JP2003129341A - Flame retardant polyester and fiber comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyester fiber having a good hue (b value), expressing excellent antistatic properties, generating remarkably little adherent to a spinneret and excellent in formability and provide a method for producing the same. SOLUTION: A specific polyoxyalkylene-based polyether and an organic sulfonic acid metal salt are added to and blended with the polyester at an arbitrary stage before the polyester is finished by using a catalyst for producing the polyester containing a specific titanium compound and a phosphorus compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester for antistatic fibers, and more specifically, it uses a catalyst for polyester production containing a specific titanium compound and phosphorus compound,
It has a good color tone (b value) and has excellent antistatic property. Furthermore, even if it is continuously spun through the spinneret for a long period of time, the amount of spinneret deposits is very small and moldability is excellent. Regarding polyester.

[0002]

2. Description of the Related Art Polyesters, particularly polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate are excellent in mechanical, physical and chemical properties, and therefore, fibers, films and other molded products are obtained. Widely used in.

For example, polyethylene terephthalate is usually obtained by directly esterifying terephthalic acid and ethylene glycol, transesterifying a lower alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol, or terephthalic acid and ethylene. Reacting with oxide to form an ethylene glycol ester of terephthalic acid and / or a low polymer thereof,
Then, this reaction product is heated under reduced pressure in the presence of a polymerization catalyst to carry out a polycondensation reaction until a predetermined degree of polymerization is achieved. Also, polyethylene naphthalate,
Polytrimethylene terephthalate and polytetramethylene terephthalate are also produced by the same method as described above.

It is well known that the type of catalyst used in these polycondensation reaction steps greatly influences the reaction rate and the quality of the obtained polyester. As a polycondensation catalyst for polyethylene terephthalate, antimony compounds are most widely used because of having excellent polycondensation catalyst performance and obtaining a polyester having a good color tone.

However, when an antimony compound is used as a polycondensation catalyst, when polyester is continuously melt-spun for a long period of time, foreign matter (hereinafter, sometimes simply referred to as die foreign matter) adheres and deposits around the mouth of the die. The bending phenomenon (bending) of the flow of the molten polyester occurs, which causes fluff and / or yarn breakage in the spinning and drawing steps, which causes a problem of moldability and lowers productivity.

It has been proposed to use a titanium compound such as titanium tetrabutoxide as a polycondensation catalyst other than the antimony compound. However, when such a titanium compound is used, the above-mentioned deposition of foreign matter on the spinneret is prevented. Although the problem of moldability due to the problem can be solved, a new problem arises in that the obtained polyester itself is colored yellow and the melt thermal stability is poor.

In order to solve the above coloring problem, it is generally practiced to add a cobalt compound to polyester to suppress yellowing. It is true that the color tone (b value) of the polyester can be improved by adding the cobalt compound, but the melt heat stability of the polyester is lowered by the addition of the cobalt compound and the decomposition of the polyester is likely to occur. There is.

Further, as another titanium compound, Japanese Patent Publication No.
No. 8-2229 discloses titanium hydroxide and Japanese Patent Publication No.
JP-A 7-26597 discloses the use of α-titanic acid as a catalyst for polyester production. However, in the former method, it is not easy to pulverize titanium hydroxide into powder, while in the latter method, α-titanic acid is likely to be deteriorated, so that its storage and handling are not easy,
Therefore, neither is suitable for industrial use, and it is also difficult to obtain a polyester having a good color tone (b value).

Further, JP-B-59-46258 discloses a product obtained by reacting a titanium compound with trimellitic acid, and JP-A-58-38722 discloses a titanium compound and a phosphite. It is disclosed that each of the products obtained by reacting with and is used as a catalyst for producing polyester. Indeed, according to this method,
Although the melt heat stability of the polyester is improved to some extent, the color tone of the obtained polyester is not sufficient, and therefore, further improvement of the color tone of the polyester is desired.

Further, in JP-A-7-138354, it has been proposed to use a complex of a titanium compound and a phosphorus compound as a catalyst for polyester production. According to this method, the melting heat stability is improved to some extent. Though
The color tone of the obtained polyester is not sufficient. Incidentally, these titanium-phosphorus-based catalysts often have a problem that the catalyst itself remains as foreign matter in the polyester, and as a result, yarn breakage easily occurs in the spinning / drawing process, and this problem is also solved. Was desired.

In general, when polyester is used as the fiber, the obtained fiber itself is liable to be charged with static electricity and has a drawback that it is inferior in antistatic property. Conventionally, as a method of imparting antistatic properties to polyester fibers, before the yarn is made, the polyester is
Method of blending polyalkylene ether or polyalkylene ether and organic sulfonic acid metal salt (Japanese Patent Publication No.
No. 31828, Japanese Patent Publication No. 60-11944, Japanese Patent Laid-Open No. 3-139556, etc.) have been proposed.

However, when the polyester chips obtained by these methods are remelted in a ruder and melt-spun, the chips slip on the ruder to cause defective biting, and stable melt spinning is possible. There was a problem that it was difficult.

Therefore, as a method of improving the stability of melt spinning and obtaining a polyester having an excellent antistatic property, a method of defining the dispersed state of the antistatic agent in the polyester within a specific range (Japanese Patent No. 3130624). Gazette) has been proposed. Certainly, this method solves the problem of poor stability of melt spinning. However, the fiber using such polyethylene terephthalate is soft due to its chemical modification, and is produced by the generation of foreign matter in the spinneret as when the above-mentioned antimony compound is used as a catalyst during melt spinning. There is a problem that the tendency to decrease the sex.

The problem of foreign matter in the die is solved by not using an antimony compound as described above. However, the method using no antimony compound cannot actually be used because the color tone of the yarn is deteriorated. Therefore, there has been a demand for a polyester fiber which is less likely to cause foreign matter in the die, has an excellent color tone, is excellent in hygroscopicity and water absorption, is excellent in moldability, and has high productivity.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to use a catalyst for producing polyester containing a specific titanium compound and phosphorus compound, to have a good color tone (b value) and to have an excellent antistatic property. In addition, the amount of foreign matter generated in the spinneret is extremely small even when continuously spun through the spinneret for a long time.
It is intended to provide a polyester fiber having excellent moldability and a method for producing the same.

[0016]

The present inventors have completed the present invention as a result of intensive investigations in view of the above-mentioned prior art. That is, the present invention comprises a polyester having ethylene terephthalate as a main repeating unit, and contains A) a titanium compound soluble in the polyester with respect to all dicarboxylic acid residue components, as a titanium metal element, in an amount of 2 to 10 mmol%, The titanium compound and the phosphorus compound are represented by the following formula (1) and / or formula (2) 2 ≦ P / Ti ≦ 15 (1) 10 ≦ Ti + P ≦ 100 (mmol%) (2) (where Ti is in the polyester) The concentration of the titanium metal element of the titanium compound soluble in the contained polyester (mmole%) and the concentration of P of the phosphorus compound contained in the polyester (mmole%) are satisfied. B) a polyester containing B) as an antistatic agent at any stage before the spinning step of the polyester, represented by the following formula (3)

[0017]

[Chemical 5]

(In the above formula, Z is an organic compound residue having 1 to 6 active hydrogens, R ¹ is an alkylene group having 6 or more carbon atoms or a substituted alkylene group, and R ² is a hydrogen atom or a carbon atom. A monovalent hydrocarbon group having 1 to 40 carbon atoms, a monovalent hydroxyhydrocarbon group having 2 to 40 carbon atoms or a monovalent acyl group having 2 to 40 carbon atoms, k represents an integer of 1 to 6, s is an integer satisfying s ≧ 70 / k, and t is an integer of 1 or more.), which is 0.2 based on the weight of the polyester.
30 wt%, and the following formula _{^{(4) (R 3 SO 3}} ) r M (4) ( In the formula, R ³ is substituted by an alkyl group or an alkyl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms An aryl group which may be substituted, M is an alkali metal or an alkaline earth metal, r is 1 when M is an alkali metal, and 2 when M is an alkaline earth metal) Sulfonic acid metal salt, based on the weight of the polyester, 0.05
C) The following formula (5) X = N × W (5) (N and W in the above formula are polyester 20 respectively)
Insert mg between two slides and load 10g under load 285 ℃
The number of particles having a diameter of 2.5 μm or more (particles / cm ² ) observed when the film was melted to form a thin film having a diameter of 1 cm, and the amount of the antistatic agent in the polyester composition (polyester 1
Parts by weight relative to 00 parts by weight). ), The dispersibility X of the antistatic agent is 0.1 to 1, and D) and the intrinsic viscosity are 0.55 (in accordance with the detailed description).
This is achieved by the above polyester for antistatic fibers.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

The polyester for antistatic fibers of the present invention contains a titanium compound soluble in the polyester in an amount of 2 to 10 mmol% as a titanium metal element with respect to all dicarboxylic acid residue components. The following general formula (1) and / or (2) 2 ≦ P / Ti ≦ 15 (1) 10 ≦ Ti + P ≦ 100 (mmol%) (2) (where Ti is in the polyester contained in the polyester) It is necessary to contain the concentration of the titanium metal element of the soluble titanium compound (mmole%) and the concentration of P of the phosphorus compound contained in the polyester (mmole%). There is. In the above formula (1), when (P / Ti) is less than 2, the color tone is remarkably yellowed, which is not preferable. Also, (P / Ti) is 1
When it exceeds 5, the polymerization reactivity of the polyester is significantly lowered and the intended polyester cannot be obtained. In the polyester used in the present invention, the proper range of (P / Ti) is characteristically narrower than that of a normal metal catalyst,
When it is within the proper range, it is possible to obtain an effect which has not been heretofore obtained by the present invention. On the other hand, when (Ti + P) is less than 10, the productivity in the yarn making process is significantly reduced,
Satisfactory performance cannot be obtained. Also, (Ti + P) is 1
If it exceeds 00, a small amount of foreign matter due to the catalyst is generated, which is not preferable.

The ranges of formulas (1) and (2) are preferably in the range of (P / Ti) of 3 to 12 in the formula (1) and in the range of (Ti + P) of 15 to 85 in the formula (2). It is more preferable that (P / Ti) in the formula (1) is in the range of 4 to 10, and (Ti + P) in the formula (2) is in the range of 20 to 70.

Further, as the titanium compound used in the present invention, it is necessary to use a titanium compound which is soluble in the polyester from the viewpoint of reducing foreign matters caused by the catalyst,
Formula (7) below

[0023]

[Chemical 6]

(Wherein R ^{6 to} R ⁹ each independently represents an alkyl group having 2 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m represents an integer of 1 to 3). Preferably, the compound is More specifically, examples of the titanium compound represented by the general formula (7) include titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetranormal propoxide, titanium tetraalkoxide such as titanium tetraethoxide, and octaalkyl trititanate. Hexaalkyl dititanate and the like can be mentioned.

Further desirable in the present invention is the above formula (7).
Or a titanium compound represented by the above formula (7) and the following formula (8)

[0026]

[Chemical 7]

(Wherein n represents an integer of 2 to 4) is a product obtained by reacting with an aromatic polycarboxylic acid or its acid anhydride.

As the aromatic polycarboxylic acid represented by the general formula (8) or its acid anhydride to be reacted as the titanium compound, there are phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and these. The acid anhydride of is preferably used. When the titanium compound and an aromatic polyvalent carboxylic acid or an acid anhydride thereof are reacted, a part of the aromatic polyvalent carboxylic acid or an acid anhydride thereof is dissolved in a solvent, and a titanium compound is added dropwise thereto. Then 0-2
The reaction may be performed at a temperature of 00 ° C for 30 minutes or more.

The polyester of the present invention must contain a titanium compound soluble in the polyester as a titanium metal element in an amount of 2 to 10 mmol% based on all dicarboxylic acid residue components. When the titanium metal element is less than 2 mmol%, the productivity of the polyester is lowered and a polyester having a target molecular weight cannot be obtained. On the other hand, when the content of the titanium metal element exceeds 10 mmol%, the thermal stability is decreased to the contrary, and the decrease in the molecular weight at the time of fiber production becomes large, and a polyester fiber of excellent quality cannot be obtained. The amount of titanium metal element is preferably in the range of 2.5 to 8 mmol%, more preferably in the range of 3 to 7 mmol%. Incidentally, the titanium compound soluble in the polyester referred to here means the amount when a titanium compound is used as the polycondensation reaction catalyst, and when the titanium catalyst is also used in the first step reaction by the transesterification reaction. Shows the total amount of the titanium compound used as the transesterification reaction catalyst and the titanium compound used as the polycondensation reaction catalyst. In the present invention, it is also preferable that a part or the whole amount of the titanium compound is added before the start of the transesterification reaction, and the transesterification reaction catalyst and the polycondensation reaction catalyst to be carried out thereafter are used in combination as two kinds of catalysts. It is mentioned as one aspect.

Further, in the present invention, examples of the phosphorus compound used include phosphoric acid, phosphorous acid, phosphonic acid, phosphonate compounds and their derivatives, which may be used alone or in combination of two or more kinds. You may use together. Among these phosphorus compounds, a phosphonate compound represented by the following general formula (6) is particularly preferable.

[0031]

[Chemical 8]

(In the above formula, R ⁴ and R ⁵ may be the same or different and represent an alkyl group having 1 to 4 carbon atoms, and X represents —CH 2 — or —CH (Y). (Y represents a benzene ring.) As the above-mentioned phosphonate compound, dimethyl-, diethyl-, dipropyl- and dibutyl esters of phosphonic acid can be mentioned, and specifically, carbomethoxymethanephosphonic acid, carboethoxymethane. Phosphonic acid, carbopropoxymethanephosphonic acid, carboptoxymethanephosphonic acid, carbomethoxy-phosphono-phenylacetic acid, carboethoxy-phosphono-phenylacetic acid, carboprotoxy-phosphono-phenylacetic acid, carbobutoxy-phosphono-phenylacetic acid, etc. Can be mentioned.

The reason why the above phosphonate compound is preferable is that the catalytic activity of the titanium compound is maintained during the polycondensation reaction because the reaction with the titanium compound proceeds relatively slowly as compared with the phosphorus compound which is usually used as a stabilizer. Long time,
As a result, the amount added to the polyester can be reduced, and even when a large amount of stabilizer is added to the catalyst as in the present patent, the thermal stability of the polyester is not impaired.

The phosphorus compound may be added at any time after the transesterification reaction or the esterification reaction is substantially completed. For example, the polycondensation reaction may be performed under atmospheric pressure before the polycondensation reaction is started. It may be added under reduced pressure after the start of, or at the end of the polycondensation reaction, or after the end of the polycondensation reaction, that is, after the polyester is obtained.

Generally, a production method using an aromatic dicarboxylic acid typified by terephthalic acid as a raw material for a polyester containing ethylene terephthalate as a main repeating unit, and an ester-forming derivative of an aromatic dicarboxylic acid typified by dimethyl terephthalate are used as raw materials. There are two known methods used as. The polyester in the present invention is
The production method is not particularly limited, but is preferably a production method via a transesterification reaction in which dimethyl terephthalate as a raw material is 80 mol% or more of all dicarboxylic acid components. In the present invention, the term “ethylene terephthalate as a main repeating unit” means that 90 mol% or more of ethylene terephthalate is based on all repeating units.

The above-mentioned dimethyl terephthalate is specifically 10 mol% or less, preferably 10 mol% or less based on the total molar amount of the aromatic dicarboxylic acid components, within a range in which the effect of the method of the present invention is not substantially impaired. Other difunctional carboxylic acid ester copolymerizable therewith may be contained as an additional component in the range of 5 mol% or less.

Copolymerizable additional components which are preferably used are aliphatic and cycloaliphatic difunctional dicarboxylic acids and their ester-forming derivatives, hydroxycarboxylic acids and their ester-forming derivatives, and aliphatic,
Examples thereof include alicyclic and aromatic diol compounds and polyoxyalkylene glycols. For example, adipic acid,
Sebacic acid, 1,4-cyclohexanedicarboxylic acid and the like are mentioned as examples of the aliphatic and alicyclic difunctional dicarboxylic acids and their ester-forming derivatives. For example, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid and the like are mentioned as examples of hydroxycarboxylic acids and their ester-forming derivatives. For example, alkylene glycol having 2 or more constituent carbon atoms, 1,4-
Cyclohexanedimethanol, neopentyl glycol, bisphenol A, bisphenol S, polyethylene glycol and the like are specific examples of the aliphatic, alicyclic or aromatic diol compound and polyoxyalkylene glycol. The above-mentioned additional components may be used alone or in combination of two or more. However, the copolymerization needs to be within the above range.

Further, in the production method using dimethyl terephthalate as the raw material, the addition amount of the titanium compound can be reduced, and a part and / or the total amount of the titanium compound is added before the start of the transesterification reaction so that the transesterification catalyst and the catalyst can be mixed with each other. A production method in which the two catalysts of the condensation reaction catalyst are also used is preferable, and the transesterification reaction is further performed at 0.05 to 0.20 MP.
The method of carrying out under a pressure is more preferable.

The pressure during the transesterification reaction is 0.05 M
If it is less than or equal to pa, the reaction by the catalytic action of the titanium compound is not sufficiently promoted. On the other hand, if it is more than 0.20 MPa, the content of diethylene glycol, which is a by-product, in the polyester is remarkably increased, and the thermal stability of the polyester, etc. Is inferior in characteristics.

The following formula (3) used as an antistatic agent in the present invention

[0041]

[Chemical 9]

(In the above formula, Z is an organic compound residue having 1 to 6 active hydrogens, R ¹ is an alkylene group or a substituted alkylene group having 6 or more carbon atoms, and R ² is a hydrogen atom or carbon atom number. A monovalent hydrocarbon group having 1 to 40, a monovalent hydroxyhydrocarbon group having 2 to 40 carbon atoms, or a monovalent acyl group having 2 to 40 carbon atoms, k is an integer of 1 to 6, and s
Represents an integer satisfying s ≧ 70 / k, and t represents an integer of 1 or more. Specific examples of the polyoxyalkylene-based polyether represented by) are polyoxyethylene glycol having a molecular weight of 4000 or more, polyoxypropylene glycol having a molecular weight of 2000 or more, polyoxytetramethylene glycol, ethylene oxide having a molecular weight of 2000 or more,
Examples include propylene oxide copolymers, trimethylolpropane ethylene oxide adducts having a molecular weight of 4000 or more, octylphenylethylene oxide adducts having a molecular weight of 3000 or more, and compounds in which a substituted ethylene oxide having 6 or more carbon atoms is added to these terminal hydroxyl groups. To be

The amount of the polyoxyalkylene-based polyether blended in the polyester is based on the weight of the fiber.
It is necessary to set it in the range of 0.2 to 30%. If the blending amount is less than 0.2%, the antistatic property of the fiber obtained by melt spinning cannot be sufficiently obtained. On the other hand, if it exceeds 30%, the effect of improving the minimum antistatic property is not recognized, and the mechanical properties are impaired, which is not preferable.

In the production method of the present invention, in order to improve the antistatic property, it is necessary to further mix a specific metal salt of an organic sulfonic acid. Here organic sulfonic acid metal salt used is the following formula _{^{(4) (R 3 SO 3}} ) r M (4) ( the formula R ³ is an alkyl group having 3 to 30 carbon atoms, or 6 to 30 carbon atoms An aryl group which may be substituted with an alkyl group, M represents an alkali metal or an alkaline earth metal, r represents 1 when M is an alkali metal, and 2 when M is an alkaline earth metal). Represented.

When an alkyl group is used as R ³ in the above formula (4), it may be linear or may have a side chain. From the viewpoint of compatibility with polyester, R
³ is an alkyl group, an aryl group substituted with an alkyl group,
Alternatively, organic sulfonic acid metal salts other than aryl groups are not preferred.

M is an alkali metal such as Na, K or Li, M
Examples thereof include alkaline earth metals such as g and Ca, and among them, Na and K are preferable. When using the organic sulfonic acid metal salt, it is not necessary to use a single compound, and it may be a mixture of organic sulfonic acid metal salts having various alkyl groups.

Specific examples of the organic sulfonic acid metal salt include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, sodium stearyl benzene sulfonate, sodium octyl benzene sulfonate, and sodium dodecyl benzene sulfonate. Alternatively, a mixture of sodium alkylsulfonate having an average number of carbon atoms of 14 and the like can be mentioned as a preferable example.

The content of the organic sulfonic acid metal salt in the polyester must be in the range of 0.05 to 10% by weight based on the weight of the fiber. If the blending amount is less than 0.05% by weight, the antistatic property of the polyester fiber obtained by melt spinning is not sufficient, and if it is more than 10% by weight, the mixing operation, spinning and the like become difficult, which is not preferable.

The polyoxyalkylene-based polyether and the antistatic agent of the organic sulfonic acid metal salt are added to and blended with the polyester at any stage before the completion of the spinning process. For example, it may be added in advance to a raw material for polyester production, or may be added during the first stage reaction or during the subsequent second stage polycondensation reaction, and the polyester and antistatic agent obtained after the polycondensation reaction may be added. It is also possible to employ, for example, a method of melt mixing with and using a melt extruder, a method of adding and mixing with polyester at a stage before the exit of the melt molding machine, and the like. Further, the polyoxyalkylene-based polyether and the organic sulfonic acid metal salt may be added in separate steps. Further, in the present invention, the following formula (5) X = N × W (5)

(In the above formula, N and W are each 1 mm sandwiching 20 mg of the polyester composition between two preparations.
The number of particles having a diameter of 2.5 μm or more (particles / cm ² ) observed when melted at 285 ° C. under 0 g load to form a thin film having a diameter of 1 cm, and the amount of antistatic agent in the polyester composition (polyester Parts by weight based on 100 parts by weight). ), The dispersibility X of the antistatic agent is 0.1 to 1. When the dispersibility X defined above is less than 0.1, the antistatic agent is extremely finely dispersed, and the antistatic performance of the fiber obtained from such a composition is insufficient, which is not preferable. On the other hand, when the dispersibility exceeds 1.0, the antistatic agent is insufficiently dispersed, and the antistatic agent easily exudes onto the chip surface or the fiber surface. For this reason, when the chips are melt-spun by an extruder, the chips may not be bitten in, and the antistatic performance of the fibers may be deteriorated.

When spinning the polyester blended with the antistatic agent, it is not necessary to adopt special conditions, and it is possible to adopt arbitrary conditions. In the production method of the present invention, the cross-sectional morphology of the fiber can be arbitrarily selected as long as the effects intended by the present invention can be obtained, and the round shape,
A shape such as an irregular shape may be appropriately selected, and the size (fineness) of the cross section is not limited.

The polyester fiber obtained by the production method of the present invention may optionally contain a catalyst, an anti-coloring agent,
A heat-resistant agent, a fluorescent agent, a flame retardant, a dye, a pigment, inert fine particles and the like may be contained.

Further, in order to finely adjust the color of the obtained polyester, azo type, triphenylmethane type, quinoline type,
A color-matching agent composed of one or more of organic blue pigments such as anthraquinone type and phthalocyanine type and inorganic blue pigments can be added. In the production method of the present invention, naturally, it is not necessary to use an inorganic blue pigment containing cobalt or the like which lowers the melt thermal stability of the polyester as a color-matching agent, and thus the resulting polyester is substantially It is preferably free of cobalt.

The polyester obtained by the method of the present invention usually has an L value of 80.
It is 0 or more and the b value is in the range of -2.0 to 5.0. When the L value of the polyester is less than 80.0, the whiteness is low, and thus a molded product with high whiteness that can be put to practical use may not be obtained. Further, when the b value is less than -2.0, the yellowness of the polyester is small, but the bluishness is increased, while when the b value exceeds 5.0, the yellowness of the obtained polyester is strong. However, it may not be possible to use it for the production of a practically useful molded product. The L value of the polyester obtained by the method of the present invention is preferably 82 or more,
It is particularly preferably 83 or more, the preferable range of the b value is -1.0 to 4.5, and particularly preferably 0.0 to 4.
It is 0.

The polyester of the present invention is substantially free of cobalt atoms derived from the cobalt compound for color matching. Polyesters containing cobalt atoms have the drawbacks of low melt heat stability and easy decomposition. The term "substantially free" as used herein means that a cobalt compound is not used as a color-matching agent or a polycondensation catalyst,
Therefore, it means that the obtained polyester does not contain a cobalt atom derived from the above cobalt compound. Therefore, the polyester of the present invention may contain a cobalt atom derived from the cobalt compound added for the purpose other than the color-matching agent and the catalyst.

The intrinsic viscosity of the polyester in the present invention may be appropriately selected, but is preferably in the range of 0.55 to 1.0. When the intrinsic viscosity is within this range, melt molding is easy and the strength of the molded product is high. The more preferable range of the intrinsic viscosity is 0.60 to 0.90.
And particularly preferably 0.62 to 0.80.

[0057]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples. However, as described above, the intrinsic viscosity, hue,
The titanium content, dispersibility, layer of deposits generated on the spinneret and antistatic durability were measured by the methods described below.

(1) Intrinsic viscosity: The intrinsic viscosity of the polyester was determined from the viscosity value measured at 35 ° C. for the orthochlorophenol solution.

(2) Color tone (L value and b value): A polyester sample was melted at 290 ° C. under vacuum for 10 minutes, and immediately after molding this into an aluminum plate having a thickness of 3.0 ± 1.0 mm. Quench the plate in ice water and add 160
After dry crystallization treatment at 1 ° C for 1 hour, place on a white standard plate for color difference meter adjustment, the Hunter L value of the plate surface and b
The value was measured using a Hunter type color difference meter CR-200 manufactured by Minolta. The L value indicates lightness, the larger the value, the higher the lightness, and the larger the value, the larger the degree of yellowness.

(3) Titanium content of catalyst: The titanium concentration in the catalyst compound is determined by the fluorescent X-ray measuring device 3270 manufactured by Rigaku Corporation.
Was measured using.

(4) Layer of deposits generated on the spinneret: Polyester is made into chips, which are melted at 290 ° C.,
It was discharged from a spinneret having a hole diameter of 0.15 mmφ and 12 holes, and was spun at 600 m / min for 2 days, and the height of a layer of deposits generated on the outer edge of the discharge port of the spinneret was measured. The larger the height of the deposit layer, the easier the bending of the discharged filament of the polyester melt is, and the lower the moldability of the polyester. That is, the height of the deposit layer generated on the spinneret is an index of the moldability of the polyester.

(5) Antistatic durability: A knitted fabric prepared by a conventional method using the obtained polyester fiber was treated with a 0.3% aqueous solution of anionic detergent ("Zab" manufactured by Kao Soap Co., Ltd.). Was washed in a household electric washing machine at 40 ° C. for 30 minutes, and the knitted fabric was dried.

The dried sample was immersed in water for 30 minutes or more and then dehydrated for 5 minutes with a dehydrator of a domestic electric washing machine.
The specific resistance value was measured after the samples before and after washing were allowed to stand overnight at 25 ° C. and 65% relative humidity for one day.

(6) Dispersibility X of antistatic agent: 20 mg of the obtained polyester was sandwiched between two preparations and melted at 285 ° C. under a load of 10 g to form a thin film having a diameter of 1 cm. Number of particles of 5 μm or more (number / cm
² ) and the amount of antistatic agent in the polyester composition (parts by weight relative to 100 parts by weight of polyester).

[Example 1] Dimethyl terephthalate 194
Parts by weight, 124 parts by weight of ethylene glycol and tetra-
0.017 parts by weight of n-butyl titanate was charged into a SUS container capable of pressure reaction, and under pressure of 0.07 MPa,
After conducting a transesterification reaction at 220 ° C., 0.08 part of triethylphosphonoacetate was added to the reaction mixture to complete the reaction of the first step. Then, the reaction mixture was placed in a polycondensation flask equipped with a rectification column, and 0.0002 parts by weight of terazol blue as a color-adjusting agent was added to the reaction mixture.

This reaction system was heated at 280 ° C. under atmospheric pressure for 3 hours.
React for 0 minutes, then 4.0 kPa (30 mmHg)
After reacting under reduced pressure for 15 minutes, the pressure is returned to atmospheric pressure once, and then the following formula (9)

[0067]

[Chemical 10]

(However, j is an integer of 18 to 28 and averages 2
1, P is 100 as an average value, and m is 5 as an average value. 8 parts of a polyoxyethylene-based polyether represented by), and 10 parts of a mixture of sodium alkylsulfonate having 8 to 20 carbon atoms and 14 carbon atoms in average,
The system was gradually depressurized and reacted for 80 minutes with stirring. The final internal temperature was 280 ° C., the final internal pressure was 0.32, and the intrinsic viscosity of the obtained polyester was 0.651. The addition amount of polyoxyethylene-based polyether and sodium alkyl sulfonate in polyester was 2.5 each.
% By weight, 3% by weight, and dispersibility X was 0.65.

After the reaction was completed, the polyester was made into chips and dried according to a conventional method. Then, using this dry-processed chip, a 333 dtex / 36 fil raw yarn was prepared in accordance with a conventional method and stretched 4.0 times to obtain 83.25 dtex / 36 fi.
l of multifilament was obtained. A knitted fabric was obtained from this filament. The results are shown in Tables 1 and 2.

[Example 2] In Example 1, 0.031 parts of titanium trimellitate obtained by synthesizing a titanium compound by the method of the following reference example, and polyoxyalkylene glycol-based polyether of polyoxyethylene glycol 8 having a molecular weight of 4000 were used. Part, organic sulfonic acid metal salt having 8 to 20 carbon atoms
A polycondensation reaction was carried out in the same manner except that 9 parts of sodium alkylsulfonate having an average carbon number of 12 was used to obtain polyester and fibers. The amounts of polyoxyethylene polyether and sodium alkyl sulfonate added to the polyester were 2.5% by weight and 3% by weight, respectively, and X = 0.76. The results are shown in Tables 1 and 2.

[Reference Example] Method for synthesizing titanium trimellitate An ethylene glycol solution of trimellitic anhydride (0.2
%) Of tetrabutoxytitanium to trimellitic anhydride, and allowed to react for 60 minutes in air at 80 ° C. under atmospheric pressure, then cooled to room temperature and produced with 10 times the amount of acetone. The catalyst was recrystallized, the precipitate was filtered through filter paper, dried at 100 ° C. for 2 hours,
The desired compound was obtained.

[Examples 3 to 6, Comparative Examples 1 to 3] Polycondensation reaction was carried out in the same manner as in Example 1 except that the titanium compound and phosphorus compound were changed to the compounds and values shown in Table 1 to obtain polyester and fiber. Obtained. The amounts of polyoxyethylene-based polyether and sodium alkylsulfonate added to the polyester were 2.5% by weight and 3% by weight, respectively. The results are shown in Tables 1 and 2.

Comparative Example 4 0.003 parts by weight of tetra-n-butyl titanate was added to a mixture of 194 parts by weight of dimethyl terephthalate and 124 parts by weight of ethylene glycol in a container made of SUS capable of pressurizing and reacting with 0.2. After applying a pressure of 07 MPa and raising the temperature from 140 ° C. to 240 ° C. to cause an ester exchange reaction, triethylphosphonoacetate.
01 part was added to complete the transesterification reaction.

Thereafter, 0.101 part by weight of diantimony trioxide was added to the reaction product, and the mixture was transferred to a polymerization vessel.
The temperature was raised to 290 ° C., and the polycondensation reaction was performed in a high vacuum of 0.3 mmHg or less.

In the same manner as in Example 1, polyoxyethylene type polyether and sodium alkyl sulfonate were added to carry out polycondensation reaction to obtain polyester and fibers. The results are shown in Tables 1 and 2. The amounts of polyoxyethylene-based polyether and sodium alkylsulfonate added to the polyester were 2.5% by weight and 3% by weight, respectively.

[Comparative Example 5] In Comparative Example 4, a polyoxyalkylene glycol-based polyether was used with a molecular weight of 4000.
Polyoxyethylene glycol of 8 parts and the organic sulfonic acid metal salt are replaced with 9 parts of sodium alkyl sulfonate having 8 to 20 carbon atoms and 12 carbon atoms on average to carry out polycondensation reaction in the same manner to obtain polyester and fiber. Obtained. The results are shown in Tables 1 and 2. The amounts of polyoxyethylene-based polyether and sodium alkylsulfonate added to the polyester were 2.5% by weight and 3% by weight, respectively.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

According to the polyester for antistatic fibers of the present invention, it is possible to provide a polyester for antistatic fibers which has a good color tone (b value) and exhibits excellent antistatic properties. Further, the polyester obtained by the method of the present invention,
Even when continuously spun for a long time through the spinneret, the amount of spinneret deposits is very small and the moldability is excellent.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D01F 6/62 306 D01F 6/62 306E 306G // (C08L 67/02 C08L 71:02 71:02) F Term (reference) 4J002 CF061 CF111 CF151 CH052 EV256 FD102 GK01 4J029 AA03 AB01 AB07 AC01 AC02 AD01 AE02 BA03 CB06A HA01 HB03A JB131 JB132 JB133 JC373 JC571 JC572 JC75 JKB07K05 JK75 JK75JK02 JC753 KB05JF02 JC753 KB05JF02 JC753 KB05JF02 JC753 KB05JF02 JC753 KB05JF02 JC753 KB05JF02 JC753 KB05JF02 JC753 KB05JF05 KB02 JC753 KB05JF02 KB02 JC753 KB05JF05 KB02 JC753 KB05JF02 KB02 JC753 KB05JF05 KB02 JC073 EE14 GG02 GG03 JJ05 JJ25 KK05 KK08

Claims (6)

[Claims] 1. A polyester comprising ethylene terephthalate as a main repeating unit, wherein A) a titanium compound soluble in the polyester with respect to all dicarboxylic acid residue components is contained in an amount of 2 to 10 mmol% as a titanium metal element. A titanium compound and a phosphorus compound are represented by the following formula (1) and / or formula (2) 2 ≦ P / Ti ≦ 15 (1) 10 ≦ Ti + P ≦ 100 (mmol%) (2) (where Ti is contained in the polyester) The concentration of the titanium metal element of the titanium compound soluble in the polyester (mmole%), and P represents the concentration of the phosphorus element of the phosphorus compound contained in the polyester (mmole%). B) a polyester containing B) as an antistatic agent at any stage before the completion of the spinning process of the polyester, represented by the following formula (3): (In the above formula, Z is an organic compound residue having 1 to 6 active hydrogen, R ¹ is an alkylene group having 6 or more carbon atoms or a substituted alkylene group, R ² is a hydrogen atom, 1 to 1 carbon atoms. 40 monovalent hydrocarbon groups, 1 having 2 to 40 carbon atoms
A valent hydroxyhydrocarbon group or a monovalent acyl group having 2 to 40 carbon atoms, k is an integer of 1 to 6, and s is s ≧ 70.
An integer satisfying / k and t is an integer of 1 or more. The polyoxyalkylene polyether represented by) 0.2 to 30 wt% based on the weight of the polyester, and the following formula _{^{(4) (R 3 SO 3}} ) r M (4) ( In the formula, R ³ is an alkyl group having 3 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms which may be substituted with an alkyl group, M is an alkali metal or an alkaline earth metal, and r is an alkali metal. When the M is an alkaline earth metal, it represents 2.), based on the weight of the polyester, an organic sulfonic acid metal salt represented by
C) the following formula (5) X = N × W (5) (N and W in the above formula are each polyester 20)
Insert mg between two slides and load 10g under load 285 ℃
The number of particles having a diameter of 2.5 μm or more (particles / cm ² ) observed when the film was melted to form a thin film having a diameter of 1 cm, and the amount of the antistatic agent in the polyester composition (polyester 1
Parts by weight relative to 00 parts by weight). The dispersible X of the antistatic agent represented by) is 0.1 to 1, and D) and the polyester for antistatic fiber having an intrinsic viscosity of 0.55 or more. 2. The phosphorus compound is represented by the following formula (6): (In the above formula, R ⁴ and R ⁵ represent the same or different alkyl groups having 1 to 4 carbon atoms, and X is —CH.
_2- or -CH (Y) is shown (Y represents a benzene ring). 2. The polyester for an antistatic fiber according to claim 1, which is a phosphonate compound represented by the formula (1). 3. A titanium compound soluble in the polyester is represented by the following formula (7): (In the above formula, R ^{6 to} R ⁹ each independently have 2 to 10 carbon atoms.
Represents an alkyl group or an aryl group having 6 to 10 carbon atoms, and m represents an integer of 1 to 3. ) A compound represented by
Alternatively, a compound represented by the above formula (7) and the following formula (8): The antistatic fiber according to claim 1 or 2, which is a product obtained by reacting an aromatic polycarboxylic acid represented by the formula (n represents an integer of 2 to 4) or an acid anhydride thereof. For polyester. 4. The polyester for an antistatic fiber according to claim 1, wherein dimethyl terephthalate as a raw material starting material for ethylene terephthalate is 80 mol% or more of all dicarboxylic acid components. 5. A part of and / or the total amount of a titanium compound soluble in the polyester is added before the start of the transesterification reaction so that two kinds of catalysts, that is, a transesterification reaction catalyst and a polycondensation reaction catalyst, can be used in combination. The polyester for antistatic fiber according to any one of claims 1 to 4. 6. The transesterification reaction is 0.05 to 0.2.
The polyester for antistatic fiber according to any one of claims 1 to 5, which was carried out under a pressure of 0 MPa.