JP2001030446A - Laminated cloth sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated cloth sheet with which a product with strong adhesiveness, excellent strength and high seal strength can be inexpensively produced even by an extrusion lamination processing method without restricting a material of a woven fabric base material. SOLUTION: After the surface of a woven fabric base material consisting of a thermoplastic resin drawn thread is anchor coat-treated, the treated surface is laminated with a resin layer comprising a polyethylene resin material wherein an ethylene-α-olefin copolymer with a density of 0.870-0.920 g/cm3, a MFR of 1-100 g/10 min, the max. peak temp. of an eluation curve by TREF of 25-85 deg.C, and an amt. of eluation at 90 deg.C or lower being at least 90 wt.% is a main ingredient to prepare a laminated cloth sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminated cloth sheet formed by laminating a woven (cloth) base material and a resin layer. More specifically, the present invention relates to a laminated cloth sheet which is sealed by a method such as a high-frequency welder or a heat seal and used as a flexible container, a cover, a bag, or the like.

[0002]

2. Description of the Related Art Conventionally, as a cross sheet used for a flexible container or the like, a laminated cloth sheet in which a polyvinyl chloride resin is laminated on a woven cloth (cloth) made of a drawn yarn of a thermoplastic resin such as polyester or polyamide is used. Have been. However, since a large amount of a plasticizer is blended into the polyvinyl chloride resin for the purpose of improving flexibility and the like, the plasticizer bleeds (dissolves) and easily migrates to the filler or adheres to dirt. The problem has been pointed out.

Therefore, recently, instead of polyvinyl chloride resin, an ethylene / vinyl acetate copolymer system is laminated (Japanese Patent Application Laid-Open Nos. 58-148760 and 59-22).
No. 4341, Japanese Patent Publication No. 3-46330, etc.), lamination of a resin containing linear low-density polyethylene as a main component (Japanese Utility Model Publication No. 4-32273, etc.), and ethylene produced using a metallocene catalyst. .Laminates of α-olefin copolymers (JP-A-9-201924, etc.)
And the like, a laminated cross sheet using a polyethylene resin has been developed.

However, since the adhesiveness to the woven fabric substrate is not sufficient, the sealing strength by a high-frequency welter, a heat seal or the like is not sufficient. In particular, in the case of manufacturing by an extrusion laminating method, the thermoplastic resin of the woven fabric substrate is limited to the polyethylene resin because the adhesion of the polyethylene resin to the woven fabric substrate is heat fusion. For this reason, a woven fabric substrate of another stretched thermoplastic resin yarn having excellent strength cannot be used, and only poor strength is obtained.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a product having strong adhesiveness, excellent strength, and high sealing strength without limiting the resin material of the woven fabric substrate, even if the extrusion lamination method is used. It is an object of the present invention to provide a laminated cross sheet that can be manufactured at a high speed.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, compared a specific ethylene / α-olefin copolymer with a woven fabric substrate having been subjected to anchor coating treatment. Lamination by extrusion lamination at a low temperature, it is possible to obtain a laminated cloth sheet with strong tensile strength, strong adhesion and high sealing strength without deterioration of the woven fabric substrate, and completed the present invention. did.

That is, the present invention provides a woven fabric formed of a stretched thermoplastic resin yarn, at least one surface of which is anchor-coated, and laminated on the anchor-coated surface of the woven fabric. A laminated cloth sheet having a resin layer, wherein the resin layer is formed of a polyethylene-based resin material mainly composed of an ethylene / α-olefin copolymer satisfying the following physical properties (a) to (c). To provide a laminated cross sheet. (A) The density is 0.870 to 0.920 g / cm ³ . (B) MFR is 1 to 100 g / 10 minutes. (C) The maximum peak temperature of the elution curve by temperature rise elution fractionation (TREF) is 25 to 85 ° C, and the elution amount at 90 ° C or lower is 90% by weight or more based on the total amount of the ethylene / α-olefin copolymer. That.

Further, the present invention provides the laminated cloth sheet, wherein the ethylene / α-olefin copolymer is polymerized using a metallocene compound as a polymerization catalyst. Further, in the present invention, the polyethylene-based resin material may be such that the ethylene / α-olefin copolymer: 30 to 9
9% by weight and a density of 0.915 to 0.950 g / cm ³
Ethylene resin having an MFR of 1 to 100 g / min: 7
0 to 1% by weight of the laminated cloth sheet. Further, the present invention provides the laminated cross sheet obtained by press-laminating the woven fabric substrate and the resin layer by an extrusion laminating method.

[0009]

Embodiments of the present invention will be described below. The laminated cloth sheet of the present invention is a laminate of a woven fabric substrate and a resin layer.

(1) Woven Fabric Substrate The woven fabric substrate is formed of a woven fabric made of drawn thermoplastic resin yarn. Examples of the thermoplastic resin constituting the drawn yarn include polyethylene and polypropylene (including propylene-based copolymers such as ethylene-propylene copolymer, propylene-butene copolymer, and propylene-hexene copolymer). Examples include polyolefin-based resins, polyester-based resins, polyamide-based resins, polyacryl-based resins, and polyvinyl alcohol-based resins. The molecular weight of the thermoplastic resin is not particularly limited. Further, a lubricant, an antiblocking agent, a stabilizer, an antioxidant, an antistatic agent, an antifogging agent, a flame retardant, a colorant, and other additives may be appropriately blended with the thermoplastic resin.

The drawn yarn is obtained by drawing the thermoplastic resin into a fiber shape. The fiber shape may be any shape such as a tape shape, a monofilament, a multifilament, and a mixed yarn. The woven fabric used in the present invention is woven into a cloth using the drawn yarn. The thickness of the drawn yarn is not particularly limited, but is preferably 100
It is about 3000 denier.

(2) Resin Layer The resin layer in the laminated cloth sheet of the present invention is formed of a polyethylene resin material mainly composed of an ethylene / α-olefin copolymer. Ethylene / α-olefin copolymer The ethylene / α-olefin copolymer needs to satisfy the following physical properties (a) to (c).

(A) Density The ethylene / α-olefin copolymer has a density of 0.870 to 0.920 g / cm ³ , preferably 0.8
80 to 0.905 g / cm ³ . 0.870 density
If it is less than g / cm ³ , the moldability such as the roll release property at the time of extrusion lamination molding is inferior, and the blocking property of the product also deteriorates.
On the other hand, if the density exceeds 0.920 g / cm ³ , the sealing properties will deteriorate. The density referred to here is JIS-K711.
It is a value measured according to the 2-A method.

(B) MFR The ethylene / α-olefin copolymer has a MFR
Is 1 to 100 g / 10 min, preferably 3 to 40 g / 10
Minutes. Any having an MFR outside the above range has too high or too low a melt viscosity, and thus is inferior in film-forming properties during extrusion lamination molding. The MFR mentioned here is JIS
It is a value measured according to -K7210 (condition 4).

(C) Elevated temperature fractionation fractionation The ethylene / α-olefin copolymer has a maximum peak temperature of 25 to 85 ° C. in an elution curve obtained by measurement by temperature-increased fractionation, and the peak temperature is 90 ° C. or less. The elution amount is 90% by weight or more based on the total amount of the ethylene / α-olefin copolymer.

Here, the temperature rising elution fraction in the present invention (Temperature Rising Elution Fraction: hereinafter referred to as “T
REF ”may be abbreviated as“ Journa
l ofApplied Polymer Science, Vol26, 4217-4231 (198
1) ”and“ Polymer Symposium Proceedings 2P1C09 (1985) ”.

First, the polymer to be measured is completely dissolved in a solvent and then cooled to form a thin polymer layer on the surface of the inert carrier. Such a polymer layer is formed such that an easily crystallizable material is formed on the inner side (closer to the surface of the inert carrier), and a hardly crystallizable material is formed on the outer side. next,
The temperature is increased continuously or stepwise, and components eluted at each temperature are collected. At this time, at the low temperature stage, the polymer is eluted from the amorphous portion in the polymer composition, that is, the polymer having a short-chain branch having a high degree of branching. , And the measurement is completed. In this way, the concentration of the eluted component recovered at each temperature is detected, and the elution amount and elution temperature are determined. A graph drawn by the elution amount and the elution temperature is an elution curve, from which the composition distribution of the polymer can be known.

The ethylene / α-olefin copolymer used in the present invention has a maximum peak temperature of 25 to 85 ° C., preferably 35 to 65 ° C. in an elution curve obtained by the TREF. Further, the elution amount at 90 ° C. or less is 9 to the total amount of the ethylene / α-olefin copolymer.
It is at least 0% by weight, preferably at least 95% by weight. When the maximum peak temperature is less than 25 ° C., the blocking resistance tends to be inferior. Further, those having the maximum peak temperature exceeding 85 ° C. and those having an elution amount of less than 90% by weight are not preferred because the sealing properties tend to deteriorate.

The ethylene / α-olefin copolymer satisfying the physical properties (a) to (c) is preferably a linear chain obtained by copolymerizing ethylene with an α-olefin having 3 to 12 carbon atoms. Ethylene-α-olefin copolymer. Specific examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, and 1-dodecene. These may be used alone or as a blend of two or more kinds to form a tertiary or higher multi-component copolymer.

The above-mentioned ethylene / α-olefin copolymer is a copolymer component other than the above-mentioned α-olefin, for example, unsaturated carboxylic anhydride such as maleic anhydride and itaconic anhydride, and aromatic vinyl such as styrene. A compound obtained by graft polymerization of a compound or the like may be used. In addition, it is preferable that the content of the copolymer component to be graft-polymerized is about 0.05 to 5% by weight. When the content of the graft component is within this range, the adhesion to the woven fabric substrate is improved.

The ethylene / α-olefin copolymer used in the present invention may be produced by any method as long as it satisfies the above physical properties (a) to (c). It is particularly preferable to use those obtained by copolymerizing ethylene as a main component and α-olefin as a subcomponent using a metallocene compound.

Specifically, JP-A-58-19309,
JP-A-59-95292, JP-A-60-35005
No., JP-A-60-35006, JP-A-60-3500
7, JP-A-60-35008, JP-A-60-350
09, JP-A-61-130314, JP-A-3-16
No. 3088, European Patent Application Publication No. 42
No. 0,436, U.S. Pat. No. 5,055,438, and International Publication WO 91/04257, etc., by polymerization using a metallocene catalyst or a metallocene / alumoxane catalyst. Obtained or, for example, International Publication WO92 / 071
Examples thereof include those obtained by polymerization using a catalyst composed of a metallocene compound as disclosed in JP-A No. 23, etc. and a compound that reacts with the metallocene compound to become a stable ion.

Here, the compound which reacts with the metallocene compound to form a stable ion is an ionic compound or an electrophilic compound formed from an ion pair of a cation and an anion, and reacts with the metallocene compound. And a stable ion to form a polymerization active species.

Among them, examples of the ionic compound include those represented by the following formula (I). Note that the formula (I)
In the formula, m is an integer of 1 or more.

[0025]

Embedded image [Q] ^{m +} [Y] ^m- (I)

In the formula (I), Q is a cation component of the ionic compound. Specific examples include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and the like. Further, a cation of a metal which is itself easily reduced or an anion of an organic metal. Can also be mentioned.

These cations are described in JP-T-1-5019.
Not only a cation capable of giving a proton as disclosed in Japanese Patent Publication No. 50 and the like, but also a cation which does not provide a proton may be used.

Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylammonium, dipropylammonium, dicyclohexyl Ammonium, triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, palladium ion, Mercury ions, ferrocenium ions and the like can be mentioned.

In the formula (I), Y is an anionic component of an ionic compound, which is a component which reacts with a metallocene compound to form a stable anion, such as an organic boron compound anion, an organic aluminum compound anion, and an organic gallium compound. Compound anions, organic phosphorus compound anions, organic arsenic compound anions, organic antimony compound anions, and the like.

Specifically, tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron,
Tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (3,5- (t-butyl) phenyl) boron, tetrakis (pentafluorophenyl)
Boron, tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum,
Tetrakis (3,5-di (trifluoromethyl) phenyl) aluminum, tetrakis (3,5-di (t-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, tetraphenylgallium, tetrakis (3,4) 5-trifluorophenyl)
Gallium, tetrakis (3,5-di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t
-Butyl) phenyl) gallium, tetrakis (pentafluorophenyl) gallium, tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic,
Examples include tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, decaborate, undecaborate, carbadodecaborate, and decachlorodecaborate.

Among the electrophilic compounds, compounds known as Lewis acid compounds, which react with metallocene compounds to form stable ions to form polymerization active species, include various metal halide compounds. And metal oxides known as solid acids. Specific examples include magnesium halides and Lewis acidic inorganic compounds.

These catalyst components can be used by appropriately supporting them on an inorganic solid carrier, an organic solid carrier or the like.
Examples of the loading include the methods described in JP-A-61-296008, JP-A-1-101315, JP-A-5-301917, and the like. Examples of the method of copolymerization using these catalysts include a gas phase method, a slurry method, a high pressure ionic polymerization method, and a solution method. Examples of the high pressure ionic polymerization method include JP-A-56-18607 and JP-A-58-18607.
No. 225106, the pressure is 100
kg / cm ² or more, preferably 300 to 2000 kg /
cm ² or more, the temperature is 125 ° C. or more, preferably 130 to
A method for producing an ethylene polymer, which is performed under a reaction condition of 250 ° C, particularly preferably 150 to 200 ° C, can be adopted.

Polyethylene Resin Material The polyethylene resin material forming the resin layer of the present invention is:
The above-mentioned ethylene / α-olefin copolymer is a main component, and may be composed of only the ethylene / α-olefin copolymer. Agents, lubricants, antiblocking agents, stabilizers, antioxidants, antistatic agents, antifoggants, flame retardants, colorants, and other additives may be added as necessary.

Further, the polyethylene resin material is obtained by adding the ethylene / α-olefin copolymer to the ethylene / α-olefin copolymer.
A resin mixture containing an ethylene resin other than the α-olefin copolymer may be used. Examples of the ethylene resin used in combination with the ethylene / α-olefin copolymer include:
Branched high-pressure low-density polyethylene, and monomers copolymerizable with ethylene (excluding α-olefins having 3 to 12 carbon atoms), for example, vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, methacryl methacrylate And the like. Specifically, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer,
Examples thereof include an ethylene-ethyl acrylate copolymer, and these may be used alone or in combination of two or more. The ethylene-based resin may be a resin obtained by graft-polymerizing an unsaturated carboxylic anhydride such as maleic anhydride or itaconic anhydride, or an aromatic vinyl compound such as styrene.

The density of the ethylene resin (JIS-K7
112-A method) is 0.915 to 0.950 g / cm ³ ,
Preferably from 0.915 to 0.940 g / cm ^3.
If the density is less than 0.915 g / cm ³ , the film formability at the time of extrusion lamination is inferior, and if it exceeds 0.950 g / cm ³ , the sealing property is deteriorated. The MFR (JIS-K7
210-Condition 4) is 1 to 100 g / 10 min, preferably 3 to 40 g / 10 min. Any having an MFR outside the above range has too high or too low a melt viscosity, and thus is inferior in film-forming properties during extrusion lamination molding.

When the ethylene / α-olefin copolymer and the ethylene-based resin are used in combination, the preferred composition is 30 to 99% by weight of the ethylene / α-olefin copolymer.
It is preferably 40 to 95% by weight, and the content of the ethylene resin is 70 to 1% by weight, preferably 60 to 5% by weight. The ethylene / α-olefin copolymer exceeds 99% by weight,
When the amount of the ethylene-based resin is less than 1% by weight, the film-forming property at the time of extrusion lamination is inferior. On the other hand, if the ethylene resin is 70
% By weight and the ethylene / α-olefin copolymer is 3%
If the amount is less than 0% by weight, the sealing property is deteriorated.

(3) Laminated Cross Sheet The laminated cross sheet of the present invention is a laminated body including the above-described woven fabric substrate and a resin layer. The thickness of the entire sheet and each layer is not particularly limited, but the thickness of the resin layer is preferably about 30 to 500 μm.

The laminated cloth sheet of the present invention is obtained by subjecting the surface of the woven fabric base material to an anchor coat treatment and laminating a resin layer on the treated surface. The anchor coat treatment is indispensable in the present invention. The resin layer may be laminated on only one side of the woven fabric substrate, or may be laminated on both sides. Therefore, the anchor coat treatment may be performed on only one side, or may be performed on both sides.

It is desirable that the woven fabric substrate is subjected to an oxidizing treatment such as a corona treatment and a frame treatment, if necessary, before the anchor coat treatment is performed. In particular, when the woven fabric substrate is made of a drawn polyolefin resin yarn, it is preferable to perform a corona treatment on the woven fabric substrate before performing the anchor coat treatment.

Examples of the anchor coating agent used in the present invention include polyurethane, isocyanate compounds, urethane prepolymers, mixtures thereof and reaction products, mixtures of polyester or polyol with isocyanate compounds and reaction products, solutions thereof, and mixtures thereof. And known anchor coating agents (primers) such as polyethyleneimine, alkyl titanates, and modified polyolefins, and adhesives.

The method of laminating the ethylene / α-olefin copolymer on the woven fabric substrate having been subjected to the anchor coating treatment is not particularly limited, but is preferably extrusion lamination.
That is, as the laminated cross sheet of the present invention, a sheet obtained by pressing and laminating a woven fabric base material and a resin layer by an extrusion laminating method is preferable. When laminating by extrusion lamination, the processing temperature is not particularly limited, but is preferably 150 to 310 ° C, particularly preferably 220 to 3C.
00 ° C is desirable. In addition, it is preferable to perform an ozone treatment in advance between the anchor coat treated surface of the woven fabric substrate and the melted ethylene / α-olefin copolymer film before laminating.

As described above, by laminating the specific ethylene / α-olefin copolymer by extrusion lamination at a relatively low temperature on the woven base material subjected to the anchor coating treatment, the woven base material is not deteriorated. Thus, a laminated cloth sheet having high tensile strength, strong adhesiveness and high sealing strength can be obtained. The laminated cloth sheet of the present invention thus obtained can be suitably used as a flexible container, a cover, a bag, or the like by sealing with a method such as a high-frequency welder or a heat seal.

[0043]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention. The method for evaluating the characteristics of the laminated cross sheet in the example is as follows.

(1) Adhesion The sample of the laminated cloth sheet was rubbed by hand 20 times, and the laminated resin film in the portion where the contact portion of the woven fabric substrate was covered was manually peeled off from the woven fabric substrate. Evaluation was made according to the following criteria. ◎: Excellent adhesion (non-peelable) ○: Good adhesion (difficult to peel) △: Good adhesion (peelable) ×: Poor adhesion (easy peelable)

(2) Tensile strength and elongation In accordance with JIS-L-1096 (Method A, slip method), using a tensile tester, a gripping distance of 200 mm and a tensile speed of 3
At 00 mm / min, MD direction and T
The tensile strength and tensile elongation in the D direction were measured.

(3) Hot Air Seal Peeling Strength Two laminated cloth sheets are superimposed and the end is
mm width, the fusing temperature is 270, 30
0, 330 ° C., pressure 2 kg / cm ³ , fusing speed 3 m /
The test pieces were heat-fused under the conditions of minutes and cut to a width of 30 mm, and the test pieces were gripped by a tensile tester at a gripping interval of 200 mm and a pulling speed of 100 mm / min.

(4) Measurement of elution curve obtained by TREF: Measurement of the elution curve by TREF in the present invention uses a cross-separation apparatus (CFC-T150A, manufactured by Mitsubishi Chemical Corporation) as a measuring apparatus, and uses an attached operation. The measurement was performed according to the manual measurement method. This cross sorter,
A temperature-rise elution fractionation (TREF) mechanism for fractionating a sample using the difference in dissolution temperature, and a size exclusion chromatograph (Size Chromatograph) for further fractionating the fractionated fractions by molecular size.
atography: SEC) connected online.

First, the sample to be measured (ethylene · α
-Olefin copolymer) using a solvent (o-dichlorobenzene) to give a concentration of 4 mg / ml.
It was melted at ℃ and injected into a sample loop in the measuring device. The following measurements were performed automatically according to the set conditions.

The sample solution held in the sample loop is separated using a TREF column (internal diameter of 4 m filled with glass beads as an inert carrier) by utilizing the difference in dissolution temperature.
m, 150mm length stainless steel column attached to the device)
Was injected 0.4 ml. The sample was cooled at a rate of 1 ° C./min from 140 ° C. to 0 ° C. and coated on the inert carrier. At this time, from the high crystal component (the one that is easy to crystallize) to the low crystal component (the one that hardly crystallizes)
The polymer layer is formed on the surface of the inert carrier in this order. TR
After holding the EF column at 0 ° C. for an additional 30 minutes, 2 ml of the component dissolved at a temperature of 0 ° C. was added at a flow rate of 1 ml / min.
From REF column to SEC column (Showa Denko KK,
AD80M · S, 3 tubes). While fractionation by molecular size was being performed by SEC, the temperature of the TREF column was raised to the next elution temperature (5 ° C.) and maintained at that temperature for about 30 minutes. The measurement of each elution section by SEC was performed at intervals of 39 minutes. The following temperature is used as the elution temperature,
The temperature was raised stepwise.

Elution temperature (° C.): 0, 5, 10, 15, 2
0, 25, 30, 35, 40, 45, 49, 52, 5
5,58,61,64,67,70,73,76,7
9,82,85,88,91,94,97,100,1
02,120,140 ° C.

With respect to the solution separated according to the molecular size in the SEC column, the absorbance in proportion to the concentration of the polymer was measured with an infrared spectrophotometer attached to the apparatus (wavelength 3.42 μm).
m, detection by stretching vibration of methylene) to obtain chromatograms for each elution temperature category. Using built-in data processing software,
A baseline of the chromatogram of each elution temperature section obtained by the above measurement was drawn and subjected to arithmetic processing. The area of each chromatogram was integrated and an integrated elution curve was calculated. From the integrated elution curve, the peak temperature and the area ratio of the elution amount of 90 ° C. or less to the total area were determined.

[0052]

Example 1 Drawing yarn width 8 mm, thickness 26 μm, thickness 17
00 denier, number of shots 14 vertical / inch x 14 horizontal
Woven fabric of high-density polyethylene uniaxially drawn yarn (hereinafter abbreviated as “HDPE-FY cloth”) as a base material, and corona treatment on both surfaces thereof (30 watts on one side)
min / m ² ), an isocyanate-based anchor coat agent (hereinafter abbreviated as “AC agent”) on one side: Nippon Soda Co., Ltd., trade name “Titabond 120”, active ingredient 4% by weight acetic acid Ethyl solution) was applied, and the solvent was removed with a drier to perform an anchor coating treatment. Further, the opposite surface was also subjected to the same anchor coating treatment.

Next, an extrusion laminating apparatus was used to produce an ethylene / α-olefin copolymer, “Kernel KS560” (trade name, manufactured by Nippon Polychem Co., Ltd., ethylene-hexene-1 copolymer obtained with a metallocene catalyst). :
MFR = 16.5 g / 10 min, density 0.898 g / cm
³ , TREF peak temperature = 55 ° C., elution amount at 90 ° C. or less = 100% by weight) 80% by weight, and high-pressure low-density polyethylene manufactured by Nippon Polychem Co., Ltd., trade name “Novatech LC604 (MFR = 8 g / 10 min.) , Density = 0.
918 g / cm ³ ) of 20% by weight was used as a laminate resin (a polyethylene resin material for a resin layer).

The laminated resin was heated at a resin temperature of 280 ° C. and a width of 50 from a T-die mounted on an extruder having a diameter of 90 mm.
It was extruded into a film having a thickness of 0 mm and a thickness of 200 μm to form a molten film. Ozone treatment was performed between the anchor-coated woven fabric substrate and the molten film, and both were pressure-bonded and laminated by a pressure roll. Next, a laminate resin was similarly laminated on the opposite surface side of the woven fabric substrate to obtain a laminated cross sheet. Table 1 shows the property evaluation results of the obtained laminated cloth sheet.

[0055]

Comparative Example 1 The procedure of Example 1 was repeated except that corona treatment, anchor coating treatment, and ozone treatment between the molten films of the laminated resin were not performed on the “HDPE-FY cloth”. Table 1 shows the evaluation results.

[0056]

Example 2 Laminating resin was changed to "Kernel KS56"
0 ": 60% by weight, and" Novatech LC604 ": 40
The procedure was the same as in Example 1 except that the mixture was changed to a mixture with% by weight. Table 1 shows the evaluation results.

[0057]

Example 3 The laminating resin was changed to "Kernel KS56".
0 ": 40% by weight, and" Novatech LC604 ": 60
The procedure was the same as in Example 1 except that the mixture was changed to a mixture with% by weight. Table 1 shows the evaluation results.

[0058]

Comparative Example 2 The procedure of Example 3 was repeated except that the corona treatment, the anchor coating treatment, and the ozone treatment between the molten films of the laminated resin were not performed on the “HDPE-FY cloth”. Table 1 shows the evaluation results.

[0059]

Comparative Example 3 The laminating resin was an ethylene / vinyl acetate copolymer (trade name: Novatec L, manufactured by Nippon Polychem Co., Ltd.)
V570 (MFR 15 g / 10 min, vinyl acetate content 2
0% by weight) in the same manner as in Example 1. Table 1 shows the evaluation results.

[0060]

Examples 4 to 9 The same procedures as in Example 1 were carried out except that the woven fabric substrates shown in Table 2 were used and the thickness of the laminate layer was changed. Table 2 shows the characteristic evaluation results of the obtained laminated cloth sheet.
Shown in

[0061]

Comparative Examples 4 to 9 Examples 4 to 9 were respectively performed except that the corona treatment, the anchor coating treatment, and the ozone treatment between the molten films of the laminated resin were not performed in Examples 4 to 9. Same as. Table 2 shows the results.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

The laminated cloth sheet of the present invention is obtained by laminating a resin layer composed of a specific ethylene / α-olefin copolymer on the surface of a woven fabric substrate of a stretched thermoplastic resin yarn, which is treated with an anchor coat. Thereby, even if the thermoplastic resin material of the woven fabric substrate is not limited, by laminating by extrusion lamination at a low temperature, it has sufficiently strong adhesiveness,
In addition, a laminated cloth sheet having high strength and good sealing properties can be obtained. Therefore, a material having high strength can be selected as the woven fabric base material, whereby a laminated cross sheet having further excellent tensile strength and elongation can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F100 AK01A AK04A AK05 AK06 AK07 AK41 AK61A AL05A BA02 BA03 BA06 BA10B BA10C DG01A DG11A DG11B DG11C DG12 EH23 EH232 EJ37 EJ37A EJ65BJ16A06J16A

Claims (4)

[Claims] 1. A woven fabric substrate formed of a woven fabric made of a stretched thermoplastic resin yarn, at least one surface of which is anchor-coated, and a resin layer laminated on the anchor-coated surface of the woven fabric substrate. Wherein the resin layer is formed of a polyethylene-based resin material mainly composed of an ethylene / α-olefin copolymer satisfying the following physical properties (a) to (c). And a laminated cross sheet. (A) The density is 0.870 to 0.920 g / cm ³ . (B) MFR is 1 to 100 g / 10 minutes. (C) The maximum peak temperature of the elution curve by temperature rise elution fractionation (TREF) is 25 to 85 ° C, and the elution amount at 90 ° C or less is 90% by weight or more based on the total amount of the ethylene / α-olefin copolymer. That. 2. The laminated cloth sheet according to claim 1, wherein the ethylene / α-olefin copolymer is polymerized using a metallocene compound as a polymerization catalyst. 3. The polyethylene-based resin material contains 30 to 99% by weight of the ethylene / α-olefin copolymer.
And a density of 0.915 to 0.950 g / cm ³ and M
The laminated cloth sheet according to claim 1 or 2, wherein the FR is a mixture of 1 to 100 g / min of an ethylene-based resin: 70 to 1% by weight. 4. The laminated cloth sheet according to claim 1, wherein the woven fabric substrate and the resin layer are obtained by press-lamination using an extrusion laminating method.