JPH0772392B2 - Method of modifying polyester fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to modification of polyester fibers.

[Prior Art] Conventionally, methods for imparting antistatic property, sweat absorbing property, and antifouling property to polyester fibers have been studied for a long time, and many methods have been proposed so far. For example, a method of attaching a hydrophilic polymer compound to the fiber surface (Japanese Patent Publication No. 53-47435, etc.)
Alternatively, there is a method of forming a film by polymerizing a polymerizable monomer having a hydrophilic group on the fiber surface (such as JP-A-53-130396). However, in such a method, if severe washing treatment is repeated, Often the effect disappears, and if you increase the amount of treatment agent to increase durability even a little,
There are problems such as rough texture and poor dyeing fastness.

In addition, a major drawback of the polyester fiber that has been subjected to the above-mentioned processing is that it is not durable against heat. For example, when performing an ironing or pressing process, it is attempted to enhance the effect of the ironing or pressing. There is also a problem that as the heat treatment conditions are strengthened, the performance of antistatic property, sweat absorption property and antifouling property is lost.

In addition, recently, there have been many attempts to modify the surface of the polyester by treating the surface of the polyester with low-temperature plasma to enhance hydrophilicity. (Example: JP-A-59-97476, JP-A-61-9
However, these methods have major facility restrictions such as the need for a special plasma generator, and in terms of performance, the expected levels of antistatic properties, sweat absorption properties, and antifouling properties are not always sufficient. Have problems such as.

On the other hand, as an antifouling polyester fiber with improved redeposition property at the time of washing, we have a general formula R ₁ O (R ₂ O _n (wherein R ₁ is a monovalent organic group having no active hydrogen, R ₂ is an alkylene group, and n is an integer of 20 to 140. A fiber comprising a modified polyester obtained by copolymerizing a polyalkylene glycol component represented by 1 to 8% by weight has been proposed (JP-A-63-
35824, 63-35825).

This modified polyester fiber is particularly excellent in preventing redeposition during oil washing due to oil stains, and this performance is maintained even after repeated washing. For this reason, it has been proposed that this modified polyester fiber is suitable for commercial applications, such as linen supply or rental, in which the washing process is frequently repeated.

Of course, in these applications, it is an essential condition that the anti-soil redeposition property at the time of washing is excellent, so that the modified polyester fiber effectively exhibits its effect. However, work clothes that are repeatedly washed include work clothes worn in various workplaces, in addition to preventing recontamination during washing, static electricity is a problem during attachment / detachment or during work, or during wear. It is often required to have a so-called sweat absorbing property that absorbs rid of sweat. The modified polyester fiber is excellent in preventing recontamination at the time of washing, but does not have antistatic property for spinning static electricity and sweat absorbing property for absorbing sweat.

[Object of the Invention] An object of the present invention is to provide polyester fibers with excellent antistatic properties, sweat absorption properties, and antifouling properties even after repeated washing and heat treatment in addition to washing. It is to propose a method for modifying a fiber.

[Structure of the Invention] The present invention is configured as follows.

(1) General formula [1] R ₁ O (R ₂ O _n ... [1] (in the formula, R ₁ is a monovalent group having no active hydrogen) at least at a part of the terminal of the polyester having ethylene terephthalate as a main constituent unit. Of an organic group, R ₂ is an alkylene group, and n is an integer of 20 to 140), and a fiber made of polyester copolymerized with 1 to 8% by weight of a polyalkylene glycol component is heated with a treatment liquid containing a polyepoxide compound. After the dipping treatment, the polyester fiber is polyoxyalkylene (wherein the alkylene group has 2 carbon atoms).
To 4) A method for modifying polyester fiber, which comprises impregnating a treatment liquid containing a diamine having a unit and then subjecting it to heat treatment.

(2) The method for modifying a polyester fiber according to claim 1, wherein the polyester fiber is treated in an alkaline liquid before the heat dipping treatment with the treatment liquid containing the polyepoxide compound.

The polyester referred to in the present invention is intended for polyesters having terephthalic acid as a main acid component and ethylene glycol as a main glycol component, and such polyester is obtained by partially converting terephthalic acid as an acid component into another difunctional carboxylic acid. May be replaced with. Examples of such other carboxylic acid include isophthalic acid, 5-sodium sulfoisophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β
-Difunctional aromatic carboxylic acids such as -oxyethoxybenzoic acid and p-oxybenzoic acid, difunctional aliphatic carboxylic acids such as sebacic acid, adipic acid and oxalic acid, and difunctionality such as 1,4-cyclohexanedicarboxylic acid Examples thereof include alicyclic carboxylic acid. Further, a part of the ethylene glycol component may be replaced with another glycol component, and examples of such a glycol component include trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol and the like, and other diol compounds such as Cyclohexane-1,4-dimethanol,
Examples thereof include aliphatic, alicyclic and aromatic diol compounds such as neopentyl glycol, bisphenol A and bisphenol S, and polyoxyalkylene glycol whose both ends are not blocked.

Such polyester can be produced by any method. For example, polyethylene terephthalate will be described. Direct esterification reaction of terephthalic acid and ethylene glycol, transesterification of a fixed alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or terephthalic acid and ethylene glycol. A first-stage reaction for forming a glycol ester of terephthalic acid and / or a low polymer thereof by reacting with oxide, and then heating the product under reduced pressure to a polycondensation reaction until a desired degree of polymerization is obtained. It is easily produced by the second step reaction.

In the present invention, it is necessary that at least a part of the polymer chain of the polyester is copolymerized with a polyoxyalkylene glycol having one end blocked represented by the following general formula R ₁ O (R ₂ O _n). is there.

In this formula, R ₁ is a monovalent organic group having no active hydrogen, and particularly preferably a hydrocarbon group, among which an alkyl group,
A cycloalkyl group, an aryl group or an alkylaryl group is preferable. R ₂ is an alkylene group and usually has 2 to 2 carbon atoms.
An alkylene group of 4 is preferred. Specifically, ethylene group,
A propylene group and a tetramethylene group are exemplified. Also,
It may be a mixture of two or more kinds, for example, a copolymer pair having an ethylene group and a propylene group. Moreover, n shows an average degree of polymerization and is in the range of 20 to 140. When trying to copolymerize a polyoxyalkylene glycol in which n is less than 20,
To obtain sufficient antifouling property, a high copolymerization rate is required,
In such a case, the degree of polymerization of the polyether itself cannot be sufficiently increased because the ends of the polyester are blocked,
Consequently, the mechanical properties of the obtained fiber cannot be secured. On the other hand, when n is larger than 140, the reaction between the polyoxyalkylene glycol and the polyester does not proceed sufficiently,
Eventually, the same result as when polyoxyalkylene glycol is mixed with polyester is obtained, and high antifouling property cannot be obtained. In particular, the preferred average degree of polymerization lies in the very limited region of 30-80.

Preferred specific examples of such one-end-blocked polyoxyalkylene glycols include polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monophenyl ether, polyoxyethylene glycol monooctyl phenyl ether, polyoxyethylene glycol monononyl phenyl ether, and polyoxy. Ethylene glycol monocetyl ether, polyoxypropylene glycol monophenyl ether, polyoxypropylene glycol monononylphenyl ether, polyoxytetramethylene glycol monomethyl ether, polyoxyethylene glycol / polyoxypropylene glycol copolymer monomethyl ether, and the like. Mention may be made of ester-forming derivatives.

To copolymerize the above-mentioned one-end-capped polyoxyalkylene glycol to the end of the polyester chain, any step before the completion of the above-mentioned polyester synthesis, for example, the first step
It may be added at any stage, such as before the start of the reaction of the stage, during the reaction, after the completion of the reaction, during the reaction of the second stage, and the production reaction may be completed after the addition.

If the amount used in this case is too small, the antifouling property and the washing durability of the finally obtained polyester resin will be insufficient, and conversely, if it is too large, the degree of polymerization of the polyester will be too low in the course of the polycondensation reaction. Since the level is reached at the level, yarn properties such as strength of the finally obtained polyester fiber are deteriorated. In addition, when a large amount of polyoxyalkylene glycol is contained, among the expected performances, there is a tendency that the sweat absorption property rather deteriorates or the light resistance of the obtained fiber deteriorates.

In the present invention, the copolymerization amount of polyoxyalkylene glycol should be in the range of 1 to 8% by weight, preferably 2 to 5% by weight, based on the polyester. As described above, in the present invention, the copolymerization amount of polyoxyalkylene glycol can be suppressed to a small amount, and thus the obtained fiber can also retain sufficient light resistance.

If necessary, stabilizers, matting agents, oxidizing agents, flame retardants, electrifying agents, fluorescent whitening agents, catalysts, coloring agents, heat-resistant agents, coloring agents, inorganic particles, etc. may be used in combination. . In particular, when polyoxyalkylene glycol is left at a high temperature such as under melt spinning conditions, it easily oxidizes to cause problems such as a decrease in polymerization degree and coloration. Is often preferred.

The degree of polymerization of R ₁ O (R ₂ O _n copolyester (hereinafter referred to as copolyester)) thus obtained is preferably 0.58 or more, and 0.6 or more in terms of intrinsic viscosity in order to exhibit sufficient fiber characteristics. The copolymerized polyester is fiberized by a melt spinning method, and the fiber to be spun out may be a solid fiber having no hollow portion or a hollow fiber having a hollow portion. Further, the outer shape of the fiber to be spun in cross section and the shape of the hollow portion may be circular or irregular.

As the polyepoxide compound used in the present invention, a compound containing at least two epoxy groups in one molecule in an amount of 0.2 g or more per 100 g of the compound is preferably used. Ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethylene glycol Reaction products of polyhydric alcohols such as and the like and halogen-containing epoxides such as epichlorohydrin, polyhydric phenols such as resorcin / bis (4-hydroxyphenyl) dimethylmethane, phenol / formaldehyde resin, resorcin / formaldehyde resin and the halogen A reaction product with a contained epoxide, a polyepoxide compound obtained by oxidizing an unsaturated compound with peracetic acid or hydrogen peroxide,
I.e. 3,4-epoxycyclohexene epoxide, 3,4
-Epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-
6-methyl-cyclohexylmethyl) adipate and the like can be mentioned. Of these, a reaction product of a polyhydric alcohol and epichlorohydrin, that is, a polyglycidyl ether compound of a polyhydric alcohol is preferable because it exhibits excellent performance. It is preferable that such a polyepoxide compound is usually used as an emulsion.

An emulsified liquid or solution can be prepared, for example, by adding such a polyepoxide compound as it is or dissolving it in a small amount of solvent as necessary, and adding a known emulsifier, for example, sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol ethylene oxide addition. It is emulsified or dissolved using a substance or the like.

The amount of the polyepoxide compound used is not particularly limited, but in order to impart antistatic performance and water absorption performance to the polyester fiber, it is sufficient to use it in the range of 0.1 to 10% by weight based on the polyester fiber. . When the amount used exceeds 10% by weight, the antistatic performance and water absorption performance of the polyester fiber are adversely affected, but on the other hand, a problem that the texture becomes too hard occurs, which is not preferable.

Further, it is desirable that the treatment temperature of the polyepoxide compound is within the range of 80 to 130 ° C, preferably within the range of 95 to 120 ° C.

When the treatment temperature is 80 ° C or lower, the antistatic and sweat absorbing durability is insufficient, and when the treatment temperature exceeds 135 ° C, the washing durability of these performances is further improved. There is a case where it does not occur, but rather decreases, so it is desirable to use within the above range.

Further, it is desirable that the processing time is 1 minute or longer, preferably 5 minutes or longer.

As long as such conditions are satisfied, the treatment method may be a high-temperature continuous treatment, or a so-called batch-type treatment in which fibers are introduced at room temperature and then heated to a predetermined temperature.

Then, polyoxyalkylene units diamine containing used in the present invention, the general formula _{H 2 N- (CH 2) n} -O (CH 2 CH 2 O) m - (CH 2) n NH 2 (CH ₂ CHO) _m (CH ₂ ) _n NH ₂ (1 is preferably 1 to 150, m is 1 to 200, and n is preferably an integer of 1 to 4) are preferable, and polyoxyalkylenes are preferable. As a unit, a unit having a molecular weight of 44 to 40,000, preferably an average molecular weight of 400 to 20,000 is preferable in terms of antistatic and sweat absorbing durability.

In the treatment method using the polyoxyalkylene unit-containing diamine, the polyester fiber treated with the treatment liquid containing the polyepoxide compound as described above is immersed in the treatment liquid containing the diamine, and then heat treated.

As the heat treatment, a dry heat treatment at a temperature of 110 to 190 ° C. for 1 second to 30 minutes, or a steam heat treatment using saturated steam or heated steam at a temperature of 100 to 190 ° C. is applied.

The amount of the diamine used is 0.5 to 10% by weight, preferably 1 to 5% by weight.

If the amount used is 0.5% or less, the antistatic water absorption performance is insufficient, and if it is 10% or more, the texture becomes hard and discoloration due to processing occurs, which is not preferable.

If the alkali treatment is performed in advance in an alkaline liquid before the heat dipping treatment with the treatment liquid containing the polyepoxide compound, the modifying effect is further improved. As the alkali, alkali metals having an effect of hydrolyzing polyester fiber are preferable, and caustic soda is particularly preferable. Regarding the degree of alkali treatment, if the amount of copolymerized polyester is reduced, the modifying effect is improved, but if the amount is reduced too much, problems such as insufficient strength when woven or knitted may occur. Therefore, it is preferably 35% or less, more preferably 30% or less. The alkali treatment may be carried out by various methods such as a method of heating and dipping in an alkaline liquid, a method of impregnating an alkaline liquid and heat-treating after squeezing, a method of impregnating an alkaline liquid and leaving it for a certain period of time. Yes, but either method is fine.

[Operation of the Invention] The reason why the copolyester fiber thus obtained exhibits superior antistatic property, sweat absorption property, and antifouling property as compared with the conventional materials is not fully understood. However, it is presumed that it is due to the following mechanism.

It is well known that polyester is lipophilic.
Copolymerizing a hydrophilic polyoxyalkylene glycol and a lipophilic polyester in a block, that is, a polyoxyalkylene in which one end has a group having active hydrogen and the other end is blocked with a group having no active hydrogen. When glycol (PAG) and polyester (PE) are copolymerized, PAG-PE-PAG or PAG-PE molecules are present in a large amount of PE. It is shown in JP-A-63-35824 and 63-35825 that the PAG molecule is likely to localize in a polyoxyalkylene glycol-rich region and two polyester-rich regions in the polymer because PAG molecules are easily assembled in PAG.
As shown in the issue.

A fiber using polyethylene terephthalate (PET), which is a representative polymer in the present invention, that is, PEG (polyoxyethylene glycol) having active hydrogen only at one end, has a high crystallinity and a crystal size. Is also large, and the birefringence Δn indicating the degree of orientation and the specific gravity are rather small values.
And a considerably disordered amorphous part. The structure can be more sufficiently obtained by applying a strong heat treatment for promoting the crystal of the polyester component. As described above, by using the modified polyester and sufficiently crystallizing, phase separation of the polymer in the polyester crystal-polyoxyalkylene glycol amorphous and the fiber, that is, a micelle structure can be efficiently formed. Therefore, when the oily stain component tries to penetrate into the polyester fiber, the hydrophilic polyoxyalkylene glycol component existing in the amorphous portion prevents the oily stain component from entering the polyester fiber, and the mechanism of easily separating from the fiber by washing with water works. It is estimated to be.

Since the hydrophilic component has such a fiber structure, the hydrophilic component easily adheres to the fiber, and when it infiltrates into the amorphous part or the crystalline micelle gap, it becomes difficult to be separated due to the mutual affinity. This property is effectively utilized in the modification processing method in which the copolyester fiber is subjected to a heat dipping treatment with a polyepoxide compound and then treated with a treatment liquid containing a diamine having a polyoxyalkylene unit.

The copolymerized polyester fiber has a hydrophilic polyoxyalkylene glycol component in its amorphous portion,
It does not reach the antistatic and sweat absorbing properties. By this processing, in addition to the excellent antifouling property of the copolyester fiber, it becomes possible to exhibit high anti-static property and sweat absorption property with high durability.

This is because, as described above, the copolyester fiber has a hydrophilic polyoxyalkylene glycol component in its amorphous portion, so that the polyepoxide compound easily adheres to the copolyester fiber and further It also penetrates into the crystal parts and the crystalline micelle gaps and adheres or sticks to each other with mutual affinity in a compatible manner, and the epoxy group of this polyepoxide compound reacts with a diamine having a polyoxyalkylene unit to be added next, resulting in A hydrophilic structure is formed on the surface of the polymerized polyester fiber and in the amorphous part or the crystal micelle gap. This is different from conventional surface treatment such as attaching a hydrophilic polymer compound to the surface of the fiber or polymerizing a polymerizable monomer having a hydrophilic group on the surface of the fiber to form a film. This is the reason why it shows a high degree of durability against repeated use.

Further, another characteristic showing the durability effect is the behavior to heat. Conventionally, in order to show the modification effect of the modification method for antistatic property, sweat absorption property and antifouling property, in the washing treatment,
Alternatively, the durability to the dry cleaning process has been mainly studied, and there is not much that aims at improving the durability in the washing process to which the heat treatment is added. The above-described surface treatment technology for polyester fibers using a hydrophilic substance rapidly loses its effect when heat-treated. The reason for this is still unknown, but with the originally hydrophobic polyester fiber,
It is presumed that the hydrophilic structure adhered or coated on the surface may undergo phase separation on the fiber surface due to the heat treatment and may be easily dropped off by the washing treatment performed after the heat treatment.

Since the copolyester fiber has a hydrophilic polyoxyalkylene glycol component in its amorphous portion,
Even if the hydrophilic structure is subjected to heat treatment, the hydrophilic structure is less likely to undergo phase separation with the copolyester fiber, and as in the case of the conventional hydrophobic polyester fiber, the hydrophilic structure is formed by the washing treatment performed after the heat treatment. There are few phenomena that it is easy to fall off. In addition, the polyepoxide compound is considered to have penetrated not only the surface of the copolyester fiber but also the amorphous part and the crystalline micelle gap, which will be described later,
The hydrophilic structure formed by reacting the epoxy group of the polyepoxide compound with a diamine having a polyoxyalkylene unit, which is subsequently applied, is difficult to phase separate from the copolyester fiber even after heat treatment, and even in the subsequent washing. Dropouts are unlikely to occur.

On the other hand, it is also a feature of the present invention that the sweat absorption performance is further improved by performing the alkali treatment in advance, and the reason for this is considered as follows. Conventionally, when a polyester fiber is treated with an alkali metal such as caustic soda, the polyester fiber is gradually hydrolyzed and its weight is reduced. This is widely known as a weight reduction process for improving the feel of the polyester fiber. As described above, when the polyester fiber is treated with alkali, it is hydrolyzed. At that time, a hydroxyl group or a carboxyl group is formed in the hydrolyzed part, and the polyester fiber surface often shows hydrophilicity. Are known.

From this, naturally, it is expected that the alkali-treated polyester fiber will have improved antifouling property against oily stains, sweat absorption property, and further antistatic property. In fact, although there is such an improvement trend, the level is practically ineffective.

Alkali treatment is almost always performed as a texture-improving process of polyester fiber as described above, for example, in applications where a supple texture for women is required. For the purpose of improving antistatic property, sweat absorption property, and antifouling property, a hydrophilic polymer compound is attached to the surface of the fiber, or a polymerizable monomer having a hydrophilic group is polymerized on the surface of the fiber to form a film. Many surface treatments such as formation have been attempted. In this case, these surface treatments were not able to exert a durability effect particularly in antistatic property and sweat absorption property as compared with the polyester fiber which was subjected to the alkali treatment but not subjected to the alkali treatment.

The reason for this is not clear yet, but the hydrophilic polymer compound used for the purpose of improving the antistatic property, the sweat absorption property and the antifouling property of the polyester fiber and the monomer having the hydrophilic group are present on the polyester fiber surface. The hydrophilic structure formed by the polymerization is compatible with the relatively low crystallinity or amorphous portion of the polyester fiber which is easily hydrolyzed by alkali, and therefore, the polyester fiber not treated with alkali is Although it exhibits excellent durability, it is presumed that the durability may be lost due to the lack of compatible parts in the alkali-treated polyester fiber.

The present invention has sufficient antistatic property even if alkali treatment is performed.
The purpose of the present invention is to provide a polyester fiber capable of maintaining sweat absorption property and antifouling property. Originally, the polyester fiber is modified by a polyepoxide compound and a diamine having a polyoxyalkylene unit proposed in the present invention. The anti-static, sweat absorbing and antifouling durability against washing is equal to or slightly superior to the case without alkali treatment, even if alkali treatment is performed. Disappears. By subjecting the copolymerized polyester referred to in the present invention to a modifying treatment with a polyepoxide compound and a diamine having a polyoxyalkylene unit, the effect on heat treatment does not decrease,
On the contrary, the sweat absorbing property and the antifouling property against oily stains have an extremely excellent effect that they come to exhibit a better level than those not subjected to the alkali treatment.

This means that the hydrophilic structure composed of the polyepoxide compound and the diamine having a polyoxyalkylene unit is the conventional hydrophilic polymer compound described above for the polyester fiber, or the monomer having the hydrophilic group is the polyester fiber. It seems that the existing state is different from that of the hydrophilic structure formed by polymerization on the surface. Probably there is some interaction with the polyester fiber, but unlike the conventional hydrophilic polymer compound or the hydrophilic structure formed by the monomer having the hydrophilic group is present on the surface or covers the surface. , The polyepoxide compound in the heat dipping treatment in the treatment liquid containing the polyepoxide compound as the pretreatment, not only the polyester fiber surface,
It has penetrated to some extent into the amorphous parts that are not affected even by the alkali treatment, which is why not only the washing resistance but also the heat resistance is particularly high for the copolyester of the present invention. It is thought that they can also impart excellent antistatic properties, sweat absorption properties, and antifouling properties.

[Examples] The present invention will be further described with reference to Examples. Parts and% in the examples mean parts by weight and% by weight, respectively.

In the examples, the methods for obtaining stain resistance, antistatic property, sweat absorption property, and washing and heat treatment were performed under the following conditions.

(1) Contamination (i) Contamination treatment Put 300 cc of the following composition into the pot of a color pet dyeing tester (manufactured by Nippon Dyeing Machine), and immerse a 10 cm x 13 cm sample sandwiched in a holder into the pot. The mixture was stirred at 100 ° C for 100 minutes.

Contaminated liquid composition Artificial dirt liquid ^* 1% Sodium alkylbenzene sulfonate 0.02% Sodium sulfate 0.03% Sodium tripolyphosphate 0.02% ^* Motor oil 99.335% by weight (Dia Queen Motor Oil M-2 manufactured by Mitsubishi Motors) with the following mixture as artificial dirt liquid Heavy oil B 0.634% by weight Carbon black 0.031% by weight After treatment, the sample was lightly washed with water, and then the sample was sandwiched between papers to remove excess contaminated liquid. This contamination treatment, washing with water, and treatment for removing excess contamination liquid were repeated 4 times.

Next, half of the contaminated sample was washed for 10 minutes in a warm water of 40 ° C. containing 2 g / mL of Marcel soap under a weak condition of a home washing machine. Then, the contamination degree was determined by the following method.

(Ii) Determining contamination and removability Macbeth MS-2020 (Instrumental Color System Limite
(manufactured by d) was used to determine E * of the CIE colorimeter by a conventional method, and the stain resistance and removability were calculated as follows.

ΔE * A = E * _1- E * ₂ ΔE * B = E * _1- E * ₃ ΔE * A: Contamination ΔE * B: Removability E * ₁ : E * of sample before contamination treatment E * ₂ : E * of the sample after the contamination treatment E * ₃ : E * of the sample after the washing treatment (2) Antistatic property Friction electrification voltage (V) with a Kyoto University Kaken rotary static star (manufactured by Koa Shokai) ) Is measured.

Temperature 40% RH, Temperature 20 ℃ Rotation speed 400rpm, Load 500g Applicable cotton broad (3) Sweat absorbency According to JIS L-1096A method (dripping method).

(4) Washing treatment The following is the washing treatment for checking the durability against the antistatic, sweat absorbing and antifouling washing treatment. Using a household washing machine (National NA-680L), new enzyme Zab (made by Kao) 2g /
Put 30 solution (bath ratio 1:30), put a test cloth,
Wash at 40 ° C for 10 minutes with automatic swirling water flow. Then, it was dehydrated, washed with hot water of 40 ° C. (bath ratio 1:30) for 5 minutes in hot water and dehydrated, and then washed with overflow water for 10 minutes, dehydrated and dried. In the durability test, the above washing was performed once and this was repeated as many times as necessary. After this, it was air dried.

(5) Heat treatment In a hot-air dryer, treatment was carried out at a temperature of 170 ° C for 1 minute, and this was treated once. Therefore, the repetition of washing to heat treatment means that the above washing was performed once and then the heat treatment was performed once, and this was set as washing to heat treatment once, and the combination treatment was repeated as many times as necessary.

Example 1 100 parts of dimethyl terephthalate, 60 ethylene glycol
Parts, calcium acetate monohydrate 0.06 parts (0.066 mol% with respect to dimethyl terephthalate) and cobalt acetate tetrahydrate 0.009 parts (0.007 with respect to dimethyl terephthalate) as a color matching agent.
(Mol%) was charged into a transesterification can, and the transesterification reaction was performed while distilling out the methanol produced by raising the temperature from 140 ° C. to 220 ° C. over 4 hours in a nitrogen gas atmosphere to the outside of the system.
After the completion of the transesterification reaction, 0.058 part of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) was added as a stabilizer. Then, 10 minutes later, 0.04 part of antimony trioxide (0.027 mol% with respect to dimethyl terephthalate) was added, and at the same time, while excess ethylene glycol was being expelled, 24
After raising the temperature to 0 ° C., it was transferred to a polymerization vessel. After adding 4 parts of polyoxyethylene glycol monomethyl ether having an average molecular weight of 2,000 to the polymerization can, it is 760 mmHg to 1 mmHg over 1 hour.
The pressure was reduced to 240 ° C. to 280 ° C. over 1 hour and 30 minutes. Further 2 up to a polymerization temperature of 280 ° C under reduced pressure of 1 mmHg or less
Irganox 10 as antioxidant at the time of polymerization
0.4 part of 10 (manufactured by Ciba-Geigy) was added under vacuum, and the polymerization was continued for another 30 minutes. The obtained polymer was made into chips according to a conventional method.

After drying the obtained chips by a conventional method, melt spinning at 285 ° C using a spinneret in which 48 circular spinning holes with a hole diameter of 0.3 mm are formed, and then the elongation of the finally obtained drawn yarn is 30%. Was drawn and heat-treated with a heating roller of 84 ° C. and a slit heater of 180 ° C. to obtain a drawn yarn of 150 denier / 48 filaments. The obtained polyester filament yarn was false twisted, woven into a plain woven fabric, relaxed and scoured, and then heat treated at 190 ° C. for 1 minute. Then, using a jet dyeing machine, immerse in the treatment liquid adjusted to the following formulation (A) (bath ratio 1:20), raise the temperature from room temperature (heating rate 2 ° C / min), and temperature
It was treated at 100 ° C for 30 minutes, washed with water and dried. Next, the woven fabric was impregnated with a padding bath prepared by the following formulation (B), squeezed with a squeezing ratio of 100%, dried at a temperature of 120 ° C. for 1 minute, and then heat-treated at a temperature of 160 ° C. for 1 minute.

<Prescription (A)> (Brand name, Denacol EX-611, manufactured by Nagase Kasei Co., Ltd.) The sorbitol polyglycidyl ether (Denacol EX-611) is previously emulsified with an emulsifier (Brand name, Neocor SW, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). (Use ratio Denacol EX-611 / Neocor SW = 5/4) was used.

<Formulation (B)> polyoxyethylene diamine _{5% soln H 2 N · CH} 2 CH 2 CH 2 -. (OCH 2 CH 2) n -OCH 2 CH 2 CH 2 · NH 2 ( average molecular weight about 8,000) Example 2 After relaxing and scouring the fabric obtained in Example 1, it is used for industrial purposes.
Alkaline treatment was carried out in a boiled bath of NaOH (flake-like) 35 g / to reduce the amount by 30% and wash thoroughly with water. Then, the same processing as in Example 1 was performed.

Comparative Example 1 A woven fabric similar to that of Example 1 was woven using 150 denier / 48 filaments of polyester filament false twisted yarn made of polyethylene terephthalate, and then processed under the same conditions as in Example 1.

Comparative Example 2 A polyester filament false twisted yarn 150 denier / 48 filaments made of polyethylene terephthalate was used to weave a fabric similar to that of Example 1, and then relaxed,
After scouring, alkali treatment was carried out in a bath of industrial NaOH (flake) 35 g / foil, the amount was reduced by 30%, and the product was thoroughly washed with water. Then, processing was performed under the same conditions as in Example 1.

Comparative Example 3 After relaxing and refining the woven fabric obtained in Example 1, 5 parts of the processing agent (dispersion liquid of about 10% of the polymer) obtained below was used,
Immerse in a treatment solution consisting of 95 parts of water, squeeze with a squeezing rate of 100%, dry at 80 ° C for 5 minutes, then heat treat at 70 ° C for 30 seconds,
It was washed with water and dried.

Dimethyl terephthalate and dimethyl isophthalate were mixed in a molar ratio of 80:20 at a total of 150 parts, ethylene glycol monophenyl ether (average molecular weight 3100) at 340 parts (molar ratio to all acid components 1/7), and a small amount of catalyst was added. , At normal pressure 1
The reaction was carried out at 75 to 235 ° C. for 180 minutes to distill off almost the theoretical amount of methanol to complete the transesterification reaction. Then, after adding a small amount of a solution of phosphoric acid in ethylene glycol to this, under reduced pressure of 5 mmHg at 230 to 260 ° C., 2
The reaction was carried out for 0 minutes and then at 0.05 to 0.1 mmHg at 275 ° C. for 40 minutes, and the obtained polymer was immediately put into water at room temperature with stirring to give an aqueous dispersion of about 10%.

Comparative Example 4 Polyester filament made of polyethylene terephthalate The false-twisted yarn 150 denier / 48 filament was used to weave the same fabric as in Example 1, and then relaxed,
After scouring, it was treated with alkali in a bath of industrial NaOH (flakes) 35 g / boil to reduce the amount by 30% and washed thoroughly with water. Then, processing was performed under the same conditions as in Comparative Example 3.

Table 1 shows the change in performance of each of the fabrics obtained in Examples and Comparative Examples due to antistatic property, sweat absorption property, antifouling property, repeated washing and repeated washing to heat treatment.

In Example 1, the antistatic property, the sweat absorption property, and the antifouling property were all at a good level, and the durability effect was obtained even after repeated washing and washing to heat treatment, and Comparative Example 1 processed into a normal polyester fiber had any performance. In addition, it can be seen that the durability effect is extremely excellent as compared with the case where the washing-heat treatment is not durable.

Further, Comparative Example 3 is a well-known process as a water absorption / fouling treatment, but it does not have a well-balanced durability level in terms of anti-static property, sweat absorption, and anti-fouling property as described in the present invention. It cannot withstand repeated washing and heat treatment.

On the other hand, in Example 2, the copolymerized polyester which has been subjected to the alkali treatment was subjected to the processing of the present invention, but Comparative Example 4 in which typical processing as ordinary water absorption / fouling processing was performed.
When is subjected to an alkaline treatment, sweat absorption and the like do not show a durable effect, whereas it is found that the durability is extremely good,
It can also be seen that the alkali treatment results in higher levels of sweat absorption and antifouling properties than in Example 1 in which the alkali treatment is not performed.

In Comparative Example 2, ordinary polyester fiber that has been subjected to alkali treatment is processed with the polyepoxide compound of the present invention and a diamine having a polyoxyalkylene unit. It seems to be due to the alkali treatment, but it shows some improvement in antifouling property as compared with Comparative Example 1 of non-alkali treatment, but does not withstand antistatic and sweat absorbing co-washing to heat treatment. .

EFFECTS OF THE INVENTION The modified polyester fiber according to the present invention can maintain excellent antistatic property, sweat absorption property and antifouling property even after repeated washing and heat treatment such as ironing and pressing.
It is a suitable material for applications where heat treatment is frequently performed and antistatic properties, sweat absorption properties, and antifouling properties are required.

In recent years, it is used in uniforms or uniforms worn in various workplaces, work clothing worn for improvement work, white clothing worn in workplaces related to medical care or food, hospitals, hotels, etc. Bedding, sleeping bags, etc. such as sheets, duvet covers, or yukata
Furthermore, table cloths used in restaurants and various banquets and gathering venues are called linens, and are often rented to places where they are used, and the weight is increasing year by year. These product fields are also called linen supply fields. In this field, products are required to be clean and comfortable to use or wear from the side of using the product, while renting the product after use It is to keep the product easy to clean and to prevent the product from deteriorating even after repeated washing, ironing, pressing, etc., because the dirt does not reattach during washing. The content of comfort varies depending on the application and place of use, but it does not absorb perspiration (sweat absorbency) while wearing it or does not generate static electricity (antistatic property)
That is a typical thing. Therefore, these products in the field of linen supply are easy to remove stains, do not reattach stains during washing, that is, have anti-staining properties, have sweat absorption, antistatic contracting, and these performances make washing repeatable. However, it is desirable that the initial performance be maintained even after repeated heat treatment such as ironing and pressing after washing.

The polyester modified according to the present invention has antifouling properties, sweat absorption properties, antistatic properties, and excellent wash resistance and heat resistance, and is suitable for products in the linen supply field.

Furthermore, if necessary, natural fibers such as cotton and wool, recycled fibers such as rayon and acetate, and synthetic fibers other than those mentioned in the present invention may be mixed, woven or knitted.

Claims (2)

[Claims] 1. A polyester represented by the general formula [1] R ₁ O (R ₂ O _n ... [1] (wherein R ₁ has no active hydrogen) at least at a part of the terminal of a polyester having ethylene terephthalate as a main constituent unit. Monovalent organic group, R ₂ is an alkylene group, and n is an integer of 20 to 140) A treatment liquid containing a fiber made of a polyester copolymerized with 1 to 8% by weight of a polyalkylene glycol component and containing a polyepoxide compound. After heat-immersion treatment with, the polyester fiber is treated with polyoxyalkylene (wherein the alkylene group has 2 carbon atoms).
To 4) A method for modifying polyester fiber, which comprises impregnating a treatment liquid containing a diamine having a unit and then subjecting it to heat treatment. 2. The method for modifying polyester fiber according to claim 1, wherein the treatment is carried out in an alkaline liquid before the heat dipping treatment with the treatment liquid containing the polyepoxide compound.