JP2002240220A - Abrasion-resistant laminated sheet of polyolefin resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet of a polyolefin resin excellent in pliability, abrasion resistance, high humidity-barrier properties and high-frequency weldability, and excellent in the breaking strength and thermal creep resistance of an adhering part. SOLUTION: A surface film layer (A) which is constituted of a blended resin of an ethylene-α-olefin (C3-C18) copolymer and an ethylene-vinyl acetate or (met)acrylic acid (ester) copolymer and of which the weight percentage of the total contents of copolymer constituents (vinyl acetate + (met)acrylic acid (ester)) is 4-16 wt.%, and a rear film layer (B) which is constituted of the same blended resin (wherein the weight percentage of the total contents of the copolymer constituents is higher than 16 wt.% and equal to or lower than 30 wt.%) as the above or a rear film layer (C) which is constituted only of the copolymer resin in the same way as the above, are formed on the surface and the rear of a base cloth. The thickness ratio of the film layer (A)/the film layer (B) or (C) is 1:1-3:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an abrasion-resistant polyolefin resin laminated sheet. More specifically, the present invention is obtained by laminating a specific polyolefin-based resin film on both surfaces of a base cloth made of a fiber cloth, which is particularly suitable for use in a flexible container, and has high flexibility and high abrasion resistance. And a high-frequency fusion-bondable polyolefin-based resin laminated sheet. Further, the abrasion-resistant polyolefin-based resin laminated sheet of the present invention further has excellent breaking strength and thermal creep resistance at the joint, and has high humidity barrier properties.

[0002]

2. Description of the Related Art Conventionally, sheet materials for forming a flexible container include a composite sheet of a fiber woven fabric and a soft polyvinyl chloride resin film, a composite sheet of a fiber woven fabric and a synthetic rubber layer, and a composite sheet of a fiber woven fabric and a polyurethane resin layer. A composite sheet, a composite sheet of a fiber woven fabric and a polyolefin resin layer, and the like are used. Originally, flexible containers are used repeatedly for logistics, so the ideal for users is to use flexible containers that are more durable and more economical, and for the transportation business that handles logistics, the flexible containers return to the manufacturer with empty bags. At times, they want to be able to fold compactly and still be lightweight.
In addition, manufacturers who sew flexible containers strongly desire sewing machines that can be sewn using a high-frequency welder machine and that have high flexibility and are therefore convenient for sewing work. Among these flexible containers, the reason why flexible polyvinyl chloride resin is conventionally used most often is that all other requirements are satisfied except for the requirement of "lightweight".

Originally, flexible polyvinyl chloride resin is a synthetic resin material which is flexible and tough, and is excellent in transparency, processability and low cost. Therefore, it is widely used in many fields other than flexible containers. I have. However, recently, suspicions that phthalate esters contained as a plasticizer in polyvinyl chloride resin products are hormone-disrupting substances have been discussed, and this plasticizer has been added to the groundwater system during landfill disposal. It is feared to be mixed. On the other hand, polyvinyl chloride resin products containing phthalic acid esters have attracted strong interest in generating dioxin derivatives when incinerated. Therefore, from the viewpoint of suppressing the generation of dioxin in the incineration process, not only the polyvinyl chloride resin products, but also the burning of all synthetic resin products has begun to be regulated. From the viewpoint of evacuation safety in the event of a fire, there is a social demand for all of these synthetic resin processed products to be able to suppress the generation of toxic combustion gases. From such a social background, for example, in disposable applications such as packaging materials, various measures have been developed to reduce the use of polyvinyl chloride resin products, and products using polyolefin resins such as polyethylene resins and polypropylene resins have been widely used. It is beginning to spread. Further, for synthetic resin products in general, there is a demand for synthetic resin products that are easily recyclable.

[0004] Conventionally, as a flexible container made of a polyolefin resin, a flexible container made of an ethylene-vinyl acetate copolymer resin, which can be fused and sewn with a high-frequency welder, has been used. Polyethylene resins and ethylene-vinyl acetate copolymer resins used as raw materials for these flexible containers are registered in the Voluntary Regulation Standards of the Polyolefin Hygiene Council, and the Food Hygiene Notification No. 434 of the Ministry of Health and Welfare Notification Conforms to test standards, and D. A. (§1
21, 2570), it is possible to obtain a product having a higher safety particularly for the transportation of food raw materials, and to use a flexible container made of these synthetic resins as a flexible polyvinyl chloride resin. It is used more quantitatively than flexible containers. Further, when it is not preferable that the acetic acid odor peculiar to the ethylene-vinyl acetate copolymer resin is transferred to food raw materials,
Other high-frequency weldable polyolefin resins include ethylene- (meth) acrylic acid (ester)
Copolymer resins are used in some flexible containers.

However, these ethylene-vinyl acetate copolymer resins and ethylene- (meth) acrylic acid (ester) copolymer resins have a vinyl acetate component and a (meth)
As the content of a polar component such as an acrylic acid (ester) component increases, the crystallinity decreases and the flexibility increases. However, on the other hand, such a copolymer is inferior in moisture barrier properties due to its low crystallinity and is not suitable for powder transport, but also has poor resin strength and abrasion resistance. Practical utility cannot be obtained. For this reason, ethylene-vinyl acetate copolymer resin and ethylene-
By blending a polyethylene resin or an ethylene-α-olefin copolymer resin with a (meth) acrylic acid (ester) copolymer resin, the resin strength and abrasion strength can be improved, or the polyethylene resin and ethylene- Based on α-olefin copolymer resin,
It is generally used to blend an ethylene-vinyl acetate copolymer resin or an ethylene- (meth) acrylic acid (ester) copolymer resin with the resin, thereby imparting high-frequency fusion property.

According to the above-mentioned method, it is possible to impart a certain degree of high-frequency weldability to the obtained flexible container and to improve resin strength and abrasion strength to a certain degree at the same time. I couldn't get a flexible container to get. This is because if the blending ratio of the polyethylene resin and the ethylene-α-olefin copolymer resin used in the blend resin is increased, the resin strength and wear strength can be certainly improved, but the high frequency weldability becomes insufficient. And the sewing work becomes difficult. Conversely, ethylene-vinyl acetate copolymer resin and ethylene- (meth) acrylic acid (ester)
By increasing the blending ratio of the copolymer resin, the high-frequency weldability can be certainly improved, but this time, the resin strength and wear strength become insufficient.

Further, in any of the blend resins,
By containing a highly crystalline polyethylene resin and an ethylene-α-olefin copolymer resin, the texture of the resulting flexible container becomes hard, folding becomes difficult, and the folded body becomes bulky, which is inconvenient for logistics. Problems are inevitable. Further, at this time, wrinkles are left due to excessive folding, which causes a problem such as causing resin fatigue deterioration in the bent portion. Therefore, in the method using the above-mentioned blended resin, the application range is too narrow for a flexible container requiring a high degree of flexibility and durability.

An ethylene-α-olefin copolymer resin polymerized in the presence of a metallocene-based homogeneous catalyst has a high molecular weight distribution and has neither a high molecular weight region nor a low molecular weight region, thereby providing high flexibility. Although it is suitable as a component for a blend resin for the purpose, it has a characteristic that its melting point is about 5 to 10 ° C. lower than that of a conventional ethylene-α-olefin copolymer resin because the crystalline lamellar structure is uniform and thin. I have. This lowering of the melting point is not a desirable property for flexible container applications where further improvement of the heat-resistant creep strength is required.

On the other hand, ethylene having a polar component
A vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) -based copolymer resin as an intermediate layer, and a polyethylene resin, a polypropylene resin, or an ethylene-α-olefin copolymer resin on both front and back surfaces thereof A multilayer film laminate having a thin wear-resistant olefin-based resin layer has been proposed. Certainly, these multi-layered olefin resin films are excellent in wear resistance and flexibility.
Since it is manufactured by a stretching technique, it is difficult to control the thickness of each layer accurately, and therefore, the thickness of the intermediate layer is apt to vary, so that high-frequency welding conditions are not stable, However, since the non-polar polyolefin layer is disposed as the outermost layer, there is a disadvantage that the high-frequency fusion property is worse than expected. In addition, the production method of these multi-layered films is greatly restricted by the production method.For example, in order to cope with the production of small-lot, multi-product products with different coloring types and additive types, the compound loss due to resin replacement is large, and The fact is that they are shunned.

Furthermore, a flexible container made of a polyolefin resin composition, particularly an ethylene-vinyl acetate copolymer resin, and made by high frequency fusion, has a joint portion which is smaller than that of a flexible container made of a soft polyvinyl chloride resin. For example, when a raw material at 50 ° C. or higher is filled, the resin at the sewn portion at the bottom of the container is softened, and there is a problem in that the bottom breakout occurs. Since the breakage of the sewn portion is also caused by the substantial poor adhesiveness between the fiber cloth and the ethylene-vinyl acetate copolymer resin film, the breakage of the sewn portion with respect to the fiber cloth is performed for the purpose of fundamentally improving the adhesiveness. Agent treatment is required. However, most of the adhesives (primers) that can bond the polyolefin resin are adhesives. Therefore, even if a sufficient adhesive effect can be obtained at room temperature, the adhesive is not heat-resistant at 50 ° C. or more. Since the plastic resin is softened, there is a disadvantage that the adhesive effect is extremely reduced, and it cannot be used for a flexible container. On the other hand, by using a polyisocyanate-based compound curing agent in combination with the adhesive, it is possible to certainly satisfy the heat creep resistance. There are many disadvantages such as a large decrease.

Therefore, as a substitute for a flexible container made of a polyvinyl chloride resin, a polyolefin-based material having a sufficiently soft texture, excellent durability such as abrasion resistance, and capable of easily performing high-frequency fusion. Resin sheet,
Further, in addition to the above performance, there is a strong demand for providing a polyolefin-based resin sheet having high breaking strength of a high-frequency welded portion, excellent heat creep resistance, and high humidity barrier properties.

[0012]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has a sufficiently flexible feel and excellent abrasion resistance. It is an object of the present invention to provide a suitable polyolefin-based resin laminated sheet and a polyolefin-based resin laminated sheet having a high breaking strength of a high-frequency-welded portion, excellent heat creep resistance, and high humidity barrier properties.

[0013]

The present invention has been studied and studied in order to solve the above-mentioned problems. As a result, ethylene and α-olefin having 3 to 18 carbon atoms are formed on both front and back surfaces of a base cloth made of fiber cloth. Is a linear low-density polyethylene obtained by copolymerizing ethylene-vinyl acetate copolymer resin and / or ethylene- (meth) acrylic acid (ester) copolymer resin. Polyolefin resin sheets (1) and (2) on which a film layer (A) made of a resin blend is laminated,
(1-1). The surface film layer (A) has a total content of the vinyl acetate component and the (meth) acrylic acid (ester) component of 4 to 4.
(1-2). The film layer (B) formed on the back surface contains a polyolefin resin blend containing 16% by weight.
It is a polyolefin-based resin blend having a total content of a vinyl acetate component and a (meth) acrylic acid (ester) component of 16 to 30% by weight, and (1-3). Polyolefin-based laminated resin sheet (1) having a thickness ratio of 1: 1 to 3: 1 with respect to the thickness of the film layer (B), and (2) a surface film formed on the surface of a base cloth made of a fiber cloth A polyolefin resin sheet in which a layer (A) and a film layer comprising a back film layer (C) formed on the back surface are laminated, and (2-1). A total content of a vinyl acetate component and a (meth) acrylic acid (ester) component of 16 which is a blend of a vinyl acetate copolymer resin and / or an ethylene- (meth) acrylic acid (ester) copolymer resin; (2-2). The thickness ratio of the front surface film layer (A) to the rear surface film layer (C) is 1: 2.
1-3: 1 polyolefin resin sheet (2)
However, they have found that they have excellent flexibility, abrasion resistance, high-frequency weldability, and heat creep resistance and have good humidity barrier properties, and have completed the present invention.

More specifically, the abrasion-resistant polyolefin resin laminated sheet (1) of the present invention comprises a base fabric made of a fiber cloth, and a front film layer (A) and a back film layer laminated on both front and back surfaces of the base fabric. (B) and (1-1)
The surface film layer (A) comprises (a) a main component comprising a linear low-density ethylene-α-olefin copolymer comprising a copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms. , (B) a blend component of at least one selected from an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylic acid (ester) copolymer, wherein the copolymerization is carried out in the blend component (b). The main component (a) and the blend component (b) based on the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as components
Is formed of a blend resin (1-1) having a ratio to the total weight of 4 to 16% by weight, and (1-2) the back film (B) is composed of (c) ethylene and 3 to 4 carbon atoms. (D) an ethylene-vinyl acetate copolymer and ethylene- (meth) acrylic acid (a main component consisting of a linear low-density ethylene-α-olefin copolymer comprising an α-olefin copolymer); Ester) a blend component of at least one selected from copolymers,
The ratio of the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymer component in the blend component (d) to the total weight of the main component (c) and the blend component (d) is 16 % By weight and 30
(1-3) The ratio of the thickness of the front film layer (A) to the thickness of the back film layer (B) is 1: 1 to 1%. 3: 1
It is characterized by the following. In the abrasion-resistant polyolefin-based resin laminated sheet (1) of the present invention, at least one of the front film layer (A) and the back film layer (B) has a weight of 1 to 10% by weight of synthetic amorphous silica. Is preferably contained. In the wear-resistant polyolefin-based resin laminated sheet (1) of the present invention,
The moisture permeability (according to JIS Z0208) of the laminate with the front film layer (A) and the back film layer (B) is 10
g / m ² · 24 hours or less. The abrasion-resistant polyolefin-based resin laminated sheet (2) of the present invention comprises:
A base cloth made of fiber cloth, and a front film layer (A) and a back film layer (C) laminated on both front and back surfaces of the base cloth
(2-1) wherein the surface film layer (A) comprises:
(A) a main component composed of a linear low-density ethylene-α-olefin copolymer composed of a copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms;
A vinyl acetate copolymer comprising at least one selected from the group consisting of a vinyl acetate copolymer and an ethylene- (meth) acrylic acid (ester) copolymer, wherein vinyl acetate is contained as a copolymer component in the blend component (b). And the total weight of (meth) acrylic acid (ester) and the main component (a)
And the ratio to the total weight of the blend component (b) is 4
(2-2) The back film (C) is made of (e)
Ethylene-vinyl acetate copolymer and ethylene- (meth)
Vinyl acetate and (meth) formed of a copolymer resin comprising at least one selected from acrylic acid (ester) copolymers and contained as a copolymer component in the copolymer resin (e) The ratio of the total weight of acrylic acid (ester) to the total weight of the copolymer resin (e) is higher than 16% by weight and 30% by weight or less, and (2-3) the surface film layer (A). ) And the thickness of the back film layer (C) is 1: 1 to 3: 1. In the abrasion-resistant polyolefin resin laminated sheet (2) of the present invention, at least one of the front film layer (A) and the back film layer (C) has a synthetic amorphous content of 1 to 10% by weight based on the weight thereof. Preferably, it contains silica. In the abrasion-resistant polyolefin-based resin laminated sheet (2) of the present invention, the moisture permeability (according to JIS Z0208) of the laminate with the front film layer (A) and the back film layer (C) is 10 g.
/ M ² · 24 hours or less. In each of the abrasion-resistant polyolefin-based resin laminated sheets (1) and (2) of the present invention, the fiber fabric for a base fabric is pretreated with a treating agent containing at least one silicon compound. Is preferred. In each of the abrasion-resistant polyolefin resin laminated sheets (1) and (2) of the present invention, the silicon compound contained in the treating agent for the base fabric is selected from synthetic amorphous silica, colloidal silica, and a silane coupling agent. Preferably. In each of the abrasion-resistant polyolefin-based resin laminated sheets (1) and (2) of the present invention, the fiber fabric for a base fabric is composed of multifilament yarns, and has a porosity between yarns of 5 to 30%. It is preferable to have In each of the abrasion-resistant polyolefin-based resin laminated sheets (1) and (2) of the present invention, the surface film layer (A) preferably has a thickness of at least 0.1 mm. In each of the abrasion-resistant polyolefin-based resin laminated sheets (1) and (2) of the present invention, the main component (a) contained in the surface film layer (A) contains ethylene and 3 in the presence of a metallocene catalyst. It is preferable to include a linear low-density ethylene-α-olefin copolymer obtained by copolymerizing an α-olefin having from 18 to 18 carbon atoms. In the abrasion-resistant polyolefin-based resin laminated sheet (1) of the present invention, the main component (c) contained in the back film layer (B) contains ethylene and 3 to 18 carbon atoms in the presence of a metallocene catalyst. It is preferable to include a linear low-density ethylene-α-olefin copolymer obtained by copolymerizing an α-olefin having the following formula:

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION A laminated sheet (1) of a wear-resistant polyolefin resin according to the present invention comprises a base fabric made of a fiber fabric, and a front film layer (A) and a back film layer laminated on both sides of the base fabric. (B). The surface film layer (A) is composed of (a) ethylene and three to three carbon atoms.
(B) an ethylene-vinyl acetate copolymer and ethylene- (meth) acrylic acid (a main component comprising a linear low-density ethylene-α-olefin copolymer comprising an α-olefin copolymer); Ester) and a blend resin (1) containing at least one blend component selected from copolymers, provided that the blend component (b) contains vinyl acetate and ( The ratio of the total weight of the (meth) acrylic acid (ester) to the total weight of the main component (a) and the blend component (b) is 4 to 16% by weight, preferably 6 to 12% by weight.
It is. The back film (B) is composed of (c) ethylene and α of 3 to 18, preferably 4 to 10 carbon atoms.
A main component consisting of a linear low-density ethylene-α-olefin copolymer consisting of a copolymer with an olefin; and (d)
Ethylene-vinyl acetate copolymer and ethylene- (meth)
A blend resin (2) containing at least one blend component selected from acrylic acid (ester) copolymers, provided that acetic acid contained as a copolymer component in the blend component (d) The ratio of the total weight of vinyl and (meth) acrylic acid (ester) to the total weight of the main component (c) and the blend component (d) is higher than 16% by weight and 30% by weight or less, preferably 18 to 26%. % By weight. Further, the thickness ratio between the front film layer (A) and the back film layer (B) is 1: 1 to 3: 1, preferably 1.2: 1 to 2: 1,
It is.

In the laminated sheet (1) of the present invention,
At least one of the front film layer (A) and the back film layer (B) may contain 1 to 10% by weight, preferably 3 to 8% by weight of the synthetic amorphous silica based on the weight thereof. preferable. Further, it is preferable that the fiber base cloth for the base cloth is pretreated with a silicon compound-containing treating agent. Further, the moisture permeability (according to JIS Z 0208) of at least one of the front film layer (A) and the back film layer (B) of the laminated sheet (1) of the present invention is 10 g / m.
Is preferably not more than ² · 24 h, more preferably the moisture permeability is less than 6 g / m ² · 24 hr.

The laminated sheet of abrasion-resistant polyolefin resin (2) of the present invention comprises a base cloth made of a fiber cloth, and a front film layer (A) and a back film layer (C) laminated on both sides of the base cloth. And The surface film layer (A) of the laminated sheet (2) has the same constitution and composition performance as the surface film layer of the laminated sheet (1) of the present invention. The back film (C) is (e) ethylene-
A copolymer resin made of at least one selected from a vinyl acetate copolymer and an ethylene- (meth) acrylic acid (ester) copolymer, and contained in the copolymer resin (e) The ratio of the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as the polymerization component to the total weight of the copolymer resin (e) is 16
% And up to 30% by weight, preferably 18%
~ 26% by weight. Further, the surface film layer (A)
And the thickness ratio of the back film layer (C) is 1: 1 to 1
3: 1, preferably 1.2: 1 to 2: 1.

In the abrasion-resistant polyolefin-based resin laminate sheet (2) of the present invention, 1 to 10% by weight of the weight of at least one of the front film layer (A) and the back film layer (C) is preferable. Preferably contains 3 to 8% by weight of synthetic amorphous silica. Further, it is preferable that the fiber fabric for the base fabric is pretreated with a silicon compound-containing treating agent. Further, at least one of the surface film layer (A) and the back film layer (C) of the laminated sheet (2) has a moisture permeability (JIS Z020).
8) is preferably 10 g / m ² · 24 hours or less, and more preferably 6 g / m ² · 24 hours or less.

In the present invention, the (meth) acrylic acid (ester) includes acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester.

The polyolefin resin usable for the resin blend (1) for the front film (A) and the resin blend (2) for the back film (B) of the wear-resistant polyolefin resin sheets (1) and (2) of the present invention. Used is a linear low-density polyethylene-α-olefin copolymer resin obtained by copolymerizing ethylene and an α-olefin containing 3 to 18, preferably 4 to 10 carbon atoms. Can be The ethylene-α-olefin copolymer resin is obtained by mixing an ethylene monomer and an α-olefin monomer having 3 to 18 carbon atoms in the presence of a Ziegler-Natta catalyst.
It may be obtained by polymerization by a gas phase method, a slurry liquid phase method, or a high pressure method. Examples of the α-olefin include propylene, butene-1,4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, tetradecene-
1, hexadecene-1, heptadecene-1, octadecene-1, etc., having a carbon number of 4 to 10
It is particularly preferred to use the α-olefin of the formula (1). Also,
An ethylene-α-olefin obtained by copolymerizing one or more of these α-olefins with an ethylene monomer
Olefin copolymer resins can also be used.

The Ziegler-Natta catalyst is used in the Periodic Table IV-
Group VI transition metal compounds and Periodic Table Groups I-III gold
Transition composed of compounds of the genus and having a metal-carbon bond
Catalyst containing a metal compound, usually a transition metal halide
It is composed of a salt and a metal alkyl compound.
You. As the halogenated transition metal salt, for example, MgC
l _Two, AlCl_Three, TiCl_Three, TiCl_FourEtc. are used
As the metal alkyl compound, for example, triethyl
Aluminum, triisobutyl aluminum, etc. are preferred
It can be used properly.

The polyolefin resin usable for the blend resin (1) for the front film (A) and the blend resin (2) for the back film (B) of the abrasion-resistant polyolefin laminate resin sheets (1) and (2) of the present invention. The resin is a linear low-density ethylene resin obtained by copolymerizing an ethylene monomer and the α-olefin in the presence of a metallocene catalyst.
An α-olefin copolymer resin may be used. Examples of the metallocene-based catalyst include a catalyst containing an organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative. The transition metal of the organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative is selected from Group IVB of the Periodic Table of the Elements,
For example, zirconium, titanium, hafnium and the like can be mentioned. Specific examples of the organic transition metal compound containing a cyclopentadienyl derivative include bis (n-propylcyclopentadienyl) zirconium dichloride,
-Methyl-1ethylidene (cyclopentadienyl-1-
Examples thereof include fluorenyl) zirconium dichloride and bis (cyclopentadienyl) hafnium dichloride. Specific examples of the organic transition metal compound containing an indenyl derivative include ethylene bis (indenyl) zirconium dichloride, bis (indenyl) titanium dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, and the like. The metallocene-based catalyst may be used in combination with at least one of an alkylaluminoxane compound, a protonic acid, a Lewis acid, and a Lewis acidic compound as a co-catalyst.

The ethylene-α-olefin copolymer resin may be used alone or as a blend of two or more. In particular, one or more ethylene-α-olefin copolymer resins (i) polymerized in the presence of a Ziegler-Natta catalyst, and an ethylene-α-olefin copolymer polymerized in the presence of a metallocene catalyst One or more resins selected from the resins (ii) may be used in combination as a blend. The ethylene-α-olefin copolymer resin used in the present invention is ethylene-α-olefin.
The olefin copolymer resin (i) and the ethylene-α-olefin copolymer resin (ii) are in a weight ratio of 25:75 to 7:
It is preferred that they are blended at 5: 25% by weight. When the content of the ethylene-α-olefin copolymer resin (i) is less than 25% by weight, the resulting polyolefin resin laminated sheet (1) or (2) may have insufficient heat creep resistance. Also, the texture of the ethylene-α-olefin resin laminated sheet (1) or (2) may be hard. It is suitable for the present invention that the melt index of these ethylene-α-olefin copolymer resins and the blended composition thereof is from 0.3 to 20 g / 10 min. This melt index is 0.3g
If it is less than / 10 min, the forming process of the obtained polyolefin resin laminated sheet (1) or (2) of the present invention may be extremely difficult. It is 20g / 10
If it is higher than min, the resulting polyolefin resin laminated sheet (1) or (2) may have insufficient abrasion resistance and heat creep resistance, and may have increased tackiness and cause blocking. There is.

Ethylene which can be used for the front film layer (A), back film layer (B) or (C) of the abrasion-resistant polyolefin resin laminated sheets (1) and (2) of the present invention.
The vinyl acetate copolymer resin and the ethylene- (meth) acrylic acid (ester) copolymer resin can be produced by a radical polymerization method. (Meth) acrylic acid (ester) monomers capable of radical polymerization with ethylene monomers include acrylic acid, methacrylic acid, and esters thereof. Examples of the ester of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, and glycidyl (meth) acrylate. These monomers may be used alone or in combination of two or more. Further, the ethylene-vinyl acetate copolymer resin is obtained by polymerization of an ethylene monomer and a vinyl acetate monomer. Examples of the ethylene- (meth) acrylic acid (ester) copolymer resin include an ethylene-acrylic acid copolymer resin obtained by polymerizing an ethylene monomer and an acrylic acid monomer, and a polymer obtained by polymerizing an ethylene monomer and an acrylate monomer. Ethylene-acrylic acid copolymer resin,
Ethylene-acrylate copolymer resin obtained by polymerization of ethylene monomer and acrylate monomer, ethylene-methacrylic acid copolymer resin obtained by polymerization of ethylene monomer and methacrylate monomer, ethylene monomer and methacrylate There are ethylene-methacrylate copolymer resins obtained by polymerization with acrylic acid ester monomers and the like.
It may be used alone or as a mixture of two or more.

The blend components of the blend resin (1) for the front film layer (A) and the blend resin (2) for the back film layer (B) of the abrasion-resistant polyolefin resin laminate sheets (1) and (2) of the present invention. )) And the ethylene-vinyl acetate copolymer resin used as the copolymer resin for the back film layer (C) preferably have a vinyl acetate component content of 5 to 60% by weight. In the (meth) acrylic acid (ester) copolymer resin, the content of the (meth) acrylic acid (ester) component is 5 to 5.
When the ethylene-vinyl acetate copolymer resin and the (meth) acrylic acid (ester) copolymer resin are used in combination, the weight ratio is preferably 100: 0 to 60% by weight.
0: 100, and the total amount of the vinyl acetate component and the (meth) acrylic acid (ester) component contained in the mixture is preferably 5 to 60% by weight based on the total weight.
The melt index of the blend resin (1) for the front film layer (A) and the blend resin (2) for the back film layer (B) can be suitably used in the present invention in the range of 0.3 to 20 g / 10 min. This melt index is 0.3g
If it is less than / 10 min, the forming process of the polyolefin resin laminated sheet of the present invention may be extremely difficult,
If it is higher than 20 g / 10 min, the resulting polyolefin-based resin laminated sheet may have insufficient abrasion resistance and heat creep resistance, and may further increase adhesiveness and cause blocking.

In the abrasion-resistant polyolefin resin laminated sheet (1) of the present invention, a front film layer (A) and a back film layer (B) are formed on the front and back surfaces of the base fabric, and the laminated sheet (2) In (2), a front film layer (A) and a back film layer (C) are formed on the front and back surfaces of the base fabric. The surface film layer (A) is formed of the ethylene-α-
It is formed by a blend resin (1) of an olefin copolymer resin main component and an ethylene-vinyl acetate and / or (meth) acrylic acid (ester) copolymer resin. The ratio of the total weight of the vinyl acetate component and the (meth) acrylic acid (ester) component to the total weight of the blend resin (1) is 4 to 16% by weight. When the ratio of the total amount of the vinyl acetate component and the (meth) acrylic acid (ester) component is less than 4% by weight, the high-frequency weldability of the resulting polyolefin resin laminated sheet is insufficient, and the ratio of the total amount If it exceeds 16% by weight, the resulting polyolefin resin laminated sheet will have insufficient abrasion resistance and humidity barrier properties.

The back film layer (B) formed on the back surface of the laminated sheet (1) of the present invention comprises the ethylene-α-
It is formed by a blend resin (2) obtained by blending an olefin copolymer resin with the above-mentioned ethylene-vinyl acetate and / or (meth) acrylic acid (ester) copolymer resin. A blend resin (2) having a total weight of a nivir acetate component and a (meth) acrylic acid (ester) component contained as a copolymer component.
Is 16% by weight or more and 30% by weight or less based on the total weight. When the ratio of the total amount of the vinyl acetate component and the (meth) acrylic acid (ester) component is 16% by weight or less, the high-frequency weldability of the obtained polyolefin-based resin laminated sheet becomes insufficient, and it is 30% by weight. %, The heat-resistant creep property and the humidity barrier property of the obtained polyolefin resin laminated sheet become insufficient.

The back film layer (C) of the laminated sheet (2) of the present invention is formed of the above-mentioned ethylene-vinyl acetate and / or (meth) acrylic acid (ester) copolymer resin. , The total amount of the vinyl acetate component and the (meth) acrylic acid (ester) component is 16 to
Contains 30% by weight. When the total amount of the vinyl acetate component and the (meth) acrylic acid (ester) component is less than 16 parts by weight, the high-frequency weldability of the obtained polyolefin resin laminated sheet becomes insufficient, and the total amount is 3 parts.
If it exceeds 0% by weight, the resulting polyolefin resin laminated sheet will have insufficient heat creep resistance.

The melt index of the blend resin (2) for the back film layer (B) and the copolymer resin for the back film layer (C) is preferably 0.3 to 20 g / 10 min. This melt index is 0.3 g /
If it is less than 10 min, it may be difficult to form the obtained polyolefin resin laminated sheet, and if it is higher than 20 g / 10 min, the abrasion resistance and heat resistance of the obtained polyolefin resin laminated sheet may be reduced. It may be insufficient and may increase the tackiness and cause blocking.

The surface film layer (A) of the abrasion-resistant polyolefin resin laminated sheet (1) or (2) of the present invention is obtained by self-polymerization of a propylene monomer in the presence of a metallocene catalyst or a Ziegler-Natta catalyst. The isotactic polypropylene resin or the zindiotactic polypropylene resin may contain about 5 to 10% by weight for the purpose of improving the surface wear strength and the heat creep resistance.

At least one of the front film layer (A) and the back film layer (B) of the abrasion-resistant polyolefin resin laminated sheet (1) of the present invention, or the laminated sheet (2)
At least one of the front film layer (A) and the back film layer (C) may contain 3 to 10% by weight of synthetic amorphous silica. As the synthetic amorphous silica (silicon dioxide), it is preferable to use synthetic amorphous silica obtained by a wet method in which sodium silicate, a mineral acid (sulfuric acid) and salts are reacted in an aqueous solution. Since this synthetic amorphous silica has, as bound moisture, moisture bonded to a silanol group (Si-OH group) on the silica surface by a hydrogen bond and water present as a hydroxyl group contained in the silanol group itself. Is distinguished from anhydrous silica having a very low water content obtained by other dry synthesis methods or aerogel synthesis methods of silica.

In the abrasion-resistant polyolefin resin laminated sheets (1) and (2) of the present invention, a synthetic non-woven fabric used in combination with the front film layer (A) or the back film layer (B) or (C) layer. The average aggregated particle size of the crystalline silica is not particularly limited, but it is preferable to use those having an average aggregated particle size (a coal counter method) of 1 to 20 μm, more preferably 2 to 10 μm. Silica is used. The water content of the synthetic amorphous silica is preferably 3 to 15% by weight, more preferably 5 to 1% by weight.
0% by weight. 3% by weight of synthetic amorphous silica
If the amount is less than the above, the heat-resistant fracture strength of the obtained fusion-bonded polyolefin resin laminated sheet may be insufficient. If the amount of the synthetic amorphous silica exceeds 10% by weight, the front or back film In some cases, the molding fluidity of the layer-forming resin is deteriorated to make the processing difficult, and the film abrasion strength of the obtained laminated sheet is reduced, so that sufficient durability may not be obtained. By including 3 to 10% by weight of the synthetic amorphous silica in the front or back film layer of the abrasion-resistant polyolefin-based resin laminated sheet of the present invention, the high-frequency weldability is further improved,
Further, the heat-resistant creep property of the fusion bonded article can be improved.

The front and back film layers (A), (B), and (4) of the abrasion-resistant polyolefin resin laminated sheet of the present invention.
(C) may be colored with an organic pigment and / or an inorganic pigment. As the organic pigment, conventionally known organic pigments can be used. Pigments, isoindolinone-based pigments, quinophthalone-based pigments and the like, as well as nitroso pigments, alizarin lake pigments, metal complex azomethine pigments, and aniline-based pigments can be exemplified. Examples of the inorganic pigment include zinc oxide (zinc white), titanium oxide (rutile type, anatase type), antimony trioxide,
Iron oxide, lead oxide, chromium oxide, zirconium oxide, spinel (XY ₂ O ₄ ) structure oxide, rutile type [Ti (X
Y) O ₂ ] Metal oxides such as structural oxides, composites of zinc sulfide and barium sulfate (lithopone), metal sulfides such as calcium sulfide and zinc sulfide, and metal sulfates such as barium sulfate, calcium sulfate and lead sulfate Metal carbonates such as barium carbonate, calcium carbonate, magnesium carbonate, a composite of lead carbonate and lead hydroxide (lead white), magnesium hydroxide,
Metal hydroxides such as aluminum hydroxide (alumina white), a composite of aluminum hydroxide and calcium sulfate (satin white), a composite of aluminum hydroxide and barium sulfate (gloss white), lead chromate (graphite), Metal chromate such as barium chromate, other carbon black, titanium black, acetylene black, graphite, white carbon, diatomaceous earth, talc, clay, aluminum powder, colored aluminum powder, crushed metal-deposited film, silver-white mica Examples include titanium, colored mica titanium, and dichroic interference mica titanium. These pigments are of a single type, and the formulas can be used in combination of two or more types, and the amount of addition is not limited. Further, a combination in which the coloring of the film layers on the front and back sides is different from each other may be employed.

The front and back film layers (A), (B), and (C) of the abrasion-resistant polyolefin resin laminated sheet of the present invention may contain additives as necessary. Especially for the purpose of improving the durability of the front and back film layers, ultraviolet absorbers,
It is preferable to add an antioxidant and / or a light stabilizer. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylic acid-based, and anilide-based ultraviolet absorbers, and examples of the antioxidant include hindered phenol-based, amine-based, and phosphite-based antioxidants. . Examples of the light stabilizer include hindered amine light stabilizers. In addition, it is preferable to add a phosphate ester-based, aliphatic amide-based, or montanic acid-based lubricant for the purpose of improving the processability during film formation.

The front and back film layers (A), (B), and (C) of the abrasion-resistant polyolefin resin laminated sheet of the present invention comprise:
It can be processed by a conventionally known molding processing method, for example, a T-die extrusion method, an inflation method, a calendar method, or the like. The resin compound for forming the front and back films (A), (B) and (C) is formed by kneading and kneading the compound by a known method, for example, using a Banbury mixer, a kneader, a twin-screw kneader, or the like, or And / or after melt-kneading, it can be obtained by a method of granulating and pelletizing with a single-screw extrusion pelletizer, a twin-screw extrusion pelletizer, or the like. Front and back film layers (A), (B) and (C) of the present invention
Each of the films for T
-Can be manufactured by processing techniques such as die extrusion, inflation and calendering, but especially for the production of films colored with organic pigments, inorganic pigments, etc. A simple calendar method with little loss is suitable. The films (A), (B), and (C) of the present invention are preferably subjected to a molding process in a temperature range of 100 to 200 ° C. by a calender method. Films for front and back film layers formed by calendering (A), (B),
The thickness of (C) is preferably from 80 to 500 μm, and more preferably from 150 to 350 μm. If the thickness is less than this range, it is difficult to mold and, when laminated to the base fabric, the film breaks at the weaving intersection of the fiber fabric, which not only impairs waterproofness but also reduces the durability of the sheet. May worsen sex. The thickness of the abrasion-resistant polyolefin-based resin laminate sheet of the present invention is not limited, but it is preferable to laminate it with a fiber cloth using 1 to 4 films of 80 to 500 μm. Especially thickness 1
It is most preferable that the front or back film layer is formed on both sides of the fiber fabric using two 80-300 μm films.

The thickness ratio (A) :( B) of the front film layer (A) to the back film layer (B) of the abrasion-resistant polyolefin resin laminated sheet (1) of the present invention is 1: 1 to 1: 1. 3:
1, particularly preferably 1.2: 1 to 1.
2: 1. The minimum thickness of the surface film layer (A) is preferably 0.1 mm. For example, specifically, the film thickness ratio (A) :( B) is 0.2 mm: 0.2 mm to 0.2 mm.
6 mm: 0.2 mm. At this time, the surface film layer (A)
Permeability (JIS) of the laminate of the resin and the back film layer (B)
Z 0208) is preferably 10 g / m ² · 24 hours or less, more preferably 6 g / m ² · 24 hours or less.

The thickness ratio (A) :( C) of the front film layer (A) to the back film layer (C) of the abrasion-resistant polyolefin resin laminated sheet (2) of the present invention is 1: 1 to 1: 1.
The ratio is preferably 3: 1, particularly preferably 1.2:
1-2: 1. The minimum thickness of the film layer (A) is preferably 0.1 mm. For example, specifically, the film thickness ratio (A) :( C) is 0.2 mm: 0.2 mm to 0.2 mm.
6 mm: 0.2 mm. At this time, the surface film layer (A)
Permeability (JIS) of the laminate of
Z 0208) is preferably 10 g / m ² · 24 hours or less, more preferably 6 g / m ² · 24 hours or less.

If the ratio of the thickness of the front film layer (A) to the back film layer (B) or (C) is less than 1: 1, the durability of the resulting polyolefin resin laminated sheet will be insufficient. There is. When the ratio of the thickness of the front film layer (A) to the thickness of the back film layer (B) or (C) exceeds 3: 1 and is large, the resulting polyolefin resin laminated sheet is excessively heavy (thick). ), And the handleability may be poor.

The fiber fabric which can be used as the base fabric of the abrasion-resistant polyolefin resin laminated sheet of the present invention may be either a woven fabric or a knitted fabric. However, a polyolefin-based resin laminate sheet from which a plain woven fabric can be obtained has an excellent balance of physical properties in the warp and weft directions. The warp and weft yarns of the fiber cloth may be composed of any of synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of these. Considering, polypropylene fiber, polyethylene fiber, vinylon fiber, polyester fiber, aromatic polyester fiber, nylon fiber,
Synthetic fiber yarns such as aromatic polyamide fibers, acrylic fibers, and polyurethane fibers can be preferably used. In addition, as the inorganic fiber, glass fiber, silica fiber, alumina fiber,
Multifilament yarns such as carbon fibers may be used.

These fiber yarns are multifilament yarns, short fiber spun yarns, monofilament yarns,
Although any shape such as a split yarn or a tape yarn can be used, a multifilament yarn is most preferably used as a fiber yarn used for a flexible container. The fiber woven fabric used for the base fabric of the abrasion-resistant polyolefin resin laminated sheet of the present invention may be a plain woven fabric made of a multifilament fiber yarn composed of polyester fiber, nylon fiber, polypropylene fiber, vinylon fiber, and a mixed fiber thereof. Preferably, it is a cloth.

As a method of spinning a synthetic fiber multifilament yarn, a thermoplastic resin such as polyester, polypropylene or nylon is heated to a temperature higher than a melting temperature (melting point) to form a viscous melt having fluidity. This is passed through a spinneret having a large number of pores having a specific diameter (about 0.2 to 0.6 mmφ) and extruded into an inert cooling medium such as air, nitrogen, or water, and rapidly cooled and solidified. A method for producing a long fiber spun yarn by using a conventionally known melting prevention method and equipment is used. The unstretched long fiber spun yarn is stretched 3.0 to 5.0 times by heating at 80 to 100 ° C. or by cold stretching at about normal temperature to arrange and crystallize the microstructure of the fiber into fiber. It can have strength. This drawing step may be incorporated in the spinning step, and it is preferable that the multifilament drawing step and the twisting step are performed simultaneously. Further, two-stage heat treatment may be performed if necessary. These anti-melting speeds are not particularly limited, since the applied spinning speed varies depending on the type and equipment of the thermoplastic resin used, but there is no particular limitation. / Min, and more preferably those spun at a speed of 2000 to 6000 m / min.

As the multifilament yarn used for the fiber fabric of the abrasion-resistant polyolefin resin laminated sheet of the present invention, 139 dtex (125 denier) to 2222
dtex (2000 denier), especially 278 dtex (2
Multifilament yarns of 50 denier to 1111 dtex (1000 denier) can be used. When the multifilament yarn is less than 139 dtex, the tear strength of the obtained sheet may be insufficient, and when it exceeds 2222 dtex, the breaking strength and tear strength are improved, but the diameter of the yarn increases, At the same time as the sheet becomes thicker, the irregularities at the weave intersections of the fiber cloth become larger and the smoothness may become insufficient. The fiber fabric used for the abrasion-resistant polyolefin-based resin laminated sheet of the present invention is preferably an open plain weave (a plain weave fabric having voids formed between yarns). Although the number of warp yarns and weft yarns of the fiber cloth is not particularly limited, it is 139 dtex to 2222 dtex (125 to 2000 dtex).
Denier) multi-filament yarn, warp and weft 2
A woven fabric obtained by driving 8 to 38 yarns per 1 inch (5.4 mm), for example, a multifilament yarn of 555 dtex (500 denier) is obtained by driving 14 to 24 yarns per 2 inch (5.4 mm). Plain woven cloth, 11
In the case of a multifilament yarn of 11 dtex (1000 denier), a plain woven fabric obtained by driving about 12 to 22 yarns per 25.4 mm (1 inch) can be exemplified.

Further, the porosity (opening) between yarns of these fiber cloths is preferably 5 to 30%, more preferably 8 to 24%. If the porosity is less than 5%, the yarn density is too high, and the flexibility of the obtained sheet may be insufficient. And (B), or between the film layers (A) and (C), and the dynamic durability may be insufficient. If the porosity exceeds 30%, the flexibility and the bridge fusion property between the film layers are improved, but the density of the fiber yarns in each direction of the process becomes too small, so that the dimensional stability of the obtained laminated sheet is reduced. May be insufficient, and the tear strength of the laminated sheet may be insufficient, which may result in lack of practicality. The porosity can be obtained by calculating the percentage of the area occupied by the fiber yarn in the unit surface area of the fiber cloth, and subtracting this from 100. The porosity is 10 cm in longitude and 1 in weft.
It is preferable to calculate the area of 0 cm as the surface unit area.

The fiber fabric used for the abrasion-resistant polyolefin resin laminated sheet of the present invention is preferably pretreated with a silicon compound-containing treating agent. The silicon compound-containing treating agent is selected from synthetic amorphous silica, colloidal silica, a treating agent containing at least one selected from silane coupling agents, and synthetic amorphous silica, colloidal silica, and silane coupling agents. A treating agent containing a composition of at least one of the above and a thermoplastic resin. Among these silicon compounds, synthetic amorphous silica includes water adsorbed on the surface of silica particles generated by a dry method by heating or baking at a high temperature of 1000 ° C. or higher, anhydrous silica having a low hydroxyl group content, sodium silicate and mineral oxide. Silica obtained from an acid, silica obtained by an airgel method of drying an organosol in which water in the silica gel is replaced with an organic solvent such as alcohol, and a wet method of reacting sodium silicate with a mineral acid and salts in an aqueous solution Can be used. These silicas preferably have an average particle size of about 1 to 20 μm. SiO ₂ content concentration 10 pretreatment of the fiber fabric obtained by uniformly dispersing the synthetic amorphous silica in water
Dipping the fiber fabric in a 30% by weight aqueous silica dispersion bath,
It can be applied by pulling it out of the bath and passing it through a nip roll to remove excess silica dispersion and drying the water. The adhesion rate of the silicon compound to the fiber cloth is not particularly limited, but is preferably 3 to 10% by weight. At this time, it is preferable to use the synthetic amorphous silica and the silane coupling agent in combination.

The colloidal silica is obtained by cation exchange of a sodium silicate solution,
An aqueous dispersion medium colloidal silica sol (SiO ₂ ) having an average particle diameter of 10 to 50 nm or a BET average particle diameter 10 to 50 nm colloidal silica sol (SiO ₂ ) using an organic solvent as a dispersion medium can be used. The pretreatment of the fiber fabric is as follows.
Immersing the fiber fabric in a colloidal silica bath having a SiO ₂ content of 5 to 30% by weight, pulling the fiber fabric out of the bath and passing it through a nip roll, removing excess colloidal silica, and drying water or an organic solvent Can be applied. The adhesion rate of silica to the fiber cloth is not particularly limited, but is preferably 3 to 10% by weight. At this time, it is preferable to use colloidal silica and a silane coupling agent in combination.

The silane coupling agent has the general formula:
A compound represented by XR-Si (Y) ₃ and having two or more different reactive groups in a molecule, for example, X = amino group, vinyl group, epoxy group, chloro group, or mercapto group; Those having R = alkyl chain, Y = methoxy group, ethoxy group and the like are used. Hydrolysates of these silane coupling agents, co-hydrolysis compounds with alkoxysilane compounds, and the like can also be used. Specifically, silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane,
β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ-
Methacryloxypropyltriethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane , Γ-mercaptopropyltrimethoxysilane, etc., and it is particularly preferable to use an epoxy silane coupling agent.

The silane coupling agent is preferably used at a concentration of 1 to 5% by weight, and is preferably adjusted to pH 3 to 5 using an acid such as formic acid or acetic acid. The pretreatment of the fiber fabric is performed by immersing the fiber fabric in a silane coupling agent aqueous solution bath, pulling the fiber fabric out of the bath, passing through the nipple, removing excess silane coupling agent aqueous solution, and drying the water. Can be. At this time, it is preferable to use synthetic amorphous silica or colloidal silica in combination, and the adhesion rate of the silane coupling agent to the fiber cloth is not particularly limited, but is preferably 3 to 10% by weight.

The thermoplastic resin to be used together with the silicon compound in the preparation of the above-mentioned fiber fabric for the base fabric was prepared in the form of an aqueous dispersion such as an emulsion or dispersion of the thermoplastic resin, or solubilized in an organic solvent. Forms include, for example, ionomer resins, acrylic resins, vinyl acetate resins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymer resins, polyurethane resins, polystyrene resins, saturated polyester resins, polyamide resins and These modified resins can be used. In particular, it is preferably selected from glycidyl methacrylate, dimethylaminoethyl methacrylate, itaconic anhydride, maleic anhydride, an ethylene copolymer resin modified with N-methylmaleimide, an acrylic copolymer resin, and the like. If necessary, phenolic resin, melamine resin, urea resin, unsaturated polyester resin,
A thermosetting resin such as an epoxy resin, a thermosetting polyurethane resin, or an allyl phthalate resin can be blended and used.

The pretreatment of the fiber cloth is carried out by immersing the fiber cloth in an aqueous treatment liquid bath prepared by mixing the silicon compound in these thermoplastic resin emulsions or dispersions, pulling the fiber cloth out of the bath, and simultaneously nip-rolling. To remove excess silicon compound coating composition and to dry the water. In the case of a solvent-based thermoplastic resin, it can be used for the preparation by the same method. The weight ratio of the solid content of the thermoplastic resin to the solid content of the silicon compound is not particularly limited.
It is preferably about 0.

The fiber cloth pretreated with these silicon compound-containing treating agents contains the synthetic amorphous silica in 3 to
It is preferable to laminate a front or back film layer containing 25% by weight, and in the present invention, furthermore, the above-mentioned thermoplastic resin: silicon compound weight ratio = 10 to 50:90 to 50: It is preferable that a front and / or back film layer containing a ring agent and containing 3 to 25% by weight of the synthetic amorphous silica is laminated.

The laminated sheet (1) or (2) of the abrasion-resistant polyolefin resin of the present invention has a surface film layer (A) and a back film layer (B) or (C) laminated on both sides of the above-mentioned fiber woven fabric. ing. As a lamination method, an adhesive layer may be provided between the film and the fiber cloth, or may be laminated and fused without an adhesive. The laminating method used for the abrasion-resistant polyolefin-based resin laminated sheet of the present invention is a calendar topping method in which the front and back films (A) and (B) or (C) are simultaneously formed and thermally laminated on each side of the fiber cloth. Alternatively, a T-die extrusion laminating method may be used, or the films (A) and (B) may be formed by a calendar method, a T-die extrusion method, an inflation method, or the like.
Alternatively, a method of laminating the two films (A) and (B) or (C) at a time by using a laminator and laminating them to a fiber cloth after performing (C) a single molding process. . In the production of the abrasion-resistant polyolefin-based resin laminated sheet of the present invention, a production method by thermocompression bonding of the film (A) and (B) or (C) formed by a calender method and a fiber cloth is efficient and effective. Economical and preferred. At this time, the two films (A) and (B) on the front and back, or (A) and (C) are hot-melt bridged through the void space of the fiber cloth, so that a special adhesive is used. Good adhesion and durability can be obtained without the need for coating and extra steps.

For joining the abrasion-resistant polyolefin resin laminated sheet of the present invention, a fusion method using a high-frequency welder can be easily used. As the high-frequency welder joining method, specifically, two or more polyolefin-based resin laminated sheets of the present invention, or a polyolefin-based resin laminated sheet of the present invention, and another thermoplastic resin molded product that can be heat-sealed. A part of each is overlapped, placed between two electrodes (one electrode is a weld bar), and a high frequency (1 to 200 MHz) is applied to the electrodes while applying pressure by a weld bar to a joint. A method of applying an oscillating potential difference, applying pressure by a weld bar, and bonding and sealing the overlapped portions by heat fusion by the molecular frictional heat of the thermoplastic resin generated in the applied portions. In this case, the dielectric loss factor of the thermoplastic resin, that is, the product (ε.tanδ) of the dielectric constant (ε) and the dielectric loss tangent (tanδ) is related to the magnitude of the internal molecular frictional heat oscillating at a high frequency.
The dielectric loss tangent is the relationship of the part where high-frequency electromagnetic radiation energy absorbed by the thermoplastic resin is converted to heat,
The dielectric loss factor is preferably at least 0.01 or more. As the high-frequency welder used for the laminated sheet (1) or (2) of the present invention, commercially available models, for example, YC-7000FT, YF-Yamamoto Binita Co., Ltd.
7000, KM-5000 of Seidensha Electronics Co., Ltd.
TAW, KA-7000TE, and the like, such as LW-4000W and LW-4060S of Quinlite Electronic Seiko Co., Ltd. can be used.

As another joining method of the abrasion-resistant polyolefin resin laminated sheet of the present invention, the amplitude of ultrasonic energy (16 to 30 KHz) generated from an ultrasonic vibrator is amplified through the tip of a tool horn and fused. An ultrasonic welder fusing method is used in which welding is performed instantaneously in about one second by utilizing frictional heat generated at a boundary surface of the thermoplastic resin welded material by unloading the plurality of layers of the thermoplastic resin welded material. Or by electrical control of the heater
Hot air that is set in a stepless manner at 0 to 700 ° C. is blown between the adherends through a nozzle selected according to the fusion specification of the fused body to instantaneously melt the surface of the adherend and immediately adherend Hot-plate fusion method of pressing and bonding, or hot plate fusion method of compressing and sealing the adherend using a mold (trowel) heated with a built-in heater above the melting temperature of the thermoplastic resin Although fusion bonding is possible also by a method, it is preferable from the viewpoint of efficiency to perform sewing by high-frequency welding using a dedicated mold for a complicated flexible container bag.

[0054]

EXAMPLES The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to the scope of these examples. In the following Examples and Comparative Examples, the test methods for evaluating the flexibility, abrasion resistance, high-frequency welder fusing property, heat creep resistance and humidity barrier property of the polyolefin resin laminated sheet are as follows.

(I) Evaluation of Flexibility of Laminated Polyolefin Resin Sheet A test piece sampled 70 mm wide × 30 mm long was rounded to a diameter of 2 mm.
A cylinder having a size of 0 mm × 30 mm was prepared (the paste was fixed with a cyanoacrylate-based instant adhesive). JIS K
6382-1978 compression test, 50% compression (upper crushed at 20 ° C. until cylinder diameter is 10 mm)
Was measured, and it was determined that the smaller the value, the better the flexibility of the test piece. As a tester for evaluating flexibility, a loop stiffness tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used. ：: good flexibility (compressive stress: 150 g or less) △: slightly poor flexibility (151 to 199 g) ×: poor flexibility (200 g or more)

(II) Evaluation of abrasion resistance of polyolefin resin laminated sheet i) Abrasion resistance of the specimen surface was evaluated by abrasion strength test C method (Taber type method) specified in JIS L1096-1990. . A rotary abrasion tester (manufactured by Toyo Seiki Seisaku-Sho, Ltd.) was used as a tester for evaluating the wear strength, and a wear test was performed under the conditions of a wear wheel (H-18), a wear load of 1 kg, and a wear frequency of 1,000 times. The difference in mass (loss of wear) between the sample before and after the test was measured, and it was determined that the smaller the value, the better the wear resistance of the test piece. ii) Under the above conditions, the number of wears until the fiber fabric was exposed on the sheet surface was determined.

(III) Evaluation of high-frequency welder fusing property The ends of two polyolefin-based resin laminated sheet test pieces were linearly overlapped with a width of 4 cm, and a 4 cm × 30 cm weld bar (teeth shape: convex portions at regular intervals) 4cm width linear molding 9/2
5.4 mm, height of convex part 0.5 mm: high frequency welder fusion machine (Yamamoto Nivita Co., Ltd.) equipped with nine linear molds of 4 cm in width and 25.4 mm in depth of concave part, with a concave part depth of 0.5 mm. YF
High-frequency fusion bonding of the polyolefin-based resin laminated sheet was performed by using -7000 type: output 7 KW). In addition, a sample having a width of 3 cm including the fusion joint was sampled, and a shear test (JIS L-1096) was performed on the fusion joint, and the destruction state of the fusion joint was evaluated according to the following criteria. <High frequency fusing property> ：: Fusing is easy. * Welder fusion conditions: fusion time 5 seconds, cooling time 5 seconds anode current 0.8 A, weld bar temperature 40 to 50 ° C. Δ: fusion is possible by making the fusion conditions strong and long. * Welder fusion conditions: fusion time 10 seconds, cooling time 5 seconds anode current 1.0 A, weld bar temperature 40-60 ° C ×: fusion does not occur even if the fusion conditions are set strong and long. * Welder fusion conditions: fusion time: 10 seconds, cooling time: 5 seconds, anode current: 1.3 A, weld bar temperature: 40-60 ° C <destruction state of joint by shearing> ○: main body is destroyed. Δ: The joint is broken. ×: The thread breakage at the joint is broken.

(IV) Evaluation of heat creep resistance In the heat creep resistance test, a test piece having a width of 3 cm and a test piece length of 30 cm, including a lamination width of 4 cm, was taken from the welder-fused sheet prepared as described in (IV) above. This was used as a heat-resistant creep test specimen, and a creep tester (manufactured by Toyo Seiki Seisaku-sho, Ltd .: 100 LDR type 9; 50 ° C. ×
Subjected to a heat resistance creep test of 25 kgf load x 24 hours,
The results were evaluated as follows. ：: After 24 hours, there was no breakage of the joint, and the load of 25 kgf was endured. X: The joint part was sheared and fractured within 24 hours. (VI) a polyolefin-based resin laminate sheets and films of moisture (water vapor) water content J to transmit the barrier properties Evaluation polyolefin-based resin laminate sheet or film 25 cm ²
It was measured by the test method specified in IS Z-0208, and the moisture permeability (g / m ² · 24 hours) was calculated and evaluated. ：: moisture permeability 5 (g / m ² · 24 hours) or less: excellent in moisture barrier properties. ：: Moisture permeability 5.1 to 10 (g / m ² · 24 hours): Good humidity barrier property. ×: Moisture permeability exceeds 10 (g / m ² · 24 hours): Humidity barrier property is insufficient.

Example 1 1) Preparation of Surface Film Layer (A) A linear film obtained by copolymerizing ethylene and hexene-1 in the presence of a Ziegler-Natta (ZN catalyst) catalyst. 60 parts by weight of a low-density ethylene-α-olefin copolymer resin (trade name: Sumikacene Hiα-CW-2004, MFR2.0, density 0.909, manufactured by Sumitomo Chemical Co., Ltd.) and an ethylene-vinyl acetate copolymer resin (1) 40 parts by weight of a resin blend composed of (trademark: Evatate K2010, MFR 3.0, VA content 25% by weight, manufactured by Sumitomo Chemical Co., Ltd.), and a phosphate ester lubricant (trademark: LTP) -2, manufactured by Kawaken Fine Chemical Co., Ltd.)
0 parts by weight, 0.3 parts by weight of a benzotriazole ultraviolet absorber (trade name: Biosorb 510, manufactured by Kyodo Yakuhin Co., Ltd.), and a hindered amine light stabilizer (trade name: Tinuvin 770, Ciba Specialty Chemicals Co., Ltd.) Made)
0.2 parts by weight and 4 parts by weight of a coloring pigment [(organic pigment colored pellets: trademark: HCM1617 blue, cyanine blue (α) content: 20% by weight, Dainichi Seika Kogyo Co., Ltd.]
2 parts by weight + inorganic pigment colored pellets: Trademark: H
CM2060 White, 60% by weight of titanium dioxide (R), 2 parts by weight of Dainichi Seika Kogyo Co., Ltd.], and the compound is melt-kneaded with a Banbury mixer for 3 minutes. The mixture is uniformly kneaded with the set two rolls for 3 minutes, and from this kneaded composition, 0.25 mm
A blue film for the surface film layer (A) having a thickness of 10% by weight of a vinyl acetate component was calendered and rolled.

2) Preparation of Back Film Layer (B) In the presence of a Ziegler-Natta catalyst (ZN catalyst),
Linear low-density polyethylene-α-olefin copolymer resin obtained by copolymerizing ethylene and hexene-1 (trade name: Sumikacene Hiα-CW-2004, MFR2.
0, density 0.909, manufactured by Sumitomo Chemical Co., Ltd.) and 30 parts by weight of ethylene-vinyl acetate copolymer resin (1) (trademark: Evatate K2010, MFR 3.0, VA content: 25% by weight, Sumitomo Chemical) Industrial Co., Ltd.) 40 parts by weight, ethylene-vinyl acetate copolymer resin (2) (trade name: Evaflex EV45LX, MFR2.5: VA content 46% by weight, manufactured by Mitsui DuPont Polychemical Co., Ltd.) 30 3 parts by weight of a synthetic amorphous silica (trade name: Nip Seal E200, water content 6% by weight, average particle diameter 3 μm, manufactured by Nippon Silica Kogyo Co., Ltd.) per 100 parts by weight of the resin blend consisting of 1.0 part by weight of a lubricant (trade name: LTP-2, manufactured by Kawaken Fine Chemical Co., Ltd.) and a benzotriazole ultraviolet absorber (trade name: Biosorb 51)
0, manufactured by Kyodo Yakuhin Co., Ltd.), 0.2 parts by weight of a hindered amine light stabilizer (trade name: Tinuvin 770, manufactured by Ciba Specialty Chemicals Co., Ltd.), and an inorganic pigment colored pellet ( Trade name: HCM2060 White, 60% by weight of titanium dioxide (R), 3 parts by weight (manufactured by Dainichi Seika Kogyo Co., Ltd.), and the compound was melt-kneaded with a Banbury mixer for 3 minutes and then set at 140 ° C. The roll was uniformly kneaded for 3 minutes, and a white film for the back film layer (B) having a thickness of 0.2 mm and containing 23.8% by weight of a vinyl acetate component was calendered from the kneaded composition.

Next, the obtained film for the front film layer (A) and the film for the back film layer (B) were combined with a polyester fiber plain fabric (833.3 dtex (750 denier) polyester multifilament, yarn density: 19 warps. /
2.54 cm x 20 wefts / 2.54 cm, porosity 18%,
Both sides having a mass of 75 g / m ² ) were bonded by thermocompression bonding using a laminator set at 140 ° C. to a thickness of 0.75 m.
m, and a polyolefin resin laminated sheet having a mass of 715 g / m ² . The weight ratio of the film layer (A) :( B) was 5: 4.

Example 2 A polyolefin resin laminated sheet was produced in the same manner as in Example 1. However, the linear low-density ethylene-α-olefin copolymer resin (trade name: Sumikacene Hiα-CW-200) of the surface film layer (A)
4, manufactured by Sumitomo Chemical Co., Ltd.), 60 parts by weight of a linear low-density ethylene-α-polymerized in the presence of a metallocene catalyst.
Olefin copolymer resin (trademark: Kernel KF270,
Nippon Polychem Co., Ltd.)
A 5 mm-thick film for the surface film layer (A) containing 10% by weight of a vinyl acetate component was obtained. In addition, a linear low-density ethylene-α-olefin copolymer resin (trade name: Sumikacene Hiα-CW-2) for the back film layer (B) in Example 1
004, manufactured by Sumitomo Chemical Co., Ltd.) was mixed with 30 parts by weight of a linear low-density ethylene polymerized in the presence of a metallocene catalyst.
α-olefin copolymer resin (trademark: Kernel KF27)
0, manufactured by Nippon Polychem Co., Ltd.)
A film for a back film (B) having a thickness of 0.20 mm and containing 23.8% by weight of a vinyl acetate component was obtained. The modified films (A) and (B) were adhered to the polyester fiber plain fabric (833.3 dtex (750 denier)) described in Example 1 by the same method as in Example 1, and the thickness was changed to 0. A polyolefin resin laminated sheet having a thickness of 75 mm and a mass of 715 g / m ² was obtained. The weight ratio of the film layer (A) :( B) was 5: 4.

Example 3 A laminated sheet of a polyolefin resin was produced in the same manner as in Example 1. However, a linear low-density ethylene-α-olefin copolymer resin for the surface film layer (A) (trade name: Sumikacene Hiα-CW-200)
4, 30 parts by weight of 60 parts by weight of Sumitomo Chemical Co., Ltd.), a linear low-density ethylene-α-olefin copolymer resin (trade name: Kernel KF270, polymerized in the presence of a metallocene catalyst) The surface film was changed to 30 parts by weight (manufactured by Nippon Polychem Co., Ltd.) and had a thickness of 0.25 mm and contained 10% by weight of a vinyl acetate component. In addition, a linear low-density ethylene-α-olefin copolymer resin (trade name: Sumikacene Hiα-CW-200) for the back layer film layer (B)
4, 10 parts by weight of 30 parts by weight of Sumitomo Chemical Co., Ltd.) is a linear low-density ethylene-α-olefin copolymer resin (trade name: Kernel KF270, polymerized in the presence of a metallocene catalyst). Nippon Polychem Co., Ltd.) was changed to 10 parts by weight, and 0.28 mm thick vinyl acetate component was changed to 23.8 parts.
A film was obtained with a weight percent content. The films (A) and (B) for which the blending was changed were combined with the polyester fiber plain fabric (833.3 dtex (750) described in Example 1.
(Denier)) to obtain a polyolefin resin laminated sheet having a thickness of 0.75 mm and a mass of 715 g / m ² . The weight ratio of the film layer (A) :( B) was 5: 4.

Example 4 1) Preparation of Surface Film Layer (A) Linear low-density ethylene-α-olefin copolymer resin (trademark) polymerized in the presence of a Ziegler-Natta catalyst (ZN catalyst) : Sumikasen Hiα-CW-2004, MFR
2.0, density 0.909, manufactured by Sumitomo Chemical Co., Ltd.) 30
30 parts by weight of a linear low-density ethylene-α-olefin copolymer resin (trade name: Kernel KF270, MFR2.0, density 0.907, manufactured by Nippon Polychem Co., Ltd.) polymerized in the presence of a metallocene catalyst And ethylene-vinyl acetate copolymer resin (1) (trademark: Evatate K201)
0, MFR 3.0, VA content 25% by weight, 20 parts by weight of Sumitomo Chemical Co., Ltd.) and an ethylene-methyl methacrylate copolymer resin (trade name: Aclift WH-206)
MMA content 20% by weight, MFR 2.0, density 0.9
4, 100 parts by weight of a polyolefin resin blend consisting of 10% by weight of Sumitomo Chemical Industries, Ltd., 5 parts by weight of synthetic amorphous silica (trade name: Nip Seal E200, manufactured by Nippon Silica Co., Ltd.) and phosphoric acid Ester lubricant (trademark:
1.0 parts by weight of LTP-2, manufactured by Kawaken Fine Chemical Co., Ltd., 0.3 parts by weight of a benzotriazole-based ultraviolet absorber (trade name: Biosorb 510, manufactured by Kyodo Yakuhin Co., Ltd.), and a hindered amine-based light stabilizer (Trademark: Tinuvin 77
0, Ciba Specialty Chemicals Co., Ltd.)
2 parts by weight and 4 parts by weight of a coloring pigment [(organic pigment colored pellets: trademark: HCM1617 blue, manufactured by Dainichi Seika Industry Co., Ltd.) 2 parts by weight + inorganic pigment colored pellets: trademark: HCM2060 white, Dainichi Seika Industrial Co., Ltd.)
2 parts by weight], melt-kneaded with a Banbury mixer for 3 minutes, and then set at 140 ° C.
Knead uniformly with this roll for 3 minutes, and from this kneaded composition,
A blue film for the surface film layer (A) having a thickness of 0.27 mm and containing 7% by weight of the total amount of the vinyl acetate component and the methacrylate component was calendered and rolled.

2) Preparation of Back Film Layer (B) Linear low-density ethylene-α-olefin copolymer resin (trade name: Sumikacene Hiα-CW) polymerized in the presence of a Ziegler-Natta catalyst (ZN catalyst) -2004, MFR
2.0, density 0.909, manufactured by Sumitomo Chemical Co., Ltd.) 20
10 parts by weight of a linear low-density ethylene-α-olefin copolymer resin (trade name: Kernel KF270, MFR2.0, density 0.907, manufactured by Nippon Polychem Co., Ltd.) polymerized in the presence of a metallocene catalyst And ethylene-vinyl acetate copolymer resin (1) (trademark: Evatate K201)
0, MFR 3.0, VA content 25% by weight, 40 parts by weight (manufactured by Sumitomo Chemical Co., Ltd.) and ethylene-vinyl acetate copolymer resin (2) (trade name: Evaflex EV45LX,
MFR2.5: VA content 46% by weight, Mitsui DuPont
20 parts by weight of Polychemical Co., Ltd.) and an ethylene-methyl methacrylate copolymer resin (trade name: ACLIFT WH)
-206, 100% by weight of a polyolefin resin blend consisting of 20% by weight of MMA, MFR 2.0, density of 0.94, 10% by weight of Sumitomo Chemical Co., Ltd. (Trademark: Nip Seal E2
00, manufactured by Nippon Silica Industry Co., Ltd.), 1.0 part by weight of a phosphate ester lubricant (trade name: LTP-2, manufactured by Kawaken Fine Chemical Co., Ltd.), and a benzotriazole-based ultraviolet absorber (trade name: Biosorb 510, Kyodo Yakuhin Co., Ltd.
0.3 parts by weight), 0.2 parts by weight of a hindered amine light stabilizer (trade name: Tinuvin 770, manufactured by Ciba Specialty Chemicals Co., Ltd.), and inorganic pigment colored pellets (trade names: HCM2060 White, Dainichisei) 3 parts by weight), and the resulting compound was melted and kneaded with a Banbury mixer for 3 minutes.
The mixture was uniformly kneaded with a hot roll (two rolls) set at 0 ° C. for 3 minutes, and a 0.18 mm-thick white back film layer containing 21.0% by weight of a vinyl acetate component was obtained from the kneaded composition. The film for B) was calendered and rolled.

Next, the film for the front film layer (A) and the film for the back film layer (B) were combined with a polyester fiber plain fabric (833.3 dt) which had been subjected to the following preparation (1).
ex (750 denier) polyester multifilament, yarn density: 19 warps / 2.54 cm x 20 wefts /
2.54 cm, porosity 18%, mass 75 g / m ² ), bonded to both surfaces by thermocompression bonding using a laminator set at 140 ° C., 0.75 mm thick, 723 g / m ² thick polyolefin resin laminated sheet I got Film layer (A):
(B) The weight ratio was 3: 2.

<Preparation agent composition (1) of polyester fiber plain woven fabric> Trade mark: Nip Seal E200, manufactured by Nippon Silica Industry Co., Ltd., synthetic amorphous silica, water content 6% by weight, average particle diameter 3 μm 10 parts by weight : Aquatex E-1800, manufactured by Chuo Rika Kogyo Co., Ltd., ethylene-vinyl acetate copolymer resin emulsion (solid content 40% by weight) 50 parts by weight Diluent: distilled water 150 parts by weight The above-mentioned pretreatment agent (1) The polyester fiber plain fabric is immersed in the bath, and the plain fabric is pulled up and simultaneously squeezed with a nip roll (wet adhesion mass: 36 g / m ² ).
This was dried in a hot air oven at 100 ° C. for 2 minutes. The mass of the polyester fiber plain fabric obtained by the pretreatment was 83.3 g / m ² . The weight ratio of the synthetic amorphous silica to the thermoplastic resin was 1: 2.

Example 5 A laminated sheet of a polyolefin resin was produced in the same manner as in Example 4. However, the preparation of the polyester fiber plain fabric was changed to the following preparation (2). A polyolefin resin laminated sheet having a thickness of 0.75 mm and a mass of 721 g / m ² was obtained. Film layer (A):
The weight ratio of (B) was 3: 2. <Preparation agent composition (2) for polyester fiber plain fabric> Trademark: Snowtex C, manufactured by Nippon Silica Industry Co., Ltd., silicic anhydride content 20% by weight, average particle diameter 10-20 nm, 100 parts by weight Trademark: KBM303, Shin-Etsu Chemical Co., Ltd., epoxy silane coupling agent (100% by weight of active ingredient) 3 parts by weight Diluent: distilled water 50 parts by weight Dipping, pulling up the plain fabric and simultaneously squeezing with a nip roll (wet attached mass 38 g / m ² );
This was dried in a hot air oven at 100 ° C. for 2 minutes. The mass of the polyester fiber plain fabric obtained by the preparation is 8
0.7 g / m ² . The weight ratio of silicic anhydride: silane coupling agent was 20: 3.

Example 6 A polyolefin resin laminated sheet was produced in the same manner as in Example 4. However, the preparation of the polyester fiber plain fabric was changed to the following preparation (3). A polyolefin resin laminated sheet having a thickness of 0.75 mm and a mass of 718 g / m ² was obtained. Film layer (A):
The weight ratio of (B) was 3: 2. <Preparation agent composition (3) of polyester fiber plain fabric> Trade mark: Nip Seal E200, manufactured by Nippon Silica Industry Co., Ltd., synthetic amorphous silica, water content 6% by weight, average particle diameter 3 μm 10 parts by weight Trade mark: KBM303, Shin-Etsu Chemical Co., Ltd., epoxy silane coupling agent (active ingredient 100% by weight) 3 parts by weight Diluent: distilled water 150 parts by weight A polyester fiber plain fabric is immersed, and the plain fabric is pulled up and simultaneously squeezed with a nip roll (wet adhesion mass 35 g / m2).
² ) Then, it was dried in a hot air oven at 100 ° C. for 2 minutes. The mass of the polyester fiber plain woven fabric obtained by the pretreatment was 77.8 g / m ² . The weight ratio of the synthetic amorphous silica to the silane coupling agent was 10: 3.

Example 7 A polyolefin resin laminated sheet was produced in the same manner as in Example 4. However, the preparation of the polyester fiber plain fabric was changed to the following preparation (4). A polyolefin resin laminated sheet having a thickness of 0.75 mm and a weight of 719 g / m ² was obtained. Film layer (A):
The weight ratio of (B) was 3: 2. <Preparation agent composition (4) for polyester fiber plain fabric> Trade mark: Nip Seal E200, manufactured by Nippon Silica Co., Ltd., synthetic amorphous silica, water content 6% by weight, average particle diameter 3 μm 10 parts by weight Trade mark: KBM303, Shin-Etsu Chemical Co., Ltd., epoxy silane coupling agent (active ingredient 100% by weight) 3 parts by weight Trademark: Aquatex E-1800, manufactured by Chuo Rika Kogyo Co., Ltd., ethylene-vinyl acetate copolymer resin emulsion (Solid content 40% by weight) 50 parts by weight Diluent: distilled water 150 parts by weight The polyester fiber plain fabric described in Example 4 is immersed in a bath of the above-mentioned pretreatment agent (4), and the plain fabric is pulled up. Simultaneously squeeze with a nip roll (wet adhesion mass 38g / m
² ) Then, it was dried in a hot air oven at 100 ° C. for 2 minutes. The mass of the polyester fiber plain woven fabric obtained by the preparation was 79.2 g / m ² . Synthetic amorphous silica: silane coupling agent: thermoplastic resin weight ratio is 1
0: 3: 20.

Example 8 A polyolefin-based resin laminated sheet was produced in the same manner as in Example 4. However, instead of the polyester fiber plain fabric, a polypropylene fiber plain fabric (755.6 dtex) 680 denier) polypropylene multifilament, yarn density: 24 warps / 2.54 cm
× 25 wefts / 2.54 cm porosity 13%, mass 150 g
/ M ²⁾ using, also change the surface film layer thickness of the (A) film from 0.27mm to 0.3 mm, the thickness of the film for the back film layer (B) from 0.18 mm 0.24
mm. A polyolefin resin laminated sheet having a thickness of 0.89 mm and a mass of 845 g / m ² was obtained. The weight ratio of the film layer (A) :( B) was 5: 4.

Table 1 shows the composition of the front film layer (A) in Examples 1 to 8, Table 2 shows the composition of the rear film layer (B), and Table 3 shows the properties of the obtained laminated sheet.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[Effects of Embodiments 1 to 8]
The polyolefin-based resin laminated sheet of Example 8 is excellent in flexibility and humidity barrier properties, and has a soft texture equivalent to that of an untreated sheet, especially in a sheet prepared by treating a fiber fabric with a silicon compound. In addition, the tear strength of the fiber woven fabric was maintained irrespective of the presence or absence of the pretreatment of the fiber woven fabric. In the polyolefin-based resin blend of the surface film layer (A) of Examples 1 to 8, the total weight of the vinyl acetate component and the (meth) acrylic acid (ester) component is set to 4 to 16% by weight. As shown in Examples 1 to 3 and Example 8, the film thickness ratio (A) :( B) was set to 5: 4, or as shown in Examples 4 to 7, By setting the film thickness ratio (A) :( B) to 3: 2, the wear durability of the polyolefin-based resin laminated sheet obtained could be dramatically improved. Further, in the high frequency weldability (fusibility) test of these laminated sheets, fusion was easily performed under the conditions of an anode current value of 0.8 A, a fusion time of 5 seconds, a cooling time of 5 seconds, and a weld bar temperature of 40 to 50 ° C. Joining was possible. Although the state of shear fracture of these joints did not reach the main body failure in Examples 1 to 3 and Example 8, the joint fracture at a strength of 85% or more of the main body fracture strength. There was no problem. In particular, it was confirmed that in the laminated sheet obtained by subjecting the fiber fabrics obtained in Examples 4 to 7 to a pretreatment with a silicon compound, a strong joint was formed such that the main body was broken. When the heat-resistant creep properties of these laminated sheets were evaluated, all of the polyolefin-based resin laminated sheets of Examples 1 to 8 were 50 ° C. × 25 kgf load × 24.
Time passed the heat creep test. Particularly, in the laminated sheets of Examples 4 to 7, 55 ° C. × 25 kgf load × 24.
It also passed the time heat creep test.

Example 9 A polyolefin resin laminated sheet was produced in the same manner as in Example 1. However, the back film layer (B) was changed to the following front film layer (C). 1) Preparation of Back Film Layer (C) 100 parts by weight of ethylene-vinyl acetate copolymer resin (1) (trademark: Evatate K2010, manufactured by Sumitomo Chemical Co., Ltd.) and 100 parts by weight of synthetic amorphous silica (trademark: Nip Seal) E2
00, manufactured by Nippon Silica Industry Co., Ltd.), 1.0 part by weight of a phosphate ester lubricant (trademark LTP-2, manufactured by Kawaken Affine Chemical Co., Ltd.), and a benzotriazole infrared absorber (trademark) : Biosorb 510, Kyodo Yakuhin Co., Ltd.
0.3 parts by weight), a hindered amine light stabilizer (trade name: Tinuvin 770, 0.2 parts by weight, manufactured by Ciba Specialty Chemicals Co., Ltd.), and an inorganic pigment colored pellet (trade name: HCM2060 White, Dainichi Seika) And 3 parts by weight (manufactured by Kogyo Co., Ltd.).
The contained white film for the back film layer (C) was calendered and rolled.

Example 10 A polyolefin resin laminated sheet was produced in the same manner as in Example 2. However, the back film layer (B) was changed to the same back film layer (C) as in Example 9.

Example 11 A polyolefin resin laminated sheet was produced in the same manner as in Example 3. However, the back film layer (B) was changed to the same back film layer (C) as in Example 9.

Example 12 A polyolefin resin laminated sheet was produced in the same manner as in Example 9. However, the ethylene-vinyl acetate copolymer resin (1) (trade name: Evatate K201) contained in the film for the back film layer (C)
0, manufactured by Sumitomo Chemical Co., Ltd.)
The parts by weight were replaced with 40 parts by weight of an ethylene-methyl methacrylate copolymer resin (trade name: ACLIFT WH-206, manufactured by Sumitomo Chemical Co., Ltd.). The ratio of the total content of the vinyl acetate component and the methacrylate component in the film for the back film layer (C) is 23% by weight.
Met.

Example 13 A laminated sheet of a polyolefin-based resin was produced in the same manner as in Example 5. However, the film for the back film layer (B) was changed to the same film for the back film layer (C) as in Example 12.

Example 14 In the same manner as in Example 6, a polyolefin resin laminated sheet was produced. However, the film for the back film layer (B) was changed to the same film for the back film layer (C) as in Example 12.

Example 15 In the same manner as in Example 7, a polyolefin resin laminated sheet was produced. However, the film for the back film layer (B) was changed to the same film for the back film layer (C) as in Example 12.

Example 16 A laminated sheet of a polyolefin-based resin was produced in the same manner as in Example 8. However, the film for the back film layer (B) was changed to the same film for the back film layer (C) as in Example 12.

Table 4 shows the compositions of the films for the back film layer (C) in Examples 9 to 16, and Table 5 shows the properties of the obtained laminated sheets.

[0086]

[Table 4]

[0087]

[Table 5]

[Effects of Embodiments 9 to 16] Embodiment 9
All of the polyolefin resin laminate sheets of Examples 16 to 16 have excellent flexibility and humidity barrier properties. In addition, the tear strength of the laminated sheet was maintained irrespective of the presence or absence of the fiber fabric pretreatment. In the films for the surface film layer (A) in Examples 9 to 16, the total weight of the vinyl acetate component and the (meth) acrylic acid (ester) component was set to 4 to 16% by weight. As shown in 9 to Example 11 and Example 16, the film thickness ratio (A) :( C) was set to 5: 4, or as shown in Examples 12 to 15, the film thickness By setting the ratio (A) :( C) to 3: 2, the wear durability of the resulting polyolefin-based resin laminated sheet could be dramatically improved. Further, in the high frequency weldability (fusibility) test of these laminated sheets, fusion was easily performed under the conditions of an anode current value of 0.8 A, a fusion time of 5 seconds, a cooling time of 5 seconds, and a weld bar temperature of 40 to 50 ° C. Joining was possible. The states of shear fracture of these joints are described in Examples 9 to 11 and Example 16.
Did not lead to the destruction of the main body, but the joint was broken at a strength of 85% or more of the destruction strength of the main body, and there was no problem in practicality. In particular, Examples 12 to 15
It was confirmed that in the laminated sheet obtained by subjecting the fiber woven fabric obtained in the above to a pretreatment with a silicon compound, a strong joint was formed such that the main body was broken. When the heat-resistant creep properties of these laminated sheets were evaluated, Examples 9 to
Each of the polyolefin-based resin laminated sheets of Example 16 passed the heat-resistant creep test at 50 ° C. × 25 kgf load × 24 hours. In particular, the laminated sheets of Examples 12 to 15 passed the heat-resistant creep test at 55 ° C. × 25 kgf load × 24 hours.

Comparative Example 1 A polyolefin-based resin laminated sheet was produced in the same manner as in Example 1. However, 100 parts by weight of the blend resin of the surface film layer (A) was entirely used as the ethylene-vinyl acetate copolymer resin (2) (trade name: Evaflex EV45LX, MFR2.5, VA content 46).
% By weight, manufactured by Mitsui Dupont Polychemical Co., Ltd.) 100
Parts by weight, and the film thickness ratio between the film layer (A) and the back film layer (B) was changed to 2: 3. A polyolefin resin laminated sheet having a thickness of 0.75 mm and a mass of 715 g / m ² was obtained. (Thickness of film (A): 0.
18mm, thickness of film (B): 0.27mm)

Comparative Example 2 A polyolefin resin laminated sheet was produced in the same manner as in Example 2. However, 100 parts by weight of the blend resin of the surface film layer (A) was replaced with ethylene-vinyl acetate copolymer resin (1) (trademark: Evatate K)
2010, manufactured by Sumitomo Chemical Co., Ltd.) and 40 parts by weight of ethylene-vinyl acetate copolymer resin (2) (trade name: Evaflex EV45LX, manufactured by Sumitomo Chemical Co., Ltd.) Further, the film thickness ratio between the front film layer (A) and the back film layer (B) was changed to 2: 3. A polyolefin resin laminated sheet having a thickness of 0.75 mm and a mass of 715 g / m ² was obtained. (Thickness of film (A): 0.18 mm, thickness of film (B): 0.27 m
m)

Comparative Example 3 A polyolefin resin laminated sheet was produced in the same manner as in Example 3. However, 100 parts by weight of the blend resin of the surface film layer (A) was replaced with ethylene-vinyl acetate copolymer resin (1) (trademark: Evatate K)
2010, 60 parts by weight of Sumitomo Chemical Co., Ltd.) and 40 parts by weight of ethylene-methyl methacrylate copolymer resin (trade name: Acryft WH-206, manufactured by Sumitomo Chemical Co., Ltd.) Further, the film thickness ratio of the film layer (A) to the back film layer (B) was changed to 2: 3. A polyolefin resin laminated sheet having a thickness of 0.75 mm and a mass of 715 g / m ² was obtained. (Thickness of film (A): 0.18 mm, thickness of film (B): 0.27 mm)

Comparative Example 4 A polyolefin resin laminated sheet was prepared in the same manner as in Example 4. However, the composition of the blended resin of the front film layer (A) is the same as that of the blend resin of the back film layer (B) of Example 4, and the film thickness of the film layer (A) and the back film (B) is further Was changed to 2: 3. Further, the pretreatment (1) of the polyester fiber plain woven fabric was changed to the following urethane resin pretreatment. A polyolefin resin laminated sheet having a thickness of 0.75 mm and a mass of 723 g / m ² was obtained. (Thickness of film (A): 0.18 mm, thickness of film (B): 0.27 m
m) <Urethane-based resin pretreatment> Trademark: 100 parts by weight of polycarbonate type polyurethane emulsion (solid content: 40% by weight), manufactured by Stall Japan KK, manufactured by Stahl Japan KK Trademark: Chemitite DZ-22: Nippon Shokubai ( Aziridine compound (solid content 25% by weight) 10 parts by weight Diluent: distilled water 50 parts by weight

Comparative Example 5 A polyolefin-based resin laminated sheet was produced in the same manner as in Example 5. However, the blend resin composition of the surface film layer (A) was all linear low-density polyethylene resin (trademark: Sumikasen Hiα-CW-20)
04, manufactured by Sumitomo Chemical Co., Ltd.)
At the same time, the blend resin composition of the backside film layer (B) is also all linear low-density polyethylene resin (trademark: Sumikasen Hi)
α-CW-2004, manufactured by Sumitomo Chemical Co., Ltd.). Furthermore, the ratio of the film thickness of the film layer (A) to the back film layer (B) was changed to 2: 3.
Further, the pretreatment (2) of the polyester fiber plain fabric was changed to the following urethane resin pretreatment. A polyolefin resin laminate sheet having a thickness of 0.75 mm and a mass of 725 g / m ² was obtained. (Thickness of film (A): 0.18 mm, thickness of film (B): 0.27 mm) <Acrylic resin pretreatment> Trademark: Acronal YJ-1510D, manufactured by Mitsubishi Yuka Birdish Co., Ltd., styrene -Acrylic acid alkyl ester copolymer resin emulsion (solid content 50% by weight) 100 parts by weight Diluent: distilled water 50 parts by weight

Comparative Example 6 A polyolefin resin laminated sheet was produced in the same manner as in Example 6. However, the blended resin composition of the surface film layer (A) was adjusted to a linear low-density polyethylene resin (trademark: Kernel KF270, MFR2.0, density 0.
907, manufactured by Nippon Polychem Co., Ltd.), and at the same time, the blended resin composition of the back film layer (B) was also changed to a linear low-density polyethylene resin (trademark: Kernel: all polymerized in the presence of a metallocene catalyst) KF270, M
FR2.0, density 0.907, manufactured by Nippon Polychem Co., Ltd.)
Changed to 100 parts by weight. Furthermore, surface film layer (A)
The ratio of the film thickness of the back film layer (B) to that of the back film layer (B) is 2: 3.
Changed to Further, the preparation (3) of the polyester fiber plain fabric was changed to the following preparation of a polyester resin. A polyolefin resin laminated sheet having a thickness of 0.75 mm and a mass of 724 g / m ² was obtained. (Thickness of film (A): 0.
18 mm, thickness of the film (B): 0.27 mm) <Preparation of polyester resin> Trademark: Vylonal MD1250, manufactured by Toyobo Co., Ltd., 100 weight parts of polyester resin emulsion (solid content 30% by weight) Trademark: Chemitite DZ-22, manufactured by Nippon Shokubai Co., Ltd., aziridine compound (solid content 25% by weight) 10 parts by weight Diluent: distilled water 50 parts by weight

Comparative Example 7 A laminated sheet of a polyolefin-based resin was produced in the same manner as in Example 7. However, the blend resin composition of the surface film layer (A) was all linear low-density polyethylene resin (trademark: Sumikasen Hiα-CW-20)
04, manufactured by Sumitomo Chemical Co., Ltd.)
Further, the ratio of the film thickness of the front film layer (A) to the back film layer (B) was changed to 3: 1. Also, the preparation (4) of the polyester fiber plain fabric was omitted. Thickness 0.7
A polyolefin resin laminated sheet having a thickness of 8 mm and a mass of 725 g / m ² was obtained. (Thickness of film (A): 0.36 mm,
(Thickness of film (B): 0.12 mm)

Comparative Example 8 A polyolefin resin laminated sheet was produced in the same manner as in Example 8. However, a linear low-density polyethylene resin (trade name: Kernel KF270, MFR2.0, density 0.
907, manufactured by Nippon Polychem Co., Ltd.), and the ratio of the film thickness of the front film layer (A) to the back film layer (B) was changed to 3: 1. A polyolefin resin laminate sheet having a thickness of 0.91 mm and a mass of 855 g / m ² was obtained. (Thickness of film (A): 0.4
2mm, thickness of film (B): 0.14mm)

Table 6 shows the compositions of the surface film layers of Comparative Examples 1 to 8, and Table 7 shows the properties of the obtained polyolefin resin laminated sheet.

[0098]

[Table 6]

[0099]

[Table 7]

[Results of Comparative Examples 1 to 8] Comparative Examples 1 to
Although the laminated sheet obtained in Comparative Example 4 is particularly excellent in flexibility and high-frequency weldability, the total content of the vinyl acetate component and (meth) acrylic acid (ester) in the surface film layer (A) is 20. Weight percent or more,
Further, the ethylene-α-olefin copolymer resin was not blended in the surface film layer (A) of Comparative Examples 1 to 3,
Further, in Comparative Examples 1 to 6, the ratio of the film thickness (A):
By setting (B) to 2: 3, in the abrasion test, the more the fiber fabric was exposed, the lower the abrasion resistance. Further, the laminated sheets obtained in Comparative Examples 1 to 4 are:
It was also inferior in humidity barrier property and heat creep resistance. In particular, in Comparative Example 4, the textile fabric was subjected to a pretreatment with a polyurethane resin, but not only the adhesive effect was not exhibited, but also the texture of the laminated sheet was hardened, and at the same time, the tear strength of the laminated sheet was reduced to 40. % Has been confirmed. Comparative Example 5,
In Comparative Example 6, the pretreatment of the base fabric was changed to an acrylic resin and a polyester resin, respectively. It was clarified that it decreased by almost 40%. In particular, the laminated sheets obtained in Comparative Example 5 and Comparative Example 6 were very excellent in abrasion resistance.
The hand was hard and high frequency welder fusion was impossible. Therefore, the sheet of Comparative Example 5 and Comparative Example 6 is pressed and heat-fused with a mold (trowel) heated with a heater above the melting temperature of the thermoplastic resin (Quinlite Electronics Seiko Co., Ltd.) : LHP-W603 hot plate heat sealing machine) to produce a joint test piece and evaluate the joint strength and the heat creep resistance. As a result, the joints of the sheets of Comparative Example 5 and Comparative Example 6 were all broken. In particular, in the laminated sheet of Comparative Example 6, which contains a large amount of a linear low-density polyethylene resin polymerized with a metallocene catalyst in both the film layer (A) and the film layer (B), the heat-resistant creep is The properties were extremely poor. Comparative Example 7 in which only the film layer (A) was changed to a linear low-density polyethylene resin
In Comparative Example 8 as well, high frequency weldability was similarly impossible.

[0101]

As is clear from the above Examples and Comparative Examples, the present invention provides a polyolefin-based resin laminated sheet having a soft feel and excellent abrasion resistance and capable of high-frequency welder fusion, and It has become possible to obtain a polyolefin-based resin laminated sheet having excellent fracture strength and heat-resistant creep resistance of a fusion-bonded portion and high humidity barrier properties. Therefore, the polyolefin-based resin laminated sheet obtained by the present invention is particularly suitable for a raw material for a flexible container, and can be used in a field where a soft polyvinyl chloride resin product was conventionally used as a sheet for industrial materials. It is a very useful laminated sheet as a substitute for a flexible polyvinyl chloride resin product.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4F100 AA20A AA20B AA20C AA20H AH06B AK63A AK63C AK68A AK68C AK70A AK70C AK71A AK71C AL05A AL05C BA06 BA10A BA10C BA25 BA27 CA23A CA23C DG11J12 EJ11J12

Claims (12)

[Claims] 1. A base fabric made of a fiber fabric, and a front film layer (A) and a back film layer (B) laminated on both front and back surfaces of the base fabric, and (1-1) the front film layer (A) is: (a) a main component comprising a linear low-density ethylene-α-olefin copolymer comprising a copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms; Ethylene-vinyl acetate copolymer and ethylene-
A blend component comprising at least one selected from (meth) acrylic acid (ester) copolymers, and vinyl acetate and (meth) acrylic acid (ester) contained as copolymer components in the blend component (b). ) Is formed of a blend resin (1) in which the ratio of the total weight of the main component (a) and the blend component (b) to the total weight of the blend resin (1) is 4 to 16% by weight; (B) a main component comprising: (c) a linear low-density ethylene-α-olefin copolymer comprising a copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms; Ethylene-vinyl acetate copolymer and ethylene-
A blend component of at least one selected from (meth) acrylic acid (ester) copolymers, and vinyl acetate and (meth) acrylic acid (ester) contained as copolymer components in the blend component (d). Is formed of a blend resin (2) having a ratio of the total weight of the main component (c) and the blend component (d) to the total weight of the main component (c) and the blend component (d) of more than 16% by weight and 30% by weight or less; 1-3) A wear-resistant polyolefin-based resin laminated sheet, wherein the thickness ratio between the front film layer (A) and the back film layer (B) is 1: 1 to 3: 1. . 2. The method according to claim 1, wherein at least one of the front film layer (A) and the back film layer (B) has a weight of 1 to 10%.
The abrasion-resistant polyolefin-based resin laminated sheet according to claim 1, wherein the sheet contains synthetic amorphous silica by weight. 3. The moisture permeability (JIS Z 020) of a laminate with the front film layer (A) and the back film layer (B).
8) is 10 g / m ² · 24 hours or less, the wear-resistant polyolefin-based resin laminated sheet according to claim 1 or 2. 4. A base fabric made of a fiber cloth, and a front film layer (A) and a back film layer (C) laminated on both front and back surfaces of the base fabric, and (2-1) the front film layer (A) is: (a) a main component comprising a linear low-density ethylene-α-olefin copolymer comprising a copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms; Ethylene-vinyl acetate copolymer and ethylene-
A blend component of at least one selected from (meth) acrylic acid (ester) copolymers, and vinyl acetate and (meth) acrylic acid (ester) contained as copolymer components in the blend component (b). And (2) the back film. (C) is (e) an ethylene-vinyl acetate copolymer and ethylene-
Vinyl acetate which is formed of a copolymer resin comprising at least one selected from (meth) acrylic acid (ester) copolymers and which is contained as a copolymer component in the copolymer resin (e); The ratio of the total weight of (meth) acrylic acid (ester) to the total weight of the copolymer resin (e) is higher than 16% by weight and 30% by weight.
(2-3) abrasion resistance, wherein the ratio of the thickness of the front film layer (A) to the thickness of the back film layer (C) is 1: 1 to 3: 1 Polyolefin resin laminated sheet. 5. The method according to claim 1, wherein at least one of the front film layer (A) and the back film layer (C) has a weight of 1 to 1
4. The composition of claim 3, comprising 0% by weight of synthetic amorphous silica.
2. The abrasion-resistant polyolefin-based resin laminated sheet according to item 1. 6. The moisture permeability (JIS Z 020) of a laminate with the front film layer (A) and the back film layer (C).
8) is 10 g / m ² · 24 hours or less. 7. The abrasion resistance according to claim 1, wherein the base fabric is pretreated with a treating agent containing at least one silicon compound. Polyolefin resin laminated sheet. 8. The abrasion-resistant polyolefin-based resin laminated sheet according to claim 7, wherein the silicon compound is selected from synthetic amorphous silica, colloidal silica, and a silane coupling agent. 9. The fiber fabric for a base fabric according to any one of claims 1 to 8, wherein the fabric for a base fabric is constituted by multifilament yarns and has a porosity between yarns of 5 to 30%. Abrasion resistant polyolefin resin laminated sheet. 10. The abrasion-resistant polyolefin-based resin laminated sheet according to claim 1, wherein the surface film layer (A) has a thickness of at least 0.1 mm. 11. The main component (a) contained in the surface film layer (A) is obtained by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms in the presence of a metallocene catalyst. The resulting linear low-density ethylene-α-
The wear-resistant polyolefin-based resin laminated sheet according to any one of claims 1 to 10, comprising an olefin copolymer. 12. The main component (c) contained in the back film layer (B) is obtained by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms in the presence of a metallocene catalyst. The resulting linear low-density ethylene-α-
Claims 1, 2, 3, 7, 7, comprising an olefin copolymer.
The wear-resistant polyolefin-based resin laminated sheet according to 8, 9, 10, or 11.