JP2003119666A - Polyester fiber and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester fiber having excellent performance to be excellent in tint, generating very little deposit to a spinneret even when carrying out a continuous spinning for a long time through the spinneret and excellent in formability and improved in clarity and provide a method for producing the same. SOLUTION: This method for producing the polyester fiber is to carry out a polycondensation reaction of polymerization starting raw materials comprising an aromatic dicarboxylic acid glycol ester and/or a low molecular polymer of the same by using the reaction product of a specific titanium compound with a specific phosphorus compound as a catalyst, add a metal-containing phosphorus compound and an alkaline earth metal compound to the polyester synthesizing system in an arbitrary stage before the polyester synthesis is finished, subsequently obtain the polyester polymer by finishing the synthesis, carry out a melt spinning of the polyester polymer to form a fiber and elute 2-40 wt.% of the fiber with the aqueous solution of an alkali compound and form micropores on the surface of the fiber.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester fiber and a method for producing the same. More specifically, using a catalyst for producing a polyester containing a specific titanium compound and phosphorus compound, the color tone is excellent, and the amount of spinneret deposits is extremely small even when continuously spun through the spinneret for a long time. The present invention relates to a polyester fiber having improved sharpness, which has an excellent performance of being excellent, and a method for producing the same.

[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.

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. However, there is a problem of moldability that a bending phenomenon (bending) of the flow of the molten polymer occurs, which causes fuzz and / or yarn breakage in the spinning and drawing steps.

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 (color b value) of polyester can be improved by adding the cobalt compound, but the addition of the cobalt compound lowers the melt heat stability of the polyester and facilitates decomposition of the polymer. There's a problem.

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 polymer 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 polyester is improved to some extent, the color tone of the obtained polymer is not sufficient,
Therefore, further improvement in polymer color tone 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 polymer is not sufficient.

Incidentally, these titanium-phosphorus-based catalysts often remain as foreign substances in the polyester polymer, and it has been desired to solve this problem.

Polyester is widely used as a synthetic fiber because of its excellent mechanical, physical and chemical properties. However, compared to natural fibers such as wool and silk, semi-synthetic fibers such as rayon and acetate, and acrylic fibers, polyester fibers do not have deep color when dyed, and thus are inferior in color development and sharpness. There is a drawback that.

Conventionally, in order to improve the dyeing sharpness of the polyester fiber, attempts have been made to improve the dye and chemically modify the polyester, and various proposals have been made.
For example, in Japanese Patent Publication No. 62-44064, a specific amount of a pentavalent phosphorus compound and a specific amount ratio of a calcium compound with respect to the phosphorus compound are added to polyethylene terephthalate to obtain a color when colored. It has been reported that a polyester having excellent depth and sharpness, sufficiently small discoloration due to friction, and excellent fibril resistance can be obtained.

Certainly, this method solves the above-mentioned problems. However, the fiber using such polyethylene terephthalate is soft due to its chemical modification, and is therefore easily affected by the foreign substance in the die. As described above, it is effective to use antimony as a catalyst to suppress foreign matter from the spinneret.However, the method without antimony reduces the color of the yarn. I couldn't.

Therefore, there is a demand for a polyester fiber which does not use antimony as a catalyst and which is excellent in color tone, color depth and vividness when colored, has a sufficiently small discoloration due to friction, and is excellent in fibril resistance. It was

[0016]

The object of the present invention is that the color tone is excellent, the amount of spinneret deposits is extremely small even when continuously spun through the spinneret for a long time, and the moldability is excellent. Another object of the present invention is to provide a polyester fiber having improved sharpness and improved sharpness, and a method for producing the same.

[0017]

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 object of the present invention comprises a step of polycondensing a polymerization starting material comprising at least one selected from alkylene glycol esters of difunctional aromatic carboxylic acids and low polymers thereof in the presence of a catalyst. The catalyst is (A) a titanium compound (1) represented by the following general formula (I):

[0019]

[Chemical 5] And a titanium compound (2) obtained by reacting the titanium compound (1) of the formula (I) with a polyvalent carboxylic acid represented by the following general formula (II) or an anhydride thereof:

[0020]

[Chemical 6] A titanium compound component of at least one selected from (B) a phosphorus compound (3) represented by the following general formula (III):

[0021]

[Chemical 7] Of the reaction product obtained by reacting with at least one phosphorus compound component, and the titanium atom equivalent amount of the catalyst is the difunctional aroma contained in the polymerization starting material. It is from 10 to 40 mmol% with respect to the total amount of the group carboxylic acid component, and further, at any stage before the completion of the synthesis of the polyester, it is 0. 5-1.8 mol% of the metal-containing phosphorus compound (4) represented by the following general formula (IV):

[0022]

[Chemical 8] And 0.25 to 3.6 mol% of an alkaline earth metal compound based on the total acid components constituting the polyester, without reacting the metal-containing phosphorus compound with the alkaline earth metal in advance. After being added to the synthesis system, the polyester polymer obtained by completing the synthesis is melt-spun to form a fiber, and 2 to 40% by weight of the fiber is eluted with an aqueous solution of an alkaline compound to form a fiber surface. This is achieved by a method for producing a polyester fiber, which is characterized by forming fine pores.

Still another object of the present invention is achieved by the fiber obtained by the method for producing a polyester fiber of the present invention.

[0024]

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

The catalyst for producing polyester of the present invention contains a reaction product of a titanium compound component (A) and a phosphorus compound component (B) described in detail below.

The titanium compound component (A) used in the catalyst of the present invention is a titanium compound (1) represented by the following general formula (I):

[0027]

[Chemical 9]

A titanium compound (2) obtained by reacting the titanium compound (1) of the general formula (I) with a polyvalent carboxylic acid represented by the following general formula (II) or an anhydride thereof:

[0029]

[Chemical 10] It consists of at least one selected from.

The phosphorus compound component (B) used in the catalyst of the present invention is a phosphorus compound (3) represented by the following general formula (III):

[0031]

[Chemical 11] Of at least one of.

In the reaction product of the titanium compound component (A) and the phosphorus compound component (B) used in the polyester-producing catalyst of the present invention, the titanium compound molar amount of the titanium compound component (A) in terms of titanium atom. The reaction molar ratio (mTi / mP) of (mTi) to the phosphorus atom conversion molar amount (mP) of the phosphorus compound component (B) is (1: 1) to
It is preferably within the range of (1: 4), and (1: 1.
More preferably, it is within the range of 5) to (1: 2.5).

The molar amount of titanium compound component (A) in terms of titanium atom means the molar amount of each titanium compound contained in the titanium compound component (A) and the number of titanium atoms contained in one molecule of the titanium compound. Is the sum of the product of
The phosphorus compound equivalent molar amount of the phosphorus compound component (B) is
It is the total value of the products of the molar amount of each phosphorus compound contained in the phosphorus compound component (B) and the number of phosphorus atoms contained in one molecule of the phosphorus compound. However, since the phosphorus compound of the formula (III) contains one phosphorus atom per molecule, the molar amount of phosphorus compound in terms of phosphorus atom is equal to the molar amount of the phosphorus compound.

The reaction molar ratio (mTi / mP) is (1: 1).
When it becomes larger, that is, the titanium compound component (A)
If the amount is too large, the color tone (b value) of the polyester obtained by using the obtained catalyst may become poor, and the heat resistance thereof may deteriorate. Further, the reaction molar ratio is
When it is less than (1: 4), that is, when the amount of the titanium compound component (A) is too small, the catalyst activity of the resulting catalyst for the polyester-forming reaction may be insufficient.

The titanium compound (1) of the general formula (I) used in the titanium compound component (A) includes titanium tetraalkoxides such as titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide and titanium tetraethoxide. Examples thereof include octaalkyl trititanate and alkyl titanates such as hexaalkyl dititanate. Among them, it is preferable to use titanium tetraalkoxide having good reactivity with the phosphorus compound component used in the present invention. It is more preferable to use titanium tetrabutoxide.

The titanium compound (2) used as the titanium compound component (A) is the titanium compound (1) of the general formula (I).
And a polycarboxylic acid of general formula (II) or an anhydride thereof. Examples of the polycarboxylic acid of general formula (II) and its anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, Cyclohexanedicarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, phthalic acid or anhydrides thereof can be preferably used, and particularly trimellitic acid anhydride and phthalic acid having good reactivity with the titanium compound (1). It is preferable to use the anhydride.

The reaction of the titanium compound (1) with the polyvalent carboxylic acid of the general formula (II) or its anhydride is carried out by mixing the polyvalent carboxylic acid or its anhydride with a solvent and partly or wholly dissolving it. Titanium compound (1)
Is added dropwise and heated to a temperature of 0 to 200 ° C. for 30 minutes or more, preferably 30 to 150 ° C. for 40 to 90 minutes. The reaction pressure at this time is not particularly limited, and normal pressure is sufficient. The solvent can be appropriately selected from those capable of dissolving a part or all of the compound of formula (II) or its anhydride, and preferably ethanol, ethylene glycol, trimethylene glycol, tetra It is selected from methylene glycol, benzene, xylene and the like.

The molar ratio of the titanium compound (1) to the compound of the formula (II) or its anhydride in this reaction can be appropriately selected, but it is obtained when the ratio of the titanium compound (1) is too large. The color tone of polyester deteriorates,
The softening point tends to decrease, and conversely, if the amount of the titanium compound (1) is too small, the polycondensation reaction tends to be difficult to proceed. Therefore, the titanium compound (1) and the compound of the formula (II) or a compound thereof The reaction molar ratio with the anhydride is (2/1) to
(2/5) is preferable. The reaction product obtained by this reaction is the above-mentioned phosphorus compound (3) as it is.
It may be subjected to a reaction with, or may be purified by recrystallizing it with acetone, methyl alcohol and / or ethyl acetate, and then reacting it with the phosphorus compound (3).

In the phosphorus compound (3) of the general formula (III) used in the phosphorus compound component (B), the C ₆ -C ₂₀ aryl group or C ₁ -C ₂₀ alkyl group represented by R ₃ is It may be substituted or may be substituted with one or more substituents, and examples of the substituents include a carboxyl group, an alkyl group, a hydroxyl group and an amino group.

The phosphorus compound (3) of the general formula (III) is
For example, monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monoheptyl phosphate, monohexyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono ( Four
-Dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4-ethylphenyl)
It is selected from phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolyl phosphate, monoxylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, monoanthryl phosphate and the like.

The catalyst preparation of the titanium compound component (A) and the phosphorus compound component (B) is carried out, for example, by mixing the component (B) consisting of at least one phosphorus compound (3) of the formula (III) with a solvent. , A part or all of the phosphorus compound component (B) is dissolved in a solvent, and the titanium compound component (A) is added to the mixed solution.
Is added dropwise, and the reaction system is heated to a temperature of 0 to 200 ° C. for 30 minutes or more, preferably 60 to 150 ° C. for 40 to 90 minutes. In this reaction, the reaction pressure is not particularly limited, and it is under pressure (0.1 to 0.5 MPa), under normal pressure, or under reduced pressure (0.
001 to 0.1 MPa), but it is usually performed under normal pressure.

Further, the formula (I
The solvent for the phosphorus compound component (B) of II) is not particularly limited as long as it can dissolve at least a part of the phosphorus compound component (B), and examples thereof include ethanol, ethylene glycol, trimethylene glycol, and tetramethylene glycol. A solvent consisting of at least one selected from benzene, benzene, xylene and the like is preferably used. In particular, it is preferable to use the same compound as the glycol component constituting the polyester to be finally obtained as a solvent.

In this catalyst preparation reaction, the mixing ratio of the titanium compound component (A) and the phosphorus compound component (B) in the reaction system is such that the titanium compound component (A) and the phosphorus compound component contained in the obtained catalyst. In the reaction product with, the molar amount of titanium compound component (A) in terms of titanium atom (mT
The reaction molar ratio (mTi / mP) of i) to the phosphorus atom-equivalent molar amount (mP) of the phosphorus compound component (B) is (1:
It is set so as to fall within the range of 1) to (1: 4). A preferable reaction molar ratio (mTi / mP) is (1: 1) to (1 :).
3).

The reaction product of the titanium compound component (A) and the phosphorus compound component (B) is separated from the reaction system by means such as centrifugal sedimentation or filtration, or without separation. It may be used as it is as a catalyst for polyester production. Alternatively, the separated reaction product is recrystallized with a recrystallization agent such as acetone, methyl alcohol and / or water and purified, and then the purified product is used as a catalyst. You may use as.

In the polyester production method of the present invention,
A polymerization starting material composed of an alkylene glycol ester of a bifunctional aromatic carboxylic acid and at least one selected from its low polymers (oligomers) is polycondensed in the presence of the catalyst. At this time, the titanium atom conversion amount of the catalyst is set to 10 to 40 mmol% with respect to the total amount of the bifunctional aromatic carboxylic acid component contained in the polymerization starting material. The amount of this catalyst is preferably 10 to 25 mmol%. When the amount of the catalyst is less than 10 mmol%, the effect of accelerating the catalyst for the polycondensation reaction of the polymerization starting material becomes insufficient, the polyester production efficiency becomes insufficient, and a polyester having a desired degree of polymerization is obtained. I can't. On the other hand, when the amount of the catalyst exceeds 40 mmol%, the color tone (b value) of the obtained polyester becomes insufficient and becomes yellowish, and the practicality thereof deteriorates.

In the alkylene glycol ester of a bifunctional aromatic carboxylic acid used as a polymerization starting material used in the method for producing a polyester of the present invention, the bifunctional aromatic carboxylic acid is terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid. , Diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, and β-hydroxyethoxybenzoic acid, and terephthalic acid and naphthalenedicarboxylic acid are particularly preferably used. The alkylene glycol is preferably selected from ethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, and hexamethylene glycol.

The above alkylene glycol ester of difunctional aromatic carboxylic acid and / or its low polymer may be produced by any method.
Usually, it is produced by heating a difunctional aromatic carboxylic acid or its ester-forming derivative with an alkylene glycol or its ester-forming derivative.

For example, the ethylene glycol ester of terephthalic acid, which is a raw material of polyethylene terephthalate, and / or its low polymer will be explained. Either terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of terephthalic acid and ethylene glycol are used. Generally, a method of transesterifying and with or an addition reaction of ethylene oxide with terephthalic acid is adopted.

The alkylene glycol ester of the above-mentioned difunctional aromatic carboxylic acid and / or its low polymer is, to the extent that the effect of the method of the present invention is not substantially impaired, specifically, an acid component. 1 based on total molar amount
Other difunctional carboxylic acid ester copolymerizable therewith may be contained as an additional component in an amount of 0 mol% or less, preferably 5 mol% or less.

Copolymerizable additional components preferably used are acid components such as adipic acid, sebacic acid,
Aliphatic and cycloaliphatic difunctional dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and hydroxycarboxylic acids such as β-hydroxyethoxybenzoic acid, p
-One or more such as oxybenzoic acid and a glycol component, for example, an alkylene glycol having 2 or more constituent carbon atoms, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A, bisphenol S.
Can be selected from esters with one or more of aliphatic, alicyclic and aromatic diol compounds and polyoxyalkylene glycols or their anhydrides. 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.

In the polyester production method of the present invention,
The catalyst may be added to the polymerization starting material at any stage before the polycondensation reaction of the bifunctional aromatic carboxylic acid alkylene glycol ester and / or its low polymer is started. As the method, any conventionally known method can be adopted, for example, after the preparation of the bifunctional aromatic carboxylic acid ester, a solution or slurry of the catalyst is added to the reaction system to start the polycondensation reaction. Alternatively, the catalyst solution or the slurry may be added to the reaction system before the preparation of the difunctional aromatic carboxylic acid ester, simultaneously with the starting materials, or after the preparation thereof.

There are no particular restrictions on the reaction conditions for polyester production in the process of the present invention, but the polycondensation reaction is generally 23.
It is preferable to carry out polycondensation at a temperature of 0 to 320 ° C. under normal pressure or under reduced pressure (0.1 Pa to 0.1 MPa) or by combining these conditions for 15 to 300 minutes.

In the method of the present invention, if necessary, a stabilizer such as trimethyl phosphate may be added to the reaction system at any stage in the production of polyester, and further, an antioxidant, an ultraviolet absorber, a flame retardant, an optical brightening agent may be added. Agent, matting agent,
You may mix | blend a toning agent, a defoaming agent, and other additives.

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.

In the production method of the present invention, it is further necessary to add a metal-containing phosphorus compound represented by the following general formula (IV).

[0059]

[Chemical 12]

[0060] Here, in the formula, but R ₄ and R ₄ 'is a monovalent organic group, specifically an alkyl group, an aryl group, an aralkyl group or _{- [(CH 2) l O} ] k R ₅ (However, R ₅ is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,
1 is preferably an integer of 2 to 10 and k is an integer of 1 to 5), and M is Li, Na, K, Mg, Ca,
Sr and Ba are preferable, and Ca, Sr and B are particularly preferable.
It is preferable to use a.

In place of the metal-containing phosphorus compound of the above general formula (IV), R ₄ and / or R ₄ 'is a metal (particularly an alkali metal,
When a phosphorus compound substituted with an alkaline earth metal) is used, the resulting fine pores in the polyester fiber become too large, and the intended sharpening effect cannot be obtained.
Further, it also becomes inferior in fibril resistance.

In order to produce the compound, it can be easily obtained by reacting the corresponding orthophosphoric acid ester (mono, di or tri) with a predetermined amount of the corresponding metal compound by heating in the presence of a solvent. You can Further, in the production method of the present invention, it is necessary to use an alkaline earth metal compound together with the metal-containing phosphorus compound, and the alkaline earth metal compound is insoluble in polyester by reacting with the metal-containing phosphorus compound. Any salt may be used as long as it can form a salt.

Examples of the alkaline earth metal compound include organic carboxylates such as acetates, oxalates, benzoates, phthalates and stearates of alkaline earth metals, sulfates, silicates, Inorganic salts such as carbonates and bicarbonates,
Examples thereof include halides such as chlorides, chelate compounds such as ethylenediaminetetraacetic acid complex salts, alkoxides such as hydroxides, oxides, methoxides, ethoxides, phenoxides and glycoloxides, and among others, trimethylene glycol. It is preferable to use an organic carboxylic acid salt, a halide, a chelate compound, or an alkoxide that is soluble in water, and an organic carboxylic acid salt is particularly preferable. The alkaline earth metal salts may be used alone or in combination of two or more.

When the above-mentioned metal-containing phosphorus compound and an alkaline earth metal compound are used in combination, when the polyester fiber thus obtained is alkali-reduced, it is contained in order to provide excellent color depth and its friction durability. The amount of the metal phosphorus compound used and the ratio of the amount of the alkaline earth metal compound used with respect to the amount of the phosphorus compound used need to be set as in the production method of the present invention.

That is, if the addition amount of the phosphorus-containing compound used in the present invention is too small, the color depth of the fiber after the alkali reduction treatment becomes insufficient. Although the color depth increases as the amount is increased, when the amount is too large, the color depth does not show a significant improvement anymore, and on the contrary, the abrasion resistance is deteriorated, and further, the polymerization degree and the softening point are increased. It becomes difficult to obtain a polyester polymer having the above-mentioned property, and a problem of frequent yarn breakage during spinning occurs. Therefore, the amount of the metal-containing phosphorus compound added is 0.5 to 1.8 mol% based on the acid component constituting the polyester.
In the range of 0.6 to 1.7 mol%.

The amount of the alkaline earth metal compound added is
0.25 based on the total acid components that make up the polyester
When the amount is less than mol%, the depth of color of the obtained polyester fiber is insufficient, and the polycondensation rate decreases, and it becomes difficult to obtain a polyester having a high degree of polymerization,
In addition, the softening point of the produced polyester is significantly lowered. If it exceeds 3.6 mol% based on the total acid components constituting the polyester, coarse particles are formed inside the polymer, and the depth of color is not improved, but the visual density is rather lowered. Therefore, the amount of the alkaline earth metal compound added needs to be in the range of 0.25 to 3.6 mol% based on the total acid components constituting the polyester, and preferably 0.35 to 2.2 mol. %, Particularly preferably 0.4 to 1.8 mol%.

Here, when the alkaline earth metal is added, it is necessary to add it to the polyester synthesis system without previously reacting with the metal-containing phosphorus compound. By forming a salt insoluble in the polyester in the synthetic system, the inert particles can be dispersed in the polyester in a uniform ultrafine particle state.

The addition of the metal-containing phosphorus compound and the alkaline earth metal compound can be carried out in any order at any stage until the synthesis of the polyester is completed. However, if only the metal-containing phosphorus compound is added in the stage before the completion of the reaction in the first stage, the completion of the reaction in the first stage may be hindered, and only the alkaline earth metal compound in the first stage may be added. If added before the end of the reaction, coarse particles are likely to be generated during the reaction when the first-step reaction is an esterification reaction, and the transesterification reaction rate is abnormal when a transesterification reaction is performed. When the addition timing of these is selected, it is preferable to keep the content of the compound to be added to about 20% by weight or less based on the total weight of the compound to be added.

Further, when the metal-containing phosphorus compound and the alkaline earth metal compound are added at a stage where the reaction in the second stage has proceeded too much, aggregation and coarsening of particles are likely to occur and the color of the polyester fiber finally obtained. Since there is a tendency for the depth of the reaction mixture to become insufficient, it is preferable to add it before the intrinsic viscosity of the reaction mixture in the second step reaction reaches 0.3.

The metal-containing phosphorus compound and the alkaline earth metal compound may be added at one time, divided into two or more times, or continuously added.

In the present invention, any catalyst can be used in the first-step reaction, but among the above alkaline earth metal compounds, a catalyst for the first-step reaction, particularly a transesterification reaction, can be used. Those having a function are included, and when using the compound, it is not necessary to use a catalyst separately, and the alkaline earth metal compound is added before or during the reaction in the first step, Although it can be used as a catalyst, it may cause a bumping phenomenon as described above. Therefore, the amount used is preferably 20% by weight or less based on the total weight of the alkaline earth metal compound to be added. .

As described above, by adding a specific amount of the above metal-containing phosphorus compound and the alkaline earth metal compound to the polyester reaction system without reacting them in advance and then completing the synthesis of the polyester, a high degree of polymerization is obtained. It is possible to obtain a polyester having a high softening point and a good threading process passing property, and finally capable of giving a fiber having both excellent color depth and excellent friction durability.

In order to melt-spin the polyester thus obtained into a fiber, it is not necessary to employ a special method, and a usual polyester fiber melt-spinning method can be arbitrarily adopted. The fiber to be discharged may be a solid fiber having no hollow portion or a hollow fiber having a hollow portion. Further, the cross-sectional shape of the fiber to be spun and the shape of the hollow portion may be circular or irregular.

Further, in spinning, a core-sheath type, a side-by-side type, and a multi-layer laminated type composite are prepared by using the polyester containing the above-mentioned metal-containing phosphorus compound and the alkaline earth metal compound and the polyester not containing it. It may be fiber.

From the polyester fiber thus obtained,
It can be easily carried out by removing the part thereof by subjecting it to a stretching heat treatment or false twisting as necessary, or after making it into a cloth, and then subjecting it to alkali weight reduction treatment using an aqueous solution of an alkali compound. . Here, as the alkali compound used, sodium hydroxide, potassium hydroxide,
Examples thereof include tetraethylammonium hydroxide, sodium carbonate, potassium carbonate, etc. Among them, sodium hydroxide and potassium hydroxide are particularly preferable.

Although the concentration of the aqueous solution of the alkali compound varies depending on the kind of the alkali compound employed, the treatment conditions, etc., it is usually preferably in the range of 0.01 to 40% by weight, particularly 0.1 to 30%. It is preferably in the range of wt%.

Further, the alkali weight reduction treatment temperature is from room temperature to
It may be set to about 100 ° C., and the processing time is 1 minute to 4 minutes.
It is usually done within a time range. Further, the amount of the alkaline compound eluted and removed by the treatment of the aqueous solution should be in the range of 2 to 40% by weight based on the weight of the fiber.

By carrying out the alkali weight reduction treatment under the above-mentioned conditions, they are arranged in parallel with the fiber axis direction, and the maximum value of the frequency distribution is 0.1 to 0.3 in the width in the direction perpendicular to the fiber axis.
It is possible to form a large number of micropores having a size in the range of 0.1 to 5 μm in the axial direction of the fiber in the range of 0.1 to 5 μ, and it is possible to form an excellent color when dyed. Comes to exhibit the depth of.

[0079]

EXAMPLES 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.

The intrinsic viscosity, the hue, the titanium content, the number of foreign substances, the thermal stability of fusion and the layer of deposits generated on the spinneret were determined by the methods described below.

(1) Intrinsic viscosity: The intrinsic viscosity of the polyester polymer is 3 for the orthochlorophenol solution.
It was determined from the viscosity value measured at 5 ° C.

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

(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) Depth of color: As a scale showing the depth of color, the depth of chromaticity (K / S) was used. This value was measured by measuring the spectral reflectance (R) of the sample cloth with a Shimadzu RC-330 type spectrophotometer, and the following Kubelka (Kubelka)
Munk) formula. The larger this value, the greater the bathochromic effect.

[0086]

## EQU1 ## K / S = (1−R) ² / 2R where K is the absorption coefficient and S is the scattering coefficient.

(6) Friction and discoloration resistance: Using a Gakushin type flat friction machine for friction fastness test, a georgette made of 100% polyethylene terephthalate was used as a friction cloth, and the test cloth was subjected to a load of 500 g. The surface was rubbed a predetermined number of times, and the degree of occurrence of discoloration was judged by a gray scale for discoloration. The case where the abrasion resistance was extremely low was classified as the first grade, and the case where the abrasion resistance was extremely high was classified as the fifth grade. Practical level 4 or higher is required.

(7) Elastic modulus, elastic recovery rate, strength: Tensile tester (“Autograph AG
-100E "(manufactured by Shimadzu Corporation). Elastic modulus is 25 ° C., test length is 25 cm, pulling speed is 20 c
It was determined from the initial slope of the load elongation curve obtained from m / min. The strength was determined by the same method as the strength per 1 dtex when the yarn breaks. Further, the elastic recovery rate was obtained from the yarn length when the elongation rate was extended to 20% by the above method, allowed to stand for 1 minute, and then returned to the original length at the same speed again.

[Example 1] Preparation of catalyst (A): 0.8 parts of trimellitic anhydride was dissolved in 2.5 parts of ethylene glycol, and then 0.7 parts of titanium tetrabutoxide (based on trimellitic anhydride was set to 0). ．
5 mol%) was added dropwise, and the mixture was kept at 80 ° C. in the air under atmospheric pressure for reaction aging for 60 minutes. After that, the mixture was cooled to room temperature, 15 parts of acetone was added, and the precipitate was collected. Filter with 5 filter paper, 10
It was dried at 0 ° C. for 2 hours. The titanium content was 11.5% by weight.

Further, 3.5 parts of mono-n-butyl phosphate was dissolved in 131 parts of ethylene glycol at 120 ° C. for 10 minutes. After adding 40 parts of ethylene glycol to 134.5 parts of this ethylene glycol solution, 5.0 parts of the titanium compound was dissolved and stirred at 120 ° C. for 60 minutes to obtain a white slurry of the catalyst (A) containing the reaction product. Got The titanium content of this catalyst (A) slurry was 0.3%.

Production of polyester: terephthalic acid 166
Parts by weight and 75 parts by weight of ethylene glycol were subjected to an esterification reaction at 240 ° C., and with respect to the obtained reaction product, 0.97 parts of trimethyl phosphate (0.693 mol% based on the total acid components) 0.60 parts of calcium acetate monohydrate (1/2 mole based on trimethyl phosphate)
And 16.49 parts of ethylene glycol were reacted at a temperature of 120 ° C. under a total reflux for 60 minutes to obtain 18.06 parts of a clear solution of a calcium phosphate salt, and 1.22 parts of calcium acetate at room temperature. 19.28 parts of a mixed transparent solution of calcium phosphate diester calcium salt obtained by dissolving hydrous salt (1.0 moles with respect to trimethyl phosphate) and calcium acetate was added, and the above catalyst was used as a polycondensation catalyst. (A) 0.95 part by weight of slurry (20 mmol% in terms of titanium atomic weight based on the amount of terephthalic acid) and 0.0002 part by weight of terazol blue as a color-matching agent were added, and the resulting reaction system was heated at a temperature of 285 ° C. , At atmospheric pressure for 30 minutes, and at the above temperature, 4.0 kPa (30 m
After heating for 15 minutes under reduced pressure (mHg) to allow the reaction to proceed, the pressure in the reaction system was gradually reduced and the reaction was completed by heating for 110 minutes while stirring at the above temperature. The final internal temperature at this time was 285 ° C, and the final internal pressure was 49.3 Pa.
(0.37 mmHg), and the intrinsic viscosity of the obtained polyethylene terephthalate was 0.640. The physical properties of this chip are summarized in Table 1.

This chip was dried by a conventional method to give a pore size of 0.
Melt-spinning was performed at 270 ° C. using a spinneret in which 36 circular spinning holes of 3 mm were formed, and then stretched at a draw ratio of 3.5 times in accordance with a conventional method to obtain a raw yarn of 82.5 dtex and 36 filaments. .

This original yarn was subjected to strong twist of S twist 2500 T / m and Z twist 2500 T / m, and then the strong twist yarn was heated at 80 ° C.
Was subjected to steam heat treatment for 30 minutes to prevent twisting.

The twist-defining strong-twisted yarn has a warp density of 47 yarns / cm,
A satin georgette fabric was woven by alternately arranging two S and Z twists with a weft density of 32 strands / cm.

The obtained green machine was subjected to reflux treatment with a rotary washer at a boiling temperature for 20 minutes to form a grain, preset by a conventional method, and then treated with a 3.5% sodium hydroxide aqueous solution at a boiling temperature, Weight loss rate is 10%. Two
Fabrics of 0% and 30% were obtained.

These alkali-treated fabrics were treated with Dian.
ix Black HG-FS (Mitsubishi Chemical Industries, Ltd. product) 15% owf, after dyeing at 130 ° C. for 60 minutes, sodium hydroxide 1 g / L and hydrosulfite 1 g / L
Was reduced and washed at 70 ° C. for 20 minutes in an aqueous solution containing to obtain a black-dyed cloth. Table 1 shows the depth of color of these black cloths and the resistance to discoloration after abrasion 200 times.

[Example 2] Production of polyester: 194 parts by weight of dimethyl terephthalate, 124 parts by weight of ethylene glycol and 0.12 part by weight of calcium acetate were charged into a reaction tank equipped with a rectification column, and 220
After the transesterification reaction was carried out at ℃ and the theoretical amount of methanol produced was distilled off, 0.97 parts of trimethyl phosphate (0.693 mol based on the total acid component) was added to the obtained reaction product. %) And 0.60 part of calcium acetate monohydrate (1/2 mol based on trimethyl phosphate) in 16.49 parts of ethylene glycol.
18.06 parts of a clear solution of a calcium phosphate phosphate salt obtained by reacting for 60 minutes under a total reflux at a temperature of ℃ was added to 1.10 parts of calcium acetate monohydrate (1.0 to trimethyl phosphate at room temperature). 19.16 parts of a mixed transparent solution of a phosphoric acid diester calcium salt and calcium acetate obtained by dissolving (a double mole) was added, and a polycondensation catalyst (A) obtained by the same method as in Example 1 (A) was further added. ) 3.2 parts by weight of slurry (content of titanium compound (2) is 20 mmol% in terms of titanium atomic weight based on the amount of dimethyl terephthalate), and 0.0002 parts by weight of terazol blue as a color adjusting agent are added. .

This reaction system was heated at a temperature of 285 ° C. and normal pressure for 30 minutes and further heated to 4.0 kPa (30 mm) at the above temperature.
Hg) was heated under reduced pressure for 15 minutes to allow the reaction to proceed,
The pressure in the reaction system was gradually reduced and the mixture was stirred at the above temperature for 1
The reaction was completed by heating for 10 minutes. Final temperature in the flask is 285 ° C, final internal pressure is 49.3 Pa (0.37 m
mHg). The intrinsic viscosity of the obtained polyethylene terephthalate was 0.640. The test results of this polymer are shown in Table 1. In addition, dyeing and weaving dyeing is performed in Example 1.
I went the same way. The results are shown in Table 1.

[Comparative Example 1] The same as Example 1 except that only titanium tetrabutoxide was used as the polycondensation catalyst, and the addition amount was 20 mmol% in terms of titanium atomic weight based on the amount of terephthalic acid. Went to. The results are shown in Table 1.

Comparative Example 2 Preparation of catalyst (B): 0.8 parts by weight of trimellitic anhydride was dissolved in ethylene glycol, 0.7 parts by weight of titanium tetrabutoxide was added dropwise to this solution, and the resulting reaction was obtained. The system was kept in air at a temperature of 80 ° C. under atmospheric pressure for 60 minutes to react titanium tetrabutoxide with trimellitic anhydride, followed by aging. After aging the reaction, cool the reaction system to room temperature,
To this, 15 parts by weight of acetone was added, and the generated precipitate was collected by filtration. The titanium content of the catalyst (B) thus obtained was 11.4% by weight.

Production of polyester: As a polycondensation catalyst,
Example 1 was repeated except that the above catalyst (B) was used. At this time, the addition amount of the catalyst (B) was 20 mmol% in terms of titanium atomic weight based on the amount of terephthalic acid.
The results are shown in Table 1.

Comparative Example 3 The procedure of Example 1 was repeated, except that diantimony trioxide was used as the polycondensation catalyst.
Based on the amount of terephthalic acid, the concentration of the catalyst and the amount of addition of the catalyst were adjusted so as to be 25 mmol% in terms of antimony atomic weight. The results are shown in Table 1.

[0103]

[Table 1]

[0104]

EFFECTS OF THE INVENTION According to the catalyst of the present invention and the method for producing polyester fiber using the same, the color tone is excellent, and the amount of spinneret deposits is extremely small even when continuously spun through the spinneret for a long time. It is possible to provide a polyester fiber having an improved sharpness and an excellent production property and a method for producing the same.

Continued front page    F-term (reference) 4J029 AA03 AA05 AB04 AC01 AE02                       BA02 BA03 BA04 BA05 BA10                       CB05A CB06A CB10A CC05A                       CF08 CF15 CH02 DB13 EB06A                       HA01 HB01 JA063 JA093                       JA123 JA253 JA283 JB131                       JB133 JB171 JB173 JB203                       JC573 JC583 JF023 JF033                       JF043 JF133 JF143 JF153                       JF163 JF321 KB04 KB05                       KD01 KE06                 4L031 AA18 BA11 CA01 DA00 DA09                       DA11                 4L035 AA10 BB31 BB91 CC20 DD07                       EE08 EE20 FF10 GG02

Claims (11)

[Claims] 1. A step of polycondensing a polymerization starting material comprising at least one selected from alkylene glycol esters of difunctional aromatic carboxylic acids and low polymers thereof in the presence of a catalyst, wherein the catalyst comprises: (A) Titanium compound (1) represented by the following general formula (I): And a titanium compound (2) obtained by reacting the titanium compound (1) of the formula (I) with a polyvalent carboxylic acid represented by the following general formula (II) or an anhydride thereof: A titanium compound component comprising at least one selected from the group (B) and a phosphorus compound (3) represented by the following general formula (III): Of the reaction product obtained by reacting with a phosphorus compound component consisting of at least one of the above, and the titanium atom conversion amount of the catalyst is the difunctional aroma contained in the polymerization starting material. It is from 10 to 40 mmol% with respect to the total amount of the group carboxylic acid component, and further, at any stage before the completion of the synthesis of the polyester, it is 0. 5-1.8 mol% of the metal-containing phosphorus compound (4) represented by the following general formula (IV): And 0.25 to 3.6 mol% of an alkaline earth metal compound based on the total acid components constituting the polyester, without reacting the metal-containing phosphorus compound with the alkaline earth metal in advance. After being added to the synthesis system, the polyester polymer obtained by completing the synthesis is melt-spun to form a fiber, and 2 to 40% by weight of the fiber is eluted with an aqueous solution of an alkaline compound to form a fiber surface. A method for producing a polyester fiber, which comprises forming fine pores. 2. A reaction product of the titanium compound component and the phosphorus compound, wherein the titanium atom-equivalent molar amount (mTi) of the titanium compound component is relative to the phosphorus atom-equivalent molar amount (mP) of the phosphorus compound component. Reaction molar ratio mT
The method for producing polyester fiber according to claim 1, wherein a catalyst for producing polyester having an i / mP in the range of (1: 1) to (1: 4) is used. 3. The titanium compound (1) of the formula (I) is
The method for producing a polyester fiber according to claim 1, wherein a catalyst for producing a polyester selected from titanium tetraalkoxides, octaalkyl trititanates, and hexaalkyl dititanates is used. 4. The polyester fiber according to claim 1, wherein the polyvalent carboxylic acid of the formula (II) or its anhydride uses a catalyst for polyester production selected from trimellitic acid, phthalic acid or their anhydrides. Production method. 5. The reaction molar ratio (2: 1) of the titanium compound (2) between the titanium compound (1) of the formula (I) and the polyvalent carboxylic acid of the formula (II) or an anhydride thereof. ~
The method for producing a polyester fiber according to claim 1, wherein a catalyst for producing a polyester which is a reaction product in (2: 5) is used. 6. The phosphorus compound (3) of the formula (III)
Is a mono-n-butyl phosphate and / or monododecyl phosphate, The manufacturing method of the polyester fiber of Claim 1 which used the catalyst for polyester production. 7. The production of polyester fiber according to claim 1, wherein a reaction product of the titanium compound component and the phosphorus compound component is a polyester production catalyst produced at a reaction temperature of 0 to 200 ° C. Method. 8. The difunctional aromatic carboxylic acid is terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, and β- The method for producing a polyester fiber according to claim 1, which is selected from hydroxyethoxybenzoic acid. 9. The method for producing a polyester fiber according to claim 1, wherein the alkylene glycol is selected from ethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, and hexamethylene glycol. 10. The polycondensation reaction is 230 to 320 ° C.
The method for producing a polyester fiber according to claim 1, which is performed at the temperature of. 11. A polyester fiber produced by the method according to any one of claims 1 to 10.