JPH09201924A - Laminate sheet - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a lightweight, robust, and inexpensive laminated sheet that can be processed into a bag by a heat fusion method. A laminated sheet in which a coating layer is formed on both sides of a woven fabric made of a stretched yarn made of a thermoplastic resin, wherein the coating layer is produced by using a metallocene catalyst and has ethylene and carbon atoms of 3 A laminated sheet characterized by being an ethylene / α-olefin copolymer comprising the above α-olefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminer for a base material of a large transport bag or a flexible container used for transporting various powders such as synthetic resin pellets, medicines, grains, feeds and minerals. It is related to the sheet.
More specifically, the present invention relates to a laminated sheet obtained by coating both surfaces of a woven fabric of synthetic resin fiber yarn with a thermoplastic resin excellent in low-temperature sealing property, peeling strength and breaking strength.

[0002]

2. Description of the Related Art Conventionally, as a flexible container,
Woven fabrics made of polyester-based, polyamide-based, etc. synthetic resin fibers and other fibers are made into a bag using a soft tarpaulin with a coating layer formed of polyvinyl chloride resin, rubber, etc. as the base material. Was used. The polyvinyl chloride resin forming the coating layer contains a large amount of a plasticizer for the purpose of improving thermal stability, flexibility, etc., so that the liquid component elutes (bleeds) and migrates to the filler. It has been pointed out that problems such as hygiene, handling, and safety are pointed out because dirt tends to adhere, the specific gravity of the resin itself is heavy, workability is poor, and toxic hydrogen chloride gas is generated during combustion.

Therefore, recently, an ethylene-vinyl acetate copolymer is used instead of the polyvinyl chloride resin.
Although this resin is relatively lightweight and excellent in safety, it has problems in that it is inferior in heat resistance, durability and abrasion resistance and has an odor.

As a material that is easily moldable, lightweight, and inexpensive, a base material in which a low-density polyethylene resin is coated on the surface of a woven fabric made of polyolefin fibers such as polypropylene and high-density polyethylene has been proposed. There are disadvantages that the strength of the base material is likely to decrease during the dressing process, and the fusion strength and peel strength of the seal portion are not sufficiently expressed.

Therefore, the resin of the coating layer is characteristic: (1) As a tarpaulin suitable for a flexible container base material having high strength and excellent weldability, a specific ethylene-vinyl acetate copolymer A specific inorganic substance is mixed with the coalesced body and bonded and integrated on both sides of a coarse base cloth (JP-A-58).
-148760), (2) As a tarpaulin suitable for a base material for a flexible container having excellent bending resistance and washing resistance,
A resin with a stress cracking resistance F ₅₀ according to ASTM D-1693 of 50 hours or more bonded to a cloth (Japanese Patent Laid-Open No. 58-15364).
No. 2), (3) Welder-a laminate sheet suitable for a flexible container substrate having a high peel strength, which is obtained by laminating an ethylene resin on a woven fabric made of a polyolefin resin stretched yarn (Japanese Patent Laid-Open No. Sho 63-135). 58-201643), (4)
As a laminate sheet suitable for a flexible container that is flexible, lightweight and has good fusion properties, ethylene-α, β
-Coating a composition composed of an unsaturated carboxylic acid ester copolymer and a tackifier into a woven fabric composed of a drawn polyolefin yarn-
(Japanese Patent Application Laid-Open No. 59-11250), (5) A specific ethylene-α-olefin copolymer is coated on a fiber base material as a raw material for a flexible container having improved heat resistance and abrasion resistance. (6) Japanese Patent Laid-Open No. 4-74646
As a tarpaulin suitable for flexible container base materials with improved heat resistance and welder workability,
A cloth coated with a composition prepared by kneading an olefin polymer with a vinyl acetate copolymer (Japanese Patent Laid-Open No. 104683/1993)
(7) As a polyethylene cloth suitable for a flexible container substrate with improved seal strength, a woven fabric made of synthetic resin flat yarn coated with a resin mainly composed of linear low-density polyethylene (actual fairness). 4-32273) and the like are disclosed.

Further, the structure of the woven fabric and the yarn to be used are characteristic. (8) As a tarpaulin suitable for a flexible container substrate having improved fusion processability, a multi-layer made of isotactic polypropylene is used. A mesh woven fabric in which filaments are used as a background and coated with ethylene-vinyl acetate copolymer (Japanese Patent Laid-Open No. 59-224341), (9) Flexible container with improved durability, flexibility and creep resistance As a base material, a resin layer is laminated on a woven fabric made of a multi-layer tape having polypropylene as a core layer and high-density polyethylene as an outer layer (JP-A-1-124649), (10) Light weight, high strength and high frequency As a tarpaulin suitable for a flexible container base material having a good sealing property, a woven fabric having a entangled weave structure composed of a polyolefin-based drawn yarn is coated with an ethylene-vinyl acetate copolymer (special Flat 3-46303 JP), (1
1) As a woven fabric for a flexible container having excellent heat creep resistance, a woven fabric made of a mixed twisted filament of polypropylene multifilament and polyethylene multifilament, laminated with ethylene-vinyl acetate resin (Japanese Patent Laid-Open No. 7- No. 54239) is disclosed.

[0007]

However, in any of the above-mentioned methods, the tensile strength, fusion strength, peeling strength, heat resistance, etc. of the base material for flexible containers are insufficient, and the formation and coating of woven cloth Since the method and bag-making method are complicated and the productivity is poor, further improvement has been demanded. INDUSTRIAL APPLICABILITY The present invention solves the above-mentioned conventional drawbacks, enables bag making by a heat fusion method, is lightweight and robust, and can be manufactured at low cost, and is particularly effective as a flexible container substrate. The purpose is to provide a laminate sheet.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies and found that the above problems can be solved by laminating a specific resin on a base cloth which is a woven cloth of thermoplastic resin yarns. The present invention has been completed and the present invention has been completed.

That is, the present invention provides the following (1) to (5):
The present invention relates to a laminate sheet characterized in that

(1) A laminate sheet in which a coating layer is formed on both sides of a woven fabric woven of a thermoplastic resin stretched yarn, the coating layer comprising ethylene produced using a metallocene catalyst. A laminate sheet, which is an ethylene / α-olefin copolymer composed of an α-olefin having 3 or more carbon atoms.

(2) A laminate sheet in which a coating layer is formed on both sides of a woven fabric woven of a stretched yarn made of a thermoplastic resin, the coating layer being produced by using A) a metallocene catalyst. Linear ethylene / α-olefin copolymer 95 consisting of ethylene and α-olefin having 3 to 20 carbon atoms
5% by weight and B) low density polyethylene 5 to 95% by weight
2. A laminate sheet comprising the resin composition of

(3) A) of the resin composition constituting the coating layer
Linear ethylene / α composed of ethylene and an α-olefin having 3 to 20 carbon atoms, which is produced by using a metallocene catalyst
-The olefin copolymer has the following properties (a) to (d), the laminate sheet according to item (2) above.

(A) Density: 0.880 to 0.935 g / cm ³ (b) Melt Flow Rate (MFR): 1.0 to 50 g
/ 10 minutes (c) Weight average molecular weight (Mw) and number average molecular weight (Mn)
Ratio (Mw / Mn): 3 or less (d) One melting point measured by DSC, 65-1
Range of 25 ° C. (4) B) Low-density polyethylene of the resin composition constituting the coating layer is obtained by high-pressure radical polymerization, and has a density of 0.9.
The low density polyethylene having a melt flow rate (MFR) in the range of 10 to 0.935 g / cm ^{3 in} the range of 1.0 to 20 g / 10 min. (2) or (3). The laminated sheet according to item.

(5) A woven fabric obtained by weaving a stretched yarn made of a thermoplastic resin, the first polyolefin resin as an inner layer, and the outer surface of the second polyolefin resin having a melting point lower than that of the first polyolefin resin. (1) to (4), characterized in that a flat yarn having a multilayer structure or a flat monofilament having a core-sheath structure obtained by drawing a composite yarn having an outer layer as a warp is formed as warp and weft. Laminated sheet.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the synthetic resin used as the coating layer of the laminate sheet is ethylene and α-C3 or more having a carbon number of 3 or more produced by using a metallocene catalyst.
An ethylene / α-olefin copolymer composed of an olefin, more preferably a linear ethylene / α-olefin copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms, which is produced by using a metallocene catalyst. It is united.

The metallocene catalyst used for producing the ethylene / α-olefin copolymer is an organic transition metal compound (I) containing a cyclopentadienyl derivative, and reacts with this to form an ionic complex. It is a catalyst composed of the compound (II) and / or the organometallic compound (III).

The organic transition metal compound (I) which constitutes the metallocene catalyst is, for example, an organic transition metal compound containing a transition metal of Group 4 of the periodic table and has the following general formula (1) or (2):

[0018]

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[Wherein, M ¹ is a titanium atom, a zirconium atom or a hafnium atom, Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, wherein R ¹ and R ² are each independently the following general formula (3), (4), (5) or (6)

[0020]

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(In the formula, each R ⁶ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms). Is a ligand, and the ligand is M
^A sandwich structure is formed together with ^1, and R ⁴ and R ⁵ are each independently the following general formula (7), (8), (9) or (1
0)

[0022]

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(In the formula, each R ⁷ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms). Is a ligand, and the ligand is M
^A sandwich structure is formed with ¹ and R ³ is represented by the following general formula (11).

[0024]

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(In the formula, each R ⁸ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms, and M ² is a carbon atom. Atom, a silicon atom, a germanium atom or a tin atom), acting to crosslink R ⁴ and R ⁵ , and p is an integer of 1 to 5].

Specific examples of the organic transition metal compound (I) represented by the general formula (1) or (2) include, for example,
Bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) zirconium Dichloride, bis (methylcyclopentadienyl) hafnium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) hafnium dichloride, bis (pentamethyl) Cyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclope Tajieniru) hafnium dichloride, bis (indenyl) titanium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) hafnium dichloride, methylenebis (cyclopentadienyl) titanium dichloride,
Methylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) hafnium dichloride, methylenebis (methylcyclopentadienyl) titanium dichloride, methylenebis (methylcyclopentadienyl) zirconium dichloride, methylenebis (methylcyclopentadienyl) Hafnium dichloride, methylenebis (butylcyclopentadienyl) titanium dichloride, methylenebis (butylcyclopentadienyl) zirconium dichloride, methylenebis (butylcyclopentadienyl) hafnium dichloride, methylenebis (tetramethylcyclopentadienyl) titanium dichloride, methylenebis ( Tetramethylcyclopentadienyl) zirconium dichloride Methylenebis (tetramethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride, ethylenebis (tetrahydro) Indenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) hafnium dichloride, ethylenebis (2-methyl-1-indenyl) titanium dichloride, ethylenebis (2-methyl-1-indenyl) zirconium dichloride, ethylenebis (2-methyl) -1-Indenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-9-fluorene) ) Titanium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,7-dimethyl-9) -Fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, isopropylidene (Cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butyl-
9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-)
Butyl-9-fluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopenta) Dienyl-2,
7-dimethyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-
2,7-Dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-) Butyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-) Butyl-9
-Fluorenyl) hafnium dichloride, dimethylsilanediylbis (cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) hafnium dichloride, dimethylsilanediylbis ( Methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) titanium dichloride , Dimethylsilanediylbis (butylcyclopentadienyl) zirconium dichloride, dimethylsilane Ilbis (butylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, dimethyl Silanediylbis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) titanium Dichloride, dimethylsilanediylbis (indenyl) titanium dichloride, dimethylsilanediylbis (2-methyl-indenyl) titanium dichloride, dimethylsilanediyl S (tetrahydroindenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (Cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,2 4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (4-t-butyl-2) -Methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium Dichloride, dimethylsilanediyl (cyclopentadienyl-
2,7-Dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilanediylbis (2,4,5- Trimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (2-
4-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, dimethyl Silanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, dimethylsilanediylbis (2-methyl-indenyl) hafnium dichloride, dimethylsilanediylbis (tetrahydroindenyl) hafnium dichloride, Dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2, -Dimethyl-9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopenta) Dienyl) titanium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (4-t-butyl) 2-Methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (indenyl) titanium dichloride Id, diethylsilanediylbis (2-methyl-indenyl) titanium dichloride, diethylsilanediylbis (tetrahydroindenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclo) Pentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diethylsilanediylbis (2,2) 4,5-Trimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis ( 3-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride,
Diethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, diethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium Dichloride, diethylsilanediyl (cyclopentadienyl-
2,7-dimethyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diethylsilanediylbis (2,4,5- Trimethylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (3-
Methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (4-t-butyl-2-
Methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (indenyl) hafnium dichloride,
Diethylsilanediylbis (2-methyl-indenyl)
Hafnium dichloride, diethylsilanediylbis (tetrahydroindenyl) hafnium dichloride,
Diethylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9)
-Fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-
Butyl-9-fluorenyl) hafnium dichloride,
Diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) ) Titanium dichloride, diphenylsilanediylbis (4
-T-butyl-2-methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (indenyl) titanium dichloride, diphenylsilanediylbis (2
-Methyl-indenyl) titanium dichloride, diphenylsilanediylbis (tetrahydroindenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl) -9-Fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) )
Zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (3-
Methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t-butyl-2)
-Methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, diphenylsilanediylbis (2-methyl-)
Indenyl) zirconium dichloride, diphenylsilanediylbis (tetrahydroindenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9- Fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride , Diphenylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (4-t-buter-2-methylcyclo) Pentadienyl) hafnium dichloride. Diphenylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (indenyl) hafnium dichloride, diphenylsilanediylbis (2-methyl-indenyl) hafnium dichloride, diphenylsilanediylbis (tetrahydroindenyl) hafnium dichloride , Diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-
2,7-dimethyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, and other dichlorates and Group 4 transition metal compounds Dimethyl form, diethyl form, dihydro form,
Examples thereof include a diphenyl form and a dibenzyl form.

Examples of the compound (II) which forms an ionic complex include a protic acid, a Lewis acid, an ionized ionic compound and a Lewis acidic compound.

Examples of the protonic acid include, for example, the following general formula (12) [HL1 _l ] [M ³ R ⁹ ₄ ] (12) (wherein, H is a proton and L 1 is independently a Lewis base, l is 0 <l ≦ 2, M ³ is a boron atom, an aluminum atom or a gallium atom, and R ⁹
Are each independently a halogen-substituted aryl group having 6 to 20 carbon atoms. )).

As the Lewis acid, for example, the following general formula (1
3) A compound represented by [C] [M ³ R ⁹ ₄ ] (13) (wherein C is a carbonium cation or a tropylium cation, and M ³ and R ⁹ are the same as defined above). You can

As the ionized ionic compound, for example, the following general formula (14) [M ⁴ L2 _m ] [M ³ R ⁹ ₄ ] (14) (wherein, M ⁴ is group 2, 8 or 9 of the periodic table) Tribe, 10 tribe, 1
A cation of a metal selected from Group 1 or Group 12,
L2 is a Lewis acid or a cyclopentadienyl group,
m is 0 ≦ m ≦ 2, and M ³ and R ⁹ are the same as defined above).

Examples of the Lewis acidic compound include compounds represented by the following general formula (15) [M ³ R ⁹ ₃ ] (15) (wherein M ³ and R ⁹ are the same as defined above). it can.

Further, as the compound (II) forming an ionic complex, a compound having a bond of aluminum and oxygen can be mentioned. As a concrete example, the following general formula (1)
6) or (17)

[0033]

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[Wherein each R ¹⁰ is independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 24 carbon atoms, or an aryl group, an aryloxy group, an arylalkyl group having 6 to 24 carbon atoms, An arylalkoxy group, an alkylaryl group or an alkylaryloxy group, wherein at least one R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group or an alkylaryl group. And t is an integer of 0 to 100. ] It is an aluminoxane represented by. Specific examples of R ¹⁰ include chlorine, bromine, iodine, methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, methyl group, ethyl group, propyl group, butyl group, hexyl group, phenyl group,
Examples thereof include a benzyl group, a tolyl group and a cyclohexyl group.

The compound (II) forming an ionic complex used as a constituent component of these metallocene catalysts is
It is a compound capable of converting the above organic transition metal compound (I) into a cationic compound, and is a compound that provides a counter anion that weakly coordinates and / or interacts with the produced cationic compound but does not react.

Specific examples of the protonic acid represented by the above general formula (12) include, for example, diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis ( Pentafluorophenyl) borate, Hydronium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (pentafluorophenyl)
Borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) Aluminate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilium tetrakis (pentafluorophenyl) aluminate, tri-
Examples thereof include, but are not limited to, n-butylammonium tetrakis (pentafluorophenyl) aluminate.

Specific examples of the Lewis acid represented by the general formula (13) include trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tropylium tetrakis (pentafluorophenyl). Examples thereof include borate and tropylium tetrakis (pentafluorophenyl) aluminate, but are not limited thereto.

Specific examples of the ionizable ionic compound represented by the general formula (14) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate, or ethers thereof. Complexes, ferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium salts such as ferrocenium tetrakis (pentafluorophenyl) aluminate, silver tetrakis (pentafluorophenyl) borate, silver such as silver tetrakis (pentafluorophenyl) aluminate Salts may be mentioned, but are not limited to these.

Specific examples of the Lewis acidic compound represented by the general formula (15) include, for example, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris ( 2, 3, 4, 5
-Tetraphenylphenyl) borane, Tris (3,4,
5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum and the like,
It is not limited to these.

The organometallic compound (III) constituting the metallocene catalyst in the present invention is represented by the following general formula (18) M ⁵ R ¹¹ _n (18) (wherein, M ⁵ is a group 1, 2 or 13 group in the periodic table). R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group, or an alule group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, or aryl. It is an alkoxy group, an alkylaryl group or an alkylaryloxy group, and at least one R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. Yes, n is M ⁵
Equal to the oxidation number of. ).

Specific examples of the compound represented by the general formula (18) include, for example, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, and thoria. Mill aluminum, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di-n-propyl aluminum ethoxide, diisobutyl aluminum ethoxide,
Di-n-butyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum hydride, di-n-propyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride and the like can be exemplified. It is not limited to these.

A metallocene catalyst is prepared from an organic transition metal compound (I) containing a cyclopentadienyl derivative, a compound (II) which reacts with the organic transition metal compound (II) and / or an organic metal compound (III). Examples of the method include, but are not limited to, a method of mixing these compounds in an inert solvent. The amount of the compound (II) forming an ionic complex in the metallocene catalyst is determined by the amount of the organic transition metal compound (I)
It is preferably 0.1 to 100 times mol, and particularly preferably 0.5 to 30 times mol. further,
The amount of the organometallic compound (III) is not particularly limited,
Preferably 1 to 10 relative to the organic transition metal compound (I)
It is 000 times the molar amount.

The linear ethylene / α-olefin copolymer used in the coating layer of the laminate sheet of the present invention has ethylene and 3 to 2 carbon atoms in the presence of the above metallocene catalyst.
It can be suitably produced by copolymerizing 0 α-olefin.

As the α-olefin having 3 to 20 carbon atoms, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene, 1-nonene, 1-
Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, and the like can be given.

The method for polymerizing ethylene and α-olefin is not particularly limited, but the following polymerization methods can be exemplified.

The polymerization conditions for the solution polymerization method are as follows. The polymerization temperature is preferably the melting point or higher in consideration of the fact that the copolymer is in a solution state and improving productivity. Although the upper limit of the polymerization temperature is not particularly limited, it is preferably 300 ° C. or lower in order to suppress the chain transfer reaction that causes a decrease in the molecular weight and not decrease the catalyst efficiency. The pressure during the polymerization is not particularly limited, but is preferably at least atmospheric pressure in order to increase the productivity.

The polymerization conditions for the high pressure polymerization method are as follows. The polymerization temperature is preferably 120 ° C. or higher in consideration of the fact that the copolymer is in a solution state and improving productivity. Although the upper limit of the polymerization temperature is not particularly limited, it is preferably 300 ° C. or lower in order to suppress the chain transfer reaction that causes a decrease in the molecular weight and not decrease the catalyst efficiency. The pressure during the polymerization is not particularly limited, but a stable polymerization state can be obtained in the high pressure process 20.
It is preferably 0 kgf / cm ² or more.

In the gas phase polymerization method, the high temperature is not preferable because the copolymer is in a powder state, and it is preferably 100 ° C. or lower. The lower limit of the polymerization temperature is not particularly limited, but is preferably 50 ° C. or higher in order to increase productivity.

A linear ethylene / α-olefin copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms, which is produced by using a metallocene catalyst, is represented by (a) to (d) below. Those having characteristics are preferable as the coating layer of the laminate sheet.

(A) Density: 0.880 to 0.935 g /
cm ^3, preferably the increases the self-adhesive laminate sheet and 0.890~0.925g / cm ³ density of less than 0.880 g / cm ^3, the blocking occurs is not preferable. When the density exceeds 0.935 g / cm ³ , the effect of improving the adhesiveness is not seen, which is not preferable. In the ethylene / α-olefin copolymer used in the present invention, even if the density is lowered, the low molecular weight component that causes stickiness does not rapidly increase, and a copolymer in the low density region as described above can be realized. As a result, strong adhesion with base materials such as drawn yarn is obtained,
Furthermore, low-temperature fusion processing and the like can be easily realized.

(B) Melt flow rate (MFR):
1.0 to 50 g / 10 minutes, preferably 3 to 30 g / 10
The MFR in the present invention is in accordance with JIS K 6760, 190
It was measured under a load of 2160 g at ℃. MFR
Is less than 1.0 g / 10 minutes, the melt shear viscosity is high and the load on the extruder is high, which is not preferable. Further, the drawdown property is also deteriorated, which is not preferable. MFR is 50g /
If it exceeds 10 minutes, the stability of the ears becomes poor and the neck-in becomes large, so that the film forming stability becomes poor, which is not preferable.

(C) Ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn): 3 or less, preferably 1.5 to 3.0 If Mw / Mn deviates from the above range, The effect of improving the adhesiveness with the drawn yarn becomes insufficient. Mw and Mn
Is, for example, Waters 150C ALC / GP
C (column: Tohso GMHHR-H (S), solvent:
GPC using 1,2,4-trichlorobenzene)
Method, and Mw / Mn may be calculated. The column elution volume is calibrated by the universal calibration method using Tosoh standard polystyrene.

(D) One melting point measured by DSC, in the range of 65 to 125 ° C. If the melting point deviates from the above range, the effect of improving the adhesiveness to drawn yarn or the like becomes insufficient. In addition, when the melting points are plural, the compositional distribution of the copolymer becomes wide, and the effect of improving the adhesiveness with the drawn yarn becomes insufficient.

The melting point may be measured using a differential scanning calorimeter "DSC-7" manufactured by Perkin Elmer. The sample was melted in the apparatus at 200 ° C. for 5 minutes and then cooled to 30 ° C. at a cooling rate of 10 ° C./min.
The temperature at the position of the maximum peak of the endothermic curve, which is obtained when the temperature is raised at a heating rate of 0 ° C./min, is the melting point.

The ethylene / α-olefin copolymer used in the coating layer of the laminate sheet of the present invention, when used in combination with low density polyethylene, has a lower temperature sealing property,
A laminated sheet having excellent peel strength and breaking strength can be obtained.

The low density polyethylene used in combination with the ethylene / α-olefin copolymer has a melt flow rate (MFR) in the range of 0.910 to 0.935 g / cm ³ obtained by high pressure radical polymerization. Is 1.0 to 20
The range of g / 10 minutes is suitable, and ethylene / α-
Like the olefin copolymer, it is appropriately selected depending on the application.

Low density polyethylene has an MFR of 1.0 to
20 g / 10 minutes, preferably 3.0-15.0 g / 10
Minutes are excellent in terms of workability balance. MFR
Of less than 1.0 g / 10 minutes is not preferable because the drawdown property is poor. If it exceeds 20 g / 10 minutes, the neck-in becomes large, which is not preferable.

When used in combination with low density polyethylene, the proportion of ethylene / α-olefin copolymer to be blended is 5
˜95% by weight, preferably 10 to 90% by weight. When the ethylene / α-olefin copolymer exceeds 95% by weight, the melt tension of the composition becomes low and the neck-in becomes large,
Further, the decrease in melt shear viscosity is insufficient and the motor load of the extruder is high, which is not suitable for extrusion laminate molding. On the other hand, when the content of the ethylene / α-olefin copolymer is less than 5% by weight, the improvement of the adhesive strength of the laminated raw fabric becomes insufficient.

In terms of adhesion, MFR of both low density polyethylene and ethylene / α-olefin copolymer
Is within the above range, but the MFR ratio of the low density polyethylene and the ethylene / α-olefin copolymer is 1: 1.
When it is in the range of 1 to 20, the moldability during extrusion lamination is improved.

In the present invention, the material for laminating comprising the composition of the linear ethylene / α-olefin copolymer and the low density polyethylene is a dry blend of the copolymer pellets and the low density polyethylene pellets. Also good, single screw extruder, twin screw extruder, Banbury mixer,
Melt-kneading with various kneaders or the like is preferable because a stable quality can be obtained. Also, the composition comprises
Antioxidant, antistatic agent, lubricant, neutralizing agent, if necessary
Additives that are usually used for polyolefins, such as antiblocking agents, may be added, but it is preferable not to add additives that inhibit adhesion.

As the base fabric of the laminated sheet of the present invention, a woven fabric obtained by weaving a stretched yarn made of a thermoplastic resin having good weather resistance is used.

As a yarn made of a thermoplastic resin used as a base cloth, a fiber having a high strength as a fiber shape, little deterioration during weaving, and good weaving can be used as a multifilament, a monofilament, a flat filament. Monofilaments, flat yarns, etc. are not particularly limited, but multifilaments tend to break easily during weaving and are inferior in handleability. Monofilaments have a relatively large cross-sectional diameter and a large woven fabric thickness, resulting in flexibility. However, flat monofilaments and flat yarns are preferably used.

As the thermoplastic resin used for the base cloth,
Any yarn or woven fabric can be used as long as it can obtain high strength, and examples thereof include polyolefin resin, polyester resin, polyamide resin, polyvinyl chloride resin, polyvinylidene chloride-vinyl copolymer resin. However, in order to maintain high strength, it is necessary to withstand the processing temperature at the time of forming the laminate coating layer.

Of these, polyolefin resins are preferably used because of their stable quality in continuous production and economical mass production. In other words, polyolefin resins such as high-density polyethylene and polypropylene are resins with a relatively low melting point, and in conventional containers for flexible containers that use polyvinyl chloride or ethylene-vinyl acetate copolymer for the laminate coating layer. However, heat deterioration is likely to occur and its use is limited, but when a specific resin composition having good melt adhesion is used for the laminate coating layer as in the present invention, heat deterioration is suppressed and it is sufficiently used. It is suitable for use because of its advantages such as ease of molding, low cost and light weight.

In particular, the structure of the composite yarn is preferable as a method for suppressing the thermal deterioration of the yarn made of the polyolefin resin. Specifically, a multilayer structure obtained by stretching a composite yarn having a first polyolefin-based resin as an inner layer and a second polyolefin-based resin having a lower melting point than the first polyolefin-based resin as an outer layer on the outer surface thereof. Flat yer
It is a flat monofilament with a core or sheath structure.

That is, since the second polyolefin resin is firmly bonded to the laminate coating layer without losing the stretching effect of the first polyolefin resin forming the composite yarn, The difference in melting point of the second polyolefin resin should be 5 ° C. or higher, preferably 10 ° C. or higher. Here, specifically, as the first polyolefin-based resin, medium density polyethylene, high density polyethylene, polypropylene, polybutene-1, poly-4-
Methyl pentene-1 etc. are mentioned, and as the second polyolefin resin, ultra low density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, Examples include maleic anhydride-modified polyolefin, ethylene-propylene copolymer, and the like.

As a method for molding such a composite yarn, a well-known technique may be adopted, and a flat yarn having a multilayer structure is coextrusion laminated by a multilayer T die flat method or an inflation method. Alternatively, it can be obtained by chopping a three-layer film composed of a core layer and both outer layers laminated by a sequential extrusion laminar method, and then longitudinally uniaxially stretching it, and then subjecting it to a heat treatment. The flat monofilament of is a composite filament in which a core layer and a resin layer of a sheath layer are extruded and coated on the outer surface of a core layer from a die provided with discharge holes in a substantially concentric shape, and then the filament is uniaxially stretched, followed by heat treatment. Obtainable.

The fineness of the above-mentioned thermoplastic resin yarn is determined in consideration of the mechanical strength required for the woven fabric, and is not particularly limited, but for example, a flexible container substrate and If so, preferably the fineness is 500
~ 5,000dr, more preferably 1,000-3,000dr. That is, if the fineness is less than 500dr, the mechanical strength of the yarn constituting the base material for the flexible container is not sufficient,
On the other hand, when the fineness exceeds 5,000dr, not only the weaving efficiency is poor, but also the flexibility as a woven fabric is poor, and further, the lamination with the laminate coating layer is not formed tightly, and the peel strength and the welding strength are This is a problem in that the physical properties required for the base material for flexible containers such as the above cannot be satisfied.

The thermoplastic resin yarn is woven into a woven fabric by using a known loom such as a circular loom, a sulzer type loom, and a water jet type loom, and the weaving structure is Various shapes such as plain weave, twill weave, and entangled weave are applied.

This woven fabric is provided with a coating layer of the above-mentioned resin or resin composition on both front and back surfaces thereof, and is laminated sheet.
It becomes By forming this coating layer, the mechanical strength of the sheet is increased, and the sheet has a strong heat-sealing property due to the heat seal. The contamination of the filler due to the mixture of foreign substances and the penetration of moisture into the bag body is prevented.

In forming the coating layer, extrusion laminae are used.
Known techniques such as a coating method, a calendar method, a coating method, and a dipping method are adopted. At the time of this resin coating, the molten resin bites into the interstices of the woven fabric so that they adhere to each other, or the resin penetrates between the front and back of the gap created at the intersection of the warp and weft yarns, thereby binding the front and back layers and creating a bridge effect This is effective because the peel strength can be improved. Further, the thickness of the coating layer is not particularly limited, but in general, it is preferably about 40 to 100 μm per side in view of the strength of the base material and the heat fusion property.

The laminate sheet of the present invention thus obtained has a good sealing property at low temperature and is effective as a sheet excellent in peel strength and rupture strength of a heat-sealed portion, and is particularly useful for bonding. This is the most suitable laminate sheet for the base material for flexible containers etc. to which the fusion method is adopted.

[0073]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 (Production of Linear Ethylene / α-Olefin Copolymer) The linear ethylene / α-olefin copolymer was polymerized using a high temperature and high pressure reactor. Ethylene and 1-butene or 1-hexene as a comonomer for adjusting the density were continuously pressed into the reactor, and the total pressure was 950 kgf / cm ^2.
Kept. The reactor was stirred at 1,500 rpm, the following catalyst solution was supplied to the reactor at a rate of 120 cm ³ / hour, the temperature of the reactor was set to 193 ° C., and continuous polymerization was performed.

A toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride as a transition metal compound (I) containing a cyclopentadienyl derivative and a toluene solution of triisobutylaluminum as an organometallic compound (III) were prepared. , Aluminum was added in an amount of 250 times mol per zirconium. Further, as a compound (II) that reacts with the catalyst component to form a complex, a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate is added so that the boron content is 2 times the mole of zirconium. To obtain a catalyst solution. The characteristics of the linear ethylene / α-olefin copolymer produced according to the above production example are as follows: density = 0.898 g / cm ³ , MFR = 10.5 g / 10 min,
Mw / Mn = 2.0, melting point = 88 ° C.

Example 1 Using high-density polyethylene (MFR = 1.0 g / 10 min), the film was put into an extruder and extruded from a circular die by an inflation method to form a film, which was then cut into a tape shape. age,
Fineness of 2,000 drawn by hot plate contact drawing method with a draw ratio of 5.2
A flat woven fabric having a striking density of 15 × 15 yarns / inch was made into a base sheet by using 0 dr flat yarn for the warp yarn and the weft yarn. In forming the coating layers on the front and back surfaces of the base sheet, the linear ethylene.α-
Low density polyethylene obtained by high-pressure radical polymerization for olefin copolymers (density = 0.918 g / cm ³ , MFR = 4.
(0 g / 10 min) was changed to a compounding amount of 20, 50, and 80% by weight, and coated on the front and back sides to a thickness of 60 μm by a melt extrusion lamination method to obtain a laminate sheet.

Comparative Example 1 Similar to Example 1 except that linear low density polyethylene (MFR = 8.0 g / 10 min) produced by using a Ziegler catalyst was used as the laminate resin in the formation of the coating layer. Then, a laminate sheet was prepared.

Example 2 High density polyethylene (MFR = 1.0 g / 10 min) was used as the core layer resin,
Ethylene-vinyl acetate (MFR = 4.5g / 10min, VA content
15%) is used as the outer layer resin, and each is put into two series of extruders to be extruded from the T-type die by the multi-layer T-die flat method to form a three-layer film, which is then shredded into a tape shape, and then heated. Fineness drawn by the contact drawing method at a draw ratio of 4.8 times
A 1,500-dr multi-layer flat yarn was used for the warp and the weft, and a plain weave fabric with a shot density of 16 × 16 / inch was made into a base sheet. When forming coating layers on the front and back surfaces of the base sheet, a low density polyethylene (density = 0.918) obtained by radical polymerization of the linear ethylene / α-olefin copolymer as a laminate resin is used. g / cm ³ , MF
R = 4.0 g / 10 min) was changed to a compounding amount of 20, 50, and 80% by weight, and the front and back sides were 60 by the melt extrusion laminating method.
Coated to a thickness of μm, a laminate sheet was obtained.

Comparative Example 2 In the formation of the coating layer, ethylene-methyl methacrylate (MFR = 8.0 g / 10 min, MMA content 20) was used as the laminate resin.
%) Was used in the same manner as in Example 2 except that
Created.

When the laminate sheets of Examples and Comparative Examples according to the present invention were used as a substrate for a flexible container, their performances were measured and evaluated.
Shown in

[0081]

[Table 1]

In the measurement items in Table 1, the tensile strength and tear strength were measured by a tensile tester at a gripping interval of 150 mm and a tensile speed of 200 mm / min in accordance with JIS-Z1651. The fusing peel strength is obtained by stacking two base materials and covering the edges over a width of 40 mm with a welding temperature using a hot air pressure bonding machine.
Instead of 310, 365, 390 ℃, the pressure is 2 Kg / cm ² ,
Heat-bonded at a fusion speed of 2.1 m / min and cut into a piece with a width of 30 mm as a test piece.
Peeling was performed at 180 degrees at m 2 and a pulling speed of 200 mm / min.

From the results shown in Table 1, the laminator sheet of the present invention
The adhesiveness of the coating layer to the base sheet is good, and the tensile strength, tear strength, and peeling strength are stronger than those using the conventional coating resin. It was confirmed that the wearability was excellent. A resin composition containing a linear ethylene / α-olefin copolymer and low-density polyethylene obtained by high-pressure radical polymerization has a processability in forming a coating layer by a melt extrusion lamination method. It was in a very good condition such as stability.

[0084]

INDUSTRIAL APPLICABILITY As described above, the laminated sheet of the present invention has good low-temperature sealability and excellent peeling strength and breaking strength at the heat-sealed portion, and is particularly useful as a base material for flexible containers. . The laminated sheet of the present invention can be manufactured at low cost by using a woven cloth obtained by weaving a stretched yarn made of an inexpensive thermoplastic resin as a base cloth and forming a coating layer of a specific resin.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hitoshi Asabe 2111-1, Chayamachi, Kurashiki City, Okayama Prefecture

Claims (5)

[Claims] 1. A laminate sheet in which a coating layer is formed on both sides of a woven fabric woven from a stretched yarn made of a thermoplastic resin, the coating layer being produced by using a metallocene catalyst.
A laminate sheet, which is an ethylene / α-olefin copolymer composed of ethylene and an α-olefin having 3 or more carbon atoms. 2. A laminate sheet in which a coating layer is formed on both sides of a woven fabric obtained by weaving a stretched yarn made of a thermoplastic resin, wherein the coating layer is ethylene produced by using A) a metallocene catalyst. And a linear ethylene / α-olefin copolymer (95 to 5% by weight) composed of α-olefin having 3 to 20 carbon atoms and B) low density polyethylene (5 to 95% by weight). Laminated sheet. 3. Ethylene and C3 to C3 produced using a metallocene catalyst A) of the resin composition constituting the coating layer.
The linear ethylene / α-olefin copolymer consisting of 20 α-olefins has the following properties (a) to (d), and the laminate sheet according to claim 2. (A) Density: 0.880 to 0.935 g / cm ³ (b) Melt flow rate (MFR): 1.0 to 50 g
/ 10 minutes (c) Weight average molecular weight (Mw) and number average molecular weight (Mn)
Ratio (Mw / Mn): 3 or less (d) One melting point measured by DSC, 65-1
25 ° C range 4. The melt flow rate (MFR) of B) low density polyethylene of the resin composition constituting the coating layer is obtained by high pressure radical polymerization, and has a density in the range of 0.910 to 0.935 g / cm ^3. Is a low-density polyethylene in the range of 1.0 to 20 g / 10 minutes, and the laminated sheet according to claim 2 or 3, wherein 5. A woven fabric obtained by weaving a stretched yarn made of a thermoplastic resin, wherein a first polyolefin resin is used as an inner layer and a second polyolefin resin having a lower melting point than the first polyolefin resin is provided on the outer surface thereof. The laminated sheet according to any one of claims 1 to 4, wherein a flat yarn having a multilayer structure or a flat monofilament having a core-sheath structure obtained by drawing a composite yarn as an outer layer is configured as a warp and weft yarn.