drum rotation speed: 700 rpm Equilibrium charging time: 1 minute Contact pressure load: 600 g One test piece is placed on the rotary drum of the rotary stick tester, and the lower part Attach a piece of friction cloth to the clips at both ends of the
Apply a load of 0 g. Operate the recorder (5 cm / min), rotating drum, and oscilloscope in this order. When charging equilibrium is reached, read the triboelectric voltage (V) and extreme values (±,-) and represent the average value of the three images (integer) Up to 10th place).

Note that the relationship between the antistatic effect and the frictional band voltage is sufficient if the frictional band voltage is 1500 V or less.

(2) Visual infectious color of dyed fabric Knitted fabric is refined by a standard method and preset (180 ° C)
× 1 minute) and the knitted fabric A ₀ and the knitted fabric A ₀ were subjected to alkali weight reduction treatment with a 30 g / l sodium hydroxide aqueous solution at a boiling temperature to reduce the alkali weight loss rate (referred to as N rate) to 25%. Knitted fabric B
₀ , 4% w of Sumikalon Navy Blue S-2GL (Sumitomo Chemical)
f, Disper VG (Meisei Chemical Industry) 0.5 g / l and acetic acid 0.
After dyeing at 130 ° C. for 60 minutes at a bath ratio of 1:50 in a dye bath containing 3 g / l, sodium hydroxide 1 g / l and hydrosulfite
After reducing and washing with an aqueous solution containing 1 g / l at 70 ° C. for 20 minutes, a final set (160 ° C. × 1 minute) is applied by a conventional method to dye the knitted fabric A (N ratio 0%) and the weight-reduced dyed knitted fabric B ( N rate 25
%). The L ^* value (brightness index) of each dyed knitted fabric was measured using Macbeth MS-2020 (Instrumental Color System Limite).
d). The smaller the L ^* value, the higher the luminous density and the better the visual infectious color.

(3) Fibril resistance The above-mentioned dyed knitted fabric A and weight-reduced dyed knitted fabric B, using a Gakushin type flat wear machine for friction fastness test, using a georgette made of 100% polyethylene terephthalate as a friction cloth,
Was abraded 200 times under a load of 500 g, and the degree of discoloration was determined by a discoloration gray scale. The case where the wear resistance (fibril resistance) was extremely low was defined as Class 1, and the case where it was extremely high was defined as Class 5. Practical grade 4 or higher is required for practical use.

(4) refining by a conventional method weight loss staining pressure resistance whitening of hosiery knitted fabric, the knitted fabric A ₀ obtained by preset, after passing through between the calendar roll multiplied by the pressure of 20kg / cm ^2, and the above-mentioned In the same manner, the weight reduction dyed knitted fabric C is subjected to the respective processes of alkali weight reduction, dyeing, and final setting with an N rate of 25%.
I got The L ^* value (brightness index) of the weight loss dyed knitted fabric B and the weight loss dyed knitted fabric C was calculated using Macbeth MS-2020 (Instrumental Color Sys
tem Limited) and the difference between the two L ^* values (ΔL
^* ), The degree of pressure whitening resistance was evaluated.

ΔL ^* = L ^* (knitted fabric C) −L ^* (knitted fabric B) The smaller the ΔL ^* value, the better the pressure-resistant whitening resistance of the weight-reduced dyed fabric.

The washing process for checking the antistatic washing resistance was as follows.

(Washing treatment) Using a household washing machine, add 30 l (bath ratio 1:30) of 2 g / l solution of the new enzyme Zab (made by Kao), put the sample, and wash it at 40 ° C for 10 minutes with an automatic vortex water flow. Then dehydrate, warm water at 40 ° C
Washing with 30 l (bath ratio: 1:30) for 5 minutes and dehydration, followed by overflow washing with water for 10 minutes and dehydration. The washing was performed once, and this was repeated as many times as necessary.

Examples 1 to 10 and Comparative Example 1 100 parts of dimethyl terephthalate, ethylene glycol 60
Part, 0.06 part of calcium acetate monohydrate (0.066 mol% based on dimethyl terephthalate) and 0.009 part of cobalt acetate tetrahydrate as a tinting agent (0.09 part based on dimethyl terephthalate)
(07 mol%) in a transesterification vessel, and the temperature was raised from 140 ° C. to 220 over 4 hours in a nitrogen gas atmosphere to carry out a transesterification reaction while distilling off the generated methanol to the outside of the system.

After completion of the transesterification, 0.058 parts of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) as a stabilizer and 0.024 parts of dimethylpolysiloxane as an antifoaming agent were added to the reaction mixture. Then, 10 minutes later, 0.04 parts of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added, and the temperature was raised to 240 ° C. while simultaneously removing excess ethylene glycol, and then transferred to a polymerization reactor. Next, the following chemical formula was added to the reaction mixture. (However, m is 3 as an average value, p is 111 as an average value,
j is an integer of 18 to 28 and is an average of 21) represented by an average molecular weight of 6930 and a hydrophilic-hydrophobic relational expression value
0.42 water-insoluble polyoxyethylene compound (Table 1)
No. 1) was added in the amount shown in Table 2, and the pressure in the reactor was reduced from 760 mmHg to 3 mmHg over 1 hour.
Ten minutes after the degree of pressure reduction reached 3 mmHg, sodium dodecylbenzenesulfonate as an ionic compound was added under reduced pressure in an amount shown in Table 2. The pressure was further reduced to 1 mmHg, and at the same time, the temperature of the reaction mixture was increased over 1 hour and 30 minutes.
The temperature was raised from 240 ° C to 280 ° C. Under a reduced pressure of 1 mmHg or less, polymerization was carried out at a polymerization temperature of 280 ° C. for 2 hours, and at this stage, 0.1 part of Cyanox 1790 (manufactured by American Cyanamid) and Mark AO-412S were added to the reaction mixture as an antioxidant.
0.3 parts (made by Adeka Argus Chemical Co., Ltd.)
Thereafter, polymerization was further performed for 30 minutes. The intrinsic viscosity of the obtained polymer is in the range of 0.645 to 0.655, and the softening point is 260 to 263 ° C.
Was in the range. This polymer was formed into chips by a conventional method.

The thus obtained aromatic polyester containing a water-insoluble polyoxyethylene compound was used as a core polymer, dried by a conventional method, melted by a screw type extruder, and supplied to a two-component composite spinning head via a gear pump. On the other hand, a polyethylene terephthalate chip having an intrinsic viscosity of 0.64 as a polymer for the sheath portion was dried by a conventional method, melted by a screw-type extruder, and simultaneously supplied to a composite spinning head.
The supply amounts of the core polymer and the sheath polymer were set so that the area ratio of the core became the value shown in Table 2. The molten polymer of the core and the sheath supplied at the same time has a nozzle diameter of 0.
After extruding at 285 ° C. using a composite spinneret having 24 round composite spinning holes of 3 mm, 1 was passed through a goded roll.
It was once wound at a speed of 500 m / min. Next, the stretched yarn was subjected to a stretching heat treatment at a stretching ratio of 35% by a heating roller at 90 ° C. and a stretching superheater at 170 ° C. to obtain a stretched yarn of 50 denier / 24 filaments. In addition, composite spinning and stretching were performed in exactly the same manner as in Example 1 except that a polyethylene terephthalate chip having the same intrinsic viscosity of 0.64 as the polymer for the sheath was used as the polymer for the core, and a stretched yarn of Comparative Example 1 was obtained. .

The obtained drawn yarn is made into a knitted knitted fabric, and the knitted fabric A (N ratio 0%) refined, preset, dyed, and final set by the above-described method, and refined, preset, alkali reduction, dyeing, and final set dyeing Knitted fabric B (N ratio
About 25%), washing 0 times (L ₀ and referred) and the washing 30
Times repeated (L referred to as ₃₀₎ friction zone voltage after, visual infectious color properties were measured resistance fibrillation resistance. Furthermore, the pressure-resistant whitening resistance of the dyed knitted fabric C (N ratio: 25%) subjected to refining, presetting, pressure treatment using a calendar, alkali weight loss, dyeing, and final setting was measured. Table 2 shows the results of Examples 1 to 10, and Table 3 shows the results of Comparative Example 1.

The obtained antistatic polyester fiber has sufficient antistatic properties even under low temperature and low humidity conditions such as 10 ° C. and 30% RH, and has a high alkali weight loss treatment with an N ratio of 25% by weight, and The antistatic property was not affected by the subsequent washing treatment, and the decrease in visual infectious color and fibril resistance was extremely small. In addition, even if there is a portion to which pressure is applied before the weight reduction processing, there is no problem that the fiber in the portion becomes fibrillated due to the weight reduction and the dyed fabric becomes white.

Examples 11 to 13 The same operation as in Example 5 was performed. However, a water-insoluble polyoxyethylene-based polyether having the following chemical formula was used.

However, in Example 11, m is 3, as an average value, p
Is 181 as an average value, j is an integer of 18 to 28 and is an average of 21, an average molecular weight of 10010, a value of a hydrophilic-hydrophobic relational expression of 0.26
Water-insoluble polyoxyethylene-based polyether (No. 6 in Table 1) was used, and in Example 12, m was an average value of 10, p was an average value of 180, and j was an integer of 14 to 16. A water-insoluble polyoxyethylene-based polyether (No. 15 in Table 1) having an average molecular weight of 13018 and a value of 0.65 in the hydrophilic-hydrophobic relational expression, which is an average of 15, was used.
Is 10 as an average value, p is 115 as an average value, j is 18 to 28
A water-insoluble polyoxyethylene-based polyether (No. 16 in Table 1) having an average molecular weight of 11838 and a hydrophilic-hydrophobic relation value of 1.35, which is an average of 21 as an integer of, was used. Table 2 shows the results.

All of the polyester fibers obtained in Examples 11 to 13,
It has sufficient antistatic properties even under low temperature and low humidity conditions, and also has antistatic weight loss durability and washing durability at an N ratio of 25% by weight, visual infection color resistance, fibril resistance, pressure reduction whitening resistance. It was good.

Comparative Example 2 The same operation as in Example 3 was performed. However, a water-soluble polyoxyethylene glycol having an average molecular weight of 20,000 was used instead of the water-insoluble polyoxyethylene-based polyether. Table 3 shows the results.

The obtained polyester fiber is subjected to normal temperature and humidity (20 ° C, 4
Under the condition of (0% RH), the antistatic weight loss durability and the washing durability at an N ratio of 25% by weight were good, but the antistatic durability under low temperature and low humidity conditions was poor. The visual infection color and fibril resistance at an N ratio of 25% by weight were good, but the weight-loss dyed cloth to which pressure was applied before weight-loss processing was whitened. It was observed that the fibers were partially fibrillated on the side surfaces of the fibers of the weight-loss dyeing cloth to which pressure was applied, and were inferior in resistance to pressure-loss whitening.

Comparative Examples 3 to 6 The same operation as in Example 1 was performed. However, the amount of the water-insoluble polyoxyethylene compound (No. 1 in Table 1) and the amount of sodium dodecylbenzenesulfonate (ionic compound) listed in Table 3 are used as the core polymer and the polyester for the core. Supply amount of polymer and polymer for sheath part,
The area ratio of the core was set so as to be the value shown in Table 3. Table 3 shows the results.

In Comparative Example 3 having a value of more than 5, antistatic and antistatic weight loss durability (N ratio: 25% by weight) and washing durability were good, but fibril resistance was inferior, and pressure was applied before weight reduction processing. The dyed cloth was whitened. It was observed that the fibers were partially fibrillated on the side surfaces of the fibers of the weight-loss dyeing cloth to which pressure was applied, and were inferior in resistance to pressure-loss whitening. on the other hand, Comparative Example 4 and Comparative Example 5 with less than 2.2 had insufficient hydrophilicity and were inferior in antistatic properties. Further, Comparative Example 6 having a core area ratio of less than 5% was inferior in antistatic durability under low-temperature and low-humidity conditions.

Comparative Example 7 The same operation as in Example 1 was performed. However, a water-insoluble polyoxyethylene-based polyether having the following chemical formula was used.

However, m is 2 as an average value, p is 70 as an average value, j
Was an integer of 24 to 30 and an average of 26, a water-insoluble polyoxyethylene-based polyether having an average molecular weight of 4874 and a value of the hydrophilic-hydrophobic relationship of 0.59 was used. Table 3 shows the results.

In Comparative Example 7 in which the molecular weight of the water-insoluble polyoxyethylene-based polyether was less than 5,000, the hydrophilic durability was insufficient, and the antistatic weight loss durability (N ratio: 25% by weight) and the washing durability were poor. Was.

Comparative Examples 8 and 9 The same operation as in Example 5 was performed. However, a water-insoluble polyoxyethylene-based polyether having the following chemical formula was used.

However, in Comparative Example 8, m is 6, as an average value, p
Is an average value of 350, j is an integer of 18 to 28 and is an average of 21, an average molecular weight of 19474 , and a value of the hydrophilic-hydrophobic relational expression of 0.26.
In Comparative Example 9, m is 8 as an average value, p is 270 as an average value, j is an integer of 18 to 28 and is 21 on average, and has an average molecular weight of 17306 , A water-insoluble polyoxyethylene-based polyether having a hydrophilic-hydrophobic relation value of 0.46 was used. Table 3 shows the results.

In Comparative Examples 8 and 9 in which the molecular weight of the water-insoluble polyoxyethylene-based polyether exceeded 16,000, the polyoxyethylene-based polyether was easily thermally decomposed during melt spinning and had low miscibility with the aromatic polyester. Therefore, the hydrophilic durability becomes insufficient, and the antistatic weight loss durability (N rate
(25% by weight), the washing durability was poor, and the visual infectious color after 25% by weight was also poor. In addition, due to the large molecular weight, the antistatic durability was poor under low-temperature and low-humidity conditions, and the weight-loss dyed fabric to which pressure was applied before the weight-loss processing was significantly whitened. It was observed that the fiber side surfaces of the weight-loss dyeing cloth to which pressure was applied were partially fibrillated, and were extremely poor in resistance to pressure-loss whitening.

Continued on the front page (72) Inventor Yasuo Yamada 3-4-1, Amihara, Ibaraki-shi, Osaka Teijin Inside the Osaka Research Center Co., Ltd. (72) Toshimasa Kuroda 3-4-1, Mihara, Ibaraki-shi, Osaka Teijin Shares (56) References JP-A-62-133118 (JP, A) JP-A-56-49018 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) D01F 8 / 00-8/18

Claims (1)

(57) [Claims] 1. A core-sheath composite fiber whose core and sheath components are both made of an aromatic polyester, wherein the core component is a polyoxyethylene-based poly (polyethylene) -based polymer which satisfies the following (i) and (ii) simultaneously with respect to an aromatic polyester. A polyoxyethylene-based compound present in the core component in which the ether is present at most 10% by weight and the ionic compound is present at 0.1 to 5% by weight, and the core / sheath area composite ratio is 5/95 to 50/50. The total blending amount C (% by weight) of the polyether and the ionic compound, the outer peripheral length L ₀ of the composite fiber in a cross section perpendicular to the fiber axis, and the outer peripheral length L ₁ of the figure formed by the core portion , Satisfying the following formula (II): (I) Non-random copolymerizable polyoxyethylene polyether represented by the following general formula (I). (Ii) The average molecular weight is 5000-16000.