JPH04153319A - Antistatic polyester fiber - Google Patents

Abstract

PURPOSE:To obtain the subject fiber having antistaticity and dyeable with cationic dye by using an aromatic polyester containing a specific polyether and an organic ionic compound as a core component and using a polyester dyeable with cationic dye as a sheath component. CONSTITUTION:The objective fiber is produced by using a core component consisting of an aromatic polyester containing (A) 1-10wt.% of a non-random copolymerized polyether having an average molecular weight of 5,000-16,000 and expressed by formula Z-[(CH2CH2O)l-(R<1>O)m-R<2>]k (Z is organic compound residue containing 1-6 active hydrogen atoms and having a molecular weight of <=300; R<1> is >=6C alkylene, etc.; R<2> is H, 1-40C univalent hydrocarbon group, etc.; k is integer of l-6; l is integer satisfying the relationship kXl <=70; m is integer of >=1) and (B) 0.1-5wt.% of an organic ionic compound and a sheath component consisting of a polyester copolymerized with 0.1-10mol% of sulfonic acid phosphonium salt. The areal ratio of core/sheath is 5/95 to 50/50.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to antistatic polyester fibers having excellent cationic dye dyeability, and more specifically to antistatic polyester fibers having excellent durability even under low temperature and low humidity conditions. The present invention relates to polyester fibers having antistatic properties.

<Prior Art> Polyester fibers are widely used as synthetic fibers because they have many excellent properties. However, polyester fibers have the disadvantage that they have low dyeability, and are particularly difficult to dye with dyes other than disperse dyes, and because they are hydrophobic, they tend to generate static electricity, which causes a crackling discharge phenomenon when putting on and taking off clothes. The disadvantage is that the clothes tend to stick while being worn. For this reason, its field of use is limited, and polynisder fibers that have both cationic dye dyeability and antistatic properties are required.

In the past, many proposals have been made to improve the drawbacks of polyester fibers. For example, in order to improve the dyeability, cationic dyes can be produced by copolymerizing polyester with an isophthalic acid component containing a sulfonic acid metal base. Method for making dyed polyester fiber (Special Publication Publication No. 34-104
Although it improves dyeing properties, it has the disadvantage that static electricity is extremely likely to be generated. In addition, a method using an isophthalic acid component having a phosphonium sulfonate group (Japanese Patent Publication No. 47-22334, U.S. Pat. No. 3,732,183), a method in which a specific amount of polynisdel is copolymerized with an isophthalic acid component having a phosphonium sulfonate group has been proposed. High whiteness and high strength cationic dyeable polyester fibers (Japanese Patent Laid-open No. 1-162822) have been proposed with improved heat resistance by adding quaternary onium salts, but these methods The drawbacks of the outbreak are not eliminated.

On the other hand, as a method for imparting antistatic properties to polyester fibers, polyoxyalkylene glycol, polyoxyalkylene glycol/polyamide block copolymer, polyoxyalkylene glycol/polyester block copolymer, or polyoxyalkylene glycol/polyester block copolymer that is substantially incompatible with polyester A method of mixing polymers and a method of blending organic or inorganic ionic compounds with the polymers have been proposed (for example, Japanese Patent Publication No. 443
1828, Japanese Patent Publication No. 60-11944, Japanese Patent Application Laid-Open No. 53-80497, Japanese Patent Application Laid-Open No. 60-39413).

Against this background, in an attempt to impart antistatic properties to polyester fibers dyeable with cationic dyes, a method of treating polynisder fibers dyeable with cationic dyes with a specific polycondensate of polyethylene glycol and terephthalic acid (JP-A-58 -16
3781), a method of treatment with a specific hydrophilic compound consisting of an alkylene ether having a vinyl group (Japanese Unexamined Patent Publication No. 5
8-220876), a method of melt spinning a cationic dye-dyable polyester containing polyoxyalkylene glycol or its derivatives using a specific spinneret (Japanese Patent Application Laid-Open No. 60-28513), a method in which a phosphonium isophthalic acid component is A method of adding polyoxyalkylene glycol, or polyoxyalkylene glycol and an organic sulfonic acid metal salt to polymerized polyester (Japanese Patent Application Laid-Open No. 1999-1-1993)
192822, 192823), etc. have been proposed. However, polyoxyethylene glycol or its derivatives specifically used in this method are water-soluble and have poor water resistance, so their antistatic properties may be affected by dyeing, alkali weight loss treatment, and even harsh repeated washing treatments. There is a problem that it is difficult to lose.

Furthermore, a method has been proposed in which a core-sheath type composite fiber is prepared in which a polyester mixed with block polyether amide is used as a core component and a cationic dye dyeable polyester is used as a sheath component (Japanese Patent Publication No. 17927/1983). However, with the polyoxyalkylene glycol/polyamide block copolymer used in this method, although it is possible to ensure water resistance by specifying the copolymer structure, as the water resistance increases, the hydrophilicity decreases. In particular, when used as a core component of polyester composite fibers, the hygroscopicity becomes low, with a
Antistatic properties are insufficient at low temperatures below 0° C. and low humidity below 40% relative humidity.

As described above, polyester fibers that can be dyed with cationic dyes and have antistatic properties that are highly durable even under low temperature and low humidity conditions have not been obtained.

<Object of the Invention> An object of the present invention is to provide an antistatic polyester fiber that has both excellent antistatic properties even under low temperature and low humidity conditions and excellent dyeability with cationic dyes.

<Structure of the Invention> In order to achieve the above-mentioned object, the present inventors focused on a core-sheath type composite fiber having the aforementioned cationic dye-dyable polyester as a sheath component and a polyester component containing an antistatic agent as a core component. We conducted a thorough study. The present inventor focused on the antinomic properties of hydrophilicity and water insolubility, and as a result of diligently searching for an antistatic agent that has excellent hygroscopicity and interfacial affinity with polyester, the above-mentioned polyoxyalkylene glycol Instead of polyoxyethylene glycol or block polyether amide, the core is a polyoxyethylene polyether with a specific molecular weight that is made water insoluble by block copolymerizing a specific amount of a specific higher olefin oxide on both ends of polyoxyethylene glycol. It has been found that by including the antistatic properties in the above, not only the antistatic properties and durability under normal temperature and humidity conditions are excellent, but also the antistatic properties at low temperatures and low humidity can be ensured. Even more surprisingly, a core-sheath type composite fiber has been developed in which the core component of such composite fiber is polyoxyethylene polyether, and the sheath component is polyester copolymerized with sulfonic acid phosphonium salt as a cationic dyeing agent. Then, as a combined effect, low temperature and
It has been found that the special effect of further improving antistatic properties under low humidity conditions is achieved. The present invention was completed as a result of further studies based on this knowledge.

That is, in the present invention, the core component is (a) 1 to 10% by weight of a non-random copolymerizable polyoxyethylene polyether having an average molecular weight of 5,000 to 16,000 represented by the following formula (E), and (b) organic ions. Sexual combination! l110.1-5
It consists of an aromatic polyester containing Z-[(
CH2CH20)1- <R10), -R2]
k...(I) [wherein Z has 1 to 6 active hydrogens and has a molecular weight of 300
The following organic compound residue, R1 is an unsubstituted or substituted alkylene group having 6 or more carbon atoms, R2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent hydrocarbon group having 2 to 4 carbon atoms.
0 monovalent acyl group, k is an integer of 1 to 6, ρ is kX, Q
m represents an integer of 70 or more, and m represents an integer of 1 or more. ] A core-sheath type composite fiber in which the sheath component is made of a modified polyester copolymerized with 0.1 to 10 mol% of a sulfonic acid phosphonium salt represented by the following formula (II), where A is aromatic group or aliphatic group, Xl is an ester-forming functional group, X2 is the same or different ester-forming functional group or hydrogen atom, R1', R2', R3'
and '' are the same or different groups selected from alkyl groups and aryl groups, and n is a positive integer. ] The core/sheath/area composite ratio of the composite fiber is 5/95 to 501.
It is an antistatic polyester fiber characterized by having a molecular weight of 50.

The reason why the antistatic polyester fiber of the present invention exhibits excellent antistatic and durable effects under low temperature and low humidity conditions is that the polyester, which is the core component of the core-sheath type composite fiber, has hydrophilicity and moisture absorption properties. A special polyoxyethylene-based polyether that has extremely excellent properties, has extremely low dissolution and elution properties in hot water, aqueous alkaline solutions, washing water, etc., and has excellent interfacial affinity with the polyester matrix is localized at a high concentration. It is thought that this is produced as a result of being dispersed. Although the polyoxyethylene-based polyether is water-insoluble, it exhibits higher hygroscopicity than water-soluble polyoxyethylene glycol (average molecular weight 20,000); for example, at a temperature of 20°C,
At a relative humidity of 86%, the latter has an equilibrium moisture absorption rate of 20%, while the former has an equilibrium moisture absorption rate of 60%, which is about three times as high, making it extremely hydrophilic.

Second, in the polynisdel, which is the sheath component of the core-sheath composite fiber,
This is an improved effect due to copolymerization of sulfonic acid phosphonium salt as a cationic dyeing agent]0. This improvement effect is not observed in core-sheath type composite fibers in which the sheath component is polyester copolymerized with a 5-metal sulfoisophthalic acid compound, which is generally widely used industrially. On the other hand, when a polyester copolymerized with a sulfonic acid phosphonium salt as a cation dyeing agent is used as a sheath component, surprisingly, an effect of improving antistatic properties at low temperature and low humidity is expressed, and the alkali weight loss is Furthermore, it has been found that this antistatic property improvement effect hardly decreases even after severe washing treatment. The reason for this improvement effect is still not clear, but by dyeing with a cationic dye, the phosphonium cation released from the sulfonic acid phosphonium salt copolymerized with the sheath component (salt combined with the anion of the dye) becomes hydrophobic. Because of its high mobility, it remains in the polyester of the sheath component, and the high-cost, high-mobility phosphonium cation species generated by hydrophobic intermolecular interactions between these phosphonium cations (Peri et al., Journal of Solutions, Chemistry, Vol. 17, No. 3, 203
It is also presumed that the antistatic properties at low temperatures and low humidity are improved by ionic conduction (see p. 212, 1988). In addition, since such excellent antistatic performance cannot be obtained with solid fibers made solely of cationic dyeable polyester copolymerized with phosphonium sulfonate salts, the above-mentioned polyoxyethylene polyether in the polyester core component cannot be obtained. A synergistic effect with the excellent hydrophilic/hygroscopic effect, or some kind of interaction with the phosphonium cation due to the organic ionic compound in the core polyester bleeding out to the sheath component, and furthermore, the polyoxyethylene polyether It is also believed that the above-mentioned improvement effect was caused by ion conduction of the phosphonium cation species near the core-sheath interface due to molecular movement. On the other hand, when a polyester copolymerized with a 5-metal sulfoisophthalic acid compound is used as the sheath component, the metal cations released after dyeing with a cationic dye easily fall off from the polyester, so the above-mentioned improvement effect is not observed. Conceivable.

The aromatic polyester used as the base of the core component in the present invention is an aromatic polyester having an aromatic ring in the chain unit of the polymer, which forms a bifunctional aromatic dicarboxylic acid or its ester-forming derivative with a diol or its ester. It is a polymer obtained by reaction with a chemical derivative.

The difunctional aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, and orthophthalic acid.

1,5-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid.

4.4'-biphenyl dicarboxylic acid, 3.3'-biphenyl dicarboxylic acid, 4.4'-diphenyl ether dicarboxylic acid, 4.4'-diphenylmethane dicarboxylic acid.

4.4'-diphenylsulfonedicarboxylic acid, 4.4'
Diphenylisopropylidene dicarboxylic acid, 1.2bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2.
5-anthracene dicarboxylic acid, 4.4'-p = ivy
Enylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, β-hydroxyethoxybenzoic acid.

Examples include p-oxybenzoic acid, and terephthalic acid is particularly preferred.

]3 Two or more of these difunctional aromatic carboxylic acids may be used in combination. In addition, in small amounts, in addition to these functional aromatic carboxylic acids, difunctional aliphatic carboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid,
One type or two or more types of difunctional aliphatic carboxylic acids such as cyclohexanedicarboxylic acid can be used in combination.

In addition, diol compounds include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1
, 3-propanediol, diethylene glycol, trimethylene glycol, alicyclic diols such as 1,4-cyclohexane dimetatool, aromatic diols such as bisphenol A, bisphenol S, and mixtures thereof. I can give it to you. In addition, if the amount is small, polyoxyalkylene glycol whose both ends or one end are unblocked can be copolymerized with these diol compounds. Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as glycerin, trimethylolpropane, and pentaerythritol can be used as long as the polyester is substantially linear.

Specifically preferred aromatic polyesters include polyethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyethylene-1,2.
-Bis(phenoxy)ethane-4,4'-dicarboxylate, etc., as well as polyethylene isophthalate and terephthalate.

Polybutylene terephthalate/isophthalate.

Examples include copolymerized polyesters such as polybutylene terephthalate and decane dicarboxylate. Among these, polyethylene terephthalate and polybutylene terephthalate, which have well-balanced mechanical properties and moldability, are particularly preferred.

Such aromatic polyesters can be synthesized by any method. For example, regarding polyethylene terephthalate, 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 reaction is to produce a glycol ester of terephthalic acid and/or its low polymer, and the second step is to perform a polycondensation reaction by heating the product under reduced pressure until a desired degree of polymerization is achieved. It is easily produced by reaction.

The polyester described above may contain other thermoplastic polymers, such as polyamides such as nylon-6, polyolefins such as polyethylene and polystyrene, etc., to the extent that the inherent physical properties of the polyester are not impaired.

Further, although it is preferable to use the same polyester for the sheath component and the core component, different types of polyesters may be combined as long as they have compatibility.

In the antistatic polyester fiber of the present invention, the sulfonic acid phosphonium salt used as a copolymerization component of the modified polyester as the sheath component of the core-sheath composite fiber is expressed by the following formula (II
). In the formula, A represents an aromatic group or an aliphatic group, and among them, an aromatic group is preferable. X represents an ester-forming functional group, and a specific example is 1□-C-R'-C-OH.

C-0-R' +cH2+, OH.

0mo CH2) [0 (CH2) ] Oh.

-c-iomoCH2)]dOH (wherein, R' is a lower alkyl group or a phenyl group, a and d are an integer of 1 or more, and b is an integer of 2 or more). X2 is preferably an ester-forming functional group that is the same as or different from Xl, or represents a hydrogen atom, and is particularly preferably an ester-forming functional group. R1',
R2', R3' and ya' represent the same or different groups selected from the group consisting of alkyl groups and aryl groups. n
is a positive integer.

Such sulfonic acid phosphonium salts can generally be easily synthesized by reacting the corresponding sulfonic acid with phosphines or by reacting the corresponding sulfonic acid metal salt with phosphonium halides.

Preferred specific examples of the sulfonic acid phosphonium salts include 3,5-dicarbomethoxybenzenesulfonic acid, 3
, 5-dicarboxybenzenesulfonic acid, 3-carbomethoxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 3,5-(βhydroxyethoxycarbonyl)
Tetrabutylphosphonium, such as benzenesulfonic acid, 3-(β-hydroxyethoxycarbonyl)benzenesulfonic acid, 4-hydroxyethoxybenzenesulfonic acid, 2,6-dicallevoxynaphthalene-4-sulfonic acid, and sulfosuccinic acid. salts, benzyltributylphosphonium salts, phenyltributylphosphonium salts, ethyltributylphosphonium salts, ethyltriphenylphosphonium salts, tetraphenylphosphonium salts, butyl)heliphenylphosphonium salts, and benzyltriphenylphosphonium salts. Such sulfonic acid phosphonium salts may be used alone or in combination of two or more.

In order to copolymerize the sulfonic acid phosphonium salt to a polyester, it is preferable to copolymerize the dicarboxylic acid component similar to the aromatic polyester used as the core component and the diol component at a stage before the completion of polymerization. It may be added at any stage before the initial stage of the reaction. The ratio of copolymerizing the sulfonic acid phosphonium salt to the polyester is determined by the proportion of the difunctional carboxylic acid component (
0.1 to 10 mol %] 9 based on the sulfonate (excluding sulfonate), and preferably 0.5 to 5 mol %.

If the copolymerization ratio is less than 0.1 mol %, the resulting antistatic polyester fiber will have insufficient dyeability with cationic dyes, and the antistatic property improving effect at low temperature and low humidity will be insufficient. On the other hand, if it exceeds 10 mol%,
The cationic dyeability and the antistatic property at low temperature and low humidity no longer show any significant improvement, and on the contrary, the physical properties of the polyester deteriorate, making it difficult to achieve the object of the present invention.

A water-soluble polyoxyethylene polyether represented by the following formula (I) is blended with the aromatic polyester core component constituting the antistatic polyester fiber of the present invention. Such polyoxyethylene-based polyethers are non-random polyethers that have a polyoxyethylene block as a main chain component and are rendered water insoluble by blocking the polyoxyethylene molecular chain terminals with one or more specific oxyalkylene units. It is a polymerized polyoxyethylene polyether. Here, water insolubility in the present invention means pure water 100%
5 g of the sample was placed in 10 g of water and heated at 100°C for 60 minutes, then allowed to cool to room temperature, and then centrifuged and the resulting transparent supernatant was evaporated to dryness until the solid content was 10 % by weight or less. As described above, since the polyoxyethylene polyether used in the present invention is water-insoluble, it has inherently excellent durability against alkali weight loss treatment, dyeing treatment, and even harsh repeated washing treatment. have

2, -[(CH2CH20)j-(RIO)□-R2]
k(I) In the above formula, Z has a molecular weight of 30 and has 1 to 6 active hydrogens.
0 or less residues of organic compounds, such as methanol, propatool, butanol, and phenol.

Ethylene glycol, bisphenol A, propylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, diglycerin.

Pentaerythritol, sorbitol, etc.] Residues of xyl group-containing compounds and residues of primary and secondary amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, etc., among which hydroxyl group-containing compounds is preferred. R1 is an unsubstituted alkylene group or substituted alkylene group having 6 or more carbon atoms, preferably a substituted alkylene group having 6 to 50 carbon atoms, and more preferably an alkylethylene group having 6 to 50 carbon atoms. Preferred specific examples of R1 include a cyclohexylene group, a phenylethylene group, a hexylethylene group, a methyl-pentylethylene group, a heptylethylene group, a methyl-hexylethylene group, and the like. Moreover, R1 may be a mixture of two or more of the above.

R2 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,
The hydrocarbon group is preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or a hydroxyalkyl group. Further, the acyl group is an alkanoyl group.

Alkenoyl group, cycloalkylcarbonyl group.

Arylcarbonyl or alkylarylcarbonyl groups are preferred. k is an integer of 1 to 6 corresponding to the number of active hydrogen atoms that the organic compound that is the basis of Z has. ρ is k
It is necessary that X and Q are integers of 70 or more,
They may be the same or different between or within molecules.

When the value of kX, 11 is less than 70, the initial antistatic performance and hot water durability of the antistatic polyester fiber finally obtained.

Washing durability is also insufficient. In addition, as the value of k Since it tends to be difficult to make ethylene polyether insoluble in water, ρ is kX! It is preferable that the value of J is an integer of 300 or less. A more preferable range of kXρ is 80 to 200. m is an integer of 1 or more, and may be the same or different between or within molecules, but all m within the branches bonded to Z must be integers of 1 or more. When a branch in which m is 0 exists, the antistatic durability of the polyester fiber finally obtained will be insufficient. CH2CH20 units and RjO constituting this polyoxyethylene polyether
The unit arrangement is such that a polyoxyethylene block consisting of CH2CH2O units constitutes the main chain, and R"0 units are localized at the end of the polyoxyethylene molecular chain forming one unit or a block of two or more units. Only by adopting such a specific structure can the polyoxyethylene polyether be made highly water insolubilizable and highly hygroscopically improved by introducing a small amount of R10 units. It becomes possible to achieve a high degree of antistatic property and its durability.If the CH2CH2O units and RIO units are arranged randomly, the object of the present invention cannot be achieved.

The molecular weight of the water-insoluble polyoxyethylene polyether described above is in the range of 5,000 to 16,000. When the molecular weight is less than 5,000, it is difficult for the polyether to take the form of long enough streaks dispersed in the polyester fibers, so that the antistatic performance is insufficient from the beginning, and no matter how much the RIO units are increased, the antistatic performance is insufficient. Hot water and hot alkali for polyoxyethylene polyether.

It is difficult to prevent it from falling into washing water, etc., and the antistatic properties and durability of the polyester fibers ultimately obtained will be insufficient.

Furthermore, if the molecular weight exceeds 16,000, the melt miscibility of the polyoxyethylene polyether in polyester fibers will deteriorate rapidly, resulting in poor dispersibility, which will not only make spinning difficult but also result in increased yield. Since the fiber physical properties such as antistatic properties and mechanical strength of the fibers obtained are poor, it is practically impossible to implement.

Furthermore, as the molecular weight increases, antistatic properties under low temperature and low humidity conditions also become poor. It is presumed that this is because the thermal movement of the polyoxyethylene polyether in the fiber matrix becomes smaller, so that the antistatic performance due to ion conduction decreases, especially at low temperatures. Among these, the preferred molecular weight range of the polyoxyethylene polyether is 5500.
~14,000.

Such a non-random type polyoxyethylene polyether can be produced by a first stage reaction in which an active hydrogen compound is reacted with ethylene oxide, then a second stage reaction in which the product is reacted with an olefin oxide having 6 or more carbon atoms, and as necessary. Accordingly, the product can be synthesized by a third step reaction in which the hydroxyl end group of the product is capped with a hydrocarbon group or an acyl group. Among these olefin oxides, nonene oxide, cyclohexene oxide, and α-olefin oxide having 12 to 40 carbon atoms are particularly preferred.

Particularly preferred specific examples of the above polyoxyethylene polyethers are shown in Table 1. In addition, in the table, the alkyl side chain of R, +O is a mixture of alkyl groups shown in parentheses, and is expressed by the average number of carbon atoms.

Specific examples of R2 other than H in the two compounds shown in Table 1 are R2= -CH3, C6R5, CH2C6H5,
Cl2H25, Cl8H37, Cl8H35゜C11H
23CO, C17H33CO, CFH35CO, etc. are preferred. Such polyoxyethylene polyether is
One type may be used alone or two or more types may be used in combination.

In the antistatic polyester fiber of the present invention, an organic ionic compound is added to the aromatic polyester core component, together with the water-insoluble polyoxyethylene polyether described above, to improve its antistatic properties. Blend. As the organic ionic compound, all organic sulfonate salts that are non-reactive with the aromatic polyester, such as organic sulfonic acid metal salts and organic sulfonic acid quaternary phosphonium salts, can be used, but among them, the following formula (I [
Compounds represented by [) to (Vl) can be mentioned.

Rso,,M-(I[I)RSO(PRIR2RIR4-(IV)R50(
R80). (CHz) p 503M, -
(V)RsO(RaO) n (CH2) p 5O3
PRtRzR+Rc” (Vl) In the above formula, R is an alkyl group having 3 to 30 carbon atoms or 7 to 40 carbon atoms
represents an aryl group or an alkylaryl group, and M represents an alkali metal. When R is an alkyl group, R may be linear or may have a branched side chain. Among these, M is preferably Li, Na, or K. R, R2, R3
and aryl are an alkyl group or an aryl group, of which a lower alkyl group, a phenyl group or a benzyl group is preferred.艮 represents a monovalent hydrocarbon group, preferably an alkyl group, a cycloalkyl group, an aryl group or an alkylaryl group. It is an alkylene group, and usually 2 to 4 alkylene groups are preferable, and specific examples thereof include ethylene group, propylene group, and tetramethylene group. Alternatively, a mixture of two or more types, for example a copolymerization having an ethylene group and a propylene group, may be used. Among these, an ethylene group is particularly preferred. n is a positive integer indicating the degree of polymerization, 1 to 10
A range of 0 is preferred, and a range of 2 to 30 is particularly preferred. p is an integer from 2 to 4.

Preferred specific examples of the compound represented by (I[I) above include sulfonic acids such as dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, nonylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, hexadecylsulfonic acid, and dodecylsulfonic acid. and an alkali metal such as sodium, potassium, lithium, etc., and a preferred specific example of the compound represented by (IV) above is a compound having an average number of carbon atoms of 1.
A sulfonic acid phosphonium salt formed from an alkylsulfonic acid, dodecylbenzenesulfonic acid, and a phosphonium ion such as tetrabutylphosphonium, tetraphenylphosphonium, butyltriphenylphosphonium, benzyltriphenylphosphonium, etc. (V) above.
Preferred specific examples of the compound represented by: C16H330(CH2CH2O) 23CH2CH2
CH2S 03NaC12H2, O(C) LICH20
) tocH2cH2sO3Na, etc., as preferred specific examples of the compound represented by (■I) above, the metal salt of the preferred specific example compound represented by (V) above, tetra n-butylphosphonium salt, tetraphenylphosphonium salt, etc. , n-butyltriphenylphosphonium salt, or a compound substituted with phenyltri-n-butylphosphonium salt.

The above organic ionic compounds may be used alone or in combination of two or more thereof. Its blending amount is 0 for aromatic polyester.
．． It is preferably in the range of 1 to 5% by weight. If the blending amount is less than 0.1% by weight, sufficient antistatic properties cannot be imparted, and even if it is increased beyond 5% by weight, the antistatic properties will no longer be significantly improved, and on the contrary, the composite This impairs the mechanical properties of the fiber.

The core aromatic polyester, which is the antistatic component of the antistatic polyester fiber of the present invention, contains antioxidants such as hindered phenol, sulfide, and phosphite, as well as benzophenone, bencitriazole, etc. It is possible to incorporate an ultraviolet absorber or the like, and this is preferable.

In addition, the above-mentioned antioxidant and/or ultraviolet absorber may be added to the sheath component of the polyester fiber of the present invention.
Furthermore, flame retardants, optical brighteners, matting agent 1 colorants, inert fine particles, and other arbitrary additives may be added to the core component and/or the sheath component.

As a method for obtaining the aromatic polyester of the core component which is the antistatic component of the antistatic polyester fiber of the present invention, the above-mentioned polyoxyethylene polyether is used.

The organic ionic compound and, if necessary, the above-mentioned antioxidant, etc. can be added separately or in advance mixed together at any time from the start of polyester synthesis to the spinning process.

The antistatic polyester fiber of the present invention has a core/sheath area composite ratio of 5/95 to 50,150. When the core/sheath area composite ratio is less than 5/95, the effects of the polyoxyethylene polyether and ionic compound blended into the core component of the polyester fiber will not be fully exhibited, and the antistatic property, especially Antistatic properties are poor under low temperature and low humidity conditions. On the other hand, when the core/sheath area composite ratio exceeds 50,150, the polyester portion constituting the sheath component becomes thinner, which reduces the fiber strength.

Physical properties such as fibril resistance and heat resistance become inferior. In addition, the antistatic property and washing durability after alkali weight loss treatment and dyeing treatment are insufficient, and the depth and clarity of the color of the dyed product is significantly inferior, making it impractical.

The external shape of the antistatic polyester fiber of the present invention and the shape of the core component affect the electrical properties, tension, and elasticity of the woven or knitted fabric.

It can take any shape depending on the purpose of texture, gloss, etc. For example, in addition to circular cross section, it can be triangular or flat.

Illustrative cross-sections include square, even-angled, star-shaped, hexagonal, ■-shaped, and C-shaped. It is preferable to use an irregularly shaped cross section in order to obtain a silky texture such as fullness and drapability. Furthermore, the outer shape of the fiber and the shape of the core component do not need to be concentric circles, and the center of the core component may be offset from the center of the fiber, and the outer shape of the fiber and the shape of the core component may be the same shape. However, if it is extremely biased or the core component is exposed on the surface, the sheath component is likely to fibrillate when rubbed, so the thickness of the thinnest part of the sheath component may be It is preferable that the thickness is 1 μm or more, more preferably 2 μm or more.

In order to produce the antistatic polyester fiber of the present invention, a conventionally known composite spinning device was used, and a water-insoluble polyoxyethylene polyether, an organic ionic compound, and an antioxidant were added to the sheath portion as necessary. Using aromatic polyester, any spinning conditions can be adopted without any problems. For example, melt spinning at a speed of 500 to 2500 m/min and stretching.

A method of heat treatment, a method of melt-spinning at a speed of 1,500 to 5,000 m/min, and performing stretching and false twisting simultaneously or successively, a method of melt-spinning at a high speed of 5,000 m/min or more, and omitting the stretching step depending on the application. , etc., any yarn spinning conditions can be adopted.

In addition, the obtained fibers or woven or knitted fabrics made from these fibers are heat-treated at a temperature of 100°C or higher to stabilize the structure and to remove the polyoxyethylene polyether and organic ionic compound contained in the composition. Furthermore, it is also preferable to promote proper arrangement by migration of various additives contained as necessary. Furthermore, relaxation heat treatment, alkano weight loss treatment, etc. can be used in combination, if necessary. In addition, it is possible to make a mixed yarn of the fiber obtained as described above and fibers with different heat shrinkability, single fiber fineness, and cross-sectional shape.
This is also preferable in order to obtain silk-like textures such as fullness and drapability.

Furthermore, if necessary, the antistatic polyester fiber of the present invention or the woven or knitted fabric produced from this fiber may be subjected to an appropriate post-hydrophilic treatment. This hydrophilic post-processing includes, for example, a method of treatment with an aqueous dispersion of a polyester polyether block copolymer consisting of terephthalic acid and/or isophthalic acid or their lower alkyl esters, lower alkylene glycol, and polyalkylene glycol. Alternatively, a method in which a hydrophilic monomer such as acrylic acid or methacrylic acid is graft-polymerized and then converted into a sodium salt can be preferably employed.

<Effects of the Invention> Since the antistatic polyester fiber of the present invention can be dyed with a cationic dye, it can obtain the vivid color characteristic of cationic dyes, and has excellent antistatic properties and durability under normal temperature and humidity conditions. Not only is it excellent, but it also has extremely excellent antistatic properties even at low temperatures and low humidity. Moreover, this antistatic property is not affected by post-processing treatments such as false twisting, hard twisting, dyeing, alkali weight reduction treatment, resin coating treatment, etc., or even by harsh repeated washing treatments, which is an extremely useful feature in practical use. has.

Therefore, the antistatic polyester fiber of the present invention is particularly useful in sports clothing applications where vivid colors are required, as it provides excellent color development and high antistatic properties. In addition, it can be made into yarns mixed with regular polyester fibers, or mixed or knitted with regular polyester yarns to make woven or knitted fabrics, and dyed with cationic dyes or disperse dyes to create high-quality marbling effects or unique color dyeing effects. It is extremely useful in applications where it is desired to express a unique dyeing effect, since it is possible to impart a high degree of antistatic property.

<Examples> In order to explain the present invention more specifically, Examples will be described below, but the present invention is not limited to these Examples. Note that parts and % in Examples and Comparative Examples indicate parts by weight and % by weight, respectively. Further, the frictional charging voltage, dyeability with cationic dyes, and fibril resistance of the silk fabric made of the obtained antistatic polyester fibers were measured by the following methods.

(1) Frictional charging voltage of dyed knitted fabrics i) Equipment and materials Rotating drum type frictional charging voltage measuring device (rotary static tester), oscilloscope, friction cloth 2-cotton broad 30/- scouring bleaching no-glue finishing ii) Preparation of test pieces Retractable type: 3.8anX3Q■ Three gold frame type: 4. OcmX8. Collect 3 vertically long pieces of o and an. Furthermore, the cotton broadcloth of the friction cloth <30.
”), 2.5 countries x 14, collect 3 Oan vertically.

1ii) Test operation - Humidity control: Leave in a desiccator at 40 parts 2% RH or 30 parts 2% RH for at least one day and night.

■Atmosphere of measurement chamber: 40 parts 2% RH (20 parts 2°C), 3
0 parts 2% RH (10 parts 2°C) ■Sample: 1 stacked sheet ■Drum rotation speed: 700r, p, m ■Charging equilibrium time: 1 minute ■Contact pressure load: 600g Rotary with one test piece facing up Attach it to the rotating drum of the static tester, and then attach a piece of friction cloth to the clips at both ends of the bottom in a balanced manner at the position where it contacts the test piece.
Apply a load of 00g. Operate the recorder (5μ/min) once, rotate the drum, and then the oscilloscope in this order. When the charging balance is not reached, read the frictional charging voltage (V) and extreme values (±, -), and express the average value of the three sheets ( (up to 10 integer values).

Note that the relationship between the antistatic effect and the frictional charging voltage indicates that the antistatic effect is good if the frictional charging voltage is 1500 V or less.

Further, the washing treatment for examining the washing resistance of antistatic properties was as follows.

(Washing process) Using a household washing machine, add 2g/(solution of New Enzyme Sub (manufactured by Kao) at 30ρ (bath ratio 1:30), add the sample and wash for 40 minutes.
Wash at ℃ for 10 minutes with self-winding water flow. After that, dehydrate, wash with hot water at 40℃ for 5 minutes (bath ratio 1:30), dehydrate, then wash with overflow water for 10 minutes, do not dehydrate. Repeat this 30 times, wash 30 times (
(referred to as L30) Toshina.

(2) Cationic dye dyeable polyester fiber 50 denier/24 filament 3
After scouring and presetting (180°C x 1 minute) the stockinette silk fabric knitted by doubling the threads in a conventional manner, Cathilon
Blue CD-PRLH/Cathilon Blue
e CDFBLH (manufactured by Hodogaya Chemical) - 1/1.2%o
It was dyed with W4 in a dye bath containing 3 f/Q, 0.3 g/ρ of acetic acid at 120°C for 60 minutes, then soaped and final set (160°CXI min) according to the usual method to obtain a bright blue cloth. Good value. Dyeability of cationic dyes is not ranked by dye exhaustion rate × = dye exhaustion rate <85%, △:
85.~99%, ○: 99%≦).

(3) Fibril resistance of dyed knitted fabrics Using a Gakushin type flat abrasion machine for rubbing fastness testing, the above dyed knitted fabric A was loaded with a load of 500 g using georgette made of 100% polyethylene terephthalate as the friction cloth. The surface was abraded 200 times, and the degree of discoloration was determined using a gray scale for discoloration and fading. If the abrasion resistance (fibril resistance) is extremely low, it will be grade 1, and if it is extremely high, it will be grade 5.
Class and class. For practical purposes, a level 4 or above is required.

Examples 1-5 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
0 parts, 0.03 parts of manganese acetate tetrahydrate (0.024 mol % based on dimethyl terephthalate) and 0.009 parts of cobalt acetate tetrahydrate as a coloring agent (0.007 mol based on dimethyl terephthalate) %), 3.5-dicarpomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt in an amount of 1.5 mol% relative to dimethyl terephthalate and tetraethylammonium hydro in an amount of 0.05 mol% relative to dimethyl terephthalate. Oxide was charged into a transesterification tank, and 14
The temperature was raised from 0°C to 220°C, and the resulting methanol was distilled out of the system while transesterification was carried out. After completion of the transesterification reaction, orthophosphoric acid (5) was added to the reaction mixture as a stabilizer.
0.03 part of a 6% aqueous solution (0.033 mol % based on dimethyl terephthalate) was added, and at the same time, expulsion of excess ethylene glycol at elevated temperature was started. After 10 minutes, 0.04 part of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added as a polycondensation catalyst, and the internal temperature was 2.
When the temperature reaches 40°C, stop purging the ethylene glycol and transfer the reaction product to the polymerization reactor. Next, the reaction was carried out under normal pressure until the internal temperature reached 260°C without raising the temperature, and then the pressure was reduced from 760 mmHg to lmmHg over 1 hour, and at the same time the internal temperature was raised to 280°C over 1 hour and 30 minutes. . Polymerization was further carried out for 2 hours at a polymerization temperature of 280°C under a reduced pressure of lmmHg, and the intrinsic viscosity was 0.630 to 0.65.
0, and the softening point was in the range of 254 to 256°C. This polymer was made into chips using a conventional method. The cationically dyeable polyester polymer obtained in this way was used as a polymer for the sheath component, and after drying by a conventional method, it was melted in a screw extruder.
It was fed to the binary composite spinning head via a gear pump.

On the other hand, 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (0.066 mol% relative to dimethyl terephthalate) and 0.0 part of cobalt acetate tetrahydrate (19 (0.007 mol% based on dimethyl terephthalate) was placed in a transesterification mill and heated at 140°C for 4 hours under a nitrogen gas atmosphere.
The temperature was raised from 1 to 220°C, and the methanol produced was distilled out of the system to carry out the transesterification reaction. After the transesterification reaction, trimethyl phosphate was added to the reaction mixture as a stabilizer.
．． 058 parts (0.080 parts relative to dimethyl terephthalate)
mol%〉 and dimethylpolysiloxane as antifoaming agent 0
．． 024 parts were added. After 10 minutes, 0.04 parts of antimony trioxide was added to 0.02 parts of dimethyl terephthalate.
7 mol %) was added thereto, the temperature was raised to 240° C. while simultaneously expelling excess ethylene glycol, and the mixture was transferred to a polymerization reactor. then 760 mm) Ig to lm over 1 hour
Reduce the pressure to mHg and simultaneously reduce the pressure to 240 mHg for 1 hour and 30 minutes.
Do not raise the temperature from ℃ to 285℃. Two hours after the start of decompression, the following chemical formula (% formula %) (where m is 3 as an average value and p is 115 as an average value)
, j is an integer from 18 to 28 with an average of 21), a water-insoluble polyoxyethylene compound having an average molecular weight of 7106 was added in a molten state in the amount shown in Table 2, and dodecylbenzenesulfonic acid was added as an ionic compound. The amount of sodium listed in Table 2 was made into a 50% ethylene glycol solution and added under reduced pressure. After further polymerization for 1 hour under reduced pressure of 1 mmHg or less with stirring, 0.1 part of Cyanox 1790 (manufactured by American Cyanamid Company) and 0.1 part of Mark AO-4123 (manufactured by Adeka Argus Chemical Company) were added as antioxidants. Add 3 parts under reduced pressure and then polymerize for an additional 20 minutes. The intrinsic viscosity of the obtained polymer is in the range of 0.640 to 0.660, and the softening point is 2.
The temperature ranged from 61.5 to 263°C. This polymer was made into chips using a conventional method. The thus obtained antistatic polyester containing no water-insoluble polyoxyethylene compound was used as a polymer for the core component, and after drying in a conventional manner, it was melted in a screw extruder and fed to a two-component composite spinning head via a gear pump. Na.

The supply amounts of the core component polymer and the sheath component polymer should be set so that the area ratio of the core component becomes the value listed in Table 2.

The molten polymers of the core and sheath components supplied at the same time are extruded at 280°C using a composite spinneret with 24 circular composite spinning holes with a hole diameter of Ojmm, and then extruded at 1500 m/min through a godet roll. It was once wound up as a concentric composite fiber at a speed of . Next, the drawn yarn was subjected to stretching heat treatment using a heating roller at 90°C and a stretching heater at 170°C at a stretching ratio such that the elongation of the obtained drawn yarn was 35%, to obtain a drawn yarn of 50 denier/24 filaments. .

The obtained drawn yarn was made into a stockinette knitted fabric, and the dyed knitted fabric was scoured, preset, cation dyed, and final set by the method described above (Examples 1 to 5), and the dyed knitted fabric was subjected to an alkali weight loss treatment after presetting. (For Example 2), the dyeability of the cationic dye, fibril resistance, and frictional charging voltage after washing 0 times (referred to as Lo) and after washing 30 times (referred to as L3o) were measured. The results are shown in Table 2.

Example 6 In place of the tetra-n-butylphosphonium 3,5-dicarpomethoxybenzenesulfonic acid salt used in the production of the cationically dyeable polyester polymer used in Example 2, 2. 5 mol%
The same procedure as in Example 2 was conducted except that polyethylene terephthalate chips copolymerized with 3,5-cycarboxybenzenesulfonic acid tetraphenylphosphonium salt were used as the polymer for the sheath component. The results are shown in Table 2.

Example 7 In place of the water-insoluble polyoxyethylene polyether used in the production of the antistatic polymer used in Example 1, the following chemical formula (% formula %) (where m is an average value of 10. p is 1 as the average value
The same procedure as in Example 1 was carried out except that water-soluble polyoxyethylene glycol having an average molecular weight of 11,898 and having an average molecular weight of 11,898 was used. The results are shown in Table 2.

Example 8 In place of the sodium dodecylbenzenesulfonate used as the organic ionic compound used in the production of the antistatic polymer that was not used in Example 1, sulfonic acid sodium salt 2 represented by the following chemical formula % formula % was used. The same procedure as in Example 1 was carried out except that .0% by weight was added in a molten state. The results are shown in Table 2.

Comparative Example 1 The same procedure as in Example 1 was carried out except that instead of the antistatic polymer used in Example 1, polyethylene terephthalate chips having an intrinsic viscosity of 0.64 were used as the core component polymer. The results are shown in Table 2.

Comparative Example 2 The same procedure as in Example 1 was carried out except that instead of the cationically dyeable polyester polymer used in Example 1, polyethylene terephthalate chips having an intrinsic viscosity of 0.64 were used as the polymer for the sheath component.

four The results are shown in Table 2.

Comparative Example 3 In place of the tetra-■-butylphosphonium 3,5-dicarbomethoxybenzenesulfonic acid salt used in the production of the cationically dyeable polyester polymer used in Example 2, dimethyl terephthalate was used. The same procedure as in Example 2 was conducted except that polyethylene terephthalate chips copolymerized with 2.5 mol % of 3.5-dicarbomethoxybenzenesulfonic acid sodium salt were used as the polymer for the sheath component. The results are shown in Table 2.

Comparative Examples 4 to 5 The same procedure as in Example 1 was conducted except that the supply amounts of the core component polymer and the sheath component polymer were set so that the area ratio of the core component became the value listed in Table 2. The results are shown in Table 2.

Comparative Example 6 Water-soluble polyoxyethylene glycol with an average molecular weight of 20,000 is used in place of the water-insoluble polyoxyethylene polyether used in the production of the antistatic polymer that was not used in Example 1. The same procedure as in Example 1 was carried out except for this. The results are shown in Table 2.

Comparative Example 7 A 45% aqueous solution of polyethylene glycol diammonium adipate obtained by a conventional method from polyethylene glycol diamine having an average molecular weight of 4000 and adipic acid was
0 kg, 6 kg of an 85% aqueous solution of caprolactam, and 8 kg of a 40% aqueous solution of hexamethylene diammonium isophthalate were placed in a concentrator, heated at normal pressure until the internal temperature reached 110°C, and concentrated to 80% concentration. Transfer to a polymerization vessel and start heating while flowing nitrogen. Internal temperature is 120℃
At the point when 0.26 kg <25% by weight> of sodium dodecylbenzenesulfonate
-hydroxyphenyl)benzene, 0.26 kg (2
, 5% by weight) and started stirring until the internal temperature reached 245℃.
It was heated for 18 hours until . After the polymerization was completed, this polymer was made into chips by a conventional method. 23 chips of the block polyetheramide composition obtained above were placed in a polyethylene derephthalate chip having an intrinsic viscosity of 0.64.
By weight% blending, an antistatic polymer containing 3.0% by weight as a polyalkylene ether component and 0.6% by weight as a sodium dodecylbenzenesulfonate component was obtained. The same procedure as in Example 1 was carried out except that the antistatic polymer thus obtained was used as the core component polymer. The results are shown in Table 2.

The antistatic polyester fibers obtained in Examples 1 to 8 were Comparative Example 2 in which a regular polyester was used as a sheath component, Comparative Example 3 in which a conventional polyester copolymerized with a 5=metal sulfoisophthalic acid compound was used as a sheath component, Compared to Comparative Example 6, in which the core component was polyester mixed with polyethylene glycol, and Comparative Example 7, in which the core component was polyester mixed with block polyether amide, the performance under low temperature and low humidity conditions such as 10°C and 130% RH was The antistatic properties were significantly improved, with extremely good antistatic properties at low temperatures and low humidity. Furthermore, compared to Comparative Example 3 in which the sheath component was polyester copolymerized with a 5-metal sulfoisophthalic acid compound, the antistatic properties were not affected at all by washing and had excellent antistatic durability.

Claims (1)

[Scope of Claims] The core component is (a) 1 to 10% by weight of a non-random copolymerizable polyoxyethylene polyether having an average molecular weight of 5,000 to 16,000 represented by the following general formula (I), and (
b) Consisting of an aromatic polyester containing 0.1 to 5% by weight of an organic ionic compound, Z-[(CH_2CH_2O)_l-(R^1O)_m
-R^2]_k...(I) [wherein, Z has 1 to 6 active hydrogens and has a molecular weight of 300
The following organic compound residues, R^1 is an unsubstituted or substituted alkylene group having 6 or more carbon atoms, R^2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a carbon atom number 2
~40 monovalent acyl groups, k is an integer of 1 to 6, l is k×
l represents an integer of 70 or more, and m represents an integer of 1 or more. ] A core-sheath type composite fiber in which the sheath component is made of a modified polyester copolymerized with 0.1 to 10 mol% of a sulfonic acid phosphonium salt represented by the following general formula (II), ▲Mathematical formula, chemical formula, table etc.▼...(II) [In the formula, A is an aromatic group or aliphatic group, X_1 is an ester-forming functional group, X_2 is the same or different ester-forming functional group or hydrogen atom as X_1, R_1' , R_2
', R_3' and R_4' are the same or different groups selected from alkyl groups and aryl groups, and n represents a positive integer. ] The composite fiber has a core/sheath/area composite ratio of 5/95 to 50/
An antistatic polyester fiber characterized by having a molecular weight of 50.