JPS6335824A - Soil release polyester fiber - Google Patents

Abstract

PURPOSE:The titled fibers without blackening even by washing the fibers many times, having a specific crystal size, birefringence, elongation and strength and obtained by partially copoilymerizing ends of a polyester such as ethylene terephthalate, etc., with a polyoxyalkylene glycol component. CONSTITUTION:Dimethyl terephthalate is reacted with ethylene glycol by heating in the presence of a catalyst and a polymerization catalyst is added to the resultant reaction, mixture, which is then thermally polymerized under reduced pressure. Then, polyoxyalkyleneglycol is added to the polymerization mixture, which is further polymerized to provided a modified polyester. Then the modified polyester is melt spun to afford the aimed fibers partially containing 0.5-10wt% polyoxyalkyleneglycol component expressed by the formula (R<1> is monovalent organic group having no active hydrogen; R<2> is alkylene; n is 20-140) at ends of a polyester containing ethylene terephthalate as a chief constituent unit and having 50-100Angstrom crystal size at (100) face, 65-170Angstrom crystal size at (010) face, >=0.15 birefringence, <=40% along action and >=c4g/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 with 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 ("Polymer' August 1978 issue 904-912)
page) etc. are known.

However, all of these methods have been proposed as finishing treatments for polyester fiber products, and they have problems in terms of processing, such as being complicated to operate, requiring special equipment, or having poor processing reproducibility. There is a problem, and even underwear,
Clothing that is washed frequently, such as white coats, has the problem that the initial effect gradually disappears as the number of washes increases.Conventionally, polyester fibers that maintain stain resistance even after repeated washing (does not darken due to washing) have been developed. The appearance of this was strongly desired.

On the other hand, it is known that polyoxyethylene glycol is copolymerized to make polyester fibers easier to dye. Therefore, an attempt was made to copolymerize polyoxyethylene glycol into polyester fibers to make the polymer itself hydrophilic and to prevent oil staining. %, 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 unusable for practical use, especially for linen supplies. It could not be used separately for cotton blends. Furthermore, in order to maintain light fastness, the copolymerization amount of polyoxyethylene glycol was set to 10% or less, particularly 5M% or less, but sufficient stain resistance 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 made extensive studies and found that 1. Excellent antifouling properties can be exhibited 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. Possibly because polyoxyethylene glycol copolymerized at the end of the main chain acts specifically, polyester fibers with It has been found that the fibers exhibit significantly improved stain resistance and washing durability compared to polyoxyethylene glycol or polyester fibers in which polyoxyethylene glycol, which is insoluble in polyester, is mixed into polyester. The present invention was completed as a result of further studies based on this knowledge.

That is, the present invention has the following general formula +1) RIO(R20hr-.-(11) where R1 is a monovalent organic compound having no active hydrogen group, R2
is an alkylene group, and n is an integer of 20 to 140).
A fiber made of 10% by weight copolymerized modified polyester, with a crystal size in the (100) plane of 50 to 100λ
, the crystal size in the (010) plane is 65 to 170 A, the birefringence is 0.15 or more, the elongation is 40% or less, and the strength is 4 g/de or more. be.

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 part of the terephthalic acid as an acid component 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 dichlorohexanedicarboxylic 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 diol compounds such as cyclohexane. Examples include -1,4-dimetatool, neopentyl glycol, bisphenol A1 bisphenol S, N fat tM, N ring group, aromatic diol compounds, polyoxyalkylene glycols with both ends unblocked, and the like.

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, 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 (1). is necessary.

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, and the result will be the same as when polyoxyalkylene glycol is mixed with polyester, resulting in high stain resistance. I can't do it. In particular, the preferred average degree of polymerization is 30 to 80.
exists in a very 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, polyoxypropylene glycol monononylphenyl ether, polyoxytetramethylene glycol 7-methyl ether, monomethyl ether of polyoxyethylene glycol/polyoxypropylene glycol copolymer, etc. These ester-forming derivatives can be listed.

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 increase during the polycondensation reaction process. Since it reaches a plateau at a low level, the yarn physical properties such as the strength of the polyester fiber finally obtained deteriorate. Furthermore, if a large amount of polyoxyalkylene glycol is contained, the light resistance of the obtained m-fiber will deteriorate, so it is preferable to keep the amount of copolymerization as small as possible. In the present invention, the copolymerization amount of polyoxyalkylene glycol is 0 relative to the 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 polyoxyalkylene glycol copolymerized can be reduced to a small amount, the resulting fibers can also maintain sufficient light resistance.

If necessary, stabilizers, matting agents, antioxidants, flame retardants, antistatic agents, fluorescent brighteners, catalysts, color inhibitors, heat resistant agents, colorants, inorganic particles, etc. may be used in combination. good. In particular, when polyoxyalkylene glycyl is left at high temperatures such as under melt-spinning conditions, it is easily oxidized and tends to cause problems such as a decrease in the degree of polymerization and discoloration. Further, 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, and the field of use thereof will further expand.

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 melt spinning. 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 portion. 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.

The spun fibers are drawn to have an elongation of 40% or less and a strength of 4 g/de or more in order to exhibit sufficient fiber performance, and are heat treated if necessary. In particular, the birefringence should be increased to 0.15 or more by stretching. When the birefringence index does not reach 0.15, it will be described later (010
) crystal size on the plane is difficult to reach a desirable value,
It is difficult to obtain sufficient stain resistance and durability. The upper limit does not need to be particularly limited, but if it is too high, the spinning properties will deteriorate, so it is preferably 0°18 or less.

The fiber of the present invention has the above characteristics and has a special fiber structure, that is, a crystal size of 50 to 100 in the (100) plane.
crystal size of (010) plane is 65
~1to, A must be within the range.

If even one of these ranges is exceeded, sufficient antifouling properties and durability cannot be exhibited. The following method is effective for obtaining such a fiber structure. That is, it is obtained by strongly heat-treating a yarn obtained from the modified polyester by a normal spinning method.

For polyester, the spinning speed is usually ioooomZ
It is common practice to further add a stretching step to ensure the mechanical properties. However, when this method is applied to the above-mentioned modified polyester, the above-mentioned fiber structure cannot be achieved as it is, and further sufficient heat treatment is required. For example, in the case of polyethylene terephthalate, its crystallization begins at temperatures above 160°C and becomes noticeable at temperatures as high as 175°C. Therefore, a method is employed in which the yarn or fabric is heat treated at a temperature exceeding 175°C, preferably at a temperature of 180°C or higher, and more preferably at a temperature exceeding 190°C. Also,
If the heat treatment temperature is too high, the fiber properties will deteriorate, so it is preferably 240°C or lower, especially 22°C.
The temperature is preferably 0°C or lower. The heat treatment of the fabric can also be carried out simultaneously with heating for smoothing out wrinkles using an iron. In the case of yarn, it is heated to 175℃ on a drawing roller or heating plate.
The preferred fiber structure described above can be obtained by heat treatment at a temperature exceeding 190° C., more preferably at a temperature exceeding 190° C. for a sufficient period of time. Furthermore, a more favorable fiber structure can be obtained when the heat treatment is combined with a fixed-length or blanket heat treatment.

The heat treatment time varies depending on the treatment temperature, and is preferably set within a range that satisfies the following formula, where the treatment temperature is T ("C) and L2 and the treatment time is t (seconds). 1000/ (T
-175) If the time is less than 2, it is difficult to form the fibrous structure,
When the time is longer than 30000/(T-175), the fiber properties begin to deteriorate. Particularly preferred is 3
000/(T-175) or less.

In the present invention, it is easy to adhere a hydrophilic resin film to the surface of the polyester fiber obtained in this way, and thereby the antifouling performance can be further improved. There is no need to specify the hydrophilic resin used here as long as it can form a hydrophilic film, but when combined with the modified polyester fiber, the antifouling performance and washing durability of the resin can be improved. A film made of polyether resin is particularly preferred since it has the effect of specifically increasing the size.

[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 (i.e., the stains are removed with water), the oil-based components are not pushed out of the fibers, causing stains and even dark spots. It will remain in the fiber. However, oil-based stains are not uniformly adsorbed onto fibers. For example, since the crystalline portion of polyester has short intermolecular distances and is compact, it is impossible for oily components to penetrate between the several crystal lattices.

On the other hand, the density of polyester molecules is low in the egg crystal parts and the gaps between crystal micelles, and this combined with the lipophilic nature of polyester allows oily components to 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 were problems with 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 the polyoxyalkylene glycol was copolymerized completely randomly into the polyester, making it impossible to effectively collect the polyoxyalkylene glycol in an amorphous form.

Recently, the use of polymers whose constituent components are bipolarly blocked, such as block copolymers and graft copolymers, has been studied. -For example, "Surface" No. 22 16 Calyx 297
(1984) and Kogyo Zasai, Vol. 33, No. 12, p. 46, research is actively being carried out to apply these polymers to polymer activators and polymer surface modification. It has become.

Block copolymerization of hydrophilic polyoxyalkylene glycol and lipophilic polyester; one end of one end is a group that grows active hydrogen, and the other end is blocked with a group that does not have active hydrogen. When oxyalkylene glycol (PAG) and polyester (PE) are copolymerized, PAG-PE-PAG or PAG-PE molecules are present in a large amount of PEO. PAG molecule is PA
This indicates that the polymer tends to be localized in two regions, one containing a lot of polyoxyalkylene glycol and the other containing a lot of polyester (polymer activator micelle structure) because it tends to aggregate in C. This is due to the polymer properties shown in the following table. You can also know.

(This page, the following margins) Table 1 PEG: Polyoxyethylene glycol Here, Tg and Tm indicate the glass transition point and melting temperature measured by DSC (differential calorimeter). Magnetic 1.20 PEG copolymerized P
The glass transition point of ET is 63° C., which allows molecular movement at low temperatures, and the glass transition point of polyester No. 3.4 is different from that of the blend. PEG (molecular weight 2000
) is in a liquid state at room temperature, it is presumed that the low Tg is due to copolymerization of polyoxyethylene glycol. On the other hand, when looking at the melting temperature Tm, only patient 1 had a low 247°C, while the others had a high 253°C. In particular, in the case of PET in which PEG is combined with active hydrogen at only one end of the binder 2, the component that moves at low temperatures and the polyester exist in the form of two completely separated components. 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 with active hydrogen and the other end of which is blocked with a group without active hydrogen, and by employing a specific spinning method, We have discovered that it is possible to obtain stain-resistant polyester fibers with a high level of durability that could not previously be expected, and have thus arrived at the present invention. In order to collect the polyester component in the crystal block and the polyoxyalkylene glycol component in the amorphous part, it is effective to promote crystallization of the polyester component. On the other hand, polyoxyalkylene glycol with a molecular weight of 500 to 5,000 is liquid or waxy even at room temperature and has poor quality. Therefore, in order to separate the two components and create a micelle structure, it is preferable to crystallize the polyester component. 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, and the synergistic effect of the polymer and the spinning method The results were found to work - i.e., yarn spinning was carried out under the same conditions with polymers of the same intrinsic viscosity and
A comparison of the fiber structures of the polymers No. 4 to 4 revealed that the fibers made of polyethylene terephthalate (PET) copolymerized with PEG (polyoxyethylene glycol), which has active hydrogen only at the ends of the polymer strips of the present invention, have a structural PE has a high degree of crystallinity and a large crystal size, and the birefringence Δn and specific gravity, which indicate the degree of orientation, are on the contrary small values.
It can be seen that the structure is largely divided into a T crystal and a considerably disordered amorphous part. Further, by applying strong heat treatment that promotes crystallization of the polyester component, the above structure can be more fully formed. In this manner, by using the modified polyester and sufficiently crystallizing it, it is possible to efficiently form a phase separation of the polyester crystal-polyoxyalkylene glycol amorphous and the polymer in the fibers, thereby forming a partial micelle structure. 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. Post-processing antifouling agents used for polyester fibers are generally
Since the modified polyester fiber of the present invention is a wood-philic polymer or a polymer containing a large amount of the same, the effects of the present invention include synergistically improving the stain-proofing level due to the interaction of the modified polyester fibers of the present invention. It turned out to be very sensitive.

〔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. Darkening does not occur.9 Therefore, the stain-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 Examples indicate parts by weight and % by weight, respectively. The intrinsic viscosity [η] of the polymer is determined from the value measured in an orthochlorophenol solution at 35°C, and the softening point (S P)
was measured by the veneration method.

The method for determining the fiber structure, contamination treatment, and contamination rate in the examples is as follows: (1) Crystal size Using a Rigaku Denki layered X-ray diffractometer model RAD-IIIA, 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 peaks of the (100) plane and the (010) plane is determined. The crystal size of the (100) plane and (010) plane is determined by the following formula.

Crystal size D-Aλ/a=y) XcosθA is the correction coefficient, b is the correction angle λ is the wavelength of (Refer to supervision) (2) Contamination treatment Pour 300 cc of washing liquid with the following composition into the pot of Colorbet dyeing tester (manufactured by Nippon Senzo Kikai), and soak a 10 cII + × 13 CI 11 fabric sandwiched in a holder in the pot. The mixture was stirred at ℃ for 100 minutes.

Artificial dirt liquid 1%・Motor oil (Dia 99.335% by weight Queen
Motor Oil M-2 manufactured by Mitsubishi Motors Corporation) A mixture of B heavy oil 0.634% by weight and carbon blank 0.031% by weight is used.

Alkylbenzenesulfonic acid sorter 0.02% Sodium sulfate 0.03% Sodium tripolyphosphate 0.02% After being lightly washed with water, the sample was sandwiched between filter papers to remove excess contaminated liquid. Next, wash the contaminated sample with Marcel soap for 2 minutes in a home washing machine on gentle conditions.
It was washed for 10 minutes in 40°C hot water containing g/j2. 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 MS-2020 (Instrumenta
l Color Systems (manufactured by Lim1ted)
L* on a CIE colorimeter was determined using a conventional method, and the degree of contamination was calculated as follows.

Degree of contamination (ΔL*) - L* before contamination - L* after treatment * Examples 1 to 4 and Comparative Examples 1 to 6 100 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 (0.007 mol based on dimethyl terephthalate) as a coloring agent. %) in a transesterification tank and heated from 140°C to 220°C over 4 hours under nitrogen gas atmosphere.
The transesterification reaction was carried out while raising the temperature to ℃ and distilling the generated methanol out of the system.

After completion of the transesterification reaction, add 0.058 parts of todimethyl phosphate (o, o to dimethyl terephthalate) as a stabilizer.
so mol %) was added. Then, after 10 minutes, 0.04 part of antimony dioxide (0.02 part for dimethyl terephthalate) was added.
7 mol %) was added thereto, the temperature was raised to 240° C. while simultaneously expelling excess ethylene glycol, and the mixture was transferred to a polymerization vessel. After adding the amount of polyoxyethylene glycol shown in Table 2 to the polymerization reactor, the pressure was reduced from 76 parts mHg to 1 mdg over 1 hour, and at the same time, the pressure was reduced to 2 parts mHg over 1 hour and 30 minutes.
The temperature was raised from 40°C to 280°C. After polymerization was further carried out for 2 hours at a polymerization temperature of 280° C. under reduced pressure of 1 n+mHG or less, 0.4 part of Irganox 1.010 (manufactured by Ciba Geigy) was added as an antioxidant under vacuum, and then polymerization was continued for another 30 minutes. The obtained polymer was made into chips according to a conventional method.

This chip was dried by a conventional method, and the pore size was 0.3ffil+.
2 using a spinneret with 24 + circular spinning holes.
Melt spinning was carried out at 85°C, and then drawing heat treatment was carried out using a heating roller at 84°C and a slit heater at 180°C at a drawing ratio such that the elongation of the final drawn yarn was 30% to obtain a filament of parent denier/24. A drawn yarn was obtained.

Obtained polyester filament yarn 50 denier/2
A circular fabric was knitted using 4 filaments.

After scouring by a conventional method and heat treatment at 170°C to eliminate scouring wrinkles, Mikawhite A was used as a fluorescent dye.
13 in a treatment bath containing 2% 0-resistant TN・(manufactured by Mitsubishi Kasei Corporation)
A fluorescently stained product was obtained by staining with Q'C for 30 minutes. Next, heat treatment with an iron was performed at the temperature and time shown in the table.

The fiber properties are shown in Table 2. The obtained sample was subjected to a contamination treatment, and the degree of contamination ΔL* was determined. The contamination level is below the garden level.
Preferably it is 20 or less.

(Real article, blanks below) Example 5 and Comparative Example 7.8 The polymers of Example 2 and Comparative Example 2.3 were prepared using a spinneret with 1008 circular spinning holes with a hole diameter of 0.281.
It was discharged at a rate of 530 g/min at 90°C and wound up over 1000 m in 7 minutes while applying an oil agent. The 165 spun undrawn yarns were simultaneously fed to a drawing machine at 70°C and 90°C.
3.74 times and 1. It was stretched at a stretching ratio of rs times, then heat treated with a set roller of 225''C, and further a spinning oil was applied (speed of 100 n+/min).

Next, the fibers were crimped with a 30 mm width push-in crimper, subjected to dry heat treatment at 90° C. in a continuous dry heat treatment, fed to a cuffer, and cut into a length of 38 nm+m to obtain stable fibers. The fiber properties are shown in Table 3.

Mixing 65% of this stable fiber with 35% cotton,
A spun yarn having an English cotton count was obtained using a conventional spinning machine. The number of twists at this time was 17.8 (11/1 nch).

This is used to weave a plain woven fabric, which is then desizing, scouring, and
Fluorescent dye Mikawhite ATN after heat treatment
(Mitsubishi Kasei M) in a treatment bath containing 2% owf at 130°C.
The cells were stained for 30 minutes to obtain fluorescently stained peritectics. This was subjected to contamination treatment to determine the degree of contamination. The passing line is 10% or less.

(Materials, blanks below) Comparative Example 7 is an example in which PEG is copolymerized within the main chain of polyethylene terephthal, and although the crystal growth is small and the degree of orientation Δn is high, the specific gravity is low, and it is a more taut non-woven material than these. It had crystalline parts, indicating that a two-component phase-separated structure was not formed, and the degree of contamination was high at 18.3. In Comparative Example 8, the contamination rate was high probably because the PEG component whose both ends were blocked with inert hydrogen was extracted into water. On the other hand, in Example 5, PEG having active hydrogen at only one end was copolymerized with polyethylene terephthalate at the end, and the heat treatment was sufficient, the crystal size grew large, the phase separation of the two components was sufficient, and the contamination rate was kept low. was completed.

Claims (1)

[Claims] At least a part of the terminal end of the polyester having ethylene terephthalate as a main constituent unit has the following general formula (1) ▲ mathematical formula, chemical formula, table, etc. ▼ (1) (in the formula, R ^1 is a monovalent organic group without active hydrogen, 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 5-10% by weight copolymerized modified polyester, with a crystal size in the (100) plane of 50-10
0 Å, a crystal size in the (010) plane of 65 to 170 Å, a birefringence of 0.15 or more, an elongation of 40% or less, and a strength of 4 g/de or more.