JPS58136828A - Fiber consisting of copolyester - Google Patents

Abstract

PURPOSE:Adhesive fibers for polyesters, consisting essentially of terephthalic acid, isophthalic acid and ethylene glycol, having a specific melt viscosity and intrinsic viscosity and improved fusibility of polyethylene terephthalate fibers, and processable easily in steps. CONSTITUTION:Copolyester fibers containing 40% or more, based on peripheral ratio in the cross section, amorphous copolyester consisting of a copolymer consisting of 40mol% or more terephthalic acid, 20-60mol% isophthalic acid and 75mol% or more ethylene glycol, with another aromatic acid component (A) and another glycol component (B) satisfying formulaIand wt% component (B) satisfying formula II, and said copolymer having substantially 0cal/g heat of melting of the crystal, 50-100 deg.C second order transition point, melt viscosity[eta0] [melt viscosity (poises) at 160 deg.C under zero shear stress]and an intrinsic viscosity[eta](dl/g) satisfying formulas III-V.

Description

Detailed Description of the Invention The present invention relates to a polyester heat-adhesive fiber, and its purpose is to have excellent heat-adhesive properties even at low temperatures, and to produce fibers and fiber aggregates using the fibers. The purpose is to provide fibers that can be manufactured in accordance with *a without any process troubles.

Thermoadhesive fibers for producing nonwoven fabrics and the like by interfiber thermal fusion are known. For example, polyethylene-polypropylene composite fibers containing polyethylene as an adhesive component, composite fibers with polypropylene containing copolymerized nylon as an adhesive component,
Alternatively, there are composite fibers with polyethylene terephthalate containing an ethylene-vinyl alcohol copolymer as an adhesive component.

In recent years, the role of polyester fibers such as xyethylene terephthalate has grown in the textile field, especially in the nonwoven fabric field, and from the viewpoint of production efficiency and energy saving, fiber aggregates or fiber parts, especially nonwoven fabrics, are manufactured using thermal bonding. Demand has increased, and adhesive fibers for polyester are strongly desired.

The above-mentioned known adhesive fibers have good thermal adhesion properties between adhesive polymers, but when used in combination with other main fibers for nonwoven fabrics, etc., the types of main fibers that can be bonded are extremely limited, and they can be bonded to polyester. We are not getting what is possible. For example, polyethylene is self-adhesive, but it hardly adheres to general commercial fibers with different chemical structures3.
．． Further, copolymerized nylon adheres to nylon ml11M, but does not adhere to polyester fibers made of the same condensed yarn polymer. Additionally, ethylene vinyl alcohol copolymers exhibit adhesion to rayon, hinilon, or nylon, which have relatively similar solubility parameters, but they also do not adhere to polyester.

In order to bond polyester fibers, it can be considered with common sense that a polyester polymer should be used as an adhesive component due to the similarity in chemical structure and solubility parameter. In fact, many copolymerized polyesters have been proposed as solvent-soluble or hot-melt adhesives that use polyester as an adhesion partner.

However, when copolyester is used as an adhesive fiber, the fiber or nonwoven fabric manufacturing process requires a unique device and a unique heat history, so that ordinary copolyester for adhesives cannot be used at all.

For example, when copolymerized polyester is removed from a polymerization tank and cut into pellets, the polymer is too soft and difficult to cut with ordinary copolymerized polyester.Furthermore, the molten polymer is extruded through a spinneret to form fibers.
When storing fiber bundles in a can or winding them onto a bobbin, there is severe agglutination between single fibers or fiber bundles, and if the fibers somehow pass through pelletization, or if they are extruded directly from the polymerizer into a fine shape and pelletization is omitted. Even in this case, it becomes difficult to obtain spun fibers. If the fibers are subsequently stretched, crimped, cut, etc., further adhesion and fusion occur, making it impossible to obtain good fibers. Also, even though it is incomplete, i*
*Even if it is made into a non-woven fabric, for example, when it is made into a non-woven fabric, the card passageability is poor, and adhesion problems occur repeatedly during the adhesive treatment, making it impossible to make it into a non-woven fabric.

On the other hand, polymers in which the copolymerization component of copolymerized polyester is reduced and the degree of modification is lowered improves the processability for manufacturing fibers or nonwoven fabrics, but the adhesion with oligoesters such as polyethylene terephthalate is low, resulting in adhesive fibers. It cannot be used as Furthermore, the bonding process requires high temperatures and is difficult to apply to conventional fusion process equipment.

The polyester currently being produced in large quantities in the art industry is polyethylene terephthalate (abbreviated as PET). Therefore, the polymer raw material terephthalic acid (TM)
If a copolymerized polyester containing ethylene glycol (E(J) and ethylene glycol (E(J)) can be used as an adhesive fiber, it will be convenient in terms of raw materials and polymerization equipment, and it will be advantageous in terms of cost.Also, since they contain the same components, the adhesiveness with PET fibers will be improved. A good result can be expected.Also, various compounds can be considered as copolymerization components, and among them, isophthalic acid (IPA) is recommended because the raw material price is low, the copolymerization rate is easy to control, and there is little decrease in the 1-combination rate. In addition, it has advantages such as less coloring of the copolymerized polyester produced and less contamination of foreign substances into the recovery system, and if IPA can be used, the advantages will be great.

Therefore, the present inventors have conducted various research on copolymerized polyester fibers that have excellent qualities such as adhesion with polyester and have good process efficiency for manufacturing fibers and nonwoven fabrics to the level that can be commercially produced. We have discovered that, for the first time, we can completely solve the above-mentioned problems and obtain inexpensive, high-quality adhesive fibers that can be bonded at low temperatures by using fibers made of copolyester polyesters having copolymer compositions and physical properties within a range of ranges.

That is, the fiber of the present invention contains 4Ω mol% or more of terephthalic acid, 20 to 60 mol% of isophthalic acid, 75 mol% or more of ethylenecrisyl, and the following formula (+), (
A copolymerized component that satisfies ii) is composed of B, and has a heat of crystal fusion of substantially 〇-power and a secondary transition temperature of 50°C to 1
00°C, the melt viscosity under zero shear stress at 140°C satisfies the following formulas (ii+) and (iv), and the intrinsic viscosity falls within the range of the following formula (V). is a fiber made of copolyester having a fiber cross-sectional circumference of 40% or more [-A].

0≦Mu10B≦25 ・・・・・・・・・・・・・・・・・・
・・・(1) Bw≦25 ・・・・・・・・・・・・・・・
・・・・・・・・・・・・(11) 2.85≦−η. ≦
6.10 ・・・・・・・・・・・・・・・(ii+)s
, o (+-[η))-1-OjO≦pupil η.

≦s, o (1+1ag(η]) + 1.30...
...(1■)0.45≦1+-[η]≦1. Q...
It is known that copolyesters similar to the composition of the present invention can be used as adhesives. Many high-quality materials are used, and those with high peel strength when bonded in film form are used.

However, it was completely unknown that it was possible to produce S-bonded fibers that took advantage of the excellent properties of such adhesives. The inventors of the present invention have researched the adhesion aim (which takes advantage of the advantages of adhesives) and have successfully produced non-woven fabrics made of copolyester with the above composition and which are more delicate or nonwoven than polymers with specific physical properties without any process troubles. I found scales. The physical properties of polyester adhesive fibers that enable them to be made into fibers or non-woven fabrics were revealed for the first time in the present invention. A particularly important point in the present invention is that when fibers are manufactured from substantially non-quality copolymerized polyesters that conventionally have good adhesion, it is practically impossible to make them into fibers, or there is a short period of time when fibers are produced. Even if it were possible to manufacture, it was practically difficult to continue the production stably for a long time. However, by using copolyester with specific polymer physical properties, it is absolutely possible for commercial producers and operational production. It has now become possible to produce fibers or nonwoven fabrics that are stable for long periods of time and also exhibit excellent properties as adhesive fibers.

In the copolymerized polyester of the present invention, the total acid component of the produced polyvarnish (if it contains an oxyacid, half of it is the acid component, 2
A material containing 40 mol% or more, preferably 50 mol% or more of TA is used as a copolymerization % (hereinafter, copolymerization % is expressed as mol % with respect to the total acid component) with respect to the diol component. When TA is less than 40 mol%, the quality of the fiber is poor.

Processability is not good, and cost is also not appropriate.

In addition, the copolymerized polyester of the present invention contains IPA of 25 to 6
Those containing 0 mol %, preferably 30 to 50 mol %, are used. If the amount is less than 25 mol %, not only the peel strength during adhesion will decrease, but also the low temperature adhesion at the adhesive processing temperature of 200° C. or less, which is a feature of the present invention, will decrease, which is not preferable. On the other hand, a content of 60 mol % or more is unsuitable because process efficiency during fiber production decreases.・“Furthermore, the copolymerized polyester of the present invention contains EG at 75 mol% or more, preferably 85 mol% or more.When EG is 75 mol% or less, it is less preferable in terms of physical properties than C, and the quality of the fibers The copolymerization component A of the present invention is TA,
It is an aromatic copolymerization component other than IPA. Various aromatic dicarboxylic acids, oxyacids and diols are used, but
In particular, those having one or two aromatic nuclei are used.

Examples of chemicals include phthalic acid and methyl terephthalic acid.

Oxybenzoic acid, oxyethoxybenzoic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, naphthalene dicarboxylic acid, bisphenol, r-
There are things like xylylene glycol.

Further, in the copolymerized polyester of the present invention, as the copolymerization component B excluding EG, an aliphatic and/or cyclic copolymerization component is used in an amount of 25 mol% or less, preferably 15 mol% or less. If it exceeds 25 mol %, processability tends to decrease, which is not preferable from the viewpoint of ensuring high processability. The type of copolymerization component to be selected and the mol% of the copolymerization amount within the range of 0 to 25 mol% vary depending on the intended use of the fiber or non-woven sheet.

For example, when the adhesive treatment temperature for fibers or nonwoven fabrics is low, such as 150°C or lower, bulky polymers with high molecular structure and high mobility may be used to properly adjust the fluidity of the polymer in the adhesive fiber. Adipic acid has a linear molecular structure with no side chains.

It is preferable to use sepacic acid, pentamethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and the like. In addition, the heat resistance of fibers or non-woven fabrics can be greatly increased, and adhesive #Ma! Degree is 150-20
In the case of a relatively high temperature of 0°C, polymers with bulky side chains are used to suppress the fluidity of the polymer at temperatures below 150°C and to optimally adjust the fluidity of the polymer at a predetermined temperature of 150 to 200°C. For example, cyclohexane dimetatool, 1,2-propylene glycol, neopentyl glycol, etc. are copolymerized with a component having low molecular mobility at low humidity in a range of 25 mol % or less depending on the purpose.

The copolymerization mol% of the Naori component with respect to the total acid components is as described above, but the B component has an ester-forming group (c
The weight percent of the resulting copolymerized polyester when based on (oon) and/or [OH] is 25 weight percent or less, preferably 15 weight percent or less. If the amount of copolymerization is 25% by weight or more, the polymer becomes flexible and the processability of fiber production deteriorates, which is not preferable.

In the present invention, the total amount of the M component and the B component is preferably 25 mol% or less. If it is more than 25 mol %, not only will the fiber manufacturing process deteriorate, but it will also be unfavorable in terms of cost.

The copolymerized polyester used in the fiber of the present invention must satisfy all of the above compositional conditions, but in order to further ensure fiber manufacturing stability and quality as an adhesive fiber at a commercial production level, The secondary transition temperature, heat of crystal fusion and fluidity must be appropriate.

That is, the copolymerized polyester of the present invention is an amorphous polymer whose heat of crystal fusion (ΔH) is substantially O. When a polymer becomes one in which ΔH can be measured, its quality as an adhesive fiber deteriorates, and in particular, the deterioration in peel strength becomes remarkable. In the present invention, ΔB refers to a sample taken from a molten polymer in the form of fine fibers or small pieces of #JIl film, cooled, and left at room temperature for 5 days or more. , the temperature is raised at a rate of 10°C/min, and the value is determined from the area of the endothermic peak when the crystalline region melts. However, since the copolymerized polyester of the present invention is of poor quality, the endothermic peak due to the melting of the crystalline region No peak occurs. Therefore, ΔH is substantially written as O. If the endothermic peak is so broad that it cannot be clearly determined, it is safe to conclude that there is substantially no endothermic peak and that ΔH is O. Further, the ΔH value did not vary depending on the intrinsic viscosity if the polymer composition was the same. If there is even a small value of ΔH based on crystals, the peel strength as an adhesive fiber will actually decrease, which is undesirable. Furthermore, since the polymer used in the present invention is substantially a non-grade polymer, there is no problem of morphological change due to fiber shrinkage due to crystallization during the heat treatment process in the adhesive treatment process. Since preheating treatment is possible in the previous process, it is not only easy to process the product, but it also has good thermal efficiency and can be operated in a transparent manner, resulting in products with good quality such as precision pouring stability. It is also advantageous in terms of operating costs.

Further, the copolymerization y and realester used in the present invention need to have a secondary transition point in the range of 50°C to 100°C. Preferably, the temperature range is from 60°C to 100°C. When the temperature is lower than 50°C, not only the delicate manufacturing process becomes extremely difficult, but also the morphological stability of the product decreases. Specifically, with regard to process efficiency, it becomes difficult to cut the polymer into pellets during polymer production. Furthermore, even if fibers are produced by spinning pelletized fibers despite the high miscut rate, 1-item attachment or yarn breakage between single yarns occurs frequently during spinning. During the subsequent stretching, crimping, cutting, etc., adhesion and fusion occur, making it impossible to obtain good la fibers.

However, it is of course possible to omit the drawing process if the spun yarn sufficiently satisfies the properties of the target adhesive fiber. Drying temperature.

By appropriately setting the stretching temperature, etc., it is possible to achieve long-term stable production that satisfies commercial productivity and operational productivity.Even if the primary-secondary transition temperature is 100°C or higher, the process efficiency in fiber manufacturing is particularly poor. However, the quality and performance as adhesive fibers will deteriorate.

In particular, low-temperature adhesion at temperatures below 150° C. is undesirable because the performance is significantly degraded.

The second-order transition point mentioned here is determined by measuring the humidity distribution and 1anJ using the "Pybron Direct Reading Dynamic Viscoelasticity Measurement Model @DDV-" manufactured by Toyo Baldwin Co., Ltd., and using the dynamic Loss modulus (E'5
was determined, and the temperature at which the f value became maximum was defined as the second-order transition point. The measurement conditions at this time were a driving frequency of 110 cps, and a temperature increase rate of 1° C./min starting from room temperature.

To prepare the quantitative sample, prepare a sample with a width of 5cm and a length of 2cm from the melted polymer.
(2) A thin film having a thickness of 0.2 (2) was prepared, and after the film was formed, it was immediately cooled and left at room temperature for 6 days or more, and measurements were taken. At this time, if there is unevenness in the thickness of the film, the measured values will vary slightly, so five separately prepared measurement films were measured, and the average value of the five measured values was determined as the secondary transition point. Moreover, E'' did not vary depending on the size of the intrinsic viscosity if the polymer composition was the same.

Furthermore, the copolymerized polyester in the present invention has physical properties such as
It has become clear that the important conditions are that the melt viscosity range is within the appropriate range for both the ΔH value and the E”ma humidity temperature. In other words, the intrinsic viscosity ([η]) and the Melt viscosity (ηρ must be within a certain range; specifically, at a temperature of 160°C, 2.85≦−η.≦6.10...
- River (...) and 5.0 (1 + Mausoleum [η)) -4-o, so≦-η.

≦s, o (t + log (η]) + lj O
It has been found that it is necessary to satisfy the relationships shown by the above two equations of , , , , (iy). Furthermore, it has been found that the intrinsic viscosity of the copolymerized polyester in the present invention satisfies both the fiber manufacturing process properties and adhesive fiber quality performance only when the following formula is satisfied.

0.45≦1+-[η]≦1.0・・・・・・・・・・・・
(More preferably, 5-0 (1+kw[η)) 10, +60≦-η.

≦5.0 (1+1w [da])+1.10...
・(iv)′ and 0.55≦1+−[η]≦0.9・・・・・・・・・・・・
The [η] defined here is the intrinsic viscosity of the copolymerized polyester component after being made into a fiber or nonwoven fabric, and η is the melt viscosity corresponding to [η].

The relationship between [η] and η will be described in detail below using the drawings. Figure 1 shows -η at 160°C. Tote W! The scope of the present invention is the responsibility for customer collection. A point is 1+*
Maximum allowable -da when (v) is 0.96. value, 1
The points indicate the maximum allowable −η0 value when 1+m(w) is 1.0. On the other hand, point E is '+', which is the minimum allowable value when (v) is 1.0. Show value. Point B is the maximum allowable mausoleum η when 1+-[η] is 0.45. 0 point is 1+-[η]
is 0.45, the minimum allowable η is 0.45. Show value. , also D
The point is the minimum allowable 1 η when 1 + Miao [η] is 0.52.

Show value.

The area above the straight line F connecting point A and point 1, that is, −η
. In the region where is larger than 6.10 and the region to the right of the straight line FE connecting point 1 and point E, that is, in the region where 1+-[η] is larger than 1.0, both fiber manufacturing processability and adhesive performance deteriorate. The fibers are not the target fibers of the present invention.

Also, the area to the left of the straight line Be connecting points B and 0, that is, the area where 1+log(v) is smaller than 0.45, and the area below the straight line CD connecting points 0 and D, that is, −da. A region smaller than .85 is also undesirable because it similarly reduces both fiber manufacturing processability and adhesion performance.Special Number It's going to disappear.

In the area above the straight line B connecting point E and point B, there are no problems in the fiber manufacturing process and the operability is sufficient, but it is difficult to obtain a fiber with sufficient adhesion performance as an adhesive fiber. This is thought to be due to poor molecular interlocking and insufficient molecular fluidity to exhibit sufficient adhesive properties as an adhesive fiber.In other words, the polymer has an appropriate flow range for [η] of t. exists, and it is thought that good adhesive performance will be exhibited within that area.A straight line D connecting points D and E
It was found that in the region below E, the adhesive performance is sufficiently exhibited, but the fiber manufacturing processability deteriorates.

In particular, when producing nonwoven fabric by the dry calender roller method, problems with adhesion or fusion of the adhesive 17aIN7 to the calender roller occurred, and it was often necessary to stop the operation and clean the roller.

This is thought to be due to the fact that the mobility of the molecules becomes too intense for a given [η], which exceeds the appropriate flow range of the polymer.

As described above, η. If the relationship between and [η] falls within the shaded area in FIG. 1, fibers with good fiber manufacturing processability and good adhesive performance can be obtained. Furthermore, in the relationship shown in FIG. 1, the shaded area naturally changes if the temperature conditions for measuring melt viscosity change. It is natural that when the measured humidity is higher than 160°C, the entire shaded area shifts downward, and conversely, when the measurement is made at a temperature lower than 160°C, the entire shaded area shifts upward. However, the copolyester in the present invention has -η. It is not the absolute value of that that matters, but the temperature and −η. Since there is an appropriate range in the correlation between -[η] and -[η], -[η] at a typical temperature of 160°C. By regulating the mer that determines the appropriate range of (and), it is possible to obtain adhesive fibers that are easy to process in fiber production and have good adhesion performance. In order to produce good adhesive fibers, it is not the absolute value of the melt viscosity that matters, but the temperature and the η. The fact that an appropriate range exists for the first time due to the correlation between and -[η] has not been known until now, and was first discovered by the present inventor.

The melt viscosity η under zero shear stress mentioned here. (Whiz) was measured using a Cavity 7 Lee Rheometer System Model 3211 manufactured by Instron.

Find the shear stress when changing the sliding speed for the polymer in a cell heated to a predetermined temperature, calculate the apparent melt viscosity from this, and calculate the stress under sero-shear stress from the relationship between the sliding speed and the apparent melt viscosity. The melt viscosity was extrapolated. There is a divine method to extrapolate the melt viscosity under zero shear stress, but here we use the reciprocal (1/ηa) of the apparent melt viscosity (η3).
) Plot the relationship between the tossing speed (~) on a graph, and from the obtained linear relationship, calculate the 1/η8 value at rW→0 to 1/η0
Assuming that η. 1, and since a pellet-shaped polymer was used as the measurement sample for ease of measurement operation, η corresponding to [η] of the copolymerized polyester, which is the adhesive component after making the fiber or non-woven fabric. . As a method of calculating the value, a polymer pellet with the same polymer composition and the same [η] value as the [η] value is prepared separately, and by measuring it, the melt viscosity of the copolymerized polyester component after fiberization is determined. Ta.

Intrinsic viscosity [η] refers to copolymerized polyester in a mixed solvent of phenol and tetrachloroethane, etc.
Intrinsic viscosity (dt/f) measured at 60°C.

The copolymerized polyester of the present invention may contain a small amount of additives, such as a matting agent such as titanium oxide, an antioxidant, an optical brightener, a stabilizer, or an ultraviolet absorber. It is preferable that the copolymerized polyester fibers of the invention and the fiber aggregates and non-woven fabrics made from the fibers be manufactured using unique machines and equipment suitable for the production. It can be manufactured without much modification. Further, the present invention has great significance in that the fibers are specified so that conventional machines and devices can be used.

The fiber of the present invention can be used as a single fiber (homofilament) spun alone, but it can also be used as a composite fiber by spinning it together with other Sat spinnable polymers. As other composite spinning components, thermoplastic polymers with a melting point of 150° C. or higher are used, such as polyethylene terephthalate.

Polybutylene terephthalate, nylon-6, nylon 616. There are polypropylene, etc. Furthermore, when used as an adhesive fiber, the ratio of the copolymerized polyester component to the total length of the composite fiber cross section, that is, the fiber cross-sectional circumference is preferably 40% or more. In this case, it goes without saying that when emphasis is placed on the morphological stability of the bonded fibers, it is necessary to use thermoplastic polymers having a melting point higher than the bonding treatment temperature as the other composite spinning components.

The fibers of the present invention can also be used as a fusion-treated fiber aggregate consisting only of copolymerized polyester single fibers or composite fibers of copolyester and other polymers, but they can also be used as a fusion-treated fiber aggregate consisting of only copolymerized polyester fibers or composite fibers of copolymerized polyester and other polymers. It is also used as a treated fiber aggregate.

As a fiber aggregate, it is particularly suitable for nonwoven fabrics, and it is possible to obtain nonwoven fabrics with high strength. In particular, in the case of polyester containing terephthalic acid as a component, such as polyethylene terephthalate or polybutylene terephthalate, which is used as a mixed wire, the dark adhesion not only between adhesive fibers but also with the terephthalic acid polyester is good, and the strength is high. It can be a non-woven fabric. There is no conventional 1m pongee that adheres to terephthalic acid polyester, making it possible to manufacture good poly'ester nonwoven fabric at a low cost! The present invention is significant in that it has made Aa possible.

The fusion-treated fiber aggregate as referred to in the present invention is useful for processing into a wide variety of nonwoven fabrics for various uses, particularly high weight nonwoven fabrics such as those with a weight of 50 g 7 pyt or more, textile fabrics, and tufted fabrics. It is especially suitable for the production of quilted or non-quilted fusion-bonded nonwoven fabrics. Specific uses include, for example, pillow stuffing, double bag stuffing, cushions, comforters, mattresses, and bed covers.

Pine tress padding, furniture and upholstery of own WJ cars.

Suitable for bed covers, industrial and clothing pile fabrics, car covers, interlining fabrics, floor covering materials, carpets, pass mats, etc.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited in any way by C. The strength of the nonwoven fabric described in the Examples is as follows: 'X 5116) a 8
The nonwoven fabric is shown as the tearing length (-) of the nonwoven fabric obtained by mixing parts by weight, carding, forming a web, dividing the circumference in 10 casting molds by pressing, and thermally bonding the adhesive fibers.

In the examples, peel strength refers to a thickness of 0. Cut the copolymerized polyester film of '5'' into 15 square squares, then sandwich the cut copolymerized polyester film piece between Mitsubishi Plastics' two-wheel stretched polyethylene terephthalate film (trade name Diafoil, thickness 0.1cm). , heated to a temperature 20°C higher than the melting point or softening temperature of the copolymerized polyester in a room at a temperature of 20°C and relative humidity of 65% to melt it, adhered at a pressure of 54°C, left for 24 hours, and pulled at a speed of 20m.
The value of the adhesive strength (1/I S wn ) measured in /min.

In the examples, the numbers indicating the polymerization composition indicate the mole % based on the total acid component of the polyester produced.

Examples are summarized in Table 1, and in Table 1, η],
V indicates the value of the copolymerized polyester component after fiberization.

The [η] value of the copolymerized polyester component after fiberization in the case of composite spinning was expressed using the measured value of [η] after spinning when only the copolymerized polyester component was spun alone.

Example 1 A polysynthesis was carried out at 280° C. using a conventional condensation reactor, and 70 moles of T and 30 moles of IP were obtained.

A monopolyester containing 95 moles of E0 and 5 moles of diethylene glycol was produced, extruded into water in the form of a sheet from the bottom of the polymerization vessel, and cut into pellets using a sheet cutter. The extrusion and cutting conditions were good, and pellets with a good shape were obtained.

The physical properties of the copolyester were measured from the obtained pellets. [η)0.69. ΔHOad/f, secondary transition point 75°C, peel strength 1.1 x 103f/15.
Met.

When this pellet was dried at 60° C. during vacuum drying, no agglutination was observed. Then, it was fed into an extruder, extruded through a spinneret with a hole diameter of 0.25 mm at a spinning head temperature of 240 DEG C., and wound up at 1000 wn for 1 minute to perform spinning. The transportability of the pellets in the extruder was good, and the wound fibers showed no sticking between single fibers or fiber bundles, allowing stable spinning for a long period of time.

This spun yarn was not drawn, but was then stuffed, crimped using a box-type crimping machine, cut, and fineness s, od
R (denier) fibers could be obtained without any particular trouble. [η] after fiberization is 0.62, and the corresponding melt viscosity at 160°C under zero shear stress is 8.95.
It was X10/is.

2031 parts of this copolyester fiber and 80 parts of polyethylene terephthalate fiber (5 dr x 51 m +)
A nonwoven fabric with a high tenacity with a tear length of 5.8 was obtained by blending the same with Miyako. No particular trouble was observed during the non-woven process.

Example 2 The T unevenness was 0 mol by the same method as in Example 1.

A copolymerized polyester consisting of 50 moles of IP and 100 moles of EG was produced. There were no problems in pelletizing the pellets, and pellets with good shapes were obtained.

The physical properties of the copolymerized polyester from the obtained pellets are as follows:
η)0.74. Δ■Od/f, second-order transition point 72℃
, peel strength is 2. It was I x 10 f/155m.

This pellet was mixed with Mariichi v++1 in the same manner as in Example 1.
+L Lda Salary, history unfavorable & ending in city, tear length 4.0
The sieve of glaze I was born with a misfortune Φ that possessed the power of the east. Fiberization [in the process], non-rutting (in the culm), no particular troubles were observed, and it was confirmed that there was a sufficient degree of fibrosis. The fiberization thickness [η] was 0.66, and the corresponding mmIll viscosity under sero-shear stress at 160° C. was 8.13×10 poise.

Example 6 The copolymerized polyester of Example 2 was used as a sheath, and [η] 0.
Core-sheath composite spinning was performed using No. 67 polyethylene terephthalate as the core and a core/sheath weight ratio of 40/60. The spinning head was extruded at a temperature of 290° C. and wound at a speed of 1000 m/min.

The wound fibers had no single fiber problems or sticking between fiber bundles, and could be stably spun for a long period of time.

This spun yarn was stretched 4.2 times in a water bath at 70°C, then shrunk by 8 cm at 75°C in a water bath, further crimped in a stuffing box type crimper, cut, and then cut to a fineness of 5. ．． O
dr, strength S, 5 f/d, elongation 45 cm fiber'
T-hemorrhoids.

This composite fiber with a weight of 20 weight and a polyethylene terephthalate fiber (3dr x 51) with a weight of 80 weight was mixed, and the tearing length was 5. A nonwoven fabric having Bk5O strength was obtained.

No particular trouble was observed during the nonwoven process. 6drX51 obtained by changing the fineness according to the manufacturing method of this example
20 parts by weight of gH composite fiber and polyethylene prephthalate lag (12dr x 64tm) 80t
When the covering was mixed into a web and heat-treated to make a nonwoven sheet, it was used as a cotton wadding for a kotatsu, and it was confirmed that it had firmness, good elasticity recovery, and excellent durability. Moreover, it was found to have sufficient heat resistance against the temperatures during use in a kotatsu.

Example 4 A four-condensation reaction was carried out at 260° C. in a conventional manner using a Shimahaba reaction apparatus g, and 50 moles of 'rA and 50 moles of IP.

A copolymerized polyester consisting of 90 moles of EG and 10 moles of triethylene glycol was loaded and extruded into water from the bottom of the polymerization vessel in the form of a strand, which was then cut using a strand cutter and pelletized. extrusion.

(Jj 1lyr is in good condition and pellets in good shape are 1L, 4. From the obtained pellets, 1.5 sweat of copolyester is [η) 0.72. Δ110 aa/
W, secondary transition point 65°C, peel strength 2.5 x 10
It was f/15 m.

When this pellet was dried at 60°C during vacuum drying,
Shoken was not accepted at all. Then, core-sheath composite spinning was carried out using the obtained copolymerized polyester as a sheath and polyethylene terephthalate with [η) of 0.67 as a core and a core/cap ratio of 40/60.

At a spinning head temperature of 290°C, extrusion was carried out for 1000 ml and wound in 1 minute. The wound fibers had no distortion in the direction of single fibers or fiber bundles, and could be stably spun for a long period of time. This spun yarn was stretched 4.0 times in a water bath at 67°C.
Next, it was shrunk 7 times at 72°C in a water bath, crimped using a stuffing box type crimper, cut, and once
．． A fiber having an Odr of 5.4 f/d, a strength of 5.4 f/d, and an elongation of 50 inches was obtained. [η] of the copolymerized polyester component after fiberization is 0
．． 64, and the corresponding η0 at 160°C is 4.2
7) C: It was 10 boys.

20 parts by weight of this composite fiber and 80 parts by weight of polyethylene terephthalate fiber (5dr x 51cm) were blended to obtain a nonwoven fabric with high strength and tear length of 4.7cm. was not recognized.

6drX5 obtained by changing the fineness according to the manufacturing method of this example
20 parts by weight of composite fiber of 1- and 80 parts by weight of polyethylene terephthalate fiber (12dr Tarini <<,
It was found to be a cotton wadding with excellent elastic recovery properties.

Mixed cotton L of composite delicate and polyethylene phthalate in this example
The adhesive heat treatment temperature for Tan*Nib is 150℃ even with the hot air method.
It performs satisfactorily at low temperatures of °C, and is suitable for applications such as pillow stuffing, cushions, floor padding, futon stuffing, mattress padding, etc., where specific heat resistance is not required. Ta.

Example 5 Using the copolymerized polyester of Example 4 as a sheath, [η)0.9
2. Pributylene terephthalate tx core/sheath:
Core-sheath composite spinning was carried out at a weight ratio of 40/60, extruded at a spinning head temperature of 260°C, and wound up at 1800 m for 7 minutes. The wound fibers showed no sticking between single fibers or fiber bundles, and could be spun constantly for a long time.

This spun yarn was directly crimped with a stuffing box type crimper without being drawn, and then cut to give a total weight of 5.0 tons.
lr fibers were obtained. 20 parts by weight of this composite fiber and polyethylene terephthalate fiber (S dr X51■)
80 weight IIS was blended to obtain a nonwoven fabric having high tenacity with a breaking length of 4.5-. There were no problems during the non-woven process.

Example 6 The polycondensation reaction was carried out by a conventional method, and the T unevenness was 0 mol.

IFum 50 mol, 8085 mol, diethylene glyco-4
15, (q')0.77, ΔHOed/f
.

Secondary transition point 67℃, peel strength 2.7 x 10 f/1
A 5-inch copolymerized polyester was obtained. There were no problems at all during the process up to pelletization.

Core-sheath composite spinning was performed using this copolymerized polyester as a sheath and nylon-6 as a core at a core/sheath weight ratio of 50,750. Extrusion 1000m/spinning head temperature 270℃
The yarn is spun in minutes, then stretched and shrunk.

Crimp and cut, fineness 5. o dr, strength 4.0
t/dr.

A fiber with an elongation of sob was obtained. The processability was good and there were no particular troubles, and no sticking between single fibers or between fiber bundles was observed. [η of the copolymerized polyester component after fiberization
] is 0.69, and the corresponding η- at 160℃ is 6
, 51X1G, tri's.

From this composite fiber and polyethylene terephthalate fiber,
A nonwoven fabric was produced in the same manner as in Example 1, and a nonwoven fabric with a tear length of 5.9 mm was obtained without any particular process trouble.Example 7 A polycondensation reaction was carried out by a conventional method, and the T unevenness was 5 mol.

IFum 50 mol, l! :G100 mol, sepacic acid 15
Consisting of moles, (y) 0.90. ΔHOa4/f,
Secondary transition point 50℃, peel strength 2. IX109715
(2) There were no troubles at all during the process up to pelletization of the copolymerized polyester.

Using this copolymerized polyester as a sheath and polypropylene as a core, core/sheath composite spinning was performed at a core/sheath weight ratio of 50,750.
Spinning at M/min, then stretching and shrinking.

Crimp and cut, fineness 5. Odr, strength 5.8
t/d.

A fiber with an elongation of 45 mm was obtained. The processability was good and there were no particular troubles, and no sticking between single fibers or between fiber bundles was observed. [η of the copolymerized polyester component after fiberization
] is 0.80, and the corresponding η0 at 160℃ is 1
．． It was 24×10 poise.

From this composite fiber and polyethylene terephthalate fiber,
A nonwoven fabric was produced in the same manner as in Example 1, and a nonwoven fabric with tear lengths of 6, 5, and 11 was obtained without any particular process trouble.

Examples 8 to 18 A copolymerized polyester having a copolymer composition and physical properties as shown in Table 1 was used as a sheath, and polyethylene terephthalate was used as a core, and fibers were made into a nonwoven fabric in the same manner as in Example 5 at a core/sheath weight ratio of 50,750. A nonwoven fabric with good strength was obtained.

The process performance of converting into kkk@ and forming into kkk@ was good, and no particular trouble was observed, and there were no problems with operability.

Comparative example 1 A polycondensation reaction was carried out by a conventional method to obtain 80 mol of T.

Consisting of 20 moles of 11'm and 10 moles of EG, [ri]G
A copolymerized polyester having a temperature of 076, a ΔBO of 17, and a secondary transition point of 76°C was obtained. At 160°C, the polymer had no fluidity at all, making it impossible to measure the melt viscosity. This pellet was spun in the same manner as in Example 1 to obtain a spun yarn.
, then stretching, shrinking, and crimp.

Cut to fineness 5・odr, strength 4.5 pea
A fiber with an elongation of 30% was obtained. The processability was good and there were no particular troubles, and no sticking between single fibers or between fiber bundles was observed.

However, when a nonwoven fabric was prepared in the same manner as in Example 1 and the tearing length was measured, the nonwoven fabric had a very low strength of 0.2 m.

Comparative example 2 A polycondensation reaction was carried out using a conventional method to obtain 45 moles of T.

A copolymerized polyester consisting of 25 moles of IPA, 100 moles of EG, and 50 moles of bacic acid was produced, extruded into water in the form of a strand from the bottom of the polymerization vessel, and cut using a strand cutter to have the physical properties listed in Table 1. Obtained pellets. However, due to the low secondary transition temperature of the polymer, the strands were soft and insertion into the cutter was quite difficult, and the cutter was often shut down due to accumulation of uncut strands and fusion of the polymer to the cutter. Therefore, the yield of pelletization was increased by extruding the strands into ice water at 0°C.

When this pellet was dried at 45°C during vacuum drying,
The material did not stand at room temperature for a long time as a sticky lump formed. Then, it is fed to an extruder, and the spinning head temperature is set to t-240°C.
Although spinning was carried out at 000 m for 7 minutes, many stictions occurred between single fibers and between fiber bundles, and good fibers could not be obtained.

Comparative Example 5 Using the copolymerized polyester of Comparative Example 2 as a sheath, [η)Oj7
of polyethylene terephthalate as the core, core/sheath = 5
Core-sheath composite spinning was performed at a weight ratio of 0.0150. 1000 m7 by changing the spinning head temperature from 275℃ to 290℃
Although spinning was carried out for 1 minute, a number of stictions occurred between single fibers and between fiber bundles, and it was not possible to obtain good fibers.

Comparative example 4 A polycondensation reaction was carried out using a conventional method to obtain 100 moles of T.

A copolymerized polyester consisting of 50 moles of EG and 50 moles of butadiol was produced, and pellets having the physical properties shown in Table 1 were obtained. At 160°C, the primer has no fluidity at all,
Measurement of melt viscosity was not possible.

Then, fiberization and nonwoven fabric were performed according to Example 1 to obtain a nonwoven fabric. Processability was good and no particular problems were encountered.

However, as in Comparative Example 1, at an adhesive treatment temperature of 200° C. or lower, only a nonwoven fabric with extremely low strength was obtained. However, it became clear that it was not practical as it required a higher fusion temperature.

Comparative example 5 A polycondensation reaction was carried out using a conventional method to obtain 100 moles of T.

A copolymerized polyester consisting of 50 moles of EG and 50 moles of hexanediol was produced, and a strand was extruded from the bottom of the polymerization vessel into ice water at 0°C and cut using a strand cutter tube to obtain pellets having the physical properties listed in Table 1. 0℃
The strand was cooled with ice water, and the strand cutting condition was generally good.

Pellets vacuum-dried at room temperature were fed in an extrusion manner, the spinning head was set at a temperature of 240° C., and spinning was performed at 1000 wx/min, but many fibers stuck and fibers could not be obtained smoothly.

Comparative Example 6 Core-sheath composite spinning was performed in the same manner as in Comparative Example 6 using the copolymerized polyester of Comparative Example 5 as a sheath. However, many stictions occurred between the single fibers of the spun yarn and in the kJA fiber bundles, making it impossible to obtain good fibers.

Comparative Example 7 A copolymerized polyester consisting of 0 mol of J)T unevenness, 5 mol of IP lam, and 100% bisphenol was produced by a conventional method, and pellets having the physical properties shown in Table 1 were obtained. The melt viscosity could not be measured as in Comparative Example 1.4. Then, according to Example 1, m1Il formation and nonwoven fabric were performed to obtain a nonwoven fabric. The processability was good and there were no particular problems.

However, as in Comparative Example 1.4, at an adhesive treatment temperature of 200° C. or lower, only a nonwoven fabric with extremely low strength was obtained. Even if the fusion humidity was set to 250° C., it was not sufficient and was completely impractical for the purpose of the present invention.

Comparative Examples 8 to 12 A core-sheath composite was prepared in the same manner as in Comparative Example 3, using a copolymerized polyester having the copolymer composition and physical properties shown in Table 1 as the sheath, and polyethylene terephthalate as the core, with a core/sheath weight ratio of 50,750. Spinning was carried out, but all involved spinning, stretching, crimping,
A lot of sticking occurs in either of the cutting steps, or adhesion troubles occur in the non-woven to fabric forming steps, resulting in poor process efficiency and failure to obtain good fibers or non-woven fabrics.

Comparative Example 13 Polycondensation was carried out in the same manner as in Example 2 and TA 50
A copolymerized polyester having a ratio of [η11.25] of 50 moles of IPA and 100 moles of EG was produced.

The pellets were made into fibers by the same method as in Example 1, and then made into a nonwoven fabric. During the fiberization process, there were many spun yarn breakages and single yarn breakages. When the strength of the nonwoven fabric was evaluated, only a low strength product with a breaking length of 0.7 g and 1 g was obtained. At this time, the [da] of the copolymerized polyester component after fiberization was 1.15, and the corresponding η was 1.15. is 7,96X10
It was Poise.

Comparative Example 14 Polycondensation was carried out in the same manner as in Example 2 to produce a copolymerized polyester with a diameter of 0.25 and consisting of 50 moles of TA, 50 moles of IP, and 100 moles of EG.

The obtained pellets were not suitable for single spinning due to frequent yarn breakage.
Since the core-sheath composite spinning was performed in the same manner as in Example 5. Extrusion 11000I at spinning head temperature 290℃
/ minute, but due to the low melt viscosity of the copolyester component, it was difficult to spin stably for a long time, and fibers with good uniformity could not be obtained.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the melt viscosity range of the copolymerized polyester used as the packaging in the present invention, and in the diagram A, B, O
, D, E, F The range enclosed by T is the formula (m), 4
v), (v), and G, H,
The range surrounded by I and J is a more suitable range that satisfies formulas 1v) and 1). 0.4 0.5 0.6 0.7 0.8
0.9 10 1.21 +log('j)
(dt/g) Masayoshi Shizuka (8th year), 3rd day, 7th year of 1980, Mr. Haruyu Shimada, official of the Patent Office, 1, case history, 157 years, Percentage Application No. 20038, 2, title of the invention, 1 case. Fiber i1 Shikiyama made of polyester //! 4i 411621 address (108) RiRa Co., Ltd. Representative Director Tsuguo Okabayashi 4, Agent 2045-1 Aoeyama, Sakazu, Kurashiki City Telephone Tokyo 03 (277) 3182 5. ” Column 6, Amendment of Internal Medicine (1) Specification Homare, page 21, line 18, “shaded area” -
Write down A, B, C, L), J! ;, The range bent by F, more preferably the range surrounded by 1, G, HlI, and J.'' (2) The descriptions "1@line customary area" on page 22, line 1, line 2, and line 4 of page 22 of the specification are corrected to read "the above range."that's all

Claims (1)

[Claims] (1) Terephthalic acid in an amount of 40 mol % or more based on the total mol % of the total acid components. 20 to 60 mol% of isophthalic acid, 75 mol% or more of ethylene glycol and the following formula (
1), consists of copolymer components A and B that satisfy (if), and has a heat of crystal fusion of substantially Od/I, a secondary transition temperature of 50°C to 100°C, and further has a temperature of 160° C. The melt viscosity under zero shear stress is expressed by the following formula (ili). (IV), and the intrinsic viscosity falls within the range of the following formula (I). Fibers made of copolyester in which the non-quality copolyester component accounts for 40% or more in terms of fiber cross-sectional circumference. 0≦A0B≦25...・・・・・・・・・・・・・・・
...(1) 2.855m η0≦ 6.10 ...・Snow...0・−...・- (iii) 5.0 (1+Temple [η)
)+o, so≦-da. ≦5.0 (1+Temple [η))+1.30. ,,,,,,
(IV) 0.45 ≦ 1 + Mausoleum [η ≦ 1. Q *@511
81111゜---(V) (2) As a non-quality copolymerized polyester component, copolymerized mol% based on the total acid component,
Terephthalic acid: 50 mol% or more, isophthalic acid: 30-30 mol%
5omol%. The content of ethylene glycol is 80 mol% or more, the secondary transition temperature is 60 to 100°C, and the melt viscosity under zero shear stress at 160°C is 1. And the intrinsic viscosity DA is expressed by the following formula (
A fiber made of the copolyester according to claim 1, which satisfies the requirements iV)' and (V)'. 0 (1+iog(η))+0.60≦Kojiη. ≦5.0 (1+m[:η]) + 1.0...
・・・・・・・・・(+v)'0.55≦1+−[η]≦
0.9・・・・・・・・・・・・・・・(I′(
3) A fiber made of a copolyester according to claims 1 or 2, wherein the components other than the amorphous copolyester component are thermoplastic polymers having a melting point zso@0 or more. (4) Non-quality Claim 1 in which the component other than the copolymerized polyester component is polyethylene terephthalate fiber.
A fiber made of the copolyester polyester according to items 5 to 6. (6) A fine fiber made of the copolyester according to claim 1, which is a single fiber of an amorphous copolyester component.