JPH08246244A - Heat adhesive conjugate filament yarn and sheet - Google Patents

Abstract

PURPOSE: To obtain the subject filament yarn free from a trouble in incineration treatment and capable of producing light sheets having good workability at a low cost. CONSTITUTION: This is a conjugate filament yarn composed of a core component consisting of a polyethylene terephthalate as polyester or a polyester mainly consisting of the polyethylene terephthalate and a sheath component consisting of a low-melting polyester having a melting point lower than that of the core component by >=20 deg.C. The weight ratio of the core component to the sheath component is 10/90 to 80/20. The birefringence of the core component is >=0.23. In the obtained heat adhesive conjugate filament yarn, the strength is >=4g/d and the peak value of the heat shrinkage stress is 0.2-0.4g/d. A sheet is produced by subjecting a woven or knit fabric made of the filament yarn to a calender processing at temperatures between a temperature lower than the melting point of the sheath component by 50 deg.C and a temperature lower than the melting point of the core component by 20 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoadhesive composite filament yarn having a strength and elongation characteristic sufficient to be used alone as a woven or knitted fabric, and a sheet obtained using the same.

[0002]

2. Description of the Related Art Conventionally, a coarse woven fabric of synthetic fibers is used as a base fabric,
Sheets (called tarpaulins) coated with vinyl chloride resin are widely used. This sheet has the advantages that it has good processability and that a sheet having appropriate flexibility can be easily obtained. On the other hand, this sheet has a problem in that it is heavy in weight, has poor workability during use, and produces toxic gases such as dioxins when incinerated as waste.

Therefore, there is a strong demand for a sheet that is light in weight, has good workability, and has no problem in the incineration process as an alternative to the sheet coated with a vinyl chloride resin. To meet this demand,
The present inventors have paid attention to the heat-adhesive composite continuous fiber yarn, and have studied a method of producing a woven or knitted product using the heat-adhesive composite continuous fiber yarn and performing heat-bonding treatment.

Heat-adhesive composite continuous fiber yarns are known, for example, in JP-A-62-184119, a composite having polyethylene terephthalate as a core component and polyester having a softening temperature of 130 to 200 ° C. as a sheath component is used. Disclosed is a thermo-adhesive composite long-fiber yarn having a boiling water shrinkage of 10% or less, a heat-shrinkage stress peak temperature of 140 ° C. or less, and a birefringence of a core component of 0.08 or more. However, this yarn is intended to fix the crossing points of the woven or knitted material by interweaving or knitting with a normal polyester yarn or the like and thermally adhering it. It is not intended to produce a sheet.

A spunbonded non-woven fabric made of heat-adhesive conjugate fibers has also been proposed, but unlike a woven or knitted fabric, it is difficult to control the strength difference between the warp direction and the weft direction.

[0006]

In view of the above situation, the present invention has a strength and elongation characteristic sufficient for use as a woven / knitted fabric by itself, and the woven / knitted fabric is heat-treated to be coated with a resin. It is an object of the present invention to provide a heat-adhesive composite continuous fiber yarn excellent in strength characteristics and thermal characteristics, which can be a sheet that is extremely lightweight and has excellent workability, and a sheet using the same.

[0007]

The present invention solves the above-mentioned problems, and the gist thereof is as follows. 1.
A composite long-fiber yarn composed of a core component made of polyethylene terephthalate or a polyester mainly composed of this and a sheath component made of a low melting point polyester having a melting point lower than that of the core component by 20 ° C. or more. Has a weight ratio of 10
/ 90-80 / 20, birefringence of core component 0.13 or more, yarn strength 4g / d or more, peak value of heat shrinkage stress 0.2-0.4
A thermoadhesive composite filament yarn that is g / d. 2. A sheet obtained by calendering a woven or knitted product using the above-mentioned thermoadhesive composite continuous fiber yarn alone at a temperature from 50 ° C. lower than the melting point of the sheath component to 20 ° C. lower than the melting point of the core component.

The present invention will be described in detail below.

In the present invention, polyethylene terephthalate or polyester mainly composed of polyethylene terephthalate is used as the core component. The core component retains strength when formed into a sheet, and is preferably a polyethylene terephthalate homopolymer, but it may be one in which a small amount of a copolymer component is introduced in order to adjust flexibility and the like.

On the other hand, the sheath component has a melting point of 20 than that of the core component.
A low melting point polyester having a temperature lower than 0 ° C. is used. Specifically, those based on polyethylene terephthalate and into which a copolymerization component such as isophthalic acid is introduced so as to have a desired melting point are preferably used. Further, a polyether ester-based or polyester-based elastomer having polyethylene terephthalate or polybutylene terephthalate as a hard segment and polyalkylene glycol such as polyethylene glycol or polytetramethylene glycol or an aliphatic polyester such as polycaprolactone as a soft segment is used. You can also do it.

The polyester as the sheath component must have a decomposition temperature higher than the melting point of the core component,
When the decomposition temperature of the sheath component is lower than the melting point of the core component, the sheath component is thermally deteriorated during spinning, and the composite continuous fiber yarn cannot be stably produced. Further, both the core component and the sheath component may contain additives such as a heat-resistant agent, a matting agent, a colorant, a flame retardant and an antistatic agent, as long as the original properties are not impaired.

The composite long-fiber yarn of the present invention must have a melting point difference of 20 ° C. or more between the core component and the sheath component.
If the melting point difference between both components is less than 20 ° C, after weaving or knitting,
During heat treatment, the core also softens or melts and becomes a state similar to a film, and mechanical properties such as tear strength and tensile strength of the sheet and durability such as abrasion resistance and weather resistance become insufficient. . In addition, it is preferable that the temperature applied to the core in each step is low in order to maintain the strength of the yarn, and it is more preferable that the melting point difference between both components is 40 ° C. or more. But,
If the melting point difference between the two components is too large, the operability at the stage of producing the raw yarn is deteriorated. Therefore, the difference between the melting points of the two components is preferably 200 ° C or less. In order to maintain sufficient strength even after the heat treatment, it is desirable to control the crystallinity and the amount of copolymerization so that the melting point of the core component is 250 ° C or higher.

In the composite continuous fiber yarn of the present invention, the weight ratio of the core component to the sheath component must be in the range of 10/90 to 80/20, preferably 20/80 to 80/20. It is better to set the range. If the ratio of the core component is too small, only yarns having inferior strength can be obtained, and even a sheet will have inferior strength. On the other hand, if the ratio of the core component is too large, it is difficult to obtain a composite continuous fiber yarn having a uniform sheath portion, and even a sheet has insufficient thermal adhesion.

Further, the composite yarn of the present invention must have a core component having a birefringence of 0.13 or more. Birefringence is 0.
If it is less than 13, the molecular orientation is insufficient and the strength / elongation property is poor, so that it cannot be put to practical use.

The composite continuous fiber yarn of the present invention has a content of 4 g / d.
It must have the above strength. If the strength is lower than this, the tensile strength of the sheet after heat treatment is low,
It is difficult to put to practical use.

Further, the composite long-fiber yarn of the present invention is required to have a peak value of heat shrinkage stress of 0.2 to 0.4 g / d. If this value is too small, slack tends to occur during heat treatment, while if this value is too large, the sheet obtained by heat treatment will wrinkle, resulting in poor product quality. In order to reduce the deterioration of the fiber during the heat treatment as much as possible, it is desirable that the peak temperature of the heat shrinkage stress be 120 ° C. or higher.

In order to obtain a composite continuous fiber yarn having the above-mentioned characteristics, a polymer having a high degree of polymerization having an intrinsic viscosity of 0.7 or more is used as a core component, and a melt-spun yarn is compared at a rate of about 500 m / min or less. It may be taken at a very low speed and hot-drawn at a draw ratio of 4.5 times or more. The temperature of hot stretching is preferably 120 ° C. or higher, and as heating means, a heating roller, superheated steam,
A hot plate, a heating furnace, etc. can be adopted. The drawing may be performed by a two-step method in which an undrawn yarn is once wound and then drawn. However, in order to produce with high productivity, it is desirable to adopt a spin draw method in which drawing is continued to spinning.

Although the single yarn fineness and the total fineness of the composite continuous fiber yarn of the present invention are not particularly limited, the single yarn fineness is 1 to 20 denier and the total fineness is 50 to 2,000 denier from the viewpoint of spinning operability. Is preferred.

In order to manufacture a sheet, first, the composite continuous fiber yarn of the present invention is used alone to weave or knit to obtain a woven or knitted product. The woven structure of the woven fabric may be a plain, twill, satin, or a modified original form, a mixed form, or another special structure, or may be an equivalent knitted fabric.

Next, the woven or knitted material is calendered to soften or melt the sheath component and heat-bond it. It is necessary that the calendering temperature is from 50 ° C. lower than the melting point of the sheath component to 20 ° C. lower than the melting point of the core component. If this temperature is too low, the sheath component will not soften or melt sufficiently and will not bond sufficiently, while if the temperature is too high, the core component will also soften or melt, becoming a state close to the film and tearing strength of the sheet. Mechanical properties such as tensile strength and tensile strength and durability such as wear resistance and weather resistance are insufficient.

Prior to calendering, heat treatment may be performed using a tenter or a cylinder roller as in the case of a normal woven or knitted fabric. Further, the obtained sheet can be subjected to processing such as dyeing and flame-retardant processing according to the required function.

[0022]

EXAMPLES Next, the present invention will be specifically described by way of examples. The measurement was carried out by the following method. (a) Intrinsic viscosity Measured at a temperature of 20 ° C using an equal weight mixed solvent of phenol and tetrachloroethane. (b) Melting point difference About 3 mg of fiber sample was measured with a differential scanning calorimeter (Perkin-Elmer).
The mixture was loaded into DSC-7), the temperature was raised from room temperature at a rate of 10 ° C./min, and the melting point difference was determined from the difference of the endothermic peaks obtained. (c) Tensile strength Using an autograph DSS-100 manufactured by Shimadzu Corporation, measurement was performed under the conditions of a sample length of 25 cm and a pulling speed of 30 cm / min. (d) Birefringence Index was measured by an interference fringe method using a transmission quantitative interference microscope manufactured by Carl Zeiss Switzerland Jena. (Δn _c represents the birefringence of the core component.) (E) Heat shrinkage stress Using a KE-2 type thermal stress measuring device manufactured by Kanebo Engineering Co., Ltd., a 16 cm long sample was looped to 8 cm, and an initial load of 1 It was measured at / 30 g / d and a heating rate of 100 ° C./min. (In Table 1, it is abbreviated as "thermal stress".)

Examples 1 to 3 and Comparative Examples 1 to 2 Polyethylene terephthalate having an intrinsic viscosity of 1.0 as the core component,
Polyethylene terephthalate with an intrinsic viscosity of 0.68 for the sheath component /
Polyethylene isophthalate copolymer (molar ratio 80/20)
Was used to produce a concentric core-sheath composite long-fiber yarn at the core-sheath weight ratio shown in Table 1 as follows. Using an extruder type composite spinning machine, the control temperature of the extruder on the sheath side is 250 ℃, the control temperature on the core side is 305 ℃, and the spinning temperature is 300 ℃.
℃, spinning using a spinneret with 48 spinning holes with a diameter of 0.5 mm, after cooling and solidification, it is taken up by a take-up roller at a speed of 330 m / min, drawn at a drawing temperature of 120 ℃, and has a total fineness of 600 denier. I got a thread. Table 1 shows the physical properties of the obtained yarn.

Example 4 Polyethylene terephthalate having an intrinsic viscosity of 0.72 as the core component /
Polyethylene isophthalate copolymer (molar ratio 92/8),
Polyethylene terephthalate with an intrinsic viscosity of 0.68 for the sheath component /
Polyethylene isophthalate copolymer (molar ratio 80/20)
Control the temperature of the core-side extruder to 280 ° C.
The yarn was spun under the same conditions as in Example 1 except that Table 1 shows the physical properties of the obtained yarn.

Comparative Example 3 A yarn was produced under the same conditions as in Example 1 except that polyethylene terephthalate having an intrinsic viscosity of 0.60 was used as the core component. Table 1 shows the physical properties of the obtained yarn.

Comparative Example 4 Spinning was carried out under the same conditions as in Example 1, the spun yarn was taken up at a take-up speed of 3500 m / min, and drawing was not carried out. Table 1 shows the physical properties of the obtained yarn.

Comparative Example 5 In Example 1, the stretching was carried out without applying heat. Table 1 shows the physical properties of the obtained yarn.

Comparative Example 6 Polyethylene terephthalate having an intrinsic viscosity of 0.70 as a sheath component /
Spinning was performed under the same conditions as in Example 1 except that a polyethylene isophthalate copolymer (molar ratio 92/8) was used and the control temperature of the extruder on the sheath side was 290 ° C. Table 1 shows the physical properties of the obtained yarn.

[0029]

[Table 1]

As is clear from Table 1, the yarns of Examples 1 to 4 satisfied the requirements of the present invention and were high in both strength and elongation. The yarn of Comparative Example 1 had a low core component and thus had low strength. Since the yarn of Comparative Example 2 has a small amount of sheath component, the core component is exposed on the surface of the fiber, and both strength and elongation are low, and it is impossible to weave because there are many yarn fluffs. The yarn of Comparative Example 3 was sufficiently stretched because the intrinsic viscosity of the core component was low, but the strength and elongation characteristics were inferior. The yarn of Comparative Example 4 had a low birefringence and was inferior in strength and elongation characteristics because it was not stretched.

Examples 5 to 8 and Comparative Examples 7 to 11 The composite continuous fiber yarns obtained in Examples 1 to 4 (actual 1 to actual 4) and the composite continuous fiber yarns obtained in Comparative Examples 4 to 6 (comparative ratio) 4 to 6)
A woven fabric having a flat design was woven at the weaving density shown in Table 2 and calendered at the heat treatment temperature shown in Table 2 to obtain the sheets of Examples 5-8 and Comparative Examples 7-11. Table 2 shows the physical property values of the obtained sheet.

Reference Example Using only polyethylene terephthalate, spinning and drawing were carried out under the same conditions as in Example 1 using a conventional extruder type melt spinning apparatus, and a yarn of 250 d / 48 f was obtained. A woven fabric having a plain design with 23 warp / 2.54 cm in both warp density and weft density was woven with the obtained yarn. This woven fabric was used as a base fabric, and a vinyl chloride resin coating of the following composition was applied to both sides with a topping machine to obtain a sheet. Vinyl chloride resin composition (parts by weight) ZEON 121 (vinyl chloride paste; manufactured by ZEON CORPORATION) 50 DOP (plasticizer; manufactured by Mitsubishi Monsanto) 15 DINP (plasticizer; manufactured by Mitsubishi Monsanto) 15 ADEKA-O-130 P ( Antioxidant; Adeka Argus Co., Ltd. 3 KV-62B-4 (Stabilizer; Kyoritsu Chemical Co., Ltd.) 3 Antimony trioxide (flameproofing agent) 7 Calcium carbonate (filler) 7 Table of physical properties of the obtained sheet 2 shows.

[0033]

[Table 2]

As is clear from Table 2, Examples 5 to 8 satisfied the physical properties required as sheets. In Comparative Example 7, the heat shrinkage stress was small, and the woven fabric was wrinkled during the heat treatment, and only a sheet of poor product quality was obtained. In Comparative Example 8, the thermal shrinkage stress of the raw yarn was large and the yarn was greatly shrunk during the heat treatment, and the sheet had poor product quality. In Comparative Example 9, since the difference in melting point between the core component and the sheath component is small, the core component is also melted by the heat treatment, and the strength cannot be maintained,
The performance as a sheet was inferior. Comparative Example 10
Since the heat treatment temperature was low, the sheath component was not sufficiently melted and the performance as a sheet was poor. In Comparative Example 11, since the heat treatment temperature was high, even the core component was melted and the performance as a sheet was poor. The reference example was a sheet having a heavy weight and poor workability. As is clear from Table 2, Example 4 satisfied the physical properties required as a sheet. In Comparative Example 6, since the difference in melting point between the core component and the sheath component was small, the core component was also melted by the heat treatment, the strength could not be maintained, and the performance as a sheet was poor.

[0035]

EFFECTS OF THE INVENTION According to the present invention, a woven or knitted fabric having strength and elongation characteristics sufficient to be used as a woven or knitted fabric by itself and heat-calendered into a woven or knitted fabric can be obtained without coating with a resin. Provided is a thermoadhesive composite continuous fiber yarn having excellent strength properties and thermal properties, which can be a sheet similar to a resin-coated sheet. Further, according to the present invention, like a sheet coated with a vinyl chloride resin,
Since there is no problem in the incineration process and the step of coating with resin is not required, a sheet that can be manufactured at low cost, is lightweight, and has good workability is provided.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Kuniaki Kubo 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Ltd. Central Research Laboratory

Claims (2)

[Claims] 1. A composite long-fiber yarn comprising a core component made of polyethylene terephthalate or a polyester mainly containing polyethylene terephthalate and a sheath component made of a low melting point polyester having a melting point lower than that of the core component by 20 ° C. or more. The weight ratio of the component to the sheath component is 10/90 to 80/20, and the birefringence of the core component is 0.13
As described above, the thermoadhesive composite continuous fiber yarn having a yarn strength of 4 g / d or more and a peak value of heat shrinkage stress of 0.2 to 0.4 g / d. 2. A woven or knitted fabric using the thermoadhesive composite continuous fiber yarn according to claim 1 alone at a temperature from 50 ° C. lower than the melting point of the sheath component to 20 ° C. lower than the melting point of the core component. A sheet that is calendered.