JP2002067250A - Laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet consisting of a base fabric consisting of drawn yarns formed by using a specified composition in which a polyethylene terephthalate is a main ingredient and a coating layer and with excellent productivity, high tenacity and excellent heat resistance and stiffness. SOLUTION: The laminated sheet prepared by forming the coating layer on at least one face of a base fabric prepared by weaving and knitting drawn yarns formed by using the specified composition in which the polyethylene terephthalate is a main ingredient by means of an extrusion lamination method using the specified composition in which the polyethylene terephthalate is a main ingredient is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated sheet, and more particularly, to a laminated sheet mainly composed of polyethylene terephthalate having excellent heat resistance and stiffness. It is suitably used for containers and the like.

[0002]

2. Description of the Related Art Conventionally, as a raw material of a flexible container, a tarpaulin obtained by laminating polyvinyl chloride or the like on a base cloth made of nylon or polyester fiber has been frequently used.
However, the laminated polyvinyl chloride is liable to be stained by bleeding of a plasticizer, and has a drawback that toxic gas is generated during incineration. Further, even when laminating a polyolefin in place of polyvinyl chloride, there is a problem that the adhesion between nylon and polyester and the polyolefin is poor and sufficient peel strength cannot be obtained.

Therefore, in recent years, a laminated sheet in which the same type of polyolefin layer is laminated by extrusion lamination on a base fabric made of a polyolefin drawn yarn using a polyolefin having excellent filament formability and a high-strength drawn yarn has been used. ing. However, a flexible container made of polyolefin has insufficient heat resistance when directly filling a high-temperature filler into the flexible container,
As a flexible container requiring heat resistance, a laminated sheet in which the same type of polyester is laminated on both sides of a woven fabric made of a drawn polyester yarn having excellent heat resistance has been tried.

[0004] Such polyesters are usually
Polyethylene terephthalate is used, but a flat yarn made of polyethylene terephthalate has a drawback that it is easily cracked vertically during molding, and there is a drawback that when weaving this flat yarn, weaving is greatly reduced and strength is significantly reduced. In addition, when laminating polyester on both sides of a woven fabric made of polyester drawn yarn by extrusion lamination, the neck-in is large and the ear part becomes unstable due to the film swaying phenomenon. There was also the problem of having to slow down.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is intended to woven and knit a drawn yarn formed by using a specific composition containing polyethylene terephthalate as a main component. At least one side of the base fabric is formed by extrusion lamination using a specific composition containing polyethylene terephthalate as a main component.Excellent productivity, high strength, heat resistance, The purpose is to provide excellent laminated sheets.

[0006]

Means for Solving the Problems To achieve the above object, the laminated sheet of the present invention is provided on at least one surface of a base fabric formed by weaving and knitting a drawn yarn formed using the following composition (1). The composition is such that a coating layer is formed by extrusion lamination using the composition (2). [Composition (1)] (A) Polyethylene terephthalate 50 to 90% by weight (B) Polybutylene terephthalate and / or polypropylene 10 to 50% by weight [Composition (2)] (a) Polyethylene terephthalate 50 to 90% by weight ( b) polyolefin 5 to 45% by weight (c) at least one selected from an epoxy group-containing ethylene copolymer, a carboxylic acid or an acid anhydride group-containing olefin-based copolymer thereof, and a styrene-based thermoplastic elastomer
Seed 5-45% by weight (however, (a) + (b) + (c) = 100% by weight)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyethylene terephthalate (PE) used in the present invention
T) is obtained by polycondensation of terephthalic acid or a derivative thereof as an acid component and ethylene glycol as a glycol component. Further, one obtained by replacing part of terephthalic acid with a copolymer component may be used. Examples of such a copolymerization component include isophthalic acid, adipic acid, and 2,6-naphthalenedicarboxylic acid as part of terephthalic acid.

Further, as the polyethylene terephthalate, a polyethylene terephthalate beverage container (commonly called a PET bottle) is crushed, and re-pelletized recycled polyethylene terephthalate can be used in place of part or all of the polyethylene terephthalate. Recycled polyethylene terephthalate can be used by adjusting the intrinsic viscosity (η value) reduced by water absorption, heat history, or the like in the repelletization step by solid phase polymerization.

The polybutylene terephthalate (PBT) used in the present invention is obtained by polycondensing terephthalic acid or a derivative thereof as an acid component and tetramethylene glycol as a glycol component. Further, one obtained by replacing part of terephthalic acid with a copolymer component may be used. Examples of such a copolymerization component include isophthalic acid, adipic acid, and 2,6-naphthalenedicarboxylic acid as part of terephthalic acid.

[0010] PET of the composition (1) used in the present invention
And PBT have an intrinsic viscosity (η value) of 0.3 to 1.1 dl.
/ G is preferred, 0.5 to 1.0 dl / g is more preferred, and 0.7 to 0.9 dl / g is most preferred. If the η value is less than 0.3 dl / g for forming a drawn yarn, the moldability is not easy, and it is difficult to obtain a drawing effect.
If it exceeds dl / g, the formability of the drawn yarn will decrease. Also,
Η of PET used as component (a) of composition (2)
The value is preferably 0.7 to 1.3 dl / g, and 0.9 to 1.1 dl / g.
dl / g is more preferred. When the η value is less than 0.7 dl / g, neck-in is large and the ear portion becomes unstable due to the film swaying phenomenon, and when it exceeds 1.3 dl / g, the drawdown property is undesirably lowered.

The polypropylene (PP) of the composition (1) used in the present invention may be any of propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer and the like. Species may be used alone or in combination of two or more.
Melt flow rate (MFR) of PP at 230 ° C
Is preferably 1 to 30 g / 10 min, and 3 to 10 g / min.
10 min is more preferable.

In the present invention, the compounding ratio of the composition (1) is 50 to 90% by weight of PET, PBT and / or P
P10 to 50% by weight, preferably PET60 to
80% by weight, 20 to 40% by weight of PBT and / or PP. If the blending ratio of PET is less than 50% by weight, it is difficult to achieve the heat resistance and the stiffness, which are the objects of the present invention, and if it exceeds 90% by weight, the formability of the drawn yarn is inferior. PBT in the composition has a remarkable effect of mainly preventing longitudinal cracks of the drawn yarn and preventing the weaving from being deteriorated during weaving, and PP has a large effect of mainly improving the formability of the drawn yarn.

In the present invention, the polyolefin (PO) used as the component (b) of the composition (2) includes, specifically, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, and metallocene-catalyzed ethylene.・ Polyethylene resins such as α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, polypropylene, propylene-ethylene block copolymer, propylene-ethylene random copolymer, etc. Examples thereof include polypropylene-based resins, and among these, low-density polyethylene is preferable. These may be used alone or in combination of two or more. The MFR of PO is 1 to 30 g / 10
min is preferable, and 3 to 10 g / 10 min is more preferable.

In the present invention, the component (c) of the composition (2) is selected from an epoxy group-containing ethylene copolymer, a carboxylic acid or its anhydride-containing polyolefin-based copolymer, and a styrene-based thermoplastic elastomer. At least one is used.

The above-mentioned epoxy group-containing ethylene copolymer comprises:
A copolymer of ethylene and an ethylenically unsaturated carboxylic acid glycidyl ester or a multi-component copolymer obtained by copolymerizing an ethylenically unsaturated compound with the copolymer, specifically,
Examples include an ethylene-glycidyl methacrylate copolymer, an ethylene-glycidyl acrylate copolymer, an ethylene-glycidyl methacrylate-methyl acrylate terpolymer, and an ethylene-glycidyl methacrylate-acrylonitrile / styrene graft copolymer.

The carboxylic acid or its anhydride-containing olefin-based copolymer includes polyolefins such as low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, polypropylene, and maleic acid. Or a copolymer obtained by grafting an anhydride thereof, fumaric acid, itaconic acid or an anhydride thereof, crotonic acid or an anhydride thereof, or a multi-component copolymer of ethylene with the carboxylic acid or an anhydride thereof and an ethylenically unsaturated compound. Polymers, specifically, maleic anhydride-modified low-density polyethylene, maleic anhydride-modified ethylene-vinyl acetate copolymer, maleic anhydride-modified polypropylene, ethylene-maleic anhydride-methyl acrylate terpolymer And the like.

The styrene-based thermoplastic elastomer is as follows:
The hard segment is polystyrene, the soft segment is polyisoprene or polybitadiene or a hydrogenated product thereof.
"Clayton D", "Clayton G" (trade name: manufactured by Shell Chemical Co., Ltd.), "HIBLER", "Septon"
(Trade name: manufactured by Kuraray Co., Ltd.).

In the present invention, the composition ratio of the composition forming the coating layer is 50 to 90% by weight of the component (a), 5 to 45% by weight of the component (b), and 5 to 45% by weight of the component (c). (However, (a) + (b) + (c) = 100% by weight)
Preferably, component (a) is 60 to 80% by weight, and component (b) 1
0 to 30% by weight, and component (c) 10 to 30% by weight (provided that (a) + (b) + (c) = 100% by weight).
If the compounding ratio of the component (a) is less than 50% by weight, it is difficult to achieve the heat resistance and the stiffness, which are the objects of the present invention.
If it exceeds 0% by weight, neck-in and film swinging phenomena are large during extrusion lamination, and the moldability is poor, which is not preferable.
The component (b) in the composition has a large effect of mainly improving the neck-in in the extrusion laminating method and reducing the film swing phenomenon, and the component (c) is a compatibilizer, and the components (a) and (b) It has the effect of improving workability or impact resistance by improving the compatibility with.

The MFR of the above composition at 280 ° C. is 1
10 to 10 g / 10 min, preferably 2 to 8 g / 10 mi
n is more preferred. If the MFR is less than 1 g / 10 min, the productivity is poor, and if it exceeds 10 g / 10 min, the moldability becomes unstable. Further, the melt tension at 280 ° C. of the composition is preferably from 1 to 10 g, more preferably from 3 to 7 g. If the melt tension is less than 1 g, neck-in is large, and the ear portion becomes unstable due to the film swaying phenomenon, and if it exceeds 10 g, the drawdown property is undesirably reduced.

Further, in the present invention, in order to improve the vertical crack, the formability, the lubricity, the surface appearance, etc. of the drawn yarn, the characteristics of the drawn yarn are not significantly impaired. An inorganic filler can be blended in the composition (1). Calcium carbonate, talc,
Silica, clay, hydrotalcite and the like are preferably used. Of these, calcium carbonate is preferred. The amount of the inorganic filler is 0.5 to 0.5 with respect to the composition (1).
It is preferably 10% by weight, more preferably 1 to 5% by weight.
If the amount is less than 0.5% by weight, it is difficult to achieve the above object. If the amount is more than 5% by weight, the flexibility of the drawn yarn is lost and the yarn breaks, which is not preferable.

For the thermoplastic resin used in the present invention, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, an antistatic agent, a pigment, a flame retardant, a crosslinking agent, a foaming agent, a nucleating agent and the like are added. Agents can be added to the extent that the properties of the present invention are not substantially impaired.

In the present invention, the drawn yarn may be formed by a known production method using the above-mentioned composition (1), as long as it has high tenacity due to the drawing effect. As the form of the drawn yarn, any of a monofilament, a multifilament, a flat yarn, a split yarn and the like can be used, and a multifilament and a flat yarn are preferable in terms of moldability, flexibility and high strength. Is most preferred.

As a method for producing the flat yarn, specifically, a raw material comprising the composition (1) is prepared by using an extruder,
The melt temperature is preferably from 260 to 290 ° C.
A film is formed by an inflation method or a T-die method, cooled, solidified, slit, stretched, and subjected to relaxation heat treatment to obtain a flat yarn. The stretching is usually preferably performed in two steps, and the first step is performed in a range of 60 to 12 steps.
The film is stretched 3 to 6 times at 0 ° C.
The film is stretched 2-3 times at 00 ° C., and then subjected to relaxation heat treatment at 180-220 ° C.

The raw material polyethylene terephthalate and polybutylene terephthalate are preferably dried at 150 to 160 ° C. for 4 to 5 hours using a drier before being fed into the extruder.

The fineness of the drawn yarn is 500 to 50.
00 dtex (dt) is preferable, and 1000 to 3000
dt is more preferred. If the fineness is less than 500 dt, the mechanical properties such as tensile strength are insufficient as the base fabric, resulting in 5000 dt
If it exceeds, the flexibility is inferior and the adhesion to the coating layer is insufficient, which is not preferable.

The drawn yarn is woven and knitted using the warp yarn to form a base fabric. The driving density is preferably 5 to 40 fibers / 2.54 cm, more preferably 10 to 20 fibers / 2.54 cm.
The basis weight of the base fabric is 100 to 500 g / m ^2.
Is preferable, and 150 to 300 g / m ² is more preferable.
Various shapes such as plain weave, twill weave, entangled weave, and mosaic weave are used as the weave structure of the woven fabric, and the knitted fabric may be either flat knit or warp knit, and specifically, tricot knit, Miranese knit, Russell Knitting and the like.

A coating layer can be formed on at least one surface of the base fabric obtained as described above by extrusion lamination using the composition (2) to obtain a laminated sheet. In the extrusion lamination method, the melting temperature is 260 to 290.
C. is preferable, and the surface temperature of the cooling roll is preferably 10 to 50C.

The thickness of the coating layer is 30 to 200
μm is preferable, and 50 to 150 μm is more preferable. Contact
When the thickness of the adhesion layer is less than 30 μm, the adhesive strength becomes insufficient.
Above, poor abrasion resistance is not preferable, and exceeds 200 μm
This increases the load and increases the rigidity, which is not preferable.
The basis weight of the laminated sheet is 150 to 800 g / m. ²
Is preferred, and 200 to 500 g / m²Is more preferred.

Before providing a coating layer on at least one surface of the base fabric by the extrusion laminating method, it is preferable that the surface of the base fabric is subjected to a surface treatment such as a corona discharge treatment or a plasma treatment in order to improve adhesion.

The laminated sheet obtained as described above is
It is excellent in heat resistance, strong in stiffness, and excellent in tensile strength due to strong peeling strength between the base fabric and the coating layer, and can be directly filled with a high-temperature product as a flexible container, and is suitably used for the purpose. Further, for a tent sheet, it is preferably used because it has a strong peeling strength against fluttering by wind and the like. Furthermore, it can be suitably used as a stiff, self-supporting container, such as a cubic sorted collection container.

[0031]

As described above, the laminated sheet according to the present invention has a structure in which at least one surface of a base fabric formed by weaving and knitting a drawn yarn composed of a specific composition (1) containing polyethylene terephthalate as a main component is used. It has a structure in which a coating layer is formed by extrusion lamination using a specific composition (2) containing terephthalate as a main component. In addition to being excellent in productivity, it is excellent in heat resistance and has a strong sheet. In addition, since the base fabric and the coating layer are made of the same type of polyester resin, the base fabric and the coating layer are excellent in adhesiveness. Therefore, a sheet having high peel strength and high tensile strength can be obtained. When this laminated sheet is used as a base material in a flexible container, it is suitably used for specific applications in which a high-temperature product can be directly filled. In addition, the laminated sheet is cut and sewn by making use of the characteristic of strong stiffness, and has an effect of being excellently used as a self-supporting container such as a cubic separated collection container having excellent shape retention.

[0032]

EXAMPLES Example 1 Polyethylene Terephthalate (η)
= 0.8 dl / g) 70% by weight and a composition consisting of polybutylene terephthalate (η = 0.9 dl / g) 30% by weight, dried by a dryer at 150 ° C for 5 hours, and then melted by an extruder. After extruding at 270 ° C., cooling by a chill roll cooling method using a T-die to form a film, slitting the cooled and solidified film to a width of 8 mm, stretching the first stage at 90 ° C. at a magnification of 4 ×, Second stage stretching is 19
After stretching at 0 ° C. at a magnification of 2 times, relaxation heat treatment was performed at 200 ° C. to form a flat yarn having a fineness of 2000 dt. As for the flat yarn, the vertical crack was reduced and a high strength flat yarn was obtained. The tensile strength of the obtained flat yarn is 4.4 cN / d
t, elongation was 11.0%. Using the above-mentioned flat yarn, a plain-woven base fabric was formed at a driving density of 14 × 14 / 2.54 cm. The basis weight of the base fabric was 220 g / m ² .
Weaving deterioration during weaving of the base fabric was small, and a high-strength base fabric was obtained. Next, as the composition for the coating layer, 70% by weight of polyethylene terephthalate (η = 1.0 dl / g) and 15% of low density polyethylene (MFR = 8.0 g / 10 min) were used.
A composition comprising 15% by weight of a styrene-based thermoplastic elastomer (trade name: Clayton G, manufactured by Shell Chemical Co., Ltd.) was prepared. The MFR of this composition at 280 ° C. was 4.5 g / 10 min, and the melt tension at 280 ° C. was 5 g. After performing corona discharge treatment on both surfaces of the base fabric, using the coating composition, an extrusion temperature of 290 ° C. and a cooling roll surface temperature of 3 were obtained by extrusion lamination.
Lamination was performed at 0 ° C. with a thickness of 50 μm to obtain a laminated sheet. The basis weight was 330 g / m ² . The tensile strength of the laminated sheet was 1600 N / 5 cm. A flexible container was obtained by sewing the laminated sheet. This flexible container made of polyester has high strength, heat resistance,
It can be directly filled with a synthetic resin product at 100 ° C. and was preferably used.

Example 2: Except that a drawn yarn was formed using a composition consisting of 85% by weight of polyethylene terephthalate (η = 0.8 dl / g) and 15% by weight of polypropylene (MFR = 5.0 g / 10 min). It carried out like Example 1. The operation of the extruder was stable without surging, and the productivity was improved by 10%. The obtained flat yarn had few vertical cracks, reduced weaving deterioration, and obtained a strong laminated sheet. The tensile strength of the laminated sheet is 1480N /
The laminated sheet was cut and sewn at 5 cm, and used as a separate collection container having a 1 m cube with an opening at the top, but it was excellent in self-sustainability and shape retention, and was suitably used.

Example 3 30% by weight of polyethylene terephthalate (η = 0.8 dl / g), 20% by weight of polybutylene terephthalate (η = 0.9 dl / g), and 50 of recycled polyester (η = 0.6 dl / g) The procedure was performed in the same manner as in Example 1 except that a flat yarn was formed using a composition consisting of% by weight as a raw material. The obtained laminated sheet had a tensile strength of 1340 N / 5 cm and was suitably used for a tent sheet.

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Claims (1)

[Claims] A coating layer is formed on at least one surface of a base fabric obtained by weaving and knitting a drawn yarn formed using the following composition (1) by an extrusion laminating method using the following composition (2). Laminated sheet. [Composition (1)] (A) Polyethylene terephthalate 50 to 90% by weight (B) Polybutylene terephthalate and / or polypropylene 10 to 50% by weight [Composition (2)] (a) Polyethylene terephthalate 50 to 90% by weight ( b) polyolefin 5 to 45% by weight (c) at least one selected from an epoxy group-containing ethylene copolymer, a carboxylic acid or an acid anhydride group-containing olefin-based copolymer thereof, and a styrene-based thermoplastic elastomer
Seed 5-45% by weight (however, (a) + (b) + (c) = 100% by weight)