JPH111823A - Polyester fiber and dyed product of its mixed fiber fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyester fibers that can be thinned with alkali at a temperature of <=60 deg.C, can be dyed with cationic dyes at a temperature of <=85 deg.C and are excellent in various kinds of fastness, mechanical characteristics and spinning properties and provide dyed products of polyester fiber-mixed fabrics that contains these polyester fibers and cellulosic fibers and are excellent in low-temperature alkali-thinning properties, low-temperature dyeability, brightness and fastness. SOLUTION: This polyester fibers are made of a polyethylene terephthalate copolymer containing a polyethylene glycol with an average molecular weight of 500-4,000, adipic acid, a salt of sulfo-isophthalic salt where individual comonomers satisfy the copolymerization proportions shown in the formulas: 1<=X<=3, 2.5<=Z/X<=3.5 and Y=Z (X is the molar % of the sulfoisophthalic acid in the whole carboxylic acid components; Y is the wt.% of adipic acid based on the weight of the whole polymer and Z is the wt.% of the polyethylene glycol based on the weight of the whole polymer) and the peak temperature of the tangential loss is 80-95 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polyester fiber which can reduce an alkali at a low temperature of 60.degree. C. and can be dyed with a cationic dye at a temperature of 85.degree. C. or less, and has excellent fastness, mechanical properties and spinnability. The present invention relates to a mixed fabric dyed product having a unique soft and soft texture excellent in low-temperature alkali weight loss, sharpness, and fastness of the fiber and regenerated cellulose fiber.

[0002]

2. Description of the Related Art In recent years, the performance required for clothing fibers has been diversified, and it has become difficult to satisfy the requirements with only a single fiber. Under such circumstances, expectations for composite materials have been greatly increased. In the case of polyester fibers as well, composites with regenerated cellulose fibers have been performed. However, in the production of these mixed fabrics, various problems occur because the physical properties thereof differ greatly from those of the regenerated cellulose fibers. In particular, the problem of the occurrence of threads and the deterioration of physical properties of the regenerated cellulose fiber when the alkali is reduced, and the problem of the same color in dyeing are extremely serious.

First, consider alkali weight loss.
It is known that by dissolving and reducing the surface of the polyester fiber of the mixed fabric composed of the polyester fiber and the regenerated cellulose fiber in an aqueous alkaline solution (reducing the alkali), a fabric having a very soft and soft unique texture can be obtained. . The alkali weight loss of a fabric composed of only polyester fibers is usually treated in an aqueous sodium hydroxide solution of about 5% by weight at 90 to 98 ° C., but under the same conditions, the mixed weight of polyester fibers and regenerated cellulose fibers is reduced. Then, since the regenerated cellulose fiber undergoes hydrolysis, a remarkable decrease in strength occurs. In particular, when copper ammonia rayon is used as the regenerated cellulose fiber, if the treatment is carried out under ordinary alkali weight loss conditions, in addition to a decrease in strength, threading occurs, and a whitening phenomenon such as generation of white streaks in the fabric occurs. Therefore, in conventional mixed fabrics composed of polyester fibers and regenerated cellulose fibers, although an improvement in texture can be achieved by reducing the alkali, reduction of the alkali is often not generally performed in consideration of a decrease in strength and whitening of the fabric.

According to the study of the present inventors, in a mixed fabric comprising a polyester fiber and a regenerated cellulose fiber,
It has been found that if the polyester fiber can reduce the alkali at 60 ° C. or less, the decrease in strength and whitening of the regenerated cellulose fiber can be suppressed. However, the existing polyester fiber improves the texture of the mixed fabric at a temperature of 60 ° C. or less. Cannot achieve only the alkali weight loss rate.

Next, the dyeability will be considered. When a cationic dyeable polyester fiber is used as the polyester fiber, different from the case where a disperse dye is used, characteristics such as good fastness and sharpness can be imparted. In addition, when a reactive dye is used in dyeing the regenerated cellulose fiber, the fastness can be improved. In the case of dyeing a mixed fabric composed of a cationic dyeable polyester fiber and a regenerated cellulose fiber, a method using a cationic dye and a reactive dye can be considered for the purpose of improving fastness and sharpness. In this case, since the dyes used for the cationic dyeable polyester fiber and the regenerated cellulose fiber are different, a two-stage two-bath dyeing method using separate dyeing baths is mainly used.

[0006] The dyeing temperature of existing polyester fibers is 11
It is 0 ° C. or higher, usually around 130 ° C. 110-130
When the mixed fabric is subjected to one-bath dyeing at a temperature of ° C., the reactive dye is thermally decomposed and does not have the same color as the polyester fiber. According to the study of the present inventors, the thermal decomposition of the reactive dye was 8%.
It has been confirmed that some of the reactive dyes proceed at once at a temperature of 5 ° C. or more and the decomposition rate reaches 10% at 90 ° C. So, first
A two-stage two-bath dyeing method in which polyester fibers are dyed at 10 to 130 ° C., and then the temperature is lowered and a reactive dye is added to dye the regenerated cellulose fibers, is generally used. However, the two-stage two-bath dyeing method is costly because the dyeing time is long.

On the other hand, in dyeing a regenerated cellulose fiber-mixed fabric using an existing polyester fiber, when the regenerated cellulose fiber is dyed at 85 ° C. at which thermal decomposition of the reactive dye can be suppressed and the regenerated cellulose fiber exhibits a sufficient dark color. Can not dye polyester fiber at all. If a one-step one-bath method in which two dyes are added to one dyeing bath and dyeing is performed at a low temperature of 85 ° C. or less can be performed, it is considered to be an effective method from the viewpoint of reduction in dyeing cost and operability.

[0008] As described above, the regenerated cellulose fiber-mixed fabric using the existing polyester fiber is difficult to reduce the alkali at a high temperature due to the decrease in the strength of the regenerated cellulose fiber and the whitening due to the generation of threads, and at the same time, it is difficult to use each fiber. It was difficult to perform one-step, one-bath dyeing due to the large difference in the dyeing temperatures. If the cationic dyeable polyester fiber which can be reduced in alkali at 60 ° C and dyeable at 85 ° C can be obtained, the problems described above can be improved, but such a polyester fiber has not been known.

With respect to the known technique for improving the alkali weight loss, it is known that the alkali weight loss temperature can be lowered by increasing the copolymerization ratio of sulfoisophthalate. The present inventors have investigated that sulfoisophthalate is added at 4 ° C. or lower to enable alkali weight loss at 60 ° C. or lower.
It was necessary to copolymerize at least mol%. However,
At this copolymerization ratio, there is a problem that the strength of the polyester fiber is remarkably reduced, and furthermore, the clogging of foreign matter into the spinneret is remarkably severe, resulting in poor spinning stability. In addition, in the case of a polymer obtained by copolymerizing both sulfoisophthalate and polyethylene glycol and a polymer obtained by copolymerizing both sulfoisophthalate and adipic acid, considering a copolymerization ratio having a sufficient thermal stability, only up to 80 ° C. When the temperature could not be lowered, and the mixed fabric with cellulose was reduced in alkali under these conditions, threading occurred and whitening of the fabric was observed.

As a technique for improving the dyeability of the cationic dyeable polyester fiber, a method of modifying a raw material polymer has been studied. First, as a method for enabling cationic dyeability of polyester fiber, a method of copolymerizing a monomer having a metal sulfonate group such as 5-sodium sulfoisophthalic acid as a dyeing seat (Japanese Patent Publication No.
No. -10497) is known. However, in this method, dyeing requires 120 ° C. to 130 ° C., and 85 ° C.
The following cannot be dyed. Also, this fiber has low strength,
As a result, the fabric has a drawback of low bursting strength and cannot be used substantially for the purpose of the present invention. Further, since the polyester obtained by copolymerizing the metal sulfonate contains a large amount of infusible material modified with the metal sulfonate, if the spinning time is long, the spinning pack is clogged and spinning becomes impossible.

As a method for improving the dyeability with a cationic dye, there is also known a method in which a polyester obtained by copolymerizing a metal sulfonate is spun at a high speed to facilitate dyeing (JP-B-60-10126, JP-A-8-269820). No.). However, these fibers also have problems such as low strength and poor spinning stability. In addition, polyester fibers prepared by copolymerizing 5-sodium sulfoisophthalic acid and adipic acid in order to enhance the dyeing properties (Japanese Patent Application Laid-Open (JP-A) Nos. 51-133529 and 55-15832).
No. 5, JP-A-61-34022, JP-A-61-34022
JP-A-239015) Further, polyester fibers prepared by copolymerizing 5-sodium sulfoisophthalic acid and polyethylene glycol by a conventional method (Japanese Patent Laid-Open No. 59-88915).
JP, JP-A-63-152403, JP-A-4-
No. 18116) is known. However, even such a polyester fiber has insufficient dyeing properties at 85 ° C. or lower, and the strength is reduced and the pack pressure is significantly increased, so that it cannot be used for the purpose of the present invention.

[0012]

SUMMARY OF THE INVENTION The object of the present invention is to achieve a temperature of 60.degree.
Alkali fibers can be reduced at a low temperature, and can be dyed with a cationic dye at a temperature of 85 ° C. or lower, and a polyester fiber excellent in fastness, mechanical properties, and spinnability; An object of the present invention is to provide a mixed fabric dyed material having a unique soft and soft texture excellent in weight loss, low-temperature dyeability, clarity, and fastness.

[0013]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that to solve the above-mentioned problems, polyethylene glycol, adipic acid and sulfoisophthalate having a very limited copolymerization ratio are used. It has been found that a fiber using copolymerized polyethylene terephthalate can solve the above-mentioned problems, and as a result of further studies, the present invention has been achieved.

That is, the first aspect of the present invention is that the average molecular weight is 5
A copolymerized polyethylene terephthalate of polyethylene glycol, adipic acid, and sulfoisophthalate having a peak tangent of 80 to 4000 which satisfies the copolymerization ratio represented by the following formula.
A polyester fiber characterized by having a temperature of 95 ° C., and a second aspect of the present invention is a copolymerized polyethylene terephthalate of polyethylene glycol having an average molecular weight of 500 to 4000, adipic acid, and 5-sodium sulfoisophthalic acid. A mixed fabric dyed product of a polyester fiber and a regenerated cellulose fiber, wherein the comonomer satisfies the copolymerization ratio represented by the following formula and the peak temperature of the loss tangent is 80 to 95 ° C.

1 ≦ X ≦ 3 2.5 ≦ Z / X ≦ 3.5 Y = Z (where X indicates mol% of sulfoisophthalate in all carboxylic acid components, and Y indicates all polymer The weight percentage of adipic acid in the weight is shown, and Z is the weight percentage of polyethylene glycol in the total polymer weight.) Hereinafter, the present invention will be described in detail.

First, in the present invention, in order to reduce the alkali at 60 ° C. or lower and obtain sufficient dyeability, fastness, mechanical properties and spinnability at 85 ° C. or lower, polyethylene glycol, adipic acid and Sulfoisophthalate 3
Two copolymer components are essential. In the case of polyethylene terephthalate in which the above comonomers are used alone or in which two kinds thereof are copolymerized, the alkali weight loss at 60 ° C. or lower and the
Both dyeing below 5 ° C cannot be achieved.

Polyethylene glycol used as a copolymer component is a copolymer component which is extremely effective for enhancing dyeing properties and maintaining high strength. When the average molecular weight is less than 500, since polyethylene glycol having a considerably low molecular weight is contained, it is distilled off under reduced pressure during polymerization under high vacuum, and the amount of polyethylene glycol contained in the obtained polymer is not constant. Therefore, the strength and elongation characteristics, dyeing properties, heat characteristics, etc. of the raw yarn are not uniform, and the characteristics of the product vary. On the other hand, when the average molecular weight exceeds 4,000, the amount of high molecular weight polyethylene glycol not copolymerized in the polymer increases, so that the dyeing properties, dry cleaning fastness, and light fastness are reduced.

The adipic acid used as a copolymer component causes an appropriate disorder of the amorphous structure of the fiber, thereby contributing to an improvement in dyeability. It also contributes to improving spinning stability. The sulfoisophthalate used as the copolymer component is a copolymer component that is extremely effective for enhancing cationic dyeability and alkali weight loss since the sulfonate group functions as a dyeing site for the cationic dye. As the sulfoisophthalate, 5-
Sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-calcium sulfoisophthalic acid, 5-
Lithium sulfoisophthalic acid, tetrabutylphosphonium 5-sulfoisophthalate, tetraethylphosphonium 5-sulfoisophthalate, tetrapentylphosphonium 5-sulfoisophthalate, tetrabenzylphosphonium 5-sulfoisophthalate, and the like. 5-sodium sulfoisophthalic acid and tetrabutyl phosphonium 5-sulfoisophthalate are particularly preferred from the viewpoint of goodness and low cost.

In the present invention, the term "excellent in alkali weight loss" refers to a weight loss rate of 15 to 15% when the alkali weight loss is 30 minutes using a 5% by weight aqueous sodium hydroxide solution at 60.degree.
20% achieved. Detailed experimental conditions will be described in embodiments of the present invention. In the case of a normal polyester fiber, a silky supple and soft texture can be obtained by reducing the amount of the polyester fiber by 15 to 40% at the above-mentioned alkali concentration at 90 to 100 ° C. for 30 minutes. Therefore, when the alkali weight loss at 60 ° C., the same alkali weight loss rate as ordinary polyester fibers, that is, 15 to 15,
If it is 40%, preferably 15 to 30%, it can be said that the alkali weight loss is excellent.

Unless a copolymerization ratio with good balance between alkali weight loss, dyeability, fastness and mechanical properties and good polymerizability and spinnability is selected, there is no practicality. In order to enhance the alkali weight loss and cationic dyeability, it is preferable to copolymerize the sulfoisophthalate as much as possible. However, when the amount of the sulfoisophthalate is large, the mechanical properties are significantly reduced, and the spinnability is also reduced. Then, instead of increasing the amount of sulfoisophthalate, copolymerization of an appropriate amount of polyethylene glycol and adipic acid was able to suppress a decrease in mechanical properties and spinnability. That is, in order to ensure alkali weight loss at 60 ° C. or less, sufficient dyeability at 85 ° C. or less using a cationic dye, fastness, mechanical properties, and spinnability, polyethylene glycol, adipic acid, and sulfoisophthalate are used. The copolymerization ratio needs to satisfy the following three equations.

1 ≦ X ≦ 3 2.5 ≦ Z / X ≦ 3.5 Y = Z (where X indicates mol% of sulfoisophthalate in all carboxylic acid components, and Y indicates all polymer The weight% of adipic acid in the weight and the weight percentage of polyethylene glycol in the weight of the whole polymer are shown.) When X is less than 1, the alkali weight loss at 60 ° C. or less becomes insufficient, and the cationic dyestuff becomes insufficient. It is difficult to obtain a sufficiently dark color because the number of metal sulfonate groups as the dyeing seat is small. When X is larger than 3, the strength decreases and the pack pressure rises remarkably, and the alkali reduction rate becomes extremely high, so that it is difficult to adjust the alkali reduction rate. Alkali weight loss, adjustment of alkali weight loss rate, dyeability,
The preferable range of X in terms of balance between mechanical properties and spinnability is 1.5 to 2.5, and more preferably 1.8 to 2.3.

When Z / X or Y / X is less than 2.5,
The strength is reduced, and the alkali weight loss is deteriorated. When Z / X or Y / X is larger than 2.5, light fastness is deteriorated. In addition, coloring occurs at the polymerization stage of the other polymer, and bumping or bubbling phenomenon becomes remarkable in the high vacuum polymerization, so that the polymer is hardly polymerized. If Z is larger than Y, there are problems with spinnability, such as a high yarn breakage and fluff generation rate, and difficulty in achieving fine denier. Conversely, Z
Is smaller than Y, there is a disadvantage that the fastness to dry cleaning is reduced.

The polyester fiber used in the present invention may contain another diol, oxycarboxylic acid or other polyester-forming copolymerizable component within a range of 10% by weight or less, preferably within a range of 5% by weight. Good. However, in this case, it is necessary that the copolymer component is such that the deterioration of the fastness does not occur. Furthermore, various additives, for example, matting agents, heat stabilizers, defoamers, tinting agents, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, crystal nucleating agents, fluorescent brighteners, etc. If necessary, they may be copolymerized or mixed.

The polymer constituting the polyester fiber used in the present invention may be used in the usual polyethylene terephthalate production process, for example, at any stage before the completion of polycondensation, in the case of polyethylene glycol, as it is in the case of adipic acid or sulfo acid. In the case of an isophthalic acid salt, it can be produced as it is or as a lower alkyl ester such as a monomethyl ester, a dimethyl ester, a diethyl ester, a bis (oxyethyl) ester and the like, added to the reaction system and copolymerized. At this time, these copolymer components can be added as they are or after being dispersed, dissolved, or heat-treated in a suitable solvent such as ethylene glycol.

In the polyester fiber used in the present invention, the peak temperature of the loss tangent determined from the dynamic viscoelasticity measurement is 8
It needs to be 0-95 ° C. This is because the low-temperature alkali weight loss and dyeability required by the present invention can be ensured in this range. The peak temperature of the loss tangent (hereinafter referred to as Tma
(abbreviated as x) corresponds to the molecular density of the amorphous portion, and the smaller this value is, the smaller the molecular density of the amorphous portion is. Further, for the same reason, since the molecular density of the amorphous portion is small, the void portion for the dye is large, the dye is easy to enter, and the exhaustion rate is high.

As described above, since Tmax is a structural factor of a fiber, spinning temperature, spinning speed, draw ratio, heat treatment temperature, refining conditions, dyeing conditions, and the like are required even for polymers having the same copolymer composition. It shows different values depending on conditions and post-processing conditions. In particular, since this value greatly changes at the heat setting temperature, the Tma is changed by changing the heat setting temperature.
It is important that x is in the above range.

The concept of setting the heat setting temperature is roughly shown in the case of the copolyester specified in the present invention.
If the heat setting temperature is between room temperature and about 150 ° C, T
The value of max gradually increases, but after 150 ° C. or more, it decreases significantly thereafter. Since the ratio of these changes differs for each copolymer composition, it is necessary to study while examining the relationship between the heat setting temperature and Tmax.

In the case of the present invention, when the temperature exceeds 95 ° C., the effect of improving the low-temperature alkali weight loss and dyeability is small, and the dyeability at 85 ° C. is not exhibited. However, it is not always better to be low, and the amorphous portion becomes too coarse, so that the alkali weight is easily reduced, and it becomes difficult to adjust the weight reduction rate. In addition, there is a disadvantage that the dye can easily enter and simultaneously come off. That is, the fastness, especially the fastness to dry cleaning, the fastness to wet friction, the fastness to washing, and the like are reduced. In addition, problems such as deterioration of texture due to curing during heat setting and decrease in dimensional stability arise. The temperature is practically 80 to 95 ° C, preferably 83 to 93 ° C.

The melting point of the polyester fiber used in the present invention is 230 to 245 ° C. If the melting point is less than 230 ° C., the polyester fiber undergoes thermal denaturation at the stage of ordinary processing represented by a heat set and ordinary use represented by an iron and the like, and physical properties and texture change. 245 melting point
When the temperature exceeds ℃, the spinnability decreases. The polyester fiber used in the present invention is wound up at a winding speed of about 1500 m / min, and the wound undrawn yarn is stretched by about 2 to 3.5 times, or a spinning-rolling method. It can be obtained by a direct drawing method in which a twisting step is directly connected. Although there is nothing that cannot be done by a high-speed spinning method with a winding speed of 5000 m / min or more, the orientation of the amorphous portion is too low (Tmax).
Is too small), and the robustness is reduced, so that it is not a very preferable spinning method. Spinning conditions are not particularly limited, and spinning can be performed under known conditions. However, it is important to control the spinning surface temperature. That is, when the spinning surface temperature is represented by 250 to 270
It is important to keep it at about ° C. If the temperature is lower than 250 ° C., the temperature becomes insufficient and a slab is generated, so that many yarn breaks occur. Also, spinning can be performed at about 270 to 300 ° C., but the number of yarn bends increases, and the occurrence of yarn breakage and fluff increases.

The strength of the polyester fiber of the present invention is 3.5 g / d or more in consideration of practical performance. If the strength is less than 3.5 g / d, problems occur during yarn processing such as intertwisting and entanglement, and the durability of the fabric after alkali weight reduction becomes poor. In the polyester fiber of the present invention, the exhaustion rate at the time of cationic dyeing at 85 ° C. or less is 75% or more. The measurement method of the exhaustion rate follows the method of an Example. If the exhaustion rate measured by this method is less than 75%, a sufficiently dark color cannot be obtained when the fabric is dyed at 85 ° C or lower.

In order for the polyester fiber dyed in this way to exhibit high fastness, it is necessary that the fastness to dry cleaning is 3 or higher. The dry cleaning fastness in the present invention evaluates liquid contamination. This evaluation method will be described in Examples. The evaluation items of the fastness include water fastness, washing fastness, sublimation fastness, friction fastness, and the like. ,
In the polyester fiber of the present invention, all of the remaining fastnesses except the light fastness have been found to be at a level that is industrially acceptable. Accordingly, the fastness to dry cleaning is an index indicating the overall fastness to dyeing of the polyester fiber of the present invention. Therefore, when the fastness is 3 or higher, the obtained dyed product is practical and has good fastness. Further, in order to be able to be used for an outer, it is necessary that the dyeing conditions of the present invention show a light fastness of 3-4 or more, preferably 4 or more.

The mixed fabric dyed article of the present invention is a mixed fabric dyed article using the polyester fiber and the cellulose fiber described in claim 1 of the present invention. In these mixed fabrics, the form and mixing method of the polyester fiber of the present invention are not particularly limited, and known methods can be used. For example, as a mixing method, a woven fabric used for warp or weft, a woven fabric such as a reversible woven fabric, a knitted fabric such as tricot or Russell, and the like may be used.

The cellulose fibers used in the present invention include:
Regenerated cellulose fibers such as cuprammonium rayon, rayon, polynosic and the like can be mentioned. The content of the polyester fiber in the mixed fabric is not particularly limited, but is preferably from 25 to 75% in order to make use of the feeling, the moisture absorbing property, the water absorbing property, and the antistatic property of the cellulose fiber. In the mixed fabric dyed product of the present invention, fibers other than those specified in the present invention can be mixed as long as the object of the present invention is not impaired. A small amount of wool, cotton, silk, rayon, copper ammonia rayon, polyamide fiber, polyacryl fiber, acetate fiber, acrylic fiber, etc. may be used. In this case,
It is possible to add physical properties unique to the fiber to be newly mixed.

After knitting and weaving, the mixed fabric dyed product of the present invention is
It is obtained by refining and dyeing at a temperature of 60C to 98C. Further, after refining, an alkali weight reduction treatment is performed before dyeing. The alkali processing conditions are not particularly limited. However, in order to suppress a decrease in the strength of the regenerated cellulose fiber and a thread, a temperature of about 60 ° C. in a 5% by weight aqueous sodium hydroxide solution is used.
The treatment is performed in a low tension state for a minute.

The dyeing was carried out without using a carrier.
The polyester fiber of the present invention is dyed with a cationic dye and the cellulose fiber is dyed with a reactive dye or a direct dye at a temperature of not more than ℃. Of course, in order to maximize the effect of the present invention, it is a preferable method to perform one-step single-bath dyeing at a temperature of 85 ° C. or less. Of course, two-stage one-bath dyeing or two-stage two-bath dyeing may be performed. After dyeing, soaping is performed by a known method. In addition, for those that perform morphological fixation before and after dyeing, a temperature of 140 to 180 ° C., preferably 150 to 180 ° C.
It is preferable to perform dry heat setting at 170 ° C.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to only examples. The main measured values in the examples were measured by the following methods. (1) Measurement of strength and elongation Using a Tensilon tensile tester UCT-10T (manufactured by Orientec), a sample test length of 20 cm and a tensile speed of 20 cm
The breaking strength at the time of elongation to the breaking point was measured. This strength was divided by the substantial total fineness to determine the cutting strength of the single fiber. Further, the elongation (%) with respect to the original length when elongating to the cutting point was determined.

(2) Melting Point The melting point was measured using a DSC manufactured by Seiko Electronics Co., Ltd. at a heating rate of 20 ° C./min in a nitrogen stream at 100 ml / min.
Here, the peak value of the melting was defined as the melting point. (3) Loss tangent Loss tangent (tan δ) and dynamic elastic modulus at each temperature were measured in dry air at a measurement frequency of 110 Hz and a heating rate of 5 ° C./min using Leo Vibron manufactured by Orientec. From the result, a loss tangent-temperature curve was obtained, and the peak temperature of the loss tangent, Tmax, was determined on this curve.
(° C.). Heating rate 5 ° C / min, Measurement frequency 110
Hz.

(4) Measurement of Alkali Weight Loss Rate The sample was a single-knit knitted fabric of polyester fiber, and was heated to 70 g using warm water containing score roll 400 at 2 g / l.
After scouring at 20 ° C. for 20 minutes, drying with a tumbler drier, and heat setting at 160 ° C. for 30 seconds using a pin tenter were used. This fabric was precisely weighed (W ₀ ), the sodium hydroxide concentration was 5% by weight, and the bath ratio was 1: 3.
At 0, the temperature was raised to 60 ° C. at a rate of 1 ° C./min. The sample after the alkali treatment was washed with water, air-dried, precisely weighed (W ₁ ), and the alkali weight loss was determined by the following formula.

Alkali weight loss rate (%) = 100 × (W ₀ −W ₁ ) / W ₀ (5) Measurement of Exhaust Rate of Polyester Fiber (Evaluation of Dyeing Property) Using hot water containing 2 g / l of roll 400, 70
After scouring at 20 ° C. for 20 minutes, drying with a tumbler drier, and heat setting at 160 ° C. for 30 seconds using a pin tenter were used. The dye used was Kayaacryl Black BS-ED (manufactured by Nippon Kayaku Co., Ltd.).
% Owf, bath ratio 1:30. 0.5 g / l of acetic acid and 3 g / l of sodium sulfate were added as additives to adjust the pH. The exhaustion rate was determined by elevating the temperature from 40 ° C. to 85 ° C., keeping the temperature for 30 minutes, and pulling up the knitted fabric, and then measuring the dye concentration in the residual dyeing solution.

(6) Fastness to Dyeing The fastness to dry cleaning was carried out according to JIS-L-0860. The light fastness was measured according to JIS-L-0842. Wet friction fastness is JIS-L-0849
It went according to. In this case, the friction tester is a friction tester I
Type I (Gakushin type) was used. The size of the test piece is about 220 ×
It was 30 mm, and two pieces each were cut long in parallel with the vertical and horizontal directions. The size of the white cotton cloth for friction is about 50 × 50
mm, the test was wetted with water and made about 100% wet. The evaluation was good if the color transfer on the side of the white cotton cloth for friction was comparable to that of the dyed mixed fabric without alkali weight loss (○)
And a little inferior, and an extremely inferior ×, 3
It was rated on a scale.

(7) Texture Supple and soft were evaluated as good (○), slightly inferior as Δ, and extremely inferior as x, and evaluated in three grades.

[0042]

Example 1 1232.1 g of dimethyl terephthalate, 900 g of ethylene glycol, 96.7 g of dimethyl adipate (hereinafter abbreviated as DMA), and dimethyl 5-sodium sulfoisophthalate (hereinafter abbreviated as SIPM)
21 g, lithium acetate 0.4 as an ether formation inhibitor
3 g, as a transesterification catalyst, calcium acetate 0.4
9 g and 0.49 g of cobalt acetate were charged, gradually heated from 150 ° C. to 240 ° C., and transesterification was performed while distilling methanol for 3 hours. Then, polyethylene glycol having an average molecular weight of 1,000 (hereinafter referred to as PE
96.9 g), 0.73 g of trimethyl phosphate as a stabilizer, 0.67 g of antimony trioxide as a polycondensation catalyst, and 3.70 g of Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant.
Add 0.60 g of silicone oil as antifoaming agent,
Prepolymerization was performed over a period of minutes. The pressure was further gradually reduced, and finally, the reaction was carried out at 275 ° C. for 2 hours and 40 minutes at 0.5 Torr to obtain a modified polyester having a reduced viscosity of 0.69 in the form of chips.

The obtained polymer chip was heated at 130 ° C. for 1 hour.
After drying under a nitrogen stream of 00 liter / min for 20 hours, the spinning temperature was 2 using a spinner having 36 round cross-section holes.
An undrawn yarn was prepared at 70 ° C. and a spinning speed of 1200 m / min. Next, the obtained undrawn yarn is hot rolled at 75 ° C.
Stretching was performed at a hot plate temperature of 140 ° C., a draw ratio of 3.0 and a drawing speed of 800 m / min to obtain a drawn yarn of 50 denier / 36 filament. Tables 1 and 2 show fiber properties such as strength, exhaustion rate, alkali weight loss rate, and dry cleaning (DC) fastness.

The spinning stability of this example was very good, and no abnormal increase in pack pressure was observed.

[0045]

Examples 2-3 A polymerization / spinning experiment was conducted in the same manner as in Example 1 except that the copolymer composition was changed. Table 1 shows the results.
~ 2. In each case, good low-temperature alkali weight loss, dyeability, fastness, and various physical properties were exhibited.

[0046]

Comparative Examples 1 to 6 Polyester fibers having various copolymer compositions shown in Tables 1 and 2 were prepared and various evaluations were made. Those deviating from the copolymer composition of the present invention have poor low-temperature alkali weight loss properties, dyeability, fastness, and other properties, and are not practical. In Comparative Example 3, the pack pressure increased during spinning, and long-time spinning was difficult.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

Example 4 A 75 denier / 72 filament polyester fiber having the same copolymer composition as in Example 1 was used as a warp yarn.
Plain fabrics were made using 75 denier / 44 filament copper ammonia rayon as the weft. This plain fabric was refined by a conventional method to reduce the amount of alkali. Alkali weight loss is 6
This was carried out by immersing in a 5% aqueous sodium hydroxide solution at 0 ° C. for 30 minutes. After neutralization, water washing, and presetting at 160 ° C. for 30 seconds, one-step single-bath dyeing with a cationic dye and a reactive dye was performed without using a carrier. As cationic dyes,
Kayacryl Black BS-ED (manufactured by Nippon Kayaku Co., Ltd.), and as a reactive dye, Dorimale Blue X-SGN (manufactured by Sandos) was used. As a dispersant, 1 g / liter of Disper TL (manufactured by Meisei Chemical Co., Ltd.) is used, and 50 g of sodium sulfate /
Liter and 15 g / liter of sodium carbonate, add p
A dye was added to the aqueous solution in which H was adjusted to 11 to obtain a dye solution.
Dyeing was performed at 85 ° C. for 1 hour at a concentration of 2% owf and a bath ratio of 1:50. After dyeing, Grand-up P (manufactured by Sanyo Kasei) 1g
/ Liter, at a bath ratio of 1:50 at 80 ° C. for 10 minutes. After dyeing, finishing was performed by a conventional method.

The resulting dyed product is uniformly dyed,
No white streaks due to threads were found. Wet friction fastness, dry cleaning (DC) fastness, light fastness,
The texture was also very good, and the dyed product was clear (see Table 3).

[0051]

Examples 5 to 6 Using polyester fibers having the same copolymer composition as in Examples 2 and 3, one-step one-bath dyeing was carried out in the same manner as in Example 4. The obtained dyed products were uniformly dyed in each case, and no white streaks caused by threads were observed. Wet friction fastness, dry cleaning (D
C) The fastness, light fastness, and texture were all good, and the sharpness was also excellent (see Table 3).

[0052]

Comparative Example 7 A polyester fiber of 75 denier / 72 filament having the same copolymer composition as in Example 1 was used as a warp yarn.
A plain woven fabric was produced in the same manner as in Example 4 using 75 denier / 44 filament copper ammonia rayon as the weft. The scouring and dyeing were performed in the same manner as in Example 4 without subjecting the plain fabric to alkali reduction. This comparative example is used as an evaluation criterion for the fastness to wet friction of the mixed fabric dyed material subjected to the alkali weight reduction treatment. Table 3 shows the results.

[0053]

Comparative Example 8 A 75 denier / 72 filament polyester fiber having the same copolymer composition as Comparative Example 4 was used as a warp yarn.
A plain woven fabric was produced in the same manner as in Example 4 using 75 denier / 44 filament copper ammonia rayon as the weft. This plain fabric was refined by a conventional method to reduce the amount of alkali. The alkali treatment conditions for reducing the polyester fiber of this plain fabric by 20% were 90 ° C., 5% by weight of sodium hydroxide aqueous solution for 30 minutes, and thus the plain fabric was subjected to alkali reduction under the same conditions. Neutralization, washing, 160
After presetting at 30 ° C. for 30 seconds, one-step single-bath dyeing with a cationic dye and a reactive dye was performed without using a carrier.
Staining was performed in the same manner as in Example 4.

The resulting dyed product had a good hand, but did not appear to be uniformly dyed. The wet rub fastness was also very poor. This is because polyester fibers have high dyeing properties and high coloring properties, but the copper ammonia rayon used for the weft is damaged in the alkali weight reduction stage due to the high alkali treatment temperature, and threading occurs in the dyeing stage. Further, the strength of the polyester fiber was low, and the strength of the copper ammonia rayon was also reduced under the influence of the alkali treatment temperature, so that the tear strength of the dyed product was low (see Table 3).

[0055]

Comparative Example 9 A 75 denier / 72 filament polyester fiber having the same copolymer composition as Comparative Example 6 was used as a warp yarn.
A plain woven fabric was produced in the same manner as in Example 4 using 75 denier / 44 filament copper ammonia rayon as the weft. This plain fabric was refined by a conventional method to reduce the amount of alkali. The alkali treatment conditions for reducing the polyester fiber of this plain fabric by 20% were 60 ° C., 5% by weight aqueous solution of sodium hydroxide for 30 minutes, and thus the plain fabric was subjected to alkali reduction under the same conditions. Neutralization, washing, 160
After presetting at 30 ° C. for 30 seconds, one-step single-bath dyeing with a cationic dye and a reactive dye was performed without using a carrier.
Staining was performed in the same manner as in Example 4. The resulting dyed product was uniformly dyed, but had a dry cleaning (DC) fastness of 2nd grade and poor fastness (see Table 3). This was because the amount of adipic acid in the copolymer component of the polyester fiber used was large, and the peak temperature of the loss tangent of the polyester fiber was as low as 77 ° C., and the molecular density of the amorphous portion was low. Therefore, it is considered that the once-taken dye easily comes out and the fastness to dry cleaning is poor.

[0056]

[Table 3]

[0057]

According to the present invention, the alkali weight can be reduced at a low temperature of 60 ° C., and the dye can be dyed with a cationic dye at a temperature of 85 ° C. or less, and it is excellent in various fastness, mechanical properties and spinnability. A polyester fiber is obtained. Therefore, by combining this polyester fiber with regenerated cellulose fiber, which has poor alkali resistance and thermal stability, it has a unique supple, soft texture with excellent low-temperature alkali weight loss, low-temperature dyeability, clarity, and various fastnesses. A mixed fabric dyed product can be obtained. Applications include lining,
Particularly useful for women's outerwear, innerwear, etc.

Claims (2)

[Claims] 1. A copolymerized polyethylene terephthalate of polyethylene glycol, adipic acid and sulfoisophthalate having an average molecular weight of 500 to 4000, wherein each comonomer satisfies a copolymerization ratio represented by the following formula and has a loss tangent of: A polyester fiber having a peak temperature of 80 to 95 ° C. 1 ≦ X ≦ 3 2.5 ≦ Z / X ≦ 3.5 Y = Z (where X represents mol% of sulfoisophthalate in the total carboxylic acid component, and Y represents The weight percentage of adipic acid is shown, and Z is the weight percentage of polyethylene glycol in the total polymer weight.) 2. A mixed fabric dyed product of the polyester fiber according to claim 1 and a regenerated cellulose fiber.