JPS6335825A - Soil release polyester fiber and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled fibers for underwear, etc., without blackening even in high washing frequency, by melt spinning a modified polymer obtained by partially copolymerizing ends of polyester such as ethylene terephthalate, etc., with a polyoxyalkyleneglycol component at a high take-off speed. CONSTITUTION:A modified polyester obtained by partially copolymerizing ends of a polyester containing ethylene terphthalate as a chief constituent unit with 0.5-10wt% polyoxyalkyleneglycol component expressed by formula I (R<1> is monovalent organic group having no active hydrogen; R<2> is alkylene; n is an integer of 20-140) is melt spun at >=4,500m/min take-off speed to provide the aimed fibers having a crystal size [(100)A] (A) at (100) face satisfying formula II (DELTAn is birefringence of product fibers) and formula III, <=100% elongation and >=3g/de strength.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to stain-resistant polyester fibers, and more particularly to stain-resistant polyester fibers with improved restaining properties, particularly during washing.

[Prior art]

Traditionally, polyester fibers have been used in many fields because they have many excellent properties such as good dimensional stability, strength, and resistance to wrinkles. However, polyester fibers have such excellent properties. However, due to the hydrophobic nature of polyester, oily stains are more likely to adhere to polyester than hydrophilic fibers such as cotton, which are difficult to remove, and stains are likely to re-deposit during washing.

This re-staining property has been developed since polyester fibers were put into practical use.
This is a problem that has always been raised and many methods have been proposed to solve this problem.

For example, a method of immersing a polyester molded product in a solution or dispersion of a copolymer of polyoxyethylene glycol and a polyester resin (see Japanese Patent Publication No. 1983-2512), hydrophilic properties such as dimethacrylate of polyoxyethylene glycol, etc. A method of steam-treating a vinyl compound after padding or spraying (see Japanese Patent Publication No. 51-2559) or a method of low-temperature plasma treatment of a gas containing oxygen ('Poly++er' August 1978 issue 904-91)
Page 2) etc. are known.

However, all of these methods have been proposed as finishing treatments for polyester fiber products;
There are problems with processing, such as complicated operations, the need for special equipment, and poor reproducibility of processing.Furthermore, clothes that are washed frequently, such as underwear and white coats, tend to deteriorate as the number of times they are washed increases. There is a problem that the effect of
There has been a strong desire for polyester fibers that retain stain resistance even after repeated washing (no darkening due to washing).

On the other hand, it is known that polyoxyethylene glycol is copolymerized for dyeing polyester fibers. Therefore, we attempted to copolymerize polyoxyethylene glycol into polyester fibers to make the polymer itself hydrophilic and prevent it from staining with oil.We found that in order to obtain a sufficient level of stain resistance, the amount of copolymerization should be reduced to 0. It has been found that the amount needs to be greater than 20% by weight, preferably 20% by weight or more. However, when such a large amount of polyoxyethylene glycol is copolymerized, the mechanical properties of the resulting fiber are impaired, the shrinkage rate increases, and the light fastness deteriorates, making it difficult to use in practical applications, especially for linen supplies. It could not be used for cotton blends. Further, in order to maintain light fastness, the copolymerization amount of polyoxyethylene glycol was set to 10% by weight or less, particularly 5% by weight or less, but sufficient antifouling properties could not be obtained.

[Purpose of the invention]

The present inventor aims to provide a polyester fiber that is particularly resistant to darkening caused by washing, and has excellent durability and antifouling properties.

[Structure of the invention]

In order to achieve the above object, the present inventors conducted extensive studies and found that excellent antifouling properties can be achieved by controlling the distribution of hydrophilic groups within the fibers.

In other words, as a result of intensive studies on the copolymerization method of polyoxyethylene glycol, which is a hydrophilic polymer, a specially selected structure consisting of a modified polyester in which one end-blocked polyoxyethylene glycol was copolymerized at the end of the main chain was developed. Perhaps because polyoxyethylene glycol copolymerized at the ends of the main chain acts specifically, polyester fibers with It has been found that this fiber exhibits significantly improved stain resistance and washing durability compared to fibers made of polyester in which blocked polyoxyethylene glycol or polyoxyethylene glycol insoluble in polyester is mixed into polyester. The present invention was completed as a result of further studies based on this knowledge.

In the present invention, a polyester having ethylene terephthalate as a main constituent unit has a terminal portion (and a part thereof) of the following general formula % (wherein R1 is a monovalent organic group having no active hydrogen, R2
is an alkylene group, n is an integer from 20 to 140).
A fiber made of modified polyester copolymerized with 10% by weight, the crystal size in the (100) plane ((100'')
A) (person) is the following formula (1) and (2) (100)A
≧(1,7xlO3) xΔn -110-<11(1
00) A≧50 ・−(2
) (where Δn is the birefringence index of the product fiber),
The present invention relates to stain-resistant polyester fibers having an elongation of 100% or less and a strength of 3 g/de or more.

In addition, the present invention provides at least a portion of the terminal end of a polyester having ethylene terephthalate as a main constituent unit, with the following general formula % formula % (wherein R1 is a monovalent organic group having no active hydrogen, R2
is an alkylene group, n is an integer of 20 to 140).
4500rn of 10% by weight copolymerized modified polyester
This invention relates to a method for producing stain-resistant polyester fibers, which is characterized by melt spinning at a preparative take-up speed.

The polyester referred to in the present invention refers to a polyester containing terephthalic acid as the main acid component and ethylene glycol as the main glycol component.

In such a polyester, a portion of its acid component terephthalic acid may be replaced with another difunctional carboxylic acid.

Examples of such other carboxylic acids include difunctional carboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-oxyethoxybenzoic acid, and p-oxybenzoic acid. Examples thereof include aromatic carboxylic acids, difunctional aliphatic carboxylic acids such as sebacic acid, adipic acid, and oxalic acid, and difunctional alicyclic carboxylic acids such as 1,4-cyclohexanedicarboxylic acid.

Further, a part of the ethylene glycol component may be replaced with other glycol components, such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc., and other diol compounds such as Examples include aliphatic, alicyclic, and aromatic diol compounds such as cyclohexane-1,4-dimetatool, neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyalkylene glycols with both ends unblocked.

Such polyesters can be produced by any method. For example, regarding polyethylene terephthalate, terephthalic acid and ethylene glycol may be directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol may be transesterified, or terephthalic acid and ethylene glycol may be transesterified. The first stage reaction is to produce a glycol ester of terephthalic acid and/or its low polymer by reacting with oxide, and then the product is heated under reduced pressure to undergo polycondensation reaction until the desired degree of polymerization is achieved. It is easily produced by the second stage reaction.

In the present invention, it is necessary that at least one end of the polymer chain of the polyester is copolymerized with a polyoxyalkylene glycol having one end blocked and represented by the following general formula %.

In this formula, R1 is a monovalent organic group having no active hydrogen, and is preferably a hydrocarbon group, especially an alkyl group,
Cycloalkyl, aryl or alkylaryl groups are preferred. R2 is an alkylene group, usually having 2 carbon atoms.
-4 alkylene groups are preferred, and specific examples include ethylene, propylene, and tetramethylene groups. It may also be a mixture of two or more types, for example a copolymer having an ethylene group and a propylene group. Further, n indicates an average degree of polymerization, and is in the range of 20 to 140. When attempting to copolymerize polyoxyalkylene glycol with n less than 20, a high copolymerization rate is required to obtain sufficient antifouling properties, and in such cases, the terminals of the polyester are blocked. It is not possible to sufficiently increase the degree of polymerization of the polyester itself, and as a result, the mechanical properties of the resulting fibers cannot be ensured. On the other hand, if n is larger than 140, the reaction between polyoxyalkylene glycol and polyester will not proceed sufficiently, resulting in the same result as if polyoxyalkylene glycol was mixed with polyester, and high antifouling properties would not be obtained. do not have. In particular, the preferred average degree of polymerization is 30 to 80.
It exists in a limited area.

Preferred specific examples of such single end-capped polyoxyalkylene glycols include polyoxyethylene glycol 7-methyl ether, polyoxyethylene glycol monophenyl ether, polyoxyethylene glycol monooctylphenyl ether, polyoxyethylene glycol monononylphenyl ether, Oxyethylene glycol monocetyl ether, polyoxypropylene glycol monophenyl ether, polyoxy, 7
°Propylene glycol monononylphenyl ether,
Examples include polyoxytetramethylene glycol monomethyl ether, monomethyl ether of polyoxyethylene glycol/polyoxypropylene glycol copolymer, and ester-forming derivatives thereof.

In order to copolymerize the single end-blocked polyoxyalkylene glycol at the end of the polyester chain, it is possible to copolymerize the polyoxyalkylene glycol at the end of the polyester chain at any stage before the synthesis of the polyester described above is completed, such as at the first stage.
It may be added at any stage, such as before the start of a stage reaction, during the reaction, after the end of the reaction, or during the second stage reaction, and the production reaction may be completed after the addition.

In this case, if the amount used is too small, the antifouling performance and washing durability of the final polyester resin will be insufficient, and on the other hand, if it is too large, the degree of polymerization of the polyester will be too low during the polycondensation reaction process. Since the level reaches a plateau, the yarn physical properties such as strength of the polyester fiber finally obtained deteriorate. In addition, if a large amount of polyoxyalkylene glycol is contained, the light resistance of the obtained fiber will deteriorate, so it is preferable to keep the amount of copolymerization as small as possible. The amount of glycol copolymerized is 0 relative to polyester.
．． It should be in the range of 5-10% by weight, especially 2-10% by weight.
A range of 5% by weight is preferred.

As described above, in the present invention, since the amount of copolymerization of polyoxyalkylene glycol can be suppressed to a small amount, the obtained fiber can also maintain sufficient light resistance.

In addition, stabilizers, matting agents, antioxidants, etc. are added as necessary! i
A fuel agent, an antistatic agent, a fluorescent whitening agent, a catalyst, an anti-coloring agent, a heat resistant agent, a coloring agent, an inorganic particle, etc. may be used in combination. °Especially,
When polyoxyalkylene glycol is left at high temperatures such as under melt-spinning conditions, it is easily oxidized and causes problems such as a decrease in the degree of polymerization and coloring. Often preferred. Furthermore, if an ionic antistatic agent is used in combination with the modified polyester of the present invention, fibers with excellent antistatic properties can be obtained, further expanding the field of use thereof.

The degree of polymerization of the modified polyester obtained in this way is
In order to exhibit sufficient fiber properties, the intrinsic viscosity is preferably 0.58 or more, particularly preferably 0.6 or more. Such modified polyester is made into fibers by a melt spinning method. Here, even if the fiber to be spun is a solid fiber without a hollow part,
It may be a hollow fiber having a hollow part. Further, the outer shape and the shape of the hollow portion in the cross section of the fiber to be spun may be circular or irregular.

During melt spinning, in order to obtain the fiber structure specified in the present invention, it is preferable to set the take-up speed, that is, the spinning speed, to a high speed of 4500 m/min or higher.

By spinning at a semi-constantly high speed of 45 QOm/min or more, large deformation stress acts during the spinning process, causing dislocation crystallization of the polymer during spinning.

As a process for the development of fiber structure in such high-speed spinning, an increase in orientation due to large spinning tension and accompanying crystallization have been recognized. Fibers having a large crystal size can be obtained, and the fiber structure specified in the present invention can be easily obtained. Crystallization during spinning occurs at a spinning speed of approximately 3,500 m/min, but this is not sufficient, and a spinning speed of 4,500 m/min is not sufficient to ensure fiber mechanical properties and maintain stain resistance at a sufficient level.
/min is required, preferably 5000m/min,
More preferably, it is 5500 m/min or more.

In addition to high speed spinning, it is also a preferred method to increase the cooling of the discharged yarn to increase the spinning tension.

For this reason, it is also a preferable method to make the yarn irregularly shaped or hollow.

It is effective to further heat-treat the yarn thus obtained. For example, in the case of polyethylene terephthalate, its crystallization begins at temperatures above 160°C;
It becomes noticeable when the temperature exceeds 175°C.

Therefore, temperatures above 175°C, more preferably 190°C
A method is employed in which the yarn or fabric is heat treated at a temperature exceeding .degree. The heat treatment of the fabric can also be carried out simultaneously with heating for smoothing out wrinkles using an iron. In that case, a preferable fiber structure can be obtained by heat-treating on a drawing roller or a heat plate at a temperature exceeding 175°C, more preferably at a temperature exceeding 190°C, over a sufficient period of time. Furthermore, when the above heat treatment is combined with heat treatment in a fixed length or relaxed state, a more preferable fiber structure can be obtained.

[Effect]

The reason why the modified polyester fiber obtained in this way has a superior level of stain resistance compared to conventional materials is not fully understood, but it is presumed to be due to the following mechanism. be done.

It is well known that polyester is lipophilic (
(hydrophobic), therefore it has an affinity for oil-based stains and is easily adsorbed into the fibers, and even when washed (by washing to remove stains with water), the oil-based components are not pushed out of the fibers, making it easier to remove stains and stains. will remain in the fibers as dark spots. By the way, oil-based stains are not uniformly adsorbed onto fibers. For example, the crystalline parts of polyester have short intermolecular distances and are compact, so oily components can penetrate between several crystal lattices. That's impossible.

On the other hand, in the amorphous parts and the gaps between crystal micelles, the density of polyester molecules is low, and combined with the lipophilic nature of polyester, oily components can easily penetrate between the fibers. Therefore, we have come to believe that the key to preventing oily components from penetrating into the fibers is to make the gaps between these amorphous parts and crystalline micelles hydrophilic as efficiently as possible.

Therefore, we have repeatedly investigated the presence of polyoxyalkylene glycol, a hydrophilic component, in polyester.

First, polyoxyalkylene glycol whose both ends were blocked with a group not having active hydrogen was mixed with polyester and its antifouling effect was confirmed, and it was found to have antifouling properties. However, after repeated wearing and washing, its performance deteriorated rapidly, and it became clear that there was a problem with its durability.

In order to clarify the mechanism, polyoxyethylene glycol in washing water and high-pressure boiling water was analyzed, and it was found that polyoxyalkylene glycol was easily extracted by water. - When polyoxyethylene glycol, which has groups with active hydrogen at both ends, is blended into polyester, copolymerization easily occurs, and even if the above-mentioned yarn spinning method is adopted, it is difficult to obtain a desirable fiber structure. , it was also inferior in antifouling properties. The reason for the poor stain resistance is presumed to be that polyoxyalkylene glycol was copolymerized completely randomly into polyester, and therefore polyoxyalkylene glycol could not be effectively collected in the amorphous portion.

Recently, the use of polymers whose constituent components are bipolarly blocked, such as block copolymers and graft copolymers, has been studied. For example, as described in "Surface", Vol. 22, No. 6, p. 297 (1984) and "Industrial Materials", Vol. 33, No. 12, p. 46, these polymers can be applied to polymer activators and polymer surface modification. There has been a lot of research being done on block copolymerization of hydrophilic polyoxyalkylene glycol and lipophilic polyester. When polyoxyalkylene glycol (PAG) whose terminal end is capped with a group that does not have active hydrogen is copolymerized with polyester (PE), PAG-PE-PAG or PAG-PE molecules are contained in a large amount of PE. It becomes a form of existence. This shows that PAG molecules tend to aggregate in PAG and are therefore likely to be localized in two regions of the polymer, one containing a large amount of polyoxyalkylene glycol and the other containing a large amount of polyester (polymer activator micelle structure). This can also be understood from the polymer properties shown in the following table.

(Real text, blank space below) Table 1 PET: Polyethylene terephthalate PEG: Polyoxyethylene glycol (Real text, white space below) Here, Tg and Tm are the glass transition point and melting temperature measured by DSC (differential calorimeter). show. PEG in column 1.2
The glass transition point of PET copolymerized with is 63° C., which allows molecular movement at low temperatures, and the glass transition point of polyester 3.4 is different from that of the blend. PEG (
Considering that the molecular weight (molecular weight 2000) is in a liquid state at room temperature, the low Tg is presumed to be due to copolymerization of polyoxyethylene glycol. On the other hand, if we look at the melting temperature Tm! Only 1h1 is as low as 247℃, the others are 2
The temperature was as high as 53℃. In particular, PET copolymerized with PEG having active hydrogen at only one end of the inhibitor 2 exists in a form in which the component that moves at low temperatures and the polyester are completely separated into two. In other words, it can be said that it is a polymer that easily forms a polymer active agent micelle structure. By using a polyester copolymerized with polyoxyalkylene glycol, one end of which has a group containing active hydrogen and the other end of which is blocked with a group that does not have active hydrogen, we were able to explore a specific thread-spinning property. The inventors discovered that it is possible to obtain stain-resistant polyester fibers with a high degree of durability that could not previously be expected, leading to the present invention. In order to collect the polyester component into a crystalline block and the polyoxyalkylene glycol component into an amorphous block, it is effective to promote crystallization of the polyester component. On the other hand, polyoxyalkylene glycol has a molecular weight of 500~
5,000 is liquid or waxy even at room temperature and is unsatisfactory, so crystallization of the polyester component is preferred in order to separate the two components and create a micelle structure. As a means for this, heat treatment as described above is effective, but surprisingly it has been found that such a method works even more effectively with the polymer of the present invention, resulting in a synergistic result between the polymer and the spinning method. was found to work.

That is, when polymers with the same intrinsic viscosity were spun under the same conditions and the fiber structures of polymers 1 to 4 in Table 1 were compared, it was found that the polymer of the present invention, that is, PEG (polyoxy Fibers made of polyethylene terephthalate (PET) copolymerized with ethylene glyconyl) have a high degree of crystallinity and large crystal size, and the birefringence Δn, which indicates the degree of orientation, and specific gravity are rather small values. From these, it can be seen that the structure is broadly divided into large, highly complete PET crystals and highly disordered amorphous crystals. Further, by applying strong heat treatment that promotes crystallization of the polyester component, the above structure can be more fully formed.

FIG. 1 shows the necessary areas for such polyester fibers with high antifouling properties. In other words, the birefringence (Δn) of the product fiber and the crystal size in the (100) plane ((1
00)A) (in) is (100)A≧(17xlO)
The range satisfying xΔn −110(100)A≧50 is the shaded area in FIG. 1, and when the crystal size takes the structure shown in the shaded area in the figure, the antifouling level is improved. For example, by performing high-speed spinning at 4,500 m for 7 minutes or more using the polymers in Table 1 and further heat-treating, the birefringence Δn and the crystal size in the (100) plane of the polymer of Inhibition 2 are shown on the solid line in (1). It can maintain the relationship and has high stain resistance. However, l1lIIL2
Polymer (5% PEG with active hydrogen only at one end)
Even if a copolymerized PET is used, if it is spun at a low speed, even if it is stretched and further heat-treated, it will not be possible to easily obtain the structure of the sloped portion, and the antifouling level will be low. The reason for this is thought to be as follows. The usual method of spinning yarn is to obtain an almost non-oriented unstretched material during low-speed spinning, and then stretch it. However, since the stretching is carried out at a temperature slightly above the glass transition point, the molecular Although the orientation of is increased significantly, the polyester portion and the polyoxyalkylene glycol portion are not separated and oriented.

When heat is applied to this highly oriented yarn, the polyester portion easily begins to crystallize, but the polyoxyalkylene glycol inserted between the polyester fibers increases, making it impossible to grow to a large polyester crystal size. . Incidentally, when the birefringence Δna of the amorphous part is calculated from the following formula, Δna = (Δn−XcrcΔn c)/(1
-X c) It can be seen that the crystal part is highly oriented.

On the other hand, when high-speed spinning is performed, crystallization begins during the spinning process, but since the crystallization occurs at high temperatures and the molecules have high mobility, polyester molecules sufficiently associate with each other and crystallization occurs, while other The component, ie, the polyoxyalkylene glycol component, is discharged to the amorphous part. For this reason, the crystal size increases significantly, and the orientation degree of the amorphous part is Δ
na becomes significantly lower, and fiber molding is completed with the polyester and polyoxyalkylene glycol separated. By further heat-treating the yarn thus obtained, the phase-separated structure can be further expanded and a structure can be taken in the direction of the upper left side in FIG. 1, resulting in a very high level of antifouling.

In addition, polymer No. 1 in Table 1 (PEG with active hydrogen at both ends)
When PET (5% copolymerized with I couldn't get anything expensive.

In this way, by using the modified polyester and sufficiently crystallizing it, phase separation of the polyester crystal-polyoxyalkylene glycol amorphous and the polymer in the fiber can be achieved.
A beaten micelle structure can be efficiently formed. Therefore, when oil-based dirt components try to penetrate into polyester fibers, they are blocked by the hydrophilic polyoxyalkylene glycol components present in the amorphous portion, and a mechanism works in which they are easily separated from the fibers by washing with water. . Due to this fibrous structure, when hydrophilic components adhere to the fibers and further penetrate into the amorphous parts or the interstices of crystalline micelles, they become difficult to separate due to their affinity for each other. The post-processing antifouling agent used for polyester fibers is generally a hydrophilic polymer or a polymer containing a large amount of hydrophilic polymers, so when the modified polyester fiber of the present invention is subjected to antifouling treatment, the interaction between It has been found that the effectiveness of the present invention is extremely high, as the antifouling level is synergistically improved.

〔Effect of the invention〕

The modified polyester fiber of the present invention exhibits its characteristics particularly when used in frequently washed clothing such as underwear and white coats, and retains its stain-resistant properties even after repeated washing. No darkening occurs. Therefore, the soil-resistant modified polyester fiber of the present invention is particularly useful in the linen supply field.

Furthermore, the modified polyester fiber of the present invention may optionally include:
It is used for blending, inter-knitting, inter-weaving, etc. with natural fibers such as cotton and wool, regenerated fibers such as rayon and acetate, and synthetic fibers other than the polyester fiber of the present invention.

〔Example〕 The present invention will be further explained below with reference to Examples.

Parts and % in the examples indicate parts by weight and % by weight, respectively. The intrinsic viscosity (77) of the polymer was determined from the value measured in an orthochlorophenol solution at 35°C, and the softening point (SP)
was measured by the venerecisin method.

In the examples, the fiber structure, contamination treatment, and contamination rate were determined using the following methods.

(1) Crystal Size Using an X-ray diffractometer model RAD-IIIA manufactured by Rigaku Denki, the sample is fixed on a fiber sample stage and set vertically on the mount of a goniometer. Diffraction at a diffraction angle of 2θ=10” to 40° is measured.

The lowest points of diffraction in the meridian direction are connected with a straight line, and based on this, the half value B of the diffraction peak of the (100) plane is determined. (1
The crystal size of the 00) plane is determined by the following formula.

Crystal size D-Aλ/ ((S:T) x cosθ)
A is the correction coefficient, b is the correction angle λ is the wavelength of the X-ray, and 1.5481A is used. B: Half price (see "X-ray Crystallography" published by Maruzen Co., Ltd., supervised by Isamu Nita) (2) Contamination treatment The following composition Pour 300 cc of washing liquid into the pot of a Colorbet dyeing tester (manufactured by Nippon Senzo Kikai), and soak a 101 x 13 C11 fabric sandwiched in a holder in the pot.
The mixture was stirred at 0°C for 100 minutes.

Artificial dirt liquid 1%・Motor oil (Dia 99.335 insect amount%Queen
Motor Oil M-2 Mitsubishi Motors! ! A mixture of 0.634% by weight of B heavy oil and 0.031% ffi of carbon black is used.

Sodium alkylbenzenesulfonate 0.02% Sodium sulfate 0.03% Sodium tripolyphosphate 0.02% After washing lightly with water,
The sample was sandwiched between filter papers to remove excess contaminated liquid. Next, the contaminated sample was washed in warm water at 40° C. containing 2 g/2 Marcel soap for 10 minutes in a household washing machine on gentle conditions. It was then air-dried.

These staining and washing treatments constituted one cycle, and this cycle was repeated eight times. Next, the degree of contamination of the fabric was determined by the following method.

(3) How to determine the degree of contamination Macbeth M S-2020 (Instrumental
ColorSystems Lin+it (manufactured by ed) was used to determine the color scale of the crE color system using a conventional method, and the degree of contamination was calculated as follows.

Degree of contamination (ΔL*) - Before contamination * - After treatment * Examples 1 to 5 and Comparative Examples 1 to 8 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
0 parts, 0.06 parts of calcium acetate monohydrate (0.066 mol % based on dimethyl terephthalate), and 0.009 parts of cobalt acetate tetrahydrate as a coloring agent (0.007 mol based on dimethyl terephthalate). %) in a transesterification tank and heated from 140°C to 22°C for 4 hours under nitrogen gas atmosphere.
After raising the temperature to 0°C and distilling the generated methanol out of the system, the transesterification reaction was carried out. After the transesterification reaction, 0.058 parts of trimethyl phosphate (0.080 parts per dimethyl terephthalate) was added as a stabilizer. (mol%) added. Then, 10 minutes later, 0.04 part of antimony dioxide (0.027 mol % based on dimethyl terephthalate) was added, and the temperature was heated at 240°C while simultaneously expelling excess ethylene glycol.
After raising the temperature to 100%, the mixture was transferred to a container. After adding the amount of polyoxyethylene glycol shown in Table 2 to the polymerization reactor, the pressure was reduced from 760 mmt (g to l mmm1) over 1 hour, and at the same time the pressure was reduced from 240°C to 28°C over 1 hour and 30 minutes.
The temperature was raised to 0°C. Blood chamber temperature under reduced pressure below 1 mmHG2
After further polymerization at 80°C for 2 hours, 0.0% of Irganox 1010 (Ciba Geigy!a) was added as an antioxidant.
4 parts were added under vacuum and then polymerized for an additional 30 minutes. The obtained polymer was made into chips according to a conventional method.

High-speed spinning was performed using this chip. Hole diameter 0°281
Using a spinneret with a circular spinning hole 24 (II), the polymer was wound at a temperature of 290° C. and at the spinning speed shown in Table 2.The resulting high-speed spun yarn was then run on a heating plate to heat it. The heat treatment temperature was 190°C and the time was 2 seconds.The obtained polyester filament yarn was circularly knitted to obtain a knit product.

After further scouring and heat treatment by conventional methods, Mi is used as a fluorescent dye.
ka White ATN (manufactured by Mitsubishi Kasei) 2% off
A fluorescently dyed product was obtained by dyeing it at 130° C. for 30 minutes in a treatment bath containing F, and the staining rate was determined by carrying out the staining treatment described above. The passing line is ΔL*-30 or less, preferably 20 or less.

(Materials, below are blanks) In addition, in Comparative Example 1.2, after spinning, 3.1
It was stretched twice. High antifouling properties were exhibited in Examples 1 to 5 in which M-PEG copolymerized polyethylene terephthalate was spun at high speed.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between the crystal size in the (100) plane and the birefringence Δn of the stain-resistant polyester fiber, and the shaded area indicates the crystal size of the stain-resistant polyester fiber of the present invention. It shows. Figure 1 Crystal size (100) Δn

Claims (2)

[Claims] (1) At least a part of the terminal end of polyester whose main constituent unit is ethylene terephthalate has the following general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R^1 is a monovalent organic compound with no active hydrogen). group, R
^2 is an alkylene group, n is an integer from 20 to 140)
The polyoxyalkylene glycol component represented by 0.
A fiber made of a modified polyester copolymerized with 5 to 10% by weight, the crystal size in the (100) plane [(100)
A] (Å) is the following formula (1) and (2) (100) A≧(
1.7×10^3)×Δn-110...(1)(10
0) A≧50...(2) (in the formula, Δn is the birefringence index of the product fiber), an antifouling polyester fiber that has an elongation of 100% or less and a strength of 3 g/de or more . (2) At least a part of the end of the polyester whose main constituent unit is ethylene terephthalate has the following general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R^1 is a monovalent organic compound with no active hydrogen). group, R
^2 is an alkylene group, n is an integer from 20 to 140)
The polyoxyalkylene glycol component represented by 0.
4500% modified polyester copolymerized with 5 to 10% by weight
A method for producing stain-resistant polyester fibers, which comprises melt spinning at a take-up speed of m/min or more.