JP2003176387A - Ethylenic polymer composition and tarpaulin using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylenic polymer composition having excellent flexibility, heat resistance and high-frequency welder processability and a tarpaulin using the same. <P>SOLUTION: This ethylenic polymer composition comprises (A) a straight- chain ethylene-α-olefin copolymer composed of ethylene and a 3-18C α-olefin and having 10-80°C temperature of the maximum peak in an elution curve obtained by temperature rising elution fractionation and 0.1-100 g/10 min melt flow rate, (B) an ethylene vinyl acetate copolymer having 0.05-100 g/10 min melt flow rate, (C) a modified ethylenic polymer with a functional group- containing ethylenically unsaturated compound and (D) a hydrous inorganic compound. The ratio of the component (A) accounts for ≥10 wt.% of the total amount of the components (A) and (B) and the content of the vinyl acetate units derived from the component (B) is 4-30 wt.%. The melt flow rate as the polymer composition is 0.1-80 g/10 min. The tarpaulin is obtained by laminating a layer of the ethylenic polymer composition onto at least one surface of a fiber knitted or woven fabric as a base fabric. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ethylene-based polymer composition and a tarpaulin in which the ethylene-based polymer composition is laminated on the surface of a base fabric, and more specifically, it has excellent flexibility and heat resistance. Excellent in high-frequency welder processability, packaging material, building material, and ethylene polymer composition suitable for use in various miscellaneous goods materials such as document holders, table cloths and curtains, and excellent flexibility In addition, it has excellent heat resistance and high-frequency welder processability, logistics materials such as flexible containers, civil engineering and construction materials such as covering sheets for construction and curing sheets, and industrial materials such as automobile hoods, tents, and water tanks. The present invention relates to a tarpaulin preferably used for.

[0002]

2. Description of the Related Art Conventionally, high-frequency welder processing is possible, and packaging materials and building materials with excellent flexibility and heat resistance,
And, as a material for various miscellaneous goods, a film or sheet of a soft vinyl chloride resin is used, but since the soft vinyl chloride resin contains a large amount of a plasticizer, for example, in contact with a printed matter, the There are problems such as printing transferred to the surface of the soft vinyl chloride resin film or sheet, contaminating the print of the printed matter itself, and the problem that the soft vinyl chloride resin film or sheet adheres to the surface of the contacted object. It is liable to occur, and has problems such as transfer of plasticizer to food in contact with food, environmental pollution in disposal and incineration, etc.
On the other hand, high-frequency welder processing is possible,
As a material having no problem as described above, although ethylene-based polymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer have been put into practical use, these ethylene-based polymers have flexibility and However, the balance between heat resistance and high-frequency welder workability is poor, and there is a strong demand for compatibility between flexibility, heat resistance, and high-frequency welder workability.

Conventionally, tarpaulins have been prepared by using a fiber knitted woven fabric as a base fabric and a soft vinyl chloride resin laminated on at least one surface thereof. In a flexible container formed by high-frequency welding of tarpaulin,
It has been pointed out that there is a problem of migration of the plasticizer in the soft vinyl chloride resin to the content, and as such a tarpaulin, ethylene-vinyl acetate copolymers and other ethylene polymers have been used. , Ethylene-vinyl acetate copolymer laminated tarpaulins have the drawbacks of lacking flexibility and poor handleability, and also poor heat resistance, while mixing soft materials to eliminate these drawbacks. However, due to the improvement in flexibility, heat resistance and high-frequency welder processability deteriorate, and heat resistance and high-frequency welder processing also occur in tarpaulins made of ethylene polymers as laminated materials. At present, there is a demand for a tarpaulin that can improve flexibility without deteriorating the properties.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art in the prior art. Therefore, the present invention is excellent in flexibility as well as in heat resistance and high-frequency welder workability. An object is to provide a polymer composition and a tarpaulin using the same.

[0005]

The present invention provides the following (A).
The component, the component (B), the component (C), and the component (D) are contained, and with respect to the total amount of the component (A) and the component (B),
The proportion of the component (A) is 10% by weight or more, and
The content of vinyl acetate units derived from the component (B) is 4 to 3
0% by weight, the melt flow rate as a polymer composition is 0.1 to 80 g / 10 minutes, and a fiber knitted fabric is used as a base fabric, and the ethylene base is provided on at least one side thereof. A gist is a tarpaulin formed by laminating layers of a polymer composition.

(A) The maximum peak temperature in the elution curve obtained by temperature rising elution fractionation is 10 to 80 ° C., which is composed of ethylene and α-olefin having 3 to 18 carbon atoms.
And the linear ethylene-α-olefin copolymer (B) having a melt flow rate of 0.1 to 100 g / 10 min has a melt flow rate of 0.05 to 100 g / 10.
Ethylene-vinyl acetate copolymer (C) functional group-containing ethylenically unsaturated compound-modified ethylene polymer (D) hydrous inorganic compound

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The linear ethylene-α-olefin copolymer as the component (A) constituting the ethylene-based polymer composition of the present invention comprises ethylene and an α-olefin having 3 to 18 carbon atoms. Become.

Examples of the α-olefin having 3 to 18 carbon atoms include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene and 4,4-. Dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-octadecene and the like,
Among them, those having 4 to 12 carbon atoms are preferable, and those having 1 to butene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene and the like have 4 to 10 carbon atoms.
Is particularly preferable. The content of this α-olefin in the ethylene-α-olefin copolymer is 5
It is preferably ˜50% by weight, particularly preferably 8 to 45% by weight.

In addition, in the linear ethylene-α-olefin copolymer as the component (A) in the present invention, it is essential that the temperature of the maximum peak in the elution curve obtained by temperature rising elution fractionation is 10 to 80 ° C. And the temperature of the maximum peak is preferably 20 to 75 ° C. If the temperature of this maximum peak is less than the above range, the heat resistance of the ethylene polymer composition will be poor, while if it exceeds the above range, the flexibility will be poor.

Further, the ratio (H / W) of the peak height (H) to the width (W) of 1/3 height in the maximum peak of the elution curve obtained by the temperature rising elution fractionation is 2 or more. Is preferable, and it is particularly preferable that the ratio (H / W) is 2.5 or more. If this ratio (H / W) is less than the above range, the flexibility of the ethylene polymer composition tends to be poor.

Here, the temperature rising elution fractionation (Temperat
What is ure Rising Elution Fractionation (TREF)?
For example, Journal of Applied Polymer Science, Vol.2
6, p4217-4231 (1981), which is an analytical method known in principle, in which the polymer is completely dissolved in a solvent at a high temperature and then cooled to allow the inert carrier to be present in the solution. Form a thin polymer layer on the surface. At this time, a highly crystalline component that easily crystallizes (for example, a straight-chain component with no branching in polyethylene) and a low crystalline or amorphous component that does not easily crystallize (for example, a component with many short chain branches in polyethylene). A polymer layer is formed. Then, when the temperature is raised continuously or stepwise, conversely to the above, the low crystalline or amorphous component is eluted, and finally the high crystalline component is eluted. The composition distribution of the polymer is analyzed from the elution curve drawn by the elution amount at each temperature and the elution temperature.

In the present invention, this elution curve is measured by
It carried out on condition of the following. As a measuring device, temperature rising elution fractionation (TREF) that separates samples using the difference in melting temperature
Mechanism and size exclusion chromatograph (Size Exclusion Chromatogra
phy; SEC) was connected online to use a cross sorting device (“CFC T150A” manufactured by Mitsubishi Chemical Corporation).

Using o-dichlorobenzene as the solvent,
The polymer is dissolved at 140 ° C. so that the concentration becomes 4 mg / ml, and this is injected into the sample loop of the measuring device. 0.4 ml of the sample solution in the sample loop was injected into a stainless steel column with an inner diameter of 4 mm and a length of 150 mm attached to a TREF device, which was filled with glass beads as an inert carrier, and then 140 ° C. at a rate of 1 ° C./min. To 0 ° C. and coat on inert carrier surface. After holding the column at 0 ° C. for 30 minutes, 2 ml of the component dissolved at a temperature of 0 ° C. was removed from the TREF column at a flow rate of 1 ml / min.
EC column (Showa Denko KK "AD80M / S", 3 pcs)
Inject. While the molecular size is being fractionated by SEC, the TREF column is heated to the next elution temperature (5 ° C.), held at that temperature for 30 minutes, and then injected into the SEC column. The measurement of each elution section by SEC was performed at intervals of 39 minutes. Elution temperature is 0, 5, 1
0, 15, 20, 25, 30, 35, 40, 45, 4
9, 52, 55, 58, 61, 64, 67, 70, 7
3, 76, 79, 82, 85, 88, 91, 94, 9
Each temperature of 7, 100, 102, 120, 140 ℃,
The temperature was raised stepwise.

The solution classified into the molecular size by the SEC column was measured for the absorbance proportional to the polymer concentration by an infrared spectrophotometer attached to the device (detected by stretching vibration of methylene having a wavelength of 3.42μ), and each elution temperature was measured. Obtain the chromatogram of the partition. Using the built-in data processing software, draw the baseline of the obtained chromatogram of each elution temperature segment and perform the arithmetic processing. The area of each chromatogram is integrated and the integrated elution curve is calculated. Also, this integrated elution curve is differentiated with temperature to calculate the differential elution curve. The plot of the calculation result was output to the printer, and the plot of the output differential elution curve was as follows: the horizontal axis shows the elution temperature per 100 ° C, 89.3 mm, and the vertical axis shows the differential amount (total integrated elution amount is standardized to 1.0, The amount of change at 1 ° C. was defined as the differential amount.

Further, the linear ethylene-α-olefin copolymer as the component (A) in the present invention is JIS K721.
The melt flow rate measured at a temperature of 190 ° C. and a load of 21.18 N in accordance with 0 is 0.1 to 100 g / 10 minutes, and preferably 0.3 to 80 g / 10 minutes. If the melt flow rate is less than the above range, the processability of forming a polymer composition into a film or sheet will be poor, while if it exceeds the range, the mechanical strength and processability of the polymer composition will be poor. Becomes

In the present invention, the linear ethylene-α-olefin copolymer has a density of 0.850-0.
It is preferably 920 g / cm ³ , and as these linear ethylene-α-olefin copolymers, copolymerization is performed in the presence of a Ziegler-Natta type catalyst or Phillips type catalyst which have been widely used in the past. It is more preferable that the copolymer is copolymerized in the presence of a Kaminsky type catalyst.

A linear ethylene-α-olefin copolymer using a Kaminsky type catalyst is disclosed, for example, in JP-A-58-1.
9309, JP-A-59-95292, JP-A-60-
35005, JP-A-60-35006, JP-A-60
-35007, JP-A-60-35008, JP-A-6
0-35009, JP-A-61-130314, JP-A-3-163088, European Patent Publication No. 420.
No. 436, U.S. Pat. No. 5,055,438, WO 91/04257, and the like, a metallocene-based catalyst, particularly a metallocene / alumoxane-based catalyst, is used, or, for example, International Publication WO92 / 0.
No. 7,123, etc., a catalyst comprising a metallocene compound and a compound that reacts with the compound to form a stable anion is used, and for example, a heavy phase method such as a gas phase method, a slurry method, a solution method, or a high pressure ionic polymerization method. It can be manufactured legally.

In the above, the linear ethylene-α-olefin copolymer in the present invention uses a mono-, di-, or tri-cyclopentadienyl ring or a substituted cyclopentadienyl ring as a ligand. It is preferably polymerized using a catalyst having a metallocene compound of a tetravalent transition metal compound such as titanium, zirconium, nickel, palladium, hafnium, or platinum.

The ethylene-vinyl acetate copolymer as the component (B) constituting the ethylene-based polymer composition of the present invention is
The content of vinyl acetate unit is preferably 7 to 50% by weight, and the melt flow rate measured under the above-mentioned conditions is from 0.05 to 100 g / 10 minutes, and is from 0.1 to 8
It is preferably 0 g / 10 minutes. If the melt flow rate is less than the above range, the processability of forming a polymer composition into a film or sheet will be poor, while if it exceeds the above range, the mechanical strength of the polymer composition will be poor.

Further, the modified ethylene polymer as the component (C) constituting the ethylene polymer composition of the present invention is a modified ethylene polymer with a functional group-containing ethylenically unsaturated compound, and is basically Examples of the copolymer include a copolymer of ethylene and a functional group-containing ethylenically unsaturated compound, and a graft product of an ethylene polymer with a functional group-containing ethylenically unsaturated compound.

Here, the functional group-containing ethylenically unsaturated compound is preferably, for example, (meth) acrylic acid [in the present invention, "(meth) acrylic" means acryl and / or methacryl). Shall mean. ], An ethylenically unsaturated carboxylic acid such as maleic acid,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Ethylenically unsaturated carboxylic acid alkyl esters such as octyl (meth) acrylate, maleic anhydride, citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride and other ethylenically unsaturated carboxylic anhydrides, glycidyl ( Epoxy group-containing ethylenically unsaturated compounds such as (meth) acrylate, methyl glycidyl maleate, ethyl glycidyl maleate, propyl glycidyl maleate, diglycidyl maleate, vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Hydroxy group-containing ethylenically unsaturated compounds such as 2-hydroxybutyl (meth) acrylate and hydroxyethyl vinyl ether, silyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane and (meth) acryloyloxypropyltrimethoxysilane Examples thereof include ethylenically unsaturated compounds.

In the present invention, among these functional group-containing ethylenically unsaturated compounds, it is particularly preferable to contain at least an ethylenically unsaturated carboxylic acid anhydride, and it is particularly preferable to contain maleic acid anhydride.

Examples of the grafted ethylene-based polymer in the latter graft product include ethylene homopolymers such as branched low-density polyethylene and linear high-density polyethylene, ethylene, propylene, and 1-butene. 3-
Methyl-1-butene, 1-pentene, 3-methyl-1-
Pentene, 4-methyl-1-pentene, 1-hexene,
Linear ethylene-α-olefin copolymers with other α-olefins such as 1-octene and 1-decene, and ethylene and other ethylenic compounds such as (meth) acrylamide, (meth) acrylonitrile and styrene As a copolymer with an unsaturated compound or the like, a grafted ethylene-based polymer of a grafted product in a modified ethylene-based polymer with two or more functional group-containing ethylenically unsaturated compounds as described below, for example, ethylene And an ethylenically unsaturated carboxylic acid such as (meth) acrylic acid, an ethylenically unsaturated carboxylic acid alkyl ester such as (meth) acrylic acid alkyl ester, an ethylenically unsaturated carboxylic acid anhydride such as maleic anhydride, glycidyl Epoxy group-containing ethylenically unsaturated compound such as (meth) acrylate, 2-hydroxyethyl (meth) Examples thereof include a copolymer with a hydroxyl group-containing ethylenically unsaturated compound such as acrylate and a functional group-containing ethylenically unsaturated compound such as silyl group-containing ethylenically unsaturated compound such as vinyltrimethoxysilane.

The former copolymer in the modified ethylene polymer as the component (C) in the present invention is specifically a binary or ternary ethylene and the functional group-containing ethylenically unsaturated compound. The above copolymers can be mentioned.
Further, as the latter graft, specifically, the functional group-containing ethylenically unsaturated compound of the ethylene polymer as a modified ethylene polymer with one kind of the functional group-containing ethylenically unsaturated compound Of the functional group-containing ethylenic polymer of ethylene homopolymer, for example, as the ethylene-based polymer modified with two or more kinds of the functional group-containing ethylenically unsaturated compound 1 of the functional group-containing ethylenically unsaturated compound, which is a graft product of two or more kinds of unsaturated compounds, and a copolymer of ethylene as the ethylene polymer and the functional group-containing ethylenically unsaturated compound Examples include graft bodies and the like.

The former copolymer is obtained by a conventionally known polymerization method such as bulk, solution or suspension, and the latter graft is obtained by a conventionally known method such as melt kneading, solution or suspension. Each can be manufactured by a chemical method. The content of the functional group-containing ethylenically unsaturated compound unit in the modified ethylene polymer is preferably in the range of 5 to 35% by weight, particularly preferably 9 to 30% by weight. .

The modified ethylene polymer as the component (C) in the present invention is a functional group-containing ethylenically unsaturated compound modified with the above ethylenically unsaturated carboxylic acid anhydride and an ethylenically unsaturated carboxylic acid alkyl ester. It is preferable that the

The modified ethylene polymer modified with an ethylenically unsaturated carboxylic acid anhydride and an ethylenically unsaturated carboxylic acid alkyl ester will be described in more detail below. A terpolymer of an ethylenically unsaturated carboxylic acid anhydride and an ethylenically unsaturated carboxylic acid alkyl ester, as a graft, the ethylenically unsaturated carboxylic acid anhydride and ethylenically unsaturated of the ethylene polymer Co-graft with carboxylic acid alkyl ester, graft with ethylenically unsaturated carboxylic acid alkyl ester of ethylene-based polymer obtained by copolymerizing with ethylenically unsaturated carboxylic acid anhydride, and ethylenically unsaturated carboxylic acid alkyl ester Of the ethylene-based polymer obtained by copolymerizing Graft body due carboxylic acid anhydride.

Among these modified ethylene-based polymers of ethylenically unsaturated carboxylic acid anhydride and ethylenically unsaturated carboxylic acid alkyl ester, the copolymer is
A terpolymer of ethylene, maleic anhydride as the ethylenically unsaturated carboxylic acid anhydride, and (meth) acrylic acid alkyl ester as the ethylenically unsaturated carboxylic acid alkyl ester is particularly preferable. or,
As the graft, ethylene homopolymer as the ethylene-based polymer, maleic anhydride as the ethylenically unsaturated carboxylic acid anhydride and (meth) acrylic acid as the ethylenically unsaturated carboxylic acid alkyl ester Co-graft with alkyl ester, copolymer of ethylene as the ethylene-based polymer and alkyl (meth) acrylate as the ethylenically unsaturated carboxylic acid alkyl ester, as the ethylenically unsaturated carboxylic acid anhydride Particularly preferred is a grafted product of maleic anhydride. Among these, a terpolymer of ethylene, maleic anhydride, and (meth) acrylic acid alkyl ester is particularly preferable.

The modified ethylenic polymer modified with an ethylenically unsaturated carboxylic acid anhydride and an ethylenically unsaturated carboxylic acid alkyl ester has a content of the ethylenically unsaturated carboxylic acid alkyl ester unit of 1 to 30% by weight, the content of the ethylenically unsaturated carboxylic acid anhydride unit is preferably 0.1 to 5% by weight, the content of the ethylenically unsaturated carboxylic acid ester unit is 4 to 25% by weight, The content of the ethylenically unsaturated carboxylic acid anhydride unit is particularly preferably 1 to 4% by weight. The melt flow rate measured under the above conditions is preferably 1 to 40 g / 10 minutes, and 2 to 25 g.
/ 10 minutes is particularly preferable.

Such an ethylene-maleic anhydride- (meth) acrylic acid alkyl ester terpolymer is commercially available from Sumitomo Chemical Co., Ltd. under the name of "Bondaine FX-800U",
"Bondaine LX4110", "Bondaine TX803
0 "," Bondyne AX8060 "," Bondyne AX
It is commercially available under a trade name such as "8390".

The water-containing inorganic compound as the component (D) constituting the ethylene-based polymer composition of the present invention is an inorganic molecular compound to which water is bonded, and typically, for example,
Silica gel [SiO ₂ · nH ₂ O], hydrated alumina [A
1 ₂ O ₃ · nH ₂ O] and hydrous aluminum silicate [Al ₂ O ₃ · mSiO ₂ · nH ₂ O], hydrous calcium silicate [CaO · mSiO ₂ · nH ₂ O], hydrous magnesium silicate [MaO · mSiO] ₂ · nH ₂ O] and the like.

In the present invention, these water-containing inorganic compounds preferably have a product of the relative dielectric constant and the dielectric loss tangent of 0.1 or more as measured according to JIS K6922-2.

The composition ratio of each component in the ethylene-based polymer composition of the present invention is such that the component (A) linear ethylene-α-olefin copolymer and the component (B) ethylene-vinyl acetate. The ratio of the component (A) to the total amount of the copolymer is 10% by weight or more, and the content of vinyl acetate units derived from the component (B) is 6 to 6.
It is essential that the content is 30% by weight, and the components (A) and (B) are
The component (A) is preferably 10 to 80% by weight, the component (B) is 90 to 20% by weight, the component (A) is 20 to 70% by weight, and the component (B) is relative to the total amount of the components. 80 ingredients
It is particularly preferable that the content is ˜30% by weight.

When the proportion of the component (A) is less than the above range and the proportion of the component (B) exceeds the above range, flexibility and heat resistance of the ethylene polymer composition tend to be poor. When the proportion of the component (A) exceeds the above range and the proportion of the component (B) falls below the above range, the high frequency welder processability tends to be poor. Further, when the content of the vinyl acetate unit derived from the component (B) is less than the above range, the high frequency welder processability tends to be poor, while when it exceeds the above range, the heat resistance tends to be poor.

Further, the linear ethylene-α of the above-mentioned component (A)
-Based on 100 parts by weight of the total amount of the olefin copolymer and the ethylene-vinyl acetate copolymer of the component (B),
The content of the modified ethylene polymer as the component (C) is 5 to 40.
Preferably, the content of the hydrous inorganic compound of the component (D) is 3 to 30 parts by weight, the content of the component (C) is 8 to 30 parts by weight, and the content of the component (D) is 4 ~
20 parts by weight is especially preferred.

When the content of the component (C) is less than the above range,
The heat resistance of the ethylene polymer composition tends to be inferior, while if it exceeds the above range, the flexibility tends to decrease. Further, when the content of the component (D) is less than the above range, the high frequency welder processability tends to be poor, while when it exceeds the above range, the processability and flexibility of a film or sheet tend to decrease.

The ethylene polymer composition of the present invention is
The melt flow rate measured under the above conditions is 0.1-8.
0 g / 10 minutes, preferably 0.3 to 60 g / 10 minutes. If the melt flow rate is less than the above range, the processability for forming a film or sheet as an ethylene-based polymer composition will be poor, while if it exceeds the above range, the mechanical strength and processability will be poor.

The ethylene-based polymer composition of the present invention may contain various kinds of resins usually used for other resins and rubbers and thermoplastic resins, if necessary, within a range that does not impair the effects of the present invention. Additives, such as antioxidants, heat stabilizers,
Light stabilizer, ultraviolet absorber, nucleating agent, neutralizing agent, lubricant, antistatic agent, antiblocking agent, slip agent, antifogging agent, dispersant, fluidity improver, release agent, adhesiveness imparting agent, Flame retardants,
A colorant, a filler other than the component (D), and the like may be added.

The ethylene-based polymer composition of the present invention comprises a linear ethylene-α-olefin copolymer as the component (A), an ethylene-vinyl acetate copolymer as the component (B),
The modified ethylene polymer of the component (C) and the hydrous inorganic compound of the component (D), together with other resins and additives used as necessary, a tumbler blender, a ribbon blender, a V-type blender, After uniformly mixed with a Henschel mixer or the like, it is prepared by melt-kneading with a single-screw or twin-screw extruder, roll, Banbury mixer, kneader, Brabender, etc., and the ethylene-based polymer composition is calendered, A film or sheet is melt-extruded into a film or sheet from a molding machine equipped with a T die or an annular die, and is cooled to be molded into a film or sheet.

The tarpaulin of the present invention comprises a fibrous knitted woven fabric as a base fabric, on at least one side of which, preferably on both sides,
The layers of the ethylene-based polymer composition are laminated,
As the lamination method, conventionally known methods such as a calendering method, an extrusion laminating method, a dry laminating method, and an impregnation method can be used. Inside,
The calendering method is preferred.

Specifically, the tarpaulin of the present invention is prepared by molding the ethylene-based polymer composition prepared above into a sheet by a calender roll and melt-laminating it on a base cloth, or
Melt extruded into a sheet from a sheet molding machine equipped with a die,
It is manufactured by extrusion laminating and laminating on a base fabric, or by dry laminating a molded sheet and a base fabric using an adhesive and laminating.

At this time, the temperature of the polymer composition in the melt lamination on one side or both sides of the base fabric is usually about 140 to 160 ° C. in the case of calendering, for example.
The thickness of the polymer composition layer is 200 to 1 per surface.
It is about 000 μm.

As the fiber knitted or woven fabric of the base fabric, those conventionally used for this kind of base fabric are used, and specifically, for example, polyester fiber, polyamide fiber, polyolefin fiber, polyacrylic fiber, etc. Woven fabrics such as plain weaves, twill weaves, satin weaves, and knitted fabrics such as synthetic fibers, natural fibers such as cotton and hemp, and the like. The fiber thickness is 5
For example, in the case of plain weave, the number of hammers is about (10 to 30) × (15 to 35) / inch. These fiber knitted fabrics have a width of 0.5 to 3
Those having a thickness of about m and a thickness of about 0.2 to 1 mm are generally used.

The ethylene-based polymer composition of the present invention is formed into a desired shape such as a film or sheet by high-frequency welding, and is used as a packaging material such as a fashion bag or a surface protective material for decorative plywood, or a wallpaper. It is preferably used for building materials such as interior materials, and various miscellaneous goods materials such as document holders, desk mats, table cloths, curtains, stationery and toys. Further, the tarpaulin of the present invention, if necessary, cut, as a desired shape such as high-frequency welder processing, logistics materials such as flexible containers, construction covering sheets, civil engineering materials such as curing sheets, It is also suitably used for industrial materials such as automobile hoods, tents, and water tanks. In addition, the high frequency welding process at that time is usually performed in a frequency range of 10 to 100 MHz and a welding time of 1 to 60 seconds.

[0045]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The linear ethylene-α-olefin copolymer as the component (A), the ethylene-vinyl acetate copolymer as the component (B), and the modified ethylene-based copolymer as the component (C) used in the following Examples and Comparative Examples. The polymer and the water-containing inorganic compound as the component (D) are shown below.

<Component (A)> A-1: Copolymerized in the presence of a Kaminsky type catalyst, containing 1-octene as an α-olefin, and having a maximum peak temperature of the elution curve of TREF. 28 ° C, H / W 3.0, density 0.
868 g / cm ³ , melt flow rate 0.5 g / 1
A linear ethylene-1-octene copolymer having 0 minutes ("EG8150" manufactured by DuPont Dow Elastomer).

A-2: Copolymerized in the presence of a Ziegler type catalyst, containing 4-methyl-1-pentene as an α-olefin, the maximum peak temperature of the elution curve of TREF was 66 ° C., H / W 0.75, density 0.9
10 g / cm ³ , melt flow rate 2.0 g / 10
A linear ethylene-4-methyl-1-pentene copolymer (“Ultzex 1020L” manufactured by Mitsui Chemicals, Inc.).

<Component (B)> B-1: Content of vinyl acetate unit is 20% by weight, melt flow rate is 2.5 g /
10 minutes ethylene-vinyl acetate copolymer ("Novatech EVA LV540" manufactured by Japan Polychem). <Component (C)>C-1; Maleic anhydride unit content 2.5% by weight, ethyl acrylate unit content 12.5% by weight, melt flow rate 3.0 g / 10 min ethylene-maleic anhydride Substance-ethyl acrylate terpolymer (“Bondaine TX8030” manufactured by Sumitomo Chemical Co., Ltd.). <Component (D)> Silica gel having a product of relative permittivity and dielectric loss tangent of 0.16 (“Tokushiru GU” manufactured by Tokuyama Corporation).

Examples 1 to 3 and Comparative Examples 1 to 7 Components (A), (B), (C) and (D) shown in Table 1 were mixed with a Henschel mixer and then biaxial. Using an extruder ("KTX40" manufactured by Kobe Steel, Ltd.),
Cylinder temperature 160 ℃, screw rotation speed 220rp
The mixture was melt-kneaded at m for 1 minute, melt-extruded into a strand, cooled and solidified, and cut to prepare ethylene-based polymer composition pellets. For each of the obtained polymer composition pellets, the content of vinyl acetate units in the composition was calculated from the blending ratio of the component (A) and the component (B), and the melt flow rate was measured. The results are shown in Table 1.

Next, each of the obtained polymer composition pellets was molded into a sheet having a thickness of 0.3 mm using a calender roll heated to 150 ° C., and each of the obtained sheets was subjected to high-frequency wave treatment by the following method. Weldability was evaluated and the results are shown in Table 1.

<High-frequency welder workability> Two strip-shaped test pieces each having a width of 30 mm and a length of 170 mm cut out from a sheet are overlapped, and a high-frequency welder (manufactured by Yamamoto Vinita Co.)
Using a mold with a width of 10 mm and a groove depth of 1 mm,
With respect to the sheets welded under the conditions of a current of 0.5 to 1.0 A, a welding time of 7 seconds, and a cooling time of 4 seconds, the peelability when peeling between the sheets by hand was evaluated according to the following criteria. ◯: Completely welded and cannot be peeled off. Δ: Peeling is possible although considerable force is required. X: Easy peeling.

On the other hand, each of the polymer composition pellets obtained above was pressed at 160 ° C. to be molded into a sheet having a thickness of 2.0 mm, and each of the obtained sheets was softened by the following method. The heat resistance was measured and evaluated, and the results are shown in Table 1.

<Flexibility> Width 30 m cut out from the sheet
40 mm wide at both ends of a m-shaped, 200 mm long strip-shaped test piece
It is sandwiched by two sets of chucks and the chuck spacing is 60 mm
The test piece is bent and fixed so that the curved portion of the test piece has a sphere with a radius of 5 mm and a length of 4 mm.
60 mm with a pressing tool having a 0 mm inverted conical head
The sample was pressed at a speed of / min, and the maximum stress until the test piece buckled at that time was measured with a strain gauge.

<Heat resistance> 30 m width cut out from the sheet
50 mm wide at both ends of a strip-shaped test piece of m and length of 150 mm
It is sandwiched by two sets of chucks and the chuck spacing is 50 mm
Was fixed so that the temperature was 60 ° C., and the time required to break when a load of 49 N was applied in the chuck spacing direction was measured.

Further, each of the polymer composition pellets obtained above was molded into a sheet having a thickness of 0.4 mm using a calender roll heated to 150 ° C., and a polyester plain woven cloth (fiber 750 denier, number of hammered in) was formed. A tarpaulin having a thickness of 0.75 mm was manufactured by melt-laminating on both sides of 20 × 21 / inch (manufactured by Teijin Ltd.) and cooling and solidifying. For each of the obtained tarpaulins, the high frequency welder processability, flexibility and heat resistance were measured and evaluated by the methods described below, and the results are shown in Table 1.

<High frequency welder workability> Similar to the case of the above-mentioned sheet, the peelability when manually peeling between the two tarpaulins welded was evaluated according to the following criteria. ◯: Sufficiently welded and cannot be peeled between polymer compositions. It should be noted that peeling occurs between the woven fabric and the polymer composition. Δ: Peeling between polymer compositions although considerable force is required. X: Easily peeled between polymer compositions.

<Flexibility> The same operation as that of the above-mentioned sheet was performed except that the strip-shaped test piece had a width of 30 mm and a length of 200 mm.

<Heat resistance> Width 3 cut out from tarpaulin
Two 0 mm, 190 mm long strip-shaped test pieces were overlapped at a length of 80 mm at the center in the longitudinal direction (total length 300
mm), using a high-frequency welder (manufactured by Yamamoto Vinita Co., Ltd.) for the overlapping portion, width 30 mm, groove depth 0.5 mm
Current of 0.5-1.0 A, welding time 7
Seconds, cooling time 4 seconds, 30 mm welding, 20 mm interval, 30 mm welding to prepare a test piece. Both ends of the obtained test piece were sandwiched by two sets of chucks each having a width of 50 mm, fixed so that the chuck spacing was 200 mm, and fractured when a load of 147 N was applied in the chuck spacing direction at a temperature of 60 ° C ( The time required to reach the shear peeling of the welded portion was measured and evaluated according to the following criteria. ◯: Time to destruction is 168 hours or more. Δ: Time to destruction is 100 hours or more and less than 168 hours. X: Time to destruction is 50 hours or more and less than 100 hours. XX: Time to destruction is less than 50 hours.

[0059]

[Table 1]

[0060]

Industrial Applicability According to the present invention, it is possible to provide an ethylene polymer composition which is excellent in flexibility, heat resistance and high frequency welder processability, and a tarpaulin using the same.

Continued front page    F-term (reference) 4F100 AA01A AA01C AA20 AK04A                       AK04C AK07 AK24A AK24C                       AK25A AK25C AK52A AK52C                       AK53A AK53C AK63A AK63C                       AK68A AK68C AL01A AL01C                       AL05A AL05C AL06A AL06C                       BA02 BA03 BA06 BA10A                       BA10C DG12B DG13B GB07                       GB15 JA06A JA06C JG05A                       JG05C JJ03 JK13 YY00A                       YY00C                 4J002 BB05W BB06X BB203 DE146                       DJ016 DJ036 DJ046

Claims (10)

[Claims] 1. The following component (A), component (B), and (C)
Component and component (D) are contained, and the ratio of component (A) to the total amount of component (A) and component (B) is 10% by weight or more and is derived from component (B) The content of vinyl acetate units is 4 to 30% by weight, and the melt flow rate as a polymer composition is 0.1 to 80 g / 10.
And an ethylene polymer composition. (A) It consists of ethylene and an α-olefin having 3 to 18 carbon atoms, and the temperature of the maximum peak in the elution curve obtained by temperature rising elution fractionation is 10 to 80 ° C. and the melt flow rate is 0.1 to 100 g / 10. Minute linear ethylene-α-olefin copolymer (B) melt flow rate is 0.05 to 100 g / 10.
Ethylene-vinyl acetate copolymer (C) functional group-containing ethylenically unsaturated compound-modified ethylene polymer (D) hydrous inorganic compound 2. The component (A) has a ratio (H / W) of the peak height (H) to the width (W) of 1/3 height in the maximum peak of the elution curve obtained by temperature rising elution fractionation is 2.
The ethylene polymer composition according to claim 1, which is the above linear ethylene-α-olefin copolymer. 3. The ethylene-based polymer composition according to claim 1, wherein the component (B) is an ethylene-vinyl acetate copolymer having a vinyl acetate unit content of 7 to 50% by weight. 4. The functional group-containing ethylenically unsaturated compound in the component (C) is an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid alkyl ester, an ethylenically unsaturated carboxylic acid anhydride, an epoxy group-containing ethylenic group. The ethylene polymer according to any one of claims 1 to 3, which is one or more compounds selected from the group consisting of an unsaturated compound, a hydroxyl group-containing ethylenically unsaturated compound, and a silyl group-containing ethylenically unsaturated compound. Composition. 5. The ethylene polymer composition according to claim 4, wherein the component (C) is a modified ethylene polymer with a functional group-containing ethylenically unsaturated compound containing at least an ethylenically unsaturated carboxylic acid anhydride. . 6. The ethylene-based polymer composition according to claim 5, wherein the component (C) is an ethylene-maleic anhydride- (meth) acrylic acid alkyl ester terpolymer. 7. The component (D) is a hydrated inorganic compound having a product of relative permittivity and dielectric loss tangent of 0.1 or more.
The ethylene polymer composition according to any one of 1. 8. The ratio of the component (A) and the component (B) to the total amount of the component (A) and the component (B) is
Component (A) is 10 to 80% by weight, component (B) is 90 to 2
The ethylene polymer composition according to claim 1, which is 0% by weight. 9. The content of the component (C) is 5 to 40 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B), and the content of the component (D) is The ethylene polymer composition according to any one of claims 1 to 8, which is also 3 to 30 parts by weight. 10. A tarpaulin comprising a fibrous woven fabric as a base fabric, and a layer of the ethylene polymer composition according to any one of claims 1 to 9 being laminated on at least one surface thereof.